Physical Chemistry (physical + chemistry)

Distribution by Scientific Domains


Selected Abstracts


Synthesis and Physical Chemistry of s -Tetrazines: Which Ones are Fluorescent and Why?

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 35 2009
Yong-Hua Gong
Abstract New fluorescent tetrazines have been prepared and their electrochemistry and fluorescence efficiency evaluated. The occurrence of fluorescence as well as the wavelength were found to be strongly dependent on the substituents, which have to be electronegative heteroatoms. This has been rationalized through a computational study that showed that the crucial factor is the nature of the HOMO, which determines the existence or not of fluorescence. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source]


Books and Multimedia Reviews

METEORITICS & PLANETARY SCIENCE, Issue 12 2002
Article first published online: 26 JAN 2010
Book reviewed in this article: Chemical Dynamics in Extreme Environments, Volume 11 of Advanced Series in Physical Chemistry edited by Rainer A. Dressler. Storms in Space by John Freeman. Major Impacts and Plate Tectonics: A Model for the Phanerozoic Evolution of the Earth's Lithosphere by Neville J. Price. Meteorite Hunter: The Search For Siberian Meteorite Craters by Roy A. Gallant. [source]


Complex 1H,13C-NMR relaxation and computer simulation study of side-chain dynamics in solid polylysine

BIOPOLYMERS, Issue 3 2005
Alexey Krushelnitsky
Abstract The side-chain dynamics of solid polylysine at various hydration levels was studied by means of proton spin,lattice relaxation times measurements in the laboratory and tilted (off-resonance) rotating frames at several temperatures as well as Monte Carlo computer simulations. These data were analyzed together with recently measured carbon relaxation data (A. Krushelnitsky, D. Faizullin, and D. Reichert, Biopolymers, 2004, Vol. 73, pp. 1,15). The analysis of the whole set of data performed within the frame of the model-free approach led us to a conclusion about three types of the side-chain motion. The first motion consists of low amplitude rotations of dihedral angles of polylysine side chains on the nanosecond timescale. The second motion is cis,trans conformational transitions of the side chains with correlation times in the microsecond range for dry polylysine. The third motion is a diffusion of dilating defects described in (W. Nusser, R. Kimmich, and F. Winter, Journal of Physical Chemistry, 1988, Vol. 92, pp. 6808,6814). This diffusion causes almost no reorientation of chemical bonds but leads to a sliding motion of side chains with respect to each other in the nanosecond timescale. This work evidently demonstrates the advantages of the simultaneous quantitative analysis of data obtained from different experiments within the frame of the same mathematical formalism, providing for the detailed description of the nature and geometry of the internal molecular dynamics. © 2005 Wiley Periodicals, Inc. Biopolymers 78: 129,139, 2005 This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source]


Physical chemistry for the biological sciences by Gordon G. Hammes

BIOCHEMISTRY AND MOLECULAR BIOLOGY EDUCATION, Issue 6 2008
James Zimmerman
No abstract is available for this article. [source]


The 50th Anniversary of the Treadwellian Father-and-Son Era (1881,1959) at the ETH

HELVETICA CHIMICA ACTA, Issue 2 2009
Wayne Craig
Abstract This year marks the 50th anniversary of the end of the Treadwellian Era. More than three quarters of a century earlier American Frederic Pearson Treadwell (1857,1918) began his research at the Eidgenössiches Polytechnikum (since June 23, 1911, known as the Eidgenössische Technische Hochschule (ETH)). After Frederic's death, William Dupré Treadwell (1885,1959), Frederic's son, was later appointed as assistant professor. Together, their publications in analytical, inorganic, and physical chemistry spanned three quarters of a century, and their impact on the usage of instrumentation at the ETH and in the chemical world is still apparent today. [source]


Some solved problems of the periodic system of chemical elements

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 8 2010
W. H. Eugen Schwarz
Abstract Basic questions on the periodic system (PS) of chemical elements are still under discussion. Several common misconceptions will be resolved. The word "chemical element" comprises more than two concepts. The PS can be rationalized on a quantum chemical basis, namely with the aid of four concepts: (1) electron configurations of bonded atoms, (2) realistic sequences of orbital energies, (3) spatial extension of valence and Rydberg orbitals, and (4) energy gaps above the closed 1s2 and np6 shells (n = 2,6). The PS of known elements cannot be naively extrapolated. The common discussion of the PS in textbooks of general, inorganic, and physical chemistry needs revision. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source]


Teaching crystallography to undergraduate physical chemistry students

JOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 5-2 2010
Virginia B. Pett
Teaching goals, laboratory experiments and homework assignments are described for teaching crystallography as part of two undergraduate physical chemistry courses. A two-week teaching module is suggested for introductory physical chemistry, including six to eight classroom sessions, several laboratory experiences and a 3,h computer-based session, to acquaint undergraduate physical chemistry students with crystals, diffraction patterns, the mathematics of structure determination by X-ray diffraction, data collection, structure solution and the chemical insights available from crystal structure information. Student projects and laboratory work for three to four weeks of an advanced physical chemistry course are presented. Topics such as symmetry operators, space groups, systematic extinctions, methods of solving the phase problem, the Patterson map, anomalous scattering, synchrotron radiation, crystallographic refinement, hydrogen bonding and neutron diffraction all lead to the goal of understanding and evaluating a crystallographic journal article. Many of the ideas presented here could also be adapted for inorganic chemistry courses. [source]


