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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.
Walter N. Harrington Christina M. Kackos Richard J. Webby 《Experimental & molecular medicine》2021,53(5):737
The influenza virus is a global threat to human health causing unpredictable yet recurring pandemics, the last four emerging over the course of a hundred years. As our knowledge of influenza virus evolution, distribution, and transmission has increased, paths to pandemic preparedness have become apparent. In the 1950s, the World Health Organization (WHO) established a global influenza surveillance network that is now composed of institutions in 122 member states. This and other surveillance networks monitor circulating influenza strains in humans and animal reservoirs and are primed to detect influenza strains with pandemic potential. Both the United States Centers for Disease Control and Prevention and the WHO have also developed pandemic risk assessment tools that evaluate specific aspects of emerging influenza strains to develop a systematic process of determining research and funding priorities according to the risk of emergence and potential impact. Here, we review the history of influenza pandemic preparedness and the current state of preparedness, and we propose additional measures for improvement. We also comment on the intersection between the influenza pandemic preparedness network and the current SARS-CoV-2 crisis. We must continually evaluate and revise our risk assessment and pandemic preparedness plans and incorporate new information gathered from research and global crises.Subject terms: Influenza virus, Infectious diseases 相似文献
3.
A Mechanistic Study on the Oxidative Degradation of Dibenzazepine Derivatives by Manganese(III) Complexes in Acidic Sulfate Media 下载免费PDF全文
The oxidative degradation of tricyclic antidepressants (TCA) was studied in the presence of a large excess of the oxidizing agent manganese(III) and its reduced form manganese(II) sulfate in acidic media. The products were detected and identified using UV–vis, ESI‐MS, IR, and EPR methods. The mechanism of the reaction was studied for the following two classes of TCA: 10,11‐dihydro‐5H‐dibenz[b, f]azepines and dibenz[b, f]azepines. The oxidative degradation between dibenz[b, f]azepines and the manganese(III) ions resulted in the formation of substituted acridine with the same substituent as in the origin dibenz[b, f]azepine derivative. The pseudo–first‐order rate constants (kobs) were determined for the degradation process. The dependences of the observed rate constants on the [MnIII] with a zero intercept were linear. The reaction between 10,11‐dihydro‐5H‐dibenz[b, f]azepines, and the manganese(III) sulfate ion resulted in oxidative dehydrogenation, which proceeded via the formation of the following two intermediates: a free organic radical and a dimer. Further oxidation of the second intermediate led to a positively charged radical dimer as the single final product. Linear dependences of the pseudo–first‐order rate constants (kobs) on the [MnIII] with a zero intercept were established for the degradation of 10,11‐dihydro‐5H‐dibenz[b, f]azepines. The observed rate constants were dependent on the [H+] and independent of the [TCA] within the excess concentration range of the manganese(III) complexes used in the isolation method. The radical product of the degradation of 10,11‐dihydro‐5H‐dibenz[b, f]azepines was not stable in the aqueous solution and was subsequently transformed to a nonradical dimer in the next slower step. The observed rate constants were independent of the [MnIII], independent of the [H+] and increased slightly with increasing TCA concentrations when TCA was used in excess. The mechanistic consequences of all of these results are discussed. 相似文献
4.
We prove the existence of global smooth solutions near a given steady state of the hydrodynamic model of the semiconductors
in a bounded domain with physical boundary conditions. The steady state and the doping profile are permitted to be of large
variation but the initial velocity must be small. Two cases are considered. In the first one the problem is three-dimensional,
the boundary conditions are insulating and the steady state velocity vanishes. In the second one, the problem is one-dimensional,
the boundary is of contact type and the steady state velocity does not vanish. 相似文献
5.
The Cauchy Problem for the relativistic Vlasov-Maxwell equations is studied in three space dimensions. It is assumed that the initial data satisfy the required constraints and have compact support. If in addition the data have sufficiently smallC
2 norm, then a uniqueC
1 solution to this system is shown to exist on all of spacetime.Research supported in part by NSF DMS 85-20662 and NSF DMS 84-20957 相似文献
6.
Werner Leißner 《Results in Mathematics》1991,20(1-2):530-537
7.
8.
Many problems arising in practical applications lead to linear programming problems. Hence, they are fundamentally tractable. Recent interior-point methods can exploit problem structure to solve such problems very efficiently. Infeasible interior-point predictor–corrector methods using floating-point arithmetic sometimes compute an approximate solution with duality gap less than a given tolerance even when the problem may not have a solution. We present an efficient verification method for solving linear programming problems which computes a guaranteed enclosure of the optimal solution and which verifies the existence of the solution within the computed interval. 相似文献
9.
Sven Walter 《Acta Analytica》2005,20(3):32-47
Frank Jackson and Philip Pettit have defended a non-reductive account of causal relevance known as the ‘program explanation
account’. Allegedly, irreducible mental properties can be causally relevant in virtue of figuring in non-redundant program explanations which convey information not conveyed by explanations in terms of the physical properties that actually do the ‘causal work’.
I argue that none of the possible ways to spell out the intuitively plausible idea of a program explanation serves its purpose,
viz., defends non-reductive physicalism against Jaegwon Kim’s Causal Exclusion Argument according to which non-reductive physicalism is committed to epiphenomenalism because irreducible mental properties are ‘screened
off’ from causal relevance by their physical realizers. Jackson and Pettit’s most promising explication of a program explanation
appeals to the idea of invariance of effect under variation of realization, but I show that invariance of effect under variation of realization is neither necessary nor sufficient for causal relevance. 相似文献
10.
We consider the differential operators Ψ
k
, defined by Ψ1(y) =y and Ψ
k+1(y)=yΨ
k
y+d/dz(Ψ
k
(y)) fork ∈ ℕ fork∈ ℕ. We show that ifF is meromorphic in ℂ and Ψ
k
F has no zeros for somek≥3, and if the residues at the simple poles ofF are not positive integers, thenF has the formF(z)=((k-1)z+a)/(z
2+β
z+γ) orF(z)=1/(az+β) where α, β, γ ∈ ℂ. If the residues at the simple poles ofF are bounded away from zero, then this also holds fork=2. We further show that, under suitable additional conditions, a family of meromorphic functionsF is normal if each Ψ
k
(F) has no zeros. These conditions are satisfied, in particular, if there exists δ>0 such that Re (Res(F, a)) <−δ for all polea of eachF in the family. Using the fact that Ψ
k
(f
′/f) =f
(k)/f, we deduce in particular that iff andf
(k) have no zeros for allf in some familyF of meromorphic functions, wherek≥2, then {f
′/f :f ∈F} is normal.
The first author is supported by the German-Israeli Foundation for Scientific Research and Development G.I.F., G-643-117.6/1999,
and INTAS-99-00089. The second author thanks the DAAD for supporting a visit to Kiel in June–July 2002. Both authors thank
Günter Frank for helpful discussions. 相似文献