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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 29 (1990), S. 1479-1489 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general method is presented for constructing a potential function for approximate conformational calculations on globular proteins. The method involves solving a nonlinear program that seeks to adjust the potential's parameters in such a way that a minimum near the native remains a minimum and does not move far away, while any alternative minima shift so as to remain local minima but eventually rise higher than the level of the near-native minimum. Although the potential trades computational speed for detail by representing each amino acid residue as only a single point, correct secondary structural preferences and reasonable tertiary folding can be built into the potential in an entirely routine way. The potential has been parameterized to agree with the crystal structure of avian pancreatic polypeptide (having 36 residues) in the sense that the lowest minimum found (-407 arbitrary units) is reasonably close to the native (1.8 Å rms interresidue distance deviation). In contrast, the lowest nonnative conformation found after extensive searches by a variety of methods was -399 units and 7.5 Å away. Such potentials may prove to be useful in predicting approximate tertiary structure from amino acid sequence, if they can be generalized to apply to more than one protein.
    Additional Material: 3 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 104 (1971), S. 2743-2750 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The Solvent Effect on the Isomerization Reaction of the trans-Diaquo-dioxalatochromium(III) AnionThe isomerization reaction of the trans-[Cr(C2O4)2(H2O)2]— ion was investigated in aqueous mixtures of methanol, ethanol, isopropyl alcohol, tert-butyl alcohol, acetone, and dioxane with up to 50% of the organic component. The distinct solvent effect on the rate constant cannot be described by a parameter characterising the solvent system. By analogy to the use of the empirical Y-parameter of Grunwald and Winstein the isomerization of the complex ion is compared with the formation reaction of epoxide from ethylenechlorohydrin. From the obtained correlation conclusions are drawn with respect to the mechanism of the isomerization reaction.
    Notes: Die Isomerisierung des trans-[Cr(C2O4)2(H2O)2] -Ions wurde in wäßrigen Mischungen von Methanol, Äthanol, Isopropylalkohol, tert.-Butylalkohol, Aceton und Dioxan mit bis zu 50 Gew.-% organischer Komponente untersucht. Der deutliche Lösungsmitteleffekt auf die Geschwindigkeitskonstante kann nicht anhand eines die Eigenschaften des Lösungsmittel-systems charakterisierenden Parameters quantitativ beschrieben werden. Analog der Verwendung des empirischen Y-Parameters von Grunwald und Winstein wird die Isomerisierungs-reaktion des Komplex-Ions mit der Reaktion der Epoxidbildung aus dem Äthylenchlorhydrin-Anion verglichen. Aus der gewonnenen Korrelation werden Schlüsse auf den Mechanismus der Isomerisierung gezogen.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal für Praktische Chemie/Chemiker-Zeitung 313 (1971), S. 411-421 
    ISSN: 0021-8383
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Russian Abstract.
    Abstract: It seems advisable to investigate polycondensation processes extended systematically from low to high conversion by carefully chosen model systems, considering the statistical data available on the processes themselves and the relationship between structure and properties of the resulting polymers. In a previous paper (Rev. Gén. Caoutchouc Plastiques, Éd. Plastiques, 4, (1967) 111) dealing with conventional crosslinking agents, the possibility was suggested to perform polycondensation processes approaching more closely the classical random distribution. This can be achieved with symmetrical monomers having functional groups well spaced out to avoid substitution effects and cyclisation. Cyclisation is also rendered more difficult by greater stiffness of the structure of the monomers. This paper shows by some examples that, in favourable cases, the deviation from the classical random distribution can be reduced to the limits of experimental error, thus enabling the physical properties to be compared with the results of comparatively simple model calculations.
