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Dynamics of grain boundaries in two-dimensional hydrogen-bonded molecular networks.

The temporal evolution of domain boundaries of hydrogen-bonded molecular monolayers at the liquid-solid interface is evaluated by recording series of subsequent scanning tunneling microscopy (STM) images. Comparison of dissimilar benzene carboxylic acids reveals a clear distinction between one- and two-dimensional H-bonded network structures. Trimesic acid forms a two-dimensionally H-bonded networked structure, whereas terephthalic acid organizes in a dense packing of H-bonded linear chains on a graphite surface. In addition, TMA forms a sixfold lattice on a threefold graphite substrate, whereas TPA exhibits only a twofold lattice, causing a high grain-boundary line energy for the latter. In the case of TMA the nanostructure was mostly stable during the observation time. For TPA, Ostwald ripening-that is, the growth of larger islands at the expense of smaller islands-was observed. To explain the various experimentally observed timescales of the dynamics occurring at grain boundaries, molecular mechanics simulations were applied to calculate the binding energy of edge molecules, that is, the line energy, of finite islands of both trimesic and terephthalic acid on a graphite substrate.

Adsorption↗

Application of a novel, plastic formed carbon as a precolumn packing material for the liquid chromatographic determination of acetylcholine and choline in biological samples.

A novel carbon material, plastic formed carbon (PFC), was prepared by mixing various amounts of pure graphite with an organic binder and pyrolysing the mixture to a "glassy carbon" at a modest final temperature of 1000-1400 degrees C. This preparation procedure allows more convenient and precise control of the final graphite adsorption characteristics. Various PFC materials were constructed and tested both as bulk adsorbents and as precolumn packings for the direct determination of ACh and Ch in brain tissue homogenates. The PFC precolumns prepared from 12.5-50% graphite, by mass, were capable of selectively removing interfering species while not adsorbing any of the desired quaternary amine analytes. The usually large solvent front was also dramatically reduced with these precolumns. These PFC precolumns are useful for the direct determination of ACh and Ch in brain tissue homogenates and other biological samples.

Acetylcholine↗

Prospective tissue-mimicking materials for use in NMR imaging phantoms.

Water-based proteinaceous gels, which--with appropriate additives--are stable with time and possess a high melting point, have been used as base materials in ultrasonically tissue-mimicking materials. In the present work, versions of these gels having various concentrations of glycerol and graphite particles were studied regarding their NMR T1 and T2 dependencies at a proton Larmor frequency of 10.7 MHz. It has been found that T1 depends primarily on the concentration of glycerol and T2 depends primarily on the graphite particle concentration. Also, the ranges of T1 and T2 likely span those which exist for soft tissue parenchymae. Thus, these materials are good candidates for use as NMR tissue-mimicking materials. T1 and T2 also vary with gelatin concentration. The latter fact, together with the strong dependence of T2 on graphite concentration, mean that effective contrast-resolution phantoms and anthropomorphic phantoms with stable T1 and T2 distributions can be produced.

Gelatin↗

A windowless 13N production target for use with low energy deuteron accelerators.

The recent development of low energy accelerators for positron emission tomography has necessitated the development of new targets for 13N production. 12C(d,n)13N reaction yields in graphite at low deuteron beam energies (0.8-3.2 MeV) are presented and a new technique for the in situ extraction of 13N activity from solid graphite and subsequent conversion to [13N] ammonia is described. The target is windowless and is reusable for multiple isotope production runs. This technique utilizes radio frequency induction heating to rapidly heat the graphite to combustion temperatures in an O2 gas stream. The conversion of activity induced in the target to [13N] ammonia in under 10 min with an overall decay-corrected efficiency of 45% is reported.

Ammonia↗

Hyaluronan conformations on surfaces: effect of surface charge and hydrophobicity.

Extended, relaxed, condensed, and interacting forms of the polysaccharide hyaluronan have been observed by atomic force microscopy (AFM). The types of images obtained depend on the properties of the surfaces used. We have investigated several different surface conditions for HA imaging, including unmodified mica, mica chemically modified with two different kinds of amino-terminated silanes (3-aminopropyltriethoxysilane and N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride), and highly oriented pyrolytic graphite. We found the degree of HA molecular extension or condensation to be variable, and the number of bound chains per unit area was low, for all of the mica-based surfaces. HA was more easily imaged on graphite, a hydrophobic surface. Chains were frequently observed in high degrees of extension, maintained by favorable interaction with the surface after molecular combing. This observation suggests that the HA macromolecule interacts with graphite through hydrophobic patches along its surface. AFM studies of HA behavior on differing surfaces under well-controlled environmental conditions provides useful insight into the variety of conformations and interactions likely to be found under differing physiological conditions.

Aluminum Silicates↗

Influence of surface and protein modification on immunoglobulin G adsorption observed by scanning force microscopy.

