10:00 AM - *NT5.2.02
Surface Structures and Defects of Detonation Nanodiamond
Shery Chang 1,Rebecca Nicholls 2,Christian Dwyer 1,Amanda Barnard 3,Eiji Osawa 4
1 Arizona State University Tempe United States,2 University of Oxford Oxford United Kingdom3 CSIRO Melbourne Australia4 Nanocarbon Research Institute Ueda Japan
Show AbstractDetonation nanodiamond (DND), with a particle size typically less than 5 nm, shows great promise in a variety of applications, including drug delivery in biomedical applications, and as an agent for biolabelling in fluorescence imaging. More recently, DND has also been identified as a viable candidate for quantum processors. Such applications capitalise on the unusual surface structure and chemistry of DND, as well as the presence of impurities and point defects. Considerable and varied efforts have been made to enhance these unusual properties, including modification of the surface chemistry, and control of the concentration and stability of point defects and impurities. However, due to the small size and complex structure of DND, characterization of its defects and surfaces is extremely challenging.
Here we address this challenge by using a state-of-the-art monochromated, spherical- (Cs-) and chromatic- (Cc) aberration-corrected TEM (PICO, FEI Company) to perform quantitative determination of the atomic structure and electronic bonding within DND. The instrument is operated at 80 kV, where the Cs-Cc correction improves the spatial resolution from about 2 Å to the sub-Å level, while this beam energy also has the important benefit of reducing electron beam damage. These benefits are demonstrated by the clearly-visible {311} reflections in the core of the DND particles. This enables us to quantitatively discern the relaxed surface structure of DND, providing an unambiguous experimental verification of the surface structure that has been predicted by ab initio calculations.
The monochromator installed on our instrument allows us to perform electron energy-loss spectroscopy (EELS) at an energy resolution of 0.2 eV, enabling us to discern the detailed bonding environments of the carbon atoms in DND. In combination with ab initio simulations of the energy-loss spectra, we have identified a pre-peak in the carbon K-edge near-edge structure that is associated with vacancies in the diamond lattice. These simulations were used to quantify the concentration of vacancies in DND. The ability to identify and quantify vacancies in DND is of great importance as it is long believed that vacancies can exist only in diamond particles with the sizes of tens of nanometers or more.
Furthermore, the approach of combining ab initio modelling with EELS measurements has also been used to estimate the probability and stability of N-V centers in DND, which is potentially of great importance for the above-mentioned applications.
11:00 AM - *NT5.2.03
Analysis of Microimpurities in Detonation Nanodiamonds
Dmitry Volkov 2,Mikhail Proskurnin 2
1 Moscow State University Moscow Russian Federation,2 Certification and Analytical Control NUST MISiS Moscow Russian Federation,2 Certification and Analytical Control NUST MISiS Moscow Russian Federation
Show AbstractMany DND properties (aggregate size, surface groups, optical and colloidal properties, etc.) that are relevant for their novel technological and medical applications depend on their production and purification technologies. The reproducibility and traceability of these technologies is a topical problem in the industry.
This is the case of microelement composition as some elements are hazardous even as traces, especially if we deal with nanomaterial entities. Microimpurities also alter the properties of DND as materials like thermal and oxidative resistance. The development of reliable and precise procedures for microelement control and assessment is the necessary step to render traceable DND properties and to advance the required technologies.
The impurities in DNDs have various nature and quantity levels: metal-oxide nanoparticles, carbides, silicon dioxide, insoluble salts as well as cations and anions adsorbed at the surface. They appear due to interactions in the detonation reaction chamber (Fe and Cr), from the explosion initiation (Cu, Pb, or Hg), or adsorbed on already formed DNDs from acids and water during the separation from the detonation-chamber charge. The assessment of such a circle of elements and their ranges requires sensitive and selective multielement techniques. To the best of our knowledge, the problem of quantitative multielement analysis of DNDs was not sufficiently investigated.
We focused on making rapid, versatile, and reliable techniques for multielement analysis of DNDs. We have developed a procedure for multielement quantification of DND impurities (70 elements) by ICP-AES using a slurry nebulization technique from just 50 mg of sample with the minimum sample preparation [1]. The sensitivity for the most of elements was about 1 ppm. This was complemented by a pyrolysis AAS technique for Hg [2]. We surveyed 20 DND trademarks and found out that the most of DNDs contain relatively high amounts (>100 ppm) of Fe, Na, Si; Cu, B, Ni, and Al, while Pb, Zn, K, Mn, B, Cr, Mg, Mo, Sn, W, Ba, Sb, Co, and Sr are at low but still significant amounts. Some elements (Ag, Ce, Zr, and Hf) providing the information about DND production technology are assessed. We compared ICP-AES and ICP-MS from the viewpoint of DND microimpurity quantification. Finally, we estimated the abilities of WD-XRF as a non-destructive technique for rapid control of DND purity under the production conditions.
ICP-AES of some DND samples after laboratory treatment (ultrasound sonication and acid purification) revealed that the laboratory glass significantly contaminates the samples and change the colloidal properties of DNDs due to its absorption properties. It is necessarily should be taken into consideration.
This work was supported by grant № К3-2015-064 from the NUST «MISiS» subsidy
[1] D.S. Volkov, M.A. Proskurnin, M.V. Korobov, Carbon, 74 (2014) 1-13
[2] D.S. Volkov, M.A. Proskurnin, M.V. Korobov, Diamond Relat. Mater., 50 (2014) 60-65
11:30 AM - NT5.2.04
Plasma Hydrogenated Nanodiamond as a Promising Material for Radiosensitization: Chemical Investigation of the Reactive Oxygen Species Production
Magdalena Kurzyp 1,Hugues Girard 1,Emilie Brun 2,Cecile Sicard-Roselli 2,Samuel Saada 1,Jean-Charles Arnault 1
1 CEA, LIST Gif sur Yvette France,2 Laboratory of Physical Chemistry Orsay France
Show AbstractDetonation nanodiamonds (DNDs) have gained world wild attention for few years for biotechnological, bioanalytical and biomedical applications as new and promising diagnostic probes, delivery vehicles, anti-bacterial agents or even tissue scaffolds [1]. Moreover, depending on their surface chemistry, NDs can also show astonishing properties such as an exceptional colloidal stability, a giant permittivity or unusual charge exchange properties which are hardly explained by the assets of their diamond core only. These phenomena are thought to result from interactions with surrounding molecules, enhanced by their high surface-to-volume ratio, and depend strongly on the NDs surface chemistry.
Recently, we reported how biomedical applications can take advantage of these surface properties, through the use of hydrogenated DNDs prepared by a CVD plasma treatment. Combining the negative electron affinity of H-NDs and the transfer doping effect and its inherent oxygen adsorbates layer, we demonstrated how an efficient radiosensitization effect for cancer treatment can be obtained [2]. H-NDs emerge as promising tools to generate a high concentration of reactive oxygen species (ROS) under X-rays irradiation, which could be efficiently used against radioresistant tumoral cells, as with High-Z metallic nanoparticles such as gold nanoparticles (GNP).
The aim of the present study is to investigate the mechanism at the origin of this ROS production under irradiation. By using a fluorescent model previously developed on gold nanoparticles (GNP) [3], we will show how this phenomenon is specific to hydrogenated terminations and can be affected by chemical surface modifications. We also aim to identify the nature of these reactive oxygen species and quantify them. Finally, a comparison with other nanoparticles of interest for radiosensitization will be given.
[1] O. A. Shenderova, G. E. Mc Guire, Science and engineering of nanodiamond particle surfaces for biological applications, Biointerphases 10 (2015) 030802
[2] Grall, R. et al., Impairing the radioresistance of cancer cells by hydrogenated nanodiamonds, Biomaterials 61 (2015) 290
[3] Sicard-Roselli, C. et al., A new mechanism for hydroxyl radical production in irradiated nanoparticle solutions, Small 10 (2014) 3338
11:45 AM - *NT5.2.05
Optically Active Diamond Particles
Olga Shenderova 1,Nicholas Nunn 1,Gary McGuire 1,Evgeny Danilov 2
1 Adamas Nanotechnologies Raleigh United States,1 Adamas Nanotechnologies Raleigh United States,2 North Carolina State University Raleigh United States
Show AbstractNanodiamond (ND) particles have recently emerged as a key platform for many sectors of nanoscience and nanotechnology due to their outstanding mechanical performance, biocompatibility and distinctive optical properties, a combination of assets not often met in the nanoworld. Optically active NDs remain one of the most popular research topics mainly due to the photoluminescent properties of crystallographic defects in the diamond lattice, referred to as color centers. In this talk, the optical properties of ND particles as well as related current and perspective applications will be discussed.
Recently our group succeeded in large scale production of fluorescent NDs containing nitrogen-vacancy (NV) color centers in hundreds of grams batches. Production of fractions of ND-NV with median sizes ranging between 10 and 100 nm was achieved. The content of NV centers in micron-sized particles and in NDs as a function of irradiation dose and particle size will be reported. Relative brightness of nanoparticles of different sizes and surface termination will be also summarized. ND-NV functionalized with bioligands have perspectives as highly photostable and non-toxic fluorescent labels in life science applications. NDs containing color centers absorbing UV light in combination with the high refractive index of diamond providing extensive UV light scattering are also appealing for use in healthcare products such as sunscreens.
