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  • 2020-2024
  • 1995-1999  (33)
  • 1965-1969  (11)
  • 1915-1919
  • Chemistry  (44)
  • 1
    Digitale Medien
    Digitale Medien
    Noncomplementarity in base sequences between the cohesive ends of coliphages 186 and λ and the formation of interlocked rings between the two DNA's (1967)
    New York : Wiley-Blackwell
    Biopolymers 5 (1967), S. 953-966 
    Details
    ISSN: 0006-3525
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The half molecules of 186 DNA have been isolated by the Hg(II)-Cs2SO4 density gradient centrifugal ion technique. The buoyant densities of the two halves in CsCI at 25°C. are 1.713 and 1.709 g./cm.3, corresponding to GC contents of 54% and 50%, respectively. Similarly, 5-bromouracil labeled λ DNA halves were separated. The isolation of the four DNA halves made it possible to test for homology in base sequences between the cohesive ends of λ and those of 186. There was no indication of any significant homology in base sequences between the cohesive ends of the two DNA's, as indicated by the absence of a band with intermediate buoyant density in CsCI when either half of 186 DNA was annealed with either half of 5-bromouracil labeled λ DNA and then centrifuged. The lack of cohesion between the two DNA's made it possible to demonstrate unequivocally the formation of interlocked rings (catenanes) between the two DNA's. The existence of a dimeric catenane is evidenced by the formation of a species of intermediate buoyant density when 5-bromouracil labeled λ DNA is cyclized in the presence of cyclic 186 DNA of a relatively high concentration. The molecular weight of one DNA relative to the other can be calculated from the position of the dimeric catenane in a density gradient by using the method of Baldwin. The result was in complete agreement with our previous measurements from the sedimentation coefficients and by electron microscopy. The probability of dimeric catenane formation when one DNA is cyclized in the presence of another DNA is discussed. The experimental results agree with the theoretical expectation.
    Zusätzliches Material: 7 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/bip.1967.360051008
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  • 2
    Digitale Medien
    Digitale Medien
    Synthesis of Aristotelia-Type Alkaloids. Part XVPart XIV: See [1].. Total synthesis of (+)-hobartinol (1995)
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 78 (1995), S. 292-300 
    Details
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Synthetic (+)-makomakine (6) was transformed in six steps into (+)-17R,18R)-17,18-dihydrohobartine-17,18-diol ((+)-5) with an overall yield of 38% (Scheme 2). This compound was shown to be identical with natural hobartinol, a monoterpene indole alkaloid from Aristotelia australasica, originally believed to be the (17S)-epimer 1. At the same time, the synthesis of (+)-5 delineates the hitherto unknown absolute configuration of this metabolite.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/hlca.19950780204
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  • 3
    Digitale Medien
    Digitale Medien
    Viscosities of moderately concentrated solutions of polyethylene in ethane, propane, and ethylene (1969)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 117-131 
    Details
    ISSN: 0021-8995
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: The viscosities of moderately concentrated solutions of low-density polyethylenes in ethane, propane, and ethylene have been measured at low shear rate in the temperature range of 150-250°C and in the pressure range of about 15000-30000 psi. Within the precision of the measurements, the relative viscosity is independent of pressure over the range investigated but increases as the solvent is changed from propane through ethane to ethylene. The activation energy for the relative viscosity in ethane varies from about 0.5 to 2.5 kcal/mole as the concentration changes from 5 to 15 g/dl. Effects of polymer concentration and molecular weight on solution viscosity in ethane at 150°C have been determined, and all of the data can be represented by a single straight-line plot of the logarithm of relative viscosity versus the intrinsic viscosity (in p-xylene at 105°C) times concentration. This simple relation is valid over wide ranges of polymer concentration and molecular weight and over more than two orders of magnitude of relative viscosity. The solution viscosities of the polyethylenes in the three supercritical fluid solvents used appear surprisingly low at first sight. This behavior is partly a result of the low solvent viscosities but also might mean that the polymer has an abnormally low segmental friction factor compared to that in solutions under more familiar conditions.
