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81.
Julia Ertl Dr. Maria Elena Ortiz-Soto Thien Anh Le Julian Bechold Junwen Shan Dr. Jörg Teßmar Prof. Bernd Engels Prof. Jürgen Seibel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6533-6541
Selective chemical modification of proteins plays a pivotal role for the rational design of enzymes with novel and specific functionalities. In this study, a strategic combination of genetic and chemical engineering paves the way for systematic construction of biocatalysts by tuning the product spectrum of a levansucrase from Bacillus megaterium (Bm-LS), which typically produces small levan-like oligosaccharides. The implementation of site-directed mutagenesis followed by a tyrosine-specific modification enabled control of the product synthesis: depending on the position, the modification provoked either enrichment of short oligosaccharides (up to 800 % in some cases) or triggered the formation of high molecular weight polymer. The chemical modification can recover polymerization ability in variants with defective oligosaccharide binding motifs. Molecular dynamic (MD) simulations provided insights into the effect of modifying non-native tyrosine residues on product specificity. 相似文献
82.
Dr. Julia Stroh Torvid Feiler Dr. Naveed Zafar Ali Prof. Manuel E. Minas da Piedade Dr. Franziska Emmerling 《ChemistryOpen》2019,8(7):1012-1019
Mechanochemistry offers an environmentally benign and facile synthesis method for a variety of cement paste constituents. In addition, these methods can be used to selectively tune the properties of cement components. The mineral ettringite is an important component of cementitious materials and has additional technological potential due to its ion exchange properties. Synthesis of ettringite via mechanochemistry is an environmentally friendly alternative to conventional wet-chemical synthesis established in industry. This contribution explores the mechanism of a two-step mechanochemical synthesis of ettringite, which was previously found to greatly improve the reaction conversion as compared with one-pot synthesis. The crystallinity of Al(OH)3 was found to decrease during the first stage of this mechanochemical synthesis. This was correlated to a significant decrease in the particle size of Al(OH)3 in this stage. No other significant changes were found for the other components, suggesting that mechanochemical activation of Al(OH)3 is responsible for the enhanced formation of ettringite by the two-step approach. The environmentally friendly approach developed for ettringite synthesis offers a versatile synthetic strategy, which can be applied to synthesise further cementitious materials. 相似文献
83.
Julia Vallejo Alejandro Pascual‐Álvarez Dr. Joan Cano Dr. Isabel Castro Prof. Dr. Miguel Julve Prof. Dr. Francesc Lloret Dr. J. Krzystek Prof. Dr. Giovanni De Munno Dr. Donatella Armentano Prof. Dr. Wolfgang Wernsdorfer Dr. Rafael Ruiz‐García Dr. Emilio Pardo 《Angewandte Chemie (International ed. in English)》2013,52(52):14075-14079
84.
Julia Calatayud Juan Carlos Corts Marc Jornet 《Mathematical Methods in the Applied Sciences》2019,42(18):7259-7267
In this paper, we address the problem of approximating the probability density function of the following random logistic differential equation: P′(t,ω)=A(t,ω)(1?P(t,ω))P(t,ω), t∈[t0,T], P(t0,ω)=P0(ω), where ω is any outcome in the sample space Ω. In the recent contribution [Cortés, JC, et al. Commun Nonlinear Sci Numer Simulat 2019; 72: 121–138], the authors imposed conditions on the diffusion coefficient A(t) and on the initial condition P0 to approximate the density function f1(p,t) of P(t): A(t) is expressed as a Karhunen–Loève expansion with absolutely continuous random coefficients that have certain growth and are independent of the absolutely continuous random variable P0, and the density of P0, , is Lipschitz on (0,1). In this article, we tackle the problem in a different manner, by using probability tools that allow the hypotheses to be less restrictive. We only suppose that A(t) is expanded on L2([t0,T]×Ω), so that we include other expansions such as random power series. We only require absolute continuity for P0, so that A(t) may be discrete or singular, due to a modified version of the random variable transformation technique. For , only almost everywhere continuity and boundedness on (0,1) are needed. We construct an approximating sequence of density functions in terms of expectations that tends to f1(p,t) pointwise. Numerical examples illustrate our theoretical results. 相似文献
85.