    Notes: Es ist ratsam, Polykondensationsprozesse an äußerst sorgfältig gewählten Modellsystemen zu studieren, und zwar systematisch von niedrigeren nach höheren Umsätzen, und indem man die Kenntnis der Prozesse selbst, der resultierenden Struktur der Produkte, und deren strukturgebundenen physikalischen Eigenschaften gleichzeitig auf statistischer Basis vertieft. In einem früheren Bericht (Rev. Gén. Caoutchouc Plastiques, Éd. Plastiques, 4, 1967, 111) über bekannte organische und anorganische Netzformer wurde auf die Möglichkeit hingewiesen, Polykondensationssysteme zu entwickeln, die den reinen klassischen Zufallsverteilungen in viel besserer Näherung folgen. Hierzu wählt man symmetrische Monomere mit räumlich weit auseinanderliegenden Funktionen, um Substitutionseffekte und Ringschlüsse weitgehend zu vermeiden; weiterhin werden Ringschlüsse auch durch Steifheit der Monomerstruktur sehr erschwert. In diesem Vortrag wird an einigen Beispielen belegt, daß man so tatsächlich die Abweichungen vom klassischen (cyclenfreien) Zufallsmodell in günstigen Fällen erwartungsgemäß bis zur Grenze der Unmeßbarkeit zurückdrängen kann, und daß sich das deshalb lohnt, weil man dann physikalische Eigenschaften der Produkte mit relativ einfachen Modellrechnungen vergleichen kann.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 152 (1972), S. 233-246 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein Zustand der kritischen Verzweigung (d. h. bei Systemen in der Nähe des Gelpunktes), der eine zentrale Rolle in der Biologie spielt, wird bei synthetischen Hochpolymeren nur vorübergehend beobachtet. Gut charakterisierte Polykondensate aus Decamethylenglykol (DMG)/Benzol-1.3.5-triessigsäure (BTA) sind nahe des Gelpunktes durch quantitative Umsetzung der freien Carboxylgruppen mit Diphenyldiazomethan stabilisiert worden. Ein derartiges Polymersystem vom Molekulargewicht ca. 105 war so stabil, daß es selbst nach zweistündigem Tempern bei 150°C in Luft unverändert war. Die Viskosität solcher Flüssigkeiten wurde als Funktion der Temperatur bezüglich der WLF-Gleichung untersucht. Das Versagen der Theorie des Glasübergangs im Sinne der isoviscosen Zustände wird erläutert. Die Kristallisation von etwa zwei Prozent nicht umgesetztem DMG verursacht einen scharfen, reversiblen Gelübergang in diesen Flüssigkeiten. Wahrscheinlich treten Wechselwirkungen zwischen dem flüssingen Polykondensat und der Kristalloberfläche auf. Der Tribenzhydrylester von BTA ist eine neue kristalline Verbindung mit einem Molekulargewicht von ca. 750.
    Notes: The critically branched state of matter (i.e. systems near their gel point), which occupies a central role in biology, is usually observed only fleetingly in synthetic polymers. Well characterised polycondensates of decamethylene glycol (DMG)/benzene 1.3.5-triacetic acid (BTA) have now been stabilised near gelation by quantitative benzhydrylation of the free carboxyls with diphenyl diazomethane. Such a polymer system, of weight av. mol. wt. about 105 was so stable that it remained unchanged after heating in air to 150°C for two hrs. The bulk viscosity of such liquids is studied as a function of temp. in relation to the WLF transform. The manner in which the isoviscous-state theory of Tg fails is elucidated. The crystallisation of about two per cent residual DMG causes a sharp a sharp reversible gelation in these liquids, probably because of some sort of interaction between the liquid polycondensate and the crystal surfaces. The tribenzhydryl ester of BTA is a new crystalline compound of mol. wt. about 750.
    Additional Material: 8 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 152 (1972), S. 277-289 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Neuere Daten von STEPTO und WAYWELL zur Ring-Ketten-Konkurrenz bei der kinetisch kontrollierten Polyaddition (d. h. mit der Rückreaktionsgeschwindigkeit = 0) im System Polyäthylenglykol/Hexamethylendiisocyanat wurden durch exakte Computerberechnungen untersucht, und zwar unter Voraussetzung einer GAUSS-Statistik. Es konnte eine gute Ein-Parameter-Anpassung erzielt werden. Die optimalen Werte der Parameter wurden mit der Theorie verglichen. Die Ergebnisse deuten darauf hin, daß das verwendete Lösungsmittel (Benzol bei 70°C) für dieses Polymersystem „thermodynamisch schwach“ ist.
    Notes: Recent data of STEPTO and WAYWELL for ring-chain competition in the kinetically controlled polymerizing system (i.e. backward rate = 0) of (polyethylene glycol)/(hexamethylene diisocyanate) have been fitted by exact computer calculations, assuming GAUSSian chain statistics. A good one-parameter fit is obtained. The optimum value of the parameter is compared with theory. The results suggest that the solvent used (benzene at 70°C) is thermodynamically poor for this polymer system.
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 29 (1991), S. 463-482 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two different theoretical approaches have been developed to describe network formation in a six-component, three-stage process with the stochastic theory of branching processes. Both approaches make use of probability-generating functions and cascade substitutions. In the POLYM approach, the products of the previous stage, namely, complete (branched) molecules, are used as building units in the subsequent stage. The molar masses and unreacted functionalities are identified by means of dummy variables. In the resulting formulas the sequence of the three stages is clearly visible. In the MONOM approach, the system is treated as a quasi-one-stage process; the original monomers are the building units in all three stages, the sequence of which is only apparent from the input parameters. In the MONOM approach the original monomers are used as building units, irrespective of the stage in which they react. A separate dummy variable is chosen for each possible reaction in each stage in the MONOM approach, so that the two approaches give analytically identical results, but along completely different derivations. This avoids correlation errors in the MONOM approach. Both approaches have incorporated kinetic effects by way of substitution effects in two of the monomers. The two approaches are prefaced by the treatment of several paradigms of increasing complexity to show the unity and strength of the theory and to warn against typical pitfalls.
