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Build-up cap materials for measurement of photon head-scatter factors.

The suitability of high-Z materials as build-up caps for head-scatter measurements has been investigated. Build-up caps are often used to enable characterization of fields too small for a mini-phantom. We have studied lead and brass build-up caps with sufficiently large wall thicknesses, as compared to the range of contaminating electrons originating in the accelerator head, and compared them with build-up caps made of ionization chamber equivalent materials, i.e. graphite. The results were also compared with measurements taken using square and cylindrical polystyrene mini-phantoms. Field sizes ranging from 3 cm x 3 cm up to 40 cm x 40 cm were studied for nominal photon energies of 4, 6, 10 and 18 MV. The results show that the use of lead and brass build-up caps produces normalized head-scatter data slightly different from graphite build-up caps for large fields at high photon energies. At lower energies, however, no significant differences were found. The intercomparison between the two different plastic mini-phantoms and graphite caps showed no differences.

Alloys↗

Comparison of two dose-area-product ionization chambers with different conductive surface coating for over-table and under-table tube configurations.

A custom-built graphite-coated transmission ionization chamber is compared to the VacuDAP 2001 (VacuTec, Dresden, Germany), which has transparent conductive electrodes. A study was made of the dependence of response on x-ray tube potential for both types of chamber under identical conditions of exposure using over-table and under-table x-ray tubes. Since the calibration factor is the dose-area product of the radiation incident on the patient per chamber reading, it depends on the intrinsic response of the chamber as well as the effect of material in the beam between the x-ray tube and patient. Differences of about 20% were measured between the intrinsic and the over-table calibration factors and between the over-table and the under-table calibration factors for both chambers. The VacuDAP display is specifically calibrated for the over-table condition and would overstate the actual DAP in the under-table case. The intrinsic response of the graphite chamber is nearly independent of tube potential. Although the variation of response with tube potential of the graphite chamber is increased when it is used as an over-table and an under-table patient monitor, it shows less overall variation of response than the VacuDAP. The average deviation of each calibration factor from the mean is less than 5% over the range of 40 to 140 kVp for both chambers.

Equipment Design↗

Geological constraints on detecting the earliest life on Earth: a perspective from the Early Archaean (older than 3.7 Gyr) of southwest Greenland.

At greater than 3.7 Gyr, Earth's oldest known supracrustal rocks, comprised dominantly of mafic igneous with less common sedimentary units including banded iron formation (BIF), are exposed in southwest Greenland. Regionally, they were intruded by younger tonalites, and then both were intensely dynamothermally metamorphosed to granulite facies (the highest pressures and temperatures generally encountered in the Earth's crust during metamorphism) in the Archaean and subsequently at lower grades until about 1500 Myr ago. Claims for the first preserved life on Earth have been based on the occurrence of greater than 3.8 Gyr isotopically light C occurring as graphite inclusions within apatite crystals from a 5 m thick purported BIF on the island of Akilia. Detailed geologic mapping and observations there indicate that the banding, first claimed to be depositional, is clearly deformational in origin. Furthermore, the mineralogy of the supposed BIF, being dominated by pyroxene, amphibole and quartz, is unlike well-known BIF from the Isua Greenstone Belt (IGB), but resembles enclosing mafic and ultramafic igneous rocks modified by metasomatism and repeated metamorphic recrystallization. This scenario parsimoniously links the geology, whole-rock geochemistry, 2.7 Gyr single crystal zircon ages in the unit, an approximately 1500 Myr age for apatites that lack any graphite, non-MIF sulphur isotopes in the unit and an inconclusive Fe isotope signature. Although both putative body fossils and carbon-12 enriched isotopes in graphite described at Isua are better explained by abiotic processes, more fruitful targets for examining the earliest stages in the emergence of life remain within greater than 3.7 Gyr IGB, which preserves BIF and other rocks that unambiguously formed at Earth's surface.

Evolution, Planetary↗

Efficient laser-ultrasound generation by using heavily absorbing films as targets.

