Gianluca Farinola, University degli Studi-Bari Aldo Moro
Eric Glowacki, Linkoping Unversity
Radislav Potyrailo, GE Global Research
Silvia Vignolini, University of Cambridge
APL Photonics | AIP Publishing
BM03.01: Biological Materials for Photonics
Monday AM, November 27, 2017
Sheraton, 2nd Floor, Back Bay D
8:45 AM - *BM03.01.01
Biomaterial-Based Optical Interfaces and Devices
Fiorenzo Omenetto 1 Show Abstract
1 , Tufts University, Medford, Massachusetts, United States
Light control in natural structures is a based on wondrous interplay between electromagnetic radiation and the patterns and compositions of natural materials compounded by biochemical processes that lead to spectral selectivity, reflections, diffusion, and photoconversion, to name a few. These natural strategies have offered inspiration on how to emulate their behavior and performance and considerable effort is dedicated in mimicking the structures that are ubiquitous in the world that surrounds us.
In this context, a particularly interesting approach is to employ Nature’s materials to generate structures that manipulate light in controllable and efficient ways.
In this talk we will review different uses and transformation of structural proteins (with specific focus on silk) to describe active and passive optical devices based on biopolymers substrates. Multiple devices, ranging from diffractive optics, photonic crystals, microresonators and lasers, will be described. The possibility of embedding seamlessly into the biopolymeric matrices biological function allows for facile fabrication and doping of photonic components that have renewed utility at the interface between biology and photonics.
9:15 AM - BM03.01.02
Study of Rare-Earth-Doped Silk Fibroin for the Development of Photonic Devices
Roberta Pugina 1 , Euzane da Rocha 1 , José Maurício Caiut 1 Show Abstract
1 , University of São Paulo, Ribeirão Preto Brazil
The present work aims to study an innovative approach for the development of photonic devices based in Silk Fibroin (SF) doped with Rare Earth (RE) ions. There are no studies about light emission in rare earth doped fibroin, however, the combination of mechanical and optical properties of fibroin with the multifunctionality of rare earth ions can be a way to develop new and distinguished photonic devices. The initial interest is due to the matrix being biocompatible, biodegradable and from renewable origin; it also has high transparency in different spectral regions and variable refractive index. Furthermore, the fibroin matrix could be easily functionalized and the physical-chemistry properties can be tunable, which can provide a greater versatility of the proposed materials. In addition, the use of rare earth doped materials on photonics is well-known, as solid-state lasers at UV-vis NIR spectral region, light emitting devices, fibers for optical amplifier, and data storage systems. This study will allow the use of europium ions as structural probes in composite fibroin matrix and to get systems with potential application in random Laser emission. Self-supported films were obtained from silk fibroin doped with rare earth ions and the samples were noted as SF_film+X%RE3+ (X = 0.0; 0.1; 0.5; 1.0; 2.0; and RE = Eu3+ or Tb3+ or Gd3+). Among all 5263 amino acid residues present at the Bombyx mori silk fibroin, there are aromatic amino acids with fluorescent behavior, as tyrosine (Tyr) and tryptophan (Trp). Both are well-known as fluorescent probes of physical-chemistry properties, and in the presence of rare earth ions, these amino acids may act as a sensitizer in energy transfer process. The results have shown an emission of rare earth ion associated with an antenna effect by amino acids, and distinct photophysical properties were obtained for different ions. To understand the whole process, the Triplet state of tryptophan in SF was determined, and the energy process was described. The energy of Trp triplet state allows a quite efficient energy transfer from Trp to the Tb3+ ion. In addition, beta-diketones ligands were added to the rare-earth-doped silk fibroin to improve the emission of rare earth ion. New composites were synthetized, SF_film+X%RE3+-Lig (Lig = Acetylacetone or 2-Thenoyltrifluoroacetone, for film with terbium or europium, respectively). The emission enhancement has been achieved for Eu3+ ion, and these results corroborated with the distinct mechanism to the energy transfer process among the SF and Tb3+ and Eu3+. In conclusion, the results obtained in this research allowed understanding the mechanism of excitation of rare earth ion into silk fibroin matrix; and this work becomes a background for the development of new photonic systems.
Acknowledgements: FAPESP (Grant n°. 2016/11670-5), CNPq and USP.
9:30 AM - BM03.01.03
Bio Inspired Bragg Reflector Made of Silk-Titanates Nanocomposite as Platform for Humidity Sensing
Elena Colusso 1 , Fiorenzo Omenetto 2 , Alessandro Martucci 1 Show Abstract
1 , Universita di Padova, Padova Italy, 2 , Tufts University, Boston, Massachusetts, United States
In this work, we report a structurally-colored multilayer film, which can be considered a Bragg reflector, with humidity-responsive optical properties, inspired to the cuticle of Hoplia coerulea. This beetle is able to modify its color in the presence of moisture, which affect the thickness and refractive index of the cuticle. In the same way, our multilayer structure responds to changes in the environmental humidity with a reversible color change. For the generation of interference color, we combined the regenerated silk fibroin, which has a refractive index of 1.55, with a nanocomposite made of silk and titanate nanosheets, a novel 2D material that presents a high refractive index. The multilayer film was fabricated through a layer by layer deposition from the respective water-based solutions by spin coating. The final structure exhibits an interference peak in the transmittance spectrum centered at 400 nm, whose position responds to changes in the relative humidity of the environment. The stimuli-responsive properties of the film were characterized and a simple optical model for the sensing mechanism was proposed. Specifically, the silk-based multilayer showed a reversible color change when exposed to different relative humidity, and good performances in term of reproducibility and stability over time.
9:45 AM - BM03.01.04
Vapor Sensing Properties of Photonic Nanoarchitectures of Biological Origin
Gabor Piszter 1 , Krisztián Kertész 1 , Géza Márk 1 , Zsolt Bálint 2 , Zsolt Horváth 1 , László Biró 1 Show Abstract
1 , Centre for Energy Research, Hungarian Academy of Sciences, Budapest Hungary, 2 , Hungarian Natural History Museum, Budapest Hungary
The photonic crystal type nanoarchitectures occurring in the wing scales of the butterflies are widely investigated both structurally and from the optical point of view . These nanoarchitectures are mainly constituted of chitin and air, and the structural coloration they generate is modulated by the periodicity and characteristic dimensions of the nanostructure, and also by the refractive indices of the building materials. Small changes in the refractive index or in the periodicity, like which are induced by different vapors in the surrounding atmosphere, can generate color variation of the wings perceptible with optical spectrometry . The mechanism beyond vapor sensing is the capillary condensation of the volatiles in the nanocavities of the photonic nanoarchitecture . It was shown that these color changes are substance-specific , and can be enhanced by the pretreatment of the wings . We also showed recently that when using Lycaenid butterfly wings, the color changes can be best interpreted in their visual space .
In the present work the general findings regarding the mechanism of sensitivity and selectivity, and the parameters influencing the sensing will be discussed. The work is also focused on the comparison of wing scales of different butterfly species as their various nanoarchitectures react differently for different vapor types and external temperatures. The diversity of the measured signals, in combination with proper data processing methods, is used for enhancing selective vapor sensing. As vapor sensing measurements require high reproducibility of the measured signals, the variability of the biological sensor materials – the polyommatine butterfly wings – were investigated, too. We tested the stability of the wing coloration in the case of Polyommatus icarus butterflies collected from a local population , and from a large temporal and spatial range.
 L.P. Biró & J.P. Vigneron: Photonic nanoarchitectures in butterflies and beetles: valuable sources for bioinspiration, Laser Photon. Rev. 5, (2011) 27.
 R.A. Potyrailo, H. Ghiradella, A. Vertiatchikh, K. Dovidenko, J.R. Cournoyer, E. Olson: Morpho butterfly wing scales demonstrate highly selective vapour response, Nat. Phot. 1, (2007) 123.
 K. Kertész, G. Piszter, E. Jakab, Zs. Bálint, Z. Vértesy, L.P. Biró: Color change of Blue butterfly wing scales in an air-vapor ambient, Appl. Surf. Sci. 281, (2013) 49.
 G. Piszter, K. Kertész, Z. Vértesy, Zs. Bálint, L.P. Biró: Substance specific chemical sensing with pristine and modified photonic nanoarchitectures occurring in blue butterfly wing scales, Opt. Express 22, (2014) 22649.
 G. Piszter, K. Kertész, Zs. Bálint, & L.P. Biró: Pretreated Butterfly Wings for Tuning the Selective Vapor Sensing, Sensors 16, (2016) 1446.
 K. Kertész, G. Piszter, Z.E. Horváth, Zs. Bálint & L.P. Biró: Changes in structural and pigmentary colours in response to cold stress in Polyommatus icarus butterflies, Sci. Rep. 7, (2017) 1118.
10:30 AM - *BM03.01.05
Light-Emitting Diatoms as Hybrid Photonic Biomaterials
Thomas Fuhrmann-Lieker 1 Show Abstract
1 , University of Kassel, Kassel Germany
The ornamental structure of the diatom cell wall is a perfect example for a self-organized biophotonic structure. From the optical point of view, the cell wall can be regarded as a slab waveguide with a more or less regular photonic crystal pattern, thus defining a photonic resonator with distinct optical modes. The functionality can be further enhanced by the incorporation of laser dyes with in vivo fluorochromation techniques which results in biological-artificial hybrid materials. We demonstrate recent advances in our lab in applying these structures for elucidating the photonic properties of the cell wall. By dual staining, donor-acceptor dye pairs for resonant energy transfer can be incorporated which allows us an estimation of the incorporation density. By conoscopic measurements we show the angle-dependent emission of the slab and identify potential resonances for lasing modes. An understanding of the photonic properties of diatom biosilica may reveal possible light-harvesting mechanisms contributing to efficient photosynthesis and may find applications in the design of solar cells.
11:00 AM - *BM03.01.06
Properties and Uses of Diatoms and Diatom Biosilica in Optics and Photonics
Eike Brunner 1 , Matthias Finger 1 , Anne Jantschke 2 , Janine Kaden 1 , Susanne Machill 1 , Cathleen Oschatz (née Fischer) 1 , Nathalie Pytlik 1 Show Abstract
1 , TU Dresden, Dresden Germany, 2 , Weizmann Institute of Science, Rehovot Israel
Diatoms are single-celled microorganisms capable of forming remarkable SiO2 (silica) based cell walls. Diatom biosilica represents a hierarchically structured organic-inorganic hybrid material of elaborate composition and supramolecular architecture which is studied for example by solid-state NMR spectroscopy [1,2]. It exhibits hierarchical patterns of nano- to microscale features which endow the material with interesting properties that are difficult to reproduce synthetically. This is also true with respect to the optical properties. It is sometimes speculated that the siliceous cell walls of diatoms may act as photonic crystals . Diatom biosilica uniformly coated with noble metal nanoparticles exhibits favorable Surface Enhanced Raman Scattering (SERS) activities . This property turns out to be useful for signal enhancement with respect to the study of silica-attached biomolecules and also with respect to future applications of nanoparticle-coated biosilica as SERS substrates. It is even possible to couple nanoparticles regioselectively to certain regions of the diatom cell walls . 2D arrays of diatom cell walls could successfully be generated by micromanipulation.
Finally, remarkable SERS effects from the cell interior of intact diatoms could recently be observed by our group  following an in vivo gold nanoparticle synthesis approach  by adding dissolved gold salts to the growth medium of the algae. Gold nanoparticles of two different size classes (10-20 nm and about 50 nm in diameter) were synthesized in the algae-containing growth medium. 3D Raman imaging unequivocally revealed the presence of gold nanoparticles inside intact cells as could be proven by strong SERS enhancements located inside the cell. These spectra even allowed identification of certain biomolecules. That means, the novel in situ approach paves the way to Raman spectroscopic studies on intact diatom cells.
In summary, diatoms and diatom biosilica exhibit remarkable optical properties which are promising for various applications.
 A. Jantschke, E. Koers, D. Mance, M. Weingarth, E. Brunner, M. Baldus, Angew. Chem. Int. Ed. 2015, 54, 15069.
 D. Wisser, S.I. Brückner, F.M. Wisser, G. Althoff-Ospelt, S. Kaskel, E. Brunner, Solid State Nucl. Magn. Reson. 2015, 66/67, 33.
 T. Fuhrmann, S. Landwehr, M. El Rharbi-Kucki, M. Sumper, Appl. Phys. B 2004, 78, 257.
 A. Jantschke, A.-K. Herrmann, V. Lesnyak, A. Eychmüller, E. Brunner, Chemistry - An Asian Journal 2012, 7, 85.
 A. Jantschke, C. Fischer, R. Hensel, H.-G. Braun, E. Brunner, Nanoscale 2014, 6, 11637.
 N. Pytlik, J. Kaden, M. Finger, S. Machill, E. Brunner, submitted.
 R.H. Lahr, P.J. Vikesland, ACS Sustain. Chem. Eng. 2014, 2, 1599.
11:30 AM - BM03.01.07
Random Lasers from All-Marine Materials
Wei-Ju Lin 1 , Cheng-Han Chang 1 , Shih-Yao Lin 1 , Yang-Fu Huang 1 , Yu-Ming Liao 1 , Golam Haider 1 , Hung-I Lin 1 , Tai-Yuan Lin 2 , Yang-Fang Chen 1 Show Abstract
1 Department of Physics, National Taiwan University, Taipei Taiwan, 2 Institute of Optoelectronic Science, National Taiwan Ocean University, Taipei Taiwan
With the greatly rising awareness of environmental protection, future optoelectronic devices are expected to possess characteristics with biodegradability, biocompatibility, and biometabolizability. This work has been a desirable but challenging issue for years.
In this experiment, we first fabricate the random laser (RL) consisting of chlorophyll extracted from diatoms, which serves as the gain medium, and blue coral skeleton powders as the scattering centers. As a bio-material, chlorophyll is non-toxic to human beings. Besides, it is abundant, and available from living creatures not only on land, but also in the ocean, like algae. The ubiquitous existence of diatoms in the ocean makes the source of this all-marine random laser device easily accessible. Chlorophyll plays a central role in photosynthesis, under photoexcition it will initiate the electron-transfer process. Therefore, studies of photosensitization of chlorophyll may benefit many future optoelectronic research. For example, the porphyrin structure in chlorophyll is the light-absorbing chromophore and has been used in optoelectronic technology. Chlorophyll has also been applied to organic photovoltaics and phototransistors. In addition, there are many applications based on photoluminescence of chlorophyll, such as evaluation of stress in plants, species differentiation, screening, and diagnostic tools. Marine creatures such as abalone, clam, nacre, and coral produce mineralized tissues such as shells and skeletons by sophisticated biomineralization process. The well-defined structures of these tissues confer superior mechanical strength and toughness that make these shells and skeletons durable and reusable materials. In addition, such layer-by-layer, brick-and-mortar, and nanopillar structures can be used to fabricate other hybrid materials with both excellent mechanical and optical properties in biomimetics. Among these marine materials, we select the blue coral skeletons as the scattering centers to assist the occurrence of laser action. Blue coral skeletons possess compact structures on the fracture surface, which makes blue coral skeleton powders a good scattering medium. Besides, the nanostructures on the fracture surface can be easily obtained by simply breaking or grinding the coral skeletons in comparison with the complicated and time-consuming procedures of building scattering media and cavities in conventional laser devices. Using coral skeletons to serve as the scatterers can greatly simplify the fabrication process and reduce the cost of the building devices.
The observed random lasing action can be well understood based on the enhanced light emitted from chlorophyll and scattered by the fracture surfaces of coral skeleton. We stress that the first all-marine based random laser presented here meets the major trend toward biological devices for the development of future sustainable society.
11:45 AM - BM03.01.08
Natural Inspiration and Natural Materials for Lasing Action
Cefe Lopez 1 Show Abstract
1 , CSIC, Madrid Spain
The use of self-assembling monodisperse colloidal particles has been observed in animal physiology such as fireflies  where it is used to enhance the light emitted by chemiluminescence and laser technology has adopted it to create resonant random lasers  and this required the scattering properties of the passive part of the systems to be accounted for which is here done by analyzing the scattering properties of fabricated photonic glasses . When polydisperse granular systems are used instead, it is possible to separate the gain and feedback functions by physically separating the associated materials . Here the natural inspiration is substituted for the use of natural materials such as DNA that has proven a very versatile optical material since it thermally very stable and permits customization of solubility, casting or spin coating processing, laser ablation and a long etc.
 L. Chen, et al. Sci. Rep. 5, 12965 (2015).
 S. Gottardo, et al. Nat. Photonics 2, 429–432 (2008).
 D. Montesdeoca, et al. Part. Part. Syst. Charact. 33, 871–877 (2016).
 A. Consoli, et al. Sci. Reports 5, 16848 (2015); A. Consoli, et al. Opt. Express, 23, 29954 (2015)
BM03.02: Biotic/Abiotic Interfaces and Hybrid Photonics Structures
Monday PM, November 27, 2017
Sheraton, 2nd Floor, Back Bay D
1:30 PM - *BM03.02.01
Organic Bio Photonics
Guglielmo Lanzani 1 2 Show Abstract
1 , Italian Institute of Technology, Milano Italy, 2 Physics, Politecnico di Milano, Milan Italy
Organic semiconductors in different shapes and composition can be interfaced with living cells. This provides a new, exciting route towards optical control of physiological functions or the restoring of natural functions. Abiotic-biotic coupling is evident in a number of experiments in cells and small animals, up to the demonstration of restored visual acuity in blind animals . Yet the mechanism explaining such coupling is still unknown. Thermal, capacitive, faradaic or chemical coupling are all options to be carefully evaluated. In the talk, after a review of a number of practical applications, and hypothesis will be discussed on the possible mechanism.
 José Fernando Maya-Vetencourt et al. “A fully organic retinal prosthesis restores vision in a rat model of Degenerative blindness” DOI: 10.1038/NMAT4874 .
