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Molecular Skeleton (molecular + skeleton)
Selected AbstractsHeavy atom motions and tunneling in hydrogen transfer reactions: the importance of the pre-tunneling stateJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 7 2010Hans-Heinrich Limbach Abstract Arrhenius curves of selected hydrogen transfer reactions in organic molecules and enzymes are reviewed with the focus on systems exhibiting temperature-independent kinetic isotope effects. The latter can be rationalized in terms of a ,pre-tunneling state' which is formed from the reactants by heavy atom motions and which represents a suitable molecular configuration for tunneling to occur. Within the Bell,Limbach tunneling model, formation of the pre-tunneling state dominates the Arrhenius curves of the H and the D transfer even at higher temperatures if a large energy Em is required to reach the pre-tunneling state. Tunneling from higher vibrational levels and the over-barrier reaction via the transition state which lead to temperature-dependent kinetic isotope effects dominate the Arrhenius curves only if Em is small compared to the energy of the transition state. Using published data on several hydrogen transfer systems, the type of motions leading to the pre-tunneling state is explored. Among the phenomena which lead to large energies of the pre-tunneling state are (i) cleavage of hydrogen bonds or coordination bonds of the donor or acceptor atoms to molecules or molecular groups in order to allow the formation of the pre-tunneling state, (ii) the occurrence of an energetic intermediate on the reaction pathway within which tunneling takes place, and (iii) major reorganization of a molecular skeleton, requiring the excitation of specific vibrations in order to reach the pre-tunneling state. This model suggests a solution to the puzzle of Kwart's findings of temperature-independent kinetic isotope effects for hydrogen transfer in small organic molecules. Copyright © 2010 John Wiley & Sons, Ltd. [source] From the discovery of sodiumoxyorganoalkoxysilanes to the organosilicon dendrimers and backJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2008Aziz M. Muzafarov Abstract Upon being discovered 20 years ago, sodiumoxyorganoalkoxysilanes became the key to the world of organoelement dendrimers. Even considering the great variety of objects that had appeared in this area during the last 20 years, the organosilicon dendrimers are still one of the most actual objects in this class. Above all, this is fair concerning the carbosilane systems. The high reactivity of the functional groups, the well controlled chemistry of their transformations, and the inertness of the molecular skeleton are the reason for making these systems highly actual in two main regards: as model objects for the deep research of the dendrimers' properties and as polyfunctional matrixes for numerous derivatives. In this review, we were mainly focusing on the importance of the former part. In the conclusion, we showed the motivation for further development of this area both in regard of synthesis of new carbosilane systems and further development of siloxane dendrimers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4935,4948, 2008 [source] DOSY NMR applied to analysis of flavonoid glycosides from Bidens sulphureaMAGNETIC RESONANCE IN CHEMISTRY, Issue 12 2009Edilene Delphino Rodrigues Abstract 2D DOSY 1H NMR has proved to be a useful technique in the identification of the molecular skeleton of the four major compounds of ethyl acetate extract of aerial parts of Bidens sulphurea (Asteraceae). The combination of this technique with HPLC, mass spectrometry and other NMR techniques enabled the identification of four flavonoid glycosides: quercetin-3- O -,- D -galactopyranoside, quercetin-3- O -,- D -glycopyranoside, quercetin-3- O -,- L -arabinofuranoside and quercetin-3- O -,- D -rhamnopyranoside. Copyright © 2009 John Wiley & Sons, Ltd. [source] Allosteric ligands for G protein-coupled receptors: A novel strategy with attractive therapeutic opportunitiesMEDICINAL RESEARCH REVIEWS, Issue 3 2010Marco De Amici Abstract Allosteric receptor ligands bind to a recognition site that is distinct from the binding site of the endogenous messenger molecule. As a consequence, allosteric agents may attach to receptors that are already transmitter-bound. Ternary complex formation opens an avenue to qualitatively new drug actions at G protein-coupled receptors (GPCRs), in particular receptor subtype selective potentiation of endogenous transmitter action. Consequently, suitable exploitation of allosteric recognition sites as alternative molecular targets could pave the way to a drug discovery paradigm different from those aimed at mimicking or blocking the effects of endogenous (orthosteric) receptor activators. The number of allosteric ligands reported to modulate GPCR function is steadily increasing and some have already reached routine clinical use. This review aims at introducing into this fascinating field of drug discovery and at providing an overview about the achievements that have already been made. Various case examples will be discussed in the framework of GPCR classification (family A, B, and C receptors). In addition, the behavior at muscarinic receptors of hybrid derivatives incorporating both an allosteric and an orthosteric fragment in a common molecular skeleton will be illustrated. © 2009 Wiley Periodicals, Inc. Med Res Rev, 30, No. 3, 463,549, 2010 [source] Suppressing One-Bond Correlations in HMBC Spectra: Improved Performance for the BIRD,HMBC Pulse SequenceMAGNETIC RESONANCE IN CHEMISTRY, Issue 3 2009Julien Furrer Abstract An improved version of the BIRD,HMBC experiment is proposed. In comparison to the original version, the filtering (suppression of 1JCH signals) is accomplished using a double tuned G-BIRD filter positioned in the middle of the long-range correlations evolution period. Compensation of offset dependence by replacing the rectangular 180° pulses with the broadband inversion pulses (BIPs), with superior inversion performance and improved tolerance to B1 field inhomogeneity, significantly improves the sensitivity of the original BIRD,HMBC experiment. For usual one-bond coupling constants ranges (115,180 Hz), optimal results are easily obtained by adjusting the delays, ,, of the BIRD elements to an average J value. For larger ranges (e.g. 110,260 Hz), the use of a double tuned G-BIRD filter allows excellent suppression degrees for all types of one-bond constants present in a molecule, superior to the original scheme and other purging schemes. These attributes make the improved version of the BIRD,HMBC experiment a valuable and robust tool for rapid spectral analysis and rapid checks of molecular skeletons with a minimum spectrometer time. Copyright © 2009 John Wiley & Sons, Ltd. [source] | ||||||||||