A quantum mechanics/molecular mechanics study on the hydrolysis mechanism of New Delhi metallo-β-lactamase-1

New Delhi metallo-β-lactamase-1 (NDM-1) has emerged as a major global threat to human health for its rapid rate of dissemination and ability to make pathogenic microbes resistant to almost all known β-lactam antibiotics. In addition, effective NDM-1 inhibitors have not been identified to date. In spite of the plethora of structural and kinetic data available, the accurate molecular characteristics of and details on the enzymatic reaction of NDM-1 hydrolyzing β-lactam antibiotics remain incompletely understood. In this study, a combined computational approach including molecular docking, molecular dynamics simulations and quantum mechanics/molecular mechanics calculations was performed to characterize the catalytic mechanism of meropenem catalyzed by NDM-1. The quantum mechanics/molecular mechanics results indicate that the ionized D124 is beneficial to the cleavage of the C–N bond within the β-lactam ring. Meanwhile, it is energetically favorable to form an intermediate if no water molecule coordinates to Zn2. Moreover, according to the molecular dynamics results, the conserved residue K211 plays a pivotal role in substrate binding and catalysis, which is quite consistent with previous mutagenesis data. Our study provides detailed insights into the catalytic mechanism of NDM-1 hydrolyzing meropenem β-lactam antibiotics and offers clues for the discovery of new antibiotics against NDM-1 positive strains in clinical studies.     

Synthesis of high molecular weight and narrow molecular weight distribution poly(acrylonitrile) via RAFT polymerization

Well‐defined polyacrylonitrile (PAN) of high viscosity‐average molecular weight (M_η = 405,100 g/mol) was successfully synthesized using reversible addition‐fragmentation chain transfer polymerization. The polymerization exhibits controlled characters: molecular weights of the resultant PANs increasing approximately linearly with monomer conversion and keeping narrow molecular weight distributions. The addition of 0.01 equiv (relative to monomer acrylonitrile) of Lewis acid AlCl₃ in the polymerization system afforded the obtained PAN with an improved isotacticity (by 8%). In addition, the influence of molecular weights and molecular weight distributions of PANs on the morphology of the electrospun fibers was investigated. The results showed that, under the same conditions of electrospinning, average diameter (247–1094 nm) of fibers increased with molecular weights of PANs, and it was much easier to get “uniform” diameter fibers while using PANs with narrow molecular weight distributions as the precursor of electrospinning. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Electrical properties of La0.6Ca0.4MnO3–Bi3.4Nd0.6Ti3O12 thin films derived by a sol–gel process

Magnetoelectric (ME) xLa_0.6Ca_0.4MnO₃–(1 ? x)Bi_3.4Nd_0.6Ti₃O₁₂ (LCMO–BNT) composite thin films have been prepared by a sol–gel process and spin-coating technique. The effects of LCMO content on the microstructure, leakage current density, ferroelectric properties, fatigue endurance and ME voltage coefficient of LCMO–BNT thin films derived by sol–gel method were studied. It was found that the composite thin films have better fatigue endurance properties and lower leakage current densities compared with pure BNT thin films, as well as large ME voltage coefficients.     

From Nitro‐ to Sulfonyl‐Based Chromophores: Improvement of the Comprehensive Performance of Nonlinear Optical Dendrimers

Through the combination of the divergent and convergent approaches, coupled with the utilization of the powerful Sharpless “click‐chemistry” reaction, two series of sulfonyl‐based high‐generation NLO dendrimers were conveniently prepared with high purity and in satisfactory yields. Thanks to the perfect three‐dimensional (3D) spatial isolation from the highly branched structure and the isolation effect of the exterior benzene moieties and the interior triazole rings, these dendrimers exhibited large second harmonic generation coefficient (d₃₃) values up to 181 pm V^?1, which, to the best of our knowledge, is the highest value so far for polymers containing sulfonyl‐based chromophore moieties. Meanwhile, compared with the nitro‐chromophore‐based analogues, their optical transparency and NLO stability were improved in a large degree, due to the lower dipole moment (μ) and the special main‐chain structure of sulfonyl‐based chromophore in these dendrimers.     

