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1.
Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study
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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
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Annals of the Institute of Statistical Mathematics - The segmentation of a time series into piecewise stationary segments is an important problem both in time series analysis and signal processing.... 相似文献
3.
Claudia Poloni Marc C. A. Stuart Pieter van der Meulen Wiktor Szymanski Ben L. Feringa 《Chemical science》2015,6(12):7311-7318
The external photocontrol over peptide folding, by the incorporation of molecular photoswitches into their structure, provides a powerful tool to study biological processes. However, it is limited so far to switches that exhibit only a rather limited geometrical change upon photoisomerization and that show thermal instability of the photoisomer. Here we describe the use of an overcrowded alkene photoswitch to control a model β-hairpin peptide. This photoresponsive unit undergoes a large conformational change and has two thermally stable isomers which has major influence on the secondary structure and the aggregation of the peptide, permitting the phototriggered formation of amyloid-like fibrils. 相似文献
4.
Guanidine‐Based Polymer Brushes Grafted onto Silica Nanoparticles as Efficient Artificial Phosphodiesterases
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Claudia Savelli Riccardo Salvio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5856-5863
Polymer brushes grafted to the surface of silica nanoparticles were fabricated by atom‐transfer radical polymerization (ATRP) and investigated as catalysts in the cleavage of phosphodiesters. The surfaces of silica nanoparticles were functionalized with an ATRP initiator. Surface‐initiated ATRP reactions, in varying proportions, of a methacrylate moiety functionalized with a phenylguanidine moiety and an inert hydrophilic methacrylate species afforded hybrid nanoparticles that were characterized with potentiometric titrations, thermogravimetric analysis, and SEM. The activity of the hybrid nanoparticles was tested in the transesterification of the RNA model compound 2‐hydroxypropyl para‐nitrophenylphosphate (HPNP) and diribonucleoside monophosphates. A high catalytic efficiency and a remarkable effective molarity, thus overcoming the effective molarities previously observed for comparable systems, indicate the existence of an effective cooperation of the guanidine/guanidinium units and a high level of preorganization in the nanostructure. The investigated system also exhibits a marked and unprecedented selectivity for the diribonucleoside sequence CpA. The results presented open up the way for a novel and straightforward strategy for the preparation of supramolecular catalysts. 相似文献
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Claudia Garetto 《Acta Appl Math》2004,80(2):123-174
The aim of this work is to develop a global calculus for pseudo-differential operators acting on suitable algebras of generalized functions. In particular, a condition of global hypoellipticity of the symbols gives a result of regularity for the corresponding pseudo-differential equations. This calculus and this frame are proposed as tools for the study in Colombeau algebras of partial differential equations globally defined on R
n
. 相似文献
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Ralf Jäger Anatolij I. Saprykin J. Sabine Becker Hans -Joachim Dietze José A. C. Broekaert 《Mikrochimica acta》1997,125(1-4):41-44
The analytical capabilities of a high-resolution mass spectrometer in combination with a 13.56 MHz glow discharge ion source for the analysis of semiconducting materials (silicon carbide and gallium arsenide) were studied. It was shown that single positively charged ions of sample material have about 10 eV higher average energy than the ions of the discharge and residual gas. Therefore effective energy separation of the ions of analyte from the ions of the discharge and residual gas was achieved by adjusting the ion transfer optics (breadth and position of energy slit), which improves the analytical capabilities of the developed method.Some analytical applications are presented to illustrate the performance of r.f. GDMS for the bulk analysis of semiconducting materials. The results of the trace element analysis of gallium arsenide and silicon carbide samples are compared with data of independent methods (LIMS, ICP-AES, SIMS).Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthdayOn leave from the Institute of Inorganic Chemistry, 630090 Novosibirsk, Russia 相似文献
10.
Wilson A. Cañas-Marín Julián D. Ortiz-Arango Uriel E. Guerrero-Aconcha Claudia P. Soto-Tavera 《Fluid Phase Equilibria》2007
The ability of Soave–Redlich–Kwong cubic equation of state (SRK EoS) to predict densities and thermodynamic derivative properties such as thermal expansivity, isothermal compressibility, calorific capacity, and Joule–Thompson coefficients, for two gas condensates over a wide range of pressures (up to 110 MPa) was studied. The predictions of the EoS were compared to Monte Carlo simulation data obtained by Lagache et al. [M.H. Lagache, P. Ungerer, A. Boutin, Fluid Phase Equilibr. 220 (2004) 221]. Two completely different alpha functions for the SRK EoS attractive term were used and their respective effects on the predictions of such properties were analyzed. Also, two different forms of the crossed terms of the attractive parameter, aij, and three expressions of the crossed terms of the repulsive parameter, bij, were combined in different ways, and predictions were carried out. Little sensitivity of the properties on the chosen alpha function, except for the calorific capacities, was found in the systems studied. The most commonly used combination rules to model phase behavior of reservoir fluids, i.e. geometric and arithmetic forms of aij and bij, respectively, predicted very deficient results for these fluids at extreme conditions, specially for density calculations. 相似文献