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91.
Dr. Debora Scuderi Prof. Enrico Bodo Dr. Barbara Chiavarino Prof. Simonetta Fornarini Prof. Maria Elisa Crestoni 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17239-17250
The redox activity of cysteine sulfur allows numerous post‐translational protein modifications involved in the oxidative regulation of metabolism, in metal binding, and in signal transduction. A combined approach based on infrared multiple photon dissociation spectroscopy at the Centre Laser Infrarouge d'Orsay (CLIO) free electron laser facility, calculations of IR frequencies, and finite temperature ab initio molecular dynamics simulations has been employed to characterize the gas‐phase structures of deprotonated cysteine sulfenic, sulfinic, and sulfonic acids, [cysSOx]? (x=1, 2, 3, representing the number of S‐bound oxygen atoms), which are key intermediates in the redox‐switching chemistry of proteins. The ions show different structural motifs owing to preferential binding of the proton to either the carboxylate or sulfur‐containing group. Due to the decreasing basicity of the sulfenic, sulfinic, and sulfonic terminals, the proton bound to SO? in [cysSO]? migrates to the carboxylate in [cysSO3]?, whereas it turns out to be shared in [cysSO2]?. Evidence is gathered that a mixture of close‐lying low‐energy conformers is sampled for each cysteine oxo form in a Paul ion trap at room temperature. 相似文献
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Ute Heinze Jens Schaller Thomas Heinze Stefan Horner Bodo Saake Jürgen Puls 《Cellulose (London, England)》2000,7(2):161-175
The determination of the molecular structure of 2,3-O-carboxymethyl cellulose (2,3-O-CMC), prepared via 6-O-(4-monomethoxy)triphenylmethyl cellulose, was carried out in detail by means of enzymatic and chemical methods. The 2,3-O-CMCs had degrees of substitution (DS) in the range of 0.5–1.2 showing a narrow molar mass distribution as revealed by SEC. As a result of an endoglucanase treatment, an intensive depolymerization of the samples occurred which was more pronounced for 2,3-O-CMC with comparatively low DS. All degraded samples could be separated into 18 fractions by preparative SEC and the proportion of each individual repeat unit was analysed by anion exchange chromatography (AEC) following complete hydrolytic chain degradation. The results indicated a homogeneous distribution of the functional groups within the polymer chain. Moreover, it became obvious that a preferred carboxymethylation of O-2 compared with O-3 occurred and that a preferred functionalization of already carboxymethylated units occurred as the reaction progressed. AEC with pulsed amperometric detection, which was used to separate and analyse the differently functionalized repeating units as well as glucose, had to be calibrated. Therefore, a method to determine the response factors of the individual carboxymethylated glucose units was developed using 13C NMR spectroscopic measurements (inverse gated decoupling) of depolymerised 2,3-O-CMC. 相似文献
96.
Bodo Manthey 《Discrete Applied Mathematics》2009,157(7):1470-1480
A cycle cover of a graph is a set of cycles such that every vertex is part of exactly one cycle. An L-cycle cover is a cycle cover in which the length of every cycle is in the set L⊆N.We investigate how well L-cycle covers of minimum weight can be approximated. For undirected graphs, we devise non-constructive polynomial-time approximation algorithms that achieve constant approximation ratios for all sets L. On the other hand, we prove that the problem cannot be approximated with a factor of 2−ε for certain sets L.For directed graphs, we devise non-constructive polynomial-time approximation algorithms that achieve approximation ratios of O(n), where n is the number of vertices. This is asymptotically optimal: We show that the problem cannot be approximated with a factor of o(n) for certain sets L.To contrast the results for cycle covers of minimum weight, we show that the problem of computing L-cycle covers of maximum weight can, at least in principle, be approximated arbitrarily well. 相似文献
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Haojie Zhang Dr. Dirk J. Hagen Prof. Xiaopeng Li Dr. Andreas Graff Dr. Frank Heyroth Dr. Bodo Fuhrmann Dr. Ilya Kostanovskiy Dr. Stefan L. Schweizer Dr. Francesco Caddeo Prof. A. Wouter Maijenburg Prof. Stuart Parkin Prof. Ralf B. Wehrspohn 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17324-17329
99.
Bodo Felsner Dr. Volodymyr Bon Dr. Jack D. Evans Friedrich Schwotzer Dr. Ronny Grünker Dr. Irena Senkovska Prof. Dr. Stefan Kaskel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(37):9708-9715
The switching mechanism of the flexible framework Zn4O(benztb)1.5 (benztb=N,N,N’,N’-benzidine tetrabenzoate), also known as DUT-13, was studied by advanced powder X-ray diffraction (PXRD) and gas physisorption techniques. In situ synchrotron PXRD experiments upon physisorption of nitrogen (77 K) and n-butane (273 K) shed light on the hitherto unnoticed guest-induced breathing in the MOF. The mechanism of contraction is based on the conformationally labile benztb ligand and accompanied by a reduction in specific pore volume from 2.03 cm3 g−1 in the open-pore phase to 0.91 cm3 g−1 in the contracted-pore phase. The high temperature limit for adsorption-induced contraction of 170 K, determined by systematic temperature variation of methane adsorption isotherms, indicates that the DUT-13 framework is softer than other mesoporous MOFs like DUT-49 and does not support the formation of overloaded metastable states required for negative gas-adsorption transitions. 相似文献
100.
Andrea Mignone Petros Tzeferacos Gianluigi Bodo 《Journal of computational physics》2010,229(17):5896-5920
We present and compare third- as well as fifth-order accurate finite difference schemes for the numerical solution of the compressible ideal MHD equations in multiple spatial dimensions. The selected methods lean on four different reconstruction techniques based on recently improved versions of the weighted essentially non-oscillatory (WENO) schemes, monotonicity preserving (MP) schemes as well as slope-limited polynomial reconstruction. The proposed numerical methods are highly accurate in smooth regions of the flow, avoid loss of accuracy in proximity of smooth extrema and provide sharp non-oscillatory transitions at discontinuities. 相似文献