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101.
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103.
Modeling the consequences of crystalline defects requires efficient interaction sampling. Empirical potentials can identify relevant pathways if the energetics and configurations of competing defects are captured. Here, we develop such a potential for an alloy of arbitrary point defect concentration, body-centered cubic alpha-Fe supersaturated in C. This potential successfully calculates energetically favored defects, and predicts formation energies and configurations of multicarbon-multivacancy clusters that were not attainable with existing potentials or identified previously via ab initio methods. 相似文献
104.
Planar laser-induced fluorescence (PLIF) of seeded nitric oxide was used to obtain mean 2-D temperature and pressure fields
in the near-wake region of a thick flat plate in a Mach 3 flow. A two-line ratio technique was used to obtain the temperature
field, while an image obtained at the limit of low quenching rate was used to infer the pressure field. An analysis shows
that these time-average measurements can suffer from significant weighted averaging bias errors in regions where there are
large temperature fluctuations; however, these bias errors can be minimized by judicious selection of the absorption lines
used. The resulting temperature field reveals the warm upstream boundary layer, the temperature jump across the recompression
shocks and the expected minimum and maximum temperatures in the expansion and recirculation regions, respectively. The pressure
measurements indicate a uniform low pressure in the base region, a rapid increase near reattachment, followed by a gradual
approach to the free stream value farther downstream.
Received: 25 July 1996 / Accepted: 11 September 1997 相似文献
105.
Ali Gooneie Stephan Schuschnigg Clemens Holzer 《Macromolecular theory and simulations》2016,25(2):170-186
Polydisperse linear polymers are studied in startup of steady shear flow simulations using dissipative particle dynamics. The results show that with an increase in polydispersity the stress overshoot declines while the steady‐state stress increases. Various physical characteristics of the systems are studied including frequency of nonbonded interactions, gyration radius data, flow alignment angles, and average bond lengths. The patterns in the data suggest higher forces are necessary to orient and stretch long chain fractions in the flow direction. Relaxation modulus data prove the broad range of relaxation mechanisms in polydisperse systems. Linear viscoelasticity theory is used to quantify the relaxation spectrum. The results indicate an increase in the longest relaxation time in systems with higher polydispersity. The steady‐state shear viscosity results show higher viscosities with an increase in polydispersity at all shear‐rates. The good agreement of the characteristic behaviors of modeled polydisperse polymers with experiments is encouraging for future work.
106.
Dr. Rajesh Seenivasan Charles Kolodziej Prof. Chandran Karunakaran Prof. Clemens Burda 《Chemical record (New York, N.Y.)》2017,17(9):886-901
Over the past several decades, nanotechnology has contributed to the progress of biomedicine, biomarker discovery, and the development of highly sensitive electroanalytical / electrochemical biosensors for in vitro and in vivo monitoring, and quantification of oxidative and nitrosative stress markers like reactive oxygen species (ROS) and reactive nitrogen species (RNS). A major source of ROS and RNS is oxidative stress in cells, which can cause many human diseases, including cancer. Therefore, the detection of local concentrations of ROS (e. g. superoxide anion radical; O2•−) and RNS (e. g. nitric oxide radical; NO• and its metabolites) released from biological systems is increasingly important and needs a sophisticated detection strategy to monitor ROS and RNS in vitro and in vivo. In this review, we discuss the nanomaterials‐based ROS and RNS biosensors utilizing electrochemical techniques with emphasis on their biomedical applications. 相似文献
107.
Kyra L. Sedransk Clemens F. Kaminski Lian R. Hutchings Geoff D. Moggridge 《Polymer Degradation and Stability》2011,96(6):1074-1080
A degradation study of polystyrene-polybutadiene-polystyrene and polyisoprene-polystyrene-polyisoprene in both dichloromethane and hexane solvents is presented. Alternative solvents for metathetic degradation provide the potential for greener chemistry, better selectivity, and control over the products. The catalyst concentration and solvent selection both determine the products formed. The degradation of polyisoprene and polybutadiene in a particular solvent was controlled by the solubility of polyisoprene/polybutadiene, and by its solubility relative to polystyrene. A large difference in solubility between the polymers in the selected solvent provides an additional driving force for block separation, encouraging reaction close to the interface between different blocks. Furthermore, solubility of the block copolymer speeds the degradation reaction. This tailoring of the reaction mechanism yields a new control over the products of polymer degradation. 相似文献
108.