Derek Yiren Ong Zhihao Yen Asami Yoshii Julia RevilloImbernon Ryo Takita Shunsuke Chiba 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):5046-5051
New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX2). Use of a different halide on ZnX2 dictates the selectivity, wherein the NaH‐ZnI2 system delivers alcohols and NaH‐ZnCl2 gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH2)∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)2 is the key species for the production of amines. 相似文献
86.
Gloria Subías Joaquín García Javier Blasco Javier Herrero‐Martín M. Concepción Sánchez Julia Orna Luis Morellón 《Journal of synchrotron radiation》2012,19(2):159-173
The pattern of charge modulations and local anisotropies below the Verwey transition has been determined and quantified in high‐quality Fe3O4 single crystals and thin films grown on MgO by using resonant X‐ray scattering at the Fe K‐edge. The energy, polarization and azimuthal angle dependencies of an extensive set of reflections with potential sensitivity to charge or local anisotropy orderings have been analyzed to explore their origins. A charge disproportion on octahedral B sites of 0.20 ± 0.05 e? with [0 0 1] and cubic periodicities has been confirmed, while no significant charge disproportion has been obtained with [0 0 1/2] cubic periodicity. Additional charge modulations in the monoclinic a–b plane are also present. In addition, the occurrence of new forbidden (1, 1, 0) and (0, 0, 2n + 1/2) cubic reflections that arise from the anisotropy of the local structure around different tetrahedral and octahedral Fe atoms is shown. This complex pattern of weak charge modulations and local anisotropies is fully compatible with the low‐temperature crystal structure refined in the non‐polar C2/c space group and disproves any bimodal charge disproportion of the octahedral Fe atoms. 相似文献
87.
Andrii Lozynskyi Borys Zimenkovsky Iryna Ivasechko Julia Senkiv Andrzej Gzella Olexandr Karpenko 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):1149-1157
AbstractThe synthesis and anticancer activity evaluation of new thiazolo[4,5-b]pyridine-5-carboxylic acid amides is described. The structures of the synthesized compounds were confirmed by spectroscopic data and a single crystal X-ray diffraction analysis for 2.4. The synthesized compounds were screened for their in vitro anticancer activity according to US NCI protocols. The most active 7-(4-fluorophenyl)-2-oxo-2,3-dihydrothiazolo[4,5-b]pyridine-5-carboxylic acid (4-chlorophenyl)amide 2.2 and 7-(4-chlorophenyl)-2-oxo-2,3-dihydrothiazolo[4,5-b]pyridine-5-carboxylic acid (4-chlorophenyl)amide 2.5 were screened for their cytotoxicity effects on C6 Rat glioma cells and U373 Human glioblastoma astrocytoma cells which revealed promising results comparable to temozolamide as reference control according MTT assay data. 相似文献
88.
Aromatic substituents migrate in a novel oxidative cyclization mediated by iodine(III) reagents. 4-Arylbut-3-enoic acids are cyclized and rearranged to 4-arylfuran-2(5H)-ones by hypervalent iodine compounds in good to excellent yields under mild reaction conditions. Other ring sizes are also accessible. The mechanism of the reaction is described in detail, and calculations highlight the cationic nature of the intermediates in the rearrangement. The fast access to heavily substituted furanones is used for the synthesis of biologically active derivatives. 相似文献
89.
90.
Ella Kazakova Julia Morozova Diana Mironova Victor Syakaev Liya Muslinkina Alexander Konovalov 《Supramolecular chemistry》2013,25(12):831-841
Here, we report on the study of cationic amidoammonium calix[4]resorcinarenes 1–5 of various lipophilicity capable of binding acid–base indicator methyl orange (MO). We identified the contributions of macrocycle aggregation and conformational mobility in the binding of MO. The effective pKa values of bound MO systematically decrease as the size and the packing density of the aggregates increase with an increase in calixresorcinarene lipophilicity. Consideration of a series of macrocycles clearly shows that large aggregates form most stable complexes, binding guests not on individual level but as aggregates. It was found that the most stable MO complex with 5 is formed due to electrostatic binding with ammonium groups of the macrocycle and incapsulation of MO in a hydrophobic layer of the aggregates. We have shown that competitive binding of MO and cationic surfactants by aggregates of 5 is suitable for visual/spectrophotometric detection of colourless anionic substrates. 相似文献