Molecular and group relaxation studies in parasubstituted benzenes in various media

1979 ◽  
Vol 57 (21) ◽  
pp. 2843-2847 ◽  
Author(s):  
J. Crossley ◽  
J. P. Shukla ◽  
S. P. Tay ◽  
M. S. Walker ◽  
S. Walker
Keyword(s):  
Group Process ◽  
Activation Enthalpy ◽  
Small Contribution ◽  
Molecular Processes ◽  
Dielectric Absorption ◽  
Polystyrene Matrix ◽  
Absorption Studies ◽  
The Matrix ◽  
Intramolecular Motion ◽  
Relaxation Studies

Dielectric absorption studies have been made on molecules of the type [Formula: see text][Formula: see text] where X—Y is —OCH3, —COCH3, —CH2Cl, and —CH2CN. The molecules have been dissolved in (a) a polystyrene matrix and (b) in the viscous liquid o-terphenyl. For 1,4-dimethoxybenzene the group process dominates in both media, and estimates have been made of the activation enthalpy for group relaxation. For 1,4-dimethoxybenzene in benzene, decalin, Nujol, and o-terphenyl solutions, however, there appears to be a small contribution from the molecular process. No such contribution was detected in the matrix studies on this solute molecule. For 1,4-diacetylbenzene, 1,4-bis(chloromethyl)benzene, and 1,4-bis(cyanomethyl)benzene in o-terphenyl solution it again seems that the group and molecular processes overlap. However, in polystyrene the enthalpies of activation which emerge are characteristic of the group relaxation process as determined by the nmr approach. Altogether, the work illustrates that o-terphenyl may be a useful solvent in helping to decide whether a solute has contributions from an intramolecular motion.

Acetyl group relaxation in four aromatic ketones

1977 ◽  
Vol 55 (4) ◽  
pp. 583-587 ◽  
Author(s):  
C. K. McLellan ◽  
S. Walker
Keyword(s):  
Energy Barrier ◽  
Benzene Solution ◽  
Far Infrared ◽  
Aromatic Ketones ◽  
Dielectric Absorption ◽  
Nmr Data ◽  
Polystyrene Matrix ◽  
Absorption Studies ◽  
Acetyl Group ◽  
Experimental Errors

Dielectric absorption studies have been made of group relaxation of acetophenone, 1,4-diacetylbenzene,4-acetylbiphenyl, and 2-acetylfluorene in a polystyrene matrix, and two rigid molecules have also been examined. For acetyl group relaxation in acetophenone, ΔHE = 29.6 ± 0.6 kJ mol−1 and ΔSE = 26 ± 3 JK−1 mol−1 (95% confidence intervals). The energy barrier for acetyl group relaxation is of the same order as that obtained from nmr data. Our results for acetophenone differ appreciably from the values reported for the gaseous phase by the far-infrared approach and from those by the dielectric absorption of aromatic ketones in benzene solution. The enthalpies of activation for acetyl group relaxation in 1,4-diacetylbenzene, 4-acetylbiphenyl, and 2-acetylfluorene are 29, 30, and 32 kJ mol−1, respectively, which values are identical within their experimental errors. These three substances have also been examined as pure solids, yielding enthalpies of activation for acetyl group relaxation of a similar magnitude.

Dielectric absorption of a few aromatic amines in a polystyrene matrix

1981 ◽  
Vol 59 (2) ◽  
pp. 232-237 ◽  
Author(s):  
S. P. Tay ◽  
S. Walker
Keyword(s):  
Aromatic Amines ◽  
Amino Group ◽  
Torsional Barrier ◽  
Dielectric Absorption ◽  
Enthalpy Of Activation ◽  
Polystyrene Matrix ◽  
Absorption Studies ◽  
Intramolecular Process ◽  
Nitrogen Bond

Dielectric absorption studies in the ranges 77–373 K and 102–107 Hz have been made on aniline, poly(4-aminostyrene), p-toluidine, 4-chloroaniline, 1-aminopyrene, and 4-aminobiphenyl in a polystyrene matrix. An intramolecular process has been observed in poly(4-aminostyrene) and 1-aminopyrene with enthalpies of activation of 25 and 26 kJ mol−1 respectively. The enthalpy of activation of the intramolecular process is of the same order as that found for the torsional barrier in aniline and 4-fluoroaniline. The most likely candidate for the intramolecular process appears to be rotation of the amino group about the carbon–nitrogen bond.

