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891.
Zhaohui Li David Hughes Jill P.G. Urban Zhanfeng Cui 《Journal of membrane science》2008,310(1-2):237-245
There is a growing interest in using large pore size probes for microdialysis of macromolecular markers to monitor cell and tissue functions. Fluid balance could be an important issue when using large pore size microdialysis probes, which are affected by the mode of operation. In this study, the effect of pumping systems, push, pull, push-and-pull, and the resulting transmembrane pressure on the fluid balance, as well as, the relative recovery of small molecular nutrients and metabolites and macromolecules (proteins) were examined. The validity of the internal reference in situ calibration was examined in detail. It is concluded that a push-and-pull system is the only effective method of eliminating fluid loss or gain. The relative recovery of small solutes is not affected much by the applied pumping methods; however, the relative recovery of macromolecules is significantly influenced by them. The in situ calibration technique using Phenol Red can provide reliable results for small molecules including glucose and lactic acid. Using 10 and 70-kDa fluorescent dextrans as the internal standard for large molecules in situ calibration of similar size does not work for the pull pump system, but does work well when using a push-and-pull pumping method. 相似文献
892.
A Monte Carlo model is utilized for studying the behavior of electrons in the afterglow of an analytical microsecond dc pulsed glow discharge. This model uses several quantities as input data, such as electric field and potential, ion flux at the cathode, the fast argon ion and atom impact ionization rates, slow electron density, the electrical characterization of the pulse (voltage and current profiles) and temperature profile. These quantities were obtained by earlier Monte Carlo — fluid calculations for a pulsed discharge. Our goal is to study the behavior of the so-called Monte Carlo electrons (i.e., those electrons created at the cathode or by ionization collisions in the plasma which are followed by using the Monte Carlo model) from their origin to the moment when they are absorbed at the cell walls or when they have lost their energy by collisions (being transferred to the group of slow electrons) in the afterglow of the pulsed discharge. The thermalization of the electrons is a phenomenon where the electron-electron Coulomb collisions acquire a special importance. Indeed, in the afterglow the cross sections of the other electron reactions taken into account in the model are very low, because of the very low electron energy. We study the electron energy distributions at several times during and after the pulse and at several positions in the plasma cell, focusing on the thermalization and on the behavior of the electrons in the afterglow. Also, the time evolution of the rates of the various collision processes, the average electron energy, the densities of Monte Carlo and slow electrons and the ionization degree are investigated. 相似文献
893.
Simcha Srebnik 《Journal of polymer science. Part A, Polymer chemistry》2008,46(24):2711-2718
We use a coarse-grained Monte Carlo model to further investigate the association of polymers with carbon nanotubes (CNTs). Previous studies have shown ordered helical wrapping conformations for a range of investigated parameters. Such adsorbed conformations allow the polymers to spiral up and down the surface of the nanotube, retaining their helical state. We analyze the helical pitch of such conformations, and relate it to nanotube radius and chain stiffness using a simple model. The model reveals that the helical pitch is approximately determined by the matching between the radius of curvature of the helix with the average bending angle of the polymer, determined by its persistence length. In addition, we simulate adsorption of block and triblock copolymers (BCPs) whose different blocks are differentiated by their degree of association with the nanotube (hydrophobic or polar). The hydrophobic blocks of the copolymers initially adsorb in both helical and random conformations of the hydrophobic block, depending on which part of the chain (center or ends) adsorbs first on the CNTs surface. In both configurations, however, the polar block extends away from the nanotube, forming loops and tails for triblock and diBCPs, respectively. Such configurations may improve the interfacial adhesion in polymer–CNTs composites. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2711–2718, 2008 相似文献
894.
895.
David Lee Duewer 《Accreditation and quality assurance》2008,13(4-5):193-216
While estimation of measurement uncertainty (MU) is increasingly acknowledged as an essential component of the chemical measurement
process, there is little agreement on how best to use even nominally well-estimated MU. There are philosophical and practical
issues involved in defining what is “best” for a given data set; however, there is remarkably little guidance on how well
different MU-using estimators perform with imperfect data. This report characterizes the bias, efficiency, and robustness
properties for several commonly used or recently proposed estimators of true location, μ, using “Monte Carlo” (MC) evaluation of “measurement” data sets drawn from well-defined distributions. These synthetic models
address a number of issues pertinent to interlaboratory comparisons studies. While the MC results do not provide specific
guidance on “which estimator is best” for any given set of real data, they do provide broad insight into the expected relative
performance within broadly defined scenarios. Perhaps the broadest and most emphatic guidance from the present study is that
(1) well-estimated measurement uncertainties can be used to improve the reliability of location determination and (2) some
approaches to using measurement uncertainties are better than others. The traditional inverse squared uncertainty-weighted
estimators perform well only in the absence of unrepresentative values (value outliers) or underestimated uncertainties (uncertainty
outliers); even modest contamination by such outliers may result in relatively inaccurate estimates. In contrast, some inverse
total variance-weighted-estimators and probability density function area-based estimators perform well for all scenarios evaluated,
including underestimated uncertainties, extreme value outliers, and asymmetric contamination. 相似文献
896.
