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Electrochemical oxidation of chlorophenols at a boron-doped diamond electrode and their determination by high-performance liquid chromatography with amperometric detection.

Anodically pretreated diamond electrodes have been used for the detection of chlorophenols (CPs) in environmental water samples after high-performance liquid chromatographic (HPLC) separation. The anodization of as-deposited boron-doped polycrystalline diamond thin-film electrodes has enabled the stable determination of phenols over a wide concentration range. Prior to the HPLC analysis, a comparative study with ordinary glassy carbon, as-deposited diamond, and anodized diamond was made to examine the oxidative behavior of phenols by cyclic voltammety and flow injection analysis with amperometric detection. At anodized diamond electrodes, reproducible, well-defined cyclic voltammograms were obtained even at high CP concentration (5 mM), due to a low proclivity for adsorption of the oxidation products on the surface. In addition, after prolonged use, the partially deactivated diamond could be reactivated on line by applying a highly anodic potential (2.64 Vvs SCE) for 4 min, which enabled the destruction of the electrodeposited polymer deposits. Hydroxyl radicals produced by the high applied potential, in which oxygen evolution occurs, are believed to be responsible for the oxidation of the passivating layer on the surface. When coupled with flow injection analysis (FIA), anodized diamond exhibited excellent stability, with a response variability of 2.3% (n = 100), for the oxidation of a high concentration (5 mM) of chlorophenol. In contrast, glassy carbon exhibited a response variability of 39.1%. After 100 injections, the relative peak intensity, for diamond decreased by 10%, while a drastic decrease of 70% was observed for glassy carbon. The detection limit obtained in the FIA mode for 2,4-dichlorophenol was found to be 20 nM (S/N = 3), with a linear dynamic range up to 100 microM. By coupling with the column-switching technique, which enabled on-line preconcentration (50 times), the detection limit was lowered to 0.4 nM (S/N = 3). By use of this technique, anodized diamond electrodes were demonstrated for the analysis of CPs in drainwater that was condensed from the flue gas of waste incinerators.

Boron↗

Comparison of cutting rates among single-patient-use and multiple-patient-use diamond burs.

PURPOSE: The purpose of this study was to compare the volumetric cutting rates of 6 cylindrical-shaped single-patient-use and 2 cylindrical-shaped multiple-patient-use diamond burs using a machinable ceramic material. The degree of wear among burs from each type was also compared using scanning electron microscopy. MATERIALS AND METHODS: Six types of single-patient-use diamond burs and 2 types of multiple-patient-use diamond burs with similar cylindrical shape and dimensions were selected. Five burs of each type were evaluated using a high-speed handpiece mounted on a custom testing device. Using a 6-mm cutting length of each bur, 20 cuts, each 12.2-mm long, were made at exactly one half the diameter of the bur. Mean volumetric cutting rate through the ceramic substrate for Cuts 1 through 20 was calculated for each bur type in cubic millimeters prepared per second. A repeated measures analysis of variance (alpha = 0.05) and post hoc one-way analysis of variance with Scheffé's test was used to compare cutting rates among bur types for Cuts 2, 10, and 20. The topography of one bur from each group was evaluated with scanning electron microscopy after Cut 2 and again after Cut 20. RESULTS: For Cut 2, the mean cutting rates ranged from 3.3 to 5.3 mm3/s. The mean cutting rates for all bur types decreased approximately 20% by Cut 20. Bur type and length of use significantly influenced cutting rate (p < .002). However, only one type of single-patient-use diamond bur had a significantly lower mean cutting rate after Cut 2, 10, and 20, compared with other single- and multiple-patient-use diamond burs. Scanning electron microscopy showed all burs exhibited wear of diamond particles, as well as loss of diamond particles and binder. CONCLUSIONS: Five of six single-patient-use diamond burs had mean volumetric cutting rates through a ceramic that were similar to 2 multiple-patient-use diamonds for as many as 20 cuts. The gradual reduction in cutting rate during the 20 cuts for all bur types was a result of bur wear.