An efficient all-fiber optic source is presented; it adopts absorbing films, deposed directly over the fiber tip, as targets. It is demonstrated that the use of absorbing films made of pure graphite, or graphite powder mixed with epoxy resin, has produced a conversion efficiency increase of two orders of magnitude with respect to metallic materials. It is observed that the conversion efficiency increases monotonically as thickness is reduced down to the material optical penetration depth. Moreover, the conversion efficiency rises with the concentration of graphite powder. Principal advantages of this kind of source are the ease of production and miniaturization, the excellent electromagnetic compatibility, wide ultrasonic bandwidth and, consequently, high spatial resolution. The ultrasonic bandwidth can be controlled by varying the laser pulse duration. The possibility of generating ultrasonic signals with high frequency and flat spectral distribution makes the proposed device suitable for biological tissue spectral characterization.

Fiber Optic Technology↗

An EGSnrc investigation of cavity theory for ion chambers measuring air kerma.

The EGSnrc system is used to compare the response of an aluminum-walled thimble chamber to that of a graphite-walled thimble chamber for a 60Co beam. When compared to previous experimental results, the EGSnrc values of the ratios of chamber response differ by as much as 0.7% from the experiment. However, it is shown that this difference can be more than accounted for by switching from using the graphite mean excitation energy of 78 eV used in dosimetry protocols to the value of 86.8 eV suggested by more recent stopping-power experiments. This suggests that the uncertainty analysis of Monte Carlo results must be done more carefully, by taking into account uncertainties in the underlying basic data such as the electron and photon cross sections. In comparison to Spencer-Attix cavity theory for a thick-walled ion chamber, the Monte Carlo calculated values of the chamber response differ from the expected ones by 0.15% and 0.01% for the graphite and aluminum chambers, respectively, which are comparable to previously reported values for the Spencer-Attix correction factors. EGSnrc is also used to investigate the effect on the chamber response of thin dag layers on the inside of the aluminum wall. There is good agreement between the calculated and measured changes in chamber response versus the thickness of the dag. The results are compared to the predictions of the Almond-Svensson extension of cavity theory and show that the theory does not correctly predict the chamber response in the presence of thin dag layers. This finding is in agreement with previously reported experimental results. It is demonstrated that the values of alpha, the fraction of ionizations in the gas arising from electrons generated in the dag layer, used in the theory, are not the source of the disagreement.

Algorithms↗

Oriented carbon nanostructures containing nitrogen obtained by ion beam assisted deposition.

In this paper, we report the deposition of graphite multilayer containing nitrogen covering nanometric nickel particles. In-situ photoelectron emission spectroscopy (XPS) reveals the presence of nitrogen in the carbon layer covering the nickel particles. The field emission properties of the structures are reported. Atomic force microscopy displays regular domelike structures. Raman spectroscopy shows the characteristic frequencies associated with graphite and disordered structures. High-resolution transmission electron microscopy confirms the presence of multiwall well-organized graphite layers covering the nickel particles. Disorder increases on increasing nitrogen content. The samples were prepared in-situ by depositing first a few atomic layers of nickel and subsequent islands formation by thermal annealing. Then, an argon ion beam bombards an ultrapure carbon target and simultaneously the growing film is assisted with a second low-energy nitrogen ion beam (ion beam assisted deposition).

Argon↗

Self-organized monolayer formation from binary mixtures of substituted alkyl chains studied by STM.

The molecular assembly of p-iodo-phenyl octadecyl ether (I-POE), p-iodo-phenyl docosyl ether (I-PDE) and a binary mixture of these two molecules on graphite has been studied using a scanning tunneling microscope. Each molecular system self-assembles on the graphite surface to form a stable monolayer. For the binary system, the I-POE and I-PDE molecules do not mix on the surface, preferring instead to form isolated monolayer domains. Here, the I-POE molecules are preferentially adsorbed on the graphite surface, due to the effects of alkyl chain length and the functional group on the monolayer structure.

Adsorption↗

Microscopic mechanism of attenuation of compressional ultrasonic waves in tissue-mimicking phantom materials.

An investigation was performed to determine whether the sound-attenuation-insuspensions theory of Allegra and Hawley can be used to explain the compressional (longitudinal wave) attenuation of ultrasonically tissue-mimicking materials commonly used in phantoms for testing the performance of medical ultrasound systems. These materials are composed of microscopic graphite particles suspended in a gel. The theory was first tested using materials containing spherical glass beads instead of graphite particles because these materials more closely fit the geometric conditions assumed in the theory. For the glass bead type materials as well as the graphite particle type materials, the attenuation coefficients predicted using the Allegra and Hawley model agreed rather well with experimental measurements over the diagnostic frequency range.