Review: physical chemistry of solid dispersions

JOURNAL OF PHARMACY AND PHARMACOLOGY: AN INTERNATI ONAL JOURNAL OF PHARMACEUTICAL SCIENCE, Issue 12 2009
Sandrien Janssens
Abstract Objectives With poorly soluble drug candidates emerging in the drug discovery pipeline, the importance of the solid dispersion formulation approach is increasing. This strategy includes complete removal of drug crystallinity, and molecular dispersion of the poorly soluble compound in a hydrophilic polymeric carrier. The potential of this technique to increase oral absorption and hence bioavailability is enormous. Nevertheless, some issues have to be considered regarding thermodynamic instability, as well in supersaturated solutions that are formed upon dissolution as in the solid state. Key findings After a brief discussion on the historical background of solid dispersions and their current role in formulation, an overview will be given on the physical chemistry and stability of glass solutions as they form supersaturated solutions, and during their shelf life. Conclusions Thorough understanding of these aspects will elicit conscious evaluation of carrier properties and eventually facilitate rational excipient selection. Thus, full exploitation of the solid dispersion strategy may provide an appropriate answer to drug attrition due to low aqueous solubility in later stages of development. [source]


Crystallizing proteins on the basis of their precipitation diagram determined using a microfluidic formulator

JOURNAL OF SYNCHROTRON RADIATION, Issue 6 2005
Morten O. A. Sommer
Crystallization of proteins from a purified protein solution remains a bottleneck in the structure determination pipeline. In this paper the crystallization problem is addressed using a microfluidic device capable of determining detailed protein precipitation diagrams using less than 10,µL of protein sample. Based on the experimentally determined protein phase behavior, a crystallization screen can be designed to accommodate the physical chemistry of the particular protein target. Such a tailor-made crystallization screen has a high probability of yielding crystallization hits. The approach is applied to two different proteins: the calcium pump (SERCA), an eukaryotic integral membrane protein, and UMP kinase, a prokaryotic soluble kinase. Protein phase behavior is mapped for both proteins and tailor-made crystallization screens are designed for the two proteins resulting in about 50% crystallization probability per experiment. This illustrates the power of using microfluidic devices for detailed characterization of protein phase behavior prior to crystallization trials. [source]


Effects of molecular crowding by saccharides on ,-chymotrypsin dimerization

PROTEIN SCIENCE, Issue 5 2002
Chetan N. Patel
Abstract Given the importance of protein complexes as therapeutic targets, it is necessary to understand the physical chemistry of these interactions under the crowded conditions that exist in cells. We have used sedimentation equilibrium to quantify the enhancement of the reversible homodimerization of ,-chymotrypsin by high concentrations of the osmolytes glucose, sucrose, and raffinose. In an attempt to rationalize the osmolyte-mediated stabilization of the ,-chymotrypsin homodimer, we have used models based on binding interactions (transfer-free energy analysis) and steric interactions (excluded volume theory) to predict the stabilization. Although transfer-free energy analysis predicts reasonably well the relatively small stabilization observed for complex formation between cytochrome c and cytochrome c peroxidase, as well as that between bobtail quail lysozyme and a monoclonal Fab fragment, it underestimates the sugar-mediated stabilization of the ,-chymotrypsin dimer. Although predictions based on excluded volume theory overestimate the stabilization, it would seem that a major determinant in the observed stabilization of the ,-chymotrypsin homodimer is the thermodynamic nonideality arising from molecular crowding by the three small sugars. [source]