2:30 PM - *NT5.3.01
Nanodiamond/Silicon Carbide Nanocomposites for Membranes Applications
Johan Alauzun 1,Anthony Ballestero 2,Samuel Bernard 2,Philippe Miele 2,P. Hubert Mutin 1
1 Inst Charles Gerhardt-Montpellier Montpellier France,2 Institut Européen des membranes Montpellier France
Show AbstractPreceramic polymers have been proposed in the late seventy’s as non-oxide silicon based ceramic precursors generally called PDCs for “Polymer Derived Ceramics”.
Compared to traditional synthesis ways, the PDCs route can offer many advantages in terms of compositions, structures and textures of ceramics. Furthermore, the synthesis and cross-linking of the preceramic polymers offer the possibility to modify some characteristics of these compounds such as their solubility, viscosity and fusibility allowing the elaboration of shaped ceramics in a way not known by conventional routes.
Due to its intrinsic properties (thermal, chemical and mechanical resistance, semi-conductor behavior,...), silicon carbide (SiC) and their derivatives with nitrogen (silicon carbonitride, SiCN) can be considered as one of the best materials for the next generation of ceramic based membranes, in particular in the hydrogen production processes (from CO2, CH4 or through the water gas shift reaction for example).
By investigating the PDCs route, a hydrophobic and amorphous SiC material suitable for hydrogen separation process exhibiting good permeability/selectivity ratio, high thermal mechanical and chemical resistance coupled with a good stability under wet atmosphere up to 500°C can be proposed.
However, the disadvantage of the preceramic polymers is their volume shrinkage which occurs during the pyrolysis to convert the polymer into ceramic. Indeed, preceramic polymers lose weight (evolution of gaseous by-products), whereas their density increases during their transformation into ceramics both inducing volume shrinkage. Residual stresses caused by the volume shrinkage lead to the formation of defects, cracks or even delamination of the coatings.
Within this context, the solution considered to limit the volume shrinkage was addition of nano-sized diamond fillers in the polymer to form nanocomposites.
Nano-sized diamond particles known as nanodiamonds (NDs) have remarkable properties (hardness, thermal conductivity, chemical inertness, etc) leading to many potential applications and are relatively inexpensive.
The talk will so be dedicated to the description of ND@SiC nanocomposites by the PDCs route, its application to membrane elaboration, the characterization of the membranes and their application to gas separation.
3:00 PM - NT5.3.02
Usage of Detonation Nanodiamonds for Improving Properties of Various Polymer Materials
Hisayoshi Ito 1
1 DAICEL Corporation Himeji Japan,
Show Abstract[Introduction]
Daicel is a Japanese company, which was formed through the merger of eight celluloid producers in 1919. As a part of our effort to create new business domains, we started developing the detonation nanodiamond taking full advantage of our long experiences in pyrotechnics. We have already established semi-commercial production capacity for the detonation as well as for purification of the detonation soot to provide nanodiamonds(ND). While brushing up the technologies for the production, we have been working on developing application of the material, especially of single digit nano-dispersed diamonds (SDND).
As a manufacturer of functional plastic films and chemical raw materials applied for those films, one of the potential applications we have been concentrating on is to use SDND in this field as a modifier. For this application, a couple of properties are expected to be given additional values by SDND. One is high refractive index and the other is scratch resistance of various types of films.
[Applications]
Due to its intrinsic high refractive index and relatively low specific gravity compared to known inorganic additives, when combined with polymers to form thin films SDND can give high reflective index to which other inorganic additives can’t match. Highly functionalized ND can be dispersed in water without any surfactant. Therefore the actual concentration of the ND can reach higher than of other additives which are stabilized by relatively high amount of surfactant.
We have been trying to use abundant functional groups on the surface of each SDND as reactive site to curable monomers. With suitable chemical modifications of the surface, we succeeded to disperse SDND in versatile organic solvents such as MEK as well as to give ability to react with curable monomer groups such as acrylates or epoxies. Using those modified ones, we will introduce some cases of SDND effectively incorporated in polymer networks leading to improvement of mechanical properties such as the scratch resistance.
Within our company group, we possess various thermoplastic polymers from commodity resin to so-called super engineering plastics as product lineups. There are several long-touted applications of ND as additives to thermoplastic polymers. We have newly found that ND can be used as radical trapping stabilizer for thermal processing of polymers. Heat resistance of commercial stabilizers represented by hindered phenols are not high enough for some of super engineering plastics. On the assumption that ND have chemical structures similar to hindered phenols on their surface, we added ND to poly ether ether kethone (PEEK) and poly phenylene sulfide (PPS) both of which are known to have no suitable stabilizer. These polymers show viscosity thickening phenomenon when mixed at high temperature without the stabilizer. Addition of small amount (
3:15 PM - NT5.3.03
Spontaneous (Bio)Functionalization of Hydrogenated Nanodiamonds
Sebastien Ruffinatto 1,Hugues Girard 1,Andre Roget 3,Pascal Mailley 2,Samuel Saada 1,Jean-Charles Arnault 1
1 CEA LIST Gif sur Yvette France,3 CEA INAC Grenoble France2 CEA LETI Grenoble France
Show AbstractInexpensive and large scale synthesis of detonation nanodiamonds (NDs) has gained world wild attention for few years. Attractive properties and promising results ensure NDs good prospects for biotechnological, bioanalytical and biomedical applications [1]. Indeed, it is anticipated that NDs will be used as diagnostic probes, delivery vehicles, anti-bacterial agents, tissue scaffolds or purification and even radiosensitizers [2]. However, regarding all these biological purposes, a (bio)functionalization of the particles is required to target a specific receptor, avoid or enhance opsonisation, or to conjugate with a drug. Such nanomaterials functionalization generally involves several steps with extensive purification/washing procedures, making processes tedious and time consuming. Moreover, biological experiments require uncontaminated and highly reproducible samples. Thus, aqueous, soft pH and straightforward techniques are highly promoted.
We report here a new “one-step” grafting technique of any amino-ended moiety onto NDs. This aqueous route is perfectly adapted for such biofonctionnalisation. Already used on hydrogenated diamond bulk [3], we have successfully transferred this technique onto 5 nm H-terminated NDs. The grafting of aminated modified ferrocene or biotin onto NDs has been carried out through a spontaneous approach. The quality and the efficiency of the grafting process were characterized through XPS, FTIR and TGA. Furthermore, to assess the bio-activity of the resulting conjugates, biotin modified H-NDs were further locally immobilized on substrate through an avidin/biotin biological model. Combining cleanliness, rapidity and efficiency, this new “one-step” grafting route aims at developing new insight for NDs.
References
[1] O. A. Shenderova, G. E. Mc Guire, Science and engineering of nanodiamond particle surfaces for biological applications, Biointerphases 10 (2015) 030802
[2] R. Grall et al., Impairing the radioresistance of cancer cells by hydrogenated nanodiamonds, Biomaterials 61 (2015) 290-298
[3] C. Agnes et al., New one step functionalization of polycrystalline diamond films using amine derivatives, IOP Conf. Ser.: Mater. Sci. Eng. 16 (2010) 012001
4:00 PM - *NT5.3.04
Surface Chemistry of Nanodiamond for Biomedical Application
Naoki Komatsu 1
1 Kyoto University Kyoto Japan,
Show AbstractNanodiamond holds great potential for biomedical applications, in particular, as drug carrier and imaging probes. For these purposes, nanodiamond are required to be functionalized to add the requisite properties such as enough dispersibility and stability under physiological conditions, and maximal targeting and stealth character. In this talk, I will present surface chemistry of nanodiamond including polyglycerol functionalization, further derivatization and their characterization based on organic chemistry, and biomedical application of the chemically functionalized nanodiamond [1-8].
1. T. Takimoto, T. Chano, S. Shimizu, H. Okabe, M. Ito, M. Morita, T. Kimura, T. Inubushi, and N. Komatsu, Chem. Mater., 22 (11), 3462-3471 (2010).
2. L. Zhao, T. Takimoto, M. Ito, N. Kitagawa, T. Kimura, and N. Komatsu, Angew. Chem. Int. Ed., 50 (6), 1388-1392 (2011).
3. L. Zhao, Y.-H. Xu, H. Qin, S. Abe, T. Akasaka, T. Chano, F. Watari, T. Kimura, N. Komatsu, and X. Chen Adv. Funct. Mater., 24 (34), 5348-5357 (2014).
4. L. Zhao, Y.-H. Xu, T. Akasaka, S. Abe, N. Komatsu, F. Watari, and X. Chen, Biomaterials, 35 (20), 5393-5406 (2014).
5. L. Zhao, Y. Nakae, H. Qin, T. Ito, T. Kimura, H. Kojima, L. Chan, and N. Komatsu, Beilstein J. Org. Chem., 10, 707-713 (2014).
