Kinetics of cooperative conformational transitions of lineal biopolymers

Cooperative conformational transitions of proteins and nucleic acids are of decisive importance to many processes of molecular biology, and particularly to their regulation. They proceed via numerous interdependent elementary processes, and their kinetics are therefore often complicated. They are frequently also very fast. However, kinetic analyses can be carried out by chemical relaxation methods. The theoretical interpretation is comparatively simple in the case of linear biopolymers. When the linear Ising model extended for kinetics was applied to model peptides and polynucleotides, it provided an insight into the fundamental principles of cooperative transformations.     

The influence of “two-phase” synthesis conditions on blown film extrusion of LDPE

LDPE synthesized under two-phase conditions is known to have a good balance of blown film properties. Good optical properties and high impact strength are characteristic for two-phase LDPE grades. In order to obtain systematic information, LDPE was synthesized at several different pressures with two different melt index levels. Blown film was extruded at different output rates and melt temperatures. The influence on haze and dart drop impact was studied. Two-phase conditions were found to improve haze and dart drop impact and the improvement was impressive, especially for the low melt index grades. By increasing the output rate, the dart drop values were further improved. The influence of melt temperature on dart drop impact goes through an optimum and overall haze decreases with increasing melt temperature. For films made from two-phase grades, dart drop impact decreases as internal haze increases. For corresponding internal haze values, the films made from single-phase grades have lower dart drop values and they are somewhat scattered.     

Kinetic study of copper(II) complexation with 9-ethyl-3-carbazolecarboxaldehyde-thiosemicarbazone and kinetic-spectrophotometric determination of copper(II)

The kinetics of complexation reaction of Cu(II) with 9-ethyl-3-carbazolecarboxaldehyde-thiosemicarbazone (ECCAT) has been examined spectrophotometrically. The ligand was synthesized for the first time. The complexation reaction was carried out in a DMF-water medium at 35°C. The complex has maximum absorbance at 393 nm. Kinetic and activation parameters of the complexation reaction were calculated by the Arrhenius and Eyring equations using the data obtained from investigating the effect of temperature on reaction rates under the specified conditions. We also proposed reaction rate equations. Based on the studied complexation reaction, a simple kinetic method for the spectrophotometric determination of copper(II) has been developed. The calibration graphs are linear in the concentration range 0.2–1.9 μg/mL. The species that caused interference were investigated. The text was submitted by the authors in English.     

Epoxy Composites Modified with Finely Dispersed Fillers

The thermal stability and mechanical strength of composites based on ED-20 epoxy oligomer cured with isomethyltetrahydrophthalic and methylendic anhydrides was studied as influenced by the nature and properties of finely dispersed inorganic fillers, such as carbon black, aluminum oxide, and silica nanoparticles.     

Zur Ermittlung und rechnerischen Überprüfung thermodynamischer Daten aus experimentell gefundenen Werten, 10. Mitt.: Zur Frage der Parameterzahl und Fehlerverteilung bei einigen Rechenansätzen für binäre thermodynamische Systeme

Zusammenfassung Es wird eine vergleichende Untersuchung über die Anwendungsmöglichkeit zweier dreiparametriger und zweier zweiparametriger Ansätze angestellt. Die Bestimmung der Konstanten erfolgt nach der Methode der kleinsten Quadrate, die entstehenden Fehlerquadratsummen werden als Funktion der Iterationszahl dargestellt und verglichen. Ebenso wird mit den Verbesserungen _i und den mittleren Fehlern der einzelnen Parameter verfahren. Es ergibt sich, daß der Ansatz vonWilson für stark assoziierende Systeme mit nahezu horizontaler Grenztangente die kleinste Fehlerverteilung aufweist. Die beiden dreiparametrigen Ansätze vonRedlich-Kister und vonMusil-Breitenhuber zeigen sich für das Systemn-Hexan-Methylamin besser geeignet als für die Systeme Benzol-Methanol und CCl₄-Methanol. Die Problematik der Parameterzahl wird an Hand der Fehlerverteilung bei den Ansätzen vonMB undRK aufgezeigt und diskutiert.Das Programm wurde in der Programmiersprache FORTRAN erstellt und mit der UNIVAC-490-Computer-Anlage des Grazer Rechenzentrums gerechnet.

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Four thermodynamical statements are tested with regard to their applicability to binary systems, two statements having three and two only two parameters. The least square method ofGauss shows that theWilson statement has the smallest dispersion of errors for systems with nearby horizontal boundary tangent. [vv], _i and are shown as functions of the number of iterations. The problem of the parameters' number is shown and discussed by means of the dispersion of errors for theMusil-Breitenhuber (MB) andRedlich-Kister (RK)-statements.The programme is written in FORTRAN and has been used the UNIVAC-490-Computer of the Graz Computer Centre.

