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  • Articles: DFG German National Licenses  (112)
  • Electronic Resource  (112)
  • Chemistry  (112)
  • 1
    Electronic Resource
    Electronic Resource
    General theory of stationary random sequences with applications to the tacticity of polymersPaper presented at the 142nd Meeting of the American Chemical Society, Atlantic City, New Jersey, September 1962. (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 1635-1649 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: When, in a poly-α-olefin, the probability that a given placement be isotactic depends upon the tacticity of only a finite number of immediate predecessors, the resulting diastereosequence distribution obeys the theory of Markoff chains. When this is not the case, one says that the resulting diastereosequence distribution is non-Markoffian. A special case of a Markoffian distribution is given by a simple Markof chain in which the tacticity of a given placement is assumed to be affected by only the tacticity of the immediately preceding placement. Another special case is, of course, the Bernoulli trial distribution in which the probability that a given placement be isotactic is independent of the tacticity of all other placements. A high resolution NMR spectrum can sometimes yield a quantitative determination of the concentrations of isotactic and syndiotactic placements and the concentrations of the three types of possible adjacent pairs of such placements (i.e., isotactic, syndiotactic, and heterotactic pairs). When this is the case, the spectrum can be used to determine whether or not a given diastereosequence distribution is Bernoullian. However, because the longest diastereosequences whose concentration can be measured by NMR spectroscopy involve only two placements, an NMR spectrum cannot check whether a given non-Bernoullian distribution be simple Markoffian or Markoffian in general. In fact, non-Markoffian distributions are compatible with existing NMR spectra on polymers prepared by anionic polymerizations. In this paper we work within the framework of Kac's theory of stationary statistical processes and point out some general results which are valid for both Markoffian and non-Markoffian processes. The results are applied to NMR spectroscopy and it is pointed out which calculations used to check the self-consistency of NMR data and to obtain the mean length of closed diastereosequences are valid for both Markoffian and non-Markoffian distributions.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1996.838
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Chain-Cleavage and hydrolysis of activated polyethylene glycol derivatives: Evidence for competitive processes (1990)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 3337-3346 
    Details
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Studies have been carried out with the tosylate of the monomethyl ether of polyethylene glycol (MeO-PEG-OTs) and with low molecular weight models to assess whether the neighboring oxygen at position 3 or 6 provides the driving force for hydrolytic cleavage of these activated derivatives. Our results reveal that MeO-PEG-OTs undergoes hydrolysis by competitive pathways. Water directly displaces the tosylate group to give the original PEG alcohol and the oxygen at position 6 nucleophilically displaces the tosylate group to give a cyclic oxonium ion as an intermediate. This intermediate can react by three pathways. First, it can lead to the production of the original PEG alcohol by attack of water on a ring carbon; second, dioxane and a lower molecular weight PEG alcohol is produced by water attack at the nonring carbon next to the charged oxygen; and third dioxane can be displaced by the oxygen atom at position 6 in the chain.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pola.1990.080281213
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  • 3
    Electronic Resource
    Electronic Resource
    Erhöhung der Verschleißfestigkeit der TiAl6V4-Legierung durch Implantieren mit Stickstoff-Ionen (1996)
    Weinheim : Wiley-Blackwell
    Materialwissenschaft und Werkstofftechnik 27 (1996), S. 9-13 
    Details
    ISSN: 0933-5137
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Increasing of wear resistance of Ti-6Al-4V alloy by nitrogen implantationNitrogen ion implantation is used to improve the wear resistance of Ti-6Al-4V alloy. Different implantation doses up to 1 · 1018N+/cm2 and E = 170 KeV were used. The unimplanted and the implanted specimens were tested in a wear model system with oscillation loading. The results show, that the wear performance was influenced by implantation dose and also by mean pressure. It was found, that surfaces, which are produced by a high implantation dose (1 · 1018N+/cm2), exhibited greater were resistance than untreated Ti-6Al-4V alloy. The best wear behaviour was achieved by a high implantation dose (1 · 1018N+/cm2) and a low mean pressure (p =0.22 MPa) at the wear test. The difference between the wear rate of the untreated and of the implantated specimen can obtain a factor about 10. The effective depth of the implantation action is greater than the penetration depth of the nitrogen ions.