Biocompatible Materials↗

Study of a reagent- and mediator-less biosensor for D-amino acids based on co-immobilized D-amino acid oxidase and peroxidase in carbon paste electrodes.

A biosensor for the analysis of D-amino acids is described. Carbon paste (graphite/paraffin oil) was chemically modified with immobilized D-amino acid oxidase and either horse-radish peroxidase or fungal peroxidase from Arthromyces ramosus. The two enzymes dissolved in buffer, together with an amine containing oligomer or polymer, were adsorbed on dry graphite. Prior to immobilization, the graphite was heat treated at 700 degrees C for 15 s to promote an efficient electron transfer between graphite and the peroxidase. The mixture was dried before addition of the pasting liquid. The sensor is based on the fact that the hydrogen peroxide produced by the action of D-amino acid oxidase is electrocatalytically reduced through the action of the peroxidase. The amine containing compound acted as a stabilizer and activator of the enzymes in the paste. The enzyme electrode was investigated as a sensor for D-phenylalanine and hydrogen peroxide in a flow through electrochemical cell connected to a single line flow injection system. The influences on the response by different additives to the paste and pH are reported. Linear calibration curves were obtained between 0.1 and 1.4 mM for D-phenylalanine and 5 and 1000 microM for hydrogen peroxide at an applied potential of -50 mV vs. Ag/AgCl. The sensor was also active for the following D-amino acids: D-alanine, D-valine, D-leucine, D-isoleucine, D-serine, D-aspartic acid, D-glutamic acid, D-lysine, D-histidine, D-arginine, D-tryptophan, D-methionine, and D-proline.

Amino Acids↗

Preconcentration and determination of mercury(II) at a chemically modified electrode containing 3-(2-thioimidazolyl)propyl silica gel.

A mercury-sensitive chemically modified graphite paste electrode was constructed by incorporating modified silica gel into a conventional graphite paste electrode. The functional group attached to the (3-chloropropyl) silica gel surface was 2-mercaptoimidazole, giving a new product denoted by 3-(2-thioimidazolyl)propyl silica gel, which is able to complex mercury ions. Mercury was chemically adsorbed on the modified graphite paste electrode containing 3-(2-thioimidazolyl)propyl silica (TIPSG GPE) by immersion in a Hg(II) solution, and the resultant surface was characterized by cyclic and differential pulse anodic stripping voltammetry. One cathodic peak at 0.1 V and other anodic peak at 0.34 V were observed on scanning the potential from -0.1 to 0.8 V (0.01 M KNO3; v = 2.0 mV s(-1) vs. Ag/AgCl). The anodic peak at 0.34 V show an excellent sensitivity for Hg(II) ions in the presence of several foreign ions. A calibration graph covering the concentration range from 0.02 to 2 mg L(-1) was obtained. The detection limit was estimated to be 5 microg L(-1). The precision for six determinations of 0.05 and 0.26 mg L(-1) Hg(II) was 3.0 and 2.5% (relative standard deviation), respectively. The method can be used to determine the concentration of mercury(II) in natural waters contaminated by this metal.

Calibration↗

Solid materials with high dielectric constants for hyperthermia applications.

The manufacture of solid components with high permittivities epsilon r of 1-100 and differing conductivities sigma of 0-1.0 S/m has practical significance for fabricating applicators and phantoms in radiofrequency hyperthermia. For this purpose, various plastics (resins, polyurethane and silicone) were combined with additives (graphite and metal powder) and tested to assess their radiofrequency and mechanical characteristics and to identify manufacturing problems. Most of the plastics could be made highly dielectric and conductive by adding graphite in the range of muscle tissue (i.e. epsilon r approximately 80, sigma approximately 0.8 S/m). However, there are major differences between the materials with respect to mechanical behaviour, durability, feasibility of manufacture, and reproducibility. Manufacturing water-equivalent plastics (low conductivity sigma < 0.05 S/m and epsilon r value of 70-80) is particularly difficult. A less filled polyester resin in which concentration of brass powder can achieve an epsilon r value of up to 100 at low conductivity proved to be the only suitable medium. Such a plastic can be used for future applicator designs. Other materials of interest include plastics equivalent to lossy media (e.g. sigma = 0.45-0.55 S/m, epsilon r = 70-80), fat-equivalent plastics (polyurethane with graphite) and higher dielectric flexible plastics (silicone with brass powder).

