The chemistry of the surface of modified detonation nanodiamonds of different types

The influence of standard chemical treatment used to extract interstellar nanodiamonds from meteorites on the chemical composition of the surface of synthetic nanodiamonds with substantially different properties was studied by thermal desorption mass spectrometry and IR spectroscopy. The chemistry of the surface of nanodiamonds after treatment was substantially different from that of initial particles. The suggestion was made that the chemical structure of the surface of diamond particles in the interstellar space could be reconstructed from the data on meteorite diamonds. Mass spectrometric studies also gave information about possible mechanisms of the release of noble gases from meteorite diamonds at various temperatures.     

Nanodiamonds Used as a Platform for Studying Noncovalent Interaction by MALDI‐MS

作为一种新的,易于实现的快速分析方法,纳米金刚石被应用基于基质隔离激光解吸附电离质谱的非共价相互作用的研究中。表面覆盖有“饵分析物”的纳米金刚石被加入到含有“目标分析物”的溶液中,通过离心的方法进行分离,并用水清洗后再利用基质隔离激光解吸附电离质谱进行分析。同时,通过比较加入纳米金刚石前后的溶液的质谱图,亦可得到相关信息。这种平台可应用于分子间非共价相互作用的研究,并可进一步应用于选择性增强的基质隔离激光解吸附电离质谱分析中,一个例子就是表面覆盖聚赖氨酸的纳米金刚石在磷酸化多肽的质谱分析的应用。     

Effect of Armoring Composition on the Yield of Nanodiamonds and Content of Impurities

Efficiency of using detonation nanodiamonds is strongly affected by the amount and elemental composition of impurities. The study considers the possibility of affecting the yield of detonation nanodiamonds and diamond-containing stock and the content and composition of incombustible impurities in the stock and diamonds by varying the composition of the water armor (shell) of the classical TNT–hexogen (50/50) charge. As compounds affecting the above parameters were used hydrazine, urotropin, ammonia, urea, Trilon B (disodium salt of ethylene diamine tetraacetic acid), aminotetrazole, and boric acid. It was found that using urotropin was the optimal as regards a whole set of parameters. In this case, the maximum yield of detonation nanodiamonds (6.9%) and diamond-containing stock (13.4%) was obtained. A close yield of the diamond-containing stock and detonation nanodiamonds was provided by using hydrazine and urea in the armor. Use of boric acid in the armor can substantially diminish the variety of impurity elements in the diamond-containing stock and detonation nanodiamonds at an acceptable yield of the diamond-containing stock (11.1%) and detonation nanodiamonds (6.13%). Use of pure water as the armor is inefficient.     

Microdispersed sintered nanodiamonds as a new stationary phase for high-performance liquid chromatography

The microdispersed sintered nanodiamonds are evaluated as a new prospective stationary phase for normal-phase high-performance liquid chromatography.     

Properties of microdispersed sintered nanodiamonds as a stationary phase for normal-phase high performance liquid chromatography

The chromatographic properties of microdispersed sintered nanodiamonds (MSND) are studied under conditions of normal-phase HPLC. The retention characteristics of 30 substances representing four classes of aromatic compounds including monoalkylbenzenes, polymethylbenzenes, di-n-alkyl phthalates and polyaromatic hydrocarbons in n-alkane mobile phases have been measured. The selectivity of MSND was compared with literature data for other common adsorbents including silica gel, alumina and porous graphitic carbon (PGC). MSND shows the distinctive adsorption properties especially in a stronger retention of aromatic hydrocarbons and in the better selectivity of the separation of geometric isomers. The significant improvement in separation efficiency up to 45,300 theoretical plates per meter, was achieved for the first time for the columns packed with diamond related materials (DRM).     

Dangling bond-induced graphitization process on the (111) surface of diamond nanoparticles

The intrinsic mechanism of graphitization occurring on the (111) surface of nanodiamonds (NDs) during the transformation from NDs into bucky diamonds are explored using density functional theory (DFT) computations in conjunction with density functional based tight-binding simulations. The DFT results indicate that dangling bonds (DBs) on the ND surfaces play an important role in the graphitization process, and the orientation of the DBs on different ND surfaces determines whether there will be a graphitization process or not. Moreover, a criterion is proposed to estimate rupturing of the C-C bonds between different layers on the [111] direction in the NDs and is verified to be applicable to illustrate the phase transformation from sp(3) into sp(2) bonding structures. The energy contributions of the four-coordinated carbon atoms located at different positions on the (111) surface are exhibited for the first time and discussed in detail to gain a clear picture for the transition from NDs into bucky diamonds. The outcome may provide a deeper understanding on the influence of DBs upon the transformation from sp(3) into sp(2) bonding structures.     

