Supramolecular heterogeneity in β-turn forming synthetic tripeptides nucleated by isomers of fluorinated phenylalanine and aib as corner residues

The influences of fluorines in chemistry have emerged as a breakthrough in various arenas of bio-organic and medicinal chemistry. But its incorporation in β-turn design and its implications for supramolecular chemistry remains in a rudimentary stage. Inspired by the diversity displayed by the isomers of mono-fluorinated phenylalanine in biological sciences, here our effort is to modulate the solid state conformational analysis of three terminally protected synthetic tripeptides Boc-(Y)-F-Phe-Aib-Xaa-OMe, where (Y is (2)-F-Phe, Xaa; Leu in peptide I, (3)-F-Phe, Xaa; Leu in peptide II and (4)-F-Phe, Xaa; Ile in peptide III). Interestingly, all the three peptides display a conformational preference for β-turns, stabilized by 4→1 intramolecular hydrogen bonding. Our investigation further demonstrates that mere interchange of positions of fluorines in mono-fluorinated phenylalanine in peptides I–III introduces significant diversity in supramolecular chemistry. X-ray crystallography sheds some light at atomic resolution. Furthermore, this supramolecular heterogeneous behavior is evident from the morphologies obtained from the materials of all the three peptides grown from acetone to petroleum ether solution, studied by field emission scanning electron microscopy. Thus, these monofluorinated peptides I–III may serve as prominent candidates in understanding the structure and function of misfolded disease causing peptides like prion and Alzheimer's amyloid.     

Compatibilized poly(ether imide)/LCP blends: drawing ability and mechanical properties of the ribbons

The effects of the addition of polyarylate (PAr) on the drawing ability of poly(ether imide) (PEI)/Rodrun liquid‐crystalline 5000 (Ro LC5000) (Ro) blends and on the mechanical properties of their ribbons were studied. The compatibilizing effect of the PAr led to an increase in the drawing ability of the blends, as seen by the fact that the maximum Ro content compatible with the drawing process increased from 15 to 30%. This may lead to new applications in the field of gas barrier materials. The presence of PAr also led to an increase in the adhesion between the two phases of the blends and consequent improved ductility. However, the very high modulus of elasticity and tensile strength in the direction of orientation (up to three‐fold those of the matrix) due to the less developed fibrillation were smaller than the corresponding values before compatibilization. These very large modulus of elasticity and tensile strength values and those perpendicular to the direction of orientation, which were similar to those of the matrix, led to a high anisotropy in the extruded ribbons that increased with the draw ratio (DR) and the Ro contents. The high mechanical properties of the ribbons may be used and the anisotropy diminished by layering the ribbons in, and perpendicular to, the direction of orientation, according to the expected external load. Copyright © 2002 John Wiley & Sons, Ltd.     

Destruction of Landau levels in asymmetric bilayer nanographene ribbons

Magneto-electronic properties of asymmetric bilayer nanographene ribbons are enriched by geometric structures, interlayer atomic interactions, magnetic quantization and finite-size confinement. There are drastic changes on the band symmetry, the degeneracy of the partial flat bands, the number of band-edge states, the energy dispersion, the carrier density, and the spatial symmetry of the wave function. Quasi-Landau levels might be converted into oscillating bands where extra band-edge states are created. When the upper ribbon is located at the ribbon centre, the Landau wave functions are completely destroyed. Meanwhile, a charge transfer between different layers or different sublattices in the same layer occurs. Furthermore, the density of states, reflecting the band structure, is also severely altered in terms of the number, structure, energy, and height of the prominent peaks.     

Effect of the Heating Rate on Crystallization Kinetics of Mg84Ni12.5Y3.5 Amorphous Ribbons

Crystallization kinetics of Mg₈₄Ni_12.5Y_3.5 amorphous ribbons produced by the melt-spinning method, was studied by DSC analysis and X-ray diffraction. The effect of heating rate (from 2 to 240 K min^–1) was investigated in the temperature range from 298 to 673 K. The results showed that the crystallization process took place in two stages: a) crystallization of part of the amorphous matrix to an intermediate phase and hcp-Mg, and b) transformation of the intermediate phase and the remaining amorphous material to Mg₂Ni+Mg (solid solution of Y in Mg). Increasing the heating rate from 2 to 240 K min^–1 results in increases of the temperature difference between the two-step crystallization of the first stage transformation processes from 33 to 56 K and in increases of the temperature difference between the two-stage transformation from 62 to 97 K.This revised version was published online in November 2005 with corrections to the Cover Date.     

Self-assembly of twisted,multi-sheet aggregates

ABSTRACT

Hierarchical self-assembly underpins much of the diversity of form and function seen in soft systems, yet the pathways by which they achieve their final form are not always straightforward – intermediate steps, kinetic effects and finite sizes of aggregates all influence the self-assembly pathways of these systems. In this paper, we use molecular dynamics simulations of binary mixtures of spheres and ellipsoidal discs to investigate the self-assembly of anisotropic aggregates with internal structures. Through this, the full aggregation pathways of spontaneously chiral, multi-bilayer and multi-layer assemblies have been tracked and characterised via a semi-qualitative analysis. This includes the unambiguous identification of first-, second- and third-generation hierarchical assemblies within a single simulation. Given the significant challenge of tracking full aggregation pathways in experimental systems, our findings strongly support the notion that molecular simulation has much to contribute to improving our understanding of hierarchical self-assembling systems.     