Scanning force microscopy has been used successfully to produce images of individual protein molecules. However, one of the problems with this approach has been the high mobility of the proteins caused by the interaction between the sample and the scanning tip. To stabilize the proteins we have modified the adsorption properties of immunoglobulin G on graphite and mica surfaces. We have used two approaches: first, we applied glow discharge treatment to the surface to increase the hydrophilicity, favoring adhesion of hydrophilic protein molecules; second, we used the arginine modifying reagent phenylglyoxal to increase the protein hydrophobicity and thus enhance its adherence to hydrophobic surfaces. We used scanning force microscopy to show that the glow discharge treatment favors a more homogeneous distribution and stronger adherence of the protein molecules to the graphite surface. Chemical modification of the immunoglobulin caused increased aggregation of the proteins on the surface but did not improve the adherence to graphite. On mica, clusters of modified immunoglobulins were also observed and their adsorption was reduced. These results underline the importance of the surface hydrophobicity and charge in controlling the distribution of proteins on the surface.

Adsorption↗

Electrochemical activation of electrodes for amperometric detection of nitric oxide.

An open question in the literature of nitric oxide detection was investigated: does electrochemical activation account for the enhanced properties of certain presumed chemically-modified electrodes? Uniform electrodes of graphite, iridium, palladium, platinum, and ruthenium were exposed to potential cycling and then tested for amperometric response to nitric oxide to identify principles that govern electrochemical activation of nitric oxide electrodes. These electrodes were compared to similar electrodes that were not cycled. Only cycled graphite and ruthenium showed significantly increased responses. Graphite demonstrated enhanced performance after exposure to cycling potentials at which oxygen, CO(2), and soluble carbonates form, suggesting that erosion of the electrode enhanced its response by increasing the surface area accessible to nitric oxide. This may explain the performance of carbon fibers cycled to the same potentials in solutions containing metalloporphyrins. The response of ruthenium was enhanced after cycling to less extreme potentials at which soluble species do not form and at which a metallic conductive oxide, RuO(2), could lay down a stable, adherent layer on the electrode surface. Cycled ruthenium also exhibited a much greater increase in capacitance after cycling, consistent with the formation of a conductive surface layer.

Electric Capacitance↗

Characterization of airborne and bulk particulate from iron and steel manufacturing facilities.

Characterization of airborne and bulk particulate material from iron and steel manufacturing facilities, commonly referred to as kish, indicated graphite flakes and graphite flakes associated with spherical iron oxide particles were unique particle characteristics useful in identifying particle emissions from iron and steel manufacturing. Characterization of airborne particulate material collected in receptor areas was consistent with multiple atmospheric release events of kish particles from the local iron and steel facilities into neighboring residential areas. Kish particles deposited in nearby residential areas included an abundance of graphite flakes, tens of micrometers to millimeters in size, and spherical iron oxide particles, submicrometer to tens of micrometers in size. Bulk kish from local iron and steel facilities contained an abundance of similar particles. Approximately 60% of blast furnace kish by volume consisted of spherical iron oxide particles in the respirable size range. Basic oxygen furnace kish contained percent levels of strongly alkaline components such as calcium hydroxide. In addition, concentrations of respirable Mn in airborne particulate in residential areas and at local iron and steel facilities were approximately 1.6 and 53 times the inhalation reference concentration of 0.05 microg/m3 for chronic inhalation exposure of Mn, respectively. Thus, airborne release of kish may pose potential respirable particulate, corrosive, or toxic hazards for human health and/or a corrosive hazard for property and the environment.

Air Pollutants↗

Reduction of nitroglycerin with elemental iron: pathway, kinetics, and mechanisms.

Nitroglycerin (NG) is a nitrate ester used in dynamites, propellants, and medicines and is therefore a common constituent in propellant-manufacturing and pharmaceutical wastewaters. In this study we investigated the reduction of NG with cast iron as a potential treatment method. NG was reduced stepwise to glycerol via 1,2- and 1,3-dinitroglycerins (DNGs) and 1- and 2-mononitroglycerins (MNGs). Nitrite was released in each reduction step and was further reduced to NH4+. Adsorption of NG and its reduction products to cast iron was minimal. A reaction pathway and a kinetic model for NG reduction with cast iron were proposed. The estimated surface area-normalized reaction rate constants for NG and NO2- were (1.65 +/- 0.30) x 10(-2) (L x m(-2) x h(-1)) and (0.78 +/- 0.09) x 10(-2) (L x m(-2) x h(-1)), respectively. Experiments using dialysis cell with iron and a graphite sheet showed that reduction of NG to glycerol can be mediated by graphite. However, reduction of NO2- mediated by graphite was very slow. NG and NO2- were also found to reduce to glycerol and NH4+ by Fe2+ in the presence of magnetite but not by aqueous Fe2+ or magnetite alone. These results indicate that in a cast iron-water system NG may be reduced via multiple mechanisms involving different reaction sites, whereas nitrite is reduced mainly by iron and/ or adsorbed Fe2+. The study demonstrates that iron can rapidly reduce NG to innocuous and biodegradable end products and represents a new approach to treat NG-containing wastewaters.