2:00 PM - *BM03.02.02
Biophotonic Nanostructures for Medical Applications—From Low Concentration Protein Sensing to In Vivo Intraocular Pressure Sensing
Radwanul Siddique 1 , V. Narasimhan 1 , Shailabh Kumar 1 , Hyuck Choo 1 2 Show Abstract
1 Department of Medical Engineering, California Institute of Technology, Pasadena, California, United States, 2 Department of Electrical Engineering, California Institute of Technology, Pasadena, California, United States
Evolution-driven biophotonic nanostructures can effectively manipulate the flow of light as well as the surface properties for many biological processes. Mimicking such optimized photonic prototypes is playing an unprecedented important role in the design and function of optical devices and technologies. Inspired by the phase separation mechanism of self-assembled biophotonic nanostructures, we fabricated bio-inspired nanostructures using a scalable, self-assembly patterning technique based on the phase separation of binary polymers mixture for structural coloration and photovoltaic applications [1, 2]. In this talk, I will present that by integrating those nanostructures on a sub-micron implantable intraocular pressure (IOP) sensor for glaucoma management, we have found significant improvement of sensor’s IOP detection range and optical sensitivity . Furthermore, such nanostructures show remarkable antifouling property by preventing protein and bacteria adhesion and minimizing tissue proliferation that promises much improved long-term implant reliability.
In addition, we combined our biomimetic design with plasmonics to create a large-scale flexible metal-insulator-metal (MIM) metasurfaces [1,4]. Such bio-inspired metasurface consists of densely and randomly distributed aluminum nanodisk in a sub-micron cavity (n-DISC) that strongly confines broadband light in sub-10nm gap independent of their size. Using this metasurface, we have demonstrated low concentration protein sensing based on surface-enhanced fluorescence by the capture of proteins directly at the MIM ‘hotspot’ . Our promising results show that the metasurface with a unique bio-inspired architecture can serve as an inexpensive and versatile tool for in vitro as well as potentially in vivo biomolecule detection and characterizations.
 R. H. Siddique J. Mertens, H. Hölscher and S. Vignolini, Light: Science & Applications 6, e17015 (2017)
 R. H. Siddique, Y. J. Donie, G. Gomard, S. Yalamanchili, T. Merdzhanova, U. Lemmer, H. Hölscher, Submitted (2017)
 V. Narasimhan, R. H. Siddique J. O. Lee, B. Ndjamen, J. Du, N. Hong, D. Stratevan, H. Choo, Submitted (2017)
 R. H. Siddique, S. Kumar, H. Kwon, H. Choo, Submitted (2017)
2:30 PM - *BM03.02.03
Semiconducting Nanoparticles to Modulate Biological Functions—Lessons from an Ancient Model Organism
Claudia Tortiglione 1 Show Abstract
1 Istituto di scienze applicate e sistemi intelligenti "E.Caianiello", Consiglio Nazionale delle Ricerche, Pozzuoli Italy
Nanotechnologies may boost research on fundamental properties of light and how it interacts with matter. In the context of a living organism, this interaction is hampered by the complexity of the living matter, making technological advancement key aspect of this research. The development of biocompatible photonic devices may offer unique tools to finely tune biological functions. Here we demonstrated the possibility to modulate biological functions by photostimulation of polymer nanoparticles based on poly(3-hexylthiophene) (P3HT-NP), a conjugated polymer widely used in photovoltaic application. By using as model organism the freshwater polyp Hydra vulgaris, presenting photic behaviour despite the absence of proper eyes, we show that P3HT-NP internalized into animal tissues modulate the light response at two different levels: (i) by modulation of the animal photobeviour, enhancing the frequency of spontaneous contraction events and (ii) by inducing transcriptional activation of the opsin3-like gene, which in vertebrates is involved in the intracellular transduction of the light signal. Moreover, the peculiar capabilities of the polyp to regenerate missing parts of amputated body allowed us to investigate the potential of P3HT-NP to enhance tissue regeneration. We observed in treated animals a boost in the regeneration efficiency under light illumination, uncovering a new function of these light nanotransducers in regenerative medicine and opening up new scenario on future therapeutic purposes. The possibility to modulate by light biological functions in this eyeless animal put forward the potential of this approach toward the control of physiological functions in higher living organisms.
3:30 PM - *BM03.02.04
Direct Electrical Activation of a Blind Retina Mediated by Optical Stimulation of Semiconducting Organic Pigments
David Rand 2 1 , Eric Glowacki 3 , Marie Jakesova 3 , Gur Lubin 2 1 , Ieva Vebraite 5 , Oded Shoseyov 5 , Niyazi Serdar Sariciftci 4 , Yael Hanein 2 1 Show Abstract
2 Center for Nanoscience and Nanotechnology, Tel Aviv University, Tel Aviv Israel, 1 School of Electrical Engineering, Tel Aviv University, Tel-Aviv Israel, 3 Department of Science and Technology, Linköping University, Norrköping Sweden, 5 Faculty of Agriculture, Food and Environment, The Hebrew University of Jerusalem, Rehovot Israel, 4 Linz Institute for Organic Solar Cells, Johannes Kepler Universität Linz, Linz Austria
Optical stimulation of neurons using photosensitive materials was demonstrated in recent years. These materials are cheap, easy to fabricate, and have unique properties such as flexibility, ability to operate in a wet environment, and biocompatibility. Their realization on soft and transparent thin film carriers is a promising alternative for contemporary retinal implants, which are based on rigid materials and complex electronics that require dry conditions and external power source. In order to obtain precise temporal response from such a photosensitive device, a direct electrical stimulation that results in a short neuronal response-latency is required. This is achieved by a sufficient high charge separation that can drive the membrane potential to the threshold for action potential, as indicated in numerous prior investigations that used direct electrical stimulation. Such a stimulation also has to be capacitive in nature, avoiding harmful faradaic redox reactions. Currently, the activating mechanisms of these novel materials are not fully elucidated. Specifically, charge density may be too low for direct electrical activation and the response latency is very long. One plausible mechanism of activation that was recently proposed is a photo-thermal effect that induces changes in the electrical properties of the membrane by heating the close proximity of the cell. Here, we demonstrate organic photosensitive pigments that optically induce direct electrical activation of light-insensitive retinal extracts. This activation was obtained by a high capacitive photoelectric response of a functional biocompatible semiconductor film made from hydrogen-bonded organic pigments of ubiquitous commercial colorants. To design a functional implant, we also develop a thin, soft, and transparent silk fibroin film that adheres well to retinal extracts and serves as a substrate for these photosensitive pigments.
4:00 PM - BM03.02.05
Organic Haptics—Soft Materials for Artificial Touch
Darren Lipomi 1 Show Abstract
1 , University of California, San Diego, La Jolla, California, United States
Human culture is replete with artifacts that interact with the senses of sight, hearing, taste, and smell. Material objects whose purpose is to produce a thoughtful or emotional response through the sense of touch, however, are rare. In this talk, I present my group’s recent work on the intersection between the science of soft materials and the science of touch. This field, which we have named “organic haptics,” combines active polymers, contact mechanics, and psychophysics. We are beginning to understand the ways in which stick slip friction, adhesion, and capillary forces between planar surfaces and human skin affect the ways materials produce tactile objects in consciousness as mediated by the sense of touch. This work, which combines human subject experiments, laboratory mockups of human skin, and analytical models accounting for friction, has led to several important observations. In particular, we have elucidated the mechanism by which humans can differentiate hydrophilic from hydrophobic surfaces when bulk parameters such as hardness, roughness, and thermal conductivity are held constant. We examined the role of relief structures in the skin—i.e., fingerprints—in determining the human ability to differentiate between surfaces. We have taken the insights from these psychophysical experiments to design new electroactive and ionically conductive materials to produce “actuator skins” whose goal is to produce realistic sensations for applications in tactile therapy, instrumented prostheses, education and training, and virtual and augmented reality.
4:15 PM - BM03.02.06
Remote-Controlled Insect Navigation Using Plasmonic Nano Tattoos
Sirimuvva Tadepalli 1 , Sisi Cao 1 , Debajit Saha 2 , Keng-Ku Liu 1 , Alex Chen 2 , Sang hyun Bae 1 , Baranidharan Raman 2 , Srikanth Singamaneni 1 Show Abstract
1 Institute of Material Science and Engineering and Department of Mechanical Engineering and Material Science, Washington University in St. Louis, St. Louis, Missouri, United States, 2 Department of Biomedical Engineering, Washington University in St. Louis, St Louis, Missouri, United States
Developing insect cyborgs by integrating external components (optical, electrical or mechanical) with biological counterparts has a potential to offer elegant solutions to complex engineering problems.1 A key limiting step in the development of such biorobots arises at the nano-bio interface, i.e. between the organism and the nano implant that offers remote controllability.1,2 Often, invasive procedures are necessary that tend to severely compromise the navigation capabilities as well as the longevity of such biorobots. Therefore, we sought to develop a non-invasive solution using plasmonic nanostructures that can be photoexcited to generate heat with spatial and temporal control. We designed a ‘nanotattoo’ using silk that can interface the plasmonic nanostructures with a biological tissue. Our results reveal that both structural and functional integrity of the biological tissues such as insect antenna, compound eyes and wings were preserved after the attachment of the nanotattoo. Finally, we demonstrate that insects with the plasmonic nanotattoos can be remote controlled using light and integrated with functional recognition elements to detect the chemical environment in the region of interest. In sum, we believe that the proposed technology will play a crucial role in the emerging fields of biorobotics and other nano-bio applications.
1 Giselbrecht, S., Rapp, B. E. & Niemeyer, C. M. The Chemistry of Cyborgs—Interfacing Technical Devices with Organisms. Angewandte Chemie International Edition 52, 13942-13957, doi:10.1002/anie.201307495 (2013).
2 Bozkurt, A., Gilmour Jr, R. F., Sinha, A., Stern, D. & Lal, A. Insect–machine interface based neurocybernetics. IEEE Transactions on Biomedical Engineering 56, 1727-1733 (2009).
4:30 PM - BM03.02.07
Microlasers for Dynamic Refractive Index Sensing within Live Cells
Marcel Schubert 1 , Isla Barnard 1 , Klara Volckaert 1 , Lewis Woolfson 1 , Frederik Van Acker 1 , Markus Karl 1 , Simon Powis 1 , Andrew Morton 1 , Malte Gather 1 Show Abstract
1 , University of St. Andrews, St Andrews United Kingdom
The change of cell morphology and phenotype is an impressive demonstration of nature’s ability to adapt to external stimuli. It is of fundamental importance for a number of biological processes ranging from neuronal development, and wound healing to cancer progression. While optical methods promise to sense these changes remotely, with high sensitivity and in real time the integration of photonic devices in tissue and single cells has proven extremely difficult.
Intracellular lasers are a revolutionary new way to combine optical devices with living cells and organisms. We have recently demonstrated that microscopic organic whispering gallery mode (WGM) lasers can be transferred into live cells. These lasers are formed by polymer microspheres doped with highly fluorescent dye molecules. Due to the broad gain spectrum, they provide multi-modal barcode-like emission which allows long term tagging and tracking of thousands of cells, in various cell types and even over several cell generations.
Furthermore, by maximizing the evanescent field component of WGM microlasers, the lasing wavelength becomes sensitive to the refractive index (RI) close to the microsphere surface. Analysing the laser spectra allows to extract both, the exact size of the laser tag and the refractive index simultaneously, introducing exciting new ways to study the function and properties of individual cells over long periods of time. To demonstrate the practicability of this method, we present data taken during internalization of WGM lasers, cell division, as well as cell differentiation, and calculate the change in local RI from the observed spectral shifts. The unique and novel combination of cell tagging and highly sensitive RI measurements will help to understand the functional complexity of live cells during differentiation and cancer metastasis.
 M. Schubert et al., Lasing within Live Cells Containing Intracellular Optical Microresonators for Barcode-Type Cell Tagging and Tracking, Nano Letters, 5647 (2015).
 M. Schubert et al., Lasing in Live Mitotic and Non-Phagocytic Cells by Efficient Delivery of Microresonators, Scientific Reports, 40877 (2017).
4:45 PM - BM03.02.08
Radiate Like an Ant—Polymer Metamaterial Fabrics for Personal Passive Thermal Management
Hadi Zandavi 1 , George Ni 2 , Richard Pang 2 , Richard Osgood 2 , Preet Kamal 3 , Amit Jain 3 , Gang Chen 1 , Svetlana Boriskina 1 Show Abstract
1 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States, 2 Materials Science and Engineering Branch, Warfighter Directorate, US Army Natick Soldier Research, Development, and Engineering Center, Natick, Massachusetts, United States, 3 , Shingora Textiles Limited, Ludhiana India
Nature has developed a bounty of passive optical technologies for visible light reflection and structural color formation via scattering by nano- and micro-scale features. While reflection and color formation are important for communications and protection, the sun and animal (including human) bodies also generate invisible photon emission. About half of solar energy reaching the Earth surface is delivered by invisible infrared photons, and human bodies emit exclusively in the IR spectral range.
We will report on design, fabrication, and testing of flexible metamaterials (fabrics) that can provide either passive radiative cooling or radiative heat trapping by utilizing optical resonant effects in polymer microfibers. The fabrics can be designed to help people feel cooler by allowing thermal infrared emission from the skin to pass through the clothes, or, alternatively, to act as a thermal blanket by trapping the radiation inside . This passively-cooling technology is similar to the survival mechanism of Saharan silver ants, whose bodies reflect the heat from the sand while emitting thermal radiation from their backs into the sky to stay cool in the desert heat [2,3].
The developed wearable technology is based on optimal material composition as well as on different mechanisms of electromagnetic waves scattering on obstacles that are either smaller or larger than the photon wavelength. Synthetic polymers that support few vibrational modes were identified as candidate materials to reduce intrinsic material absorption in the infrared wavelength range. Individual fibers were designed to be comparable in size to visible wavelengths in order to minimize reflection and absorption of the infrared photons by virtue of weak Rayleigh scattering while remaining optically opaque in the visible wavelength range due to strong Mie scattering. Compared to conventional cooling technologies, the radiatively-engineered fabrics can provide fully passive means to cool the human body regardless of the person’s physical activity level [1,4,5]. We will also report on our research on improving optical and thermal characteristics of the new fabrics as well as on their applications beyond personalized cooling, including radiative heating and heat spreading.
This work was supported by the US Department of Energy, Office of Basic Energy Sciences, Award DE-FG02-02ER45977. We thank Ms. Mare Dockery of Minifibers, Inc. for providing some of the fibers used in this work.
1. J. K. Tong, X. Huang, S. V. Boriskina, J. Loomis, Y. Xu, and G. Chen, ACS Photonics 2, 769 (2015).
2. N. N. Shi, C.-C. Tsai, F. Camino, G. D. Bernard, N. Yu, and R. Wehner, Science 349, 298 (2015).
3. S. V Boriskina, A. V Boriskin, H. Qu, M. Skorobogatiy, D. Simpson, and R. Osgood, Opt. Photonics News (2017), in press.
4. S. V. Boriskina, Science. 353, 986 (2016).
5. G. Chen, J. K. Tong, S. V. Boriskina, X. Huang, J. Loomis, and L. Xu, "Infrared transparent visible opaque fabrics," U.S. patent WO2016044609 (2015).
Gianluca Farinola, University degli Studi-Bari Aldo Moro
Eric Glowacki, Linkoping Unversity
Radislav Potyrailo, GE Global Research
Silvia Vignolini, University of Cambridge
APL Photonics | AIP Publishing
BM03.03: Biophotonic Structures and Structural Colors I
Tuesday AM, November 28, 2017
Sheraton, 2nd Floor, Back Bay D
8:00 AM - *BM03.03.01
The Optical Janus Effect—Asymmetric Structural Color Reflection Materials
Joanna Aizenberg 1 2 3 , Grant England 1 , Calvin Russell 1 , Elijah Shirman 1 2 , Theresa Kay 2 , Nicolas Vogel 4 Show Abstract
1 John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts, United States, 2 Wyss Institute for Biologically Inspired Engineering, Harvard University, Boston, Massachusetts, United States, 3 Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts, United States, 4 Institute of Particle Technology, Friedrich-Alexander University Erlangen-Nürnberg, Erlangen Germany
Structurally colored materials are often used for their resistance to photobleaching and their complex viewing direction-dependent optical properties. Frequently, absorption has been added to these types of materials in order to improve the color saturation by mitigating the effects of nonspecific scattering that is present in most samples due to imperfect manufacturing procedures. The combination of absorbing elements and structural coloration often yields emergent optical properties. Here, we introduce a new hybrid architecture that leads to an interesting, highly directional optical effect. By localizing absorption in a thin layer within a transparent, structurally colored multilayer material, we create an optical Janus effect, wherein the observed reflected color is different on one side of the sample than on the other. We perform a systematic characterization of the optical properties of these structures as a function of their geometry and composition. The experimental studies are coupled with a theoretical analysis that enables a precise, rational design of various optical Janus structures with highly controlled color, pattern and fabrication approaches. These asymmetrically colored materials will open applications in art, architecture, semitransparent solar cells and security features in anti-counterfeiting materials.
8:30 AM - *BM03.03.02
Artificial Selection for Structural Color
Hui Cao 1 , Antonia Monteiro 2 3 Show Abstract
1 Applied Physics, Yale University, New Haven, Connecticut, United States, 2 Biological Sciences, National University of Singapore, Singapore Singapore, 3 , Yale-NUS College, Singapore Singapore
Despite significant efforts to study structural colors in nature, little is known about how such colors and structures evolved in the first place. To address this key question, we performed the first artificial selection (to our knowledge) on a structural color using butterflies. We demonstrated rapid evolution of violet structural color from ultra-violet brown scales in Bicyclus anynana butterflies with only six generations of selection. Furthermore, we identified the structural changes responsible for color evolution, which involve changes in the thickness of a chitin lamina in individual wing scales. By examining other violet-banded species that occur naturally in the Bicyclus genus, we found the colors are produced via the same mechanism and thus may have evolved via similar scale modifications.
