Asymmetric Total Syntheses,Stereostructures, and Cytotoxicities of Marine Bromotriterpenoids Aplysiol B (Laurenmariannol) and Saiyacenol A

There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis.     

对称向量拟均衡问题有效解的存在性

利用标量化方法建立对称向量拟均衡问题有效解的存在性定理。作为标量化方法的应用，利用这一方法得到向量变分不等式和拟向量变分不等式有效解的存在性定理。     

Insights into MWCNTs/polyimide nanocomposites: from synthesis to application as free-standing flexible electrodes in low-cost micro-supercapacitors

In the pursuit to enlarge the library of polyimide materials for energy applications, new polyimide/MWCNTs composite films have been developed by MWCNTs-assisted polycondensation reaction of a hydroxyl and triphenylmethane-containing diamine with benzophenone tetracarboxylic dianhydride targeting to highlight their electrical storage capability as flexible electrodes in micro-supercapacitors (mSCs). The Fourier-transform infrared spectroscopy, proton nuclear magnetic resonance, UV–vis, fluorescence, and Raman spectroscopies were used to demonstrate the evolution of interfacial interactions between MWCNTs and the precursors (diamine monomer and intermediate polyamidic acid) and polyimide matrix that proved to be the origin of MWCNTs homogeneous dispersion. Thus, composite films incorporating 1, 3, 5, and 10 w.t.% MWCNTs were obtained and thoroughly investigated with regard to their morphology, mechanical behavior, thermal stability, and electrical conductivity. The electrochemical performance of these composites was first analyzed in a classical three-electrode cell by cyclic voltammetry and galvanostatic charge-discharge in both aqueous and organic electrolyte systems. By far, the best electrical storage capacity was obtained with the composite polyimide film containing 10% MWCNTs that was further used as both active material and current collector in a flexible symmetric mSC realized by a straightforward and low-cost procedure. In the attempt to better exploit the advantages of this composite film, it was layered with a graphite-containing paint and tested as an electrode in a flexible mSC, which provided satisfactory results. To our knowledge, this is the first report on the electrical charge storage capability of a polyimide/MWCNTs free-standing film as a flexible electrode in mSCs, which do not require time- and resource-consuming processing steps.     

紫色球杆菌视紫红质光谱特性的机器学习研究

近年来，机器学习等人工智能技术被应用于蛋白质工程，其在蛋白质结构、功能预测、催化活性等研究中具有独特优势。在未知蛋白质结构的情况下，将蛋白质序列和功能特性与机器学习相结合，基于序列-活性关系（innovative sequence-activity relationship，ISAR）算法，将蛋白质氨基酸序列数字化，用快速傅里叶变换（fast four transform，FFT）进行预处理，再进行偏最小二乘回归建模，可在数据集较少情况下拟合得到最佳模型。通过机器学习对紫色球杆菌视紫红质（gloeobacter violaceus rhodopsin，GR）的突变体蛋白质氨基酸序列与光谱最大吸收波长进行建模，获得了最佳模型。用最佳索引LEVM760106建模得到的确定系数R² 为0.944，均方误差E为11.64。用小波变换进行的预处理，其R² 虽也约为0.944，但E大于11.64，不及FFT进行的预处理。方法较好地解决了蛋白质序列与功能特性之间的数学建模问题，在蛋白质工程中可为预测更优的突变体提供支持。     

明代生命损失型地震的时空分布特征及成因分析

利用史料记录建立了明代生命损失型地震的数据库，构建生命损失型地震等级序列、10 a尺度上生命损失型地震的频次序列和县次序列，再现明代生命损失型地震的时空分布特征，探讨了生命损失型地震发生及导致人口死亡的时空差异原因。结果表明：（1）从明初到明末，生命损失型地震等级强度有逐渐扩大的趋势。（2）明代前期处于生命损失型地震发生较少的稳定时期；明代中后期处于生命损失型地震发生较多的波动时期。明代生命损失型地震发生频次存在明显的周期性变化特征。（3）生命损失型地震在明代大部分区域皆有分布。灾害重心随时间变化发生移动，由西南到中部再到华北、华东。（4）明代地震频繁的原因除地球本身因素外，太阳活动通过影响气候变化，进而间接影响地壳活动。气候寒冷与干旱和地震有较好的对应关系。明代后期生命损失型地震导致死亡人数大量增加，与明代经济发展，人口密度逐渐增长有关；不同地区生命损失型地震导致的死亡人数不同，且死亡人数与地震频发地区是否处于板块之间的活动构造带和人口分布密度有关。     

