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Selective voltammetric and amperometric detection of uric acid with oxidized diamond film electrodes.

Electrochemically anodized diamond film electrodes were used for selective detection of uric acid (UA) in the presence of high concentrations of ascorbic acid (AA) by differential pulse voltammetry and chronoamperometry. Because the oxidation peak potential for AA is approximately 450 mV more positive than that for UA at anodized diamond electrodes, UA can be determined with very good selectivity. By use of chronoamperometry, linear calibration curves were obtained for UA over the concentration range up to 1 x 10(-6) M in 0.1 M HClO4 solution, with the lowest experimental value measured being 5 x 10(-8) M. This is consistent with the fact that a statistical analysis of the calibration curve yielded a detection limit of 1.5 x 10(-8) M (S/N = 3). AA in less than 20-fold excess does not interfere. The practical analytical utility of the method is demonstrated by the measurement of UA in human urine and serum without any preliminary treatment.

Diamond↗

Surface-modified diamond nanoparticles as antigen delivery vehicles.

Recognition of antigens by immunocompetent cells involves interactions that are specific to the chemical sequence and conformation of the epitope (antigenic determinant). Adjuvants that are currently used to enhance immunity to antigens tend to either alter the antigen conformation through surface adsorption or shield potentially critical determinants, e.g., functional groups. It is demonstrated here that surface-modified diamond nanoparticles (5-300 nm) provide conformational stabilization, as well as a high degree of surface exposure to protein antigens. By enhancing the availability and activity of the antigen in vivo, a strong, specific immune response can be elicited. Results are demonstrated for mussel adhesive protein (MAP), a substance for which conventional adjuvants have proven only marginally successful in evoking an immune response. Surface-modified diamond nanoparticles as antigen delivery vehicles are a novel example of the exciting marriage of materials science, chemistry, and biology.

Animals↗

Electron-transfer doping on a (001) surface of diamond: quantum mechanical study.

The electron-transfer process from an H-terminated diamond (001) surface to an acidic water adlayer, leaving an induced p-type doping in the carbon layers, has been studied using first-principal density functional theory (DFT). The effect of various oxygen-containing species adsorbed to the surface (in the form of an OH group and an oxygen atom in both the ether and ketone positions) on the possibility for electron transfer was also investigated. The results show that a perfect H-termination, as well as the presence of one OH group (equivalent to a surface coverage of approximately 8%), will give an electron transfer of 1.76 and 1.89 e, respectively. There will then be a transfer of electrons from the upper diamond valence band to the lowest unoccupied level in the adsorbate. A corresponding percentage of 8 (Oketone) and 17 (Oether) will effectively hinder the electron-transfer process from occurring.

Diamond↗

Interaction between co-deposited metals during stripping voltammetry at boron-doped diamond electrodes.

Electrochemical processes, which underlie the use of conductive diamond electrodes for the simultaneous detection of two or more metal ions in solution by anodic stripping voltammetry (ASV), have been investigated. The model analyte system studied contains the two metal species, Ag+(aq) and Pb2+(aq), and the experimental techniques employed include cyclic and square wave voltammetries, along with X-ray photoelectron spectroscopy and secondary electron microscopy. Although the bulk metallic forms of Ag and Pb are immiscible, several interactions in the system between the two metal species present are observed, which significantly influence the electrodeposition and electrodissolution processes which underlie ASV. The subsequent nucleation and growth of a given metal on the electrode surface is enhanced by the presence of the second metal on the surface. The encapsulation of one metal by the other, within the metal particulates that form on the electrode surface, significantly reduces the stripping yield at the potentials characteristic of the individual metals. The stripping potentials are also influenced by bonding interactions between deposited Ag and Pb, which broaden the characteristic stripping peaks in cyclic voltammetry, as well as producing underpotential deposition and stripping. Given these interactions, the extent to which ASV at diamond electrodes can be used to determine the solution concentrations of Ag+(aq) and Pb2+(aq) is considered.

Boron↗

The electrochemical oxidation of ammonia at boron-doped diamond electrodes exhibits analytically useful signals in aqueous solutions.

Boron-doped diamond electrodes are shown to exhibit well-defined analytically useful voltammetric signals for the electrochemical oxidation of ammonia in aqueous solutions in comparison to commonly used carbon based electrode substrates. Proof-of-concept is shown for the construction of a miniature amperometric ammonia gas sensor utilising conductive boron-doped diamond.

Ammonia↗

An in vitro study comparing root-end cavities prepared by diamond-coated and stainless steel ultrasonic retrotips.

