Helicate tris(aryl)carbinolates bearing pendant NR2 donors – a new family of supporting ligands for the synthesis of Sc3+ alkyl complexes

The reactions of aryllithium reagents o-LiC₆H₄CH₂NR₂ with (MeO)₂CO afford two new tris(aryl)carbinols bearing pendant-NR₂ donor groups in the side chain [o-R NCH C H ] COH [R = Me, R + R = (CH) ]. These alcohols feature helical chirality due to differently inclined aromatic fragments and are presented in a crystalline cell as two M and P enantiomers. Carbinol (R = Me) readily reacts with (Me3SiCH2)3Sc(THF)2 to give a scandium bis(alkyl) complex [(o-C₆H₄CH₂NMe₂)₃CO]Sc(CH₂SiMe₃)₂ featuring rigid binding of the alkoxy anion through a κ¹-O, κ²-N chelating coordination mode     

Formation of Supramolecular Nanostructures through in Situ Self-Assembly and Post-Assembly Modification of a Biocatalytically Constructed Dipeptide Hydrazide**

Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging.     

Self‐Assembly and Gelation of Poly(aryl ether) Dendrons Containing Hydrazide Units: Factors Controlling the Formation of Helical Structures

Self‐assembly of AB₂ and AB₃ type low molecular weight poly(aryl ether) dendrons that contain hydrazide units were used to investigate mechanistic aspects of helical structure formation during self‐assembly. The results suggest that there are three important aspects that control helical structure formation in such systems with acyl hydrazide/hydrazone linkage: i) J‐type aggregation, ii) the hydrogen‐bond donor/acceptor ability of the solvent, and iii) the dielectric constant of the solvent. The monomer units self‐assemble to form dimer structures through hydrogen‐bonding and further assembly of the hydrogen‐bonded dimers leads to macroscopic chirality in the present case. Dimer formation was confirmed by NMR spectroscopy and by mass spectrometry. The self‐assembly in the system was driven by hydrogen‐bonding and π–π stacking interactions. The morphology of the aggregates formed was examined by scanning electron microscopy, and the analysis suggests that aprotic solvent systems facilitate helical fibre formation, whereas introduction of protic solvents results in the formation of flat ribbons. This detailed mechanistic study suggests that the self‐assembly follows a nucleation–elongation model to form helical structures, rather than the isodesmic model.     

Dielectric effect on the rf characteristics of a helical groove travelling wave tube

A new type of partial-dielectric-loaded helical groove slow-wave structure (SWS) for millimetre wave travelling wave tube (TWT） is presented in this paper.The radio-frequency characteristics including the dispersion properties,the longitudinal electric field distribution and the beam-wave coupling impedance of this structure are analysed.The results show that the dispersion of the helical groove circuit is weakened,the phase velocity is reduced and the position of the maximum Ez is moved from the mouth to the inside of the groove after partially filling the dielectric materials in the helical groove SWS.Therefore,the dielectric-loaded helical groove SWS is suitable for a multi-beam TWT with broad band and high gain.     

岩芯筒压入地层的塑性力学问题

摘要首先从库仑定律出发导出了地层介质塑性流动条件。其结果类似于一般塑性力学中的Tresca,Mises条件。其次列出了轴对称地层塑性流动的微分方程组,并推出了其简化近似方程。最后提出了简化方程的特征线解法,并举例说明。     

Separation of screw-sensed particles in a homogeneous shear field

The Stokes motions of three-dimensional screw-sensed slender particles in a homogeneous shear field are investigated, including the effects of buoyancy. Conclusions are drawn about the possibility of achieving a separation of mixtures of right- and left-handed particles. The linearity of the Stokes equations allows complex flows to be solved by adding the effects of the several terms which describe the flow in which the particle is immersed. The homogeneous shear flow considered here consists of three such terms; solutions for a series of 12 unit motions are sufficient to determine the hydrodynamic resistance tensors. The forces and torques experienced by screw-sensed particles are calculated from these 51 resistance tensors, using slender-filament theory. The results allow an estimate of the range of buoyancy parameters for which gravitational sedimentation can be neglected. The fundamental component of the particle motion is a rotation, at approximately the same angular velocity as that of the fluid. Superimposed on this are variations, of large period, in the particle orientation. A phase plane analysis is used to find the terminal orientations. Very long calculation times are required for the phase portrait. An approximate method based on azimuthally-averaged equations is developed to avoid the requirements for long time integration.     

催化裂解法制备螺旋状碳纳米管的实验研究

在硅片上用直流溅射镀铁的方法制备催化剂 ,通过乙炔在 70 0°C下催化裂解制备碳纳米管 .对热解产物进行了扫描电镜观察和 X射线衍射测试 .本文通过对有氢气预处理和没有氢气预处理两种情况下催化裂解法制备的碳纳米管的形貌、管径大小等性质的研究 ,来初步揭示螺旋状碳纳米管的生长机理 .     

风速计调节喷泉喷水量问题的分析

针对大型喷泉系统喷水量调节问题，采用流体力学风洞模型试验得出的三维物体型阻理论、微气象学、建筑给水、排水工程喷泉设计导论，以及物理学基本运动学理论，得出了喷泉喷水量调节的基本理论依据以及解决方法，为大型喷泉调节系统设计工作提供了有力支持。     

Synthesis of optically active poly(N‐propargylsulfamides) with helical conformation

A novel chiral N‐propargylsulfamide monomer ( 1a ) and its enantiomer ( 1b ) were synthesized and polymerized with (nbd)Rh⁺B^?(C₆H₅)₄ as a catalyst providing poly(1) (poly( 1a ) and poly( 1b )) in high yields (≥99%). Poly(1) could take stable helices in less polar solvents (chloroform and THF), demonstrated by strong circular dichroism signals and UV–vis absorption peaks at about 415 nm and the large specific rotations; but in more polar solvents including DMF and DMSO, poly(1) failed to form helix. Quantitative evaluation with anisotropy factor showed that the helical screw sense had a relatively high thermal stability. These results together with the IR spectra measured in solvents showed that hydrogen bonding between the neighboring sulfamide groups is one of the main driving forces for poly(1) to adopt stable helices. In addition, copolymerization of monomer 1a and monomer 2 was conducted, the solubility of poly(1) was improved drastically. However, the copolymerization had adverse effects on the formation of stable helices in the copolymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 500–508, 2007