9:00 AM - BM03.03.03
Finding Nanostructures that Reproduce Colors with Adaptive Mesh Search Techniques
Emma Vargo 1 , Kyle Keane 1 , W Craig Carter 1 Show Abstract
1 Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
Colors created by photonic structures have a number of benefits over pigment-based colors: they tend to be more vivid, they don’t fade over time, they can be made from benign materials, and they can be dynamically tuned with slight changes in the structure. The percieved color of a photonic structure comes from its characteristic interactions with light, which are dictated by its materials, geometry, and orientation to the viewer. Working in reverse, material, geometric, and orientational parameters can be selected to create a photonic structure with a specific desired color. Directly calculating photonic structures from a desired color is an under-constrained task, because many different structures are able to produce the same color. This paper describes an adaptive mesh search technique used to perform color-directed searches through large parameter spaces of different photonic structures. The method can be applied to any well-characterized geometry, and can thus be used for all color-based applications of photonic structures, including pigment-free paints, anti-counterfeiting materials, and reflective displays. The adaptive mesh search technique is very efficient and results are returned within seconds or minutes on a laptop computer, eliminating the need for cluster computing. In this work, the adaptive mesh search is applied to 1D, 2D, and 3D photonic structures, and the resulting designs are satisfactory matches with the desired colors.
9:15 AM - BM03.03.04
Understanding Structural Colors in Three-Dimensional Mesoporous Network Metamaterials
Alejandra Ruiz de Calvijo 1 , Yoichiro Tsurimaki 2 , Olga Caballero-Calero 1 , George Ni 2 , Gang Chen 2 , Svetlana Boriskina 2 , Marisol Martin-Gonzalez 1 2 Show Abstract
1 , Inst de Micro y Nanotecnologia, CSIC, Madrid Spain, 2 Department of Mechanical Engineering, , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
Structural coloration is the production of color by the material microstructure in such a way that can interfere with visible light. In nature, they are abundant, robust, and can be reversibly changed by temperature variations, material deformations, and saturation with gases or liquids. Materials with engineered colorimetric signatures detectable by the naked eye can find use, for example, in optical sensing [1,2]. However, those artificial structural colors rely on low-throughput fabrication techniques, and so are limited in size. Here, we report on the optical design of a large area high-throughput fabrication nanostructure that is composed of all-dielectric mesoporous alumina with engineered colorimetric signatures and macroscopic footprints.
These mesoporous network metamaterials were fabricated via hard and mild aluminum anodization  and by selectively etching of the hard anodization areas to create ordered quasi-periodic internal structure of layers with different porosity.
The developed porous alumina network metamaterials can serve as colorimetric sensing platforms. We observed dramatic color changes in the material. High porosity of the structures offers promise for strong color variations upon permeation with gas molecules or liquids. The alumina structures can be further used as templates in cheap, and large area fabrication of inverse-structure metamaterials made of plastics, metals, and semiconductors. This can expand their application range and achieve sensing selectivity.
This research was partially supported by the Salvador Madariaga fellowship from MINECO.
1. S. V Boriskina, S. Y. K. Lee, J. J. Amsden, F. G. Omenetto, and L. Dal Negro, Opt. Express 18, 14568–14576 (2010).
2. J. J. Amsden, H. Perry, S. V Boriskina, A. Gopinath, D. L. Kaplan, L. Dal Negro, F. G. Omenetto, Opt. Express 17, 21271–21279 (2009).
3. J. Martín, M. Martín-González, J. Francisco Fernández, O. Caballero-Calero, and A. M. Stacy, Nat. Commun. 5, 5130 (2014).
4. T. Smith and J. Guild, Trans. Opt. Soc. 33, 73–134 (1931).
9:30 AM - BM03.03.05
From Disordered to Quasi-Ordered Structures—Bioinspired Angle-Independent Structural Colors from Phase-Separated Polymer Blend Films
Asritha Nallapaneni 1 , Markus Bleuel 2 , Jan Ilavsky 4 , Matthew Shawkey 3 , Alamgir Karim 1 Show Abstract
1 , The University of Akron, Akron, Ohio, United States, 2 , National Institute of Standards and Technology, Gaithersburg, Maryland, United States, 4 , Argonne National Laboratory, Lemont, Illinois, United States, 3 , University of Gent, Gent Belgium
Structural colors, have gained lot of prominence in the recent years, owing to their vibrancy, durability, environment friendliness, choice of materials, stimuli responsiveness and long-lasting performance with special emphasis on angle-independent colors due to their applicability in LCD displays, coatings, and paints. Numerous studies on using colloids and block copolymers for fabricating angle-independent colors have been reported in literature. However, there is still need for a system that mimics colors in nature from porous materials, which are lightweight. Here, we demonstrate a facile two-step temperature-induced phase-separation in polymer blend films as a strategy to achieve angle-independent colors closely mimicking colors in nature (blue color of barbs in Eastern bluebird and white color of beetle scales). We have employed PS/PMMA blend system as a model system of study. The polymer blend films were thermally annealed above the glass-transition temperature of the polymer blend components and then the PS is selectively removed in order to enhance refractive-index contrast. Tuning the composition of the polymer blend film selectively controls the morphology and the associated structural length scales. Characterization of the films using SEM, USAXS and UV-Visible spectroscopy revealed that white and blue color of the films arose from disordered and quasi-ordered structures based on incoherent and coherent scattering respectively. The strategy employed is thus compatible via a roll-to-roll assembly facilitating us to fabricate these colors on a large-scale. In future, we would like to expand this study to achieve green and red colors based on a self-assembly process.
 M. Harun-Ur-Rashid, A. Bin Imran, T. Seki, M. Ishii, H. Nakamura, Y. Takeoka, ChemPhysChem 2010, 11, 579.
 J. K. D. Mapas, T. Thomay, A. N. Cartwright, J. Ilavsky, J. Rzayev, Macromolecules 2016, 49, 3733.
 E. R. Dufresne, H. Noh, V. Saranathan, S. G. J. Mochrie, H. Cao, R. O. Prum, Soft Matter 2009, 5, 1792.
 P. Vukusic, B. Hallam, J. Noyes, Science 2007, 315, 348.
9:45 AM - BM03.03.06
Ultra-Antireflective Synthetic Brochosomes
Shikuan Yang 2 , Nan Sun 1 , Birgitt Stogin 1 , Jing Wang 1 , Yu Huang 1 , Tak Sing Wong 1 Show Abstract
2 , Zhejiang University, Hangzhou China, 1 , The Pennsylvania State University, University Park, Pennsylvania, United States
Minimizing reflected light from a surface has important implications for applications ranging from corrective lenses to solar cells to astronomical telescopes. Since the early discovery (1960s) of the antireflection properties of insect compound eyes [1, 2], new and distinct examples of natural antireflective coatings have been rare. Here we report the fabrication and optical characterizations of a new class of biologically inspired antireflective surface that emulates the intricate surface architectures of leafhopper-produced brochosomes — soccer ball-like microscale granules with nanoscale surface indentations [3, 4]. Our method utilizes double-layer colloidal crystal templates in conjunction with site-specific electrochemical growth to create these structures using various metals and conductive polymers. These brochosome coatings (BCs) can be designed to exhibit strong omnidirectional antireflective performance of wavelengths from 250 nm to 2000 nm, outperforming state-of-the-art antireflective coatings of similar thickness. Our results may also suggest a previously unidentified function of brochosomes as a camouflage coating against the predators of leafhoppers. The discovery of the antireflective function of BCs may find applications in solar energy harvesting, photovoltaics, and sensing devices .
Keywords: Anti-reflective coating | brochosomes | bioinspired surface | camouflage
1. W.H. Willer, G.D. Bernard, & J.L. Allen, The optics of insect compound eyes. Science 162, 760 – 767 (1968).
2. P.B. Clapham & M.C. Hutley, Reduction of lens reflection by Moth eye principle. Nature 244, 281-282 (1973).
3. R.A. Rakitov, Powdering of egg nests with brochosomes and related sexual dimorphism in leafhoppers (Hemiptera : Cicadellidae). Zool J Linn Soc-Lond 140, 353-381 (2004).
4. R. Rakitov & S.N. Gorb, Brochosomes protect leafhoppers (Insecta, Hemiptera, Cicadellidae) from sticky exudates. J R Soc Interface 10, 20130445 (2013).
5. S.K. Yang, X. Dai, B. B. Stogin, & T.-S. Wong, Ultrasensitive surface-enhanced Raman scattering detection in common fluids. Proc. Natl. Acad. Sci. USA 113, 268 – 273 (2016).
10:30 AM - *BM03.03.07
Inspired by Nature—Photonic Materials Based on the Gyroid Nanogeometry
Gerd Schroeder-Turk 1 2 3 Show Abstract
1 School of Engineering and Information Technology, Murdoch University, Perth, Western Australia, Australia, 2 Applied Maths, Research School Physical Sciences and Engineering, The Australian National University, Canberra, Australian Capital Territory, Australia, 3 Theoretische Physik, Friedrich-Alexander-Universität Erlangen-Nürnberg, Erlangen, Bayern, Germany
Insects have developed amazing functional nanostructures, such as the chiral 'gyroid' nanostructure in the wing scales of several green butterfly species [1,2]. This structure is a network-like highly symmetric nanoporous solid material that is related to Allan Schoen's famous Gyroid minimal surface . In the specific case of the Green Hairstreak butterfly, this ordered porous chitin structure acts as a biophotonic crystal that emulates the reflection spectra of common leafs to allow near-perfect camouflage.
A striking property of the gyroid geometry is its chirality which translates into circular-polarisation effects of the optical material. I will discuss the nature of these effects in gyroid-like photonic materials, both from a theoretical point of view that employs the circular dichroism index as a new way to discuss circular polarisation in the context of the photonic band structure [4,5] and from an experimental point of view using high-resolution nanofabrication methods [6,7]. This biomimetic replication has led to the development of a circular-polarisation beam splitter based on the very structure that the butterfly employs to produce its coloration .
The gyroid structure, also known as the srs net, is defined by a single solid component in network-like topology, embedded in otherwise empty space. It is now conceivable [8,9], and experimentally realisable as a nanophotonic material , to intergrow a pair of these networks, giving the 2-srs structure, a triplet of such networks called 3-srs, a quartet called 4-srs or an octet called 8-srs. Notably, all of these structures are structurally strongly chiral, as all components are networks of the same handedness. As nanofabricated photonic materials, these higher-order gyroid materials possess strong and surprising chiro-optical properties [3,9,10,11] some of which can be rationalised by group theoretic and representation theory  and which offer some promise for functional photonic materials.
 G.E. Schröder-Turk et al, J. Struct. Biol. 174, 290-295 (2011)
 B. Winter et al, Proceedings of the National Academy of Sciences 112(42), 12911-12916 (2015)
 S.T. Hyde et al, Angew. Chemie Int. Ed., 47, 7996-8000 (2008)
 M. Saba et al, Phys. Rev. Lett. 106, 103902 (2011)
 M. Saba, B.D. Wilts et al, Materials Today: Proceedings 1, 193-208 (2014)
 B.P. Cumming et al, Optics Express 22, 689-698 (2014)
 M.D. Turner et al, Nature Photonics 7(10), 801-805 (2013)
 S.T. Hyde & S. Ramsden, Europhys. Lett., 50, 135-141, (2000).
 G.E. Schröder-Turk et al, Faraday Discussions 161, 215-247 (2013)
 F. Turella et al, Observation of optical activity in dielectric 8-srs networks, Optics Letters 40, 4795-4798 (2015)
 M. Saba, Physical Review B 88(24), 245116 (2013)
 B.P. Cumming et al, Light: Science & Applications 6, e16192 (2016)
 B.W. Wilts et al, Science Advances 3, e1603119 (2017)
11:00 AM - *BM03.03.08
Biologically Inspired Soft and Fluid Optical Materials
Mathias Kolle 1 , Sara Nagelberg 1 , Joseph Sandt 1 , Marie Elimbi Moudio 1 Show Abstract
1 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
A curious look at biological photonic systems reveals a myriad of versatile approaches for the creation of multifunctional, hierarchically structured, dynamic bio-inspired materials. Here, we present a choice of materials that employ bio-inspired photonic architectures, implemented in soft, and fluid materials, with tunable and stimuli-responsive behavior.
The first part of this presentation will be focused on elastic, mechano-sensitive, color-tunable bio-inspired photonic fibers, which mimic the photonic structures found in a tropical plant’s blue seed coat. The fibers consist of an elastomeric multilayer cladding, rolled onto a stretchable core. Their reflection color can be tuned reversibly by applying an axial strain or a lateral compression. This effect persists even after several thousand deformation cycles. Potential applications for mechano-responsive, color-tunable photonic fibers include the optical sensing of mechanical deformations and stress distributions in medical and civil engineering applications, solvent vapor analyzers, dynamic textiles, and components for fiber-optic signal processing.
In the second part, we explore the use of emulsions for the creation of liquid compound micro-lenses with dynamically tunable focal lengths, inspired by the architectures found in the retina of nocturnal animals. We employ bi-phase emulsion droplets in responsive micro-lenses that can be reconfigured to focus or scatter light, and to form images. We provide evidence of the micro-lenses’ functionality for two potential applications – integral micro-scale imaging devices and light field display technology – thereby demonstrating both the fundamental characteristics and the promising opportunities for fluid-based dynamic refractive micro-scale compound lenses.
11:30 AM - BM03.03.09
Construction of Biopolymer-Based Photonic Crystals with Programmable Multispectral Responses
Yu Wang 1 , Wenyi Li 1 , Meng Li 1 , Siwei Zhao 1 , Elena Colusso 1 , David Kaplan 1 , Fiorenzo Omenetto 1 Show Abstract
1 , Tufts University, Medford, Massachusetts, United States
Natural organisms use hierarchical photonic structures ranging from the nano-, micro- to the macroscale to produce striking optical effects, such as iridescence, low angle-dependency of color, color-mixing, polarization, antireflection, ultra-blackness, ultra-whiteness, light focusing and dynamic structural color. These complex architectures have been a source of inspiration for the fabrication of synthetic photonic materials that attempt to mimic their structure and optical property. So far, great process has been made in preparation bio-inspired or biomimetic hierarchical photonic structures, however, the natural complex structure designs, and particularly their impressing optical phenomena are still difficult to reproduce in synthetic photonic crystals, especially in three-dimensional form.
Colloidal self-assembly has provided an effective pathway to fabricate 3D photonic structures. Topographically patterned substrates, which can guide and shape the assembly of colloidal particles into designed structures, offer a promising pathway for the fabrication of composite photonic structures with novel optical features
Silk fibroin, collected from the domesticated Bombyx mori (B. mori) silkworm, has proven to be a candidate for optical or photonic material due to its excellent combination of biocompatibility, biodegradability, transparency, programmability, and mechanical durability.
Based on these facts, we fabricate a series of silk hierarchical 3D photonic crystals (PCs) based on the use of polystyrene colloidal crystal multilayers on topographically patterned surface as template. These 3D photonic crystals not only possess hierarchy at multiple scales, but also have unique optical properties, such as color-mixing, diffuse reflection/transmission, and tunable diffraction performance. By controlling the conformation of the silk material and starting from an amorphous silk format, the stopbands of such PCs can be reconfigured and “designed” with water vapor and UV light. Modified composite photonic structures are also presented through the combination of colloidal self-assembly and imprinting techniques. Finally, we show that these hierarchical photonic crystals can be used for simultaneous photonic bandgap and diffraction-based sensing applications.
11:45 AM - BM03.03.10
Bioinspired Multifunctional Light-Scribe Etched Graphene-Enabled Surface with Robust Light Management and Self-Cleaning
Shengjie Zhai 1 , Hui Zhao 1 Show Abstract
1 , University of Nevada, Las Vegas, Las Vegas, Nevada, United States
Surfaces, with efficient light management and self-cleaning, are fundamental to optoelectronics. For practical implementations, it is essential to design surfaces whose light-management and self-cleaning are durable under the real-world environment. However, the lack of robustness is still a critical bottleneck. Here, we present a new design method based on principles derived from two distinct biological samples: Aeshna cyanea and Nelumbo. This approach synergistically combines the exceptional omnidirectional anti-reflection of glasswing dragonfly and robustness of Nelumbo. The robustness of lotus leaf is attributed to the high density of papillae with varying heights and exceptional dense continuously cuticular wax layer, effectively resisting external environment stresses. The omnidirectional anti-reflection of dragonfly is due to the irregular arranged transparent wax pruinosity featuring a random height. Consider the similarity between the wax layer in lotus leaf and dragonfly. We integrate transparent multilayer graphene with a designed light-management nanostructure, mimicking the wax layer. The designed surface is then coupled with the flexible thin-film amorphous silicon solar cell, leading to an 8.9% increase in the efficiency and a contact angle of 158o. The unique combination of the nanostructure and graphene, capturing key characteristics of lotus leaf and dragonfly, leads to extraordinary robustness for both light management and self-cleaning under mechanical abrasion, UV exposure, and corrosions. Even more remarkably, both the efficiency enhancement of the solar cell and self-cleaning capability are preserved after 10-day outdoor exposure. For a reference, without our designed surface, the solar cell efficiency decreases significantly by 56.2% due to the severe environmental degrading.
BM03.04: Biophotonic Structures and Structural Colors II
Luisa De Cola
Tuesday PM, November 28, 2017
Sheraton, 2nd Floor, Back Bay D
1:30 PM - *BM03.04.01
Biologically Inspired Photonics—The Image Forming Mirror in the Eye of the Scallop
Benjamin Palmer 1 , Gavin Taylor 2 , Vlad Brumfeld 1 , Dvir Gur 1 , Michal Shemesh 1 , Nadav Elad 1 , Aya Osherov 1 , Dan Oron 1 , Steve Weiner 1 , Lia Addadi 1 Show Abstract
1 , Weizmann Institute, Rehovot Israel, 2 , Lund University, Lund Sweden
Guanine crystals are found commonly in biological photonic systems (1) where they are responsible for the metallic silvery reflectance of fish scales (2) and the brilliant iridescent colors of planktonic crustaceans (3) and tropical fish (4). A wide range of different optical phenomena are produced by organisms "simply" by varying the size, morphology and arrangement of the guanine crystals. Organisms display an extraordinary ability to manipulate and control crystal growth producing crystal morphologies which are highly optimized for a particular optical function. The most complex of all these functions is in vision.
