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991.
It is well known that N(2) in the ion source of a mass spectrometer interferes with the CO background during the δ(18)O measurement of carbon monoxide. A similar problem arises with the high-temperature conversion (HTC) analysis of nitrogenous O-bearing samples (e.g. nitrates and keratins) to CO for δ(18)O measurement, where the sample introduces a significant N(2) peak before the CO peak, making determination of accurate oxygen isotope ratios difficult. Although using a gas chromatography (GC) column longer than that commonly provided by manufacturers (0.6 m) can improve the efficiency of separation of CO and N(2) and using a valve to divert nitrogen and prevent it from entering the ion source of a mass spectrometer improved measurement results, biased δ(18)O values could still be obtained. A careful evaluation of the performance of the GC separation column was carried out. With optimal GC columns, the δ(18)O reproducibility of human hair keratins and other keratin materials was better than ± 0.15 ‰ (n=5; for the internal analytical reproducibility), and better than ± 0.10 ‰ (n=4; for the external analytical reproducibility). 相似文献
992.
Liu Y Irving D Qiao W Ge D Levicky R 《Journal of the American Chemical Society》2011,133(30):11588-11596
Morpholinos (MOs) are DNA analogues whose uncharged nature can bring fundamental advantages to surface hybridization technologies such as DNA microarrays, by using MOs as the immobilized, or "probe", species. Advancement of MO-based diagnostics, however, is challenged by limited understanding of the surface organization of MO molecules and of how this organization impacts hybridization kinetics and thermodynamics. The present study focuses on hybridization kinetics between monolayers of MO probes and DNA targets as a function of the instantaneous extent of hybridization (i.e., duplex coverage), total probe coverage, and ionic strength. Intriguingly, these experiments reveal distinct kinetic stages, none of which are consistent with Langmuir kinetics. The initial stage, in which duplex coverage remains relatively sparse, indicates confluence of two effects: blockage of target access to unhybridized probes by previously formed duplexes and deactivation of the solid support due to consumption of probe molecules. This interpretation is consistent with a surface organization in which unhybridized MO probes localize near the solid support, underneath a layer of MO-DNA duplexes. As duplex coverage builds, provided saturation is not reached first, the initial stage can transition to an unusual regime characterized by near independence of hybridization rate on duplex coverage, followed by a prolonged approach to equilibrium. The possible origins of these more complex latter behaviors are discussed. Comparison with published data for DNA and peptide nucleic acid (PNA) probes is carried out to look for universal trends in kinetics. This comparison reveals qualitative similarities when comparable surface organization of probes is expected. In addition, MO monolayers are found capable of a broad range of reactivities that span reported values for PNA and DNA probes. 相似文献
993.
A study of radiation damping e ects in inhomogeneously broadened systems leads to an analytical theorem that relates the time integral area of the nuclear magnetic resonance signal to the tipping angle of the magnetization caused by the circuit generated reaction field. The theorem is applied to predict relative signal areas in examples of pulse sequences. In a few selected cases these predictions are also checked by experiment. 相似文献
994.
Wiebe van der Hoek Cees Witteveen Michael Wooldridge 《International Journal of Game Theory》2013,42(3):639-671
The concept of program equilibrium, introduced by Howard (Theory and Decision 24(3):203–213, 1988) and further formalised by Tennenholtz (Game Econ Behav 49:363–373, 2004), represents one of the most ingenious and potentially far-reaching applications of ideas from computer science in game theory to date. The basic idea is that a player in a game selects a strategy by entering a program, whose behaviour may be conditioned on the programs submitted by other players. Thus, for example, in the prisoner’s dilemma, a player can enter a program that says “If his program is the same as mine, then I cooperate, otherwise I defect”. It can easily be shown that if such programs are permitted, then rational cooperation is possible even in the one-shot prisoner’s dilemma. In the original proposal of Tennenholtz, comparison between programs was limited to syntactic comparison of program texts. While this approach has some considerable advantages (not the least being computational and semantic simplicity), it also has some important limitations. In this paper, we investigate an approach to program equilibrium in which richer conditions are allowed, based on model checking—one of the most successful approaches to reasoning about programs. We introduce a decision-tree model of strategies, which may be conditioned on strategies of others. We then formulate and investigate a notion of “outcome” for our setting, and investigate the complexity of reasoning about outcomes. We focus on coherent outcomes: outcomes in which every decision by every player is justified by the conditions in his program. We identify a condition under which there exist a unique coherent outcome. We also compare our notion of (coherent) outcome with that of (supported) semantics known from logic programming. We illustrate our approach with many examples. 相似文献
995.
996.
