The application of INAA to the geochemical analysis of single diamonds

Instrumental neutron activation analysis (INAA) has been applied to the analysis of 62 small (0.01–0.5 carat), single, inclusion-bearing and inclusion-free diamonds from South Africa, Brazil and Colorado. Up to 40 elements were detected at the ppb and ppt levels in individual diamonds of the eclogitic (basaltic affinity) and the peridotitic (ultramafic) paragenesis. The data obtained in this study can be used to distinguish between diamonds from the eclogitic and peridotitic parageneses and provides geochemical information on the environment in which diamonds crystallize. Further, the technique may prove to be useful in fingerprinting diamonds of different provenance areas.     

The determination of oxygen and silicon in diamond by 14 MeV neutron activation analysis

Techniques for the measurement of low levels of oxygen and silicon, using fast neutron activation analysis, have been developed and applied to high-quality diamonds. For oxygen, a limit of detection of approximately 5 μg has been established. Sources of error have been studied and eliminated, the ubiquitous occurrence of oxygen being the major problem. Within the accuracy of this work, the results obtained show no significant differences in the oxygen contents of diamonds of different types, or of diamonds from different sources. An oxygen content of 35±4 ppm has been established for high-quality colourless diamonds. For silicon, a limit of detection of 25 μg was established and the average silicon content of these diamonds was found to be less than 3 ppm. It is concluded that the oxygen in high-purity diamonds is present as CO₂ or H₂O and not in silicate inclusions.     

The determination of zonally distributed impurities in diamond by instrumental neutron activation analysis

A technique is described for the determination by instrumental neutron activation analysis of the zonal distribution of trace elements in diamond. Individual diamonds were irradiated and then dissolved in stages into 10 to 20 fractions in molten sodium nitrate. The activity of the material dissolved in each fraction was measured using a well-shielded Ge(Li) detector. Because of the small sample sizes involved, many elements typically found in diamond were below the limits of detection even though the experimental conditions were optimised for high sensitivity. The data obtained for a clear, a green and a coated diamond are given here to show the scope of the method. High levels of some elements in the outermost layers of all the diamonds are thought to have been due the implantation of surface contaminants during neutron irradiation. Removal of the outer few microns of irradiated diamonds before counting will avoid this source of error.     

Measuremets of presolar grain in meteorite using neutron activation analysis with multi-parameter coincidence method

Neutron activation analysis with multi-parameter coincidence method was developed at the Japan Atomic Energy Agency (JAEA) and a non-destructive, ultra-high sensitive multi-elemental determination has been realized. The multi-parameter coincidence method is carried out with an array of 19 germanium detectors, GEMINI-II. Using this system, very weak γ-rays emitted from trace amounts of elements can be detected. The presolar grains were extracted from the Allende meteorite. Trace elements in the presolar diamonds were measured by neutron activation analysis with multi-parameter coincidence method.     

Trace-element analysis of argyle diamonds using instrumental neutron activation analysis

Thirty four elements were determined by instrumental neutron activation analysis in colourless, brown, and pink diamonds, with and without inclusions. These were compared with data obtained for similar elements in the host lamproite rock. The natural radioactivity of these samples was measured by instrumental techniques, and found to be negligible.     

Brown diamonds from an eclogite xenolith from Udachnaya kimberlite, Yakutia, Russia

We have performed petrographic and spectroscopic studies of brown diamonds from an eclogite xenolith from the Udachnaya pipe (Yakutia, Russia). Brown diamonds are randomly intermixed with colorless ones in the rock and often located at the grain boundaries of clinopyroxene and garnet. Brown diamonds can be characterized by a set of defects (H4, N2D and a line at 490.7 nm) which are absent in colorless diamonds. This set of defects is typical for plastically deformed diamonds and indicates that diamonds were likely annealed for a relatively short period after deformation had occurred. Excitation of brown colored zones with a 632.8 nm He-Ne laser produced the typical diamond band plus two additional bands at 1730 cm(-1) and 3350 cm(-1). These spectral features are not genuine Raman bands, and can be attributed to photoluminescence at ～710 nm (1.75 eV) and ～802 nm (1.54 eV). No Raman peak corresponding to graphite was observed in regions of brown coloration. Comparison with previous reports of brown diamonds from eclogites showed our eclogitic sample to have a typical structure without signs of apparent deformation. Two mechanisms with regard to diamond deformation are proposed: deformation of eclogite by external forces followed by subsequent recrystallization of silicates or, alternatively, deformation by local stress arising due to decompression and expansion of silicates during ascent of the xenolith to surface conditions.     