Analysis of Variance↗

Diamond coated total hip replacements.

Diamond has many superior, desired characteristics of implant materials such as low friction, high wear and corrosion resistance, and well bonding surface to bone. The potential of diamond for total hip replacement implants was studied in the form of amorphous diamond coatings on conventional metal implant materials. Amorphous diamond coatings (sp3 bonding fraction 80%, thickness 0.2 to 10 microns) were deposited on stainless steel AISI316L, Ti6A14V, and CoCrMo alloys using filtered pulsed plasma are discharge method. Superior attachment of coatings to the implant materials was achieved by using high energy plasma beams to deposit amorphous diamond and proper intermediate layers. Previously it was shown that these coatings are biocompatible causing no local tissue reactions. Tribologic studies using a pin on disk apparatus with coated or uncoated implant materials in 1 wt.% NaCl distilled water were performed. A simplified hip joint simulator was used for preliminary testing of metal on polyethylene and metal on metal artificial hip joints modified with amorphous diamond coating. The average coefficients of friction were typically in the range of 0.03 to 0.11 for amorphous diamond coated materials. In the case of metal on metal hip implants, the average friction during initial running in period was improved (coefficient of friction = 0.07) compared with the same metal on metal pair (coefficient of friction = 0.22) and sliding was significantly smoother. In pin on disk wear tests, the average wear factors obtained were 140.10(-6), 5.0.10(-6), and << 0.1.10(-6) mm3/Nm for the pairs of AISI316L, CoCrMo, and the same materials with amorphous diamond coating. The corrosion rates of these implant materials in 10 wt.% HCl solution were decreased by a factor of 10,000 to 15,000 and any damage of the coatings was not observed in 6 months. The results of the tests show that in all the combinations studied, amorphous diamond coating improved definitely the wear and corrosion resistance compared with the uncoated materials.

Biocompatible Materials↗

Field emission from diamond particles studied by scanning field emission microscopy.

Field emission properties from diamond particles (DPs) are studied. The DPs with thin chemically vapor deposited (CVD) diamond overcoat, dispersed onto metal substrate, essentially exhibit negative electron affinity (NEA). Field emission, approximately 1mA/cm(2) under a macroscopic electric field of 3.5kV/mm are observed. Microscopic electrical properties were studied by scanning tunneling microscopy/spectroscopy. Most parts of the DP surface exhibit narrow gap and p-type characteristics. The localized regions, which have wide gap like bulk diamond properties, are randomly distributed near the top of DP. The field emission current distribution depicted by scanning field emission microscopy (SFEM) show that the electron emission is originating from a localized region on the selected DPs. We found, through SFEM measurement, some favorable field emission spots ("hot spots") where measured emission current is several orders higher than that of the other DPs ("normal spots"). Field emission spectroscopy (FES) results suggest that a poorly conducting layer is present along the electron path from the metal electrode to vacuum.We propose two models for field emission from "hot spots", which involve two main mechanisms. One is electron injection from the metal substrate to the DP, which is attributed to the electric field enhancement at intrinsic non-doped diamond (i-diamond) layer sandwiched between the metal substrate and the surface conductive layer (p-diamond) of the CVD diamond overcoat on the DP. The other is electron emission at the top site of NEA DP through the local i-diamond region or the depletion region of the p-diamond, which is caused by the applied electric field.

Journal Article↗

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 1mu (natural diamond), synthetic diamond 50mu (synthetic-1), and synthetic diamond 1mu (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%).

Chromium↗

Effectiveness of diamond-impregnated felt wheels for polishing a hybrid composite.