Thyroid hormones and their effects: a new perspective

BIOLOGICAL REVIEWS, Issue 4 2000
A. J. HULBERT
ABSTRACT The thyroid hormones are very hydrophobic and those that exhibit biological activity are 3,,5,,3,5-Ltetraiodothyronine (T4), 3,,5,3-L-triiodothyronine (T3), 3,,5,,3-L-triiodothyronine (rT3) and 3,5,-Ldiiodothyronine (3,5-T2). At physiological pH, dissociation of the phenolic -OH group of these iodothyronines is an important determinant of their physical chemistry that impacts on their biological effects. When non-ionized these iodothyronines are strongly amphipathic. It is proposed that iodothyronines are normal constituents of biological membranes in vertebrates. In plasma of adult vertebrates, unbound T4 and T3 are regulated in the picomolar range whilst protein-bound T4 and T3 are maintained in the nanomolar range. The function of thyroid-hormone-binding plasma proteins is to ensure an even distribution throughout the body. Various iodothyronines are produced by three types of membrane-bound cellular deiodinase enzyme systems in vertebrates. The distribution of deiodinases varies between tissues and each has a distinct developmental profile. Thyroid hormones have many effects in vertebrates. It is proposed that there are several modes of action of these hormones.(1) The nuclear receptor mode is especially important in the thyroid hormone axis that controls plasma and cellular levels of these hormones.(2) These hormones are strongly associated with membranes in tissues and normally rigidify these membranes.(3) They also affect the acyl composition of membrane bilayers and it is suggested that this is due to the cells responding to thyroid-hormone-induced membrane rigidification. Both their immediate effects on the physical state of membranes and the consequent changes in membrane composition result in several other thyroid hormone effects. Effects on metabolism may be due primarily to membrane acyl changes. There are other actions of thyroid hormones involving membrane receptors and influences on cellular interactions with the extracellular matrix. The effects of thyroid hormones are reviewed and appear to be combinations of these various modes of action. During development, vertebrates show a surge in T4 and other thyroid hormones, as well as distinctive profiles in the appearance of the deiodinase enzymes and nuclear receptors. Evidence from the use of analogues supports multiple modes of action. Re-examination of data from the early 1960s supports a membrane action. Findings from receptor ,knockout' mice supports an important role for receptors in the development of the thyroid axis. These iodothyronines may be better thought of as ,vitamone' -like molecules than traditional hormonal messengers. [source]


Dissecting membrane protein architecture: An annotation of structural complexity

BIOPOLYMERS, Issue 10 2009
Jaime Arce
Abstract ,-Helical membrane proteins exist in an anisotropic environment which strongly influences their folding, stability, and architecture, which is far more complex than a simple bundle of transmembrane helices, notably due to helix deformations, prosthetic groups and extramembrane structures. However, the role and the distribution of such heterogeneity in the supra molecular organization of membrane proteins remains poorly investigated. Using a nonredundant subset of ,-helical membrane proteins, we have annotated and analyze the statistics of several types of new elements such as incomplete helices, intramembrane loops, helical extensions of helical transmembrane domains, extracellular loops, and helices lying parallel to the membrane surface. The relevance of the annotation scheme was studied using residue composition, statistics, physical chemistry, and symmetry of their distribution in relation to the immediate membrane environment. Calculation of hydrophobicity using different scales show that different structural elements appear to have affinities coherent with their position in the membrane. Examination of the annotation scheme suggests that there is considerable information content in the amino acid compositions of the different elements suggesting that it might be useful for structural prediction. More importantly, the proposed annotation will help to decipher the complex hierarchy of interactions involved in membrane protein architecture. © 2009 Wiley Periodicals, Inc. Biopolymers 91: 815,829, 2009. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source]


Effect of Counter Ions on the Silica Oligomerization Reaction

CHEMPHYSCHEM, Issue 11 2009
Thuat T. Trinh
Abstract The silicate oligomerization reaction is key to sol-gel chemistry and zeolite synthesis. Numerous experimental and theoretical studies have addressed the physical chemistry of silicate oligomers in the prenucleation stage of siliceous zeolite formation. Here we report a study of a silica condensation reaction in aqueous solution in the presence of counter ions (Li+ and NH4+). Ab-initio molecular dynamics simulations have been used to construct reaction energy diagrams including transition state free energies. Contact with Li+ as well as NH4+ increases the activation energies of the dimerization step compared to the situation in the absence of counterions. The presence of NH4+ has no effect on consecutive oligomerization steps. Hence NH4+ will increase the relative formation rate of larger oligomers. [source]


Laser Microbeams and Optical Tweezers in Ageing Research

CHEMPHYSCHEM, Issue 1 2009
Paulius Grigaravi
Abstract We show how a technique developed within the framework of physics and physical chemistry,in a true interdisciplinary approach,can answer questions in life sciences that are not solvable by using other techniques. Herein, we focus on blood-pressure regulation and DNA repair in ageing studies. Laser microbeams and optical tweezers are now established tools in many fields of science, particularly in the life sciences. A short glimpse is given on the wide field of non-age-research applications in life sciences. Then, optical tweezers are used to show that exerting a vertical pressure on cells representing the inner lining of blood vessels results in bursts of NO liberation concomitant with large changes in cell morphology. Repeated treatment of such human umbilical vein endothelial cells (HUVEC) results in stiffening, a hallmark of manifest high blood pressure, a disease primarily of the elderly. As a second application in ageing research, a laser microbeam is used to induce, with high spatial and temporal resolution, DNA damages in the nuclei of U2OS human osteosarcoma cells. A pairwise study of the recruitment kinetics of different DNA repair proteins reveals that DNA repair starts with non-homologous end joining (NHEJ), a repair pathway, and may only after several minutes switch to the error-free homologous recombination repair (HRR) pathway. Since DNA damages,when incorrectly repaired,accumulate with time, laser microbeams are becoming well-used tools in ageing research. [source]