AIM: This study compared the appearance of root-end cavity preparations and the time required to prepare them using prototype ultrasonic diamond-coated (DC) and stainless-steel (SS) retrotips. METHODOLOGY: In 12 maxillary and 12 mandibular molar teeth 48 root-end cavities were prepared ultrasonically in the palatal, mesio-buccal, distal and mesial root-ends using DC and SS retrotips, alternately. Replicas of the resected root tips and the root-end cavities were examined under a scanning electron microscope (SEM), recording (i) incidence and extent of dentine cracks (ii) minimum remaining thickness of the dentine walls and (iii) surface quality of the resected root-ends. The time taken to complete the preparation was also recorded. Means of these parameters were compared for both types of retrotips using nonparametric tests. RESULTS: No resected root-ends had cracks before preparation. However, after preparation one root-end cavity shaped by an SS retrotip had a microcrack visible at 23x magnification. Four and seven other root-ends had crazed surfaces in the DC and SS groups, respectively (P > 0.05). Remaining minimum dentine thickness was 0.56 +/- 0.28 mm and 0.71 +/- 0.24 for the DC and SS groups, respectively, and this difference was significant (P < 0.05). A root-end cavity in one specimen in the DC group was perforated. Preparation times ranged from 25 s to 361 s and were significantly lower for DC tips (P < 0.01) than the SS tips. The time required to prepare root-end cavities also differed between roots; root-end preparation in mandibular molars was more time consuming. CONCLUSIONS: A better quality surface was produced by the prototype diamond-coated retrotips, in less time than the SS retrotips, which in turn caused fewer cracks than previously reported. DC retrotips removed more dentine than SS retrotips and should therefore be used with care to avoid overpreparation or perforation.

Apicoectomy↗

Blackfan-Diamond anemia and dyserythropoietic anemia presenting with increased nuchal translucency at 12 weeks of gestation.

Blackfan-Diamond anemia is a congenital hypoplastic anemia with a birth prevalence of about 1 in 200,000, usually presenting in the first few months of life and commonly associated with cardiac, urogenital and digital anomalies. Congenital dyserythropoietic anemias are a group of rare congenital anemias characterized by ineffective erythropoiesis. We report on two cases of congenital fetal anemia, one with Blackfan-Diamond anemia and one with dyserythropoietic anemia, presenting with increased nuchal translucency at 12 weeks of gestation.

Adult↗

Engineering analysis of diamond-like carbon coated polymeric materials for biomedical applications.

Diamond-like carbon (DLC) films have received much attention recently owing to their properties, which are similar to diamond: hardness, thermal conductivity, corrosion resistance against chemicals, abrasion resistance, good biocompatibility, and uniform flat surface. Furthermore, DLC films can be deposited easily on many substrates for wide area coat at room temperature. DLC films were developed for applications as biomedical materials in blood contacting-devices (e.g., rotary blood pump) and showed good biocompatibility for these applications. In this study, we investigated the surface roughness by Atomic Force Microscopy (AFM) and Hi-vision camera, SEM for surface imaging. The DLC films were produced by radio frequency glow discharge plasma decomposed of hydrocarbon gas at room temperature and low pressure (53 Pa) on several kinds of polycarbonate substrates. For the evaluation of the relation between deposition rate and platelet adhesion that we investigated in a previous study, DLC films were deposited at the same methane pressure for several deposition times, and film thickness was investigated. In addition, the deposition rate of DLC films on polymeric substrates is similar to the deposition rate of those deposited on Si substrates. There were no significant differences in substrates' surface roughness that were coated by DLC films in different deposition rates (16-40 nm). The surface energy and the contact angle of the DLC films were investigated. The chemical bond of DLC films also was evaluated. The evaluation of surface properties by many methods and measurements and the relationship between the platelet adhesion and film thickness is discussed. Finally, the presented DLC films appear to be promising candidates for biomedical applications and merit investigation.

Anticoagulants↗

New amperometric biosensors based on diamond paste for the assay of L- and D-pipecolic acids in serum samples.

Monocrystalline natural diamond, L-amino acid oxidase (L-AAOD), D-amino acid oxidase (D-AAOD), and paraffin oil were used for the design of the modified diamond paste. The technique used for the direct voltammetric assay was differential pulse voltammetry (DPV) with applied potential pulse amplitude of 25 mV vs. Ag/AgCl. Using the new amperometric biosensors L-pipecolic acid (L-PA) and D-pipecolic acid (D-PA) were determined reliably from serum samples at 700 and 200 mV vs. Ag/AgCl, respectively, with low limits of detection.

Amino Acid Oxidoreductases↗

Infrared spectroscopy of dense clouds in the C-H stretch region: methanol and "diamonds."

