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31.
Jeong Hyun Yeum Byung Chul Ji Chul Joo Lee Ji Youl Lee Sang‐Seob Lee Sam Soo Kim Joon Ho Kim Won Seok Lyoo 《Journal of polymer science. Part A, Polymer chemistry》2002,40(8):1103-1111
To prepare water‐soluble, syndiotacticity‐rich poly(vinyl alcohol) (PVA) microfibrils for various industrial applications, we synthesized syndiotacticity‐rich, low molecular weight PVA by the solution polymerization of vinyl pivalate (VPi) in tetrahydrofuran (THF) at low temperatures with 2,2′‐azobis(2,4‐dimethylvaleronitrile) (ADMVN) as an initiator and successive saponification of poly(vinyl pivalate) (PVPi). Effects of the initiator and monomer concentrations and the polymerization temperature were investigated in terms of the polymerization behaviors and molecular structures of PVPi and the corresponding syndiotacticity‐rich PVA. The polymerization rate of VPi in THF was proportional to the 0.91 power of the ADMVN concentration, indicating the heterogeneous nature of THF polymerization. The low‐temperature solution polymerization of VPi in THF with ADMVN proved to be successful in obtaining water‐soluble PVA with a number‐average degree of polymerization (Pn) of 300–900, a syndiotactic dyad content of 60–63%, and an ultimate conversion of VPi into PVPi of over 75%. Despite the low molecular weight of PVA with Pn = 800, water‐soluble PVA microfibrillar fibers were prepared because of the high level of syndiotacticity. In contrast, for PVA with Pn = 330, shapeless and globular morphologies were observed, indicating that molecular weight has an important role in the in situ fibrillation of syndiotacticity‐rich PVA. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1103–1111, 2002 相似文献
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33.
Gan Ning Bukur Dragomir Mannan M. Sam 《Journal of Thermal Analysis and Calorimetry》2018,134(2):1169-1182
Journal of Thermal Analysis and Calorimetry - Accurate data of flammability limits for flammable gases and vapors are needed to prevent fires and explosions. The flammability limit, which is the... 相似文献
34.
Hafiz Saqib Ali Dr. Richard H. Henchman Dr. Sam P. de Visser 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(57):13093-13102
A recently characterized cytochrome P450 isozyme GcoA activates lignin components through a selective O-demethylation or alternatively an acetal formation reaction. These are important reactions in biotechnology and, because lignin is readily available; it being the main component in plant cell walls. In this work we present a density functional theory study on a large active site model of GcoA to investigate syringol activation by an iron(IV)-oxo heme cation radical oxidant (Compound I) leading to hemiacetal and acetal products. Several substrate-binding positions were tested and full energy landscapes calculated. The study shows that substrate positioning determines the product distributions. Thus, with the phenol group pointing away from the heme, an O-demethylation is predicted, whereas an initial hydrogen-atom abstraction of the weak phenolic O-H group would trigger a pathway leading to ring-closure to form acetal products. Predictions on how to engineer P450 GcoA to get more selective product distributions are given. 相似文献
35.
Abstract A comparison and evaluation is made of recent proposals for multivariate matched sampling in observational studies, where the following three questions are answered: (1) Algorithms: In current statistical practice, matched samples are formed using “nearest available” matching, a greedy algorithm. Greedy matching does not minimize the total distance within matched pairs, though good algorithms exist for optimal matching that do minimize the total distance. How much better is optimal matching than greedy matching? We find that optimal matching is sometimes noticeably better than greedy matching in the sense of producing closely matched pairs, sometimes only marginally better, but it is no better than greedy matching in the sense of producing balanced matched samples. (2) Structures: In common practice, treated units are matched to one control, called pair matching or 1–1 matching, or treated units are matched to two controls, called 1–2 matching, and so on. It is known, however, that the optimal structure is a full matching in which a treated unit may have one or more controls or a control may have one or more treated units. Optimal 1 — k matching is compared to optimal full matching, finding that optimal full matching is often much better. (3) Distances: Matching involves defining a distance between covariate vectors, and several such distances exist. Three recent proposals are compared. Practical advice is summarized in a final section. 相似文献
36.