The effectiveness of diamond-impregnated felt wheels for polishing the surfaces of a fine-particle hybrid composite was studied in relation to different finishing methods. Standardised composite specimens were finished with one or a series of two or three finishing diamonds (particle size 30, 15 and 8 microns), one or two tungsten carbide finishing burs (12- and 30-fluted) or with a finishing diamond followed by a tungsten carbide bur. The final polishing of all specimens was done with the diamond-impregnated felt wheel Diafix alpha. Treatment with Sof-Lex discs after the use of a finishing diamond served as a polishing standard for comparison. Evaluation of the final surfaces was done with profilometry and by scanning electron microscopy. The profilometric results showed that the type of pretreatment was decisive for the quality of the final polishing. Nearly all surfaces polished by the diamond-impregnated felt wheels were smoother than those treated by the flexible discs (P < 0.01). The lowest roughness data were recorded following a pretreatment with a finishing diamond and a tungsten carbide finishing bur. After appropriate pretreatment, the hybrid composite surface was sufficiently polished with the diamond-impregnated felt wheels.

Analysis of Variance↗

Diamond coated dental bur machining of natural and synthetic dental materials.

Diamond coatings are attractive for cutting processes due to their high hardness, low friction coefficient, excellent wear resistance and chemical inertness. The application of diamond coatings on cemented tungsten carbide (WC-Co) burs has been the subject of much attention in recent years in order to improve cutting performance and tool life. WC-Co burs containing 6% Co and 94% WC with an average grain size 1-3 micron were used in this study. In order to improve the adhesion between diamond and the bur it is necessary to etch away the surface Co to prepare it for subsequent diamond growth. Hot filament chemical vapour deposition (H.F.C.V.D.) with a modified vertical filament arrangement has been employed for the deposition of diamond films. Diamond film quality and purity has been characterised using scanning electron microscopy (S.E.M.) and micro-Raman spectroscopy. The performance of diamond coated WC-Co burs, uncoated WC-Co burs, and diamond embedded (sintered) burs have been compared by drilling a series of holes into various materials such as human teeth, and model tooth materials such as borosilicate glass and acrylic. Flank wear has been used to assess the wear rates of the burs when machining natural and synthetic dental materials such as those described above.

Dental Materials↗

Cutting effectiveness of diamond instruments subjected to cyclic sterilization methods.

The effect of repeated sterilization on the cutting effectiveness of one brand of rotary dental diamond cutting instruments was measured. Four groups of five diamond burs were sterilized by four methods: (1) sterilization with a chemical agent (Sporicidin); (2) steam under pressure (autoclave); (3) dry heat (Dri-Clave); or (4) chemical vapor (Chemiclave). Each group of diamond instruments made a timed cut in a ceramic block. This cut and all subsequent cuts were measured and were used to determine a baseline cutting effectiveness. Each group of diamond burs was then ultrasonically cleaned, sterilized, and another cut was made. At the end of 10 cycles there was no difference in cutting efficiency of the dental diamond instruments. However, there are differences in the cutting efficiency of individual diamond instruments. The SEM evaluation made prior to cutting and at the end of the 10 cycles of sterilization demonstrated that diamond wear was similar in all groups and that little diamond particle loss occurred in any group.

Analysis of Variance↗

Adhesion, cytoskeletal architecture and activation status of primary human macrophages on a diamond-like carbon coated surface.

Diamond-like carbon is a promising surface coating for biomedicinal implants like coronary stents or hip joints. Before widespread clinical use of this material, its biocompatibility has to be thoroughly assessed. Cells likely to encounter a diamond-like coated implant in the human body are cells of the monocytic lineage. Their interaction with the diamond-like carbon coated surface will probably critically influence the fate of the implant, as monocytes orchestrate inflammatory reactions and also affect osseointegration of implants. We therefore investigated adhesion, cytoarchitecture and activation status of primary human monocytes and their differentiated derivatives, macrophages, on diamond-like coated glass coverslips using immunofluorescence technique. We show that adhesion of primary monocytes to a diamond-like-coated coverslip is slightly, but not significantly, enhanced in comparison to uncoated coverslips, while the actin and microtubule cytoskeletons of mature macrophages show a normal development. The activation status of macrophages, as judged by polarization of the cell body, was not affected by growth on a diamond-like carbon surface. We conclude that diamond-like carbon shows good indications for biocompatibility to blood monocytes in vitro. It is therefore unlikely that contact with a diamond-like carbon coated surface in the human body will elicit inflammatory signals by these cells.