    Notes: Durch Implantation von Stickstoff-Ionen wurde die Randschicht der Ti-Al6-V4-Legierung mit dem Ziel der Verbesserung des Verschleißverhaltens modifiziert. Es wurde dazu mit unterschiedlichen Stickstoffdosen bis 1 · 1018N+/cm2 bei E = 170 keV implantiert. Die Modellverschleißuntersuchungen bei oszillierender Beanspruchung wiesen nach, daß die Implantationsdosis in Abhängigkeit von der im Tribosystem wirkenden mittleren Pressung den Verschleiß deutlich beeinflußt. Wird mit einer hohen Dosis (1 ·1018N+/cm2) implantiert und werden die Beanspruchungsbedingungen so gewählt, daß nur eine relativ geringe Pressung von p ≤ 0.22 MPa auftritt, dann ist mit einer Erhöhung der Verschleißbeständigkeit mindestens um den Faktor 10 zu rechnen. Für größere Pressungen nimmt die Erhöhung des Verschleißwiderstandes ab. Die verschleißmindernde Wirktiefe der Implantation liegt weit über der Eindringtiefe der implantierten Stickstoffionen.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/mawe.19960270106
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  • 4
    Electronic Resource
    Electronic Resource
    Preparation of bis(chloroformate)s for use in cyclization reactionsPresented at ‘MacroAkron '94, 35th IUPAC Symposium on Macromolecules Akron’, Ohio, 11-15 July 1994. (1995)
    New York, NY [u.a.] : Wiley-Blackwell
    Polymer International 37 (1995), S. 179-186 
    Details
    ISSN: 0959-8103
    Keywords: bis(chloroformate) ; cyclization ; interfacial condensation ; phosgene ; cyclic carbonate ; chloroformate ; bisphenol ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Cyclic oligomeric carbonates are prepared by a hydrolysis/condensation reaction from aromatic bis(chloroformate)s. Three methods for convenient preparation of bis(chloroformate)s have been developed: (1) use of diethylaniline to scavenge HCl, in a modification of an earlier procedure; (2) low pH, low temperature interfacial condensation of bisphenols with phosgene; and (3) use of Ca(OH)2 in interfacial condensation with phosgene. Reaction parameters which control formation of monomeric bis(chloroformate)s versus higher oligomerization include temperature, pH, and rate of phosgene addition. For water-soluble bisphenols such as hydroquinone, the phase ratio of water to CH2Cl2 can also be important.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pi.1995.210370305
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  • 5
    Electronic Resource
    Electronic Resource
    The properties of mica-filled polypropylenes (1984)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 169-174 
    Details
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Water-ground Phlogopite micas were classified into narrow particle-size distributions containing flakes with well-defined diameters and thicknesses in order to evaluate the influence of particle size and flake aspect ratio on the mechanical properties of mica-filled polypropylenes, For the purposes of comparison, most of the injection-molded specimens contained 40 percent (by weight) mica. As expected, the flexural and tensile modulus values increased in proportion to the aspect ratio over the range from 30 to 60 to a maximum of 8 GPa. The measured tensile strengths of the mica-filled polypropylenes increased substantially as the flake diameter became smaller, but did not correlate with the flake aspect ratio. The attainable properties were frequently dependent upon the method of mixing, and considerable care was necessary to ensure proper dispersion and adequate coupling. Intensive mixing, as in a Gelimat Mixer, may cause in situ delamination and particle-size reduction of the mica filler particles, leading to a marked increase in tensile strength of the resulting composite. The mica-filled compounds could be reprocessed many times without significant loss of properties, particularly compounds having mica particles less than 40 μm in diameter. The fracture energies (notched Izod) and the heat-distortion temperatures were not appreciably influenced by the size or aspect ratios of the mica within this range. Increased fracture toughness could be achieved by reducing the mica concentration or employing a polypropylene copolymer. Guidelines are presented to indicate the preferred characteristics of mica fillers and the influence of mixing conditions on performance.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760240303
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  • 6
    Electronic Resource
    Electronic Resource
    Thermal Conversion of closo-1,2-(SiMe3)2-1,2-C2B4H4 to closo-1,6-(SiMe3)2-1,6-C2B4H4: Structure Determination by Ab Initio Calculations, Gas-Phase Electron Diffraction, and Low-Temperature X-Ray Diffraction (1997)
    Weinheim : Wiley-Blackwell
    Chemistry - A European Journal 3 (1997), S. 1059-1063 
    Details
    ISSN: 0947-6539
    Keywords: ab initio calculations ; carboranes ; electron diffraction ; rearrangements ; structure elucidation ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: closo-1,2-(SiMe3)2-1,2-C2B4H4 undergoes thermal conversion to 1,6-(SiMe3)2-1,6-C2B4H4. The reaction pathway was monitored by 11B NMR spectroscopy. The structures of the 1,2- and 1,6-isomers were optimized at the HF/6-31 G* ab initio level. Gas-phase electron diffraction studies for both isomers are reported, as well as low-temperature X-ray crystal structure determinations. Comparison of calculated structural data with the data obtained experimentally shows good agreement between theory and experiment.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/chem.19970030712
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  • 7
    Electronic Resource
    Electronic Resource
    Wood fibers as reinforcing fillers for polyolefins (1984)
    Stamford, Conn. [u.a.] : Wiley-Blackwell
    Polymer Engineering and Science 24 (1984), S. 1166-1171 
    Details
    ISSN: 0032-3888