Bizarre alterations of the morphology of pineal synaptic bodies under constant light and an evaluation of suitable 3D-reconstruction software

Three dimensional (3D) reconstruction and modelling software was evaluated to find a procedure suitable for visualization of small subcellular structures in transmission electron microscope images. The method applied in this study demonstrates bizarre alterations of the structure of synaptic bodies (SBs) in pinealocytes of the guinea-pig pineal gland caused by constant illumination. It can, in general, be used for any 3D reconstruction from serial sections.

Pineal glands of five guinea-pigs (two kept under a LD cycle of 12:12 h; three kept in constant light, for 4 months) were investigated. SBs consist of an electron-dense centre with attached vesicles. Under normal lighting conditions most SBs are flat plates (about 35 nm in thickness), which eventually may be bent. The proteins comprising the molecular basis of SBs, mainly RIBEYE A and B are polymerised in a regular manner in these plates. This is not the case in other SBs, which appear as spheres or irregular lumps. SBs lie in groups in which usually some of the plates are arranged in parallel arrays

Constant illumination caused different changes in morphology: many of the SBs lie in ‘paired fields’, i.e. appear in groups attached to the cell membranes of two pinealocytes directly opposite to each other. Some of the SBs in such groups are strongly bent, showing blebs and irregular thickened areas, others seem to aggregate and show inclusions of cytoplasm. Further goblet-like, shield-like and other bizarre forms of SBs occurred and the relative number of spheroid and lump-like SBs increased. Protrusions on larger SBs suggest detachment or fusion of SB material to a greater extent than in the control animals. There is a reduction of areas in which the polymerisation of the SB proteins remains well ordered, i.e. where the typical thickness of 35 nm is maintained. It remains unclear why this polymerisation pattern is only partly affected by constant light.     

B元素添加对Co-Zr-Mo合金薄带的磁性能及结构的影响

利用X射线和磁性测量研究了Co_77Zr（18-x）Mo₅B_x合金薄带的结构和磁性.实验发现,在Co-Zr-Mo合金中添加适当含量的B,可以使其矫顽力显著提高,当x=2.0时,制备出具有迄今为止Co-Zr基永磁合金最大矫顽力H_c=7.0 kOe（1 Oe=79.5775 A/m）的快淬薄带.随着B元素添加,Co₇₇Zr_18-xMo₅B_x合金薄带的晶粒逐渐细化,并根据Henkel plot模型计算得出软磁相fcc-Co与硬磁相Co₅Zr相之间的交换耦合作用逐渐增强.合金薄带的矫顽力主要受硬磁相Co₅Zr相的晶粒尺寸控制,并随着晶粒尺寸的减小先升高后降低.另一方面,Co₇₇Zr₁₈Mo₅合金薄带的矫顽力机理为反磁化核形核模型,添加B元素之后矫顽力机理变为畴壁钉扎模型.通过X射线衍射和热磁分析发现,B元素并没有进入到Co₅Zr相的晶格中,而是存在于非晶相中.     

Effects of Nb substitution for Zr on the phases,microstructure and magnetic properties of Co80Zr18−xNbxB2 melt-spun ribbons

The phases, microstructure, and magnetic properties of Co₈₀Zr_18−xNb_xB₂ (x=1, 2, 3, and 4) melt-spun ribbons were investigated. The small substitution of Nb for Zr in the Co–Zr–B melt-spun ribbons resulted in the improvement of magnetic properties, especially the coercivity. The main effect of added Nb on the coercovity of Co–Zr–Nb–B melt-spun ribbons, originated from modification of the grain size of Co₁₁Zr₂ phase. The coercivity of the Co–Zr–Nb–B melt-spun ribbons depends on the annealing temperature. The optimal magnetic properties of H_c=5.1 kOe, and (BH)_max=3.4 MGOe were obtained in the Co₈₀Zr₁₅Nb₃B₂ melt-spun ribbons annealed at 600 °C for 3 min.     

非晶态合金薄带与膜的巨磁电阻抗效应理论及计算

通过建立具有平面近横向各向异性场的非晶态合金薄带及膜的磁畴结构模型，利用线性化Maxwell方程组及Landau-Lifshitz方程，推出了在高频交变磁场及外加面内轴向直流磁场H_ex作用下的铁磁材料的与取向相关的磁导率表达式，得到了对方位角平均的相对磁导率及阻抗的计算式，导出了磁导率与张量磁化率分量间的关系，对材料磁导率的实部及虚部随H_ex的变化进行了计算，并给出了对应的磁谱图.建立的磁导率与外磁场的理论关系可将Panina及Kraus给出的理论结果统一起来. 关键词： 非晶态合金薄带及膜 取向相关磁导率 GMI效应理论与计算 近横向各向异性场     

GIANT MAGNETO-IMPEDANCE IN Fe-BASED SOFT FERROMAGNETIC RIBBONS

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