Exploring the Reactivity of Multicomponent Photocatalysts: Insight into the Complex Valence Band of BiOBr

The band structure of multicomponent semiconductor photocatalysts, as well as their reactivity distinction under different wavelengths of light, is still unclear. BiOBr, which is a typical multicomponent semiconductor, may have two possible valence‐band structures, that is, two discrete valence bands constructed respectively from O 2p and Br 4p orbitals, or one valence band derived from the hybridization of these orbitals. In this work, aqueous photocatalytic hydroxylation is applied as the probe reaction to investigate the nature and reactions of photogenerated holes in BiOBr. Three organic compounds (microcystin‐LR, aniline, and benzoic acid) with different oxidation potentials were selected as substrates. Isotope labeling (H₂¹⁸O as the solvent) was used to determine the source of the O atom in the hydroxyl group of the products, which distinguishes the contribution of different hydroxylation pathways. Furthermore, a spin‐trapping ESR method was used to quantify the reactive oxygen species (^.OH and ^.OOH) formed in the reaction system. The different isotope abundances of the hydroxyl O atom of the products formed, as well as the reverse trend of the ^.OH/^.OOH ratio with the oxidative resistance of the substrate under UV and visible irradiation, reveal that BiOBr has two separate valence bands, which have different oxidation ability and respond to UV and visible light, respectively. This study shows that the band structure of semiconductor photocatalysts can be reliably analyzed with an isotope labeling method.     

二维柱坐标系辐射输运方程保球对称的离散纵标格式

 离散纵标格式是计算辐射输运方程的常用格式之一. 但是, 传统的离散纵标格式求解二维柱坐标系辐射输运方程模拟一维球对称问题时, 会出现明显的非对称现象, 球对称性被破坏. 针对该问题, 本文分析了传统离散纵标格式不能够保持球对称性的原因, 提出了空间基于柱坐标系、方向基于球坐标系的辐射输运方程, 并对该方程设计了新的离散纵标格式, 从理论上证明了当空间网格取球对称剖分时该离散格式能够保持一维球对称性的充分必要条件. 通过对真空球区域辐射输运、与物质耦合辐射输运等球对称算例的数值模拟, 验证了该格式的保球对称性, 球对称误差能够达到机器精度. 非对称辐射驱动模型以及非对称网格剖分条件下的数值模拟等算例也取得了较好的结果.     

Edge Flips in Surface Meshes

Little theoretical work has been done on edge flips in surface meshes despite their popular usage in graphics and solid modeling to improve mesh equality. We propose the class of \((\varepsilon ,\alpha )\)-meshes of a surface that satisfy several properties: the vertex set is an \(\varepsilon \)-sample of the surface, the triangle angles are no smaller than a constant \(\alpha \), some triangle has a good normal, and the mesh is homeomorphic to the surface. We believe that many surface meshes encountered in practice are \((\varepsilon ,\alpha )\)-meshes or close to being one. We prove that flipping the appropriate edges can smooth a dense \((\varepsilon ,\alpha )\)-mesh by making the triangle normals better approximations of the surface normals and the dihedral angles closer to \(\pi \). Moreover, the edge flips can be performed in time linear in the number of vertices. This helps to explain the effectiveness of edge flips as observed in practice and in our experiments. A corollary of our techniques is that, in \(\mathbb {R}^2\), every triangulation with a constant lower bound on the angles can be flipped in linear time to the Delaunay triangulation.     

Alstolactines A–C,novel monoterpenoid indole alkaloids from Alstonia scholaris

Three novel ring-fused monoterpenoid indole alkaloids, alstolactines A–C (1–3), were isolated from the long-term stored leaves of Alstonia scholaris. Their structures were identified on the basis of extensive spectroscopic data and X-ray diffractions. Moreover, the absolute configurations of these related structures were indicated by the crystal X-ray diffractions (Mo Kα) of 1a, a chlorinated derivative of 1.     

Topologically protected interface mode in plasmonic waveguide arrays

Recent realization of nontrivial topological phases in photonic systems has provided unprecedented opportunities in steering light flow in novel manners. Based on the Su–Schriffer–Heeger (SSH) model, a topologically protected optical mode was successfully demonstrated in a plasmonic waveguide array with a kinked interface that exhibits a robust nonspreading feature. However, under the same excitation conditions, another antikinked structure seemingly cannot support such a topological interface mode, which appears to be inconsistent with the SSH model. Theoretical calculations are carried out based on the coupled‐mode theory, in which the mode properties, excitation conditions, and the robustness are studied in detail. It is revealed that under the exact eigenstate excitations, both kinked and antikinked structures do support such robust topological interface modes; however, for a realistic single‐waveguide input only the kinked structure does so. It is concluded that the symmetry of interface eigenmodes plays a crucial role, and the odd eigenmode in a kinked structure offers the capacity to excite the nonspreading interface mode in the realistic excitation of a one‐waveguide input. Our finding deepens the understanding of mode excitation and propagation in coupled waveguide systems, and could open a new avenue in optical simulations and photonic designs.