Herein we discuss how guanine crystals are used to make an image-forming mirror in one of Nature’s most spectacular visual systems – the eye of the scallop (5). The Pecten scallop possesses up to 200 eyes, each containing a concave mirror to focus light onto a retina residing above it, much like a reflecting telescope. We show how the hierarchical organization of the multilayered mirror is exquisitely controlled for image formation, from the component guanine crystals at the nanoscale to its complex 3D morphology at the millimeter level. Each layer of the mirror is formed from a tiling of regular square guanine crystals. Crystal tiling minimizes aberrations caused by optical diffraction effects at the crystal interfaces which would result in a reduction of the image contrast. The ability of the scallop to form an almost perfectly square crystal from a monoclinic crystal structure is astonishing. The organism achieves this feat by controlling crystal twinning (6) and by performing crystallization inside a confined space. Each crystal is a twinned crystal comprising 3 crystalline domains which form inside a membrane-bound cavity. We show that by controlling the orientational relationship between the twin components the scallop is able to produce the square crystal morphology. Optical ray-tracing shows that the tilted mirror forms functional images on different parts of a double-layered retina which are specialized for different functions. Understanding the strategies organisms use to control crystal morphology for complex optical functions paves the way for the construction of novel bio-inspired optical and electronic materials with tailor made crystalline morphologies.
(1) D. Gur, B. A. Palmer, S. Weiner, L. Addadi, Adv. Func. Mater. 1603514, (2017).
(2) D. Gur, B. Leshem, D. Oron, S. Weiner, L. Addadi, J. Am. Chem. Soc. 136, 17236-17242 (2014).
(3) D. Gur, B. Leshem, M. Pierantoni, V. Farstey, D. Oron, S. Weiner, L. Addadi, J. Am. Chem. Soc. 137, 8408-8411 (2015).
(4) D. Gur, B. A. Palmer, B. Leshem, D. Oron, P. Fratzl, S. Weiner, L. Addadi., Angew. Chem. Int. Edit. 54, 12426-12430 (2015).
(5) B. A. Palmer et al., under review.
(6) A. Hirsch, B. A. Palmer, N. Elad, D. Gur, S. Weiner, L. Addadi, L. Kronik, L. Leiserowitz, Angew. Chem. Int. Edit, in press.
2:00 PM - *BM03.04.02
Microfabrication Pathways for the Synthesis of Vapor-Sensitive Bio-Inspired Photonic Nanostructures
Laurent Francis 1 , Olivier Poncelet 1 , Jonathan Rasson 1 , Sébastien Mouchet 2 , Olivier Deparis 3 Show Abstract
1 ICTEAM Institute, Université Catholique de Louvain, Louvain-la-Neuve Belgium, 2 College of Engineering, Mathematics and Physical Sciences, University of Exeter, Exeter United Kingdom, 3 Department of Physics, Physics of Matter and Radiation (PMR), University of Namur, Namur Belgium
The photonic nanostructures found in insects have proven to be a source of inspiration for several engineering applications. For instance, it has been reported that the optical response of the scales of various butterfly and beetle species is selectively modified when exposed to vapors [1,2]. Although the mechanisms at work behind this phenomenon are not fully understood from a quantitative point of view, as they involve complex chemical and physical interactions with the surface and the constituting materials of the nanostructured scales, such a research can lead to a whole new class of vapor optical sensors.
Bridging the gap between natural and synthetic nanostructures is a key element to bring innovative solutions alive. It is challenging to cost-effectively synthesize or replicate large footprints of 3D bio-inspired nanostructures. In this paper, we suggest possible microfabrication approaches based on top-down techniques issued from the microelectronics sector and analyze the optical properties of the obtained micro- and nanostructures with a focus on the specific aspect of vapor sensing.
Two different nanostructures related to vapor sensing are reported here. The first one is a Morpho-inspired photonic nanostructure synthesized by atomic layer deposition (ALD) of metal oxides multilayers (Al2O3, TiO2, and HfO2), followed by their dry and selective wet etching to produce a Christmas tree-like structure . The second one is a periodic array of concave multilayers in porous silicon (PSi) inspired from the hemispherical multilayered cavities found in the scales of the Papilio blumei or of the Suneve coronata.
We studied the variations in the reflectance spectrum of the structures under a controlled flow of either ethanol or 2-propanol vapor. To gauge the efficiency of the sensing against known photonic structures, the ethanol vapor adsorption and condensation inside the bioinspired concave PSi multilayer structure were compared to the variations of a standard flat PSi Bragg mirror. The results show an enhanced response time in the case of the bioinspired concave structure. In all cases, a small shift has been observed in the reflectance peak wavelength and selective vapor response was demonstrated according to the materials combination in use. In addition, imaging scatterometry observations were performed to analyze the scattering profile of the synthetic nanostructures.
Our investigation demonstrates that complex bioinspired nanostructures can be synthesized by standard microelectronics technologies with a potential for vapor sensors. Future works should increase the number of building blocks for the synthesis of nanostructures and improve the vapor sensitivity of the resulting devices.
 G. Piszter, K. Kertész, et al., Opt. Express 22, 22649-22660 (2014)
 S. R. Mouchet, T. Tabarrant, et al., Opt. Express 24, 12267-12280 (2016)
 O. Poncelet, G. Tallier, et al., Bioinspir Biomim 11, 9 (2016)
2:30 PM - BM03.04.03
Bioinspired Camouflage with Fast Dynamic Responses
Wen Shang 1 , Jiaqing He 1 , Chengyi Song 1 , Tao Deng 1 Show Abstract
1 , Shanghai Jiao Tong University, Shanghai China
Nature provides abundant examples for camouflage in the visible spectrum. Some typical camouflage strategies include background matching, disruptive coloration, countershading, transparency, and mirror reflection. As one of the most representative biological camouflage systems, cephalopods, such as octopus, cuttlefish, etc. have the capability to adjust their coloration and texture to match their surroundings, for the purpose of concealment, predation, and reproduction. Many engineered camouflage systems have been explored using the strategies inspired from the biological camouflage systems for various utilities in both industry and military applications. Among all the efforts reported, tunable coloration that can match the changing background is one of the most studied forms of camouflage, which is also highly desirable in potential wide spread civil and military applications. Currently most technologies used for artificial adaptive camouflage systems are based on the active camouflage approaches. Such active camouflage approaches usually involve active color sensing, signal processing, and active color generation, which make both the camouflage systems and their fabrication processes relatively complex. In this presentation, I will introduce a new passive adaptive camouflage approach that is different from previous reported methods. The principle of such passive camouflage approach is based on the transportation of the native light reflected from the background and the display of such light on the target surface. With the elimination of complicated integration process between color sensing and generation, such camouflage system still showed the faithful replication of background colors. A fast dynamic responding speed and the adaptive coloration for the patterned color backgrounds were also demonstrated using this passive camouflage approach. The camouflage approach we explored in this study not only can be applied for the optical camouflage in visible range, but also can be extended to other wavelength range, including infrared and ultraviolet wavelength range, which will hopefully open up new application space for such camouflage approach.
2:45 PM - BM03.04.04
Solution-Processed Biological Materials as Electronic and Optical Components for Organic Light-Emitting Devices
Nils Juergensen 1 2 , Johannes Zimmermann 1 2 , Anthony Morfa 1 2 , Maximilian Ackermann 2 3 , Tomasz Marszalek 3 4 , Felix Hinkel 3 5 , Mathias Kolle 6 , Gerardo Hernandez-Sosa 1 2 Show Abstract
1 Light Technology Institute, Karlsruhe Institute of Technology, Karlsruhe Germany, 2 , InnovationLab GmbH, Heidelberg Germany, 3 Organisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Heidelberg Germany, 4 , Max Planck Institute for Polymer Research, Mainz Germany, 5 Center of Advanced Materials, Ruprecht-Karls-Universität Heidelberg, Heidelberg Germany, 6 Department of Mechanical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
Nature offers a brought variety of resources, as evolution enhanced wildlife to most efficiently produce high quality biological materials. Biodegradable and bioresorbable materials are of high value for the implementation in optoelectronic devices. Compostable electronics could counteract global pollution by electronic waste. Biomedical implants become significantly more versatile and compatible with human tissue if their components are readily metabolizable. We demonstrate the application of biological materials as active optoelectronic components and as light outcoupling optics for organic light-emitting devices. We introduce a vitamin B2 derived emitter material, riboflavin tetrabutyrate and its utilization in a solution processed organic light-emitting diode (OLED). While unmodified vitamin B2 cannot be processed in solution, we show that the addition of tailored side groups changes the vitamin’s solubility to enable the formation of homogeneous and smooth films via solution processing. Using grazing incidence wide-angle X-ray scattering, we prove that this chemical derivative reduces crystallinity and enhances emission by suppressing π-π stacking interactions. We will present riboflavin tetrabutyrate OLEDs with a maximum luminance of 10 cd/m2 and external quantum efficiency of 0.02% and 640 nm peak emission which exceed performance of comparable devices by five orders of magnitude.1 Further, we present biodegradable polycaprolactone as solid polymer electrolyte and its ion dissolving abilities in the active layer of light-emitting electrochemical cells.2 On the light management side we demonstrate the realization of widely established light management solutions using biological materials. Polymers like shellac, cellulose, xanthan gum and poly(lactic-co-glycolic acid) are used to form structures that enhance light outcoupling to reduce optical substrate mode losses in OLEDs.
1. Jürgensen N. et al. Solution-Processed Bio-OLEDs with a Vitamin-Derived Riboflavin Tetrabutyrate Emission Layer. ACS Sustainable Chemistry and Engineering; 2017; 5:5368-5372.
2. Jürgensen N., Zimmermann J., Morfa AJ., Hernandez-Sosa G. Biodegradable Polyaprolactone as Ion Solvating Polymer for Solution-Processed Light-Emitting Electrochemical Cells. Scientific Reports; 2016; 6:36643.
3:30 PM - *BM03.04.05
Bioreplicated Structures for Optics and Photonics
Raul Martin-Palma 1 2 Show Abstract
1 Física Aplicada, Universidad Autónoma de Madrid, Madrid Spain, 2 Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania, United States
Living organisms constitute a powerful source of inspiration for innovations in many different fields and for completely different reasons. Often, nature provides simple, elegant, and optimal solutions which can be adapted to the development of improved or novel devices with tailored functionalities. More specifically, biological species provide examples of various structures with very specific optical response characteristics to fulfill simultaneously various issues. However, the exact imitation of biological structures by using equivalent processes to those used in nature is extremely difficult, since the mechanisms of formation of these structures are tremendously complex. Bioreplication, i.e. the fabrication of replicas of biological shapes by converting templates harvested from a particular species to inorganic materials, constitutes a powerful alternative approach. Within this context, several applications of bioreplication in the broad fields of optics and photonics will be presented. This includes the successful use of bioreplicas of such biological templates as butterfly wings, fly and hornet eyes, and beetle exoskeletons among others.
4:00 PM - *BM03.04.06
Photonic Crystals Composed of 99% Water and 1% Inorganic Nanosheet
Yasuhiro Ishida 1 Show Abstract
1 , RIKEN Center for Emergent Matter Science, Wako, Saitama Japan
Fluids that contain ordered nanostructures with periodic distances in the visible-wavelength range, anomalously exhibit structural colours that can be rapidly modulated by external stimuli. Indeed, some fish can dynamically change colour by modulating the periodic distance of crystalline guanine sheets cofacially oriented in their fluid cytoplasm. In this presentation, we report that a dilute aqueous colloidal dispersion of negatively charged titanate nanosheets exhibits structural colours. In this ‘photonic water’, the nanosheets spontaneously adopt a cofacial geometry with an ultralong periodic distance of up to 675 nm due to a strong electrostatic repulsion. Consequently, the photonic water can even reflect near-infrared light up to 1,750nm. The structural colour becomes more vivid in a magnetic flux that induces monodomain structural ordering of the colloidal dispersion. The reflective colour of the photonic water can be modulated over the entire visible region in response to appropriate physical or chemical stimuli.
4:30 PM - *BM03.04.07
Bio-Inspired Functional Materials Converted from Nature Species
Di Zhang 1 , Wang Zhang 1 , Jiajun Gu 1 , Qinglei Liu 1 , Shenmin Zhu 1 , Huilan Su 1 Show Abstract
1 , Shanghai Jiao Tong University, Shanghai China
Biological materials naturally display an astonishing variety of sophisticated nanostructures that are difficult to obtain even with the most technologically advanced synthetic methodologies. Inspired from nature materials with hierarchical structures, many functional materials are developed based on the templating synthesis method. This review will introduce the way to fabricate novel functional materials based on nature bio-structures with a great diversity of morphologies, in State Key Lab of Metal Matrix Composites, Shanghai Jiao Tong University in near five years. We focused on replicating the morphological characteristics and the functionality of a biological species (e.g. wood, agriculture castoff, butterfly wings). We change their original components into our desired materials with original morphologies faithfully kept. Properties of the obtained materials are studied in details. Based on these results, we discuss the possibility of using these materials in photonic control, solar cells, electromagnetic shielding, energy harvesting, and gas sensitive devices, et al. In addition, the fabrication method could be applied to other nature substrate template and inorganic systems that could eventually lead to the production of optical, magnetic, or electric devices or components as building blocks for nanoelectronic, magnetic, or photonic integrated systems. These bio-inspired functional materials with improved performance characteristics are becoming increasing important, which will have great values on the development on structural function materials in the near future.
Gianluca Farinola, University degli Studi-Bari Aldo Moro
Eric Glowacki, Linkoping Unversity
Radislav Potyrailo, GE Global Research
Silvia Vignolini, University of Cambridge
APL Photonics | AIP Publishing
BM03.05: Bacteria, Viruses and Sub-Cellular Components
Wednesday AM, November 29, 2017
Sheraton, 2nd Floor, Back Bay D
8:30 AM - *BM03.05.01
Self-Assembly Hybrid Structures—Towards Artificial Virus
Luisa De Cola 1 Show Abstract
1 , University of Strasbourg, Strasbourg Cedex France
The creation of nano/microstructures based on molecular components possessing defined functionalities is a very fascinating field at the cross point of different disciplines. Our effort, in this talk, focuses on the assembly of functional molecules to form hybrid capsules based on a protein shell and on an inorganic template. In particular the self-assembly properties of luminescent platinum complexes have been investigated in order to replace the native template RNA for the formation of virus-like capsules. The natively icosahedral virus cowpea chlorotic mottle virus (CCMV) has been chosen for this purpose and due to the control of the self-assembly of the virus capsid proteins (CPs) via pH modulation, not only negatively charged cargos but also neutral ones can be encapsulated. The encapsulation via two different procedures into virus capsids yielded highly emissive virus like particles. Interestingly a negatively charged Pt(II) complex assembly allowed the reorganization of natively icosahedral CCMV capsid into luminescent cylindrical particles. Biological assays are in progress to understand the consequence of such constructions.
9:00 AM - BM03.05.02
Enhancing Bacterial Attachment and Growth in Three-Dimensional Porous Carbon Scaffolds
Min Soo Jeon 1 , Chang Sung Heu 1 , Yale Jeon 1 , Dong Rip Kim 1 Show Abstract
1 , Hanyang University, Seoul Korea (the Republic of)
Many microbial electrochemical applications, including microbial fuel cell and microbial electrosynthesis, require electrodes with effective attachment and confinement of bacteria. Three-dimensional (3D) porous scaffolds with large specific surface areas have received considerable interest due to their capabilities of effective cell attachment and growth. However, the previous 3D porous scaffolds had more than one-hundred micrometers pores much larger than the bacterial cell size, which impedes sustainable confinement of bacteria in those scaffolds. Herein, we developed 3D porous carbon scaffolds with pore sizes equivalent to the bacterial cell size for effective bacterial cell attachment and confinement. We successfully fabricated the 3D porous carbon scaffolds by using hot pressing method with a template consisting of polystyrene microspheres, which led to establish the well-ordered pores with large interconnected areas. We further investigated the efficacy of the fabricated 3D porous carbon scaffolds by growing E. coli as a model bacterium. As a result, the bacterial cell density of the newly developed 3D porous carbon scaffolds was about 40 times higher than that of the conventional 3D porous scaffolds. We further developed the 3D porous carbon scaffolds with hierarchical pore sizes that are the scaffolds with the outermost pores with small sizes and the centered pores with large sizes to significantly enhance the sustainable confinement of bacteria in the scaffolds. Most cells in the conventional 3D porous scaffolds were detached after repeated washing process, but the fabricated 3D porous scaffolds with hierarchical pore sizes maintained about 75% of the initial cell density because the structural feature effectively impeded the detachment of the attached bacterial cells from the scaffolds. Our results are expected to be an important guideline for improve the performance in microbial electrochemical systems.
This work was supported by the Intelligent Synthetic Biology Center of Global Frontier Project of the National Research Foundation of Korea (NRF-2012M3A6A8054889), funded by the Ministry of Science, ICT, and Future Planning. This research was also supported by the Korea Institute of Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry & Energy (MOTIE) of the Republic of Korea (No. 20164010200860).