Activation energy for methoxy group relaxation

1978 ◽  
Vol 56 (13) ◽  
pp. 1800-1803 ◽  
Author(s):  
M. A. Mazid ◽  
J. P. Shukla ◽  
S. Walker
Keyword(s):  
Activation Energy ◽  
Aromatic Ring ◽  
Energy Barrier ◽  
Methoxy Group ◽  
Steric Effects ◽  
Molecular Process ◽  
Dielectric Absorption ◽  
Polystyrene Matrix ◽  
Absorption Studies ◽  
Methoxy Groups

Dielectric absorption studies hove been made on seven compounds which hove methoxy groups attached to an aromatic ring and on some related rigid molecules. The solutes hove been dispersed in a polystyrene matrix. In some cases, the absorptions due to the group and the molecular process have been separated completely, and this has permitted the estimation of more accurate Eyring enthalpies of activation for methoxy group relaxation. These values hove been compared with those in the literature and, on the whole, it would seem likely that the energy barrier to group relaxation is small and of the order of 10 kJ mol−1 for cases where there is no mutual conjugation or steric effects.

Dielectric relaxation in 2-acetylnaphthalene and related compounds

1978 ◽  
Vol 56 (4) ◽  
pp. 567-573 ◽  
Author(s):  
J. Crossley ◽  
M. A. Mazid ◽  
C. K. McLellan ◽  
P. F. Mountain ◽  
S. Walker
Keyword(s):  
Activation Parameters ◽  
Low Frequencies ◽  
Microwave Frequencies ◽  
Dielectric Absorption ◽  
Free Energy Of Activation ◽  
Polystyrene Matrix ◽  
The Matrix ◽  
Acetyl Group ◽  
Related Compounds ◽  
Xylene Solution

The dielectric absorption of 2-acetylnaphthalene and 2- and 3-acetylphenanthrene has been studied in p-xylene solution at several microwave frequencies and in a polystyrene matrix at low frequencies. Acetyl group relaxation has been established from both sets of data. A clear separation of the dielectric absorption of the molecule and the group has been achieved for both 2- and 3-acetylphenanthrene in the matrix. The Eyring activation parameters have been established for acetyl relaxation in these molecules in the matrix. The free energy of activation values for group relaxation increase in the sequence acetophenone < 2-acetylphenanthrene < 3-acetylphenanthrene < 2-acetylnaphthalene. For the p-xylene solution data the weight factor for group relaxation, C2, is appreciably lower than the theoretical value, so that C2 < C1, bearing out the findings of Fong and Smyth for 2-acetylnaphthalene. In polystyrene matrices, the data for 2- and 3-acetylphenanthrene also indicated that C2 < C1. The enthalpy of activation for acetyl relaxation in 2- and 3-acetylphenanthrene is similar to that for acetophenone and 1,4-diacetylbenzene whereas that for 2-acetylnaphthalene would seem somewhat larger.

scholarly journals Zebrafish Xenograft: An Evolutionary Experiment in Tumour Biology

2017 ◽  
Author(s):  
Rachael A. Wyatt ◽  
Nhu P. V. Trieu ◽  
Bryan D. Crawford
Keyword(s):  
Cell Culture ◽  
Molecular Ecology ◽  
Research Community ◽  
Molecular Processes ◽  
Zebrafish Model ◽  
Tumour Biology ◽  
Cell Culture Systems ◽  
The Matrix ◽  
Human Proteins

Though the cancer research community has used mouse xenografts for decades more than zebrafish xenografts, zebrafish have much to offer: they are cheap, easy to work with, and the embryonic model is relatively easy to use in high-throughput assays. Zebrafish can be imaged live, allowing us to observe cellular and molecular processes in vivo in real time. Opponents dismiss the zebrafish model due to the evolutionary distance between zebrafish and humans, as compared to mice, but proponents argue for the zebrafish xenograft&rsquo;s superiority to cell culture systems and its advantages in imaging. This review places the zebrafish xenograft in the context of current views on cancer and gives an overview of how several aspects of this evolutionary disease can be addressed in the zebrafish model. Zebrafish are missing homologs of some human proteins and (of particular interest) several members of the matrix metalloproteinase (MMP) family of proteases, which are known for their importance in tumour biology. This review draws attention to the implicit evolutionary experiment taking place when the molecular ecology of the xenograft host is significantly different than that of the donor.