6. L. Zhao, A. Shiino, H. Qin, T. Kimura, and N. Komatsu, J. Nanosci. Nanotechnol., 15 (2), 1076-1082 (2015).
7. L. Zhao, T. Chano, S. Morikawa, Y. Saito, A. Shiino, S. Shimizu, T. Maeda, T. Irie, S. Aonuma, H. Okabe, T. Kimura, T.Inubushi, and N. Komatsu, Adv. Funct. Mater., 22 (24), 5107-5117 (2012)..
8. L. Zhao, T. Takimoto, T. Kimura, and N. Komatsu, J. Indian Chem. Soc., 88, December, 1787-1790 (2011).
9. L. Zhao, and N. Komatsu, Chemical Functionalization of Carbon Nanomaterials: Chemistry and Applications; V. K. Thakur and M. K. Thakur, Eds.; CRC Press: Chapter 28, pp. 650-663 (2015).
4:30 PM - *NT5.3.05
Nanodiamond Composites for Biomedical Applications
Anke Krueger 1
1 Wuerzburg Univ Wuerzburg Germany,
Show AbstractThe incorporation of nanoparticles into organic and inorganic matrices has a tremendous impact on the properties of the resulting composites. Not only the mechanical properties but also biomedical characteristics, thermal properties as well as electronic properties can be controlled by the production of suitably designed composite materials.
In the past years, nanodiamond-modified composites became a research focus for biomedical applications. This is due to the fact that nanodiamond is considered to be largely nontoxic, can be easily functionalized covalently and non-covalently and the availability of the starting material is not problematic.
Here we report on the production, modification and characterization of nanodiamond derivatives for applications such mechanically resistant materials and coatings and as an additive for implant materials. Starting with the production of solubilized nanodiamond with different surface terminations we developed methods for the grafting of more complex moieties including monomers, proteins and fluorescent dyes.[1,2]
Additionally, we produced benzoquinone functionalized, nanodiamond, which shows an enhanced dispersibility in organic solvents. For the direct incorporation into polymer composites this is a prerequisite.[3] After the controlled surface modification, nanodiamond can be also directly bound to polymer chains of biodegradable scaffold materials or be used as a crosslinker.[4,5]
In summary,functionalized nanodiamond is an attractive material for the production of composites for biomedical applications such as regenerative medicine and other medical treatments.
[1] Z. Xing, T.O. Pedersen, X. Wu, Y. Xue, Y. Sun, A. Finne-Wistrand, S. Hellem, F.R. Kloss, T. Waag, A. Krueger, D. Steinmüller-Nethl, K. Mustafa, Tissue Engin. 2013, 19, 1783-1791.
[2] S. Suliman, Z. Xing, X. Wu, Y. Xue, T. O. Pedersen, Y. Sun, A. P. Døskeland, J. Nickel, T. Waag, H. Lygre, A. Finne-Wistrand, D. Steinmüller-Nethl, A. Krueger, K. Mustafa, J. Control. Release 2015, 197, 148-157.
[3] Y. Sun, A. Finne-Wistrand, T. Waag, Z. Xing, M. Yassin, A. Yamamoto, K. Mustafa, D. Steinmüller-Nethl, A. Krueger, A.-C. Albertsson, Macromol. Mater. Eng. 2015, 300, 436-447.
[4] Y. Sun, P. Olsén, T. Waag, A. Krueger, D. Steinmüller-Nethl, A.-C. Albertsson, A. Finne-Wistrand, Part. Part. Part. Syst. Charact. 2015, 32, 35–42.
[5] Y. Liang, M. Ozawa, A. Krueger, ACS Nano 2009, 3, 2288-2296.
This work was supported by the FP7 project Vascubone (grant agreement n°242175) and the Deutsche Forschungsgemeinschaft (KR3316/3-1).
5:00 PM - *NT5.3.06
Polymer Coating of Fluorescent Nanodiamonds: Tuning the Functional Nanobiointerface
Petr Cigler 1
1 IOCB AS CR vvi Prague 6 Czech Republic,
Show AbstractFluorescent diamond nanoparticles (FNDs) represent a key component in recent development of ultra-high precision optical resolution techniques. FNDs can accommodate nitrogen-vacancy (NV) centers – an extremely photostable crystal lattice defect emitting in near-infrared region. Electron transitions among NV quantum states can be influenced by very weak external electric or magnetic fields, which have been utilized for construction of various types of probes and nanosensors.
For application of FNDs in biological systems and for achieving high target selectivity, a precise control of particles’ bionanointerface is urgently needed. Different synthetic approaches towards bioapplicable FNDs will be presented. Creation of different antifouling polymeric coatings on FNDs, their physico-chemical comparison, bioorthogonal modification with various (bio)molecules using click chemistry, and imaging of cancer cells using these conjugates will be shown.
5:30 PM - NT5.3.07
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Affinity of Glycan-Modified Nanodiamonds towards Lectins and Escherichia coli
Kostiantyn Turcheniuk 2,Volodymyr Turcheniuk 3,Julie Bouckaert 4,Tetiana Dumych 5,Alexandre Barras 2,Rostyslav Bilyy 5,Vladimir Zaitsev 3,Aloysius Siriwardena 7,Rabah Boukherroub 2,Sabine Szunerits 2
1 Missouri University of Science amp; Technology Rolla United States,2 Institute of Electronics Microelectronics and Nanotechnology Lille France,2 Institute of Electronics Microelectronics and Nanotechnology Lille France,3 Taras Shevchenko University Kiev Ukraine4 Lille 1 University of Science and Technology Lille France4 Lille 1 University of Science and Technology Lille France,5 Institute of Cell Biology, NAS of Ukraine Lviv Ukraine2 Institute of Electronics Microelectronics and Nanotechnology Lille France6 Pontifical Catholic University of Rio de Janeiro Rio de Janeiro Brazil,3 Taras Shevchenko University Kiev Ukraine7 University de Picardie Jules Vernes Amiens France
Show AbstractCarbohydrates are very important components of living organisms and have been identified to play a central role in a large panel of biological processes such as cell-cell communication, viral and bacterial infection, inflammation and immune responses. The extremely low affinity of carbohydrates, typically in the milli to micromolar range (mM-μM) to biological objects monovalent ones, is compensated by a clustering nature resulting in nanomolar (nM) affinities and high selectivity. These cooperative effects resulting in significantly stronger affinity than in monovalent ones. [1]
Next to design of high affinity glycan ligands, the integration of carbohydrate molecules onto nanoscale objects has become and their applications as polyvalent tools to study and intervene in carbohydrate mediated interactions have received sustained attention over the past years. [2,3,4] Next to that, nanodiamonds (NDs) are emerging and well-suited for multivalent-based applications. One of the advantages of ND-based materials over other carbon-based materials that they are completely inert, biocompatible, optically transparent and can be furthermore functionalized in many other ways. [5]
In this work we report NDs particles modified with glycan ligands as new nanomaterials for combating biofilm formation and as a promising scaffold for the development of anti-adhesive bacterial strategies. Currently, the strategies at hand to formulate glycan-modified NDs (glyco-NDs) are limited to some reports. [2b-c, 6] We use photo-chemical linking of unmodified mono-, di- and polysaccharides to nanodiamond particles pre-modified with perfluorophenylazide ligand is a general method for coupling underivatized carbohydrates to diamond nanostructures. While the coupling of disaccharides such as lactose or fructose preferential binds to one of the sugar units is observed, this problem is absent in polysaccharides such a mannan and the approach is believed to be mainly adapted for such kind of glycans. That was the motivation of investigating the potential of ND-mannan to interact with E. coli UTI89. Through a fluorescent based agglutination assay, we showed that ND-mannan display E. coli agglutination at concentrations of 10 μg/mL, being much lower than free mannan and also ND-mannose. Taken together the finding presented here, such nanostructures should be further developed and evaluated as potential anti-adhesives for countering bacterial colonization and infections in vivo.
[1] N. Sharon and H. Lis, Glycobiology 2004, 14, 53R.
[2] (a) M. Marra et al., Chem. Soc. Rev. 2013, 5, 2307; (b) A. Barras, et al., Nanoscale 2013, 5, 2307; (c) M. Khanal, et al., Nanoscale 2015, 7, 2325.
[3] J. M. de la Fuente et al., Angew. Chem. Int. Ed. 2001, 40, 2257.
[4] (a) S. Cecioni et al., Chem. Eur. J. 2011, 17, 3252; (b) M. Durka et al., Chem. Commun. 2011, 47, 1321.
[5] V. Mochalin et al., Nature Nanotech. 2012, 7, 11.
[6] M. Hartmann et al., Chem. Eur. J. 2012, 18, 6485.