Physicochemical modification of nanodiamonds

Thermal modification of nanodiamonds in the atmosphere of argon and hydrogen and their chemical modification with oleum and chlorine at different temperatures were studied. The effect of the modification conditions on the catalytic activity of palladium catalysts supported by nanodiamonds in the reaction of nitrobenzene hydrogenation and on the adsorption properties of nanodiamonds with respect to benzene, chloroform, and water was analysed.     

Detonation nanodiamonds as catalysts of steam reforming of ethanol

Physicochemical properties and catalytic performance of detonation nanodiamonds were studied. Original samples of nanodiamonds and nanodiamonds modified by hydrogen, oxygen, and nitric acid with hydrogen peroxide and infrared-treated were investigated. The catalyst structure and morphology were examined by transmission electron microscopy and IR spectroscopy. All the investigated catalysts were active in the steam reforming of ethanol. The correlation of catalytic properties with composition and structure of the described systems is discussed. The specific surface area of nanodiamonds is changed insignificantly upon modification.     

Are diamond nanoparticles cytotoxic?

Finely divided carbon particles, including charcoal, lampblack, and diamond particles, have been used for ornamental and official tattoos since ancient times. With the recent development in nanoscience and nanotechnology, carbon-based nanomaterials (e.g., fullerenes, nanotubes, nanodiamonds) attract a great deal of interest. Owing to their low chemical reactivity and unique physical properties, nanodiamonds could be useful in a variety of biological applications such as carriers for drugs, genes, or proteins; novel imaging techniques; coatings for implantable materials; and biosensors and biomedical nanorobots. Therefore, it is essential to ascertain the possible hazards of nanodiamonds to humans and other biological systems. We have, for the first time, assessed the cytotoxicity of nanodiamonds ranging in size from 2 to 10 nm. Assays of cell viability such as mitochondrial function (MTT) and luminescent ATP production showed that nanodiamonds were not toxic to a variety of cell types. Furthermore, nanodiamonds did not produce significant reactive oxygen species. Cells can grow on nanodiamond-coated substrates without morphological changes compared to controls. These results suggest that nanodiamonds could be ideal for many biological applications in a diverse range of cell types.     

Synthesis and some aspects of the formation mechanism of carbon structures under hydrothermal conditions

The formation of carbon structures upon the reactions of organic compounds with strong mineral acids under hydrothermal conditions was studied. The reactions were found to give amorphous carbon, microcrystalline graphite, nanodiamonds, diamond-like carbon, diamonds, C₆₀ and C₇₀ fullerenes, and carbolite. Hydrocarbons of various compositions including aromatics and naphthenes were detected among the reaction products. A possible mechanism of the formation of carbon structures with sp ² bond hybridization under hydrothermal conditions was proposed.     

Application of carbon-based nanomaterials in sample preparation: A review

In this paper, a broad overview on the applications of different carbon-based nanomaterials, including nanodiamonds, fullerenes, carbon nanotubes, graphene, carbon nanofibers, carbon nanocones-disks and nanohorns, as well as their functionalized forms, in sample preparation is provided. Particular attention has been paid to graphene because many papers regarding its application in this research field are becoming available. The distinctive properties, derivatization methods and application techniques of these materials were summarized and compared. According to their research status and perspective, these nanomaterials were classified in four groups (I: graphene and carbon nanotubes; II: carbon nanofibers; III: fullerenes; and IV: nanodiamonds, carbon nanocones/disks and carbon nanohorns) and characteristics and future trends of every group were discussed.     

Plasma Catalytic Synthesis of Ammonia Using Functionalized-Carbon Coatings in an Atmospheric-Pressure Non-equilibrium Discharge

We investigate the synthesis of ammonia in a non-equilibrium atmospheric-pressure plasma using functionalized-nanodiamond and diamond-like-carbon coatings on α-Al₂O₃ spheres as catalysts. Oxygenated nanodiamonds were found to increase the production yield of ammonia, while hydrogenated nanodiamonds decreased the yield. Neither type of nanodiamond affected the plasma properties significantly. Using diffuse-reflectance FT-IR and XPS, the role of different functional groups on the catalyst surface was investigated. Evidence is presented that the carbonyl group is associated with an efficient surface adsorption and desorption of hydrogen in ammonia synthesis on the surface of the nanodiamonds, and an increased production of ammonia. Conformal diamond-like-carbon coatings, deposited by plasma-enhanced chemical vapour deposition, led to a plasma with a higher electron density, and increased the production of ammonia.     

