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1.
Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study 下载免费PDF全文
Claudia Loerbroks Eliot Boulanger Prof. Dr. Walter Thiel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5477-5487
We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent. 相似文献
2.
Daniel Heinz Annette Meister Hazrat Hussain Karsten Busse Jörg Kressler 《Journal of polymer science. Part A, Polymer chemistry》2020,58(23):3322-3335
Adding perfluoroalkyl (PF) segments to amphiphilic copolymers yields triphilic copolymers with new application profiles. Usually, PF segments are attached as terminal blocks via Cu(I) catalyzed azide-alkyne cycloaddition (CuAAC). The purpose of the current study is to design new triphilic architectures with a PF segment in central position. The PF segment bearing bifunctional atom transfer radical polymerization (ATRP) initiator is employed for the fabrication of triphilic poly(propylene oxide)-b-poly(glycerol monomethacrylate)-b-PF-b-poly(glycerol monomethacrylate)-b-poly(propylene oxide) PPO-b-PGMA-b-PF-b-PGMA-b-PPO pentablock copolymers by a combined ATRP and CuAAC reaction approach. Differential scanning calorimetry indicates the PF-initiator to undergo a solid–solid phase transition at 63°C before the final crystal melting at 95°C. This is further corroborated by polarized optical microscopy and X-ray diffraction studies. The PF-initiator could successfully polymerize solketal methacrylate (SMA) under typical ATRP conditions producing well-defined Br-PSMA-b-PF-b-PSMA-Br triblock copolymers that are then converted into PPO-b-PSMA-b-PF-b-PSMA-b-PPO pentablock copolymer via CuAAC reaction. Subsequently, acid hydrolysis of the PSMA blocks afforded water soluble well-defined triphilic pentablock copolymers PPO-b-PGMA-b-PF-b-PGMA-b-PPO with fluorophilic central segment, hydrophilic middle blocks, and lipophilic outer blocks. The triphilic block copolymers could self-assemble, depending upon the preparatory protocol, into spherical and filament-like phase-separated nanostructures as revealed by transmission electron microscopy. 相似文献
3.
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The hyperfine fields for the systems140CeLa and140CeLu have been determined by time differential perturbed angular correlations (TDPAC) in the temperature range 4.2 K≤T≤330 K. Magnitude and temperature dependence of the paramagnetic enhancement factor β indicate that cerium in either system
is of intermediate valence. This behaviour is discussed in terms of a theory proposed by Ramakrishnan et al. [1–3]. 相似文献
5.
On interpolatory divergence-free wavelets 总被引:1,自引:0,他引:1
We construct interpolating divergence-free multiwavelets based on cubic Hermite splines. We give characterizations of the relevant function spaces and indicate their use for analyzing experimental data of incompressible flow fields. We also show that the standard interpolatory wavelets, based on the Deslauriers-Dubuc interpolatory scheme or on interpolatory splines, cannot be used to construct compactly supported divergence-free interpolatory wavelets.
6.
Anissa Gömann Karsten Gömann Volker Kempter Wolfgang Maus-Friedrichs 《Applied Surface Science》2005,252(1):196-199
Perovskites of ABO3 type like strontium titanate (SrTiO3) are of great practical concern as materials for oxygen sensors operating at high temperatures. It is well known that the surface layer shows different properties compared to the bulk. Numerous studies exist for the SrTiO3(1 0 0) and (1 1 0) surfaces which have investigated the changes in the electronic structure and topography as a function of the preparation conditions. They have indicated a rather complex behaviour of the surface and the near surface region of SrTiO3 at elevated temperatures. Up to now, the behaviour of the SrTiO3(1 1 1) surfaces under thermal treatment is not sufficiently known. This contribution is intended to work out the relation between alteration of the surface topography with respect to the preparation conditions and the simultaneous changes of the electronic structure. We applied scanning tunneling microscopy (STM) to investigate the surface topography and, additionally, metastable impact electron spectroscopy (MIES) to study the surface electronic structure of reconstructed SrTiO3(1 1 1) surfaces. The crystals were heated up to 1000 °C under reducing and oxidizing conditions. Both preparation conditions cause strong changes of the surface topography and electronic structure. A microfaceting of the topmost layers is found. 相似文献
7.
Bradley L. Thiel 《Mikrochimica acta》2004,145(1-4):243-247
The role of positive gaseous ions in the formation of secondary electron images in low vacuum scanning electron microscopes is discussed. This paper describes the charging processes and related effects that occur during high vacuum imaging of insulators and then discusses the influence of ions on those processes. The ions are responsible for a number of phenomena, including distortion of the electric field above and below the specimen surface due to space charge, removal of excess negative charge from the specimen, alteration of the specimen surface barrier, and scavenging/filtering of the secondary electron emission. The resulting electron-specimen-ion interactions can give rise to interesting contrast effects that are unique to this class of instruments. 相似文献
8.
Reaction diffusion systems on cylindrical domains with terms that vary rapidly and periodically in the unbounded direction can be analyzed by averaging techniques. Here, using iterated normal form transformations and Gevrey regularity of bounded solutions, we prove a result on exponential averaging for such systems, i.e., we show that traveling wave solutions can be described by a spatially homogenous equation and exponentially small remainders. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
9.
P Nürnberg I Barth E Fuhrmann C Lenzner T Losanova C Peters H P?che G Thiel 《Electrophoresis》1991,12(2-3):186-192
Germline and somatic instability of the human genome was studied, using synthetic oligonucleotides specific for simple repeat motifs. The following probes were used: (GTG)5, (GACA)4, (GATA)4, (CT)8, (TTAGGG)3, (GT)8, (GAA)6 and (GGAT)4. Each of them is unique with respect to the target regions recognized in the genome. Thus compilation of the various fingerprint data provides a complex map of the genome (and its deviations). While the fingerprints of differentiated somatic tissues never showed any alterations, in tumor tissues (namely gliomas) many changes could be detected. Most of the latter reflect secondary karyological aberrations. In nearly one third of the gliomas, drastically amplified and apparently monomorphic DNA fragments were identified. This marker should make it possible to deal with causal pathogenetic mechanisms as well as novel diagnostic strategies. 相似文献
10.