5:45 PM - NT5.3.08
UV Excitation Wavelengths for the Raman Analysis of Detonation Nanodiamond-Contributions and Pitfalls
Michel Mermoux 1,Magdalena Kurzyp 2,Cyrille Barbay 2,Hugues Girard 2,Jean-Charles Arnault 2
1 CNRS-LEPMI Saint Martin d'Heres France,2 CEA/LIST Gif sur Yvette France
Show AbstractRaman spectroscopy is known as a method of choice for the analysis of carbon materials and carbon nanostructures, allowing, among other, the identification of the type of bonding and estimations of the size of coherent domains. This method is widely used for the characterization of detonation nanodiamond (DND) of various sources.
The Raman spectrum of purified DND usually consists of several characteristic features: (i) the first-order Raman mode of the cubic diamond lattice which is broadened and red-shifted by about 3-8 cm-1 compared to bulk diamond, (ii) broad features with two apparent maxima in the 500-1250 cm-1 range, and (iii) a broad asymmetric line peaking in the 1600-1650 cm-1 (hereafter named “1650 cm-1 peak”) range, depending on the sample origin and its purification. Depending on the excitation wavelength, another feature peaking at about 1750 cm-1 is more or less clearly identified. This Raman spectrum does not strongly depend on the origin of the nanodiamond.
The main problem in Raman spectroscopy of DND is most probably related to the laser radiations commonly used as the excitation source. Local heating caused by the focused laser light must be taken in account, since it may affect the Raman spectrum even at relatively low laser power levels. In particular, it was observed that UV excitations used to get PL-free spectra induce considerable sample heating compared to visible ones, and may lead to thermal damage and/or changes in sample composition.
Experimental conditions were adapted to minimize laser-induced effects on DND, in particular using excitation wavelengths in the deep UV range (325 or 244 nm). However, even for the lowest power levels, subtle signal modifications were still observed, especially for long exposure times. In particular, the line near 1750 cm-1, the position at which the C=O bonds are detected, is observed even for fully hydrogenated samples. Subtle changes in the line shape of the 1650 cm-1 peak were also observed.
In this study, we address the problem of the stability of DND under the UV excitations used for the Raman analysis of detonation nanodiamonds.
NT5.4: Poster Session
Session Chairs
Thursday AM, March 31, 2016
Sheraton, Third Level, Phoenix Ballroom
9:00 PM - NT5.4.01
Nanospacer Lubrication with Aqueous and Alcoholic Solutions of 2.8-nm Diamond Spacers
Eiji Osawa 2,Shuichi Sasaki 1
2 NanoCarbon Res. Inst. Ltd Ueda Japan,2 NanoCarbon Res. Inst. Ltd Ueda Japan,1 Shinshu University, AREC Nagano Japan
Show AbstractFollowing previous reports in this series on the idea and conditions of nanospacer lubrication, design and manufacture of a reciprocal-movement friction testers working under low load and analysis of lubrication mechanism, we report here confirmation of rolling mechanism in hydroxylic solvents. We have so far used friction systems comprised of a sapphire ball sliding over the Si CD surface, but used here sapphire ball/polished SUS304 plates with surface roughness σR <100nm as the test system for ready comparison with real machines. Details of experimental setup and conditions will be given in poster but it should be noted that our testing equipment is specially designed for the nanospacer lubrication: applied load (perpendicular to the moving plane) and frictional force (parallel) are obtained separately.
When water is used as lubrication medium, frictional coefficient was 0.65 in average. However, the coefficient dropped to 0.07 upon dispersing 2 wt% of nanodiamond. When the lubrication medium was changed to ethylene glycol, an average frictional coefficient of 0.19 was obtained, but it dropped to a quite low value of 0.03! Consistently higher performance of more viscous ethylene glycol than water can be interpreted in terms of stronger liquid filmin the former in the boundary condition, but the remarkable reduction in the frictional coefficient upon addition of the same amounts of nanodiamond is not affected by viscosity of media. This means that the nanospacers actually rolled or at least rotated to reduce the frictional coefficient. Actually we never detected scratches on the polished SUS surface during the friction tests.
The relatively high concentrations of nanodiamond used in these lubrication tests, 1 to 2 wt%, were required by the recent observation of a puzzling phenomenon, “dilution aggregation,” wherein well-dispersed colloidal particles of nanodiamond (above 4 wt%) in water start to aggregate when diluted with water to less than 1-2 wt%. This behavior should better be suppressed. We are going to apply the following counteractions: spheroidalization of nanodiamond by self-ablation under pressure and rolling, and/or addition of appropriate dispersing agent when diluting the colloidal concentration. Results will be disclosed elsewhere.
9:00 PM - NT5.4.03
Tuning Endothelial Permeability with Functionalized Nanodiamonds
Magdiel Setyawati 1,Vadym Mochalin 1,David Leong 2
1 Chemistry Missouri University of Science amp; Technology Rolla United States,2 Chemical and Biomolecular Engineering National University of Singapore Singapore Singapore
Show AbstractDespite having all the advantages associated with being in the nano size range (e.g. more drugs get loaded, longer retention in the blood circulation, pathological site targeting, and multimodality), the promise of cancer nanomedicine has not materialized into widespread clinical practice. The cancer survival rate and the major cause of cancer mortality, the inefficiency of cancer drug delivery, remains largely unchanged since the inception of cancer nanomedicine 50 years ago. The inefficiency might have stemmed from the need of nanomedicine to cross the vasculature barrier (posed by endothelial cells) for the nanomedicinal strategy to even begin to work. Here, nanodiamonds (ND) variants were shown to induce surface dependent vascular barrier leakiness. The ND-induced leakiness was found to be mediated by the increase in intracellular reactive oxygen species (ROS) and Ca2+. These then in turn triggered the loss in endothelial cell-endothelial cell connections of the vascular barrier and also triggered their quasi stable cytoskeletal remodelling. This ND driven increase in leakiness allowed more doxorubicin drug to penetrate through the vascular barrier to reach the cancer cells. This increase in the doxorubicin penetration subsequently led to increase in the cancer killing effect. Overall, tuning the vascular barrier leakiness through ND surface group functionalization could provide an alternative strategy for the cancer nanomedicine to traverse across the vascular barrier.
9:00 PM - NT5.4.04
Round Diamond Nanoparticles
Helena Raabova 2,Ivan Rehor 1,Petr Cigler 1
1 Institute of Organic Chemistry and Biochemistry AS CR, v.v.i. Prague 6 Czech Republic,2 University of Chemistry and Technology, Prague Prague Czech Republic,1 Institute of Organic Chemistry and Biochemistry AS CR, v.v.i. Prague 6 Czech Republic
Show AbstractNanodiamonds (NDs) are highly promising material for biomedical research due to their outstanding optical and magnetic properties and low toxicity. We developed a complex route to the bioapplicable fluorescent nanodiamond particles, including boosting of NDs fluorescence, shaping the particles to become pseudospherical and coating the particles with antifouling and modifiable polymeric shell. [1, 2] Starting material used in our work is prepared under high pressure-high temperature (HPHT) conditions, particles are polydisperse and of irregular shape bearing sharp edges and spiky vertexes. Recent research of cellular fate of diamond nanoparticles has revealed that behaviour of the original angular particles differs from that of rounded NDs. [3, 4]
Here we present a procedure of rounding of NDs at a large scale and a study of rounded NDs' properties. The rounding process is based on chemical etching of rough ND particles in molten potassium nitrate and results in pseudospherical NDs with changed particle size distribution. Our study shows dependence of round NDs behaviour, shape and size distribution on etching conditions and compares the results with angular NDs. Round NDs can be easily further processed to create fluorescent and polymer-coated round NDs, unique material perfectly suitable for bioprobes and sensors construction.
Literature:
[1] Rehor, I. et al., Small, 2014, 10(6), 1106–1115. [2] Rehor, I. et al., ChemPlusChem, 2014, 79(1), 21-24. [3] Chu, Z. et al., Sci. Reports, 2014, 4, 4495. [4] Chu, Z. et al., Sci. Reports, 2015, 5, 11661.
9:00 PM - NT5.4.05
Plasmonic Enhancement of Single Photon Emission from NV Center Containing Nanodiamonds
Maneesh Gupta 3,Srikanth Singamaneni 2,Michael Check 3,Luke Bissell 3
1 University of Dayton Research Institute Dayton United States,3 Materials and Manufacturing Directorate Air Force Research Laboratories WPAFB United States,2 Washington University in St. Louis St. Louis United States3 Materials and Manufacturing Directorate Air Force Research Laboratories WPAFB United States
Show AbstractThe diamond nitrogen-vacancy (NV) center is an attractive single photon source for quantum information and computing applications, owing to its stable single photon emission and long spin-coherence times at ambient conditions. Routine techniques have been developed to deterministically create NV centers in both nano- and macroscopic diamond single crystals. For greater efficiency, the optical excitation and emission of the NV center can be enhanced by modulating the local electromagnetic field using a photonic cavity or plasmonic antenna. We present a method to couple diamond nanoparticles (DNPs) with gold nanorods (AuNRs) using a bottom-up layer-by-layer (LBL) technique to systematically vary the spacing between the NV centers and the plasmonic antenna. Effective plasmonic enhancement of solid-state emitters is dependent on a number of critical variables including the size and shape of nanoparticles, interparticle distance, and spectral relationship of fluorescent and metal nanoparticles. We have chosen gold nanorods for plasmonic enhancement since the aspect ratio and consequently extinction spectra can be precisely controlled during synthesis. Use of polyelectrolyte LBL allows for precise control of the distance between the (AuNRs) and DNPs. We have demonstrated the ability to assemble AuNRs and DNPs using polyelectrolyte LBL films with variable spacing and corresponding enhancement of single photon emission.