Preparation of fluorescent magnetic nanodiamonds and cellular imaging

Magnetic nanodiamonds were prepared via solid-state microwave arcing of a nanodiamond-ferrocene mixed powder in a focused microwave oven. High-resolution transmission electron microscope (HRTEM) images show that a magnetic nanodiamond is composed of iron nanoparticles encapsulated by graphene layers on the surface of nanodiamonds. Fluorescence property was introduced onto magnetic nanodiamonds by chemical modification of magnetic nanodiamonds via surface grafting of poly(acrylic acids) and fluorescein o-methacrylate. Fluorescent magnetic nanodiamonds are water soluble with a solubility of approximately 2.1 g/L. Cellular-imaging experiments show that fluorescent magnetic nanodiamonds could be ingested by HeLa cells readily in the absence of agonist (i.e., folate) moieties on the surface of nanodiamonds.     

Interaction of shungite carbon nanoparticles with blood protein and cell components

We have analyzed and compared the effects of aqueous dispersion of shungite carbon nanoparticles, fullerene C₆₀, and nanodiamonds on structure, dynamics, and thermodynamic and redox properties of blood proteins (serum albumin and hemoglobin), proteins of erythrocyte ghost membranes as well as on erythrocyte integrity and aggregation.. All the nanomaterials dispersions have induced similar effects; however, nanodiamonds have not influences the redox properties. Basing on the results, the experimental and theoretical approaches presented can be employed to estimate the effects of biological structures contact with the nanoparticles on the bioreactivity.     

Development of a rational technology for synthesis of high-quality detonation nanodiamonds

Concepts concerning the structure of detonation nanodiamonds were generalized on the basis of data reported in previous publications. The pH value of the nanodiamonds in an aqueous suspension was determined. The mechanism of the longest stage, washing of nanodiamonds with water to remove excess acidity, was considered. A novel method for substantially improving the quality of nanodiamonds and the stability of aqueous suspensions of nanodiamonds was suggested.     

The interaction of fluorescent nanodiamond probes with cellular media

Fluorescent nanodiamonds (FNDs) are promising tools to image cells, bioanalytes and physical quantities such as temperature, pressure, and electric or magnetic fields with nanometer resolution. To exploit their potential for intracellular applications, the FNDs have to be brought into contact with cell culture media. The interactions between the medium and the diamonds crucially influence sensitivity as well as the ability to enter cells. The authors demonstrate that certain proteins and salts spontaneously adhere to the FNDs and may cause aggregation. This is a first investigation on the fundamental questions on how (a) FNDs interact with the medium, and (b) which proteins and salts are being attracted. A differentiation between strongly binding and weakly binding proteins is made. Not all proteins participate in the formation of FND aggregates. Surprisingly, some main components in the medium seem to play no role in aggregation. Simple strategies to prevent aggregation are discussed. These include adding the proteins, which are naturally present in the cell culture to the diamonds first and then inserting them in the full medium.

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Graphical abstract Schematic of the interaction of nanodiamonds with cell culture medium. Certain proteins and salts adhere to the diamond surface and lead to aggregation or to formation of a protein corona.

     

Preparation and properties of Miramistin–hyaluronic acid coatings on the nanodiamond surface

Hyaluronic acid is a promising coating for imparting biocompatibility to nanodiamond–antibiotic composites. It has been found that the adsorption of Miramistin on nanodiamonds with an initial negative zeta-potential increases the adsorption of hyaluronic acid, which remains lower than on positively charged nanodiamonds that are not affected by the pre-adsorption of Miramistin. The highest adsorption of hyaluronic acid is observed when Miramistin neutralizes the surface charge of nanoparticles.     

Raman spectroscopy of advanced materials

Many micro-structural aspects of advanced materials and the incidence on the physical properties have been elucidated by Raman micro-spectroscopy. The potential of this technique is demonstrated with new materials interesting in both academic and industrial developments: new carbons and diamonds, superconductors, semiconductors, superhards.     

Raman spectroscopy of advanced materials

Many micro-structural aspects of advanced materials and the incidence on the physical properties have been elucidated by Raman micro-spectroscopy. The potential of this technique is demonstrated with new materials interesting in both academic and industrial developments: new carbons and diamonds, superconductors, semiconductors, superhards.     

Structure and mechanical properties of thermoplastics modified with nanodiamonds

The structure and properties of composite materials based on amorphous thermoplastics and detonation nanodiamonds are studied. The conception of the “rheological method” is advanced for compatibilization of a polymer and a filler under the regime of elastic turbulence (spurt) for preparation of composites with a high level of dispersion and a homogeneous distribution of nanodiamond particles. As a rule, the dependences of strength and physicomechanical characteristics of the nanocomposites on the content of the dispersed phase are described by curves with an extremum or saturation. The concentration of the filler corresponding to the extremum or the approach to the plateau value for a specific parameter depends on the nature of the polymer matrix and is attained at filler contents below 2.5 wt %. The elastic modulus monotonically increases as the content of nanodiamonds is increased to 5 wt %.