金钢石的制备研究

本文研究了两种不同质异构体石墨—金刚石的转化条件，以及在实验室现有条件下，利用石墨材料制备金刚石颗粒的具体方法和试验结果。     

A Three-Dimensional Two-Phase Model for Thermal Plasma Chemical Vapor Deposition with Liquid Feedstock Injection

In this paper, a comprehensive model for thermal plasma chemical vapor deposition (TPCVD) with liquid feedstock injection is documented. The gas flow is assumed to be steady, of a single temperature. Radiation and charged species contributions are excluded, but extensive homogeneous and heterogeneous chemistry is included. The liquid phase is traced by considering individual droplets. Discussion on the model's application to diamond production from acetone in a hydrogen–argon plasma is included. The major conclusions are: (1) Liquid injection possesses a capability to deliver the hydrocarbon precursor directly onto the deposition target. (2) For the case of complete evaporation of the droplet before reaching the substrate, the deposition rate is similar to that obtained with gaseous precursors. (3) The computational results compare well with experimental data. The modeling results can be used to optimize the injection parameters with regard to the deposition rate.     

Selective Electroanalytical Assay for Cysteine at a Boron Doped Diamond Electrode

The electrochemical oxidation of the cysteine‐quinone adduct has been examined as a means of providing an electroanalytical cysteine specific detection protocol. The appliance of square‐wave voltammetry allowed 0.5 μM as a limit of detection. The effects of various biologically relevant interferences including other thiols were studied and found to present no change in the voltammetric profile. The practical applicability and efficiency of the methodology was probed through the determination of cysteine concentration in growth tissue medium.     

Whitehead test modules

A (right -) module is said to be a Whitehead test module for projectivity (shortly: a p-test module) provided for each module , implies is projective. Dually, i-test modules are defined. For example, is a p-test abelian group iff each Whitehead group is free. Our first main result says that if is a right hereditary non-right perfect ring, then the existence of p-test modules is independent of ZFC + GCH. On the other hand, for any ring , there is a proper class of i-test modules. Dually, there is a proper class of p-test modules over any right perfect ring.

A non-semisimple ring is said to be fully saturated (-saturated) provided that all non-projective (-generated non-projective) modules are i-test. We show that classification of saturated rings can be reduced to the indecomposable ones. Indecomposable 1-saturated rings fall into two classes: type I, where all simple modules are isomorphic, and type II, the others. Our second main result gives a complete characterization of rings of type II as certain generalized upper triangular matrix rings, . The four parameters involved here are skew-fields and , and natural numbers . For rings of type I, we have several partial results: e.g. using a generalization of Bongartz Lemma, we show that it is consistent that each fully saturated ring of type I is a full matrix ring over a local quasi-Frobenius ring. In several recent papers, our results have been applied to Tilting Theory and to the Theory of -modules.

     

Resistance to Surfactant and Protein Fouling Effects at Conducting Diamond Electrodes

Boron‐doped diamond thin‐film electrodes display negligible fouling effects in the presence of high levels of surface‐active materials, including proteins. Dramatic improvements in the stability of the analyte response (compared to common glassy carbon and carbon paste electrodes) are illustrated using bovine serum albumin (BSA), gelatin, and Triton X‐100 in connection with repetitive square‐wave voltammetric (SWV) measurements. The voltammetric response of ascorbic acid at the diamond electrode exhibits negligible shifts in peak potentials and minimal depressions of current signals over a wide range of surfactant concentrations (0–750 ppm). For example, the diamond electrode exhibited 70, 50 and 60 mV potential shifts for 10 repetitive voltammetric scans in the presence of 100 ppm BSA, gelatin and Triton X‐100, respectively, compared to 120, 190, and 280 mV shifts observed at the glassy carbon electrode. Furthermore, only 4.3 and 6.2% of the initial current decays were observed in the presence of 100 ppm Triton X‐100 and gelatin, respectively (compared to 45.2 and 34.4% diminutions at the glassy carbon electrode). Such improved performance was also confirmed from the SWV measurements of uric acid, dihydroxyphenylacetic acid, and catechol. The greatly improved resistance to surfactant interference reflects the fact that the as‐grown diamond thin film, composed of oxide‐free and hydrogen‐terminated surface, has a relatively lower surface energy and minimal electrostatic attributes, either specific or general, so that little adsorption of surface‐active agents occurs. The topographic AFM images of the diamond electrode surface confirm a negligible BSA fouling effect after repetitive SWV measurements. Such enhanced antifouling features make diamond electrodes very attractive for numerous real‐life electroanalytical applications.     

Direct electrochemical assay of glucose using boron-doped diamond electrodes

We report linear sweep and square wave voltammetric studies on glucose oxidation at boron-doped diamond (BDD) electrodes in an alkaline medium in efforts to evaluate the techniques for electrochemically assaying glucose. The bare BDD electrode showed good linear responses to glucose oxidation for a concentration range from 0.5 to 10 mM glucose, which well encompasses the physiological range of 3-8 mM. The BDD electrodes did not experience interferences from ascorbic acid or uric acid during glucose detection. This method, when applied to real blood samples, gave results similar to those obtained by a commercial glucose monitor.     

