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  • Chemistry  (203)
  • 550 - Earth sciences  (56)
  • 2000-2004  (46)
  • 1995-1999  (213)
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  • 1
    Electronic Resource
    Electronic Resource
    P/O Ligand Systems: Facile Synthesis, Structure, and Catalytic Tests of 2′-Phosphanyl-1,1′ -phenyl-2-ols and 2′-Phosphanyl-1,1′-binaphthyl-2-ols (1997)
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 130 (1997), S. 1663-1670 
    Details
    ISSN: 0009-2940
    Keywords: Lithiation ; P ligands ; NMR spectroscopy ; Molecular structure ; Hydrogenations ; Hydroformylations ; Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A facile synthesis of 2′-phosphanyl-1,1′-biphenyl- and 2′-phosphanyl-1,1′ -binaphthyl-2-ols and their silyl ethers has been developed, consisting of electron-transfer-catalyzed ring-opening of dibenzofuran and dinaphthofuran, respectively, subsequent reaction with chlorophosphanes, and work-up with acetic acid or ClSiMe3. Studies of the molecular and crystal structures reveals the presence of P - H - O bridging bonds in the more basic tBuPhP derivative and a nearly perpendicular arrangement of the aryl planes in the biphenyl derivatives. The barrier to rotation of the aryl planes about the C-C axis was determined by NMR in the case of the P-asymmetric derivative 3d, using the appearence of diastereoisomers by atropisomerism and P-asymmetry. Comparative screening tests of the title compounds, phosphanyl phenols and phosphanylnaphthols in homogeneous Rh-catalyzed reactions demonstrate catalytic activity in hydroformylation reactions and superior properties of the biphenyl- and binaphthyl-2-ol derivatives in relation to other P-O ligands.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/cber.19971301118
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  • 2
    Electronic Resource
    Electronic Resource
    Rubber toughening of polystyrene-acrylonitrile copolymers (1997)
    Weinheim : Wiley-Blackwell
    Acta Polymerica 48 (1997), S. 553-561 
    Details
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The efficiency of rubber toughening of PSAN depends on the size of the rubber particles, their agglomeration, the deformation rate, the temperature, and the orientation of the polymer molecules. Large particles are more effective than small particles. By a suitable choice of processing, however, small particles can agglomerate, forming large soft units and improving in this way impact toughness. At high deformation rates crazing or/and stretching of the matrix wall between the rubber particles must be activated for ductility, otherwise the material is brittle. The temperature at impact must be above the glass transition temperature of the rubbery phase for toughening. Increasing the orientation of the material decreases the tendency for craze formation with the consequence of embrittlement, if stretching is not activated.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/actp.1997.010481205
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  • 3
    Electronic Resource
    Electronic Resource
    Modified syndiotactic polypropene: Poly(propene-co-octene) and blends with atactic oligopropene (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 229 (1995), S. 93-112 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Propen und 1-Octen wurden mit dem syndiospezifischen Metallocen-Katalysator Me2C(Cp)(Flu)ZrCl2/MAO copolymerisiert. Es wurde ein hoher, statistischer Octeneinbau beobachtet. Niedrige Octenkonzentrationen beeinflußten die Aktivität des Katalysators nur wenig; Molekulargewicht, Kristallinität, E-Modul und Glastemperatur wurden dagegen mit ansteigendem Octengehalt erniedrigt. Blends aus ataktischem Oligopropen und syndiotaktischem Polypropen bzw. Poly(propen-co-octen) wurden aus einer Toluol-Lösung hergestellt. Diese Lösungsblends wurden mit einem Reaktorblend verglichen, der mit einem Hybrid-Katalysator bestehend aus einer Mischung von syndiospezifischem Me2C(Cp)(Flu)ZrCl2/MAO und unspezifischem Cp2ZrCl2/MAO hergestellt wurde. Das ataktische Oligopropen wirkte als Weichmacher, der E-Modul und Glastemperatur der Blends erniedrigte.
    Notes: Propene and 1-octene were copolymerized with the syndiospecific homogeneous metallocene catalyst Me2C(Cp)(Flu)ZrCl2/MAO. Large amounts of octene were incorporated randomly. While catalyst activity was not affected markedly by low octene content, molecular weight, crystallinity, Young's modulus, and glass transition temperature were reduced with increasing octene content. Blends of atactic oligopropene with syndiotactic polypropene and poly(propene-co-octene) were prepared from toluene solution and compared with a reactor blend prepared with a hybrid catalyst containing a mixture of syndiospecific Me2C(Cp)(Flu)ZrCl2/MAO and non-specific Cp2ZrCl2/MAO. Atactic oligopropene acted as plasticizer reducing Young's modulus and glass transition temperature of the blends.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1995.052290106
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  • 4
    Electronic Resource
    Electronic Resource
    Synthesis, characterization and polymerization of waxy monomers (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 155-164 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Wachsartige Monomere und Vernetzer wurden aus kommerziellen Wachsen durch Veresterung mit 2-Hydroxyethylmethacrylat, Glycerindimethacrylat oder Glycidylmethacrylat oder durch Funktionalisierung mit 2-Isocyanatoethylmethacrylat synthetisiert. Die erhaltenen opaken Methacrylate mit Schmelzpunkten zwischen 45 und 80°C wurden in Substanz bzw. Toluollösung in Gegenwart von Radikalinitiatoren polymerisiert. Die Polymeren zeichnen sich durch eine breite Molmassenverteilung aus. Im Gegensatz zur Substanzpolymerisation ist der Doppelbindungsumsatz nach der Lösungspolymerisation nahezu vollständig. Aufgrund der hohen Molmasse der Monomeren ist der beobachtete Polymerisationsschrumpf sehr gering. Polymerisate mit Vernetzermonomeren zeigen eine verbesserte mechanische Stabilität.