    Zusätzliches Material: 6 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/app.1969.070130113
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  • 4
    Digitale Medien
    Digitale Medien
    Molecular mechanics study of zirconocenium catalyzed isospecific polymerization of propylene (1995)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 125-135 
    Details
    ISSN: 0887-624X
    Schlagwort(e): isospecific polymerization ; stereocontrol energy ; agostic interaction ; steric insertion probability ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Stereocontrol energy (ΔE0) is investigated as a measure of enantioselectivity of ansa-zircoocenium catalyst in propylene polymerization; it was calculated with MM2 (molecular mechanics) force field using π complex (°C) and transition state (TS) geometries obtained by ab initio molecular orbital methods. Both rac-ethylenebis (1-η5-indenyl) - (1) and rac-ethylenebis (1-η5-4,5,7,8-tetrahydroindenyl) (2) zirconocenium species are isospecific in either the π-complexes or the transition states. The stereoselectivity is greater if there is α-agostic interaction; it is lowered in the cases of β and γ agostic interactions. The 13C-NMR steric pentad distribution indicates the poly(propylene) to be much less stereoregular than that predicted by ΔE0. Following the occurrence of a regiochemical insertion error, the addition of another monomer via any mode is prohibitively unfavorable. The catalyst suffers loss of stereospecificity as temperature of polymerization increases. Insertion via transition states involving different agostic interactions could be one explanation for the observed loss. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/pola.1995.080330115
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  • 5
    Digitale Medien
    Digitale Medien
    Olefin terpolymerizations. II. 4-vinylcyclohexene and cyclooctadiene (1995)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2787-2793 
    Details
    ISSN: 0887-624X
    Schlagwort(e): Ziegler-Natta catalysis ; EPDM synthesis ; metallocene catalyst ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: 4-Vinylcyclohexene (VCH) and cyclooctadiene (COD) were investigated as termonomers in EPDM (ethylene/propylene/diene) synthesis by using rac-ethylenebis (1-η5-indenyl) zir-conium dichloride (1) as a catalyst precursor. Homopolymerizations of VCH, vinylcycloh-exane and cyclohexene were compared. The parameter Kπκp, which is the apparent rate constant for Ziegler-Natta polymerization, is about the same for VCH and vinylcyclohexanebut is 10 times smaller for cyclohexene. Therefore, the linear olefinic double bond is more active than the cyclic internal double bond. VCH reduces ethylene polymerization rate but not propylene polymerization rate in copolymerizations. In terpolymerizations, VCH tends to suppress ethylene incorporation especially at elevated polymerization temperature and Lowers the polymer MW by about two-fold. COD has very low activity as a termonomer. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/pola.1995.080331612
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  • 6
    Digitale Medien
    Digitale Medien
    ansa-Zirconocenium catalysis of syndiospecific polymerization of propylene: Theory and experiment (1995)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1085-1094 
    Details
    ISSN: 0887-624X
    Schlagwort(e): Ziegler-Natta catalysis ; zirconocene catalysts ; molecular modeling ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The syndiospecific propylene polymerizations catalyzed by isopropylidene(cyclopentadienyl)(fluorenyl)- and (2,2-dimethylpropylidene)(cyclopentadienyl)(fluorenyl)-zirconocenium (1+ and 2+) have been investigated theoretically and compared with experimental observations. With the ab initio calculated structures for the transition state (TS) of 1+(M)P and 2+(M)P (M = propylene, P = 2-methylpentyl), their steric energies (E°) have been computed using MM2 force-field. The difference between steric energies E°(m) and E°(r) for the meso and racemic enchainment of propylene, respectively, is defined as the stereocontrol energy [δE°(m - r)] for syndiotactic propagation. The δE°(m - r) for the TS of 1+ (M)P is about 2.1 kcal/mol, the value is 1 kcal/mol greater for 2+(M)P. The observed steric pentad distributions of the syndiotactic poly(propylene) obtained by these catalysts are consistent with smaller effective stereocontrol energy, which is about two-third as large as δE°(m - r) values calculated for the MM2 optimized structure. Syndiotactic enchainment is favored over isotactic enchainment for all combinations of site configurations in the catalyst. α-Agostic interaction seems to enhance syndioselectivity, whereas γ-agostic interaction changes the stereoselectivity to meso enchainment. The mirror plane symmetry of the syndiotactic propagating species renders the stereoselectivity of the polymerization insensitive to reaction conditions. These catalysts are also highly regiospecific. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/pola.1995.080330711
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  • 7
    Digitale Medien
    Digitale Medien
    Polymerizations of olefins and diolefins catalyzed by monocyclopentadienyltitanium complexes containing a (dimethylamino)ethyl substituent and comparison with ansa-zirconocene systems (1998)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 319-328 
    Details
    ISSN: 0887-624X
