Can Helical Peptides Unwind One Turn at a Time? ‐ Controlled Conformational Transitions in α,β2,3‐Hybrid Peptides

Unfolding of helical trans‐β^2,3‐hybrid peptides with (α–β)_nα composition, when executed by increasing solvent polarity or temperature, proceeded in a systematic manner with the turns unwinding sequentially; C‐terminal region of these peptides were first to unwind and the process propagated towards N terminus with more and more β residues equilibrating from the gauche to the anti rotameric state across C_α?C_β. This is evidenced by clear change in their C_βH signal splitting, ³J_CαH–CβH values, and sequential disappearance of i,i+2 NOEs.     

Polymeric Tubular Aromatic Amide Helices

Conjugated polymers may be induced by intra‐ and/or intermolecular non‐covalent forces to fold into helical conformations. Helices formed by aromatic amide, hydrazide, and urea polymers possess a well‐organized cavity and depth, which is defined by their degree of polymerization. Driving forces may be intramolecular hydrogen bonding and/or solvophobicity, or guest induction. The resulting long helices represent a new class of unimacromolecular dynamic tubular architectures that exhibit unique properties or functions in, for example, molecular recognition, chirality transfer, and ion transporting. The recent advances are highlighted here.

     

Formation of double helix self-assembled monolayers of ethynylhelicene oligomer disulfides on gold surfaces

Optically active ethynylhelicene pentamers and hexamers linked by disulfide bonds were synthesized. They formed self-assembled monolayers (SAMs) with double helix structure on gold surfaces, which were analyzed by infrared reflection-absorption spectroscopy (IR-RAS), quartz crystal microbalance (QCM), surface plasmon resonance (SPR), and circular dichroism (CD). Double helix SAMs could be formed on gold surfaces either from double helices or random coils in solution. The double helices on the surface were more stable than in solution. This result suggested the presence of strong intercomplex interactions between double helix complexes on the surface.     

On Darboux helices in Euclidean 4‐space

The notion of Darboux helix in Euclidean 3‐space was introduced and studied by Yayl? et al. 2012. They show that the class of Darboux helices coincide with the class of slant helices. In a special case, if the curvature functions satisfy the equality κ² + τ² = constant, then these curves are curve of the constant precession. In this paper, we study Darboux helices in Euclidean 4‐space, and we give a characterization for a curve to be a Darboux helix. We also prove that Darboux helices coincide with the general helices. In a special case, if the first and third curvatures of the curve are equal, then Darboux helix, general helix, and V₄‐slant helix are the same concepts.     

超衍射成像中 双螺旋点扩展函数的三维定位精度

开关效应和单分子定位的结合可以实现样品的超衍射分辨成像, 双螺旋点扩展函数将单分子定位纳米分辨从二维扩展到了三维.本文对双螺旋点扩展函数的三维定位精度展开了探讨.首先, 基于费希尔信息量, 计算了双螺旋点扩展函数的无偏估计, 得出其理论定位精度, 并分析了光子数、背景噪声以及有效像元尺寸大小对其定位精度的影响; 其次, 基于单分子定位实验过程中对于数据分析通常采用的高斯拟合质心定位算法, 通过误差传递函数定律求得双螺旋点扩展函数的轴向定位精度.计算机模拟结果表明, 在光子数大于1000的条件下, 高斯拟合质心定位精度和费希尔信息量理论定位精度符合较好. 本文的讨论不仅为双螺旋点扩展函数的三维定位精度提供了理论依据, 同时也可为实验提供理论指导. 关键词： 双螺旋点扩展函数 费希尔信息量 定位精度 高斯拟合     

Study on actuating voltage and switching time of a MOEMS optical switch

The micro-opto-electro-mechanical systems (MOEMS) optical switch with slant lower electrode and with torsion beam on silicon is designed and analyzed theoretically. Based on the torsion dynamics theory, the technique and relative formula are presented for the first time for analyzing the actuating voltage and the switch time. The optimized results of the structural parameters are compared between this technique and the finite element modeling (FEM). Finally, the difference between the experimental results and theoretical data is discussed.     

圆柱螺旋电磁Wiggler的场形分析

 利用载流圆柱螺旋线系统内部的磁标势满足的Laplace方程, 以及系统磁矢势的积分形式, 定出Laplace方程通解的未知系数, 求得左(右)旋单绕圆柱螺旋线的磁标势。应用磁场的叠加原理以及积分法, 给出了各种类型如双绕、双双绕、交叉绕等螺旋形Wiggler的场形分布公式。     

Assembly of Ag（I） Polymers with Thioether-S Binding and Homochiral Helices

A novel coordination polymer [Ag(pyta)]n (pyta^-=4-pyridylthioacetate) containing bound thioether sulfurs and single-stranded helical chains has been synthesized and structurally characterized.     

Metal‐cation‐induced chiroptical switching for poly(phenylacetylene) bearing a macromolecular ionophore as a graft chain

A poly(phenylacetylene) bearing a polycarbohydrate ionophore as a graft chain (copolymer 4 ) was synthesized by the copolymerization of end‐functionalized (1→6)‐2,5‐anhydro‐3,4‐di‐O‐ethyl‐D ‐glucitol with a 4‐ethynylbenzoyl group (macromonomer 2 ) with phenylacetylene. Copolymer 4 showed a split‐type circular dichroism (CD) in the long absorption region of the conjugated polymer backbone (280–500 nm), and the CD pattern varied in response to external stimuli, such as the solvents and temperature. This suggested that 4 had a predominantly one‐handed helical conformation in the polyacetylene backbone. The CD pattern of 4 was completely inverted by the formation of a complex between the macromolecular ionophore units and the selected metal cations, that is, Ba²⁺, Pb²⁺, Sr²⁺, Na⁺, and Li⁺. This suggested that copolymer 4 underwent a helix–helix transition through the host–guest complexation with achiral inorganic metal cations. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5855–5863, 2005     

Synthesis and helical conformation of poly(N‐propargylamides) carrying L‐aspartic acid in the side chain

Aspartic acid‐based novel poly(N‐propargylamides), i.e., poly[N‐(α‐tert‐butoxycarbonyl)‐L ‐aspartic acid β‐benzyl ester N′‐propargylamide] [poly( 1 )] and poly[N‐(α‐tert‐butoxycarbonyl)‐L ‐aspartic acid α‐benzyl ester N′‐propargylamide] [poly( 2 )] with moderate molecular weights were synthesized by the polymerization of the corresponding monomers 1 and 2 catalyzed with (nbd)Rh⁺[η⁶‐C₆H₅B^?(C₆H₅)₃] in CHCl₃ at 30 °C for 2 h in high yields. The chiroptical studies revealed that poly( 1 ) took a helical structure in DMF, while poly( 2 ) did not in DMF but did in CH₂Cl₂, CHCl₃, and toluene. The helicity of poly( 1 ) and poly( 2 ) could be tuned by temperature and solvents. Poly( 2 ) underwent solvent‐driven switch of helical sense, accompanying the change of the tightness. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5168–5176, 2005