Structural and bonding characteristics in transition metal-silane complexes

Transition metal-silane complexes containing metal-eta 2-H-Si coordination display different structural and bonding characteristics in comparison to other sigma-complexes, such as dihydrogen and alkane (agostic) complexes. The different characteristics can be related to the strong sigma*-accepting properties of the eta 2-silane ligand(s) because of the weaker H-Si sigma bond. Various examples of metal-silane complexes have been reviewed and their structural stabilities have been systematically discussed. Silyl-hydride complexes having substantial silyl-hydrido interactions have also been emphasized.     

Alkene insertion reactivity of a o-carboranyl-substituted 9-borafluorene

The synthesis of 9-borafluorene with an electron-withdrawing o-carboranyl substituent and its reactions with a series of alkenes are described. The o-carboranyl substituent is bonded via one of the cluster carbon atoms to the boron atom of the 9-borafluorene moiety. In all cases, the reactions afford partly saturated analogs of borepins (i.e. 6,7-dihydroborepins) by unprecedented alkene insertion into the endocyclic B–C bond of the borole ring. Comparative studies with 9-bromo-9-borafluorene illustrate the superior insertion reactivity of the carboranyl-substituted derivative. A suite of experimental and computational techniques disclose the unique properties of the 9-borafluorene and provide insight into how the 9-carboranyl substituent affects its chemical reactivity.

A 9-carboranyl-substituted 9-borafluorene is reported, which is capable of undergoing efficient ring expansion to 6,7-dihydroborepins by a previously unknown alkene insertion.     

Microstructure and Thermal and Tensile Properties of Poly(vinyl alcohol) Nanocomposite Films Reinforced by Polyacrylamide Grafted Cellulose Nanocrystals

Abstract

Polyacrylamide grafted cellulose nanocrystals (CNC-g-PAM) were incorporated into poly(vinyl alcohol) (PVA) by a solution casting method to fabricate nanocomposite films with enhanced thermal and tensile properties. The microstructure and the thermal and tensile properties of the PVA/CNC-g-PAM nanocomposite films were investigated as a function of CNC-g-PAM content. Infrared spectroscopy corroborated the presence of hydrogen bonds between PVA and the PAM on the surface of the CNC. Polarized optical microscopy and scanning electron microscopy revealed good dispersion of the CNC-g-PAM in the PVA matrix and good interfacial compatibility. Accordingly, the initial degradation temperature of the nanocomposite films was elevated slightly compared to pristine PVA film. The glass transition temperature, melting temperature, and crystallinity of the PVA also varied slightly after the incorporation of the CNC-g-PAM. At both 0% and 50% RH, the nanocomposite films showed an obvious increase of elastic modulus, no apparent change of breaking strength and a drastic reduction of elongation at break with increasing CNC-g-PAM content.     

红外成像检测中一种新型噪声抑制方法的理论模拟

根据线性微分方程的特点及两个合理的近似,提出了一种新的用计算机辅助去除红外成像检测中高功率噪声的方法,仿真结果表明方法有良好的抑制噪声效果。     

基于ABAQUS的微细电火花超声振动主轴仿真研究

微细电火花技术凭借自身的特点和优势,在航空航天、医疗器械等领域发挥着重要的作用.超声振动辅助电火花加工在传统电火花加工中引入超声振动,加工精度和加工效率明显提高.作为核心部件,超声振动主轴的设计尤为重要.但传统设计过程,大大延长了研发周期和增加了成本,因此,采用仿真方式进行研究具有重要的意义.该文对设计的微细电火花超声...     

Accurate method for measuring the thermal coefficient of group birefringence of polarization-maintaining fibers

We present a method to accurately measure the group birefringence variation with temperature in high-birefringence polarization-maintaining (PM) fibers using a distributed polarization analyzer. By analyzing polarization cross-talk peaks purposely induced at both ends of a PM fiber, the temperature coefficient of group birefringence can be accurately obtained. We confirm the theoretical prediction that the group birefringence of PANDA and TIGER PM fibers decrease linearly with temperature from -40 °C to 80 °C, and find that the temperature coefficients are -5.93 × 10(-7) °C(-1) and -5.29 × 10(-7) °C(-1) for two types of PANDA fibers, and -5.36 × 10(-7) °C(-1) for a TIGER fiber.     

Speech enhancement based on multitaper spectrum and psychoacoustical weighting rule

Multitaper spectrum has lower variance than the traditional periodogram. The noise spectrum and the noise to noisy signal spectrum ratio (NNSR) were estimated from the multitaper spectrum of the noisy signal; the pre-enhanced speech for calculating the noise masking threshold was obtained by the spectral amplitude subtraction method, whose gain is a function of NNSR; the final enhanced speech was obtained by suppressing the Fourier spectrum of the noisy speech with the psychoacoustical weighting rule incorporating the noise masking threshold. Because of the low variance feature of the multitaper spectrum, a modified offset formula was proposed to calculate the noise masking threshold, thus the reconstructed speech with this modification has an improvement in MBSD (Modified Bark Spectral Distortion). When a maximum limitation less than one to the psychoacoustical weighting rule is further proposed, the higher the input SNR (> 0 dB) is, the more improvement the segmental SNR and the overall SNR have. The informal listening tests show that there is little speech distortion for the enhanced speech processed by the proposed method, the background noise is reduced much and free of musical noise.     

A DFT study on the mechanism of hydrosilylation of unsaturated compounds with neutral hydrido(hydrosilylene)tungsten complex

Recently, Tobita et al. reported stoichiometric hydrosilylation reactions of acetone and acetonitrile with neutral hydrido(hydrosilylene)tungsten complexes Cp'(CO)2(H)W=Si(H)[C(SiMe(3))(3)] (Cp' = Cp*, C(5)Me(4)Et). The mechanisms of the hydrosilylation reactions of unsaturated compounds (ketone and nitrile) with the tungsten complexes have been investigated with the B(3)LYP density functional theory method. Four possible reaction mechanisms were studied. The results of the calculations indicate that the hydrosilylation of acetone proceeds via a metal hydride migration mechanism proposed by Tobita et al., while the hydrosilylation of nitrile occurs through a silyl migration mechanism, analogous to the modified Chalk-Harrod mechanism. The [2(sigma)+2(pi)] additions of various CX (CX = C=O or CN) multiple bonds with the Si-H bonds in the neutral complexes have very high barriers although similar additions were found feasible in other related cationic complexes. All the hydrosilylation reactions studied here give stable tungsten-silylene or tungsten-silyl products, which are not easily converted into the starting hydrido(hydrosilylene)tungsten complexes when reacting with a hydrosilane substrate molecule. Therefore, we predict that hydrosilylation of acetonitrile and acetone catalyzed by these tungsten complexes is difficult to achieve.     

Hydroxyethyl cellulose-based electrically conductive,mechanically resistant,strain-sensitive self-healing hydrogels

Cellulose - Self-healing hydrogels that mimic human skin and have numerous senses of external tension and temperature are a current topic in science. However, getting skin-compatible performance...     

Protonation and bromination of an osmabenzyne: reactions leading to the formation of new metallabenzynes

The reactivities of benzynes and metal-carbyne complexes are normally associated with the triple bond units. However, we have now found that electrophiles do not attack the formal osmium-carbon triple bond of osmabenzyne complex 1. Instead, 1 undergoes electrophilic substitution reactions-the typical reactions of aromatic systems.