    Additional Material: 8 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Microscopy Research and Technique 24 (1993), S. 106-112 
    ISSN: 1059-910X
    Keywords: Life and Medical Sciences ; Cell & Developmental Biology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Natural Sciences in General
    Additional Material: 1 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 21 (1994), S. 131-137 
    ISSN: 0142-2421
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: The need for improved characterization of materials used in the fabrication of semiconductor devices has been driven by the semiconductor industry's desire to increase device densities on substrate. This need is reflected in the analytical surface science community by efforts to develop methods for detection of trace impurities on semiconductor substrates at extremely low levels. With improvements in standard techniques continually occurring, and with new methods of trace analysis always being developed, it is important to assess the relative abilities of the suite of surface analysis techniques available for materials characterization and to develop well-characterized standard samples for these comparisons. This paper reports on a collaborative effort to review the capabilities of several approaches to trace surface analysis. As a test case, Ni contamination of Si wafers in the dose range 1014-1010 cm-2 has been chosen. The emphasis of this paper will be on the capabilities of SARISA (surface analysis by resonant ionization of sputtered atoms) as an example of laser post-ionization secondary neutral mass spectrometry for the detection of contaminants in the near-surface region. Results on analyses of the same standard samples by other techniques will also be presented. These techniques include total reflection x-ray fluorescence and heavy ion backscattering spectrometry. The results of this comparison show that there are several techniques that can accurately determine metal contaminations on Si wafers in this concentration range and that the method of choice depends on other considerations, such as speed or accuracy of analysis.
    Additional Material: 8 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 136 (1970), S. 291-296 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Unter Verwendung von Zinkdiäthyl/Menthol als Katalysatorgemisch wurde die asymmetrisch induzierte Polymerisation des Styroloxids untersucht. Es wurde gefunden, daß der Verbrauch des Monomeren nach einer Reaktion zweiter Ordnung verläuft, während aus der Bestimmung der optischen Drehung des verbleibenden Monomeren ein Reaktionsschema erster Ordnung folgt. Dieses Phänomen wird durch die Annahme erklärt, daß die Polymerisation aus einer raschen Initiierung besteht, der ein langsames, schrittweises Wachstum folgt. Es nehmen zwei Mol des Monomeren an der Polymerisation teil, von denen das eine polymerisiert, während das zweite den Katalysator aktiviert. Die Eignung des Katalysators zur asymmetrischen Selektion ist auf die Menthoxylgruppe zurückzuführen und nicht auf eine Komplexverbindung zwischen Propylenoxid und dem Katalysator.
    Notes: The asymmetric-selection polymerization of styrene oxide was investigated by using diethylzinc/menthol system as catalyst. Monomer consumption was found to follow a second order kinetic, whereas developing of the optical rotation of the remaining monomer followed a first order reaction scheme. This phenomenon is accounted for by the assumption that the polymerization consists of rapid initiation followed by slow stepwise growth. Two moles of monomer participate in the polymerization, one of which is polymerized and the other is responsible for activation of the catalyst. The asymmetric ability of the catalyst is arising from the menthoxyl group but not from propylene oxide complexed to the catalyst.
    Additional Material: 2 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Computational Chemistry 13 (1992), S. 351-361 
    ISSN: 0192-8651
    Keywords: Computational Chemistry and Molecular Modeling ; Biochemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Computer Science
    Notes: Linearized embedding is a variant on the usual distance geometry methods for finding atomic Cartesian coordinates given constraints on interatomic distances. Instead of dealing primarily with the matrix of interatomic distances, linearized embedding concentrates on properties of the metric matrix, the matrix of inner products between pairs of vectors defining local coordinate systems within the molecule. Here, the approach is used to explore the full conformation space allowed to small cyclic alkanes, given the constraint of exact bond lenghts and bond angles. Useful general tools developed along the way are expressions for rotation matrices in any number of dimensions and a generalization of spherical coordinates to any number of dimensions. Analytical results give some novel views of the conformation spaces of cyclopropane, cyclobutane, cyclopentane, and eyclohexane. A combination of numerical and analytical approaches gives the most comprehensive description to date of the cycloheptane conformation space with fixed bond lengths and angles. In this representation, the pseudorotation paths of cyclohexane and cycloheptane are closed curved lines on the surfaces of spheres.
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