9:00 PM - NT5.4.06
Structure and Optical Properties of the Amorphous Hydrogenised Carbon Films Modified by Titanium and Silver
Svetlana Mikhailova 1,Oleg Prikhodko 1,Erzhan Mukhametkarimov 1,Nazim Guseynov 1,Kuanysh Dauthan 1,Oleg Rofman 2,Renata Nemkaeva 1
1 al-Farabi Kazakh National University Almaty Kazakhstan,2 Institute on Nuclear Physics Almaty Kazakhstan
Show AbstractIn the present report structure and optical properties of the amorphous carbon films with titanium and silver impurity (a-C:H
9:00 PM - NT5.4.07
Determination of Atomic Structure of Detonation Nanodiamonds Using Simulated and Experimental Aberration-Corrected TEM Imaging at Low Voltage
Kaylie Lam 1,Amanda Barnard 2,Eiji Osawa 3,Shery Chang 1
1 Arizona State Univ Tempe United States,2 CSIRO Parkville Australia3 Nanocarbon Research Institute Nagano Japan
Show AbstractSince the discovery of nanodiamond, a diamond nanoparticle with 2-5nm in size, its atomic and electronic structure has been extensively studied using diffraction, imaging and spectroscopy techniques. Recently, the electronic structure of nanodiamond has been established using a combination of ab initio calculations and x-ray absorption spectroscopy . It was reported that the nanodiamond particle consists of a diamond core and a fullerene-like surface structure. On the other hand, transmission electron microscopy has also been extensively used to study the atomic structure of nanodiamond, as spectroscopy alone can not reveal the atomic nature of nanodiamond including the defect structure and the relationship between the surface to core structure. However, resolving the atomic structure of nanodiamond to a sufficient accuracy remains a challenge for TEM imaging as it requires high spatial resolution but with low energy electrons to avoid electron beam damage to the nanodiamond particles.
Recent advances of TEM operating at lower accelerating voltage (40-80kV) have allowed us to study the atomic structure of nanodiamond without inducing structural changes or damage. However lower the electron beam energy of a TEM also worsens the spatial resolution to typically about 2 Å in an aberration-corrected instrument, as the energy spread at lower accelerating voltage drastically increase the focal spread of the instrument. Instrumentation efforts have been made to improve the resolution at low accelerating voltage, by either using a monochromator to reduce the energy spread of electrons, or using a chromatic aberration corrector to reduce the chromatic aberration.
Here we show both the simulated and experimental study of the effect of different instrumentation of 80kV TEM on the accuracy of atomic structure determination. We used aberration-corrected TEM (Titan, FEI Company), with and without monochromator excited, and also a state-of-the-art chromatic-spherical aberration (Cc-Cs) corrected TEM (PICO, FEI Company). The information limit of these instruments are 1.8, 1.1 and 0.8 Å, respectively. For the simulated TEM study, structure model obtained using first principle calculations were used to simulate the TEM images with the corresponding parameters of the three instrumentation. The accuracy of the atomic position as well as the shell-to-core separation distance determined from these three sets of simulations was compared to show the effect of the three instrumentation.
Symposium Organizers
Vadym Mochalin, Missouri University of Science and Technology
Jean-Charles Arnault, CEA LIST
Amanda Barnard, The Commonwealth Scientific and Industrial Research Organisation
Eiji Osawa, NanoCarbon Research Institute, AREC
Symposium Support
Asama Research Extension Center
Bravus Japan Company
CEA-LIST
Daicel Corporation
Hokushin Rika Company
ITAC.LTD
NanoCarbon Research Institute
New Metals amp
Chemicals Corporation
Toyohashi Plating Company
NT5.5: Single-Digit Particles—Colloids, Dispersions and Imaging
Session Chairs
Thursday AM, March 31, 2016
PCC West, 100 Level, Room 103 B
10:00 AM - *NT5.5.01
Nanodiamonds in Water: New Perspectives from Soft X-Ray Spectroscopy in Liquid
Tristan Petit 1
1 Institute of Methods for Material Development Helmholtz Zentrum Berlin Berlin Germany,
Show AbstractUnderstanding interactions between nanodiamonds (NDs) and their environment is critical to develop new NDs applications. Aqueous environment necessitates particular attention since its influence on NDs properties is poorly understood while most of applications in nanomedicine, environmental science or photocatalysis take place in such media. Unfortunately, the influence of aqueous environment, especially when it is related to electronic processes, cannot be investigated in liquid with classical methods.
In this presentation, I will present how synchrotron-based soft x-ray absorption, emission and photoemission spectroscopies can overcome the challenge of measuring electronic structure of nanomaterials directly in aqueous environment. Using X-ray absorption spectroscopy, modification of the NDs surface chemistry induced by aqueous dispersion was recently evidenced.1 Furthermore, a significant impact of nanodiamonds on the water organization in their solvation shell was also observed.2 Future directions implementing these methods to follow electro- and photochemical reactions at the surface of NDs and other carbon nanomaterials in liquid environment will be discussed.
References
1. Petit, T.; Pflüger, M.; Tolksdorf, D.; Xiao, J.; Aziz, E. F. Valence Holes Observed in Nanodiamonds Dispersed in Water. Nanoscale 2015, 7, 2987–2991.
2. Petit, T.; Yuzawa, H.; Nagasaka, M.; Yamanoi, R.; Osawa, E.; Kosugi, N.; Aziz, E. F. Probing Interfacial Water on Nanodiamonds in Colloidal Dispersion. J. Phys. Chem. Lett. 2015, 6, 2909–2912.
10:30 AM - NT5.5.02
Application of Photothermal and Photoacoustic Spectroscopies for Detonation Nanodiamond Dispersions
Mikhail Proskurnin 2,Dmitry Volkov 2,Ivan Mikheev 1,Liliya Usol'tseva 1,Mikhail Korobov 1,Dmitry Nedosekin 3,Vladimir Zharov 3
2 Certification and Analytical Control NUST MiSIS Moscow Russian Federation,1 Chemistry Department Lomonosov Moscow State University Moscow Russian Federation,2 Certification and Analytical Control NUST MiSIS Moscow Russian Federation1 Chemistry Department Lomonosov Moscow State University Moscow Russian Federation3 Arkansas Nanomedicine Center Winthrop P. Rockefeller Cancer Institute, University of Arkansas for Medical Sciences Little Rock United States
Show AbstractPhotothermal (PTS) and photoacoustic (PAS) spectroscopies belong to calorimetric methods of absorption spectroscopy. They complement transmission spectroscopy as the signals in PTS/PAS are directly governed by the heat converted by the analyzed system under the excitation irradiation: i.e. the light absorption of chromophores and the heat distribution in the system. Being significantly more sensitive than the majority of methods of absorption spectroscopy and giving multiple signals of various nature from a single measurement, they are relevant for simultaneous estimation of light-absorption and thermophysical properties of various materials, especially for materially or optically heterogenous systems. The progress in laser technologies brings microscopical optical schemes of PTS/PAS into practice.
In this study, PTS/PAS were used for characterizing nanodiamond (ND) sols (dispersions) in aqueous and organic media. The motivation of this study is the fact that many relevant ND properties as materials, nanofluids, or biolabels depend on their production and purification technologies, and it is strongly necessary to know both the ND concentration and distribution and their primary particle and aggregate sizes. Thus, we used PTS/PAS in multiwavelength, transient, and scanning modes and in meso- and microscopic scales for physicochemical analysis and the estimation of thermophysical properties of ND dispersions from 20 trademarks from various manufacturers. The schematics and details of PTS/PAS measurements will be provided.
The estimation of ND concentrations at subnanogram amounts by PTS is shown. Extinction spectra of ND aqueous dispersions by conventional absorption spectroscopy and PAS differ significantly, and the contributions from absorption and scattering were estimated by their comparison. PTS/PAS multispectral data were correlated with the results from other methods: DSC, dynamic laser scattering (DLS), X-ray diffraction, and UV-spectroscopy.
Key thermophysical properties of ND dispersions as nanofluids—thermal diffusivity, thermal effusivity, and thermal conductivity—were estimated from PTS (thermal-lens) data, and their values were compared with pure solvents and other types of nanofluids. These parameters were measured in dynamic (time-resolved transient response profiles of thermal-lens signals) and batch (amplitude) modes of PTS. Several PTS methods and their applicability towards this aim will be compared.