Leonard D. Tijing Woorim Choi Zhe Jiang Altangerel Amarjargal Chan-Hee Park Hem Raj Pant Ik-Tae Im Cheol Sang Kim 《Current Applied Physics》2013,13(7):1247-1255
Composite nanofibrous mat composed of neat polyurethane (PU) and multiwalled carbon nanotubes/polyurethane (MWNT/PU) nanofibers have been fabricated by one-step angled two-nozzle electrospinning. The morphological, thermal, and mechanical properties of the electrospun nanofibers were evaluated. The diameters of electrospun neat PU and composite nanofibers ranged from 239 to 1058 nm. The two-nozzle electrospun (MWNT/PU)/PU composite nanofibers showed curly, and randomly-oriented fibers with interfiber bonding, and were generally bigger in size than single-nozzle electrospun nanofibers. The tensile strength of the neat PU composite nanofiber mat obtained from two-nozzle electrospinning was 25% higher than that obtained from neat PU single-nozzle electrospinning. The incorporation of MWNTs in the composite nanofiber increased the tensile strength by as much as 64% without reducing elongation, made the composite nanofiber more thermally stable, and improved the melting zone. The present results showed that side-by-side angled two-nozzle electrospinning can improve the quality of the electrospun nanofibers that could have potential application in different fields such as filtration, protective clothing and tissue engineering. 相似文献
997.
Leonard D. Tijing Altangerel Amarjargal Zhe Jiang Michael Tom G. Ruelo Chan-Hee Park Hem Raj Pant Dong-Won Kim Dong Hwan Lee Cheol Sang Kim 《Current Applied Physics》2013,13(1):205-210
In this study, tourmaline (TM) nanoparticles (NPs) were incorporated in a polyurethane (PU) matrix by electrospinning and silver (Ag) nanoparticles in the form of wire-like structure were further decorated on the TM/PU nanofibrous mat by photoreduction under ultraviolet light irradiation. The incorporation of TM NPs has increased the conductivity of the solution, thus forming thinner fiber diameters compared to neat PU, but with improved tensile strength. Wire-like, agglomerated Ag NPs were decorated on the TM/PU matrix, and exhibited high bactericidal activity depending on the Ag content. The present antibacterial Ag/TM/PU hybrid mat has potential application in water treatment. 相似文献
998.
Kamilla Malek Krzysztof Zborowski Krzysztof Gebski Leonard M. Proniewicz Grzegorz Schroeder 《Molecular physics》2013,111(14):1823-1833
The aromaticity and atomic charge distribution were investigated for the mono- and disubstituted 1,3,4-oxadiazoles. Using an electron density-based approach (B3LYP), the structures of the molecules were estimated, then the changes of π-electron delocalization of the heterocyclic ring were estimated based on geometric (HOMA) as well as magnetic properties (NICS). Aromaticity of the oxadiazole ring varies to some extend depending on the electron character of the substituent, however, the two methods do not correlate well. The HOMA approach suggests a non-aromatic character for the oxadiazole ring, while NICS predicts a relatively high aromaticity. Additionally, two computational methodologies were used for quantitative measures of atomic charges, i.e. AIM and GAPT. Results of these computations reveal accumulation of electron density inside the heterocyclic ring due to substitution by the aryl groups and its significant removal in the presence of the imino group. However, both procedures suggest different explanation of this fact. 相似文献
999.
Krzysztof K. Zborowski Mehrdad Mohammadpour Amir Sadeghi Leonard M. Proniewicz 《Molecular physics》2013,111(8):958-967
3-hydroxy-pyridin-4-one is a parent molecule for the family of hydroxypyridinones that are known in coordination chemistry as efficient metal ions chelators. In this work, relative stabilities of some possible tautomers were investigated using several quantum chemical methods: CBS (complete basis set methods), Gn, DFT (density functional theory), Hartree–Fock and MP2. Performed calculations show that the system under consideration exists as a mixture of two tautomers with comparable energies. Among them, the hydroxypyridinone structure of the studied molecular system seems to be a bit more stable than the o-dihydroxypyridine one, by a few kJ/mol only. Aromaticity and intra-molecular hydrogen bonding are the main effects influencing the stability of the studied tautomeric structures. Consequently, aromatic effects were calculated using several indices of aromaticity: HOMA (harmonic oscillator model of aromaticity), NICS (nucleus independent chemical shift), H, PDI (para delocalisation index), MCI (multi-centre index) and ASE (aromatic stabilisation energy). The strength of possible intra-molecular hydrogen bonds (H-bonds) was determined by means of the AIM (atoms-in-molecules) method and by calculating enthalpies for theoretical reactions that do or do not involve H-bonds. The AIM method was employed to understand how variations in atomic energies influence the stability of different tautomeric structures. 相似文献
1000.
A formulation is given which permits the rapid mechanical computation of the three radial distribution functions gij (r) of a binary hard-sphere mixture to any distance r, in the Percus-Yevick (P-Y) approximation. The consistency of the P-Y equation of state obtained by various methods is discussed. 相似文献