Electric Conductivity↗

Electrochemical reduction of xylose to xylitol by whole cells or crude enzyme of Candida peltata.

In this study, whole cells and a crude enzyme of Candida peltata were applied to an electrochemical bioreactor, in order to induce an increment of the reduction of xylose to xylitol. Neutral red was utilized as an electron mediator in the whole cell reactor, and a graphite-Mn(IV) electrode was used as a catalyst in the enzyme reactor in order to induce the electrochemical reduction of NAD(+) to NADH. The efficiency with which xylose was converted to xylitol in the electrochemical bioreactor was five times higher than that in the conventional bioreactor, when whole cells were employed as a biocatalyst. Meanwhile, the xylose to xylitol reduction efficiency in the enzyme reactor using the graphite-Mn (IV) electrode and NAD(+) was twice as high as that observed in the conventional bioreactor which utilized NADH as a reducing power. In order to use the graphite-Mn(IV) electrode as a catalyst for the reduction of NAD(+) to NADH, a bioelectrocatalyst was engineered, namely, oxidoreductase (e.g. xylose reductase). NAD(+) can function in this biotransformation procedure without any electron mediator or a second oxidoreductase for NAD(+)/NADH recycling.

Bioreactors↗

S-perindopril assay using a potentiometric, enantioselective membrane electrode.

A potentiometric, enantioselective membrane electrode based on graphite paste (graphite powder and paraffin oil) has been constructed. The graphite paste is impregnated with a 10(-3) mol/L 2-hydroxy-3-trimethylammoniopropyl-beta-cyclodextrin (as chloride salt) solution. The potentiometric, enantioselective membrane electrode can be used reliably for enantiopurity tests of S-perindopril using a chronopotentiometric (zero current) technique, in the 10(-5)-10(-2) mol/L concentration range (detection limit 5 x 10(-6) mol/L), with an average recovery of 99.58% (RSD = 0.33%). The enantioselectivity was determined over R-perindopril and D-proline. The response characteristics of the enantioselective, potentiometric membrane electrode were also determined for R-perindopril. It was shown that L-proline is the main interfering compound. The surface of the electrode can be regenerated simply by polishing, obtaining a fresh surface ready to be used in a new assay.

Angiotensin-Converting Enzyme Inhibitors↗

Chemical and constitutional influences in the self-assembly of functional supramolecular hydrogen-bonded nanoscopic fibres.

A new series of secondary amides bearing long alkyl chains with pi-electron-donor cores has been synthesized and characterised, and their self-assembly upon casting at surfaces has been studied. The different supramolecular assemblies of the materials have been visualized by using atomic force microscopy (AFM) and transmission electron microscopy (TEM). It is possible to obtain well-defined fibres of these aromatic core molecules as a result of the hydrogen bonds between the amide groups. Indeed, by altering the alkyl-chain lengths, constitutions, concentrations and solvent, it is possible to form different rodlike aggregates on graphite. Aggregate sizes with a lower limit of 6-8 nm width have been reached for different amide derivatives, while others show larger aggregates with rodlike morphologies which are several micrometers in length. For one compound that forms nanofibres, doping was performed by using a chemical oxidant, and the resulting layer on graphite was shown to exhibit metallic-like spectroscopy curves when probed with current-sensing AFM. This technique also revealed current maps of the surface of the molecular material. Fibre formation not only takes place on the graphite surface: nanometre scale rods have been imaged by using TEM on a grid after evaporation of solutions of the compounds in chloroform. Molecular modelling proves the importance of the hydrogen bonds in the generation of the fibres, and indicates that the constitution of the molecules is vital for the formation of the desired columnar stacks, results that are consistent with the images obtained by microscopic techniques. The results show the power of noncovalent bonds in self-assembly processes that can lead to electrically conducting nanoscale supramolecular wires.

Journal Article↗

Electrodeposition of metal nanostructures by galvanic displacement powered with insoluble crystals of a ferrocene derivative.