Imaging of thin layers of samples of ND dispersions showed a significant difference in the spatial distribution and cluster size for various ND trademarks. As a whole, thermal lensing reveals clusters of ca. 50–200 nm in ND aqueous dispersions. The estimation of the cluster size from two techniques—transient and imaging PTS–results in concordant values and agree with DLS data, which is rather invigorating for further investigations.
This study was supported by NUST MISiS (grant no K3-2015-064, M.P.) and RFBR (grant no. 16-33-60147, D.V.)
10:45 AM - NT5.5.03
Self-Supporting Nanodiamond Gels: Elucidating Colloidal Interactions through Rheology
Prajesh Adhikari 1,Nancy Burns 1,Anurodh Tripathi 1,Saad Khan 1
1 North Carolina State University Raleigh United States,
Show AbstractThis work investigates the colloidal interactions and rheological behavior of nanodiamond (ND) dispersions, which is critical for its use in composite materials. While ND represents a promising class of nanofiller due to its high surface area, superior mechanical strength, optical transparency, tailorable surface functionality and biocompatibility, much remains unknown about the behavior of ND dispersions and their responses to various processing conditions. We hypothesize that controlling interactions in ND dispersions will allow for developing systems with tunable modulus and shear response. Steady and dynamic rheology experimental techniques are thus used to systematically investigate systems of nanodiamonds dispersed in model polar and non-polar media and examine the microstructure and concomitant rheological behavior.
We find that ND forms gels almost instantaneously in a non-polar media, the strength of which follows a power-law behavior. In contrast, ND in polar media show a time-dependent behavior with the modulus increasing with time. We attribute the difference in behavior to the variation in inter-particle interactions as well as the interaction of the ND with the media. Large steady and oscillatory strains are applied to ND colloidal gels to investigate the role of shear in gel microstructure breakdown and recovery. For colloidal gels in non-polar medium, the incomplete recovery of elastic modulus at high strain amplitudes indicates dominance of particle-particle interactions; however, in polar media the complete recovery of elastic modulus even at high strain amplitudes indicates dominance of particle-solvent interactions. These results taken together provide a platform to develop self-supporting gels with tunable properties in terms of ND concentration, and solvent type.
11:30 AM - *NT5.5.04
Nanoporosity and Water Adsorptivity of Nanodiamond Aggregates Treated at Different Temperature
Katsumi Kaneko 1
1 Shinshu Univ Nagano-city Japan,
Show AbstractNanodiamonds are aggregates of primary polyhedral sp3 carbon-based particles of around 3 nm in diameter. The particles ae wrapped by graphitic or amorphous carbon layers, showing some chemical functionalities on the surface. It is known that dried diamonds are highly hygroscopic.1 Generally speaking sp2-based carbons show a hydrophobic nature and presence of micropores and small mesopores induce a kind of transformation from hydrophobicity to hydrophilicity with growth of water clusters.2-4 On the other hand, the edge-carbon rich carbon shows a hydrophilicity in the lower water vapor pressure range.5 Then, we need to understand the hydrophilic nature of nano diamonds with relevance to the nano porosity. The comparative study of water adsorption on nano diamonds and graphitic nano porous carbons will be presented.
We used nanodaiamond samples supplied by NanoAmando Hard Hydrogel. The nano diamonds of 3 nm in the average primary size were used without further purification. Nitrogen adsorption isotherms at 77 K and water vapor adsorption at 298 K were measured after outgassing at 423, 523, and 623 K. The surface chemistry of the samples was examined with XPS and TPD.
The nitrogen adsorption isotherms indicated the presence of micropores of 0.1 ml/g and mesopores of 0.35 ml/g, which do not change so much with the outgassing at different temperature. The water adsorption isotherms showed hydrophobicity below P/P0 = 0.3 and hydrophilicity above P/P0 = 0.5. The water adsorption isotherms are quite similar to nano porous sp2-based carbons, although XPS and TPD show the presence of surface functional groups.
References
1. M. V. Korovov, M. M. Batuk, N. V. Avramenko, N. I. Ivanova, N. N. Rozhkova, E. Osawa, Diamond Relate. Mater. 2010, 19, 665-672.
2. T. Ohba, H. Kanoh, K. Kaneko, Nano Lett, 2005, 5, 227-230.
3. K. Kaneko, Nature Chem. 2015, 7, 194-197.
4. E. Zoraida pina-Salazar, K. Kaneko, Colloid Interface Sci. Comm. 2015, 5, 8-11.
5. M. Asai, T. Ohba, T. Iwanaga, H. Kanoh, M.Endo, J. Campos-Delgado, M. Terrones, K. Nakai, K. Kaneko, J. Amer. Chem. Soc. 2011, 133,
14830-14833.
12:00 PM - NT5.5.05
Further Characterization of the Primary Particles of Detonation Nanodiamond
Eiji Osawa 1,Shuichi Sasaki 1,Ryoko Yamanoi 1
1 NanoCarbon Research Institute Ueda, Nagano Japan,
Show AbstractDisintegration and size. Several methods have been found to break up the commercial agglutinates of detonation nanodiamond (often offered as primary particles), but the only scalable one is attrition milling of agglutinate powder suspended in water with zirconia microbeads as attritter. Optimization of a large set of operation conditions in attrition milling posed a formidable challenge during the initial phase of our work, but adaptation of Taguchi’s method of quality engineering in 2013 finally gave us pure black and clear ‘solution’ of PPDND with an average diameter of 2.8±0.5 nm. Thus, previously reported size of 4-5 nm could be due to incomplete disintegration to give mostly dimers, which are the product of the coherent interfacial Coulombic interactions between oppositely charged facets between a couple of PPDND.
Unique properties. We have already mentioned above on the strong electrostatic fields on the surface when the old size data of PPDND were given new interpretation. We believe this unusual feature of permanent polarization as the most important feature to understand various new features in PPDND. Here we mention only one example of unique behavior in PPDND. When we succeeded in the production of concentrated (up to 5 wt%) but well dispersed aqueous colloidal solution of PPDND, we thought the dispersion will be more stable upon dilution, but the reverse was true: the more we dilute, the larger became particle size as measured by DLS method. This new phenomenon, ‘dispersion by concentration, aggregation by dilution’ can be interpreted by invoking the colloid crystal known in colloidal chemistry: well hydrated colloids are known to exhibit periodical distribution of colloidal particles in water.
Perspectives. Due to many new properties and behaviors of PPDND that we have never seen in chemistry, a number of novel applications can be readily expected. We are currently developing three potential applications: (1) as drug carriers for cancer chemotherapy, (2) as rolling spacers in a new lubricant system named nanospacer lubrication, and (3) as a Hall-Petch toughening component in solid materials like thermoplastic polymers. Preliminary tests showed much more encouraging results for all three uses compared to conventional reinforcements.
12:15 PM - NT5.5.06
Towards a Golden Standard in Single Digit Detonation Nanodiamond
Nicholas Nunn 1,Olga Shenderova 1
1 Adamas Nanotechnologies Raleigh United States,
Show AbstractAggregates of detonation nanodiamond (DND) have long been of interest for their numerous potential applications; however, no size of DND is perhaps more elusive, yet technologically important, than sub 10 nanometer (or “single-digit”) primary particles. Primary particles of DND have a number of potential applications including drug delivery, seeding in microelectronics, polymer nanocomposites, and lubricants. Nevertheless, the challenge associated with obtaining these particles from the 200-300nm aggregates of purified detonation soot has made them too expensive for widespread use. Even after overcoming the initial challenge of obtaining the primary particles, they are still often limited in their use due to the random assortment of chemical functional groups found on their surface. Therefore, an additional challenge is to gain control over the ability to tailor the surface chemistry of the particles without sacrificing their size by promoting aggregation. A final challenge is to identify useful solvents where stability and size of the functionalized particles are preserved. Here we report our work in obtaining high yields of 5nm primary particles of DND, progress made toward functionalizing these particles with a number of useful chemical structures including: amines, hydrophobic chains, and N-Hydroxysuccinimide (NHS), and the dispersion of these particles in a range of solvents such as DMSO, NMP, DMF, THF, ethylene glycol, synthetic oils, alcohols, and water.
12:30 PM - *NT5.5.07
The Nonaromatic Surface Structure of Purified Detonation Nanodiamond Particles
Klaus Schmidt-Rohr 1
1 Chemistry Brandeis University Waltham United States,
Show AbstractMany models of detonation nanodiamond show a partially aromatic surface layer, which should give a significant spectroscopic signature since a complete aromatic shell of a 5-nm diameter particle would contain nearly 25% of all carbon [1]. However, 13C nuclear magnetic resonance (NMR) shows ≤ 1% of aromatic carbons in pristine purified detonation nanodiamond [1, 2]. Instead, the surface is found to be covered by C-H, C-OH, and a few C=O moieties. The 12-14% surface carbons (i.e. those with bonds to ≤3 carbons) expected for a bulk-terminated diamond particle are thus accounted for [1]. NMR, unlike many other spectroscopies, including IR, Raman, and XANES, is intrinsically quantitative, with fractional peak areas equal to the fraction of carbons in the respective chemical environment, so that carbon percentages can be determined without an external standard. In addition, peak positions in NMR are more systematically related to structure than, for instance, in Raman spectroscopy, where quite recently the “graphitic” peak of nanodiamond at 1620 cm-1 was reassigned to OH bending vibrations [3]; the intensity loss of this band with heat treatment [4] confirms its assignment to OH moieties. Unlike NMR, XPS cannot resolve a distinct peak of a few percent of aromatic carbons.[5] Reviewing literature data from previous studies by NMR and other methods, including HRTEM, XPS, Raman, and XANES [6, 1, 7], we will demonstrate that none of these investigations have documented an aromatic fraction of >2% in pristine, properly purified detonation nanodiamond. Time permitting, other NMR-derived structural aspects of nanodiamond particles, such as the nonaromatic core–shell structure [2] and the depth of N and of unpaired electrons [2] from the surface will also be reviewed.