Adsorption↗

Molecular dynamics simulations of surfactant self-organization at a solid-liquid interface.

Self-organization of aqueous surfactants at a planar graphite-like surface is studied by means of coarse-grain molecular dynamics simulations. The nonionic surfactant, n-alkyl poly(ethylene oxide), and water are both represented by coarse-grain models while an implicit representation is used for the graphite surface. The observed morphology of the aggregated surfactants depends on the alkyl chain length. Surfactants with a short chain form a monolayer on the graphite surface with a thickness roughly equal to that of the alkane tail. On the other hand, longer-tail surfactants form continuous hemicylinders on the surface with diameter approximately 5.0 +/- 0.5 nm, in good agreement with experimental AFM data.

Adsorption↗

Direct electron transfer--a favorite electron route for cellobiose dehydrogenase (CDH) from Trametes villosa. Comparison with CDH from Phanerochaete chrysosporium.

This paper presents some functional differences as well as similarities observed when comparing the newly discovered cellobiose dehydrogenase (CDH) from Trametes villosa (T.v.) with the well-characterized one from Phanerochaete chrysosporium (P.c.). The enzymes were physically adsorbed on spectrographic graphite electrodes placed in an amperometric flow through cell connected to a flow system. In the case of T.v.-CDH-modified graphite electrodes, a high direct electron transfer (DET) current was registered at the polarized electrode in the presence of the enzyme substrate reflecting a very efficient internal electron transfer (IET) process between the reduced FAD-cofactor and the oxidized heme-cofactor. In the case of P.c.-CDH-modified graphite electrodes, the DET process is not as efficient, and the current will greatly increase in the presence of a mediator (mediated electron transfer, MET). As a consequence, when comparing the two types of enzyme-modified electrodes an inverted DET/MET ratio for T.v.-CDH is shown, in comparison with P.c.-CDH. The rates of the catalytic reaction were estimated to be comparable for both enzymes, by measuring the combined DET + MET currents. The inverted DET/MET ratio for T.v.-CDH-modified electrodes might suggest that probably there is a better docking between the two domains of this enzyme and that the linker region of P.c.-CDH might have an active role in modulating the rate of the IET (by changing the interdomain distance), with respect to pH. Based on the new properties of T.v.-CDH emphasized in the present study, an analytical application of a third-generation biosensor for lactose was recently published.

Adsorption↗

Real-time observation of tubule formation from amorphous carbon nanowires under high-bias Joule heating.

The tubule formation process from amorphous carbon nanowires under high-bias-caused Joule heating was observed in real time in a high-resolution transmission electron microscope. The crystallization of the amorphous carbon nanowires occurred in two distinct ways: the formation of tubular graphitic basal planes parallel to the nanowire axis on the surface and the formation of nano-onions in the interior of the nanowire. The tubule formation mechanism is a process of solid-state atom diffusion at high temperatures. Energetically, the tubule formation is caused by the exceptionally low surface energy of the (0002) plane of graphite. Higher input power to the amorphous nanowires generally leads to improved graphitization and, in turn, to increased conductance. The results suggest that nanotube formation in the arc-discharge growth process may involve the formation and crystallization of amorphous carbon.

Computer Systems↗

Reburial of fossil organic carbon in marine sediments.

Marine sediments act as the ultimate sink for organic carbon, sequestering otherwise rapidly cycling carbon for geologic timescales. Sedimentary organic carbon burial appears to be controlled by oxygen exposure time in situ, and much research has focused on understanding the mechanisms of preservation of organic carbon. In this context, combustion-derived black carbon has received attention as a form of refractory organic carbon that may be preferentially preserved in soils and sediments. However, little is understood about the environmental roles, transport and distribution of black carbon. Here we apply isotopic analyses to graphitic black carbon samples isolated from pre-industrial marine and terrestrial sediments. We find that this material is terrestrially derived and almost entirely depleted of radiocarbon, suggesting that it is graphite weathered from rocks, rather than a combustion product. The widespread presence of fossil graphitic black carbon in sediments has therefore probably led to significant overestimates of burial of combustion-derived black carbon in marine sediments. It could be responsible for biasing radiocarbon dating of sedimentary organic carbon, and also reveals a closed loop in the carbon cycle. Depending on its susceptibility to oxidation, this recycled carbon may be locked away from the biologically mediated carbon cycle for many geologic cycles.

Carbon↗

Protein adsorption on the hydrophilic surface of a glassy polymer: a computer simulation study.

