Stiff-Chain Polymers—Structure,Phase Behavior,and Properties

Most of the industrial plastics used up to now consist of flexible macromolecules in which the repeat units are joined together in a nonlinear fashion by rotating bonds. Stiff-chain polymers, which in the ideal case have a rodlike shape, have received much less attention. The reason for this is that such polymers usually exhibit an exceedingly low solubility. Very often, they are absolutely insoluble and do not melt. However, in recent years these polymers have aroused technical interest because high-modulus fibers and moldings can be fabricated from them. These favorable mechanical properties are directly related to the nearly parallel arrangement of the rodlike macromolecules in the solid state which is achieved through spinning or extrusion from a liquid crystalline (nematic) state. It is therefore evident that a thorough understanding of the phase behavior and the structure is required for a universal technical utilization of these materials. The great variety of methods used in polymer science today has led to a deeper understanding of stiff-chain polymers. Experimental results together with theoretical modeling of the phase behavior have direct implications for the practical use of these macromolecular materials.     

Polymers with Metal-Like Conductivity—A Review of their Synthesis,Structure and Properties

Polymers such as polyacetylene, which have an extended π-electron system in their backbone, or like poly(p-phenylene) consist of a sequence of aromatic rings are excellent insulators in their native state and can be transformed by oxidation or reduction in the solid state into conductive CT-complexes which exhibit metal-like conduction characteristics. The chemical and physical processes involved and the reasons for the observed quasimetallic conductivity are not yet fully understood. The real structure of these materials in chemical and physical terms, i. e. their complicated morphology and texture, as well as the results available on the structure-property relationships of the “organic metals” must be considered when discussing their properties. In other words, a discussion of conductive polymers should be based on what is known of the highly conducting CT-complexes of low-molecular weight compounds. The discovery of the highly conducting polymer complexes has opened up a new interdisciplinary field of research which borders on polymer science, solid-state and semiconductor physics and on organic solid-state chemistry. It is hoped that this area will lead to numerous novel materials and technical applications.     

Novel Ladder π‐Conjugated Materials—Sila‐Pentathienoacenes: Synthesis,Structure, and Electronic Properties

A novel series of ladder π‐conjugated materials—sila‐pentathienoacenes ( Si‐PTA ) are synthesized and characterized. Crystal structures of the compounds show that the length of alkyl chains substituting on the thiophene ring has a significant influence on molecular packing. A densely packed structure with an interfacial distance of about 3.66 Å between the adjacent molecules is observed for the compound with shorter alkyl chains. However, a large interfacial distance (7.99 Å) is obtained for another compound because of the insertion of long alkyl chains between two planes. The investigation of the optical and electrochemical properties shows that the silylene bridge incorporated into the pentathienoacene framework exerts a clear effect on the electronic properties by the σ*–π* conjugation. Although only a slight enhancement is observed for the HOMO levels, with respect to that of pentathienoacene, the LUMO levels are significantly lowered. The observed electronic properties are consistent with the theoretical calculations.     

高分子气体分离膜材料的化学结构与气体透过性能之间的关系

本文以硅橡胶和聚酰亚胺为基础,从高分子的化学组成、分子链段的运动能力、侧基的大小及其作用等几个方面,讨论了聚合物的化学结构对其均质膜的气体选择透过性能的影响,以溶解扩散过程对气体分离膜材料的透气行为进行了剖析,井简述高分子化学结构对其成膜时结晶情况的影响及对气体透过的作用;还概述了气体分离膜科学发展的历史以及基本原理.     

My Research History on the Chemical Standpoint—From Molecular Structure to Surface Science