Biocompatible Materials↗

Electron transfer from diamond electrodes to heme peptide and peroxidase.

Direct electron transfer from boron-doped diamond electrodes to heme undecapeptide and horseradish peroxidase (HRP) was examined and evaluated for the application to H2O2 biosensors. As-grown and oxygen plasma-treated diamond electrodes on which heme peptide is adsorbed exhibited cathodic current responses to H2O2 on the basis of the direct electron transfer. In a comparative study of carbon electrodes on which heme peptide was adsorbed, an oxygen plasma-treated diamond electrode exhibited responses comparable with those of an edge-oriented pyrolytic graphite (EOPG) electrode, despite much smaller roughness. However, electron transfer to compounds I and II of HRP from the diamond electrodes was much slower than that from EOPG or glassy carbon, suggesting that the pi electrons of an sp2 carbon may play an important role in the direct electron transfer to the heme moiety of HRP. To examine the applicability of heme peptide-modified diamond electrodes to oxidase-based biosensors, anodic current responses of the oxygen plasma-treated diamond electrode to possible interfering agents, ascorbic acid and uric acid, were examined and compared with those of EOPG. Since the diamond electrode exhibited much less sensitivity to those interfering agents, the heme peptide-modified diamond electrode should be a promising H2O2 biosensor for the application to oxidase-based biosensors.

Diamond↗

Investigating the functionality of diamond-like carbon films on an artificial heart diaphragm.

In this study, the authors used diamond-like carbon film to coat the ellipsoidal diaphragm (polyurethane elastomer) of artificial hearts. The purpose of such coatings is to prevent the penetration of hydraulic silicone oil and blood through the diaphragm. To attach diamond-like carbon film uniformly on the diaphragm, the authors developed a special electrode. In estimating the uniformity of the diamond-like carbon film, the thickness was measured using a scanning electron microscope, and the characteristics of the diamond-like carbon film was investigated using infrared spectroscopy, Ar-laser Raman spectrophotometer, and x-ray photoelectron spectrometer. Also, to estimate the penetration of silicone oil through the diaphragm, in vitro testing was operated by alternating the pressure of silicone oil for 20 days. The authors were able to successfully attach uniform deposition of diamond-like carbon film on the ellipsoidal diaphragm. In this in vitro test, diamond-like carbon film was proven to have good stability. The amount of silicone oil penetration was improved by one-third using the diamond-like carbon film coating compared with an uncoated diaphragm. It is expected that through the use of the diamond-like carbon film, the dynamic compatibility of an artificial heart diaphragm will increase.

Carbon↗

Enamel subsurface damage due to tooth preparation with diamonds.

In clinical tooth preparation with diamond burs, sharp diamond particles indent and scratch the enamel, causing material removal. Such operations may produce subsurface damage in enamel. However, little information is available on the mechanisms and the extent of subsurface damage in enamel produced during clinical tooth preparation. The aim of this study, therefore, was to investigate the mechanisms of subsurface damage produced in enamel during tooth preparation by means of diamond burs, and to examine the dependence of such damage on enamel rod orientation, diamond particle size, and removal rate. Subsurface damage was evaluated by a bonded-interface technique. Tooth preparation was carried out on two enamel rod orientations, with four clinical diamond burs (coarse, medium, fine, and superfine) used in a dental handpiece. The results of this study showed that subsurface damage in enamel took the form of median-type cracks and distributed microcracks, extending preferentially along the boundaries between the enamel rods. Microcracks within individual enamel rods were also observed. The median-type cracks were significantly longer in the direction parallel to the enamel rods than perpendicular to the rods. Preparation with the coarse diamond bur produced cracks as deep as 84 +/- 30 microns in enamel. Finishing with fine diamond burs was effective in crack removal. The crack lengths in enamel were not significantly different when the removal rate was varied. Based on these results, it is concluded that subsurface damage in enamel induced by tooth preparation takes the form of median-type cracks as well as inter- and intra-rod microcracks, and that the lengths of these cracks are sensitive to diamond particle size and enamel rod orientation, but insensitive to removal rate.

