粘接-映射混合算法及其对颗粒材料中板的振动特性分析

结构与颗粒材料相互作用广泛存在于各工程领域,其研究过程中涉及的连续-离散耦合计算方法面对诸多挑战.本文提出了粘接-映射混合算法来研究连续体与离散介质耦合动力学问题.将连续体模型划分为内部区域及与颗粒接触的边界区域.边界区域采用粘接算法模拟连续体外部形状并使用高效的球形接触判断准则;提出一种包含Rayleigh阻尼映射的有限元映射质点弹簧算法来精确计算连续体内部区域内力和变形.二者相结合构成粘接-映射混合算法,并引入计算机集群和GPU(图形处理器)并行技术,对埋没于颗粒材料中受激振动固支方板的连续-离散耦合动力学问题进行了数值仿真研究.结果表明,粘接-映射混合算法有利于双层级并行算法的程序实现及优化,并在连续-离散耦合界面进行快速接触判断的同时实现对颗粒材料中方板位移、变形、振动形态等参数的研究.通过定幅扫频和定频变幅方式考察激振力频率和幅值对振动板非线性动力学行为的影响并观察到二倍周期现象,同时给出了该连续-离散耦合系统中颗粒体系的能量耗散特性.      

Spectrophotometric and visual detection of the herbicide atrazine by exploiting hydrogen bond-induced aggregation of melamine-modified gold nanoparticles

We report on a method for the determination of the herbicide atrazine in tap water samples using melamine-modified gold nanoparticles (Mel-AuNPs). If a solution containing atrazine is added to a solution of such NPs, a color change occurs from wine-red to blue. This is due to a transition from monodisperse to aggregated Mel-AuNPs and caused by strong hydrogen bonding between atrazine and melamine. The color change can be monitored by a UV–vis spectrophotometer or with bare eyes. The ratio of the absorbances at 640 and 523 nm is linearly related to the logarithm of the atrazine concentration in the 0.165 to 16.5 μM range, and (with different slope) in the 16.5 μM to 330 μM range. The detection limit of atrazine is as low as 16.5 nM (S/N = 3). The method was successfully applied to the determination of atrazine in spiked tap water and gave recoveries that ranged from 72.5 % to 102.3 %.

ᅟ

     

Stereodivergent Synthesis of N‐Heterocycles by Catalyst‐Controlled,Activity‐Directed Tandem Annulation of Diazo Compounds with Amino Alkynes

A stereodivergent synthesis of five‐membered N‐heterocycles, such as 2,3‐dihydropyrroles, and 2‐methylene and 3‐methylene pyrrolidines, has been developed through a tandem annulation of amino alkynes with diazo compounds and involves the trapping of in situ formed intermediates. Mechanistic investigations indicate that the copper‐catalyzed tandem annulations proceed by allenoate formation and subsequent intramolecular hydroamination. In contrast, the rhodium‐catalyzed protocol features a carbenoid insertion into the N H bond and subsequent Conia‐ene cyclization.     

Base‐Promoted/Gold‐Catalyzed Intramolecular Highly Selective and Controllable Detosylative Cyclization

A highly selective, controllable and synthetically useful base‐promoted intramolecular detosylative cyclization of bis‐N‐tosylhydrazones has been achieved, affording N‐containing heterocycles and cyclic olefins under transition‐metal‐free or gold‐catalyzed procedures, respectively. Moreover, an effective and practical metal‐free or gold‐catalyzed approach to synthesize polycyclic aromatic compounds is also reported.     

Rhodium‐Catalyzed Regioselective N2‐Alkylation of Benzotriazoles with Diazo Compounds/Enynones via a Nonclassical Pathway

A novel rhodium‐catalyzed highly selective N²‐alkylation of benzotriazoles with diazo compounds/enynones is achieved, providing N²‐alkylated benzotriazoles in good to excellent yields and with excellent N² selectivities. Importantly, different to traditional carbene insertion into X?H (X=N, O etc) bonds, DFT calculations disclose that this selective N²‐alkylation probably proceeds through a formal 1,3‐ rather than 1,2‐H shift to give the final products.     

Gold‐Catalyzed Formal [4+1]/[4+3] Cycloadditions of Diazo Esters with Triazines

Reported herein is the unprecedented gold‐catalyzed formal [4+1]/[4+3] cycloadditions of diazo esters with hexahydro‐1,3,4‐triazines, thus providing five‐ and seven‐membered heterocycles in moderate to high yields under mild reaction conditions. These reactions feature the use of a gold complex to accomplish the diverse annulations and the first example of the involvement of a gold metallo‐enolcarbene in a cycloaddition. It is also the first utilization of stable triazines as formal dipolar adducts in the carbene‐involved cycloadditions. Mechanistic investigations reveal that the triazines reacted directly, rather than as formaldimine precursors, in the reaction process.     

Wide angle X‐ray diffraction and Fourier transform infrared dichroism studies of stretched‐recovery‐restretched process of polyurethane/clay nanocomposite

An intercalated polyurethane (PU) /clay nanocomposite was prepared by in situ intercalative polymerization. The PU/clay nanocomposite pellet or film samples were stretched‐recovery‐restretched, using selfmade microstretching tools. The changes of the basal spacings of clay and the orientation of polymer chain segments during the stretched‐recovery‐restretched process were studied by wide angle X‐ray diffraction (WAXD) and Fourier transform infrared (FTIR) dichoism techniques. The WAXD results show that the basal spacing of clay did not change obviously, indicating that no macromolecular chains entered or moved out of the interlayer space, and the orientations of both hard and soft segments inside the interlayer space did not change obviously, either. The FTIR dichroism tests suggest that outside the interlayer space, the orientation of the hard chain segment increased, decreased, and then increased again during the stretched‐recovery‐restretched process. However, no obvious changes of the degree of orientation of the soft segment were observed during the processes, the slightly orientation might be released during the relaxation process before the measurements. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 654–660, 2007     

Access to N‐Substituted 2‐Pyridones by Catalytic Intermolecular Dearomatization and 1,4‐Acyl Transfer

A novel rhodium‐catalyzed dearomatization of O‐substituted pyridines to access N‐substituted 2‐pyridones has been developed. A computational study suggests a mechanism involving the formation of a pyridinium ylide followed by an unprecedented 1,4‐acyl migratory rearrangement from O to C. Furthermore, the chiral dirhodium complexes serve as the catalyst for the asymmetric transformation with excellent enantioselective control. DFT calculations indicate the chirality is transferred from axial chirality to the central stereogenic centre. The stronger π–π interaction and CH–π interaction account for the high enantioselectivity.