Solvent effect on the conformational behavior of substituted spiro[4.5]decanes and spiro[5.5]undecanes

1995 ◽  
Vol 73 (5) ◽  
pp. 703-709 ◽  
Author(s):  
S. Sağ Erdem ◽  
T. Varnali ◽  
V. Aviyente ◽  
M.F. Ruiz-Lopez
Keyword(s):  
Solvent Effect ◽  
Electrostatic Interactions ◽  
Multipole Moment ◽  
Semiempirical Methods ◽  
Main Role ◽  
Solvent Interactions ◽  
Reaction Field ◽  
Solvent Models ◽  
Conformational Equilibria

We studied the relatively complex polar systems 6-substituted-1,4-dioxospiro[4.5]decanes and 7-substituted-1,5-dioxospiro[5.5]undecanes with substituents X = CH3, F, Cl, CN, OH, OCH3, and NO2. Solvent effects on the equilibrium have been analysed by means of a Self-Consistent-Reaction-Field model and the PM3 method. Complete geometry optimizations have been carried out for all the structures in the gas phase and in solution. For some substituents, a set of rotamers have been separately optimized. The discussion of the results is focussed on the effects arising from structural aspects and from steric and electrostatic interactions on the axial/equatorial relative stability. The role played by multipole moment is considered. In general, good agreement with available experimental data and with previous theoretical studies has been obtained. Though the use of semiempirical methods and simple solvent models prevents us from reaching definitive conclusions, this approach seems to be very useful in predicting the main role of solute–solvent interactions in conformational equilibria of complex systems for which ab initio calculations cannot be performed. Keywords: conformational equilibria, spiro decanes and undecanes, cavity model, SCRF, solvent effect, PM3 calculations.

Nuclear magnetic resonance studies. XIV. Conformational equilibria of α-halocyclohexanones

1967 ◽  
Vol 45 (23) ◽  
pp. 2943-2953 ◽  
Author(s):  
Yuh-Hsu Pan ◽  
J. B. Stothers
Keyword(s):  
Equilibrium Constants ◽  
Dipolar Interactions ◽  
Proton Spectroscopy ◽  
Solvent Interactions ◽  
Reaction Field ◽  
Conformational Equilibria ◽  
Classical Models ◽  
Acetonitrile Solutions ◽  
Cis And Trans ◽  
Good Agreement

The conformational equilibria of α-fluoro-, α-chloro-, and α-bromo-cyclohexanone have been examined by proton spectroscopy in cyclohexane, carbon tetrachloride, benzene, chloroform, p-dioxane, and acetonitrile solutions over a range of concentrations. The cis- and trans-4-t-butyl derivatives were used as reference compounds for the two chair conformations. Equilibrium constants were estimated from the α-proton spectral data in two ways and compared with the results obtained by a variety of methods. Consistently good agreement was found between our results and those available from dipole moment measurements. This study is the most extensive investigation of the α-halocyclohexanone equilibria to date. Calculations using simple classical models for steric, electrostatic, and induced dipolar interactions were found to predict the observed trends. The solvent effects on the axial and equatorial α-proton shieldings in the "fixed" systems are discussed in terms of solute–solute and (or) solute–solvent interactions, and evidence for reaction field contributions is presented.

scholarly journals The optimization of protein-solvent interactions: Thermostability and the role of hydrophobic and electrostatic interactions

1995 ◽  
Vol 4 (8) ◽  
pp. 1516-1527 ◽  
Author(s):  
Velin Z. Spassov ◽  
Andrej D. Karshikoff ◽  
Rudolf Ladenstein
Keyword(s):  
Electrostatic Interactions ◽  
Solvent Interactions

scholarly journals Modeling of Solute-Solvent Interactions Using an External Electric Field—From Tautomeric Equilibrium in Nonpolar Solvents to the Dissociation of Alkali Metal Halides

