Dynamics of Bacteriorhodopsin in the Dark-Adapted State from Solution Nuclear Magnetic Resonance Spectroscopy

To achieve efficient proton pumping in the light-driven proton pump bacteriorhodopsin (bR), the protein must be tightly coupled to the retinal to rapidly convert retinal isomerization into protein structural rearrangements. Methyl group dynamics of bR embedded in lipid nanodiscs were determined in the dark-adapted state, and were found to be mostly well ordered at the cytosolic side. Methyl groups in the M145A mutant of bR, which displays only 10 % residual proton pumping activity, are less well ordered, suggesting a link between side-chain dynamics on the cytosolic side of the bR cavity and proton pumping activity. In addition, slow conformational exchange, attributed to low frequency motions of aromatic rings, was indirectly observed for residues on the extracellular side of the bR cavity. This may be related to reorganization of the water network. These observations provide a detailed picture of previously undescribed equilibrium dynamics on different time scales for ground-state bR.     

Fabricating Dual-Atom Iron Catalysts for Efficient Oxygen Evolution Reaction: A Heteroatom Modulator Approach

Understanding the thermal aggregation behavior of metal atoms is important for the synthesis of supported metal clusters. Here, derived from a metal–organic framework encapsulating a trinuclear Fe^III₂Fe^II complex (denoted as Fe₃) within the channels, a well-defined nitrogen-doped carbon layer is fabricated as an ideal support for stabilizing the generated iron nanoclusters. Atomic replacement of Fe^II by other metal(II) ions (e.g., Zn^II/Co^II) via synthesizing isostructural trinuclear-complex precursors (Fe₂Zn/Fe₂Co), namely the “heteroatom modulator approach”, is inhibiting the aggregation of Fe atoms toward nanoclusters with formation of a stable iron dimer in an optimal metal–nitrogen moiety, clearly identified by direct transmission electron microscopy and X-ray absorption fine structure analysis. The supported iron dimer, serving as cooperative metal–metal site, acts as efficient oxygen evolution catalyst. Our findings offer an atomic insight to guide the future design of ultrasmall metal clusters bearing outstanding catalytic capabilities.     

Revealing and comparing different excited-state intramolecular proton transfer processes for 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-propenone and 3-(4-dimethylamino-phenyl)-1-(4-fluoro-2-hydroxy-phenyl)-3-hydroxy-propenon

Two novel 2′-hydroxychalcone derivatives (i.e., M1 and M2) are explored in this work. We mainly focus on investigating the effects of photoexcitation on hydrogen bonds and on the excited-state intramolecular proton transfer (ESIPT) process. On the basis of calculations of electrostatic potential surface and intramolecular interactions, we verify the formation of hydrogen bond O1 H2···O3 in both S₀ and S₁ states. Exploring the ultraviolet–visible spectra in the liquid phase, our simulated results reappear in the experimental phenomenon. Analyzing molecular geometry and infrared stretching vibrational spectra, we confirm O1 H2···O3 is strengthened for both M1 and M2 in the S₁ state. We further confirm that charge redistribution facilitates ESIPT tendency. Constructing potential energy curves, we find the ultrafast ESIPT behavior for M1, which is because of the deficiency of side hydroxyl moiety comparing with M2. This work makes a reasonable affiliation of the ESIPT mechanism for M1 and M2. We wish this paper could facilitate understanding these two novel systems and promote their applications.     

Synthesis and characterization of VO–vanillin complex immobilized on MCM-41 and its facile catalytic application in the sulfoxidation reaction,and synthesis of 2,3-dihydroquinazolin-4(1H)-ones and disulfides in green media

In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance.     

3d过渡金属掺杂M_2@Si_(20)(M=Sc-Zn)团簇的密度泛函理论研究

利用密度泛函理论(DFT)研究3d过渡金属掺杂硅团簇的几何结构和稳定性,计算了绝热电子亲和能和垂直电离能,内嵌双金属间距,自旋磁矩等.结果表明内嵌的Sc、Ti、V、Mn金属二聚体和十二面体硅笼构成了稳定的富勒烯结构,随着d电子数目的增加其内嵌的富勒烯构型有部分畸变,总体而言Si_(20)团簇掺杂双金属后稳定性得到了提高.     