The deposition of metal nanostructures (wires and particles) on a graphite surface from an aqueous electrolyte solution was induced by galvanic displacement, via the oxidation of insoluble crystals of a ferrocene derivative (either n-butyl ferrocene or decamethyl ferrocene) present on the same substrate. Micron-to-millimetre-scale crystallites of decamethyl ferrocene were deposited on the graphite surface by evaporation from a solution of a nonpolar solvent (1,2-dichloroethane). Immersion of this modified surface into a dilute solution of a metal ion (e.g., CuII, AgI, PdII, PtII and others) caused the deposition of metal nanoparticles at step edges present on the graphite surface. The reducing equivalents required for the metal deposition process are provided by oxidation of the ferrocene derivative on the surface, as directly evidenced by elemental analysis and chronoamperometric experimental data presented here.

Journal Article↗

Peroxide biosensors and mediated electrochemical regeneration of redox enzymes.

This article describes the research investigations on the development of the amperometric biosensors based on mediated bioelectrochemistry. The mediated bioelectrochemistry involving horseradish peroxidase and glucose oxidase within the graphite paste is reported. The enzyme horseradish peroxidase together with electrochemical mediator was incorporated within the graphite paste electrode. The amperometric response is based on the mediated electrochemical regeneration of peroxidase within the paste. The mediated electrochemical regeneration of peroxidase and glucose oxidase was studied and compared using three different electron transfer mediators-tetracyanoquinodimethane (TCNQ), tetrathiafulvalene (TTF), and dimethyl ferrocene (dmFc). The mediated electrochemistry involving these three mediators was studied based on the cyclic voltammetry. The electrochemical measurements show that TTF is better mediator for the development of peroxide biosensor compared to TCNQ and dmFc. On the other hand, TCNQ is better mediator for the development of glucose sensor. The response curves for peroxide have been reported using these three mediators. A comparative study on the amperometric response based on the mediated electrochemical oxidation of peroxidase and glucose oxidase has also been made using these three mediators. The various parameters, i.e., background current, stability of the mediator within the graphite paste during the electrochemical measurements, and reproducibility of the amperometric response, are discussed.

Biosensing Techniques↗

Calculations of van der Waals forces in 2-dimensionally anisotropic materials and its application to carbon black.

We present calculations of the van der Waals force for carbon black dispersions in both aqueous and nonaqueous media using Lifshitz theory. The microstructure and composition of carbon black are complex, but an initial approximation to the shell-like microstructure of carbon black allows the local interaction of carbon black particles to be approximated as oriented domains of graphite. The dielectric spectra for graphite, which has a 2-dimensional anisotropy due to its the layered microstructure, is required for the Lifshitz theory van der Waals force calculations. The anisotropic dielectric spectra of graphite (which behaves as a semiconductor) was constructed by modeling the conduction or free charge response separately from the polarization or bound charge response. The free charge response was modeled using the Drude model, while the dielectric spectra for the bound charge response was constructed from the spectroscopic data directly according to the Kramers-Kronig relation for the dielectric function, epsilon(omega). The expressions for calculating the fully retarded van der Waals force for half spaces with 2-dimensional dielectric anisotropy were derived as well as. The construction for the dielectric spectra of polystyrene from recent spectroscopic data from the literature according to the method outlined in (Dagastine, R. R., Prieve, D. C., and White, L. R., J. Colloid Interface Sci.231, 351 (2000)) is also presented.

Journal Article↗

Promotion of gas bubble formation by ingested nuclei in the ciliate, Tetrahymena pyriformis.

Cells of the ciliate Tetrahymena pyriformis were suspended with carmine or graphite particles or with Halobacterium gas vesicles, all of which promote bubble formation in aqueous suspensions when tested with 10 atm and above (0.1-0.5 X 10(7) Pa) (carmine and graphite) or 25 atm and above (gas vesicles) of nitrogen supersaturations. All three particles were ingested, but only the gas vesicles promoted intracellular gas bubble formation if the cells containing them were nitrogen or methane saturated in a slow stepwise fashion prior to rapid decompression. Cell rupture did not occur until gas saturation pressures greater than 25 atm were used; this suggests that the ciliate pellicle and cytoplasm cannot resist the mechanical forces of an expanding gas phase induced by decompression from between 25 and 50 atm and thus provides an estimate of the physical strength of these cellular components. The inability of the ingested carmine, graphite, and collapsed gas vesicles to induce intracellular gas bubble formation suggests that the phagocytic process somehow altered them. This procedure may thus provide a tool for the study of early events in the digestive processes of ciliates.

Animals↗

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