Schmidt H Böttcher C Trampczynska A Clemens S 《Analytical and bioanalytical chemistry》2011,399(3):1355-1361
Nicotianamine (NA) is an important metal chelator, implicated in the intra- and intercellular trafficking of several transition
metal ions in plants. To decipher its roles in physiological processes such as micronutrient acquisition, distribution or
storage, fast and sensitive analytical techniques for quantification of this non-proteinogenic amino acid will be required.
The use of a recombinant Schizosaccharomyces pombe strain expressing a nicotianamine synthase (NAS) gene allowed for the production of [15N3]-NA, which was enriched from cell extracts through cation exchange and used for stable isotope dilution analysis of NA. Such
an approach should be widely applicable to important bioanalytes that are difficult to synthesize. The analytical procedure
comprises mild aqueous extraction and rapid Fmoc derivatization, followed by fast separation using ultra-performance liquid
chromatography (UPLC) and sensitive detection by positive ion electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS)
with a chromatographic cycle time of only 8 min. Derivatization was optimized with respect to incubation time and species
suitable for quantification. The limit of detection was 0.14 to 0.23 pmol in biological matrices with the response being linear
up to 42 pmol. Recovery rates were between 83% and 104% in various biological matrices including fission yeast cells, fungal
mycelium, plant leaves and roots. 相似文献
109.
In this article, we give a new rigorous condition number estimate of the finite element tearing and interconnecting (FETI)
method and a variant thereof, all-floating FETI. We consider a scalar elliptic equation in a two- or three-dimensional domain
with a highly heterogeneous (multiscale) diffusion coefficient. This coefficient is allowed to have large jumps not only across but also along subdomain interfaces and in the interior of the subdomains. In other words, the subdomain partitioning does not need to resolve
any jumps in the coefficient. Under suitable assumptions, we derive bounds for the condition numbers of one-level and all-floating
FETI that are robust with respect to strong variations in the contrast in the coefficient, and that are explicit in some geometric
parameters associated with the coefficient variation. In particular, robustness holds for face, edge, and vertex islands in
high-contrast media. As a central tool we prove and use new weighted Poincaré and discrete Sobolev type inequalities that
are explicit in the weight. Our theoretical findings are confirmed in a series of numerical experiments. 相似文献
110.
Bhowmick R Rajasekaran S Friebel D Beasley C Jiao L Ogasawara H Dai H Clemens B Nilsson A 《Journal of the American Chemical Society》2011,133(14):5580-5586
Using in situ electrical conductivity and ex situ X-ray photoelectron spectroscopy (XPS) measurements, we have examined how the hydrogen uptake of single-walled carbon nanotubes (SWNTs) is influenced by the addition of Pt nanoparticles. The conductivity of platinum-sputtered single-walled carbon nanotubes (Pt-SWNTs) during molecular hydrogen exposure decreased more rapidly than that of the corresponding pure SWNTs, which supports a hydrogenation mechanism facilitated by "spillover" of dissociated hydrogen from the Pt nanoparticles. C 1s XPS spectra indicate that the Pt-SWNTs store hydrogen by means of chemisorption, that is, covalent C-H bond formation: molecular hydrogen charging at elevated pressure (8.27 bar) and room temperature yielded Pt-SWNTs with up to 16 ± 1.5 at. % sp(3)-hybridized carbon atoms, which corresponds to a hydrogen-storage capacity of 1.2 wt % (excluding the weight of Pt nanoparticles). Pt-SWNTs prepared by the Langmuir-Blodgett (LB) technique exhibited the highest Pt/SWNT ratio and also the best hydrogen uptake. 相似文献