High spectral resolution (nu/delta nu = 900) studies in the 3100-2600 cm-1 (3.2-3.9 microns) range are presented of the protostars NGC 7538 IRS 9, W33A, W3 IRS 5, and S140 IRS 1. This is the spectral region in which the fundamental C-H stretching vibrations of aliphatic hydrocarbons fall. Well-resolved absorption bands at about 2825 cm-1 (3.54 microns) and 2880 cm-1 (3.47 microns) were found superposed on the low-frequency wing of the strong O-H stretch feature. The 2880 cm-1 (3.47 microns) band, a new interstellar feature, is moderately strong in the spectra of all four objects studied. The 2825 cm-1 (3.54 microns) band, previously detected toward W33A, is also in the spectrum of NGC 7538 IRS 9. The relative strength of these two bands varies, showing that they are associated with two different carriers. On the basis of comparisons with laboratory spectra, the 2825 cm-1 (3.54 microns) band is assigned to methanol (CH3OH), in agreement with the earlier work of Grim et al. (1991). This assignment is further supported by a pair of weak absorptions centered at 2600 and 2540 cm-1 (3.85 and 3.94 microns) in the spectrum of W33A recently reported by Geballe (1991). These features compare very well with laboratory spectra of CH3OH/H2O ice mixtures. The CH3OH/H2O ratio derived from the 2825 cm-1 methanol band and the 3250 cm-1 (3.08 microns) H2O feature are 0.13 and 0.40 for NGC 7538 IRS 9 and W33A, respectively. These values are smaller than the ratios of 0.61 and 0.54 derived using the 1460 cm-1 (6.85 microns) band assigned to CH3OH and the 1665 cm-1 (6.00 microns) H2O band. These apparent discrepancies may be due to a combination of scattering effects within the molecular cloud, uncertainties associated with the baselines for the 2825 cm-1 feature, and the presence of other interstellar grain materials that absorb at 1460 cm-1 (6.85 microns). Nonetheless, after H2O, CH3OH is the most abundant known interstellar ice constituent. The new band at about 2880 cm-1 (3.47 microns) falls near the position for C-H stretching vibrations in tertiary carbon atoms. The strength of this feature, in combination with the lack of strong features associated with primary (-CH3) and secondary (-CH2-) carbon atoms, suggests that the carrier of the new feature has a diamond-like structure. We therefore tentatively attribute this new feature to interstellar "diamonds." The detection of this band in the spectra of all four dense molecular clouds suggests that the carrier is ubiquitous in dense clouds. Band-strength analysis indicates that a minimum of a few percent of the available cosmic carbon is tied up in this material.

Astronomical Phenomena↗

Dose rate dependence of a PTW diamond detector in the dosimetry of a 6 MV photon beam.

The dose rate dependence and current/voltage characteristics of a PTW Riga diamond detector in the dosimetry of a 6 MV photon beam have been investigated. Diamond detectors are radiosensitive resistors whose conductivity (i) varies almost in proportion to dose rate and (ii) is almost independent of bias voltage for a constant dose rate. At the recommended bias of +100 V, and also at +200 V, the detector is operating with incomplete charge collection due to the electron-hole recombination time being shorter that the maximum time for an electron to be collected by the anode. As dose rate is varied by changing FSD or depth (changing dose per pulse), detector current and dose rate are related by the expression i alpha Ddelta where delta is approximately 0.98. This manifests itself in an overestimate in percentage depth-dose at a depth of 30 cm of approximately 1% when compared to ionization chamber results. A similar sublinearity is seen when pulse repetition frequency is varied, indicating that the dependence is an on average rather than an instantaneous dose rate. The dose rate dependence is attributed to the reduction in recombination time as dose rate increases.

Diamond↗

Dosimetric characterization of silicon and diamond detectors in low-energy proton beams.

The dosimetric behaviour of a Scanditronix p-type silicon diode and a PTW natural diamond detector was studied in low-energy proton beams in the 8.3-21.5 MeV range. The properties investigated were linearity, reproducibility, dose rate dependence, energy and linear energy transfer (LET) dependence. The influence of detector thickness on the results of depth dose measurements was also demonstrated. A Markus parallel plate ionization chamber was used for reference dosimetry. Silicon diode and diamond detectors showed linearity at therapeutic dose level, reproducibility better than 1% (1sigma) and sensitivity variation with dose rate and proton energy.

Diamond↗

Characteristics of silicon and diamond detectors in a 60 MeV proton beam.

The calibration factor variation for a PTW natural diamond detector and a Scanditronix p-type stereotactic silicon diode (designed for use in photon beams) was studied in the 10-59 MeV range. Irradiations were performed in a water phantom with the 60 MeV ocular therapy beam at the CCO (UK). The diamond detector showed a sensitivity increase with energy, underestimating the dose by about 18% at the Bragg peak, by 7% at the centre and by 17% at the distal end of the SOBP region. The silicon diode did not show any significant sensitivity change with energy. However, a decrease in response of 24% was observed for an accumulated dose of 300 Gy.