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1283 ◽  
Author(s):  
Ilya G. Shenderovich ◽  
Gleb S. Denisov
Keyword(s):  
Electric Field ◽  
Solvent Effect ◽  
External Electric Field ◽  
Molecular System ◽  
Tautomeric Equilibrium ◽  
Continuum Approximation ◽  
Solvent Interactions ◽  
Reaction Field ◽  
Nonpolar Solvents ◽  
Quantum Chemistry Calculations

An implicit account of the solvent effect can be carried out using traditional static quantum chemistry calculations by applying an external electric field to the studied molecular system. This approach allows one to distinguish between the effects of the macroscopic reaction field of the solvent and specific solute–solvent interactions. In this study, we report on the dependence of the simulation results on the use of the polarizable continuum approximation and on the importance of the solvent effect in nonpolar solvents. The latter was demonstrated using experimental data on tautomeric equilibria between the pyridone and hydroxypyridine forms of 2,6-di-tert-butyl-4-hydroxy-pyridine in cyclohexane and chloroform.

Role of spectrin in membrane fusion and in shape change of human erythrocyte ghost

1978 ◽  
Vol 36 (2) ◽  
pp. 328-329
Author(s):  
Hideo Hayashi ◽  
Yoshikazu Hirai ◽  
John T. Penniston
Keyword(s):  
Conformational Changes ◽  
Human Erythrocyte ◽  
Shape Change ◽  
Membrane Surface ◽  
Slight Modification ◽  
Active Role ◽  
Main Role ◽  
Bank Blood ◽  
Human Erythrocyte Ghost

Spectrin is a membrane associated protein most of which properties have been tentatively elucidated. A main role of the protein has been assumed to give a supporting structure to inside of the membrane. As reported previously, however, the isolated spectrin molecule underwent self assemble to form such as fibrous, meshwork, dispersed or aggregated arrangements depending upon the buffer suspended and was suggested to play an active role in the membrane conformational changes. In this study, the role of spectrin and actin was examined in terms of the molecular arrangements on the erythrocyte membrane surface with correlation to the functional states of the ghosts.Human erythrocyte ghosts were prepared from either freshly drawn or stocked bank blood by the method of Dodge et al with a slight modification as described before. Anti-spectrin antibody was raised against rabbit by injection of purified spectrin and partially purified.

Mesophyll conductance: the leaf corridors for photosynthesis

2020 ◽  
Vol 48 (2) ◽  
pp. 429-439 ◽  
Author(s):  
Jorge Gago ◽  
Danilo M. Daloso ◽  
Marc Carriquí ◽  
Miquel Nadal ◽  
Melanie Morales ◽  
...  
Keyword(s):  
Molecular Mechanisms ◽  
Current Knowledge ◽  
Main Role ◽  
Mesophyll Conductance ◽  
Future Studies ◽  
Cell Structures ◽  
Leaf Tissues ◽  
Change Framework ◽  
Chloroplast Stroma

Besides stomata, the photosynthetic CO2 pathway also involves the transport of CO2 from the sub-stomatal air spaces inside to the carboxylation sites in the chloroplast stroma, where Rubisco is located. This pathway is far to be a simple and direct way, formed by series of consecutive barriers that the CO2 should cross to be finally assimilated in photosynthesis, known as the mesophyll conductance (gm). Therefore, the gm reflects the pathway through different air, water and biophysical barriers within the leaf tissues and cell structures. Currently, it is known that gm can impose the same level of limitation (or even higher depending of the conditions) to photosynthesis than the wider known stomata or biochemistry. In this mini-review, we are focused on each of the gm determinants to summarize the current knowledge on the mechanisms driving gm from anatomical to metabolic and biochemical perspectives. Special attention deserve the latest studies demonstrating the importance of the molecular mechanisms driving anatomical traits as cell wall and the chloroplast surface exposed to the mesophyll airspaces (Sc/S) that significantly constrain gm. However, even considering these recent discoveries, still is poorly understood the mechanisms about signaling pathways linking the environment a/biotic stressors with gm responses. Thus, considering the main role of gm as a major driver of the CO2 availability at the carboxylation sites, future studies into these aspects will help us to understand photosynthesis responses in a global change framework.