Characterisation of diamond coatings with different morphologies by Raman spectroscopy using various laser wavelengths

Since the beginning of low-pressure diamond synthesis, Raman spectroscopy has been widely used to identify and characterise the quality of diamonds. The diamond crystal is characterised by a Raman peak at about 1,332 cm^-1. Other peaks are associated with miscellaneous carbon structures, e.g. graphite and amorphous phases. In recent years, both well-faceted crystalline diamonds and nanocrystalline and ultrananocrystalline diamonds have been investigated. For these fine-grained materials, the diamond peak at 1,332 cm^-1 disappears and the intensities of peaks at other wavelengths increase. To study the influence of the Raman laser wavelength, three lasers were used (472.681 nm, blue; 532.1 nm, green; 632.81 nm, red). For well-faceted diamonds, the Raman spectra with blue and green laser light were similar. A shift of the peak maxima and different intensities were observed. With use of the red laser, a strong luminescence peak and low peak intensities for the various carbon-related peaks occurred. When the diamond morphology changes from well-faceted to fine-grained ballas diamond, the spectra are similar for all three lasers.     

Natural diamonds—Major,minor and trace impurities in relation to source and physical properties

Nuclear techniques for the determination of 39 impurity elements in diamonds are described. A common impurity chemistry was found for different diamonds and is considered to reflect the composition of the magma from which they crystallised. A relatively successful attempt was made to differentiate between diamonds from three different kimberlites by the application of discriminant analysis.     

Properties of hybridized DNA arrays on single-crystalline undoped and boron-doped (100) diamonds studied by atomic force microscopy in electrolytes

Properties of hybridized deoxyribonucleic acid (DNA) arrays on single-crystalline undoped and boron-doped diamonds are studied at the microscopic level by atomic force microscopy (AFM) in buffered electrolytic solutions. DNA is linked to diamond via aminodecene molecules (TFAAD) that are attached to undoped diamonds by a photochemical reaction and via nitrophenyl-diazonium molecules attached electrochemically to boron-doped diamonds. Both H-terminated and oxidized diamond surfaces are used in this process. On H-terminated surfaces, AFM measurements detect compact DNA layers. By analyzing phase and height contrast in AFM, a DNA layer height of 76 A is determined on the photochemically functionalized diamonds and a DNA layer height of up to 92 A is determined on the electrochemically functionalized diamonds. Based on the layer thickness, the DNA chains are tilted under the angle of 31 degrees . The morphology of the DNA layers exhibits long-range (30-50 nm) undulations of 20 A in height and a nanoroughness of 8 A. Using Hertz's model for calculating the contact area of the AFM tip on a DNA layer and a geometrical model of DNA arrangement on diamond yields the DNA density on diamonds of 6 x 10(12) cm(-2) on both photochemically and electrochemically functionalized diamonds. The structure of these dense DNA layers is not significantly influenced by variations in buffer salinity of 1-300 mM NaCl. DNA molecules can be removed from the diamond surface by contact-mode AFM with forces >or= 45 nN and >or= 76 nN on photochemically and electrochemically functionalized diamonds, respectively, indicating that DNA is bonded covalently and stronger on diamond than on gold substrates. The DNA arrangement and bonding strength are similar on oxidized diamond surfaces when using an electrochemical process. On oxidized surfaces after photochemical processing, DNA is bonded noncovalently as deduced from the removal force < 6 nN. The presence of hybridized DNA as well as the selective removal of DNA by AFM scanning are corroborated by fluorescence microscopy.     

Sorption of nitrogen-containing aromatic compounds on ultradispersed diamonds

Adsorption of a number of aniline and pyridine derivatives from water-acetonitrile solution on ultradispersed diamonds was investigated using dynamic sorption method. It was shown that the nature of functional substitutes and their position in molecules of nitrogen-containing compounds of pyridine and aniline have a pronounced effect on adsorption on the surface of ultradispersed diamonds. The dependence of chromatographic sorbate retention on the content of mobile phase could be described by a curve with a minimum. Such nonlinear relationship was explained by the change in the ratio of contribution of specific and non-specific interaction to the sorbate retention that was observed on varying the volume content of an organic component in mobile phase. The influence of temperature on sorption of pyridine and aniline derivatives on ultradisperesed diamonds was investigated. The changes in enthalpy and entropy factors of competitive sorption of sorbates were determined.     