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Mit 5 Abbildungen

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Herrn Professor Dr.Robert Fischer zum 65. Geburtstag in Dankbarkeit und Verehrung gewidmet.

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bis 6. Mitt.:F. Gölles, Mh. Chem.92, 981 (1961);93, 191, 201 (1962);94, 1108 (1963);95, 1656 (1964);96, 1366 (1965);7. bis 9. Mitt.:F. Gölles undA. Höpfner, Mh. Chem.97, 368, 911 (1966);99, 230 (1968).     

A field theoretical approach to calculate electronic Born-Oppenheimer coupling terms

In this paper we suggest to consider the spatial distribution of the Born-Oppenheimer nonadiabatic coupling terms as fields which are created by sources, located at degeneracy points, and which can be derived using the ordinary mathematical tools of field theory. It is shown that the curl-divergence equations as formed within a given Hilbert space [M. Baer, Chem. Phys. Lett. 35, 112 (1975)] can be converted into a set of inhomogeneous coupled Poisson equations which are solved for a given set of boundary conditions. The method is applied to the three-state Hilbert subspace of the H(3) system. The numerical results are compared with ab initio calculations for which a very encouraging fit is found.     

Nucleophilic Substitution of Chlorine with Hydrazine,Methylhydrazine, and 1,1-Dimethylhydrazine in 5-Aryl-2-chloromethyl-1,3,4-oxadiazoles

The reactions of 1,1-dimethylhydrazine, methylhydrazine, and hydrazine hydrate with 5-aryl-2-chloromethyl-1,3,4-oxadiazoles were studied. The structures and compositions of the final products were confirmed by ¹H NMR spectroscopy and elemental analysis.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 3, 2005, pp. 470–473.Original Russian Text Copyright © 2005 by Baranov, Tsypin, Malin, Laskin.     

Palladium-induced cyclizations for the synthesis of cis-2,5-disubstituted-3-methylenetetrahydrofurans: studies of the C7-C22 core of amphidinolide K

[formula: see text] The diastereoselective synthesis of cis-2,5-disubstituted-3-methylenetetrahydrofurans via Pd(0)-catalyzed cyclization of 2-methylene-1,4-diols is described. Investigations into the scope of the reaction and its application toward the synthesis of amphidinolide K is reported.     

Determination of in-core power in low energy research reactors by measurement of16N and18F in the primary coolant

The measurement of¹⁶N and¹⁸F activity in the primary coolant of the JASON Argonaut reactor has been used to monitor in-core reactor power. The¹⁶N is produced by the¹⁶O(n, p)¹⁶N reaction and the 6.1 MeV photopeak was measured on-line using a BGO detector adjacent to the primary coolant circuit. These data provided a relative measure of power stability during steady state operation and a measure of linearity at different power levels. The¹⁸F is produced in the primary coolant by the¹⁸O(p, n)¹⁸F reaction and aliquots of primary coolant were sampled from the reactor dump tank for off-line radiochemical analysis. The¹⁸F was separated as trimethylfluorosilane and the activity was determined by measurement of the 0.511 MeV annihilation photopeak using a NaI(TI) detector. The measured¹⁸F activity was used to determine actual in-core reactor power using both ab-initio calculations and by comparison of results with a calibrated power reactor. The¹⁸F data also provided a method of nomalising the¹⁶N data for direct monitoring of in-core reactor power in JASON.     

Validity of the Hammond postulate and constraints on general one-dimensional reaction barriers

The Hammond postulate is a useful, qualitative tool that interrelates structural similarities between reactants, transition structures, and products with the exo- or endothermicity of reactions. It applies to most chemical reactions, although several exceptions are known. In this study the following problem is addressed: is it possible to formulate conditions for the validity of the quantitative Hammond postulate in terms of simple physical quantities characteristic to the molecules involved? A detailed analysis is given for the conditions of validity of the postulate, in terms of bounds on the internal forces and force constants of nuclear arrangements encountered along a reaction path. We have determined a broad class of constraints on barrier shapes that must be satisfied in order to obtain a critical situation that violates the Hammond postulate: a reactant-like transition structure (“transition state”) for endothermic reactions, and a product-like one for exothermic reactions. The general constraints are formulated in terms of physically meaningful quantities: (i) energy differences, (ii) restrictions on slopes (e.g., an upper bound on internal forces), and (iii) restrictions on curvatures (e.g., upper bounds on force constants) along potential curves.