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71.
聚丙烯酰胺/醋酸铬与聚丙烯酰胺/酚醛胶态分散凝胶的纳米颗粒自组织分形结构 总被引:5,自引:0,他引:5
采用原子力显微镜 ,分别对无机交联体系聚丙烯酰胺 Cr3+ 和有机交联体系聚丙烯酰胺 酚醛胶态分散凝胶的微观结构进行了显微图像分析 .发现无论是在有机还是无机交联体系中 ,也无论聚丙烯酰胺和交联剂浓度如何变化 ,在微米尺度上最终形成的都是具有自相似性的树枝状分形图像 ,在更小尺度上则发现单个小树杈分形体都是由纳米级的颗粒紧密堆积而成 .在所研究的胶态分散凝胶体系中 ,树枝状分形结构的形成及其具体的形态取决于聚丙烯酰胺的浓度 ,而交联剂的有无及其多少只对树枝状凝胶分形的几何形态产生一定影响 .实验结果还表明纳米级 (≤ 10 0nm)的胶体颗粒构成的分形结构的凝胶其弹性模量G′比微米级的高出一个数量级 .且粒子尺度越小 ,则凝胶的力学稳定性越强 相似文献
72.
Rat V. André P. Aubreton J. Elchinger M.F. Fauchais P. Lefort A. 《Plasma Chemistry and Plasma Processing》2002,22(4):453-474
The calculation of two-temperature transport coefficients in an argon–hydrogen plasma at atmospheric pressure is performed using a new theory of two-temperature transport properties recently presented. The latter takes into account the coupling between electrons and heavy species, coupling neglected in the already existing theories of Devoto and Bonnefoi. Transport coefficients are calculated at two-temperatures, the kinetic temperature of electrons Te being different from that of heavy species Th. This paper is divided into two parts. The first one is related to elastic processes and its aim is to compare the results obtained with this new theory for viscosity , translational thermal conductivities tr
e and tr
h and electrical conductivity with the previous results of Bonnefoi. The composition is calculated with the modified equilibrium constant of van de Sanden et al. and the most recent interaction potential are discussed. As it could be expected the electron translational thermal conductivity and the electrical conductivity calculated when taking into account or not the coupling between electrons and heavy species show non-negligible discrepancies. Besides this comparison, the results also show the drastic influence of the non-equilibrium parameter =Te/Th on the values of , , tr
e, and tr
h. 相似文献
73.
Human serum is routinely measured for total calcium content in clinical studies. A definitive high-accuracy and low-uncertainty method is required for reference measurements to underpin medical diagnoses. This study presents a novel octopole collision cell ICP-MS, high-accuracy, methodology and comparison of that technique with double-focusing sector field ICP-MS and an ICP-OES method. Double-matched isotope dilution mass spectrometry (IDMS) was employed for ICP-MS techniques and an exact matching bracketing technique using scandium as an internal standard was used for ICP-OES analysis. Medium resolution mode was utilised for double-focusing sector field ICP-MS analysis to resolve the dominant interferences on the 44Ca/42Ca isotope pair. Hydrogen reaction gas was employed to chemically resolve a number of polyatomic interferences predominantly through charge transfer reactions in the octopole collision cell. Comparison data presented for NIST CRM 909b human serum analysis from all three techniques demonstrates highest accuracy (99.6%) and lowest uncertainty (1.1%) for octopole collision cell ICP-MS. Data from ICP-OES using a non-IDMS technique produces comparably accurate data and low-uncertainties. The much higher total expanded uncertainties for double-focusing sector field ICP-MS compared with octopole collision cell data are explained by lower precision on the measurement of the 44Ca/42Ca isotope ratio. Data for octopole collision cell ICP-MS submitted for an international blind trial comparison (CCQM K-14) demonstrated excellent agreement with the mean of all participants with a low expanded uncertainty. 相似文献
74.
TIMING OF COLLISION BETWEEN THE NORTH AND SOUTH CHINA BLOCKS——THE Sm-Nd ISOTOPIC AGE EVIDENCE 总被引:8,自引:0,他引:8
Sm-Nd isotopic ages for C-type eclogite (243.9±5.6 Ma) and mafic and ultramafic rocks(230.6±30.7 Ma and 402.6±17.4 Ma) from the Qinling-Dabieshan orogenic belt are reported.These ages suggest that at the early Triassic, the North and South China Blocks have beenunited along the Qinling-Dabieshan collision zone, and before the final collision, a se-ries of ophiolite obductions took place successively away from the continental marginduring the Paleozoic. 相似文献
75.
Clemens?Uanschou Roswitha?Frieht Fritz?PittnerEmail author 《Monatshefte für Chemie / Chemical Monthly》2005,136(8):1365-1381
Summary. In contrast to eukaryotic cells certain eubacterial strains have acquired the ability to utilize L-carnitine (R-(–)-3-hydroxy-4-(trimethylamino)butyrate) as sole source of energy, carbon and nitrogen. The first step of the L-carnitine degradation to glycine betaine is catalysed by L-carnitine dehydrogenase (L-CDH, EC 1.1.1.108) and results in the formation of the dehydrocarnitine. During the oxidation of L-carnitine a simultaneous conversion of the cofactor NAD+ to NADH takes place. This catabolic reaction has always been of keen interest, because it can be exploited for spectroscopic L-carnitine determination in biological fluids – a quantification method, which is developed in our lab – as well as L-carnitine production.Based on a cloned L-CDH sequence an expedition through the currently available prokaryotic genomic sequence space began to mine relevant information about bacterial L-carnitine metabolism hidden in the enormous amount of data stored in public sequence databases. Thus by means of homology-based and context-based protein function prediction is revealed that L-CDH exists in certain eubacterial genomes either as a protein of approximately 35 kDa or as a homologous fusion protein of approximately 54 kDa with an additional putative domain, which is predicted to possess a thioesterase activity. These two variants of the enzyme are found on one hand in the genome sequence of bacterial species, which were previously reported to decompose L-carnitine, and on the other hand in gram-positive bacteria, which were not known to express L-CDH. Furthermore we could not only discover that L-CDH is located in a conserved genetic entity, which genes are very likely involved in this L-carnitine catabolic pathway, but also pinpoint the exact genomic sequence position of several other enzymes, which play an essential role in the bacterial metabolism of L-carnitine precursors. 相似文献
76.