9:15 AM - BM03.05.03
Harnessing Bacterial Metabolites in a Green Everlasting Battery
Rabih Sidnawy 1 , Fatima Yassine 1 , Nathalie Bassil 1 , Mario El Tahchi 1 Show Abstract
1 , Lebanese University, Jdeidet Lebanon
Nowadays,daily life is highly dependent on mobile electronic devices and the need of everlasting mobile power sources is increasing.The most common batteries used in modern electronics are lithium ions batteries (LIB) known for their light weight,high energy density and long life cycle .However among the disadvantages of LIB are their relatively high cost and safety hazards.By looking for a greener and safer energy source,electrical power was harvested from microorganism in a microbial fuel cell (MFC). In fact bacteria can generate electric power by transforming the chemical energy of the biomass to electricity.An important advantage of MFC is that it can be miniaturized and integrated into a thin sheet of paper fulfilling the needs of modern paper electronics.The current density and voltage of such cells ranges from 0.08 to 0.98 A/cm2 .
In this work, we present a thin battery combining LIB high energy density and long life cycle to the eco-friendly trend.Our battery makes use of a bacterial metabolite that undergoes redox reactions.The bacterial strain was serendipitously discovered when a change of color of the culture broth was observed under air flow.The color changed from yellow to green when oxidized.The observed process is reversible and repeatable in relatively short time.A quick evaluation of the medium toxicity showed that the chemical is not toxic.Therefore,the metabolite was isolated,purified and used as anolyte and catholyte.
The 2x5cm2 thin battery is composed of 5 layers having a total thickness of 300μm. 250μl of the oxygenated purified metabolite (second layer) were deposited on an oxygen permeable anode membrane (first layer) and covered by a bacterial cellulose ion-exchange membrane (third layer).Another 250 μl of non oxygenated purified metabolite (forth layer) were deposited on the bacterial cellulose membrane and covered by the cathode (fifth layer).This structure produced a current density of 3.2 A/m2 at constant voltage of 2.2V.The power density did not show any decrease with load and was stable over 7 days observation period.Voltammograms proved that the process is reversible and fast.Such values are much higher than those obtained by any bacterial fuel cell .It is important to note that this new battery uses oxygen to create electricity,and releases it back when the electricity is consumed.The future development of this green always-fully-charged battery will obviously lead to their use for mobile devices and electric vehicles.
A.Chen, P.K Sen, Advancement in Battery Technology:A State-of-the-Art Review, 2016 IEEE Ind. Appl. Soc. Annual Meet. Portland, OR, pp. 1-10,2016.
A.Fraiwan,S.Mukherjee,S.Sundermier,H.S.Lee,S. Choi, A paper-based microbial fuel cell: Instant battery for disposable diagnostic devices, Biosens.Bioelectron.,vol.49,pp.410–414,2013.
S.Li, C.Cheng, A.Thomas,Carbon-Based Microbial-Fuel-Cell Electrodes: From Conductive Supports to Active Catalysts, Adv.Mater.,vol.29, no.8,pp.1–30,2017.
9:30 AM - BM03.05.04
Synthetic Biology with Nanomaterials
Sanhita Ray 1 , Ahana Mukherjee 1 , Pritha Chatterjee 1 , Kaushik Chakraborty 1 , Anjan Dasgupta 1 Show Abstract
1 Department of Biochemistry, University of Calcutta, Kolkata India
Synthetic biology traditionally focuses on construction of artificial genetic circuitry housed in a single cell in order to get an engineered output. We have targetted synthetic biology at the scale of microbial consortia. Designer biofilms have been obtained that exhibit emergent electrical properties.
Microbial crowding, via. quorum sensing, provides the signal for biofilm formation initiation. The aim of our synthetic biology approach was to obtain artificial cellular crowding in order to trigger film formation. This is important in case of biomaterial synthesis with slow growing biofilms. Spatial manipulation of microbial cells was achieved by attaching super-paramagnetic iron oxide nanoparticles. Magnetic field was applied to bring about cellular aggregation on inter-digitated electrode device surface. This artificial crowding was monitored by studying capacitance time series for this device, in presence and absence of magnetic field. A sustained plateau in capacitance values signalled biofilm seeding (compared to decay in absense of magnetic field) when static magnetic field was applied. Capacitance plateau was retained when field was subsequently removed. Repeated cycles led to dielectric transition that denoted biofilm formation. This was confirmed by using crystal violet staining assay and acridine orange fluorescence staining to quantify biofilm on device surface. Artificial crowding was used to fabricate biofilm-graphene based two-electrode device. The conductive and capacitive properties of this biofilm device indicated percolation of graphene through biofilm. This work demonstrates how synthetic biology may be augmented by including nanoparticles in the interactome. On the other hand, material science design strategies may be actuated by using synthetic biology as a tool.
 Ray, Sanhita, et al. "Emerging Electrical Properties of Graphene incorporated Photosynthetic Biofilms." bioRxiv (2017): 132225.
9:45 AM - BM03.05.05
Electron Transport through Ultrathin Membranes—Towards the Next Generation of Biohybrid Electronic Devices
Jose Cornejo 1 , Eran Edri 1 , Hua Sheng 1 , Heinz Frei 1 , Caroline Ajo-Franklin 1 Show Abstract
1 , Lawrence Berkeley National Laboratory, Berkeley, California, United States
Highly regulated transport of electrons within living cells underpins central biological processes including energy conservation, biosynthesis, and gene regulation. Interfacing living cells with electrodes offers the opportunity to control and monitor these key biological processes in biohybrid electronic devices. Most efforts to achieve this have been constrained to cm-scale separation between the abiotic and biotic components thus leading to high internal ohmic losses which decrease the efficiency in such devices. Here we introduce a new concept to address these challenges by closing the abiotic/biotic electrochemical cycle on the shortest possible length scale – the nanometer scale – while still chemically separating these components. This approach will be instrumental to solve power losses due to high internal resistance by reducing the larger distances between anode and cathode (i.e biotic and abiotic compartments, respectively) in electrochemical cells. Here we present nano-patterned biohybrid structures that serve as well-defined electron conduits. These ultrathin membranes consist of 2 nm-long molecular wires of p-oligo(phenylenevinylene) embedded in silica that are tuned to transport electrons harvested by microorganisms. To first test electron transfer efficiency, the molecular wires in silica were constructed on tin oxide-platinum supports and tested as anodes. We performed electrochemical techniques and imaging to describe electron transport and attachment from bacterial cultures to the supporting platforms with the embedded molecular wires.
We found that bacteria on anodes containing the silica-embedded molecular wires can produce substantial amounts of electrical current, when compared to the amount of current from bacteria on silica-only anodes. This absence of redox wave from silica-only coated anodes also indicates that the tin oxide layer below it is solution inaccessible, demonstrating that the silica membrane chemically separates the tin oxide layer from the aqueous compartment. In addition, microbial abundance in electrolyte solution (optical density) and in attached form to the anode surfaces containing molecular wires is also higher. This novel interface has demonstrated to effectively detect electrical current from biotic environments and communicate to the abiotic component in a very well controlled and in a short-length arrangement. These novel ultrathin membranes will provide more efficient future biohybrid electronic devices by closing the electron flow on the nanoscale.
10:30 AM - BM03.05.06
3D Printed Bacterial Nano-Bionics
Sudeep Joshi 1 , Ellexis Cook 1 , Manu Mannoor 1 Show Abstract
1 , Stevens Institute of Technology, Hoboken, New Jersey, United States
Recently, efforts of exploring life survival possibilities on neighboring planets and an opportunity for human race towards becoming an interplanetary species are growing at a considerable faster pace. Hostile temperature conditions and absence of atmosphere are two major hurdles which sets limit for achieving above mentioned goals. Acute observation of chronological history of earth’s atmosphere formation might pave the way forward. Strong evidences supporting the existence of symbiotic relationship between cyanobacteria and plants, resulting in turning them in first chloroplast overtime. These chloroplasts are responsible for photosynthesis process, which is the foundation stone of sustainable food chain supporting plethora of species on Earth. Taking a clue, these cyanobacteria can also be employed to terraform neighboring planets for generating suitable and favorable conditions for human survival. Furthermore, bacterial cellular communication in close forced colonies is highly productive and possesses enormous potential to be used for photosynthetic energy harvesting.
Here in, we have utilized 3D printing as an additive manufacturing technique to integrate cyanobacterial colonies with functional nano-electronic and scaffold materials toward creating an eco-friendly biomimetic energy harvesting architectures. Specifically, we demonstrate for the first time, 3-dimensional interweaving of cyanobacterial aggregates pre-seeded in a hydrogel with electronic nanomaterials into various complex spatial geometries to enable harvesting of photosynthetic bio-electrons. Significantly, this 3D-printing strategy can organize bacteria in complex arrangements to investigate how spatial and environmental parameters influence social behaviors and can also prevent the detrimental overcrowding of bacteria on electrodes. Confocal, fluorescence, and scanning electron microscopy studies were performed on forced cyanobacterial colonies integrated with various nanomaterials to confirm their auto-fluorescence and to examine their interaction. Electrochemical studies on energy harvesting verified that these nanomaterials help in efficient transfer of bio-electrons generated because of the water splitting reaction during the photosynthesis.
Techniques developed in this research can also be extended to 3D print other bacterial colonies with smart hydrogel materials for bionic integration studies. Taken together, present study can augment basic scientific understanding of multidimensional integration between functional nanomaterials and the living biological micro world.
10:45 AM - BM03.05.07
Bacterially Precipitated Transition Metal Nanoparticles—Synthesis, Properties and Applications
Katherine Marusak 1 , Yaying Feng 1 , Edgard Ngaboyamahina 1 , Lingchong You 1 , Jeffrey Glass 1 , Stefan Zauscher 1 Show Abstract
1 , Duke University, Durham, North Carolina, United States
We present a new method for the fabrication of semiconducting, transition metal nanoparticles (NPs) with tunable bandgap and useful photoelectric properties, through bacterial precipitation. Escherichia coli bacteria have been genetically engineered, by overexpression of a cysteine desulfhydrase gene, to precipitate transition metal NPs from solution, here more specifically, cadmium sulfide (CdS). Transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) revealed that the bacterially precipitated NPs are agglomerates of mostly quantum dots (QDs), with a diameter of 4-5 nm, in a carbon-rich matrix. We discovered that the precipitation conditions of the bacteria can be tuned to produce NPs with bandgaps that range from quantum-confined to bulk CdS. Furthermore, we determined their photoelectrochemical (PEC) properties and their energy band structure by electrochemical measurements. In addition, by taking advantage of the organic matrix, which is residual from the biosynthesis process, we fabricated a prototype photocharged capacitor electrode by incorporating the bacterially precipitated CdS with a reduced graphene oxide (RGO) sheet. Our results show that bacterially precipitated CdS NPs are potentially useful components for PEC devices with applications for energy conversion and storage.
11:00 AM - BM03.05.08
Programmable Mechanical and Proton Conducting Properties in Protein Materials
Abdon Pena-Francesch 2 1 , Huihun Jung 1 2 , Benjamin Allen 1 3 , Melik Demirel 1 2 Show Abstract
2 Engineering Science and Mechanics, The Pennsylvania State University, University Park, Pennsylvania, United States, 1 Materials Research Institute and Huck Institutes of Life Sciences, The Pennsylvania State University, University Park, Pennsylvania, United States, 3 Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania, United States
Many globular and structural proteins have repetitions in their sequences or structures. However, a clear relationship between these repeats and their contribution to the properties remains elusive. The presence of molecular defects in their structure constitutes a great challenge for the prediction and control of the physical and chemical properties of the material. We developed synthetic tandem repeat proteins with a segmented sequence topology design inspired by squid ring teeth (SRT), that self-assemble into a semicrystalline network. We quantified the morphology and network defects of the proteins with a simple predictive model and experimental validation, and investigated their effect on the mechanical and proton-conducting properties. Our findings provide experimental evidence for tunable mechanical and proton-conducting properties (among the highest repoted for biological materials) through sequence and morphology control, and introduce design rules for the development of protein-based stretchable proton conducting materials.
11:15 AM - BM03.05.09
Biomimetic Engineering of Electron Transport in E. coli Curli Protein Nanofibers
Noemie-Manuelle Dorval Courchesne 1 2 , Elizabeth deBenedictis 3 , Jason Tresback 4 , Jessica Kim 2 , David Zanuy 6 , Sinan Keten 3 , Neel Joshi 2 5 Show Abstract
1 Chemical Engineering, McGill University, Montreal, Quebec, Canada, 2 Wyss Institute for Biologically Inspired Engineering, Harvard University, Boston, Massachusetts, United States, 3 Mechanical Engineering, Northwestern University, Evanston, Illinois, United States, 4 Center for Nanoscale Systems, Harvard University, Cambridge, Massachusetts, United States, 6 Chemical Engineering, Universitat Politecnica De Catalunya, Barcelona Spain, 5 School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts, United States
Soft and biocompatible materials capable of electron transfer are attractive for several applications, including biosensors, electrobiosynthetic systems, and flexible electronics. These materials can also exhibit bioactive functionalities and can be used to interface with the body if they have the ability to interact with cells and biological molecules. Using proteins and peptides to fabricate soft electronics would allow for the production of such multifunctional bioactive and conductive devices.
Here, we report the design and synthesis of conductive proteins that can self-assemble into fibers to allow for long-range electron transfer, and that can further be processed to form macroscopic gels and films. We used the Escherichia coli curli fiber subunit protein, CsgA, as a scaffold to rationally design electron transfer. CsgA proteins fold into beta-helix structures that can then aggregate and stack on top of each other to form amyloid fibers. Their high degree of structural organization and rigidity is ideal for the precise engineering of electron transport along stacked proteins. To engineer electron delocalization along curli fibers, we sought inspiration from Geobacter pili, which have been shown to conduct charges in part due to their aromatic amino acid content. Using molecular dynamics, we refined the model structure of CsgA and identified series of residues that, when mutated to aromatic amino acids, could interact together and form π-stacks. Such CsgA mutants would mimic Geobacter pili, while remaining versatile and easy to engineer.
We expressed several mutant CsgA proteins containing stacks of aromatic residues (tryptophan, histidine, phenylalanine and tyrosine) at five different locations on the protein, and confirmed that every mutant could still form amyloid fibers using electron microscopy and Congo Red binding assays. After purifying the mutant protein fibers and casting them onto micro-patterned electrodes, we screened for conductivity. We observed a dependence of the current response on the nature of the aromatic residues in a given stack, the position of the stack and the proximity of the residues. For all conductive fibers, the current-voltage behavior varied significantly in response to humidity changes, and could be restored after drying, upon exposure to a humid environment.
Overall, our work shows that aromatic residues and π-stacking can be used as handles to engineer electron transfer in protein fibers. Conductive curli fibers could be used as humidity sensors, and, with further engineering, they could integrated in various types of sensors, electrodes or devices.
11:30 AM - BM03.05.10
Building an Efficient Molecular Electron Conduit for Biohybrid Devices
Lin Su 1 2 , Tatsuya Fukushima 1 , Moshe Baruch 1 , Jose Cornejo 1 , Caroline Ajo-Franklin 1 3 4 Show Abstract
1 Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California, United States, 2 State Key Laboratory of Bioelectronics, Southeast University, Nanjing, Jiangsu, China, 3 Molecular Biophysics and Integrated Biosciences, Lawrence Berkeley National Laboratory, Berkeley, California, United States, 4 Biological Systems and Engineering Divisions, Lawrence Berkeley National Laboratory, Berkeley, California, United States
Proteins can move electrons precisely between living organisms and devices. Some dissimilatory metal-reducing bacteria have evolved to use membrane protein complexes to move electrons to electrodes. In previous work, we transplanted the Mtr complex from Shewanella oneidensis MR-1 into Escherichia coli to give the latter electronical connection to its external environment. However, the electron flux in E. coli is relatively low, thus limiting the extent of our electronic control and downstream applications like bio-electrocatalysis and bio-sensing devices.
Here, we hypothesize that the Mtr complex needs a species-specific machinery to mature. We constructed random mutations within the cytochrome c maturation (ccm) genes by prone error PCR and screened mutations for an increase in Mtr protein production. By sequencing those selected mutations, we found they both occurred in the C-terminal domain of ccmH which has a similar structure of ccmI in Shewanella oneidensis MR-1. Then we constructed a hybrid ccmH comprising the N-terminal domain of E. coli and the C-terminal domain of Shewanella oneidensis MR-1 (ccmHN:ccmI). Indeed, cells from this engineered ccmHN:ccmI strain possess a higher expression and more balanced stoichiometry of Mtr proteins. We measured the electron flux out of these modified variants using three-electrode microbial electrochemical experiments and showed that the ccmHN:ccmI strain produces ~40% more current per cell. Thus, we successfully rebuilt the Mtr complex conduit in E. coli to be more efficient, and demonstrate that not only the increase of Mtr proteins abundance is crucial but also the adjustment of the complex internal structure stoichiometry. This work is an important step forward for bio-electrocatalysis and bio-sensing, allows to construct more reliable and efficient biohybrid devices.
11:45 AM - BM03.05.11
Detergent-Free Synthetic G Protein-Coupled Receptors (GPCR) were Produced and Purified from E.coli
Rui Qing 1 , Fei Tao 1 , Michael Skuhersky 1 , Shuguang Zhang 1 Show Abstract
1 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States
G protein-coupled receptors (GPCRs) are the largest family of cell-surface molecules that detects information (molecules and lights) outside the cell and transduce to internal signals for cell responses. Recently findings indicate that these membrane proteins play a critical role in tumor initiation, progression, invasion and metastasis. Thus they are considered to be one of the most promising drug targets against many cancers. Yet the study of structure and function of GPCRs are notoriously difficult. GPCR proteins contain 7-transmembrane alpha-helical segments that comprised of large numbers of hydrophobic residues. These membrane proteins can only be solubilized and stabilized in aqueous systems in presence of detergents. Lack of detergents will result in protein aggregation. We developed a useful tool, the QTY code, to genetically modify the hydrophobic domains of GPCR to become water-soluble without diminishing their functions. With the QTY code, up to ~56% of the 7-transmembrane segments were altered. Detergent-free CXCR4QTY, CCR5QTY, CCR10QTY and CXCR5QTY were designed and confirmed using the yeast two-hybrid system. Detergent-free synthetic GPCRs have been produced in several host systems. We focused on the expression of these proteins in E.coli. The proteins can be effectively extracted without any detergents from E.coli inclusion bodies and refolded into their functional structure. Final storage buffer of these GPCRs is detergent-free while the solubility of the proteins is regulated by adding arginine. The QTY Code modified GPCRs exhibit ligand binding activity as verified by MircoScale Thermophoresis (MST) measurements. QTY Code provide a simple method for engineering membrane proteins without the presence of detergents. This approach also enables a novel pathway through which difficult GPCR proteins may be studied, modified and utilized for in vivo and in vitro applications. Fabrication of these water-soluble receptor proteins onto bioelectronics can also provide us a next-generation sensing device with high sensitivity and selectivity.
