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  • Polymers  (7)
  • Alkenes
  • Wiley-Blackwell  (8)
  • 1985-1989  (8)
  • 1
    ISSN: 0570-0833
    Keywords: Surface recognition ; Molecular recognition ; Self-assembly ; Biological membranes ; Membranes ; Polymers ; Micelles ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Part and the Whole. The principle of self-organization for the creation of functional units is not an invention of modern natural sciences. It was already a basic idea of the ancient philosophies in Asia and Europe: only the mutuality of the parts creates the whole and its ability to function. Translated into the language of chemistry this means: the self-organization of molecules leads to supramolecular systems and is responsible for their functions. Thermotropic and lyotropic liquid crystals are such functional units, formed by self-organization. As highly oriented systems, they exhibit new properties. The importance of lyotropic liquid crystals for the life sciences has been known for a long time. They are a prerequisite for the development of life and the ability of cells to function. In materials sciences this concept of function through organization led to the development of new liquid-crystalline materials. From the point of view of macromolecular chemistry, this review tries to combine these two different fields and especially hopes to stimulate their interaction and joint treatment. To exemplify this, the molecular architecture of polymeric organized systems will be discussed. Polymeric liquid crystals combine the ability to undergo spontaneous self-organization-typical of liquid-crystalline phases-with the polymer-specific property of stabilizing these ordered states. As new materials, polymeric liquid crystals have already been investigated intensively. As model systems for biomembranes as well as for the simulation of biomembrane processes, they so far have been little discussed. The intention of this review article is to show that polymer science is able to contribute to the simulation of cellular processes such as the stabilization of biomembranes, specific surface recognition, or even the “uncorking” of cells. Polymer science, having an old tradition as an inter-disciplinary field, can no longer restrict itself to common plastics. Attempts to reach new horizons have already begun. The borderland between liquid crystals and cells will certainly play an important role. Basic requirements to work in this frontier area between organic chemistry, membrane biology, life science, and materials science will be the delight in scientific adventures as well as the courage to go ahead. The most important prerequisite will be the willingness to cooperate with disciplines which so far have not really accepted each other. From this point of view, this review does not aim at giving defined answers. It wants instead to encourage the scientific venture: too often we cling to painfully acquired knowledge, fearing adventures.
    Additional Material: 78 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0570-0833
    Keywords: Transition metals ; Polymers ; Alkene ligands ; Electrocatalysis ; Complexes ; Alkyne ligands ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An unprecedented series of highly reactive alkene-and diene-complexes of the early transition metals (Groups 3A-5A of the periodic system) have been isolated recently. Diene complexes of this sort (M = Ti, Zr, Hf, Nb, Ta) prefer, besides the (η4-s-cis-diene)metal structure, either a novel bent η4-metallacyclo-3-pentene structure or the unique (η4-s-trans-diene)metal structure. In bis(diene)metal complexes of Nb and Ta the η4-s-cis-dienes assume an unusual exo-endo (supine-prone) geometry. The M—C bonds in these diene-metal complexes generally exhibit highly polarized σ-bonding along with π-bonding character. The complexes therefore undergo a variety of regio- and stereoselective carbometalations with substrates containing C—C, C—O, or C—N multiple bonds. Examples of the products that can be obtained include ketones, vinyl ketones, unsaturated primary, secondary, and tertiary alcohols, as well as diols and unsaturated acids. Mechanistic studies on the stoichiometric and catalytic conversions of unsaturated hydrocarbons provides, inter alia, some insights into the course of polymerization reactions.
    Additional Material: 7 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0570-0833
    Keywords: Liquid crystals ; Crystalline polymers ; Polymers ; Optoelectronics ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The liquid crystalline behavior of low molecular weight compounds has been known for more than a century; synthetic polymers have been manufactured on a large scale for several decades, but just recently it was found possible to produce polymers using the structural principles of liquid crystalline compounds. The resulting materials have, as expected, unusual properties. Numerous applications, not only in opto-electronics, are already anticipated for such materials.
    Additional Material: 9 Ill.