The structure of molecules using gas electron diffraction (GED) was my graduate study. However, I was making a new apparatus for precise measurements by GED and formulated a scheme for the least‐squares analysis for a smooth continuous curve of scattering intensity. My research was completely shifted to the solid surface after moving to Gakushuin University, where I briefly studied the liquid structure of CCl₄ molecules, and I then moved to the Institute for Solid State Physics, the University of Tokyo. My studies of surface science were focused on the electronic properties and related phenomena, and various experimental methods were developed. The plasmon dispersions elucidated the initial oxidation of aluminum and one‐dimensional metal on Si(001)2 × 1–K. Irreversible phase transition was discovered on MgO(001) using the LEED Kikuchi pattern. The electronic structure of the dislocation was observed on MgO(001) by the electron time‐of‐flight method. The phase transition on Si(001) and the rotational epitaxy in a K monoatomic layer on Cu(001) were found. Next, I changed to studies of the dynamical phenomena on the surface, where very low energy reactive ion scattering on metal surfaces and laser‐induced desorption caused by electronic transition of NO and CO molecules from metal surfaces were observed, and the hydrogen atom location at the surface and interface was measured with a high depth resolution using a resonance nuclear reaction of ¹H + ¹⁵N²⁺ at 6.385 MeV. Finally, I moved to the University of Electro‐Communications and studied thin single‐crystal oxide layers on transition metals, in which the band‐gap narrowing was found, and then a Pt monoatomic layer was prepared on the α‐Al₂O₃ film.     

EuCN2 — The First,but Not Quite Unexpected Ternary Rare Earth Metal Cyanamide

Red‐orange, transparent single crystals of EuCN₂ (Pnma (62), a = 1232.41(9), b = 395.26(3) and c = 539.43(4) pm, Z = 4) are obtained by the reaction of EuN, C and NaN₃ in arc‐welded Ta ampoules at 1300 K. The first ternary rare earth metal cyanamide is isotypic to α‐SrCN₂ and shows the characteristic frequencies for the CN₂^2— unit in the optical spectra (ν_s = 1244; ν_as = 1969 and 2087; δ = 655 / 666 cm^—1).     

The Origin of Life—Out of the Blue

Either to sustain autotrophy, or as a prelude to heterotrophy, organic synthesis from an environmentally available C₁ feedstock molecule is crucial to the origin of life. Recent findings augment key literature results and suggest that hydrogen cyanide—“Blausäure”—was that feedstock.     

Synthesis of the Heaviest Chemical Elements—Results and Perspectives

All 17 artificially produced elements heavier than uranium were discovered by nuclear-chemical synthesis. The three heaviest ones–elements 107, 108 and 109–were synthesized at the heavy-ion accelerator UNILAC in Darmstadt by nuclear fusion from the heaviest stable nuclei, lead-208 and bismuth-209, and the most neutron-rich stable isotopes of chromium and iron: element 107 from bismuth-209 (atomic number Z = 83) and chromium-54 (Z = 24), element 108 from lead-208 (Z = 82) and iron-58 (Z = 26), and element 109 from bismuth-209 and iron-58. The first isotopes detected were those with mass numbers 262 (Z = 107), 265 (Z = 108) and 266 (Z = 109); these nuclei are short-lived α-emitters with half-lives of 8.2 ms, 1.8 ms and 3.4 ms, respectively. The yields of these reactions are extremely small; only three atoms of element 109 have ever been observed. Experiments to synthesize element 110 have given ambiguous results. All attempts to detect the “superheavy” elements with proton numbers near Z = 114 and neutron numbers near N = 184 have thus far failed. These elements have been predicted theoretically, and many attempts to synthesize them have been made, e.g. at UNILAC by fusion of calcium-48 (Z = 20) with curium-248 (Z = 96), or by transference of protons in the collision of two very heavy nuclei such as uranium-238 (Z = 92). Surprisingly, the heaviest known nuclei are far more stable toward spontaneous fission into two fragments than was expected, but their synthesis is strongly hindered–much more than initially anticipated. It is this hindrance rather than the decreasing nuclear stability which seems to presently limit the extent of the periodic table: even heavier elements should be able to exist, but no way has yet been found to produce them.     

Chemical Synthesis of the 12 kDa Human Myokine Irisin by α‐Ketoacid‐Hydroxylamine (KAHA) Ligation

Irisin is a recently discovered protein hormone with a conserved sequence among vertebrates and with putative functions in the regulation of adipose tissue and bone metabolism. We report the first chemical synthesis using two sequential ketoacid‐hydroxylamine (KAHA) ligations to give milligram quantities of unlabeled and fluorescence‐labeled irisin protein. The synthetic proteins were utilized in cell binding assays, which indicated the expected binding characteristics to stromal cells of white adipose tissue. These studies strongly imply the presence of a specific irisin receptor and provide a path to its identification with synthetic irisin.     