BM03.06: Optoelectronics with Photosynthetic Organisms
Wednesday PM, November 29, 2017
Sheraton, 2nd Floor, Back Bay D
1:30 PM - *BM03.06.01
Photoactive Enzymes in Hybrid Complex Systems
Massimo Trotta 1 Show Abstract
1 Istituto per i Processi Chimico Fisici, Consiglio Nazionale delle Ricerche, Bari Italy
The complexity of the natural photosynthetic systems is difficult to reproduce in vitro; however, complexity is inherently associated to the efficiency of the living multienzyme character of photosynthesis any biomimetic attempts must cope with this stringent requirement.
In this regard, we have designed and assembled efficient organic-biological hybrid systems formed by small to medium size organics molecules responsible of a given specific role and the photoenzyme responsible for energy transduction in photosynthetic organisms.
Applications of photoresponsive enzymes in different fields will be presented to show drawbacks, limitations and potentials of such hybrid systems, along with some future interesting developments.
Artificial Photosynthetic Systems P. Maróti, M. Trotta, in CRC Handbook of Organic Photochemistry and Photobiology, 2012.
Enhancing light harvesting capability of the photosynthetic reaction centre by a tailored molecular fluorophore. 2012 Angewandte Chemie Int. Ed. 51(44), 11019.
Photoactive film by covalent immobilization of a bacterial photosynthetic protein on reduced graphene oxide surface. 2015 MRS Proceedings, 1717, mrsf14-1717-a03-01.
Assembly of photosynthetic reaction center with ABA triblock polymersomes: highlights on the Protein localization (2015) Photochem & Photobiol Sci. 14, 1844.
2015 Journal of Materials Chemistry C. 3, 6471-6478
Crystallographic analysis of the photosynthetic reaction center from Rhodobacter sphaeroides bioconjugated with an artificial antenna 2016 MRS Advanced 1(57), 378
A far-red emitting aryleneethynylene fluorophore used as light harvesting antenna in hybrid assembly with the photosynthetic reaction. 2016 MRS Advanced 1(7), 495
Synthetic Antenna Functioning As Light Harvester in the Whole Visible Region for Enhanced Hybrid Photosynthetic Reaction Centers 2016 Bioconj. Chemistry 27 1614.
Highly oriented photosynthetic reaction centers generate a proton gradient in synthetic protocells (2017) PNAS 114(15), 3837-3842
2:00 PM - BM03.06.02
Tuning the Photoresponse and Photocurrent Generations from Photosystem I Assembled in Tailored Biotic-Abiotic Interfaces
Dibyendu Mukherjee 1 2 , Ravi Pamu 1 2 , Hanieh Niroomand 3 , Ramki Kalyanaraman 3 4 , Bamin Khomami 3 2 Show Abstract
1 Nano-BioMaterials for Energy, Energetics and Environment (nbml-E3) and Mechanical, Aerospace and Biomedical Engineering, University of Tennessee, Knoxville, Knoxville, Tennessee, United States, 2 Department of Mechanical, Aerospace & Biomedical Engineering, University of Tennessee, Knoxville, Knoxville, Tennessee, United States, 3 Department of Chemical & Biomolecular Engineering, University of Tennessee, Knoxville, Knoxville, Tennessee, United States, 4 Department of Materials Science & Engineering, University of Tennessee, Knoxville, Knoxville, Tennessee, United States
Photosystem I (PS I), the photosynthetic membrane protein, undergoes light activated (λ=680 nm) charge separation and unidirectional electron transfer with near-unity quantum efficiency. The robust photoelectrochemical (PEC) activities of PSI make it an ideal biomaterial for bio-hybrid photovoltaic and/or, optoelectronic devices. But, the first step towards rational design of such devices requires systematic electrochemical characterizations of PSI assembly in tailored biotic-abiotic interfaces. To this end, our past works have demonstrated photocurrent generations from PS I monolayer immobilized on SAM/Au substrates from colloidal suspensions using detergent-mediated chemistry and electric field assisted assembly.[1-4] This presentation showcases our recent efforts towards assembling PSI on thiolated Ag plasmonic truncated nano-pyramids, with plasmonic peaks at λ~650-720 nm, that indicate a 3 - 4 fold increase in photocurrent generation as compared to the planar PSI/SAM/Ag substrates. We attribute these observations to the enhanced electric field and optical absorption resulting from localized plasmon enhancement effects. Finally, the presentation will focus on our current research findings from PSI incorporated within biomimetic lipid membrane scaffolds in an effort to investigate the role of natural thylakoid membrane housing of PSI in driving its highly efficient photoactivated charge separation via optimal microenvironment confinements. Absorption/fluorescence spectroscopy and direct visualization using atomic force microscopy of PSI reconstituted in negatively charged DPhPG liposomes reveal the formation of biomimetic PSI-proteoliposomes whose unique emission signatures provide evidence that PSI confinements in synthetic lipid scaffolds can tune its photo-response. Chronoamperometry measurements reveal, for the first time, that photocurrents generated from lipid-confined PSI are 4 - 5 times higher than that from dense monolayer of individual PSI on SAM substrates with equivalent PSI concentrations. These results pave the way for future design of tailored biotic-abiotic interfaces that can optimally tune the photo activity and photo stability of PSI in solid-state bioelectronics, and PEC devices.
 D. Mukherjee, M. Vaughn, B. Khomami, B. D. Bruce, Colloids and Surfaces B: Biointerfaces 2011, 88, 181
 D. Mukherjee, M. May, B. Khomami, J. Colloid Interface Sci. 2011, 358, 477.
 D. Mukherjee, M. May, M. Vaughn, B. D. Bruce, B. Khomami, Langmuir 2010, 26, 16048.
 T. H. Bennett, H. S. Niroomand, R. Pamu, I. Ivanov, D. Mukherjee, B. Khomami, Phys. Chem. Chem. Phys. 2016, 18, 8512.
 R. Pamu, B. Lawrie, R. Kalyanaraman, D. Mukherjee, B. Khomami, To Be Submitted. 2016.
 H. Niroomand, D. Mukherjee, B. Khomami, Scientific Reports 2017, 7.
2:15 PM - BM03.06.03
Photosynthetic Electron Extraction from Thin Algal Cell Film Using a Dense Array of Sharpened Nanoelectrodes
YongJae Kim 1 , JaeHyoung Yun 1 , Seonil Kim 1 , Hyeonaug Hong 1 , WonHyoung Ryu 1 Show Abstract
1 , Yonsei University, Seoul, SE, Korea (the Republic of)
For more efficient solar energy harvesting, various technologies have been investigated for decades. Among them, solar energy conversion using biological sources such as bioethanol, biomass, or microbial fuel cell has been spotlighted to date. However, these methods have very limited energy conversion rates because such methods consume full-grown plants to generate energy and may lose significant portion of absorbed solar energy for the growth of plants. To overcome such limitation of bioenergy conversion, direct energy extraction from photosynthesis has been suggested. Limited number of researches have been performed using either living plant cells or isolated photosynthetic components such as photosystems (PS I, II) and thylakoid membranes.
However, using photosynthetic components has hurdles of poor sustainability or limited efficiency due to use of electrolytes. On the other hand, use of living cells has advantage of long-time sustainability. However, this whole cell-based energy harvesting is unsuitable for scaling up the amount of electrical currents since there are technical difficulties in inserting electrodes into individual cells without damaging the cells. In this study, we propose a combination of thin-film of algal cells and heavily-populated nanoelectrode array to scale-up the nanoelectrode-insertion approach that can extract photosynthetic electrons (PEs) directly from living cells. Nanoelectrode array was fabricated using metal assisted chemical etching (MAC-etching) which used a thin metal layer as an etching catalyst. The metal was patterned using photolithography into the hexagonal lattice. The metal-patterned silicon substrate was placed in a solution of HF and H2O2 at the mixing ratio of 6:1. After the MAC-etching process, the metal-coated spots were anoisotropocally etched and Si nanopillar array of 500 nm diameter was fabricated. To obtain sharper tips of nanoelectrodes for sustainability of algal cell after nanoelectrode insertion, silicon thermal oxidation and oxide etching was followed. Finally, Au layer was deposited on the surface of the nanoelectrodes by sputter deposition.
Algal cell, Chlamydomonas reinhardtii, monolayer film, which had 10 μm thickness, was formed using sodium alginate (NaC6H7O6) as a matrix material. 5% (w/w) of algal cell was added into sodium alginate to make a cell-alginate gel mixture. The mixture was pressed to form a thin film of uniform thickness. Then, the alginate-cell mixture gel was crosslinked by applying calcium chloride (CaCl2) to form a monolayer cell film. This cell film was placed on a nanoelectrode array and pressed to insert nanoelectrodes into algal cells in the cell film simultaneously. The conformation of inserted cells was observed using optical microscopy and SEM. About 300 nA of photosynthetic currents was measured under light illumination condition without any mediator. The nanoelectrode-inserted algal cell film maintained the function of solar energy harvester up to 7 days.
3:30 PM - BM03.06.04
Electronic Coupling with Plants
Eleni Stavrinidou 1 , Iwona Bernacka Wojcik 1 , Roger Gabrielsson 1 , Gwennael Dufil 1 , Gábor Méhes 1 , Daniel Simon 1 , Magnus Berggren 1 Show Abstract
1 , Linkoping University, Norrkoping Sweden
Plants are an indispensable part of our ecosystem and are essential for our survival and quality of life. Recently we have demonstrated the first example of electronic interface with plants and introduced the concept of Electronic Plants. We used water-soluble conducting polymers and oligomers that self organize or polymerize in vivo, reactions that are aided by the plant. We demonstrated analogue and digital circuits manufactured in the organs of a plant as well as supercapacitors for energy storage. In addition we are using bioelectronics devices to sense and actuate plant functions. Organic bioelectronics have been focus mainly on biomedical applications but we are applying devices such as ion pumps and organic electrochemical transistors in plants to control transpiration and sense molecules related to photosynthesis. In this talk, recent advancements of our technology will be presented and potential applications will be discussed.
3:45 PM - BM03.06.05
Electronic Plants and Tapping into Photosynthesis via Organic Bioelectronics
Gábor Méhes 1 , Eleni Stavrinidou 1 , Daniel Simon 1 , Magnus Berggren 1 Show Abstract
1 , Linköping University, Norrköping Sweden
Very recently, plants have come into the spotlight of our Organic Bioelectronics initiatives. Anchored to their living places, plants had to develop complex strategies for survival, e.g. collect and store solar energy, sense their environment or execute defense against predators. Our group has demonstrated the engineering possibilities of electronics in-vivo in plants: electrical-and ion conductors, organic electrochemical transistors (OECTs), and simple logic circuits inside the water-transporting xylem channels, as well as electrochromic pixels inside leaves. These ‘Electronic Plants (E-Plants)’ make use of the polymer poly(3,4-ethylenedioxythiophene) (PEDOT).
A logical next step could be exploring solar energy harvesting using plants and their predecessors, bacteria. The most efficient conversion processes from light to electrons happen in the photoprotein complexes embedded into the thylakoid membranes. We envision that bio energy harvesting at the highest efficiencies should tap into this process. Such a direct access to photosynthesis poses a great technological challenge if we want to avoid dismantling the organism. The latter approach would lead to the loss of key autonomous abilities of living organisms for survival, such as reproduction, self-healing and adaptation to changing environments.
I will discuss our results in E-Plants, and our vision and approaches for solar harvesting from photosynthesis.
 Stavrinidou et al. Sci. Adv. 2015, 1, e1501136
 Stavrinidou, Gabrielsson et al. PNAS 2017, 114, 2807
 Poxson, Karady et al. PNAS 2017, 114, 4597
 Gomez, et al. Sci. Rep. 2017, 7, 45864
4:00 PM - BM03.06.06
A Nanobionic Light Emitting Plant
Seonyeong Kwak 1 , Juan Pablo Giraldo 2 , Min Hao Wong 1 , Volodymyr Koman 1 , Tedrick Salim Lew 1 , Jon Ell 1 , Mark Weidman 1 , Rosalie Sinclair 1 , Markita Landry 3 , William Tisdale 1 , Michael Strano 1 Show Abstract
1 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States, 2 , University of California, Riverside, California, United States, 3 , University of California, Berkeley, California, United States
Lighting uses 20% of electricity output. Lighting-related CO2 emission/year is expected to be 3 Gt by 2030 and 1.6 billion people live without access to electric light at present.1 As independent energy sources, engineering plants are compelling platforms for light emission and sustainable illumination with negative carbon footprints.2 In this study, we created a wild-type living light emitting plant with a nanobionic approach that enables remarkable luminosity and lifetime, tissue specific patterning, ‘on/off’ control and nIR communication. Three chemically-interacting nanoparticles are designed such as firefly luciferase immobilized silica, D-luciferin releasing poly(lactic-co-glycolic acid), and coenzyme A loaded chitosan. An in vitro kinetic model based on nanoparticle system has developed to extend the chemiluminescent lifetime. A new technique of pressurized bath infusion allows whole plant delivery of nanoparticles in a minute. Our strategy of nanoparticle transport controls localization of nanoparticle depending on its size and charge within distinct tissues compartments. The results are a mature watercress plant that emits greater than 1.44x1012 photons/sec or 50% of commercial luminescent diodes. We also show that CdSe nanocrystals can shift the chemiluminescent emission to nIR through resonant energy transfer. These results advance the viability of nanobionic plants for potential applications as self-powered photonics, direct and indirect light sources.
1. Waide, P., Tanishima, S. & International Energy Agency. Light's labour's lost : policies for energy-efficient lighting. (OECD/IEA, 2006)
2. Giraldo, J. P. et al. Plant nanobionics approach to augment photosynthesis and biochemical sensing. Nat Mater 13, 400-408 (2014)
4:15 PM - BM03.06.07
At the Nexus between Animate and Inanimate Matter—Biological Materials, Components and Devices
Artur Braun 1 Show Abstract
1 , Empa, Swiss Federal Laboratories for Materials Science and Technology, Duebendorf Switzerland
Materials science traditionally is the science of the inorganic matter, and of the organic matter when it is maybe of biological origin but not alive anymore. Recently, research on living matter beyond the independent field of life sciences has become popular again. I will present recent studies on light antenna proteins and algae and biofilms for solar energy conversion. Specifically will I address the covalent attachment of these components with metal oxide semiconductor electrodes1, along with their assessment with electroanalytical methods and synchrotron based x-ray and photoelectron spectroscopy under electrophysiological condition 2, 3. The interface between an anabaena spirulina biofilm grown on hematite electrodes was subject to Fe 3p resonant photoemission spectroscopy while under electrochemical DC bias from 0 to 1 .5 Volt, at 150 mTorr water vapor partial pressure under dark and illuminated condition. The Fe 3p orbital resolved valence band of the bio-inorganic interface shows a characteristic shift on the excitation energy axis which is due to the specific response of the biofilm to the various thermodynamic excitations imposed on it during this operando experiment. The goal of this study is to establish an industrial infrastructure for direct solar fuel production with living and functionalized algae without using them for production of biomass fuel4, 5.
1. Schrantz K, et al. Hematite photoanode co-functionalized with self-assembling melanin and C-phycocyanin for solar water splitting at neutral pH. Catalysis Today 284, 44-51 (2017).
2. Braun A, et al. Biological components and bioelectronic interfaces of water splitting photoelectrodes for solar hydrogen production. Chemistry 21, 4188-4199 (2015).
3. Braun A. X-ray Studies on Electrochemical Systems - Synchrotron Methods for Energy Materials. Walter De Gruyter GmbH (2017).
4. Hindersin S, Leupold M, Kerner M, Hanelt D. Key parameters for outdoor biomass production of Scenedesmus obliquus in solar tracked photobioreactors. Journal of Applied Phycology 26, 2315-2325 (2014).
5. Bora DK, Braun A, Constable EC. “In rust we trust”. Hematite – the prospective inorganic backbone for artificial photosynthesis. Energy Environ Sci 6, 407-425 (2013).
4:30 PM - BM03.06.08
Plant Nanobionic Sensors for Ubiquitous Detection of Infectious Pathogens
Sudeep Joshi 1 , Kiavash Kiaee 1 , Yasamin Aliashrafi Jodat 1 , Manu Mannoor 1 Show Abstract
1 , Stevens Institute of Technology, Hoboken, New Jersey, United States
Green plants possess myriad remarkable functionalities including, being the ultimate source of food and metabolic energy for effectively supporting complex food chain in our ecosystem. Moreover, natural plant biology upholds remarkable potentials and offers a tremendous scope for compelling bionic integration resulting in hybrid next-generation devices incorporating enhanced functionalities. Leaves are plant’s photosynthetic organs housing thylakoid membrane proteins which perform light-dependent photosynthetic reaction of splitting H2O molecules to generate H+ ions, a pH gradient, high energy electrons with an unparalleled quantum efficiency, and oxygen as a by-product which is released in the atmosphere.
