Search results for "COMPUTATION"
showing 10 items of 7362 documents
Toward an Understanding of the Mechanisms of the Intramolecular [5 + 2] Cycloaddition Reaction of γ-Pyrones Bearing Tethered Alkenes. A Theoretical S…
2000
The molecular mechanism for the intramolecular [5 + 2] cycloaddition reaction of β-silyloxy-γ-pyrones bearing tethered alkenes has been characterized using ab initio methods. A comparative study for this sort of cycloaddition carried out at different computational levels points out that the B3LYP/6-31G* calculations give similar barriers to those obtained with the MP3/6-31G* level. Analysis of the energetic results shows that the reaction takes place along a stepwise process: first, the migration of the neighboring silyl group to the carbonyl group of the γ-pyrone takes place to give a weak oxidopyrylium ylide intermediate, which by a subsequent concerted intramolecular [5 + 2] cycloadditi…
Binding abilities of new cyclodextrin-cucurbituril supramolecular hosts
2015
Various combined techniques (UV–vis spectrophotometry, isothermal titration calorimetry, thermogravimetry, ESI-MS mass spectrometry, polarimetry and 1H NMR spectroscopy) were used in order to study the interaction between a new combined supramolecular host, namely a bow-tie-structured cyclodextrin–cucurbituril association solely held by non-covalent interactions, and a suitably selected guest, namely the N-(p-nitrophenyl)-1,8-diaminooctane hydrochloride. In particular, the use of different techniques highlighted the peculiar features of the possible host–guest supramolecular interactions under different concentration conditions.
Microwave-assisted synthesis of novel cyclodextrin–cucurbituril complexes
2011
Microwave irradiation was successfully used in order to obtain stable supramolecular aggregates between cyclodextrins and cucurbiturils, without the participation of any long-chain common ‘molecular thread’ guest. These aggregates were characterised by means of various different techniques, namely NMR, thermogravimetry, polarimetry and ESI-MS. Cross-analysis of experimental data allowed us to obtain insights on the stoichiometries of the composites and their thermal stabilities. The possible structures of the composites are briefly discussed, as well as the actual nature of their intrinsic stability.
Loss of Hyperconjugative Effects Drives Hydride Transfer during Dihydrofolate Reductase Catalysis
2019
Hydride transfer is widespread in nature and has an essential role in applied research. However, the mechanisms of how this transformation occurs in living organisms remain a matter of vigorous debate. Here, we examined dihydrofolate reductase (DHFR), an enzyme that catalyzes hydride from C4′ of NADPH to C6 of 7,8-dihydrofolate (H2F). Despite many investigations of the mechanism of this reaction, the contribution of polarization of the π-bond of H2F in driving hydride transfer remains unclear. H2F was stereospecifically labeled with deuterium β to the reacting center, and β-deuterium kinetic isotope effects were measured. Our experimental results combined with analysis derived from QM/MM si…
A DFT Characterization of the Mechanism for the Cycloaddition Reaction between 2-Methylfuran and Acetylenedicarboxylic Acid
1999
The molecular mechanism for the cycloaddition reaction between 2-methylfuran and acetylenedicarboxylic acid (ADA) has been characterized using density functional theory methods at the B3LYP/6-31+G* theory level. An analysis of the results on the reaction pathway shows that the reaction takes place along a stepwise mechanism. The initial step corresponds to the nucleophilic attack of the C5 position of the furan ring to one carbon atom of the conjugated acetylenic system of ADA to give a zwitterionic intermediate. Closure of this intermediate along the nucleophilic attack of the other acetylenic carbon to the substituted C2 position of the furan ring affords the Diels−Alder cycloadduct. Alth…
ChemInform Abstract: Proton Coordination by Polyamine Compounds in Aqueous Solution
2010
Abstract The present article is concerned with proton transfer reactions in aqueous solution of open-chain, macrocyclic and macropolycyclic or cage compounds having nitrogen atoms as protonation sites in the molecular framework, although several compounds with additional different donors will be considered. The main purpose of this review is to collect some significant examples of proton transfer processes in order to show how the electronic properties and molecular topology of polyamines affect the thermodynamic parameters of their protonation equilibria.
Understanding the kinetic solvent effects on the 1,3-dipolar cycloaddition of benzonitrile N-oxide: a DFT study
2011
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, ISSN : 0894-3230, DOI : 10.1002/poc.1858, Issue : 7, Volume : 24, pp. 611 – 618, JUILLET 2011.
Chapter 2 Biosynthesis in Rauwolfia serpentina Modern Aspects of an Old Medicinal Plant
1995
Publisher Summary This chapter discusses a research on Rauwolfia , which was achieved after the generation of a cell suspension with extraordinary growth characteristics and physiological behavior. The investigations demonstrated that a range of techniques is now available for the clarification of complete metabolic pathways, provided that the appropriate efficient biological system is available. The isolation and identification of each single enzyme have almost become routine, even if an extremely sensitive protein analytic technique is necessary when several kilograms of fresh plant cells are reduced to a few micrograms of homogenous protein. The successful identification of a total of 20…
Characterization of Interaction Between Humic Acids and Buckminsterfullerene Using Flourescene Spectroscopy
2017
The interaction between buckminsterfullerene C60 and humic acids (HA) of different origins was compared using fluorescence spectroscopy as a function of pH, humic acid concentration, ionic strength. Binding constants between fullerene and humic acids were calculated. It can be suggested that the complexation was driven by hydrophobic interactions depending on the properties of the interacting compounds. Hydrophobic interaction model as indicated by linear Stern-Volmer plots and high Kd values is characterizing the interaction between buckminsterfullerene C60 and humic acids The results of this study support the development of an understanding of the fate of nanomaterials in the environment …