A Monooxygenase from Boreostereum vibrans Catalyzes Oxidative Decarboxylation in a Divergent Vibralactone Biosynthesis Pathway

The oxidative decarboxylation of prenyl 4‐hydroxybenzoate to prenylhydroquinone has been frequently proposed for the biosynthesis of prenylated (hydro)quinone derivates (sometimes meroterpenoids), yet no corresponding genes or enzymes have so far been reported. A FAD‐binding monooxygenase (VibMO1) was identified that converts prenyl 4‐hydroxybenzoate into prenylhydroquinone and is likely involved in the biosynthesis of vibralactones and other meroterpenoids in the basidiomycete Boreostereum vibrans. Feeding of 3‐allyl‐4‐hydroxybenzylalcohol, an analogue of the vibralactone pathway intermediate 3‐prenyl‐4‐hydroxybenzylalcohol, generated 20 analogues with different scaffolds. This demonstrated divergent pathways to skeletally distinct compounds initiating from a single precursor, thus providing the first insight into a novel biosynthetic pathway for 3‐substituted γ‐butyrolactones from a shikimate origin.     

Computational insights into allosteric interaction between benzoazepin-2-ones and lung cancer-associated PDK1: Implications for activator design

3-Phosphoinositide-dependent kinase-1 (PDK1) plays a key role in the regulation of physiological processes and its catalytic activity is tightly regulated by allosteric modulators which bind to the PDK1 Interacting Fragment (PIF) pocket. However, details on the allosteric modulators regulation of the PDK1 catalytic activity remain elusive. Here, molecular docking and molecular dynamics (MD) simulations were performed to investigate the allosteric regulation of PDK1 induced by one of the benzoazepin-2-ones, the most potent compound 17 (BAZ2O). Molecular docking and MD simulation revealed that BAZ2O was located in the PIF pocket formed by residues from β4 and β5 sheets and helices αB and αC. BAZ2O formed a hydrogen bond with Arg131 and participated in hydrophobic interactions with Ile119, Thr148, Gln150, Leu155 and Phe157. Further comparative analyses of PDK1 in its apo and BAZ2O-bound states unveiled that BAZ2O promoted the structural coupling between the important catalytic domains of PDK1, including the activation loop and the helices αB and αC, thereby stabilizing the PDK1 conformation for catalysis. Understanding the allosteric interaction of PDK1 with small molecules provides a potentially valuable possibility of designing more potent allosteric modulators with therapeutic implications for lung cancer.     

改进法合成1-苄基-3-烷基苯并三氮唑类离子液体及其表征

通过改进的方法合成了1-苄基-3-烷基苯并三氮唑类离子液体。 目标产物结构经FT-IR、1H NMR和13C NMR确证。 当烷基取代的苯并三氮唑、催化剂CuI和溴苄的物质的量比为10∶2.5∶11时,反应5~6 h收率可达82.7%~86.1%,探讨了离子液体溶解性及熔点与结构的关系。     

铋膜电极微分电位溶出法测定环境样品中生物可利用镉

建立了环境样品中生物可利用镉的镀铋膜电极微分电位溶出分析法（DPSA）,考察了同位镀铋膜测定镉的条件。结果表明在HAc—NaAc介质中镉可在镀铋膜电极上得到灵敏的微分电位溶出峰（V=-0．84V）,最低检出质量浓度为0．6μg／L,结合3步连续萃取,利用标准加入法对环境样品中的生物可利用镉进行测定,相对标准偏差2．3％～4.1％,加标回收率97％～104％。     