Dental Enamel↗

TEM and HREM of diamond crystals grown on Si tips: structure and results of ion-beam-treatment.

Diamond single crystals were grown on the silicon whiskers by a hot filament chemical vapor deposition technique at the filament temperature about 2100 degrees C and the temperature of support 800 degrees C. Specimens were examined by SEM, TEM, HRTEM and SAED. When the filament temperature was about 1900 degrees C globular polycrystalline diamond particles were grown. At a support temperature more then 800 degrees C SiC nanoparticles were formed. To investigate the ion etching process of the silicon tip/diamond system, tips were treated with an Ar(+) beam with energy up to 30 kV. The results depend on fluence: at 4 x 10(18)ion/cm(2) diamonds and partially Si tips were destroyed, amorphous layer was formed (sometimes with nanometric size fragments of diamond); at 1 x 10(18)ion/cm(2) sharpened diamonds (radius of curvature about 20 nm) covered with amorphous layer (radius about 80 nm) probably with nanoclusters of diamond were observed; at 4.4 x 10(17) ion/cm(2) there was no visible tip sharpening but formation of amorphous thick layer occurred. The emission characteristics of Si tips covered with diamond were improved due to ion treatment. Since such tips in our case were covered with amorphous layer containing nanometric size fragments of diamond, we suppose this layer is responsible for electron emission improvement.

Journal Article↗

Superconductivity in diamond.

Diamond is an electrical insulator well known for its exceptional hardness. It also conducts heat even more effectively than copper, and can withstand very high electric fields. With these physical properties, diamond is attractive for electronic applications, particularly when charge carriers are introduced (by chemical doping) into the system. Boron has one less electron than carbon and, because of its small atomic radius, boron is relatively easily incorporated into diamond; as boron acts as a charge acceptor, the resulting diamond is effectively hole-doped. Here we report the discovery of superconductivity in boron-doped diamond synthesized at high pressure (nearly 100,000 atmospheres) and temperature (2,500-2,800 K). Electrical resistivity, magnetic susceptibility, specific heat and field-dependent resistance measurements show that boron-doped diamond is a bulk, type-II superconductor below the superconducting transition temperature T(c) approximately 4 K; superconductivity survives in a magnetic field up to Hc2(0) > or = 3.5 T. The discovery of superconductivity in diamond-structured carbon suggests that Si and Ge, which also form in the diamond structure, may similarly exhibit superconductivity under the appropriate conditions.

Journal Article↗

A comparison of the sensitivity of the InPouch TV, Diamond's and Trichosel media for detection of Trichomonas vaginalis.

OBJECTIVE: This study compared the ability of three culture media (InPouch TV, Diamond's, and Trichosel) to support the growth of clinical isolates of Trichomonas vaginalis and their relative sensitivity for detection of the organism. METHODS: The majority of the clinical isolates were obtained from two San Francisco Bay Area clinics. T vaginalis was subcultured in 4 ml of one of the InPouch, Diamond's, or Trichosel media for 24-48 hours before evaluation. Twenty isolates were initially cultured in the InPouch test, 13 with Diamond's, and 10 with Trichosel. A haemocytometer was used to measure the initial concentrations of the organisms. Then serial dilutions were made in saline to yield approximately 2.0 x 10(4), 2.0 x 10(3), and 2.0 x 10(2) motile T vaginalis per ml. A 30 microliter inoculum from each dilution was transferred into 4 ml aliquots of the three media (387 individual tests, 43 x 3 dilutions x 3 media). Microscopic examinations for viable trichomonads were made at 24, 48, and 96 hours. Microscopy was through the pouch wall for the InPouch medium, and through a cover slipped slide with one drop of Diamond's and Trichosel media. RESULTS: At 24 hours, the InPouch demonstrated 84/129 positive, Diamond's 23/129, and Trichosel 18/129. At 48 hours, an accumulative positive rate for the InPouch was 98/129, for Diamond's 55/129, and Trichosel 47/129. At 96 hours the total positives for each test were 112/129 for the InPouch, 78/129 for Diamond's, and 74/129 for Trichosel. CONCLUSIONS: The InPouch TV test was significantly more sensitive than either Diamond's or Trichosel (at 0.01 level of significance, pInPouch > pDiamond's; pInPouch > pTrichosel on all three dilutions at 24, 48, and 96 hours). This increased sensitivity was the result of either a reduced generation time or the larger volume of media examined microscopically.