Calibration↗

High dose-rate brachytherapy source localization: positional resolution using a diamond detector.

A potential real-time source position verification process for high dose-rate (HDR) brachytherapy treatment is described. This process is intended to provide immediate confirmation that a treatment is proceeding according to plan, so that corrective action can be taken if necessary. We show that three dosimeters are in principle sufficient and demonstrate the feasibility of the process using a diamond detector and an Ir-192 source. An error analysis including all identified sources of error shows that this detector is capable of locating the distance to the source to within 2 mm for distances up to 12 cm. This positional accuracy is less than the diameter of typical HDR catheters indicating that a diamond detector can be used to accurately determine the distance to the source. The uncertainty in the distance is found to increase with distance.

Algorithms↗

The use of CVD diamond to produce carbon K ultrasoft x-rays.

Carbon K ultrasoft x-rays (278 eV) interact with biological material producing random, isolated tracks of single electrons with a range < 7 nm (cf width of DNA helix approximately2 nm). The electron tracks produced by these ultrasoft x-rays are similar to the numerous secondary electrons and 'track ends' produced by essentially all ionizing radiations. They therefore provide a unique tool in the study of mechanisms of radiation action in the cell. Conventional carbon targets used with the Medical Research Councils cold-cathode discharge tubes have a limited lifetime of 40-50 min. We have investigated the use of thin, freestanding diamond films produced using chemical vapour deposition techniques as a new transmission target for a cold-cathode tube. We present here a novel use of diamond to produce CK ultrasoft x-rays for irradiation purposes. The system described produces an entrance absorbed dose rate to attached cells of approximately 0.2 Gy min(-1) which due to the long target lifetime is usable for low dose-rate CK x-ray studies.

Diamond↗

Responses of a diamond detector to high-LET charged particles.

The responses of a commercial diamond detector (type 60003, PTW-Freiburg) to several heavy ions were examined. The responses to heavy-ion beams reached stable levels with relatively small pre-irradiation doses compared to photon-beam irradiations. The responses also reached stable levels with a smaller pre-irradiation dose when the dose rate of the He beams was increased. A total accumulated dose of about 5 Gy was required for the pre-irradiation dose of heavy-ion beams. No angular dependence of the detector responses was observed within a deviation of 5%. The dose-rate dependence of the detector responses to heavy-ion beams was far smaller than that to gamma rays. The decrease in the response was within 0.9%, with a variation from 0.88 to 18.2 Gy min(-1) in the carbon beam. We examined the LET dependence of the diamond detector responses using various kinds of heavy-ion beams. The responses had particle dependence in addition to LET dependence. The responses decreased more with higher LET particles and decreased less with large-Z particles. We proposed a gradual-saturation model based on the track structure under several simple assumptions to explain the LET and particle dependences of the response.

Diamond↗

Thermoluminescent properties of Ni and Co doped synthetic, high pressure, high temperature diamonds: application to ionising radiation dosimetry.

An investigation of the thermoluminescence (TL) properties of high pressure, high temperature (HPHT) synthetic diamond crystals grown under diluted nickel or cobalt as solvent catalysts is reported. After a study of TL properties of 6 different samples, it is shown that a crystal grown with Ni+2%Ti and annealed at 2100 K presents an intense glow peak at around 490 K. This peak is characterised by a broad emission band centred at 530 nm (2.34 eV). This crystal presents a significant, reproducible and linear TL response relative to the absorbed dose up to an X ray air kerma of 10 Gy. All these features make this material suitable for ionising radiation dosimetry. A similar study is made on another crystal grown from pure Co, and a comparative review of the results does show that for dosimetry work, Ni-containing diamonds are more appropriate than those grown from Co catalyst.

Cobalt↗

Optical bleaching, TSL and OSL features of CVD diamond.

Luminescence and optical features of chemical vapour deposition (CVD) diamond have been studied in view of the potential application of this material in ionising radiation dosimetry field. For this purpose, thermally stimulated luminescence (TSL) and optically stimulated luminescence (OSL) techniques have been used. A large amount of work has emphasised the excellent dosimetric properties of CVD diamond. Nevertheless, TSL measurements showed that after irradiation, this material is extremely sensitive to ambient light and the stored dose information is drastically affected by optical bleaching. From OSL analysis, it follows that both types of processes (TSL and OSL) were characterised by the same excitation and emission spectra and that optical bleaching originated from a broad stimulation band lying from visible to near infrared with a continuous character.

Computer Simulation↗