The resolutions of determinantal ideals exhibit a remarkable stability property: for fixed rank but growing dimension, the terms of the resolution stabilize (in an appropriate sense). One may wonder if other sequences of ideals or modules over coordinate rings of matrices exhibit similar behavior. We show that this is indeed the case. In fact, our main theorem is more fundamental in nature: It states that certain large algebraic structures (which are examples of twisted commutative algebras) are noetherian. These are important new examples of large noetherian algebraic structures, and ones that are in some ways quite different from previous examples. 相似文献
37.
This paper describes the development of a lattice Boltzmann (LB) model for a binary gas mixture, and applications to channel flow driven by a density gradient with diffusion slip occurring at the wall. LB methods for single component gases typically use a non‐physical equation of state in which the relationship between pressure and density varies according to the scaling used. This is fundamentally unsuitable for extension to multi‐component systems containing gases of differing molecular masses. Substantial variations in the species densities and pressures may exist even at low Mach numbers; hence, the usual linearized equation of state for small fluctuations is unsuitable. Also, existing methods for implementing boundary conditions do not extend easily to novel boundary conditions, such as diffusion slip. The new model developed for multi‐component gases avoids the pitfalls of some other LB models. A single computational grid is shared by all the species, and the diffusivity is independent of the viscosity. The Navier–Stokes equation for the mixture and the Stefan–Maxwell diffusion equation are both recovered by the model. Diffusion slip, the non‐zero velocity of a gas mixture at a wall parallel to a concentration gradient, is successfully modelled and validated against a simple one‐dimensional model for channel flow. To increase the accuracy of the scheme, a second‐order numerical implementation is needed. This may be achieved using a variable transformation method that does not increase the computational time. Simulations were carried out on hydrogen and water diffusion through a narrow channel for varying total pressure and concentration gradients. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
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39.
Kaili Ji Wee Siang Lim Sam Fong Yau Li Kishore Bhakoo 《Analytical and bioanalytical chemistry》2013,405(21):6853-6861
Aptamers are single-stranded oligonucleotides that are capable of binding wide classes of targets with high affinity and specificity. Their unique three-dimensional structures present numerous possibilities for recognizing virtually any class of target molecules, making them a promising alternative to antibodies used as molecular probes in biomedical analysis and clinical diagnosis. In recent years, cell-systematic evolution of ligands by exponential enrichment (SELEX) has been used extensively to select aptamers for various cell targets. However, aptamers that have evolved from cell-SELEX to distinguish the “stimulus-response cell” have not previously been reported. Moreover, a number of cumbersome and time-consuming steps involved in conventional cell-SELEX reduce the efficiency and efficacy of the aptamer selection. Here, we report a “two-step” methodology of cell-SELEX that successfully selected DNA aptamers specifically against “inflamed” endothelial cells. This has been termed as stimulus-response cell-SELEX (SRC-SELEX). The SRC-SELEX enables the selection of aptamers to distinguish the cells activated by stimulus of healthy cells or cells isolated from diseased tissue. We report a promising aptamer, N55, selected by SRC-SELEX, which can bind specifically to inflamed endothelial cells both in cell culture and atherosclerotic plaque tissue. This aptamer probe was demonstrated as a potential molecular probe for magnetic resonance imaging to target inflamed endothelial cells and atherosclerotic plaque detection. Schematic of SRC-SELEX selection
The cells are activated with stimulus and incubated with single-stranded DNA library. The sequences bound on the activated cells are released and amplified to incubate with naïve cells without stimulation. The sequences unbound to the naïve cells are then incubated with activated cells again and go into the next round of selection. After the selection reaches the end point, the single-stranded DNA collected from the last round is cloned and sequenced for identification 相似文献
40.
The inhibition of mild steel corrosion in aerated acid mixture of 0.5 N H2SO4 and 0.5 N HCl solution was investigated using potentiodynamic polarization studies, linear polarization studies, electrochemical impedance spectroscopy, adsorption, and surface morphological studies. The effect of inhibitor concentration on corrosion rate, degree of surface coverage, adsorption kinetics, and surface morphology is investigated. The inhibition efficiency increased markedly with increase in additive concentration. The presence of PEG and PVP decreases the double-layer capacitance and increases the charge-transfer resistance. The inhibitor molecules first adsorb on the metal surface following a Langmuir adsorption isotherm. Both PEG and PVP offer good inhibition properties for mild steel and act as mixed-type inhibitors. Surface analysis by scanning electron microscopy (SEM) and atomic force microscopy (AFM) shows that PVP offers better protection than PEG. 相似文献