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。     

Diamonds are a chemist's best friend: diamondoid chemistry beyond adamantane

Marilyn Monroe knew that "diamonds are a girl's best friend" but, in the meantime, many chemists have realized that they are also extremely attractive objects in contemporary chemistry. The chemist's diamonds are usually quite small (herein: nanometer-sized "diamondoids") and as a result of their unique structure are unusual chemical building blocks. Since lower diamondoids (up to triamantane) have recently become available in large amounts from petroleum and higher diamondoids (starting from tetramantane) are now also accessible from crude oil new research involving them has begun to emerge. Having well-defined structures makes these cage compounds so special compared to other nanometer-scale diamonds. Selective and high-yielding synthetic approaches to the functionalization of diamondoids gives derivatives that can find applications in, for example, polymers, coating materials, drugs, and molecular electronics.     

Positron beam investigations of natural cubic and coated diamonds

Positron beam and 2D-ACAR investigation of cubic and coated diamonds are reported. In type IIA diamonds, positrons are mostly trapped in vacancies in the carbon lattice; in type Ia diamonds, two main defect-related annihilation sites are nitrogen-vacancy complexes (H2, H3) and the vicinity of split interstitial atoms. No correlation between principal nitrogen defects and annihilation rate was found. PAS data indicate the presence of a significant amount of vacancies in all studied diamonds, which increases the rate of nitrogen aggregation. It is shown that pressurised fluid inclusions may serve as a positron trap, giving rise to the long component in the lifetime spectra.     

Tracking nitrogen-to-nickel ratio and prevalent paramagnetic species in synthetic diamonds by electron spin resonance at 90 K

Nitrogen and nickel are the main impurities in the type Ib synthetic diamonds obtained under high pressure and high temperature conditions using nickel-containing catalysts. Nitrogen enters the synthesized diamond from the air. The nickel/nitrogen ratio for the two types of diamonds, obtained with and without an aluminum getter that prevents the diamond crystal lattice from nitrogen penetration, was studied by electron spin resonance at 90 K.     

Transport through a mixed-valence molecular transistor in the sequential-tunneling regime: Theoretical insight from the two-site Peierls-Hubbard model

Transport through a mixed-valence system in the sequential-tunneling region is investigated using the master equation method and a simple two-site Peierls-Hubbard model that includes electron-phonon (e-p) coupling, electron hopping, and electron-electron (e-e) repulsion. The characteristics of Coulomb diamonds in the conductance spectra under three regimes are discussed. In the regime of zero e-p coupling, we found that the widths of Coulomb diamonds are dominated by the competition of electron-hopping and Coulomb repulsion. In the regime of weak and intermediate e-p coupling, by virtue of the normal-mode transformation we found that coupling to the symmetric-mode decreases the widths of Coulomb diamonds. In the regime of strong e-p coupling, an analytical expression for the widths of Coulomb diamonds can be derived using the small polaron transformation. The derived formula provides a new way to estimate e-e interactions and e-p couplings experimentally.     

13C NMR spectroscopy in diamonds using dynamic nuclear polarization

In diamonds unpaired electrons associated with nitrogen impurities can be used to enhance the ¹³C NMR signal via the solid-state effect. ¹³C spectra of three natural and two synthetic diamonds are shown that were obtained in this manner in 10–30 min.     

Ion chromatographic investigation of the ion-exchange properties of microdisperse sintered nanodiamonds

The possibility of using sintered diamonds as a stationary phase in ion chromatography has been evaluated. Bare sintered synthetic nanodiamonds demonstrated the properties of a weak cation-exchanger. The observed ion-exchange selectivity is similar to carboxylic type cation-exchangers. The regularities of retention of alkali, alkaline-earth and transition metal ions on a column packed with sintered nanodiamonds in dilute nitric acid were studied and the occurrence of chelating properties was noted. For the first time chromatographic separations of model mixtures of cations on diamonds have been obtained.     

Industrial Synthesis of Ultradisperse Detonation Diamonds and Some Fields of Their Use

The cluster nature of detonation-synthesized ultradisperse diamonds (UDD) is considered. The industrial cycle employed for obtaining ultradisperse diamonds is described, with different variations of this process and the basic principles of design of the necessary equipment noted. Priority product areas and advantages of use of ultradisperse diamonds in metal-diamond electrochemical coatings and polymer-diamond composites are discussed in detail.     

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.