Diamond paste-based electrodes for determination of Cr(III) in pharmaceutical compounds

A new class of monocrystalline diamond paste-based electrodes is proposed for the determination of chromium(III) at trace levels in vitamins. Three types of monocrystalline diamond—natural diamond 1 (natural diamond), synthetic diamond 50 (synthetic-1), and synthetic diamond 1 (synthetic-2)—were used for electrode construction. The linear concentration ranges are between 10^–10 and 10^–8; 10^–9 and 10^–7, and 10^–10 to 10^–8 mol L^–1, with limits of detection of 10^–12, 10^–12, and 10^–11 mol L^–1, when natural diamond, synthetic-1, and synthetic-2, respectively, are used as electrode materials. For electrodes based on natural diamond and synthetic-1 it was found that Cr(III) yields a peak at about +0.275±0.015 V (vs. Ag/AgCl) within a predetermined positive potential range situated between +0.4 and +0.2 V, while for the electrode based on synthetic-2 the peaks are found at +0.300±0.015 V (vs. Ag/AgCl). The proposed method is reliable for the determination of chromium(III) at trace levels in two vitamin tablets (RSD<0.2%).     

Selective Detection of Dopamine and Its Metabolite,DOPAC, in the Presence of Ascorbic Acid Using Diamond Electrode Modified by the Polymer Film

The surface of boron‐doped diamond (BDD) electrode is modified by the polymer film for the first time. The cationic polymer film of N,N‐dimethylaniline (DMA) is electrochemically deposited on BDD electrode surface. This polymer (PDMA) film‐coated BDD electrode is used as a sensor which selectively detect dopamine (DA) in the presence of ascorbic acid (AA). This electrode also can detect both DA and its metabolite, 3,4‐dihydroxy phenyl acetic acid (DOPAC) in the presence of AA in the range of the physiological concentrations of these species. Favorable ionic interaction (i.e., electrostatic attraction) between the PDMA film and AA or DOPAC lowers their oxidation potentials and enhances the current response for AA and DOPAC compared to that at the bare electrode. The PDMA film also shows a hydrophobic interaction with DA and DOPAC. In cyclic voltammetric measurements, the PDMA film‐coated electrode can successfully separate the oxidation potentials for AA and DA coexisting in the same solution and the separation is about 200 mV. AA oxidizes at more negative potential than DA. In square‐wave voltammetry, the sensitivity of the PDMA film‐coated BDD electrode for DA in the presence of higher concentration of AA is higher than that of the PDMA film‐coated glassy carbon electrode. The hydrodynamic amperometric experiments confirm that the oxidation of AA is not affected by the oxidized product of DA and vice versa. So, unlike the bare electrode the catalytic oxidation of AA by the oxidized DA is eliminated at the PDMA film‐coated BDD electrode. The sensitivities of the modified electrode for AA, DA and DOPAC, which are present in the same solution with their physiological concentration ratios, are calculated to be 0.070, 0.363 and 0.084 μA μM^?1, respectively. The modified electrode exhibits a stable and sensitive response to DA.     

A novel zirconocene/ultradispersed diamond black powder supported catalytic system for ethylene polymerization

A novel carrier of ultradispersed diamond black powder (UDDBP) was used to support metallocene catalyst. Al₂O₃ was also used as carrier in order to compare with UDDBP. Supported catalysts for ethylene polymerization were synthesized by two different reaction methods. One way was direct immobilization of the metallocene on the support, the other was adsorption of MAO onto the support followed by addition of the metallocene. Four supported catalysts Cp₂ZrCl₂/UDDBP, Cp₂ZrCl₂/Al₂O₃, Cp₂ZrCl₂/MAO/UDDBP and Cp₂ZrCl₂/Al₂O₃/MAO were obtained. The content of the zirconium in the supported catalyst was determined by UV spectroscopy. The activity of the ethylene polymerization catalyzed by supported catalyst was investigated. The influence of Al/Zr molar ratio and polymerization temperature on the activity was discussed. The polymerization rate was also observed.     

Manganese detection in marine sediments: anodic vs. cathodic stripping voltammetry

Three different electroanalytical techniques for the detection of manganese in marine sediments are evaluated. The anodic stripping voltammetry of manganese at an in situ bismuth-film-modified boron-doped diamond electrode and cathodic stripping voltammetry at a carbon paste electrode are shown to lack the required sensitivity and reproducibility whereas cathodic stripping voltammetry at a bare boron-doped diamond electrode is shown to be reliable and selective with a limit of detection, from applying a 60 s accumulation period of 7.4 × 10⁻⁷ M and a sensitivity of 0.24 A M⁻¹. The method was used to evaluate the manganese content of marine sediments taken from Šibenik, Croatia.