热重分析-单滴微萃取-气相色谱-质谱结合傅里叶变换红外光谱考察咖啡酸的热解行为

采用热重分析-单滴微萃取-气相色谱-质谱(TG-SDME-GC-MS)联用系统和傅里叶变换红外光谱,研究了咖啡酸的热解行为。设定热重分析仪5 ℃/min的升温速率及400 mL/min的氮气流量,在160～360 ℃温度范围内,采用乙醇对热解逸出物质进行单滴微萃取,然后利用GC-MS分离分析,监测了咖啡酸5种主要热解逸出产物相对含量随温度升高的动态变化情况。使用傅里叶变换红外光谱分析了咖啡酸所对应各失重点固体剩余物的特征官能团变化情况。结果表明,咖啡酸热失重的主要原因是在240～360 ℃产生大量的邻苯二酚,在200～220 ℃热解产生4-乙基邻苯二酚。另外,咖啡酸在230 ℃下已完全裂解。该方法的建立为温度连续上升模式下的物质热解行为分析提供了借鉴和参考。     

nacl存在下氯化亚锡-十六烷基三甲基氯化铵体系浮选分离铂(ⅱ)、钯(ⅱ)、铑(ⅲ)、金(ⅲ)

pt(ⅱ);pd(ⅱ);rh(ⅲ);au(ⅲ);氯化亚锡;十六烷基三甲基氯化铵;液-固浮选分离     

石屏井水中金属元素的分析

用原子吸收光谱法测定了云南省石屏县城用于直接点制豆腐的城内(北门、西门、南门)和城郊天然井水中Ca、Mg、Fe、Zn、Cu、Co、Cr、Ni和Cd等9种金属元素的含量,方法的相对标准偏差在0.28%—1.53%之间,回收率在97.68%—107.30%之间,分析结果满意。城中天然井水Ca和Mg含量非常高,Ca和Mg含量分别在207.83—268.50μg·mL-1和30.88—35.41μg·mL-1之间,其总硬度(以CaCO3计)在646.15—816.30μg·mL-1之间,为极硬水,西门外城郊井水中Ca含量仅为99.10μg·mL-1,Mg含量28.14μg·mL-1,都未检出Cd,其余6种金属元素在城中井水与郊外井水中的含量差别不大,且都较小;城中井水Ca、Mg含量:北门井水西门井水南门井水,井水中Ca和Mg含量在207.83、30.88μg·mL-1及其以上时,具有石膏或卤水凝固剂的作用,可直接点制豆腐;城中井水中Fe、Zn、Cu、Cr、Ni和Co含量大小为FeZnCrNiCuCo。     

A Hydrolase-Catalyzed Cyclization Forms the Fused Bicyclic β-Lactone in Vibralactone

Vibralactone is isolated from the basidiomycete fungus Boreostereum vibrans as one of the strongest lipase inhibitors. Its unusual β-lactone-fused bicycle is derived from an aryl ring moiety by an oxidative ring-expansion prior to an intramolecular cyclization. Herein, we report the discovery of the cyclase VibC which belongs to the α/β-hydrolase superfamily and is involved in the vibralactone biosynthesis. Biochemical and crystal studies suggest that VibC may catalyze an aldol or an electrocyclic reaction initiated by the Ser-His-Asp catalytic triad. For the aldol and pericyclic chemistry in living cells, VibC is a unique hydrolase performing the carbocycle formation of an oxepinone to a fused bicyclic β-lactone. This presents a naturally occurring, new enzymatic reaction in both aldol and hydrolase (bio)chemistry that will guide future exploitation of these enzymes in synthetic biology for chemical-diversity expansion of natural products.     

基于函数型数据的系数正则化回归的收敛速度

本文研究了基于函数型输入和₁-正则化的最小二乘回归问题的推广性能.利用基于Rademacher平均的分析技术,获得了学习速度的估计,推广了已有的欧式空间有限维输入结果.     

Exact periodic and blow up solutions for 2D Ginzburg-Landau equation

New exact periodic wave solutions for the 2D Ginzburg-Landau equation are obtained using the homogeneous balance principle and general Jacobi elliptic-function method. Furthermore, a blow up solution is provided. At the end, some properties about these solutions are showed by the graphs.