Quantum chemistry studies of adenosine 2503 methylation by S‐adenosylmethionine‐dependent enzymes

Ribosome methylation is important for life processes and is mainly catalyzed by radical S‐Adenosylmethionine (SAM) enzymes. Two SAM molecules serve as the cofactor by providing the 5 ′‐deoxyadenosyl radical for substrate activation and the methyl. Recently, Booker and coworkers (Science 2011, 332, 604) proposed an alternative mechanism for a pair of radical SAM enzymes, RlmN and Cfr, which respectively methylate the C2 and C8 of adenosine 2503. Their deuterium labeling experiments reveal that methyl group does not transfer directly from SAM to adenosine, instead it passes to Cys³⁵⁵ first, then onto adenosine. In this article, this new reaction mechanism is studied using density functional theory with B3LYP hybrid functional. The reaction system is simulated using small model compounds in the gas phase, and the protein environment is approximated using polarizable continuum model. The structures of the transition states and the intermediates are identified, and their free energies are calculated. The activation barriers indicate that the proposed reaction mechanism is plausible. The formation of a disulfide bond is found to be the rate‐limiting step. © 2012 Wiley Periodicals, Inc.     

Nanogel Multienzyme Mimics Synthesized by Biocatalytic ATRP and Metal Coordination for Bioresponsive Fluorescence Imaging

The design of enzyme mimics from stable and nonprotein systems is especially attractive for applications in highly specific cancer diagnosis and treatment, and it has become an emerging field in recent years. Herein, metal crosslinked polymeric nanogels (MPGs) were prepared using Fe^II ion coordinated biocompatible acryloyl‐lysine polymer brushes obtained from an enzyme‐catalyzed atomic transfer radical polymerization (ATRPase) method. The monoatomic and highly dispersed Fe ions in the MPGs serve as efficient crosslinkers of the gel network, and also as active centers of multienzyme mimics of superoxide dismutase (SOD) and peroxidase (POD). The catalytic activities were compared to those of conventional Fe‐based nanozymes. Studies on both cells and animals verify that efficient reactive oxygen species (ROS) responsive biofluorescence imaging can be successfully realized using the MPGs.     

金属有机骨架高温自还原制备高性能等级孔碳负载Co基催化剂

以钴基金属有机框架为前驱体, 利用一步高温碳化自还原法, 通过精确调控碳化过程, 实现等级孔道结构及钴纳米颗粒分散性的可控调节, 制备出高催化活性及产物选择性的等级孔碳负载Co基催化剂. 研究发现, 600 ℃碳化后的催化剂为具有高比表面积的等级孔道结构和高分散的钴纳米颗粒, 在选择性催化1,3-丁二烯加氢反应中, 丁二烯完全转化温度低至60 ℃, 对应丁烯的选择性高达61%, 实现了低温高选择性催化加氢.     

Passive Q-switching of Pulsed and CW Nd: YAG Lasers with Cr~(4 ): YAG

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Six new metal-organic frameworks with multi-carboxylic acids and imidazole-based spacers: syntheses, structures and properties

Six new metal-organic frameworks [Cu(obba)(bimb)·(obbaH(2))](n) (1), [Cu(obba)(bimb)](n) (2), [Zn(2)(obba)(2)(bimb)(2)(DMF)(2)(H(2)O)(3.5)](n) (3), [Ni(3)(2,2',4,4'-bptcH)(2)(bimb)(2)(H(2)O)(2)·(H(2)O)(2)](n) (4), [Ni(2)(bimb)(3)(H(2)O)(6)·(aobtc)·(DMF)(2)·(H(2)O)(2)](n) (5) and [Cd(3,3',4,4'-bptcH(2))(H(2)O)·(bimb)](n) (6), were obtained by reactions of 4,4'-bis(1-imidazolyl)biphenyl (bimb) and multi-carboxylic acids of 4,4'-oxybis(benzoic acid) (obbaH(2)), 2,2',4,4'-biphenyltetracarboxylate acid (2,2',4,4'-bptcH(4)), azoxybenzene-3,3',5,5'-tetracarboxylic acid (aobtcH(4)), and 3,3',4,4'-biphenyltetracarboxylate acid (3,3',4,4'-bptcH(4)) with corresponding metal salts under hydro/solvothermal conditions, respectively. Complexes 1-3 have entangled structures with different topologies: 1 is a 3-fold interpenetrating NbO three-dimensional (3D) network; 2 is a 3-fold interpenetrating dmp 3D net; 3 is a 6-fold interpenetrating dia 3D chiral net containing rare 1D helical chains with the same handedness. Complex 4 is an uninodal 6-connected network with a Sch?fli symbol of (4(8)6(4)8(3)) based on the trinuclear Ni(II) subunits, while complexes 5 and 6 are 1D chains. Interestingly, compound 6 represents the rare example of MOFs that exhibit high photocatalytic activity for dye degradation under visible light and shows good stability towards photocatalysis. Complexes 3 and 6 exhibit intense blue emissions in the solid state at room temperature whereas 3 appears to be a good candidate of novel hybrid inorganic-organic NLO material.     