Sports Photography and Historical Development

2018 ◽  
Vol 5 (1) ◽  
pp. 93-115
Author(s):  
Miloš Stamenković
Keyword(s):  
Historical Development ◽  
Emotional Reaction ◽  
Main Role ◽  
Primary Role

SummarySports photography undoubtedly has a significant place in sports press and publicism. It’s main and primary role is to present sports to the readers as art, which it is. Sport is characterized by dynamic and varied movements, and the main role of sports photography is reflected in the fact that it is in this way that sport shows its essence. Having in mind that photography tells more than a thousand words it sends a clear message to the reader as well to people who are informed about events via sports portals. Sports photography is a multidimensional art for many reasons. When we say “multi”, it primarily refers to a wider range that sports photography has to offer, which means sports photography is not only directed at presenting athletes on the move and the main actors who contribute to achieving the results by their engagement – it also has the role of sports “psychophotography” which is an analysis and capture of the emotional reaction of an athlete after winning or losing from the opposing team.

Problems and prospects for the Russian banking supervision development in modern conditions

2020 ◽  
Vol 26 (6) ◽  
pp. 1283-1296
Author(s):  
K.A. Omarieva ◽  
P.G. Isaeva
Keyword(s):  
Banking System ◽  
Main Role ◽  
Banking Supervision ◽  
Monetary System ◽  
The Russian Federation ◽  
Document Flow ◽  
Development Methods ◽  
Further Development ◽  
Development Prospects

Subject. The article addresses problems and prospects for the banking supervision development in the Russian Federation under modern conditions. Objectives. We review the essence and methods of organization of the banking supervision, and identify the main problems and prospects for its development. Methods. To provide valid, reliable and reasoned recommendations, we apply normative and integrated approaches to the study of the banking supervision effectiveness in the current circumstances. Results. The paper investigates main problems and development prospects for the Russian banking supervision. The essential importance of supervision comes from the main role of the banking system in maintaining accounts of economic entities and making settlements. Even minor failures or delays in operations can lead to negative outcomes and disastrous consequences for the entire monetary system and the national economy. Therefore, we highlight issues that require attention, and make proposals for further development of the banking supervision. Conclusions. In the context of dynamically developing economy, the banking practice is becoming more complex. As a result, there is a need for new financial instruments that can reduce risks, increase the speed and efficiency of operations and document flow, and help achieve the world levels of introduced standards.

Biological Role of CDK 11 and 12 in Cell Cycle and its Function in Tumorigenesis

2020 ◽  
Author(s):  
Shamim Mushtaq
Keyword(s):  
Breast Cancer ◽  
Cell Cycle ◽  
Web Of Science ◽  
The Body ◽  
Main Role ◽  
Hallmarks Of Cancer ◽  
Cyclin Dependent Kinases ◽  
Tumor Studies ◽  
Cycle Regulation

Uninhibited proliferation and abnormal cell cycle regulation are the hallmarks of cancer. The main role of cyclin dependent kinases is to regulate the cell cycle and cell proliferation. These protein kinases are frequently down regulated or up regulated in various cancers. Two CDK family members, CDK 11 and 12, have contradicting views about their roles in different cancers. For example, one study suggests that the CDK 11 isoforms, p58, inhibits growth of breast cancer whereas, the CDK 11 isoform, p110, is highly expressed in breast tumor. Studies regarding CDK 12 show variation of opinion towards different parts of the body, however there is a consensus that upregulation of cdk12 increases the risk of breast cancer. Hence, CDK 11 and CDK 12 need to be analyzed to confirm their mechanism and their role regarding therapeutics, prognostic value, and ethnicity in cancer. This article gives an outline on both CDKs of information known up to date from Medline, PubMed, Google Scholar and Web of Science search engines, which were explored and thirty relevant researches were finalized.

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