Application of the Measurement of the Dielectric Constant and Loss Angle to the Study of the Structure of Vulcanizates Loaded with Carbon Blacks

1952 ◽  
Vol 25 (3) ◽  
pp. 533-548
Author(s):  
P. Thirion ◽  
R. Chasset
Keyword(s):  
Dielectric Constant ◽  
Carbon Black ◽  
The Other ◽  
Rubber Matrix ◽  
Loss Angle ◽  
Colloidal Structure ◽  
Dielectric Absorption ◽  
Dielectric Loss Angle ◽  
Dielectric Constant And Loss ◽  
The Matrix

Abstract In the case of vulcanizates containing carbon black the variation curves of dielectric loss angle as a function of temperature enable the Debye type absorption occurring in the rubber matrix to be distinguished from a supplementary absorption little influenced by variations in temperature and frequency which is characteristic of blacks possessing a structure. The experimental results obtained indicate no difference in physical or chemical state between the matrix occupying the space between the particles of black in a loaded mix and the vulcanizate of the corresponding pure rubber mix. The supplementary losses on the other hand seem to be closely related to the effects of structure in loaded mixes imagined by Mullins to explain the mechanical behavior of these mixes: they decrease very rapidly by elongation or swelling and give rise to various phenomena of hysteresis. It would seem that dielectric absorption could advantageously be applied as a nondestructive test revealing the colloidal structure of rubber mixes based on carbon black. Moreover the dielectric constant would enable information to be obtained on the form factor and the orientation of the particles or agglomerates of particles of black in mixes on the basis of a theory assimilating these particles (or agglomerates) to condenser armatures.

Relaxation studies on aromatic aldehydes in a polystyrene matrix

1978 ◽  
Vol 74 ◽  
pp. 727 ◽  
Author(s):  
Arunachalam Lakshmi ◽  
Stanley Walker ◽  
Neil A. Weir ◽  
James H. Calderwood
Keyword(s):  
Aromatic Aldehydes ◽  
Polystyrene Matrix ◽  
Relaxation Studies

scholarly journals Thermodynamics of the DNA Repair Process by Endonuclease VIII

Acta Naturae ◽  
2019 ◽  
Vol 11 (1) ◽  
pp. 29-37 ◽  
Author(s):  
O. A. Kladova ◽  
N. A. Kuznetsov ◽  
O. S. Fedorova
Keyword(s):  
Activation Enthalpy ◽  
Substrate Binding ◽  
Repair Process ◽  
Molecular Processes ◽  
Substrate Interaction ◽  
Enzyme Substrate ◽  
Different Temperatures ◽  
Enthalpy And Entropy ◽  
Transition Complex ◽  
Dna Substrate

In the present work, a thermodynamic analysis of the interaction between endonuclease VIII (Endo VIII) and model DNA substrates containing damaged nucleotides, such as 5,6-dihydrouridine and 2-hydroxymethyl-3-hydroxytetrahydrofuran (F-site), was performed. The changes in the fluorescence intensity of the 1,3-diaza-2-oxophenoxazine (tCO) residue located in the complementary chain opposite to the specific site were recorded in the course of the enzyme-substrate interaction. The kinetics was analyzed by the stopped-flow method at different temperatures. The changes of standard Gibbs free energy, enthalpy, and entropy of sequential steps of DNA substrate binding, as well as activation enthalpy and entropy for the transition complex formation of the catalytic stage, were calculated. The comparison of the kinetic and thermodynamic data characterizing the conformational transitions of enzyme and DNA in the course of their interaction made it possible to specify the nature of the molecular processes occurring at the stages of substrate binding, recognition of the damaged base, and its removal from DNA.

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