Structural evolution of magnesium difluoride: from an amorphous deposit to a new polymorph

The structural evolution of magnesium difluoride from an amorphous deposit has been investigated by in situ powder X-ray diffraction (XRPD) and transmission electron microscopy (TEM). Crystalline MgF(2) was evaporated at different temperatures, which define the vapor pressures in the range from 4.7 × 10(-3) to 1.6 × 10(-1) mbar, and deposited onto various substrates. The temperature of the substrate was systematically varied from -228 to 25 °C. Magnesium difluoride was obtained as an amorphous sample when deposited on a substrate kept at a temperature below -100 °C. Upon warming, the deposit transforms via the CaCl(2) type of structure (β-MgF(2), at 70 °C) into the stable rutile type (α-MgF(2), 250 °C) by a displacive order-disorder phase transition. The new β-MgF(2) polymorph was refined assuming the orthorhombic CaCl(2) type of structure (Pnnm, No. 58) with the lattice constants a = 4.592(1) ?, b = 4.938(3) ?, and c = 2.959(3) ?. When deposited above -50 °C, samples crystallize directly in the rutile structure.     

一种基于信号功率的水声通信线性调频同步信号自适应阈值检测算法

由于线性调频信号具有一定的抗多普勒效应能力,在水下突发通信中作为同步序列得到了广泛的应用。在对线性调频信号进行同步的过程中发现,当采用固定判决门限检测方法时,往往会造成检测概率的减小或者虚警概率的增大,针对这一问题,本文提出了一种根据信号功率,并在滑动窗口中进行比较判决,自动调整相关峰检测门限值的自适应算法。通过仿真和湖试验证,该方法性能良好,具有一定的实用价值。     

关于GC-Fusion框架的若干等式和不等式

人们对框架理论研究的日益广泛和深入,目前对框架的研究已做了多种推广.GC-Fusion框架就是Fusion框架的一种广义的连续形式的推广.本文针对GC-Fusion框架建立了若干等式和不等式.     

半透射高光谱成像技术与支持向量机的马铃薯空心病无损检测研究

针对马铃薯空心病的难以检测问题,提出了一种基于半透射高光谱成像技术结合支持向量机(support vector machine,SVM)的马铃薯空心病无损检测方法。选取224个马铃薯样本(合格149个,空心75个)作为研究对象,搭建了马铃薯半透射高光谱图像采集系统,采集了马铃薯样本半透射高光谱图像(390~1 040 nm),对感兴趣区域内的光谱进行平均和光谱特征分析。采用变量标准化(normalize)对原始光谱进行光谱预处理,建立了全波段的SVM判别模型,模型对测试集样本的识别准确率仅为87.5%。为了提高模型性能,采用竞争性自适应重加权算法(competitive adaptive reweighed sampling algorithm, CARS)结合连续投影算法(successive projection algorithm, SPA)对光谱全波段520个变量进行变量选择,最终确定了8个光谱特征变量(454,601,639,664,748,827,874和936 nm),所选8个光谱变量建立的SVM模型对马铃薯测试集的识别率为94.64%。分别采用人工鱼群算法(artificial fish swarm algorithm,AFSA)、遗传算法(genetic algorithm,GA)和网格搜索法(grid search algorithm)对SVM模型的惩罚参数c和核参数g进行优化。经过建模比较分析,确定AFSA为最优优化算法,最优模型参数为c=10.659 1,g=0.349 7,确定AFSA-SVM模型为马铃薯空心病的最优识别模型,该模型总体识别率达到100%。试验结果表明：基于半透射高光谱成像技术结合CARS-SPA与AFSA-SVM方法能够对马铃薯空心病进行准确的检测,也为马铃薯空心病的快速无损检测提供技术支持。