新型螯合树脂在线预富集测定海水中痕量Cd 总被引:1,自引:0,他引:1
将新型螯合树脂(XAD-H2Dz)应用于微柱现场在线采样(MFS)新技术中,实现了海水样中痕量Cd的在线原位预富集和实验室中流动注射-火焰原子吸收(FI-FAAS)系统的联机测定。采样体积为5 mL和50 mL时,检出限(3σ)分别为68和6.7 ng/L;相对标准偏差(n=7)分别为2.0%和2.6%。对国家海水微量元素标准物质GBW(E)080040和实际样品(大连老虎滩区域海水以及连云港黄海水域)中镉进行分析,均获得了满意的结果。 相似文献
897.
Cyclodextrins and antibodies have been used as affinity agents to improve relative recovery during microdialysis sampling. Two neuropeptides, methionine-enkephalin (ME) and leucine-enkephalin (LE), were chosen to compare the use of cyclodextrins and antibodies as possible affinity agents for improving their relative recovery across polycarbonate and polyethersulfone membranes during in vitro sampling. Cyclodextrins (CD) including β-CD, 2-hydroxypropyl-β-cyclodextrin (2HPβ-CD), and γ-CD gave improvements of relative recovery for both peptides of less than 2-fold as compared to controls. Comparisons of relative recovery between tyrosine–glycine–glycine, tyrosine, and phenylalanine using different cyclodextrins in the perfusion fluid were also obtained. Inclusion of an antibody against met-enkephalin in the microdialysis perfusion fluid resulted in relative recovery increases of up to 2.5-fold. These results show that using antibodies as affinity agents during microdialysis sampling may be more effective agents to improve the relative recovery of these opioid neuropeptides. 相似文献
898.
899.
Armando Berlanga-Vázquez Radu A. Talmazan Carlos A. Reyes-Mata Prof. Edmundo G. Percástegui Dr. Marcos Flores-Alamo Prof. Maren Podewitz Prof. Ivan Castillo 《欧洲无机化学杂志》2023,26(6):e202200596
Functionalization of the phenolic rim of p-tert-butylcalix[8]arene with phenanthroline to create a cavity leads to formation of two regioisomers. Substitution of positions 1 and 5 produces the known C2v-symmetric regioisomer 1,5-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L1,5 ), while substitution of positions 1 and 4 produces the Cs-symmetric regioisomer 1,4-(2,9-dimethyl-1,10-phenanthroyl)-p-tert-butylcalix[8]arene ( L1,4 ) described herein. [ Cu(L1,4)I ] was synthesized from L1,4 and CuI in good yield and characterized spectroscopically. To evaluate the effect of its cavity on catalysis, Ullmann-type C−S coupling was chosen as proof-of-concept. Selected aryl halides were used, and the results compared with the previously reported Cu(I)/ L1,5 system. Only highly activated aryl halides generate the C−S coupling product in moderate yields with the Cu(I)/ L1,4 system. To shed light on these observations, detailed computational investigations were carried out, revealing the influence of the calix[8]arene macrocyclic morphology on the accessible conformations. The L1,4 regioisomer undergoes a deformation that does not occur with L1,5 , resulting in an exposed catalytic center, presumably the cause of the low activity of the former system. The 1,4-connectivity was confirmed in the solid-state structure of the byproduct [ Cu(L1,4 − H) (CH3CN)2] that features Cu(I) coordinated inside a cleft defined by the macrocyclic framework. 相似文献
900.
Avigyan Naskar Kousik Kumar Bhanja Rakesh Kumar Roy Dr. Niladri Patra 《Chemphyschem》2023,24(21):e202300306
Mutations in multi-domain leucine-rich repeat kinase 2 (LRRK2) have been an interest to researchers as these mutations are associated with Parkinson's disease. G2019S mutation in LRRK2 kinase domain leads to the formation of additional hydrogen bonds by S2019 which results in stabilization of the active state of the kinase, thereby increasing kinase activity. Two additional hydrogen bonds of S2019 are reported separately. Here, a mechanistic picture of the formation of additional hydrogen bonds of S2019 with Q1919 (also with E1920) is presented using ‘active’ Roco4 kinase as a homology model and its relationship with the stabilization of the ‘active’ G2019S LRRK2 kinase. A conformational flipping of residue Q1919 was found which helped to form stable hydrogen bond with S2019 and made ‘active’ state more stable in G2019S LRRK2. Two different states were found within the ‘active’ kinase with respect to the conformational change (flipping) in Q1919. Two doubly-mutated systems, G2019S/Q1919A and G2019S/E1920 K, were studied separately to check the effect of Q1919 and E1920. For both cases, the stable S2 state was not formed, leading to a decrease in kinase activity. These results indicate that both the additional hydrogen bonds of S2019 (with Q1919 and E1920) are necessary to stabilize the active G2019S LRRK2. 相似文献