Direct interfacing of active photosynthetic component units of leaves with functional nano-electronic materials could lead to plant nano-bionic systems possessing enhanced supplementary functionalities resulting in next generation cyborg plants. As a demonstrative proof-of-concept, we have seamlessly integrated electronic wireless nanomaterial sensor with biologically active components of natural leaves to create a photosynthetically self-powered plant nano-bionic sensors offering ubiquitous detection of infectious pathogenic contamination. Specifically, we have integrated isolated thylakoid membrane proteins extracted from baby spinach leaves with graphene nanoribbon based transduction matrix into a 3D printed leaf-shaped hierarchical structure consisting of functional modules which are analogous to the vascular bundles of natural leaf anatomy. Graphene nanoribbon sensing matrix was functionalized with anti-hemagglutinin antibodies to detect artificially generated aerosols containing varied concentrations of Influenza viral particles. Furthermore, an interdigitated electrode with inductive coil was patterned over graphene nanoribbon sensing matrix and bio-transferred on to live leaves (Epipremnum aureum and Cactaceae) via a silk fibroin sacrificial substrate, therefore eliminating the need for an on-board power supply which enables ubiquitous pathogenic sensing.
This unique integration establishes a symbiotic relationship and derives numerous benefits, for instance: (i) nano sensors are powered by photosynthetic bioelectricity, (ii) functionalized bio-recognition molecules are embedded in suitable biophysiological environment of leaf membranes enhancing their overall lifespan, and (iii) sensors integrated with plants are ubiquitously deployed in the environment to detect potential viral threats. The proposed plant nano-bionic integration is a step forward and definitive example of expanding the frontiers of synthetic biology and functional nanomaterials towards powering the eco-friendly next-generation sensing devices.
4:45 PM - BM03.06.09
A Stomatal Electro-Mechanical Pore Size Sensor (SEMPSS) for Persistent Monitoring of Plant Physiology
Volodymyr Koman 1 , Tedrick Salim Lew 1 , Min Hao Wong 1 , Seonyeong Kwak 1 , Juan Pablo Giraldo 2 , Michael Strano 1 Show Abstract
1 , MIT, Cambridge, Massachusetts, United States, 2 Department of Chemistry, University of California, Riverside, Riverside, California, United States
Stomatal function can be used effectively to monitor plant hydraulic efficiency, photo-sensitivity and CO2 conductance. Current approaches to measure stomatal aperture size, such as mold casting or fluorometric techniques, do not allow real time or persistent monitoring of the stomata over the timescales relevant for plant physiology including growth and maturation, or gradual changes in soil water potential associated with drought conditions. Herein, we utilize a nanoparticle-based conducting ink that preserves stomatal function to print a highly stable, electrical conductometric sensor actuated by the stomata pore itself, repeatedly and reversibly for over 1 week. This Stomatal Electro-Mechanical Pore Size Sensor (SEMPSS) allows for real-time tracking of the latency of stomatal opening and closing times, which we show vary from 7±0.5 to 25±0.5 min for the former and from 53±0.5 to 45±0.5 min for the latter in Spathiphyllum. These values are shown to correlate with a drop in soil water potential and the onset of the wilting response, in quantitative agreement with a mathematical model of stomata signaling in function. A single stoma of Spathiphyllum is shown to distinguish between incident light intensities (up to 12 mW/cm2) with temporal latency slow as 7±0.5 min. Over a seven day period, the latency in opening and closing times are stable throughout the plant diurnal cycle and increase gradually with physiological changes associated with drought onset. The monitoring of stomata function over relevant timescales for plant physiology will improve understanding of plant adaptation to environmental factors.
Gianluca Farinola, University degli Studi-Bari Aldo Moro
Eric Glowacki, Linkoping Unversity
Radislav Potyrailo, GE Global Research
Silvia Vignolini, University of Cambridge
APL Photonics | AIP Publishing
BM03.08: Bioelectronics and Sensing
Thursday AM, November 30, 2017
Sheraton, 2nd Floor, Back Bay D
8:30 AM - *BM03.08.02
Organic Bioelectronics Made from Trimers, Oligomers and Polymers Based on the EDOT Monmer
Magnus Berggren 1 Show Abstract
1 , Linkoping University, Norrkoping Sweden
Short- and long-chain derivatives and material systems based on the EDOT monomer, such as the PEDOT:PSS, has found its way as the active material in various bioelectronic devices and systems to transduce biological signals into electronic ones, and vice versa. In sensor-actuator systems, we explore this dual signal translation functionality to derive artificial neural networks that record and actuate physiology in mammalians and in plants.
Here, the manufacturing approaches and applications of such artificial neural networks are reported. Even though its extensive use in bioelectronics and in electrochemical devices, the fundamental understanding of the charge-accumulation and ion exchange characteristics is still debated. From a 2D- and 2 phase modeling effort, based on a modified Nernst-Planck-Poisson approach, the fundamentals of the energetics and charge transport dynamics in PEDOT:PSS-based devices can be described accurately.
9:00 AM - *BM03.08.03
Synthesis and Characterization of Bioinspired Organic Nanowires and Nanoribbons
Alon Gorodetsky 1 Show Abstract
1 , University of California, Irvine, Irvine, California, United States
One-dimensional organic nanowires and nanoribbons represent idealized model systems for investigating charge transport mechanisms at molecular length scales. However, there are significant difficulties associated with the synthesis of organic nanowires and nanoribbons with precisely defined sequences, lengths, geometries, and terminal functionalities. By drawing inspiration from both natural systems and graphitic materials, we have developed facile strategies for the covalent assembly of organic semiconductor building blocks into well-defined one-dimensional ensembles. We have investigated the properties of these nanowires with a suite of spectroscopic, electrochemical, scanning probe microscopy, and computational techniques, discovering new properties and functionality for our constructs. Our findings hold significance both for fundamentally understanding nanoscale charge transport phenomena and for the ultimate development of next-generation molecular electronic devices.
9:30 AM - BM03.08.04
Organic Bioelectronics for Bio-Chemical Detections at Ultra-Low Detection Limits
Eleonora Macchia 1 , Gaetano Scamarcio 2 , Gerardo Palazzo 1 , Luisa Torsi 1 Show Abstract
1 Dipartimento di Chimica, University of Bari A. Moro, Bari Italy, 2 Dipartimento di Fisica “M. Merlin”, University of Bari A. Moro, Bari Italy
Counting the molecules present in a solution instead of assaying its concentration is the ultimate and visionary goal in chemical analysis. It’s actuation however, necessarily requires reliable technologies that can “count” the molecules one by one. Such an approach would enable not only fundamental understanding of subtle effects in an affinity interaction likely hidden in ensemble measurements, but also it would pave the way to striking applications. Indeed, proteins and biomolecules detection at the physical limit are foreseen to generate ground-breaking technological fallouts such as for instance, label-free biosensors endowed with high selectivity as well as sub-femtomolar (10-15 M, fM) sensitivity for non-invasive label-free quantitative analysis of pathogens or diseases’ markers in bio-fluids such as saliva or tears.
The present lecture thus aims at presenting an overview on the challenges and on the exciting perspectives, that are associated with the quantification of ultra-low concentrations of proteins. An outlook on the extremely high performance level of millimetre-size organic bioelectronic sensors integrating a trillion of capturing molecules, will be provided showing that sub-fM detection limits can be reliably reached.1 As cases of studies, the selective and ultra-sensitive assay of immunoglobulins and C-reactive protein in saliva will be discussed. The organic bioelectronic transistors used are mm-size, low-cost and are operated at physiologically relevant conditions as well as in human saliva setting the ground for a revolution in immunoassay for early bio-markers detection2-3.
References: 1.E. Macchia, et al., Advances in Sensors and Interfaces (IWASI), 2017 7th IEEE International Workshop DOI: 10.1109/IWASI.2017.7974217; 2. M.Y. Mulla et al., “Capacitance-modulated transistor detects odorant binding protein chiral interactions,” Nature Communication., vol. 6, pp. 6010, 2015. 3. E. Macchia et al., “Organic bioelectronics probing conformational changes in surface confined proteins,” Scientific Reports (Nature), vol. 6, pp. 28085, 2016.
9:45 AM - BM03.08.05
Biomimetic Sensor Platform for Point-of-Care Bacteria Detection
Kasper Eersels 1 , Bart van Grinsven 1 , Erik Steen Redeker 1 , Peter Cornelis 2 , Patrick Wagner 2 , Thomas Cleij 1 Show Abstract
1 , Maastricht University, Maastricht Netherlands, 2 , KU Leuven, Leuven Belgium
Over the past decade, various biomimetic sensor platforms based on synthetic, bio-inspired receptors have been developed. In terms of macromolecular targets, surface-imprinted polymers (SIPs) have emerged as interesting candidates for incorporation into point-of-care detection systems. Until now, SIP-based sensors have mainly been combined with quartz crystal microbalance (QCM) readout platforms.1 Although QCM is an interesting and valuable readout technique, it has some shortcomings in terms of point-of-care diagnostic applications. In 2012, a surprisingly versatile tool for label-free sensing was developed; the so-called heat-transfer method (HTM). In previous work, SIP-based detection of human cells and bacteria was demonstrated using this thermal readout strategy.2-4 In this work, the thermal sensing principle has been improved by analyzing the propagation of a thermal wave through the receptor layer rather than a constant current (thermal wave transport analysis or TWTA). The improved methodology was used for selective and quantitative identification of several bacterial species in both buffer and urine.5
The current study illustrates that it is possible to selectively distinguish between bacteria from different species using the proposed sensor, while a moderate degree is observed when exposing the sensor to two E. coli strains. The response can be quantified and bacteria can be detected in concentrations as low as 10,000 colony forming units (CFU) mL-1 in buffer solution. Additionally, a first proof-of-application is provided, illustrating the sensor’s potential for detecting bacteria in complex matrices. These experiments show that the sensor is able to detect a trace amount of the target species in a 100-fold excess of competitor bacteria. Finally, the sensor was used to detect E. coli in spiked urine samples in concentrations that would allow for urinary tract infection diagnosis.
1. Hayden, O. et al. Adv. Funct. Mater. 2006, 16, 1269-1278.
2. van Grinsven, B.; Eersels, K. et al. ACS Appl. Mater. Interfaces 2014, 6, 13309-13318.
3. Eersels, K. et al. ACS Appl. Mater. Interfaces 2013,
4. Eersels, K. et al. ACS Sens. 2016, 1, 1140-1147.
5. Steen Redeker, E.; Eersels, K et al. Acs Infect. Dis. 2017, 3, 388-397.
10:30 AM - *BM03.08.06
Proton Transport in Biomaterials—From Ion Channels to Devices
Marco Rolandi 1 Show Abstract
1 , University of California, Santa Cruz, Santa Cruz, California, United States
In 1804, Theodore von Grotthuss proposed a mechanism for proton (H+) transport between hydrogen bonded water molecules that involves the exchange of a covalent bond between H and O with a hydrogen bond. Water and associated hydrogen bonding is omnipresent in living systems and proton transport is a very common phenomenon in nature. Proton transport may serve a specific function such as in oxidative phosphorylation or the antibiotic gramicidin. Often, whether proton transport is simply a secondary property from structural hydrogen bonding is still under investigation such as in melanin. Here, I will present our efforts in developing bioelectronic devices that are able to monitor and control proton currents, and the integration of these devices with biomaterials and living systems. These include ion channels, neurons, and shark’s electrosensors.
11:00 AM - BM03.08.07
Proton Conduction in a Tyrosine-Rich Peptide/Manganese Oxide Hybrid Nanofilm
Jaehun Lee 1 , Ikrang Choe 1 , Young-O Kim 1 , Seok Namgung 2 , Jang-Yeon Kwon 2 , Yoon-Sik Lee 1 , Ki Tae Nam 1 Show Abstract
1 , Seoul National University, Seoul Korea (the Republic of), 2 , Yonsei University, Seoul Korea (the Republic of)
Proton conduction is an essential process that regulates an integral part of several enzymatic catalyses and bioenergetics. Proton flows in biological entities are sensitively controlled by several mechanisms. To understand and manipulate proton conduction in bio-systems, several studies have investigated bulk proton conduction in biomaterials such as polyaspartic acid, collagen, reflectin, serum albumin mats, and eumelanin. However, little is known about the bulk proton conductivity of short peptides and their sequence-dependent behaviour. Indeed, several amino acids take an active part as proton transporters in biological systems. In particular, amino acids having a phenol group, such as tyrosine have been known to play a critical role in proton-coupled electron transfer interplaying with a manganese-calcium cluster in photosystem II. Additionally, tyrosine can be oxidized and polymerized into eumelanins, which show hydration-dependent electrical current and high proton conductivity. Taking advantages of the characteristics of tyrosine, here, we developed a new facile strategy for fabricating peptide/manganese oxide hybrid films. The spin-coated peptide nanofilm is immersed into potassium permanganate solution to induce crosslinking and oxidation of tyrosine species, simultaneously leading to hybridization with manganese oxide (MnOx). It results in rather strong synergetic effects on proton conduction. The peptide/MnOx hybrid nanofilm can efficiently transport protons, and its proton conductivity is ~18.6 mS cm-1 at room temperature. To the best of our knowledge, no other biomaterial-based proton conductor or manganese oxide has shown such high proton conductivity. Moreover, we predict that the proton conduction across the hybrid film could be further improved by incorporating more tyrosine groups or acidic functional groups into the peptide sequence. The exploration of peptide-based hybrid films as novel proton conductors has not been documented and has significant implications for both biology and technology. This study suggests that peptide-based hybrid films can be a promising new class of proton conductor.
11:15 AM - BM03.08.08
Using Polysaccharides and Carbon Nanotubes to Enhance the Biosensing Properties of Enzyme-Lipid Nanostructured as Langmuir-Blodgett Films
Raul Rodrigues 1 , Audrey de Brito 1 , Cristina Nordi 1 , Jose Roberto Siqueira Junior 2 , Luciano Caseli 1 Show Abstract
1 , Federal University of Sao Paulo, Diadema Brazil, 2 , Federal University of Triangulo Mineiro, Uberaba, MG, Brazil
Films nanostructured at the molecular level are useful systems for several applications since their properties can be easily controlled and manipulated. Particularly, determining the catalytic activity of enzymes confined in such devices is important to regulate the biosensing properties of ultrathin films, such as Langmuir-Blodgett (LB) ones. Enzymes can be adsorbed at lipid Langmuir monolayers from aqueous subphases, and the transfer of the mixed films to solid supports as LB films provides the formation of bioinspired devices whose molecular architecture determines the catalytic and morphological properties. Enzymes confined in these devices may have catalytic activities preserved for longer times, but the fact that they are immobilized in solid supports may reduce significantly the enzyme activity owing to polypeptide conformational changes and diffusion restrictions of the analyte to the catalytic center of the enzyme. In this sense, using materials co-immobilized in the lipid-enzyme structure can help the determination of the enzyme activity as well as it can enhance the catalytic properties of the enzyme. In this work, we show how the use of polysaccharides and carbon nanotubes can help the properties of co-adsorption and molecular accommodation of the enzyme urease incorporated in Langmuir monolayers of dioctadecyldimethyl bromide (DODAB), forming a mixed film. Carboxylated carbon nanotubes and exopolysaccharides (EPS) from Cryptomonas sp were co-incorporated from the aqueous subphase. The floating monolayers were characterized with surface pressure-area and surface potential-area isotherms, polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS), Brewster angle microscopy (BAM), and interfacial shear rheological (ISR) measurements. The adsorption of this enzyme at the air-water interface condensed the lipid monolayer, altering the film compressibility at low and high surface pressures. Amide bands in the PM-IRRAS spectra were identified, revealing the structuring of the enzyme into α-helices and β-sheets. The Langmuir monolayers were transferred to solid supports as Langmuir-Blodgett (LB) films and characterized with fluorescence spectroscopy and atomic force microscopy. Catalytic activities of the films were measured and compared to the homogenous medium. The enzyme accommodated in the LB films preserved more significantly the enzyme activity and help conserve the catalytic properties for long periods of storage. EPS and the carbon nanotubes enhanced the enzymatic properties acting as a smother and electron transfer facilitator, respectively. The method presented in this work not only allows for an enhanced catalytic activity, but also can help explain why certain film architectures exhibit an improved performance.
11:30 AM - *BM03.08.09
Laser Particles for Biomedical Imaging
Nicola Martino 1 2 , Sheldon Kwok 1 3 , Sangyeon Cho 1 3 , Seok-Hyun Yun 1 2 3 Show Abstract
1 Wellman Center for Photomedicine, Massachusetts General Hospital, Cambridge, Massachusetts, United States, 2 Department of Dermatology, Harvard Medical School, Cambridge, Massachusetts, United States, 3 , Harvard–MIT Health Sciences and Technology, Cambridge, Massachusetts, United States
Lasers are ubiquitously used in biomedical research as versatile light sources because of the peculiar characteristics of their emission, such as wavelength selectivity, high intensity and spatiotemporal controllability. However, until now, laser light has always been provided to samples from external sources in a unidirectional way, i.e. with the laser affecting the object under study, but not vice-versa. Recently, our group demonstrated that it is indeed possible to integrate laser sources, in the form of micrometric resonators, inside living cells and biological tissues. This possibility opens the way to the development of such laser particles as optical contrast agents in bioimaging applications. In this contribution, we will explore some of the possible ways in which the peculiar properties of laser light emission from micrometric particles can be exploited to obtain new functionalities. For example, the output emission of a laser close to threshold has a strong non-linear behavior with respect to the pump power; this non-linearity allows to achieve sub-diffraction resolutions and optical sectioning capabilities, without the need of complex excitation and detection schemes. Also, given the narrow linewidth of laser emission (< 1 nm), it is possible to have a larger number of independent detection channels, compared to the broader bands of typically used fluorescent molecules and quantum dots (tens to hundreds of nm). The current limitations of this technology and possible future developments will also be addressed.