    Notes: Waxy monomers and crosslinkers, respectively, were synthesized from commercially available waxes by esterification with 2-hydroxyethyl methacrylate, glycerol dimethacrylate, or glycidyl methacrylate or by functionalization with 2-isocyanatoethyl methacrylate. The resulting opaque methacrylates with melting points between 45 and 80°C were polymerized in bulk and in toluene solution in presence of free radical initiators. The obtained polymers were characterized by a broad molecular weight distribution. Opposite to the bulk polymerization, the double bond conversion in solution polymerization is nearly quantitative. The observed volume shrinkage during polymerization is very low due to the high molecular weight of the monomers. Polymerizates containing crosslinking comonomers exhibit improved mechanical stability.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1997.052450114
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  • 5
    Electronic Resource
    Electronic Resource
    FKBP-like catalysis of peptidyl-prolyl bond isomerization by micelles and membranes (1997)
    New York : Wiley-Blackwell
    Biopolymers 42 (1997), S. 49-60 
    Details
    ISSN: 0006-3525
    Keywords: micellar catalysis ; cis/trans isomerization ; peptidyl-prolyl cis/trans isomerase ; proline ; FKBP12 ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Under physiological conditions, peptidyl-prolyl cis/trans isomerases catalyze powerfully the cis/trans isomerization of the -Xaa-Pro- bond (Xaa: natural amino acids) in oligopeptides and proteins (PPIases; EC 5.2.1.8). However, incorporation of proline containing tetrapeptide-4-nitroanilides in micelles and phospholipid vesicles also leads to increased rates of this unimolecular conformational interconversion. The isomerization rate was dependent on the detergent and vesicle concentration, respectively. The observed rate constants fit the pseudophase model of micellar catalysis allowing the calculation of micellar turnover numbers (kcismic) and dissociation constants (KCmic). Comparing kcismic values to the rate constants of the uncatalyzed cis to trans isomerization, an acceleration factor of about 20-fold was obtained for Suc-Ala-Phe-Pro-Phe-4-nitroanilide (Suc: succinyl) bound to zwitterionic SB12 (N-dodecyl-N,N-dimethylammonium-3-propanesulfonate) micelles. In addition, a marked increase in the population of the trans conformer relative to cis was noted for all investigated combinations of peptides and detergents. In a series of tetrapeptides, Suc-Ala-Xaa-Pro-Phe-4-nitroanilide kcismic/KCmic as well as kcismic values are linearly correlated with the high performance liquid chromatography capacity factor R′ describing the hydrophobicity of the amino acid Xaa. The same correlation can describe quantitatively the dependency of kcar/Km on substrate hydrophobicity for the FKBP12-catalyzed isomerization. Despite the great differences in catalytic power, these results confirm the suspicion that micelles and FKBP12 may share a common component in the catalytic mechanism of peptidyl-prolyl bond isomerization. © 1997 John Wiley & Sons, Inc. Biopoly 42: 49-60, 1997
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Erzeugung dünner Schichten: neue Herausforderungen für die Metallorganische Chemie (1995)
    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 29 (1995), S. 141-152 
    Details
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Metallorganische Chemie der Precursor für dünne Schichten und Schichtstrukturen ist ein junges Forschungsgebiet, in dem es, wie in vielen anderen Bereichen der modernen Chemie, weniger um die Verwirklichung völlig neuer Molekülstrukturen und Bindungsverhältnisse geht als vielmehr um ein vertieftes Verständnis und eine strategischökonomische Ausnützung chemischer Reaktivitäten. Nur ein fundamentales Verständnis aller vom molekularen Precursor bis zum endgültigen Material zu durchlaufenden Teilschritte kann hier langfristig erfolgsversprechend sein. Die Konstitutions- und Strukturvielfalt metallorganischer Komplexverbindungen bietet einen reichen Schatz an Möglichkeiten für die Synthese neuer Materialien. Die Erzeugung dünner Schichten durch Chemische Dampfabscheidung aus maßgeschneiderten flüchtigen Organometallverbindungen als Precursor, denen dieser Beitrag gewidmet war, stellt daraus nur einen kleinen Ausschnitt dar.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ciuz.19950290306
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  • 7
    Electronic Resource
    Electronic Resource