77.
A three-dimensional pharmacophore model was developed from a series of inhibitors of Aurora A kinase to discover new potent anti-cancer agents using the HypoGen module in the Catalyst software. The pharmacophore model was developed based on the structure of 20 currently available inhibitors, which were carefully selected from the literature. The best hypothesis (Hypo 1) was defined by four features: one hydrogen-bond donor and three hy- drophobic points, with the best correlation coefficient of 0.909, the lowest rms deviation of 1.563, and the highest cost difference of 99.075. The Hypo 1 was then validated by a test set consisting of 24 compounds and by a cross-validation of 95% confidence level through randomizing the data using the CatScramble program, which suggested that a predictive pharmacophore model had been successfully obtained. 相似文献
78.
Ohmiya H Tsuji T Yorimitsu H Oshima K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5640-5648
Details of cobalt-catalyzed cross-coupling reactions of alkyl halides with allylic Grignard reagents are disclosed. A combination of cobalt(II) chloride and 1,2-bis(diphenylphosphino)ethane (DPPE) or 1,3-bis(diphenylphosphino)propane (DPPP) is suitable as a precatalyst and allows secondary and tertiary alkyl halides--as well as primary ones--to be employed as coupling partners for allyl Grignard reagents. The reaction offers a facile synthesis of quaternary carbon centers, which has practically never been possible with palladium, nickel, and copper catalysts. Benzyl, methallyl, and crotyl Grignard reagents can all couple with alkyl halides. The benzylation definitely requires DPPE or DPPP as a ligand. The reaction mechanism should include the generation of an alkyl radical from the parent alkyl halide. The mechanism can be interpreted in terms of a tandem radical cyclization/cross-coupling reaction. In addition, serendipitous tandem radical cyclization/cyclopropanation/carbonyl allylation of 5-alkoxy-6-halo-4-oxa-1-hexene derivatives is also described. The intermediacy of a carbon-centered radical results in the loss of the original stereochemistry of the parent alkyl halides, creating the potential for asymmetric cross-coupling of racemic alkyl halides. 相似文献
79.
The kinetic method is one of the most widely used experimental techniques for the measurement of thermochemical parameters by mass spectrometry. Recently it has been realized that it can also be used to determine reaction entropies, but the validity of this approach has not been established. This Perspective evaluates kinetic method plots in cases where there is a significant entropy difference between the competing fragmentation channels (i.e. between sample and reference compounds in the dissociating cluster ion). The concept underlying this study is to calculate mass spectra theoretically, based on known thermochemical parameters and as a function of experimental conditions. This can be done accurately using the RRKM-based MassKinetics software. The resulting mass spectra are then interpreted by the kinetic method, yielding DeltaH and DeltaS values. These values are, in turn, compared with the true values used to generate the calculated mass spectra. The results show that the reaction entropy difference between sample and reference has a very large influence on kinetic method plots. This should always be considered when studying energy-dependent mass spectra (using metastable ions or low- or high-energy collision-induced dissociation (CID)), even if only DeltaH is to be determined. Kinetic method plots are not strictly linear and this becomes a serious issue in the case of small molecules showing a large entropy effect. In such cases, results obtained at a low degree of excitation are more accurate. Energy and entropy effects can be evaluated in a relatively straightforward manner: first, the apparent Gibbs energy (DeltaG(app)) and effective temperature (T(eff)) are determined from kinetic method plots (intercept and slope, respectively), obtained from experiments using various degrees of excitation. Second, the resulting DeltaG(app) is plotted against T(eff), the slope yielding DeltaS while the intercept (extrapolation to zero temperature) yields DeltaH. This data evaluation yields more accurate results than alternative methods used in the literature. The resulting DeltaH values are fairly accurate, with errors, in most cases, <4 kJ mol(-1). On the other hand, DeltaS is systematically underestimated by 20-40%. Empirically scaling DeltaS values determined by the kinetic method by 1.35 results in a DeltaS value within 20% (or 10 J mol(-1) K(-1)) of the theoretical value. 相似文献
80.
New spin-state-selective (S3) NMR pulse sequences exclusively applying cross-polarization schemes to achieve optimum homonuclear and heteronuclear 1H-X coherence transfer are reported for the simple and accurate measurement of the magnitude and sign of heteronuclear coupling constants for samples at natural abundance. The proposed spin-edited HCP-TOCSY experiments are based on clean heteronuclear S3 excitation, generated by simultaneous co-addition of two independent in-phase and anti-phase components created during the mixing heteronuclear J-cross-polarization (HCP) step, which is finally transferred to other protons by a conventional homonuclear TOCSY mechanism. Selective 1D and non-selective 2D approaches for the easy determination of long-range proton-carbon and proton-nitrogen coupling constants on any protonated and non-protonated heteronuclei are presented and discussed for several organic molecules. 相似文献