Animals↗

Human monocytes stimulation by particles of hydroxyapatite, silicon carbide and diamond: in vitro studies of new prosthesis coatings.

Aseptic loosening due to wear and debris formation constitutes the major problem in longevity of joint replacements. Diamond coated onto the prosthesis surface may reduce wear, owing to its excellent tribological properties. A thin diamond coating may be brittle, and we plan eventually to reinforce it with silicon carbide whiskers (SiC). In the present study we compared particles of diamond, SiC and hydroxyapatite (HA) in serum-free cultures of human monocytes. All particles were found to be phagocytozed, and monocyte morphology changed except after the ingestion of diamond. Interleukin-1 beta production was increased on average 30-fold and 38-fold in cultures exposed to HA and SiC, respectively, compared to control and diamond cultures (n = 6). Addition of the phagocytosis inhibitor cytochalasin B inhibited the morphological changes of the monocytes and reduced interleukin-1 beta production. In some experiments particles of polymethylmethacrylate were also included, and the interleukin-1 beta stimulation was in the same range as after HA and SiC stimulation. The results show that diamond particles in serum-free monocyte culture are inert, while SiC and HA have a stimulatory effect comparable to polymethylmethacrylate. With its excellent tribological and biocompatible properties, future studies with diamond coating are warranted.

Biocompatible Materials↗

Predicting facile epoxidation of the diamond (100) surface by dioxiranes and subsequent ring-opening reactions with nucleophiles.

By means of density functional theory coupled with effective cluster models, we have theoretically predicted the viability of epoxidation of the diamond (100) surface by organic dioxiranes. In addition, subsequent ring-opening reactions of the as-formed epoxide surface species with some nucleophiles, including water, ammonia, and alcohol, have also been explored. The facile epoxidation of diamond (100) by dioxiranes presents a new alternative for oxidation of the diamond (100) surface. More importantly, the as-formed epoxide-like surface species would be a useful springboard for further functionalizations of the diamond surface given the well-known abundant chemistry of organic epoxides. Therefore, this approach provides another new route to chemical functionalization of the diamond surface, which is potentially useful for leading to the improvement of diamond behavior and constructing new hybrid diamond-based materials for wide potential applications in many fields. In perspective, implications for other theoretical work are also discussed.

Diamond↗

Superior wear resistance of aggregated diamond nanorods.

The hardness of single-crystal diamond is superior to all other known materials, but its performance as a superabrasive is limited because of its low wear resistance. This is the consequence of diamond's low thermal stability (it graphitizes at elevated temperature), low fracture toughness (it tends to cleave preferentially along the octahedral (111) crystal plains), and large directional effect in polishing (some directions appear to be "soft", i.e., easy to abrade, because diamond is anisotropic in many of its physical properties). Here we report the results of measurements of mechanical properties (hardness, fracture toughness, and Young's modulus) of aggregated diamond nanorods (ADNRs) synthesized as a bulk sample. Our investigation has shown that this nanocrystalline material has the fracture toughness 11.1 +/- 1.2 MPa.m(0.5), which exceeds that of natural and synthetic diamond (that varies from 3.4 to 5.0 MPa.m(0.5)) by 2-3 times. At the same time, having a hardness and Young's modulus comparable to that of natural diamond and suppressed because of the random orientation of nanorods "soft" directions, ADNR samples show the enhancement of wear resistance up to 300% in comparison with commercially available polycrystalline diamonds (PCDs). This makes ADNRs extremely prospective materials for applications as superabrasives.

Compressive Strength↗