[1] Cui, J.-F.; Fang, X. W.; Schmidt-Rohr, K. Quantification of C=C and C=O Surface Carbons in Detonation Nanodiamond by NMR; J. Phys. Chem. C 2014, 118, 9621-9627.
[2] Fang, X.; Mao, J.; Levin, E. M.; Schmidt-Rohr, K. Nonaromatic Core-Shell Structure of Nanodiamond from Solid-State NMR Spectroscopy; J. Am. Chem. Soc. 2009, 131, 1426-1435.
[3] Mochalin, V.; Osswald, S.; Gogotsi, Y. Contribution of Functional groups to the Raman Spectrum of Nanodiamond Powder; Chem. Mater. 2009, 21, 273-279.
[4] Chen, J.; Deng, S. Z.; Chen, J.; Yu, Z. X.; Xu, N. S. Graphitization of Nanodiamond Powder Annealed in Argon Ambient; Appl. Phys. Lett. 1999, 74, 3651-3653.
[5] Butenko, Y. V.; Krishnamurthy, S.; Chakraborty, A. K.; Kuznetsov, V. L.; Dhanak, V. R.; Hunt, M. R. C.; Šiller, L. Photoemission Study of Onionlike Carbons Produced by Annealing Nanodiamonds; Phys. Rev. B 2005, 71, 07542
[6] Panich, A. M. Nuclear Magnetic Resonance Studies of Nanodiamonds; Crit. Rev. Solid State Mater. Sci. 2012, 37, 276-303.
[7] Schmidt-Rohr, K., Cui, J. Reply to a Comment on “Quantification of C=C and C=O Surface Carbons in Nanodiamond by NMR”; J. Phys. Chem. C 119, 21288–21291 (2015).
NT5.6: NV Centers, Imaging and Biomedical Applications
Session Chairs
Jean-Charles Arnault
Amanda Barnard
Thursday PM, March 31, 2016
PCC West, 100 Level, Room 103 B
2:30 PM - *NT5.6.01
New Generation of Fluorescent Nanodiamonds
Igor Aharonovich 1
1 Univ of Technology Sydney Ultimo Australia,
Show AbstractFluorescent nanodiamonds are becoming increasingly important in applications of bio-labeling and bio-imaging as well as quantum information processing and nanophotonics. This stems primarily from their unprecedented bio-compatibility and the ability to host bright fluorescent color centers.
In this talk, I will first give a brief introduction into the field of fluorescent nanodiamonds and in particular the generation of luminescent defects. In particular, I will focus on two interesting candidates – the silicon vacancy and the nitrogen vacancy color centers. I will describe how these centers are fabricated and will highlight the importance of surface modification to control and manipulate the emission properties.
I will then describe two approaches to enhance luminescence from single emitters in nanodiamonds. The first includes a single step biological coating with metalo-organic complexes that results in an enhancement of emission. This process is bio-compatible and can be easily use to achieve strong contrast of bright florescent nanodiamonds. The second approach involves a facile self assembly method to couple nanodiamonds hosting single nitrogen vacancy defects to plasmonic resonators. Controlled attachment to the apexes is realized and transmission through the silver nanowire is achieved.
I will then summarize and present a promising outlook for future directions in fluorescent nanodiamonds.
3:00 PM - *NT5.6.02
Magnetically Modulated Fluorescence of Nitrogen-Vacancy Centers for Selective Imaging and Quantification of Nanodiamonds in Biological Samples
Yuen Hui 1,Long-Jyun Su 2,Be-Ming Chang 4,Huan-Cheng Chang 4
1 Institute of Atomic and Molecular Sciences Academia Sinica Taipei Taiwan,1 Institute of Atomic and Molecular Sciences Academia Sinica Taipei Taiwan,2 Department of Chemistry National Taiwan University Taipei Taiwan1 Institute of Atomic and Molecular Sciences Academia Sinica Taipei Taiwan,3 Department of Chemistry National Tsing Hua University Taipei Taiwan,4 Taiwan International Graduate Program, Molecular Science and Technology Academia Sinica Taipei Taiwan1 Institute of Atomic and Molecular Sciences Academia Sinica Taipei Taiwan,4 Taiwan International Graduate Program, Molecular Science and Technology Academia Sinica Taipei Taiwan
Show AbstractThe negatively charged nitrogen-vacancy center (NV–) in Fluorescent Nanodiamond (FND) is an atom-like emitter with unique magneto-optical properties. Its fluorescence can be magnetically modulated, allowing for background-free detection. Here, we scrutinize this property and illustrate its potential use by applying a periodic, time-varying magnetic field to FND-containing solutions and tissue sections with lock-in detection. It is shown that ultra-sensitive mass determination of FNDs in water can be achieved at a concentration lower than 50 ng/mL, with a magnetic field strength of 200 G and a modulation frequency of 10 Hz. This enables high-sensitivity quantification of the uptake of FNDs by cells and the biodistribution of FND-labeled cells in a mouse model. The utility and versatility of the technique are further demonstrated with an application to acquire high contrast images by wide-field microscopy of FND-labeled cells in mouse tissue sections.
4:00 PM - *NT5.6.03
Integrating Nanodiamond Drug Delivery and Imaging with Precision Medicine
Dean Ho 1,theodore kee
1 UCLA Los Angeles United States,
Show AbstractNanodiamonds have been utilized for a broad spectrum of drug delivery and imaging applications with marked enhancements in efficacy and safety [1-3]. For example, the administration of nanodiamond-doxorubicin (NDX) complexes towards breast, liver, and brain cancer therapy has resulted in substantial improvements in drug tolerance and decreased systemic and localized toxicity. In addition, nanodiamond-gadolinium complexes have mediated one order of magnitude improvements in per-gadolinium relaxivity. Recently, nanodiamonds have been used to reinforce various polymeric devices including contact lenses and other platforms to enable lysozyme-triggered drug release for potential applications in glaucoma therapy [4]. Nanodiamond incorporation into these devices simultaneously enhanced the mechanical robustness of the device while also sustaining oxygen and water content properties, indicating no adverse effects upon potential wear comfort. Following the demonstration of improved monotherapy using nanodiamond drug delivery, it is becoming increasingly important to develop optimized nanomedicine-enhanced combination therapy. However, conventional approaches utilize additive dosing, which serves as a major barrier towards the systematic identification of drug-dose ratios that can realize globally optimal efficacy and safety of treatment. Our recent work has demonstrated that a powerful mechanism-independent technology platform, termed Phenotypic Personalized Medicine.Drug Development (PPM.DD) is capable of rapidly optimizing nanodiamond-modified as well as unmodified drug combinations based upon experimentally-validated data [5]. This approach will result in markedly-improved response rates to treatment through the rational combinatorial therapy design.
References
[1] Mochalin et al., Nature Nanotechnology, 2012.
[2] Chow et al., Science Translational Medicine, 2011.
[3] Chow et al., Science Translational Medicine, 2013.
[4] Kim et al., ACS Nano, 2014.
[5] Ho et al., Science Advances, 2015.
4:30 PM - NT5.6.04
Nanodiamonds for Sustainable Nanomedicine
Dong-Keun Lee 1
1 UCLA Los Angeles United States,
Show AbstractNanodiamond (ND)-mediated drug delivery has been of increasing interest due to its improved circulatory half-life, increased retention time within target cell, and decreased unintended cytotoxic effects and incidence of resistance. However, numerous challenges exist regarding implementation of ND mediated drug delivery for nanomedicine purposes such as optimizing drug combinations loaded onto ND and translational studies of ND nanotechnology to the human system. Thus, we developed an optimization method platform for drug combination therapy to achieve higher efficacy and demonstrated ND-mediated material in a human system model for future development of translational research.