Swendsen‐Wang dynamics for general graphs in the tree uniqueness region

The Swendsen‐Wang (SW) dynamics is a popular Markov chain for sampling from the Gibbs distribution for the ferromagnetic Ising model on a graph G = (V,E). The dynamics is conjectured to converge to equilibrium in O(|V|^1/4) steps at any (inverse) temperature β, yet there are few results providing o(|V|) upper bounds. We prove fast convergence of the SW dynamics on general graphs in the tree uniqueness region. In particular, when β < β_c(d) where β_c(d) denotes the uniqueness/nonuniqueness threshold on infinite d‐regular trees, we prove that the relaxation time (i.e., the inverse spectral gap) of the SW dynamics is Θ(1) on any graph of maximum degree d ≥ 3. Our proof utilizes a monotone version of the SW dynamics which only updates isolated vertices. We establish that this variant of the SW dynamics has mixing time and relaxation time Θ(1) on any graph of maximum degree d for all β < β_c(d). Our proof technology can be applied to general monotone Markov chains, including for example the heat‐bath block dynamics, for which we obtain new tight mixing time bounds.     

水下对转螺旋桨流致辐射噪声机理与预报方法*

水下对转螺旋桨流致辐射噪声的预报对于水下目标的特征提取和分类识别具有重要意义。由桨叶的旋转引起的湍流场是水下对转螺旋桨流致辐射噪声的源场。分述了水下对转螺旋桨湍流边界层脉动、旋转干涉效应和空化效应引发的水动力噪声机制和研究进展,比较了目前工程应用中的3种对转螺旋桨流致辐射噪声预报方法的特点。在分析对转螺旋桨流致辐射噪声数值预报难点的基础上,综述了对转螺旋桨流致辐射噪声计算方法的研究进展,指出间接数值模拟方法是工程中进行对转螺旋桨流致辐射噪声预报的有效方法。     

离子浓度及表面结构对岩石孔隙内水流动特性的影响

酸性环境引发的岩石孔隙表面溶解增加了孔隙内水溶液的盐离子浓度,破坏了孔隙的表面结构.本文采用分子动力学模拟的方法研究了纳米级岩石孔隙内水溶液的流动特性,分析了盐离子浓度和孔隙表面结构对水流速度分布的影响及原因.研究结果表明:纳米级岩石孔隙内的水溶液流动符合泊肃叶流动特性,流速呈"抛物线"分布;随盐离子浓度增加,水溶液内部氢键网络变得更为致密,水黏度随其呈线性增长;水溶液中离子浓度越大,孔隙表面对水流动的阻力越大,最大流速越小,速度分布的"抛物线"曲率半径越大;岩石孔隙表面结构的破坏改变了流动表面的粗糙程度,增加了孔隙表面对H2O分子的吸引力.随表面结构破坏程度的增大,水溶液在近壁区域的密度增大,流速降低;当表面破坏程度达到50%时,水溶液在近壁区域出现了明显的负边界滑移现象.     

交错跃迁Hofstadter梯子的量子流相

为玻色Hofstadter梯子模型引入交错跃迁,来扩展模型支持的量子流相.基于精确对角化和密度矩阵重整化群计算发现,无相互作用时,系统中包含横流相、涡旋相和纵流相;横流相来自均匀跃迁时Hofstadter梯子模型的Meissner相,纵流相是交错跃迁时才可见的流相.强相互作用极限下系统的超流区也包含横流相、纵流相和涡旋相,但存在更多的相变级数;超流区的横流相、纵流相之间存在相变但Mott区的不存在,把Mott区的"横、纵流相"称为Mott-均匀相,在Mott区只存在均匀相和涡旋相.跃迁的交错会压缩涡旋相存在的区域,使Mott区最终只剩下均匀相;跃迁的交错不仅能驱动Mott-超流相变,还使磁通的改变也能够驱动系统的Mott-超流相变.对这一系统的研究丰富了磁通系统中的量子流相,同时为研究拓扑流特性提供了模型支持.