Using atomistic computer simulations, we study the adsorption of different globular protein fragments with different secondary structures on the surface of a hydrophilic glassy polymer, poly(vinyl alcohol), or PVA, and compare the results with our earlier calculations on hydrophobic graphite. The simulations were mainly carried out with implicit solvent in an effective dielectric medium by energy minimizations and molecular dynamics at room temperature. We find that on the hydrophilic PVA surface the fragments basically retain their globular shape with an incomplete denaturation, at variance with our earlier results for the same fragments on graphite. Correspondingly, the interaction energy between the fragments and the surface is significantly smaller than on graphite, both because less residues are in contact with the surface, and because they interact more weakly. Moreover, very few hydrogen bonds are formed between the adsorbate and the PVA surface, since both the protein fragments and the polymer chains separately optimize these interactions. Additional molecular dynamics simulations in explicit solvent were also performed to study the hydration of the adsorbed fragments and to estimate the possible solvation effects.

Adsorption↗

Two-dimensional ordering of the DNA base guanine observed by scanning tunneling microscopy.

Guanine, one of the four DNA bases, has been observed by tunneling microscopy to form a two-dimensional ordered structure on two crystalline substrates, graphite and MoS2. The two-dimensional lattice formed by guanine is nearly identical on the two surfaces, and heteroepitaxy appears to be the growth mechanism in both cases. Although the resolution of molecular details is superior for the graphite substrate, the simpler results on MoS2 are not only easier to interpret but also facilitate the understanding of the more complex images on graphite. We propose that the interfacial structure is composed of linear chains of hydrogen-bonded molecules aligned into a closely packed two-dimensional array.

DNA↗

In situ atomic force microscopy study of Alzheimer's beta-amyloid peptide on different substrates: new insights into mechanism of beta-sheet formation.

We have applied in situ atomic force microscopy to directly observe the aggregation of Alzheimer's beta-amyloid peptide (Abeta) in contact with two model solid surfaces: hydrophilic mica and hydrophobic graphite. The time course of aggregation was followed by continuous imaging of surfaces remaining in contact with 10-500 microM solutions of Abeta in PBS (pH 7.4). Visualization of fragile nanoscale aggregates of Abeta was made possible by the application of a tapping mode of imaging, which minimizes the lateral forces between the probe tip and the sample. The size and the shape of Abeta aggregates, as well as the kinetics of their formation, exhibited pronounced dependence on the physicochemical nature of the surface. On hydrophilic mica, Abeta formed particulate, pseudomicellar aggregates, which at higher Abeta concentration had the tendency to form linear assemblies, reminiscent of protofibrillar species described recently in the literature. In contrast, on hydrophobic graphite Abeta formed uniform, elongated sheets. The dimensions of those sheets were consistent with the dimensions of beta-sheets with extended peptide chains perpendicular to the long axis of the aggregate. The sheets of Abeta were oriented along three directions at 120 degrees to each other, resembling the crystallographic symmetry of a graphite surface. Such substrate-templated self-assembly may be the distinguishing feature of beta-sheets in comparison with alpha-helices. These studies show that in situ atomic force microscopy enables direct assessment of amyloid aggregation in physiological fluids and suggest that Abeta fibril formation may be driven by interactions at the interface of aqueous solutions and hydrophobic substrates, as occurs in membranes and lipoprotein particles in vivo.

Aluminum Silicates↗

The UK primary standard calorimeter for photon-beam absorbed dose measurement.

A description is given of the UK primary standard graphite calorimeter system. The calorimeter measures absorbed dose to graphite for photon radiations from 60Co to 19 MV x-rays, and is the basis of the NPL therapy-level absorbed dose to water calibration service. Absorbed dose to graphite from the photon calorimeter has been compared with three other standards: an ionization chamber and cavity theory, for 60Co gamma radiation; the NPL electron calorimeter, for 12-14 MeV electron beams; and the BIPM 60Co absorbed dose standard. The three standards agreed within 0.5% which is similar to the measurement uncertainties.

Calorimetry↗

Characteristics of the absorbed dose to water standard at ENEA.

The primary standard of absorbed dose to water established at ENEA for the Co-60 gamma-ray quality is based on a graphite calorimeter and an ionometric transfer system. This standard was recently improved after a more accurate assessment of some perturbation effects in the calorimeter and a modification of the water phantom shape and size. The conversion procedure requires two corresponding depths, one in graphite and one in water, where the radiation energy spectra must be the same. The energy spectra at the corresponding points were determined by a Monte Carlo simulation in water and graphite scaled phantoms. A thorough study of the calorimeter gap effect corrections was also made with regard to their dependence on depth and field size. A comparison between the ionization chamber calibration procedures based on the standards of absorbed dose to water and of air kerma was also made, confirming the consistency of the two methods.

Calorimetry↗