Combinatorial chemotherapeutic drug treatment is currently used to improve efficacy for cancer treatment. However, no simple and systematic method exists to optimize the efficacy of drug combinations. Therefore, we developed Feedback System Control II (FSC II), an engineering-based screening approach; FSC II is a method that finds optimum drug combinations by converging towards the global maximum of a quadratic dose response surface constructed from the phenotypically driven drug efficacy vs drug dose data in a mechanism-independent manner. In the study, 57 randomly selected combinations of Doxorubicin, Mitoxantrone, and Bleomycin incorporated ND-drug complexes and unmodified Paclitaxel were applied on three cancer cell lines (MDB-MB-231, BT-20, and MCF-7) and three control cell lines (MCF-10A, IMR-90, and H9C2) to construct a quadratic surface map from therapeutic windows (viability of controls - viability of cancer) and drug dose information. Optimum drug combinations were then obtained by a differential evolution optimization protocol. Thus, verification of FSC II was demonstrated by optimized ND-drug complex combinations outperforming ND-mediated and unmodified single drug, randomly sampled unoptimized ND-drug complex, and optimal unmodified drug combination therapies.
Additionally, we demonstrated the model of composite materials containing ND-drug in a human system for translational research. When teeth are badly decayed or infected, the infected nerves and pulps are removed and replaced by a rubbery compound called gutta-percha to save the teeth and prevent further infection. However, teeth can get re-infected, resulting in retreatment of the root canal and/or replacement of infected teeth with expensive dental implants. Therefore, we explored ND-mediated amoxicillin combined with regular gutta-percha composite (1,4-trans-polyisoprene, ZnO2, BaSO4, and wax), which effectively killed Staphylococcus aureus, one of the bacteria responsible for root canal re-infection. Furthermore, the ND-mediated amoxicillin gutta-percha composite was mechanically stronger than regular gutta-percha.
With these recent advances of our research, the necessary improvements of ND-mediated drug therapies were demonstrated to achieve sustainable nanomedicine purposes within humans.
4:45 PM - NT5.6.05
A Nanodiamond Platform for Personalized Cancer Therapy against Liver Cancer
Edward Chow 1
1 National Univ of Singapore Singapore Singapore,
Show AbstractWhile advances have improved the overall treatment of cancer, liver cancers continues to be difficult to treat with liver cancer annual deaths continuing to rise. Our lab has shown that specific genomic alterations can influence drug sensitivity or resistance as well as targetable markers. Understanding the therapeutically targetable molecular mechanisms of specific liver cancer molecular subtypes has allowed us to intelligently design personalized nanodiamond-based drug delivery and imaging complexes for these specific molecular subtypes. Nanodiamonds (NDs) are ~4nm carbon nanoparticles with a truncated octahedral structure. We and others have show that nanodiamonds are a versatile drug delivery platform that can be functionalized with a broad array of molecules, including small molecules, proteins and genetic material, with a high level of biocompatibility. We have shown enhanced efficacy and safety of ND-anthracycline drug delivery complexes against a number of cancer models in vitro and in vivo. This included being able to enhance treatment of MYC-driven chemoresistant cancer stem cells and prevent secondary tumor formations in vivo. We have also explored the mechanisms by which ND-anthracycline drug delivery occurs at both the system and cellular level and identified several key mechanisms that contribute to enhanced drug retention, cancer cell specific drug release as well as lower systemic drug toxicity that can be applied to a wide range of other nanomedical applications for improved drug delivery. Beyond anthracyclines, we have now fabricated targeted dual-drug delivery ND complexes to delivery new classes of drugs, including mTOR and MEK inhibitors, against AKT/RAS-driven liver tumors. Additionally, we have evaluated the use of NDs as a platform for SALL4-driven tumor tissue selective therapeutic delivery and drug release. These recent advances in ND drug delivery of new classes of therapeutics as well as enhanced mechanisms of tumor specific drug delivery further demonstrate the potential for a ND-based platform for the development of personalized drug-delivery or imaging complexes as we have now demonstrated improved efficacy and/or safety against several specific liver cancer molecular subtypes.
5:00 PM - *NT5.6.06
Biomedical Applications of Diamond Nanoparticles: From Drug Delivery to Implants
Vadym Mochalin 1,James Giammarco 1,Amanda Pentecost 1,Yury Gogotsi 1
1 Department of Materials Science and Engineering and A.J. Drexel Nanomaterials Institute Drexel University Philadelphia United States,
Show AbstractNanomaterials hold tremendous potential in addressing the two major issues faced by our society: providing energy and improving healthcare. Nanodiamond powder produced by detonation and readily available in commercial quantities for moderate price, is one of the most promising carbon nanomaterials for theranostics. Made of ~5 nm diamond particles with large accessible surface and tailorable surface chemistry, it has unique optical, mechanical and thermal properties, and is non-toxic. These properties have recently started to attract much interest among researchers working on different biomaterials and drug delivery systems. For tissue engineering scaffolds, the non-toxic fluorescent nanodiamond introduced into biodegradable polymers provides increased strength, visual monitoring, and enhanced biomineralization. In drug delivery, the rational surface modification of nanodiamond allows for enhanced adsorption and chemical binding of the drugs for sustained or triggered drug release. In the area of biomedical imaging and diagnostics, luminescent nanodiamond with NV centers, as well as chemically modified fluorescent nanodiamond, hold tremendous potential to replace toxic semiconductor quantum dots, thus bringing this exciting potential application one step closer to the clinics. The purification, characterization and surface modification of nanodiamond for biomedical applications will be discussed in detail. Recent progress in development of nanodiamond-containing biodegradable polymer scaffolds for tissue engineering and bone surgery will be reviewed. Surface modifications of nanodiamond for drug delivery exploiting adsorption/desorption mechanisms will be discussed, with illustrations of the use of adsorption/desorption data for rational design of the nanodiamond surface for optimal drug delivery platforms.
5:30 PM - NT5.6.07
Development of a Novel Nanodiamond-Based Drug Delivery System for the Treatment of Chronic Inflammation
Amanda Pentecost 1,Yury Gogotsi 1,Kara Spiller 2
1 Materials Science amp; Engineering Drexel University Philadelphia United States,2 School of Biomedical Engineering, Science amp; Health Systems Drexel University Philadelphia United States
Show AbstractCommon anti-inflammatory drugs are used as short-term relief to reduce inflammation. However, they have many undesirable off-target effects, including weakening of the adaptive immune system. By attaching these drugs to nanoparticles, we hypothesize that we will be able to selectively target macrophages, a specific type of innate immune cell that has a high potential for nanoparticle uptake, thus reducing off-target effects and increase drug efficacy. By designing nanoparticles with dual therapeutic and diagnostic, or theranostic, properties, we can create an optimized drug delivery system to be used to target and track disease progression and treatment in patients with chronic inflammation. Nanodiamond (ND) is a highly versatile carbon nanomaterial, which exhibits such properties as chemical stability, and low cytotoxicity. Because of its surface, which is covered with charged functional groups, ND properties are easy to tune, allowing for the ability to create multimodal nanoparticles. In this work, we demonstrated the therapeutic potential of this system by adsorbing a model drug, dexamethasone, to the surfaces of two different types of modified ND and determined their adsorption isotherms/desorption curves in order to determine optimal conditions. We found that hydrophobic ND with octadecylamine attached to its surface (ND-ODA) has superior adsorptive properties compared to hydrophilic, carboxylated ND (ND-COOH). We also took advantage of ND-ODA’s intrinsic blue fluorescence by monitoring its uptake in and effect on human macrophages by using fluorescent microscopy and immunohistochemistry. Together, these results demonstrate the potential for ND-ODA to aid in the targeted delivery of dexamethasone to macrophages. Further studies include optimizing the drug delivery system in vitro to control macrophage behavior as well as confirm preferential uptake in macrophages compared to other cell types.
5:45 PM - NT5.6.08
Nanodiamond for Drug Delivery into Central Neural System
Vadym Mochalin 1,Chongyang Wei 2,Fang Guo 2,Yury Gogotsi 3
1 Missouri University of Science amp; Technology Rolla United States,2 Shanghai Advanced Research Institute Shanghai China3 Drexel University Philadelphia United States
Show AbstractDelivery of therapeutics into central neural system (CNS) is complicated by the need for the drugs to cross the blood-brain barrier (BBB). Polymer nanoparticles in the past have been demonstrated as efficient carriers of anesthetics and other drugs across the BBB. However, it is very difficult to produce polymer nanoparticles of very small size (~5 nm) with narrow size distribution and with highly tailorable surface chemistry necessary for delivery of various types of drugs. Thus, there is no single polymer that would work in all situations. In this research, we developed non-toxic nanodiamond particles (ND) with highly tailorable surface chemistry based on commercial inexpensive NDs produced by detonation. We performed in vitro studies of adsorption/desorption of DOX on NDs with different surface chemistries to get more insights into mechanisms and parameters governing these processes, and used this knowledge to identify the NDs which perform optimally in terms of the drug loading and binding strength. The developed NDs have then been tested in vivo as drug delivery vehicles for doxorubicin (DOX) in treatment of human glioma in the nude mice animal model. Doxorubicin, as well as many other anticancer chemotherapeutics, is extremely difficult to deliver across the BBB when the drug is injected intravenously. In contrast to pure DOX, the ND-DOX complexes injected intravenously showed much higher efficiency in treatment of the human glioma model. At the same time, ND-DOX toxicity to the animals was significantly lower compared to Temozolomide - one of a few drugs available for treatment of glioma