Molecular Imprinting in Cross-Linked Materials with the Aid of Molecular Templates— A Way towards Artificial Antibodies

Can binding sites be produced in organic or inorganic polymers—similar to those in antibodies—which are able to recognize molecules and which may have catalytic action? In this article we review a method, analogous to a mechanism of antibody formation proposed earlier, by which in the presence of interacting monomers a cross-linked polymer is formed around a molecule that acts as a template. After removal of the template, an imprint containing functional groups capable of chemical interaction remains in the polymer. The shape of the imprint and the arrangement of the functional groups are complementary to the structure of the template. If chiral templates are used, the success of the imprinting process can be assessed by the ability of the polymer to resolve the racemate of the template molecule. Through optimization of the process has led to chromatographic separation factors of α = 4–8, and to base line separations. There is also great interest in the surface imprinting of solid materials and monolayers. In all cases, the structure of the polymeric matrix in the imprinted materials and the function of the binding groups are of crucial importance. The mechanisms of imprinting and molecular recognition of substrates are by now well understood. A large number of potential applications for this class materials are being intensively developed, for example in the chromatogrphic resolution of recemates, and as artificial antibodies, chemosensors, and selective catalysts. The use of similarly produced materials as enzyme models is also of great interest.     

High-Resolution X-ray Crystallography—An Experimental Method for the Description of Chemical Bonds

By increasing the accuracy of an X-ray analysis, results are obtained which allow one to beyond the location of hydrogen atoms and say something about the distribution of electrons in molecules. Using several examples from organic and organometallic chemistry, the methods, problems, and results of this approach are described.     

Large Molecules from the Virtual Bakery— Filling a Gap in Structure Research

Traditional direct methods alone are not potent enough to solve the crystal structures of mid-sized molecules (over 200 non-hydrogen atoms). Considerably more efficient are the new methods such as shake-and-bake and SHELXD. Even the 1000-atom barrier has now been overcome, so the gap between small and large molecules is closing.     

ChemInform Abstract: Intriguing Gold Trifluoride — Molecular Structure of Monomers and Dimers: An Electron Diffraction and Quantum Chemical Study.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.     

The Myelin Membrane of the Central Nervous System—Essential Macromolecular Structure and Function

The neural sheaths that surround the nerve fibers (axons) are composed of myelin-specific complex lipids and are assembled during the myelination phase either by the oligodendrocytes in the central nervous system (CNS) or by the Schwann cells in the peripheral nervous system. These multilayered myelin membranes insulate the axons and permit a rapid, saltatory conduction of excitation and a reduced axon diameter in comparison with noninsulated axons. Myelination was hence the decisive evolutionary event in miniaturization of the central nervous system (brain and spinal cord). The morphology of the myelin membrane has been studied in detail mainly by electron microscopy. Most of its biochemistry has been elucidated in recent years by molecular-level analysis of both the lipid components (cholesterol, phospholipids and sphingolipids) and the constituent proteins. The multilamellar system is distinguished by a characteristic periodicity due to the 5-nm-thick bilayer formed by the myelin-specific lipids. The bilayer interacts with the myelin basic protein (MBP) on the cytosolic side of the plasma membrane process, while the integral membrane protein proteolipid protein (PLP) has hydrophilic domains exposed on both the cytosolic and extracytosolic faces of the bilayer. Numerous protein-chemical and -immunotopochemical findings have been summarized in a model of the myelin membrane. Through molecular biological studies, the genetic structure and chromosomal location of the myelin proteins have been determined. By employing techniques of molecular and cell biology together, it is now possible to analyze the process of myelinogenesis, the time- and location-specific expression of myelin-specific genes in the brain. Gene-technological methods have been used to define the mutations in the models jimpy mouse and myelin-deficient rat. These are animal models that correspond to genetically determined myelin defects (dysmyelinoses) in humans. Using them, it will be possible to study the cell death of oligodendrocytes on a molecular level; this process is the result of expression of mutant myelin proteins and is incompatible with life. Oligodendrocytes and the myelin structures they synthesize are the target structures of cytotoxic lymphocytes (T_c). In the course of the demyelination process in multiple sclerosis, these cause the breakdown of the myelin sheaths, in gradually appearing inflammations. T_c lymphocytes recognize myelin structures as epitopes and destroy them. The picture of the myelin membrane's molecular composition, which we are now perfecting, will also lead to a better understanding of demyelination on a molecular level, and hence to new therapeutic possibilities.