    Schlagwort(e): metallocenes ; Ziegler-Natta catalysis ; olefin polymerizations ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: {[2-(dimethylamino)ethyl]cyclopentadienyl}titanium trichloride (CpNTiCl3, 1) was activated with methylaluminoxane (MAO) to catalyze polymerizations of ethylene (E), propylene (P), ethylidene norbornene (ENB), vinylcyclohexene (VCH), and 1,4-hexadiene (HD). The dependence of homopolymerization activity (A) of 1/MAO on olefin concentration ([M]n) is n = 2.0 ± 0.5 for E and n = 1.8 ± 0.2 for P. The value of n is 2.4 ± 0.2 for CpTiCl3/MAO catalysis of ethylene polymerization; this system does not polymerize propylene. 1/MAO catalyzes HD polymerization at one-tenth of AH for 1-hexene, probably because of chelation effects in the HD case. The copolymerization of E and P has reactivity ratios of rE = 6.4 and rP = 0.29 at 20°C, and rErP = 1.9, which suggests 1/MAO may be a multisite catalyst. The copolymerization activity of CpTiCl3/MAO is 50 times smaller than that of CpNTiCl3/MAO. Terpolymerization of E/P/ENB has A of 105 g of polymer/(mol of Ti h), incorporates up to 14 mol % (∼ 40 wt %) of ENB, and high MW's of 1 to 3 × 105. All of these parameters are surprisingly insensitive to the ENB concentration. The E/P/VCH terpolymerization has comparable A value of (1.3 ± 0.3) × 105 g/(mol of Ti h). The incorporation of VCH in terpolymer increases with increasing [VCH]. Terpolymerization with HD occurs at about one-third of the A of either ENB or VCH; the product HD-EPDM is low in molecular weight and contains less than 4% of HD. These terpolymerization results are compared with those obtained previously for three zirconocene precursors: rac-ethylenebis(1-η5-indenyl)dichlorozirconium (6), rac-(dimethylsilylene)bis(1-η5-indenyl)dichlorozirconium (7), and ethylenebis(9-η5-fluorenyl)dichlorozirconium (8). The last compound is a particularly poor terpolymerization catalyst; it incorporates very little VCH or HD and no ENB at all. 7/MAO is a better catalyst for E/P/VCH terpolymerization, while 6/MAO is superior in E/P/HD terpolymerization. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 319-328, 1998
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Olefin terpolymerizations. I. 1,4-hexadiene (1995)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 979-987 
    Details
    ISSN: 0887-624X
    Schlagwort(e): Ziegler-Natta polymerization ; EPDM ; metallocene catalysts ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ethylene (E), propylene (P), and 1,4-hexadiene (HD) were terpolymerized with rac-1,2-ethylenebis (1-η5-indenyl) zirconium(IV) dichloride and methylaluminoxane (Et[Ind]2ZrCl2/MAO), and compared with the copolymerizations of E/P, E/HD, P/HD, and terpolymerization using ethylidene norbornene (ENB) as the termonomer. HD lowers the polymerization activity, the effect is more pronounced for P/HD and E/P/HD using large amount of P, than for E/HD and E/P/HD using feed low in P. The polymer molecular weight is most strongly affected by the temperature of polymerization (Tp), whereas the E/P ratio in the feed has virtually no effect. The reactivity ratios rE and rP are 3.0 and 0.3, respectively, at 20°C but rP becomes larger than rE at TP = 70°C. 1H-NMR spectra showed occurrence of cycloaddition in the homopolymerization of HD; on the other hand, HD is incorporated in the terpolymer only by linear 1,2-addition. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/pola.1995.080330612
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  • 9
    Digitale Medien
    Digitale Medien
    Olefin terpolymerizations. III. Symmetry, sterics, and monomer structure in ansa-zirconocenium catalysis of EPDM synthesis (1995)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 2795-2801 
    Details
    ISSN: 0887-624X
    Schlagwort(e): Ziegler-Natta catalysis ; EPDM synthesis ; metallocene catalyst ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Ethylenebis (η5-fluorenyl) zirconium dichloride (1) and rac-dimethylsilylene bis (1-η5-in-denyl) zirconium dichloride (2) were activated with methylaluminoxane (MAO) to catalyze ethylene (E) propylene (P) copolymerizations. The former produces high MW copolymer at 20°C rich in ethylene with reactivity ratio values of rE = 1.7 and rP 〈0.01, whereas the latter produces lower MW random copolymers with rE = 1.32 and rp = 0.36. Ethylidene norbornene (ENB) complexes with 1/MAO but does not undergo insertion in the presence of E and P. In contrast, 2/MAO catalyzes terpolymerization incorporating 9-15 mol % of ENB with slightly lower MW and activity than the corresponding copolymerizations. In comparison, 1,4-hexadiene was incorporated by 2/MAO with much lower A and MW. Terpolymerizations were also conducted with vinylcyclohexene using both catalyst systems. The steric and electronic effects in these processes were discussed. © 1995 John Wiley & Sons, Inc.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    URL: http://dx.doi.org/10.1002/pola.1995.080331613
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  • 10
    Digitale Medien
    Digitale Medien
    Syndioselective propylene polymerizations by ansa-zirconocenium catalyst (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 2945-2953 
    Details
    ISSN: 0887-624X
    Schlagwort(e): metallocene ; Ziegle-Natta catalysis ; syndioselective polymerization ; Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The effect of reaction conditions, including catalyst concentration, temperature, and immobilization on support, have been investigated for syndioselective propylene polymerization by the “bare” zirconocenium ion generated from 1,1-diphenyl-methylidene(1-η5-cyclopentadienyl)(9-η5-fluorenyl)zirconium-dichloride precursor (2). Neither variation of the catalyst concentration nor immobilization of 2 on silica support affect the syndiospecificity of polymerization. The stereoregularity of the syndiotactic polypropylene, as judged from the melting transition temperature and homosteric r-pentad population by 13C-NMR, were found to be proportional to polymer molecular weight. These behaviors are compared with a typical isoselective catalyst ethylenebis(4,5,6,7-tetrahydroindenyl) Zr precursor (4). They are in close resemblance in the case of the S-enantiomeric complex of 4, but the racemic mixture of 4 is markedly inferior. The origins of stereo- and regio-errors are discussed. © 1996 John Wiley & Sons, Inc.
    Zusätzliches Material: 3 Ill.
    Materialart: Digitale Medien
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