    Mechanical behaviour of PS/PVC blends compatibilized with block-graft copolymers based on poly(styrene-block-butadiene)Dedicated to Prof. Dr. W. Borchard on the occasion of his 60th birthday (1995)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 233 (1995), S. 77-87 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Blends aus Polystyrol (PS) und Polyvinylchlorid (PVC) sind aus thermodynamischen Gründen unverträglich und weisen deshalb nur schlechte mechanische Eigenschaften wie mangelnde Schlagzähigkeits- und Reißdehnungswerte auf. Der Grund hierfür liegt in der Natur der Grenzfläche solcher unverträglicher, heterogener Polymer-Blends. Hohe Grenzflächenspannungen und eine geringe Phasenadhäsion führen zu groben Phasenmorphologien, die kinetisch und thermodynamisch instabil sind. Jedoch gelingt es mit maßgeschneiderten Block-Pfropfcopolymeren P(S-b-(B-g-CHMA, MMA)) auf Basis von Styrol/Butadien-Blockcopolymeren P(S-b-B), auf die Polycyclohexylmethacrylat (PCHMA) oder Polymethylmethacrylat (PMMA) radikalisch ge-pfropft wurden, die Phasenmorphologien drastisch zu verfeinern, was zu einem duktilen Verhalten der modifizierten Blends führt. So steigt die Schlagzähigkeit von modifizierten gegenüber nicht modifizierten PS/PVC-Blends um den Faktor 10 und bewegt sich damit im Bereich von zähmodifiziertem PS.Elektronenmikroskopische Untersuchungen (TEM, REM) beweisen, daß die drastisch verbesserten Eigenschaften der modifizierten PS/PVC-Blends auf einer Grenzflächenselektivität der Block-Pfropfcopolymeren und einer ausgezeichneten Phasenanbindung beruhen.
    Notes: Blends composed of polystyrene (PS) and polyvinylchloride (PVC) are incompatible due to unfavourable interactions. Consequently, their mechanical properties such as impact strength and elongation at break are only very poor. The key to successfully influence the properties of such heterogeneous blends lies in the control of the interface. High interface tensions and an insufficient phase adhesion often lead to coarse phase morphologies which are thermodynamically and kinetically unstable. However, with radically synthesized, tailor made block-graft copolymers P(S-b-(B-g-CHMA, MMA)) based on a styrene/butadiene two-block copolymer P(S-b-B) which are grafted with poly(cyclohexylmethacrylate) (PCHMA) or poly(methylmethacrylate) (PMMA), the phase morphology can be markedly refined and the blends surprisingly show ductile behaviour. Thus, the impact strength of so modified PS/PVC 1 : 1 blends is about ten times higher than in the unmodified case and is thereby similar to impact modified PS.Electron microscopy (SEM, TEM) reveals that the modified PS/PVC blends owe their improved mechanical properties to the interface selectivity of the block-graft copolymers and therefore to a superior phase adhesion.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1995.052330107
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  • 8
    Electronic Resource
    Electronic Resource
    Ausbildungsintegrierter Umweltschutz durch Chemie (1995)
    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 29 (1995), S. 101-106 
    Details
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ciuz.19950290210
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  • 9
    Electronic Resource
    Electronic Resource
    Wissenschaft aktuell (1995)
    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 29 (1995), S. 322-331 
    Details
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/ciuz.19950290606
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  • 10
    Electronic Resource
    Electronic Resource
    Absolute rate Constants for the Addition of Malonyl Radicals to Alkenes in Solution (1998)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 81 (1998), S. 770-780 
    Details
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Absolute rate constants and their Arrhenius parameters are obtained for the addition of a cyclic malonyl radical derived from Meldrum's acid to 20 mono- or 1,1-disubstituted alkenes in (±)-propylene oxide and for the addition of the open-chain di(tert-butyl)malonyl radical to six mono- or 1,1-disubstituted alkenes in 1,1,2-trichloro-1,2,2-trifluoroethane by time-resolved electron spin resonance spectroscopy. At room temperature, the radicals add at the unsubstituted C-atoms with rate constants ranging from 1.1. 105 M-1S-1 (acrolein) to 2.4. 106 M-1S-1 (1,1-diphenylethene). The frequency factors are in the narrow ranges of log (A/M-1S-1) = 8.7 ± 0.1 for the cyclic and log (A/M-1S-1) = 8.2 ± 0.2 for the open-chain malonyl species, whereas the activation energies vary from 12.9 kJ/mol (1,1-diphenylethene) to 21.7 kJ/mol (acrylonitrile). They correlate with the alkene ionization potentials and, more weakly, with the reaction enthalpy. No correlation was found between the activation energies and the alkene electron affinities. Hence, the results confirm and quantify the electrophilic nature of malonyl radicals in addition reactions.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/hlca.19980810327
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