LAMOST光谱J152238.11+333136.1 P-Cygni轮廓分析

LAMOST一期巡天成功获取河外星系光谱超过150 000条,大样本光谱数据为探索奇异、稀有的天体从而完善现有的天体演化理论提供了必要的数据条件;而先进的信息技术为从海量的数据中挖掘这些珍稀样本提供了有效途径。针对采用基于DoPS的数据挖掘方法,从LAMOST DR5星系光谱数据获得的离群数据挖掘结果中,呈现出疑似P-Cygni轮廓特征的光谱J152238.11+333136.1进行了深入讨论。首先针对该光谱的基本信息、疑似P-Cygni轮廓特征以及相应的离群数据挖掘方法进行了简要表述,光谱在Hβ和[OⅢ]λ4860处呈现P-Cygni轮廓,在NeⅢλ3869和HeⅠλ5874处呈现反P-Cygni轮廓;其次,对该特征的真实性及其生成机制从以下4个角度展开讨论。(1)交叉同源观测。Sloan巡天2004年(相差11年)的同源观测,其光谱上并未呈现对应的特征,据推测可能是正在进行的演化活动或者光纤定位误差所致;(2)通过分析光谱质量、减天光残差等方法,分析P-Cygni特征是否为观测或数据处理所致。NeⅢλ3869和HeⅠλ5874处呈现反P-Cygni轮廓可信度较低;同时,通过比较目标光谱与超级天光,以及相邻光纤观测到的光谱在对应波长处的光谱特征,说明存在P-Cygni轮廓为减天光过程导致的可能性;(3)光谱子型差异。IRAS和WISE等近红外同源观测,显示其为Seyfert 2型星系,光学波段发射线强比[NⅡ]/Hα,[OⅢ]/Hβ显示其为HⅡ区,结合光学、红外测光图像特征,推测目标可能是两个星系进行并合活动;(4)从导致P-Cygni轮廓的物理机制的角度,分析了由星系并合触发外流、由恒星形成(爆发)电离气体触发的外流以及由Wolf-Rayet特征星系的超星风等原因引起的可能性。     

Molecularly Engineered 6FDA-Based Polyimide Membranes for Sour Natural Gas Separation

Glassy polyimide membranes are attractive for industrial applications in sour natural gas purification. Unfortunately, the lack of fundamental understanding of relationships between polyimide chemical structures and their gas transport properties in the presence of H₂S constrains the design and engineering of advanced membranes for such challenging applications. Herein, 6FDA-based polyimide membranes with engineered structures were synthesized to tune their CO₂/CH₄ and H₂S/CH₄ separation performances and plasticization properties. Under ternary mixed sour gas feeds, controlling polymer chain packing and plasticization tendency of such polyimide membranes via tuning the chemical structures were found to offer better combined H₂S and CO₂ removal efficiency compared to conventional polymers. Fundamental insights into structure–property relationships of 6FDA-based polyimide membranes observed in this study offer guidance for next generation membranes for sour natural gas separation.     

Biosynthesis of Indole Diterpene Lolitrems: Radical-Induced Cyclization of an Epoxyalcohol Affording a Characteristic Lolitremane Skeleton

Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome-editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical-induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue.     

Total Synthesis of Zephycarinatines via Photocatalytic Reductive Radical ipso-Cyclization

We report herein a nonbiomimetic strategy for the total synthesis of the plicamine-type alkaloids zephycarinatines C and D. The key feature of the synthesis is a stereoselective reductive radical ipso-cyclization using visible-light-mediated photoredox catalysis. This cyclization enabled the construction of a 6,6-spirocyclic core structure through the addition of a carbon-centered radical onto the aromatic ring. Biological evaluation of zephycarinatines and their derivatives revealed that the synthetic derivative with a keto group displays moderate inhibitory activity against LPS-induced NO production. This approach could offer future opportunities to expand the chemical diversity of plicamine-type alkaloids as well as providing useful intermediates for their syntheses.     

Time-averaged flow characteristics and mixing properties of double-concentric jets

We examined the flow behaviors and mixing characteristics of double-concentric jets using laser-assisted smoke flow visualization method to analyze typical flow patterns and binary boundary detection technique to investigate jet spread width. Time-averaged velocity vectors, streamline patterns, velocity distributions, turbulence properties, and vorticity contours were analyzed using Particle Image Velocimetry (PIV). Topological flow patterns were analyzed to interpret the vortical flow structures. Mixing properties were investigated using a tracer-gas concentration detection method. Four characteristic modes were observed: annular flow dominated mode, transition mode, central jet dominated mode-low shear, and central jet dominated mode-high shear. The jets’ mixing properties were enhanced by two major phenomena: the merging of annular flow and central jet at the centerline and the large turbulence fluctuations produced in the flow field. The merging of the jets induced stagnation points on the central axis in the annular flow dominated mode, which caused reverse flow on the central axis and drastic turbulence fluctuations of the near field region. When the central jet penetrated the recirculation region in the other three modes, the stagnation points on the central axis and the reverse flow vanished. Therefore, the mixing behaviors were prominently enhanced in the annular flow dominated mode.