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  • 4
    ISSN: 0570-0833
    Keywords: Chirality ; Optical activity ; Polymers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Main-chain chirality is the optical activity resulting from the configurational or conformational arrangement in the main chain of a polymer. The chirality of the most important types of structures has been investigated on the basis of systematic considerations of symmetry. This has led to the surprising result that even in polymers derived from 1-substituted or nonsymmetric 1,1-disubstituted olefins (the technologically most important polymers) several types of chiral structures exist, which are expected to result in optical activity if a particular enantiomer is favorably formed. By carrying out an asymmetric cyclopolymerization, it has been possible to obtain certain structural types in the form of optically active copolymers or homopolymers (e.g., copolymers of styrene with methyl methacrylate, or even the homopolymer of styrene). Another new group of optically active polymers consists of the atropisomeric helical polyisocyanides, poly(trityl methacrylates), and polychlorals. Optically active polymers are already used as adsorbents for the chromatographic separation of racemic mixtures. Further applications are likely to emerge.
    Additional Material: 20 Ill.
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  • 5
    ISSN: 0570-0833
    Keywords: Photochemistry ; Azoalkanes ; Strained molecules ; Alkenes ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The possibility to excite directly at 185 nm chromophores that absorb in the vacuum-UV has stimulated increased activity during the last decade in this field of photochemistry. Whereas photochemical reactions at λ〈200 nm have been thoroughly investigated in the gas phase, only recently have intensive studies on the 185-nm photochemistry of organic compounds in solution provided new insights. Despite the high excitation energies, selective photoreactions are promoted in the short-lived singlet excited states (Rydberg photochemistry). In contrast to conventional photochemistry (λ 〉 220 nm), 185-nm irradiation preferentially results in intramolecular rearrangement, fragmentation, and isomerization reactions. Intermolecular radical couplings and abstractions as well as dimerizations (π, π*-excitation) compete minimally. Besides the straightforward denitrogenation of photoresistant (“reluctant”) azoalkanes, important applications of the short-wavelength photolysis are also found in technology (photolithography) and medicine (193-nm laser). Broadening the scope of the synthetic potential of the 185-nm photochemistry, which so far has been limited to direct cis/trans isomerizations, presents a challenge for the chemist.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    ISSN: 0570-0833
    Keywords: Stiff-chain polymers ; Polymers ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 19 Ill.
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  • 7
    ISSN: 0570-0833
    Keywords: NMR spectroscopy ; 13C NMR spectroscopy ; Polymers ; Analytical methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Until a few years ago, solid-state nuclear resonance yielded spectra containing broad lines only. Meanwhile, CP/MAS-NMR spectroscopy has provided a method which gives narrow nuclear resonance lines from a solid-state specimen as well. Using this technique, it is now possible to produce spectra of “rare” nuclei (13C, 29Si, 15N etc.) which are resolved in terms of chemical structure. The analytical capabilities of NMR spectroscopy can be applied to the solid state: it may be that it is necessary to identify compounds in the solid state because, for example, a solvent would alter the coordination sphere, or that it is desired to monitor chemical reactions in the solid state, for example the baking of an enamel. Where a substance in the solid state is concerned, high-resolution 13C-NMR spectroscopy provides not only information about the chemical structure, but also about the solid state itself. To mention just a few examples, information on the conformation, crystal structure and molecular dynamics, as well as molecular miscibility is given. This opens up a broad spectrum of applications, from a statement concerning the crystal modification of an active substance in ready-to-use pharmaceutical preparations, e.g. tablets, to the question of whether two polymers are miscible with one another at a molecular level.
    Additional Material: 17 Ill.
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  • 8
    ISSN: 0570-0833
    Keywords: NMR spectroscopy ; NMR spectroscopy ; Polymers ; Analytical methods ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: NMR spectroscopy is an effective method not only for examining liquid samples but also for characterizing molecular sturcture, order and dynamics in amorphous and ordered solids. Recent developments in the area of solid-state NMR spectroscopy span from model-dependent studies of conventional one-dimensional spectra to the more definitive two-dimensional (2D) spectra which provide more specific information. For example, with 2D-NMR spectroscopy it is possible to determine the orientational distribution functions of molecular segments in drawn polymers and to distinguish different mechanisms of complex molecular motions. Following an introduction to basic NMR spectroscopy, an overview of the current state-of-the-art of 2D methods in solid-state NMR spectroscopy is presented and demonstrated with selected examples.
    Additional Material: 20 Ill.
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