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Wood pulp fibers possess strength and modulus properties which compare favorably with glass fibers when the differences in fiber densities are considered. Softwood pulp fibers with fiber aspect ratios near 100 are readily dispersed into high-density polyethylene or isotactic polypropylene with the aid of carboxyic dispersing agents to form mixtures containing 50 weight-percent wood pulp which can be readily injection molded. The mechanical properties of the molded specimens were similar for all types of pulp including Kraft (bleached and unbleached), mechanical and chemical-mechanical pulps, waste pulps, and reclaim newspapers. Comparisons of the stiffness/weight efficiencies revealed that pulp composites equal or exceed the stiffness of most traditional materials of construction including steel, aluminum, glass-fiber composites, and talefilled polyolefins, while retaining a major material cost advantage. The measured strength values of the pulp composites were less than the theoretically predicted values due to the presence of voids created by the formation of volatiles during processing. Mechanical pulps which were available in dry form were preferred because of lower cost and ease of handling. Wood fibers are non-abrasive so that relatively large concentrations may be incorporated into polyolefins without causing serious machine wear during mixing and fabrication.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pen.760241504
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  • 8
    Electronic Resource
    Electronic Resource
    Chinese hamster ovary cells with constitutively expressed sialidase antisense RNA produce recombinant dnase in batch culture with increased sialic acid (1998)
    New York, NY [u.a.] : Wiley-Blackwell
    Biotechnology and Bioengineering 60 (1998), S. 589-595 
    Details
    ISSN: 0006-3592
    Keywords: CH0 cells ; sialidase activity ; recombinant DNase ; sialic acid ; antisense DNA ; Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Under some cell culture conditions, recombinant glycoprotein therapeutics expressed in Chinese hamster ovary (CHO) cells lose sialic acid during the course of the culture (Sliwkowski et al., 1992; Munzert et al., 1996). A soluble sialidase of CHO cell origin degrades the expressed recombinant protein and has been shown to be released into the culture fluid as the viability of the cells decreases. To reduce the levels of the sialidase and to prevent desialylation of recombinant protein, a CHO cell line has been developed that constitutively expresses sialidase antisense RNA. Several antisense expression vectors were prepared using different regions of the sialidase gene. Co-transfection of the antisense constructs with a vector conferring puromycin resistance gave rise to over 40 puromycin resistant clones that were screened for sialidase activity. A 5′ 474 bp coding segment of the sialidase cDNA, in the inverted orientation in an SV 40-based expression vector, gave maximal reduction of the sialidase activity to about 40% wild-type values. To test if this level of sialidase would lead to increased sialic acid content of an expressed recombinant protein, the 474 antisense clone was employed as a host for expression of human DNase as a model glycoprotein. The sialic acid content of the DNase produced in the antisense cultures was compared with material made in the wild-type parental cell line. About 20-37% increase in sialic acid content, or 0.6-1.1 mole of additional sialic acid out of a total of 3.0 mole on the product, was found on the DNase made in the antisense cell lines. © 1998 John Wiley & Sons, Inc. Biotechnol Bioeng 60: 589-595, 1998.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Turbulent mixing with multiple second-order chemical reactions (1990)
    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 36 (1990), S. 1457-1470 
    Details
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A molecular-based statistical simulation program was developed to study the covariance terms involved in the mass balance equations for complex chemical reactions during mixing. Several closure theories were compared to the simulations and available experimental data. The simple closure by Brodkey and Lewalle was found to be an extension of Toor's analysis applied to two reactions. This closure does not satisfy the molar fluctuation balance equation and was found only to represent the high Reynolds number data of Li and Toor. This result led to examining other possible closures which were based on Damkoehler numbers, reaction rate constant ratios, and limiting forms of the covariance term. These closures also were inadequate. The second reaction's covariance term varied from the product of the average values for each component to the Brodkey and Lewalle value for the range of Reynolds numbers considered.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/aic.690361002
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  • 10
    Electronic Resource
    Electronic Resource
    Quantitative determination of sulfur compounds in FCC gasolines by AED. A study of the effect of catalyst type and catalytic conditions on sulfur distribution (1993)
    Weinheim : Wiley-Blackwell
    Journal of High Resolution Chromatography 16 (1993), S. 13-17 
    Details
    ISSN: 0935-6304
    Keywords: GC-AED ; Sulfur ; FCC gasoline ; Compound-independent calibration ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The identification and quantification of sulfur-containing compounds in gasoline has become an area of interest because of impending legislation regulating total sulfur levels in these fuels. To study the effects of catalyst type and catalytic conditions on gasoline sulfur distribution, a method has been developed employing both the compound-independent and element-specific response of the atomic emission detector (AED). Calibration and quantification can be accomplished even where standards are not available, owing to the nature of the AED response.Compounds were separated on a thick film polydimethylsiloxane column. An external calibration curve was applied to the area responses of individual sulfur components in the sulfur chromatogram, and the concentrations of each were calculated. Summation of these sulfur concentrations over the gasoline range yields the total sulfur content of the gasoline.The method is applicable to the determination of these compounds in raw crude oils, finished gasolines, fluid cracking catalyst (FCC) unit gasolines, and fluid catalytic cracking “model” compound studies. A prefractionating column was employed to remove heavy (〉C13) materials; prefractionation is not, however, necessary for distilled or commercial gasoline samples. Detection limits, linearity, detector stability, and accuracy are discussed.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/jhrc.1240160103
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