BM03.09: Biological and Biomimetic Polymers
Thursday PM, November 30, 2017
Sheraton, 2nd Floor, Back Bay D
1:30 PM - *BM03.09.01
Paul Meredith 1 , Bernard Mostert 2 , Margarita Sheliakina 2 , Shermiyah Rienecker 2 Show Abstract
1 , Swansea University, Swansea United Kingdom, 2 , The University of Queensland, Brisbane, Queensland, Australia
The melanins are a ubiquitous class of functional biomacromolecules found throughout nature in many roles including photo-protection, pigmentation and free radical scavenging . Due to their hybrid ion-electron solid-state electrical conduction properties , synthetic melanins based upon poly-indolequinones have also emerged as a classic model for bioinspired optoelectronic materials in applications such as bioelectronics . It has been known for several years that the solid-state DC and AC electrical conductivity in melanin thin films and pellets is strongly modulated by adsorbed water which takes part in a local reaction known as the comproportionation equilibrium . The mechanism is likely generic in biomaterials (and indeed certain synthetic polymers) which have ionisable groups with local pKas around neutrality .
In my talk I will describe the physics and chemistry behind these processes and also report new data from our group whereby we observe dramatically enhanced responsibility to hydration by what appears to be ‘doping’ of the melanin backbone via copper II chelation . Ordinarily, we and others have seen ~ 1.5 orders of magnitude change ‘dry to hydrated’ melanin – but the addition of Cu (II) in the form of a salt delivers a very significant 4.5 orders of magnitude change over the same hydration range. The underlying mechanism for this is unclear, but appears to be related to a coupled redox exchange between melanin and free radicals and the incorporated copper ions. We probe these dynamics with EPR and X-ray photoelectron spectroscopy. The questions as to whether the effect is generic across transition metals and indeed conducting biomacromolecules is open, but these observations present interesting new avenues for the creation of bespoke
 P. Meredith and T. Sarna, Pigment Cell Research, 2006, 19, 572-594.
 A. B. Mostert, B. J. Powell, F. L. Pratt, G. R. Hanson, T. Sarna, I. R. Gentle and P. Meredith, Proceedings of the National Academy USA, 2012, 109, 8943-8947
 P. Meredith, C. J. Bettinger, M. Irimia-Vladu, A. B. Mostert and P. E. Schwenn, Reports on Progress in Physics, 2013, 76, 034501
 L. Hong, J. D. Simon, Journal of Physical Chemistry B, 2007, 111, 7938-7947
2:00 PM - BM03.09.02
Controlled Polymerization of the Melanin Biopigment for (Photo)Capacitors
Clara Santato 1 , Dominic Boisvert 1 , Alessandro Pezzella 2 , Eduardo Di Mauro 1 Show Abstract
1 , Ecole Polytechnique de Montreal, Montreal, Quebec, Canada, 2 , Università Napoli Federico II, Napoli Italy
The strong UV-Vis absorption, free radical scavenging properties and hydration dependent electrical response of the biopolymer melanin intrigue physicists, chemists and materials scientists since decades. [Mostert et al. PNAS 2012] Recently, Pezzella et al. reported on the possibility to obtain chemically controlled melanin by solid state polymerization, thus overcoming the biggest limitation in the exploitation of the melanin technological potential, namely its limited processability in common organic solvents. [Pezzella et al Mat. Horizons 2014] By a modified version of the solid state polymerization applied at surfaces (SiO2, quartz, glass, and metals, such as Pt, Pd and Cu), we are able to follow the process of polymer formation by AFM from spin coated films of the monomers. Dendrimers of melanin form in ambient conditions on the surface of the selected substrates, in a few minutes; this is pretty surprising considering that no catalyst is added to the system. The formation of the monomer likely results from a diffusion limited growth of the polymer from the monomers.
The key aspect of our findings on the controlled polymerization of melanin is the opportunity to use chemically controlled melanin to study its optical and electrochemical properties with an unprecedented degree of detail. Recent theoretical studies shed light on the chromophores present in melanin (dimers, trimers, tetramers, eptamers, differently packed) [Buheler et al Nat Comm 2014] . On the electrochemical side, supercapacitors and batteries making use of melanin-based electrodes have been recently reported (making use of commercially available melanin or melanin extracted from Sepia ink, both not controlled chemically) [Kumar et al J Mater Chem C, Bettinger et al Adv. Mater. 2015]. Our dendritic, controlled polymers offer the opportunity to complement theoretical studies on the optical absorption properties of melanin and to gain insight on the redox processes taking place in melanin to pave the way to green solar battery devices. Results on the optical properties of the controlled polymer by spacial resolved absorption spectroscopy as well as electrochemical studies by cyclic voltammetry and electrochemical impedance spectroscopy will be included in the presentation.
2:15 PM - *BM03.09.03
Programming Function in Silk Fibroin Bulk Materials
Benedetto Marelli 1 , Fiorenzo Omenetto 2 Show Abstract
1 , Massachusetts Institute of Technology, Cambridge, Massachusetts, United States, 2 Biomedical Engineering, Tufts University, Medford, Massachusetts, United States
Structural biopolymers are materials engineered by Nature as building blocks of living matter. These materials have unique and compelling properties that allow for their assembly and degradation with minimal energy requirements as well as their performance at the biotic/abiotic interface. By combining basic material science with advanced fabrication techniques, it is possible to define new strategies to drive the assembly of structural biopolymers in advanced materials with unconventional forms and functions.
Particularly compelling is the engineering of multiple functions in a single material format as key design parameter to fabricate devices that can perform at the confluence between biology and technology. This can be achieved by designing materials with hierarchical structures across several scales or by embedding active molecules at the point of material formation. These approaches have been successfully pursued to engineer 2D materials formats. However, current technologies have limited the formation of 3D constructs with orthogonal functions. In this presentation, we demonstrate an entirely water-based sol–gel–solid process to generate 3D mechanical forms that embed biological (and other) functions, using silk fibroin materials.
This approach pushes the boundaries of the applications of structural biopolymers into new fields that were traditionally dominated by synthetic polymers and metals. Fabrication methods such as compression molding and machining are typically used to produce large and complex objects such as car parts, engines, and plane parts as well as many commodity products, such as plastic eating utensils and packaging. Here, we demonstrate that silk fibroin sol-gel-solid transition is amenable to an all-water new fabrication method that blend natural bottom-up and man-made top-down manufacturing landscapes. In particular, it is reported the design of functions in silk bulk materials by embedding functional elements, such as gold nanorods to produce screws that generate heat when exposed to infrared light and polydiacetylene vesicles that undergo a blue-to-red chromatic transition at the mechanical yield point of mechanical components.
* Benedetto Marelli
Paul M. Cook Career Development Assistant Professor
Laboratory for Advanced Biopolymers (L.A.B.)
Department of Civil and Environmental Engineering
Massachusetts Institute of Technology
77 Massachusetts Avenue, Room 1-348, Cambridge, MA, 02139-4307, USA
2:45 PM - BM03.09.04
Novel Enzymatically Synthesized Substituted Polyaniline with High Conjugation and Conductivity
Ferdinando Bruno 1 , Ramaswamy Nagarajan 2 , Weeradech Kiratitanavit 2 , Zarif Farhana 2 , Bora Yoon 1 , Stephen Fossey 1 , Manuele Bernabei 3 Show Abstract
1 , U.S. Army NSRDEC, RDECOM, Natick, Massachusetts, United States, 2 Plastic Engineering, University of Massachusetts Lowell, Lowell, Massachusetts, United States, 3 Chemistry, ITAF, Test Flight Center, Rome Italy
An efficient enzymatic route for the synthesis of conducting substituted aniline complexed with poly(sodium 4-styrenesulfonate) is presented. This polyelectrolyte assisted horseradish peroxidase catalyzed polymerization of ortho-toluidine provides a route to synthesize water-soluble, highly conductive and conjugated polymers under acidic conditions. The UV-Vis, FTIR, thin film conductivity, molecular weight assessment and modeling studies of the polymer complex indicate the presence of a thermally stable and electroactive polymer with extended conjugation that was not present in similar conductive polymers (e.g. PANI). Moreover, the use of water-soluble templates provides a unique combination of properties such as high conductivity and processability. The same procedure was also implemented for the polymerization of 2,6-xylidine. However the reaction did not occur suggesting a much more complex stereo-specificity of the enzymatic polymerization. Modeling studies were used to explain this behavior. The conductive poly(ortho-toluidine) (POTO) can be used in wireless sensors for the detection of industrial toxic gases such as ammonia.
3:30 PM - *BM03.09.05
Peptide-Based Nanomaterials—Self-Assembled Designer Biomaterials
Yasaman Hamedani 1 , Prathyushakrishna Macha 1 , Nicole Butts 1 , Milana Vasudev 1 Show Abstract
1 , University of Massachusetts Dartmouth, Dartmouth, Massachusetts, United States
Naturally occurring self-assembled structures include DNA, protein fibrils such as Amyloid fibrils which are implicated in Alzheimer’s disease, encephalopathies and Type II diabetes. The discovery of self-assembling peptides, for instance, the one which form the core motif of the Alzheimer’s B-amyloid protein that spontaneously organize into well-ordered structures has opened up a realm of opportunity for designing or tailored short peptide sequences. These peptides have several applications, specifically in regenerative medicine for tissue repair, scaffolding for tissue engineering, drug delivery and sutures. The properties of these peptides, namely; their complementary structures, hydrogen bonding and electrostatic or hydrophobic interactions between side groups, allow the formation of complex structures via self-assembly.Peptides typically self-assemble in aqueous solutions, however, there are other methods such as exposure to the plasma stream or electrostatic forces which can also lead to the formation of nanostructures. In this study, various methods of synthesizing peptide-based nanostructures composed of short oligomeric peptides, as well as amphiphilic peptides have been investigated using some common methods of self-assembly such as solvent-switch method, vapor deposition along with induced assembly due to the application of electrostatic forces, such as electrospinning in order to understand the influence on the morphology and chemical characteristics of the deposited nanomaterials. The biocompatibility of such nanostructures as well as their physiological effect on neural cells in vitro were investigated. Metabolism and excretion from the human body may prevent attainment of therapeutic concentrations of flavonoids in tissues. Encapsulation in amphiphilic peptide-based micelles presents an attractive route to delivery non-polar flavanoids to tissues/organs of interest. Electrosprayed nanospheres were utilized in the delivery of polar cranberry compounds. Preliminary in vitro studies of enhanced bioavailability, compound pharmacokinetics and targeting were performed in tumor cell cultures.
4:00 PM - BM03.09.06
DNA-Inspired Self-Assembly of Nanoscale Electronic Devices
Jason Slinker 1 , Alon Gorodetsky 2 , Kuo-Yao Lin 1 , Andrew Bartlett 2 Show Abstract
1 , The University of Texas at Dallas, Richardson, Texas, United States, 2 , University of California, Irvine, Irvine, California, United States
Despite remarkable examples of difficult-to-produce isolated molecular devices, the scalable nanomanufacturing of such electronics remains at a standstill due to fundamental roadblocks associated with the synthesis of large quantities of modular nanoscale circuit elements. We have introduced a methodology for mass production of nanoscale electronic elements. We have synthesized organic semiconductor moieties, perylene-3,4,9,10-tetracarboxylic diimides (PTCDIs), within DNA-like scaffolds, leveraging the rapid, efficient, and precise coupling afforded by traditional DNA bioconjugate chemistry. These DNA-inspired nanowires enable the self-assembly of active, nanoscale circuit elements at patterned electrodes. The assembly and electrical performance of these arrayed devices have been characterized through scanning microscopy techniques and custom, automated electrical probe measurements under controlled environments and temperature. Our unique and economically viable approach offers a new paradigm for the fabrication of nanoscale electronic circuits.
4:15 PM - BM03.09.07
Coherent Bioelectronic Interfaces Formed by Spontaneously Organized Peptides on Solid-State Devices of 2D Atomic Single Layer Materials
Mehmet Sarikaya 1 3 , David Starkebaum 1 3 , Christopher So 1 3 , Yuhei Hayamizu 2 Show Abstract
1 , University of Washington, Seattle, Washington, United States, 3 Materials Science and Engineering, GEMSEC, Seattle, Washington, United States, 2 Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo Japan
Self-assembly of biological molecules on solid materials is central to the “bottom-up” approach to directly integrate biology with electronics. Inspired by biology, exquisite biomolecular nanoarchitectures have been formed on solid surfaces. However, the effect of the biomolecular nanostructures on electronic properties of solid materials is still poorly understood. In this work, we demonstrate that a combinatorially-selected dodecapeptide and its variants self-assemble into peptide nanowires on two-dimensional nanosheets, single-layer graphene and MoS2. Utilizing a transistor platform of single-layer graphene and MoS2, we have investigated the impact of peptides to the electrical properties of nanosheets. The conductivity of graphene transistor indicates that the abrupt boundaries of nanowires create electronic junctions via spatial biomolecular doping of graphene and manifest themselves as a self-assembled electronic network. Furthermore, designed peptides form nanowires on single-layer MoS2 modifying both its electric conductivity and photoluminescence. The electronic properties of the hybrid system of peptide/nanosheet can be controlled by the sequence of peptides and the structural feature of peptide self-assembled structures. The biomolecular doping of nanosheets defined by peptide nanostructures may represent the crucial first step in integrating biology with nano-electronics towards realizing fully self-assembled bionanoelectronic devices. The research was supported by NSF-MGI Program (Materials Genome Initiative) through DMR-1629071.
4:30 PM - BM03.09.08
Optoelectronic Properties of 2D Semiconductors Doped by Solid-Binding Dodecapeptides
David Starkebaum 1 , Jason Ross 2 , Genevieve Clark 2 , Chenfeng Du 2 , Xiaodong Xu 2 , Mehmet Sarikaya 1 Show Abstract
1 GEMSEC, Materials Science and Engineering, University of Washington, Seattle, Washington, United States, 2 Nanoscale Optoelectronics Laboratory, Physics, University of Washington, Seattle, Washington, United States
Graphene field-effect transistors have been shown to be effective nanosensors, based on monitoring changes to the charge-carrier density in response to molecular adsorption onto the graphene surface. Recent work has demonstrated the utility of solid-binding peptides to perform multiple functions in this context, by: (1) Directly affecting the charge-carrier density based on molecular doping; (2) Self-assembling into a crystalline molecular monolayer which minimizes detrimental scattering effects, providing higher electron mobility; (3) Capturing targets in a solution by conjugating specific linkers; (4) Preventing non-specific adsorption by controlling the surface energy; and (5) Interfacing solid-state devices with biological systems (e.g., enzymes and bio-probes) at the molecular scale. 2D semiconductor materials (MoS2, MoSe2, WSe2, etc.) can provide a platform alternative to graphene for remotely detecting molecular adsorption by monitoring the changes in their photoluminescence spectra. In this work, several rationally-designed mutant variants of a biocombinatorially-selected graphite binding peptide were used to impart a molecular doping effect on monolayer MoSe2. We compare changes to the photoluminescence due to the adsorption of peptides with the direct control of charge-carrier density in monolayer MoSe2 by electrostatic doping. We show that the solid-binding dodecapeptide mutant GrBP5-M6 induces significant N-type doping to MoSe2 measured at cryogenic temperatures. The neutral exciton photoluminescence can then be restored by applying a -80V gate bias across a 300nm-thick SiO2 dielectric. This gives an estimation of about 6x1012 cm-2 electron doping by peptide. Various mechanisms of molecular doping are proposed, including charge induction by molecular dipoles, direct orbital overlap between HOMO/LUMO levels of adsorbed species and the substrate, as well as electrochemical doping (charge-transfer accompanying chemical oxidation or reduction of species adsorbed to the surface). Tailoring the chemical and electronic properties of the peptides by rational mutations allows us to differentiate among these doping mechanisms through the interrogation of their effects on the PL characteristics of the single layer substrates. The research was supported by NSF-MGI (Materials Genome Initiative) Program through DMR-1629071.
4:45 PM - BM03.09.09
A Scalable Hydrogel-Based Power Source Inspired by the Electric Eel
Thomas Schroeder 1 2 , Anirvan Guha 2 , Aaron Lamoureux 3 , David Sept 4 , Max Shtein 3 1 , Jerry Yang 5 , Michael Mayer 2 Show Abstract
1 Chemical Engineering, University of Michigan–Ann Arbor, Ann Arbor, Michigan, United States, 2 Biophysics, Adolphe Merkle Institute, Fribourg, Fribourg, Switzerland, 3 Materials Science and Engineering, University of Michigan–Ann Arbor, Ann Arbor, Michigan, United States, 4 Biomedical Engineering, University of Michigan–Ann Arbor, Ann Arbor, Michigan, United States, 5 Chemistry and Biochemistry, University of California San Diego, San Diego, California, United States
The electric eel (Electrophorus electricus) is a system optimized by natural selection for maximal power generation from ionic gradients, making it a compelling paradigm for bioinspired energy materials. Electrogenesis has evolved independently numerous times in fish over the course of natural history; Electrophorus in particular has developed specialized electric organs allowing it to generate voltages of up to 600 V and currents of up to 1 A by simultaneously depolarizing the posterior membranes of thousands of cells arranged in series and parallel. During an impulse, each cell membrane generates additive electrical potentials from ionic gradients across selectively permeable membranes.
The development of wearable and implantable devices must be accompanied by the development of biocompatible power generation schemes. Inspired by Electrophorus' exemplary performance despite the constraints of biology, we engineered a hydrogel-based artificial electric organ that mimics the eel's simultaneous generation of a repeating series of small potentials. This system uses stacking and folding geometries with a single degree of mechanical freedom to bring hydrogels containing electrolyte solutions of varying concentration into contact across permselective gels containing immobilized charged groups. Printing large and complex gel patterns made it possible to generate voltages exceeding 100 V. Miura-ori folding enabled the transformation of patterned 2-D arrays into self-registered stacks with small form factors, imparting a 40-fold improvement in the system's power characteristics. The artificial electric organ presented here is scalable, mechanically switchable, and rechargeable. Unlike many power sources, this system is soft, flexible, transparent, and nontoxic; these material considerations may make it attractive in the context of long-term implants and other medical devices.