Search results for "molecular conformation"
showing 10 items of 376 documents
Dynamics of surface of lipid membranes: theoretical considerations and the ESR experiment.
2016
The effect of the surface layer of model membranes on their physical properties was discussed in this paper. The research involved a physical ESR experiment with the use of spin probes and computer simulation based on the Monte Carlo technique. Liposomes formed during the process of sonication of lecithin were scanned in an ESR spectrometer. The membrane surface layer model, represented by the system of electric dipoles arranged in rectangular or hexagonal matrices, was studied. The final states of computer simulations were presented as textures. It was found that in the gel phase some ordered domain structures are formed, while in the liquid–crystal phase we got complex textures comprising…
Pressure effects on the vibrational properties of alpha-Bi2O3: an experimental and theoretical study
2014
We report an experimental and theoretical high-pressure study of the vibrational properties of synthetic monoclinic bismuth oxide (alpha-Bi2O3), also known as mineral bismite. The comparison of Raman scattering measurements and theoretical lattice-dynamics ab initio calculations is key to understanding the complex vibrational properties of bismite. On one hand, calculations help in the symmetry assignment of phonons and to discover the phonon interactions taking place in this low-symmetry compound, which shows considerable phonon anticrossings; and, on the other hand, measurements help to validate the accuracy of first-principles calculations relating to this compound. We have also studied …
Cubane-Type Mo3FeS44+,5+ Complexes Containing Outer Diphosphane Ligands: Ligand Substitution Reactions, Spectroscopic Studies, and Electronic Structu…
2012
A general protocol to access Mo(3)FeS(4)(4+) clusters selectively modified at the Fe coordination site is presented starting from the all-chlorine Mo(3)(FeCl)S(4)(dmpe)(3)Cl(3) (1) [dmpe = 1,2-bis(dimethylphosphane-ethane)] cluster and tetrabutylammonium salts (n-Bu(4)NX) (X = CN(-), N(3)(-), and PhS(-)). Clusters Mo(3)(FeX)S(4)(dmpe)(3)Cl(3) [X = CN(-) (2), N(3)(-) (3), and PhS(-) (4)] are prepared in high yield, and comparison of geometric and redox features upon modification of the coordination environment at the Fe site at parity of ligands at the Mo sites is also presented. The existence of the cubane-type Mo(3)FeS(4)(4+,5+) redox couple is demonstrated by cyclic voltammetry and for co…
The Role of Adenine Excimers in the Photophysics of Oligonucleotides
2009
Energies and structures of different arrangements of the stacked adenine homodimer have been computed at the ab initio CASPT2 level of theory in isolation and in an aqueous environment. Adenine dimers are shown to form excimer singlet states with different degrees of stacking and interaction. A model for a 2-fold decay dynamics of adenine oligomers can be supported in which, after initial excitation in the middle UV range, unstacked or slightly stacked pairs of nucleobases will relax by an ultrafast internal conversion to the ground state, localizing the excitation in the monomer and through the corresponding conical intersection with the ground state. On the other hand, long-lifetime intra…
Singlet Excited-State Interactions in Naphthalene-Thymine Dyads
2004
Two thymidine-derived nucleosides 1 and 2 were prepared by attaching a chiral naphthalene to the positions 5′ and 3′ of the sugar. The resulting dyads, which contain key substructures present in drugs and nucleic acids, exhibit different spatial arrangements (transoid or cisoid) of the fluorophore relative to the thymine unit. Emission measurements on these compounds in the presence of ROH molecules revealed a remarkable intramolecular fluorescence quenching for dyad 1. The obtained results are consistent with quenching of the singlet excited state of 1 by hydrogen-bond donor solvents. Thus, a physical deactivation process (vibronically induced internal conversion) would be the pathway resp…
Characterization of phenolic pellets for ESR dosimetry in photon beam radiotherapy
2017
This work deals with the dosimetric features of a particular phenolic compound (IRGANOX 1076 ® ) for dosimetry of clinical photon beams by using electron spin resonance (ESR) spectroscopy. After the optimization of the ESR readout parameters (namely modulation amplitude and microwave power) to maximise the signal without excessive spectrum distortions, basic dosimetric properties of laboratory-made phenolic dosimeters in pellet form, such as reproducibility, dose–response, sensitivity, linearity and dose rate dependence were investigated. The dosimeters were tested by measuring the depth dose profile of a 6 MV photon beam. A satisfactory intra-batch reproducibility of the ESR signal of the …
Detecting ni(ii) in aqueous solution by 3-(2-pyridyl)-[1,2,3]triazolo[1,5-a]pyridine and dimethyl-beta-cyclodextrin
2013
Abstract A new supramolecular sensitizer for nickel(II) ion in aqueous solution based on a pyridyltriazolopyridine-cyclodextrin inclusion complex is proposed. The inclusion complexation behavior, characterization and binding ability of pyridyltriazolopyridine (PTP) with dimethyl-β-cyclodextrin (DMβCD) has been investigated both in solution and solid state by means of absorption, fluorescence, 1H NMR, DSC, and molecular modeling methods. The stoichiometry of the inclusion complex is 1:1, and the thermodynamic studies indicate that the inclusion of PTP is mainly an entropic driven process. The 2D NMR studies revealed that the pyridyl-triazolopyridine is included by both sides of cyclodextrin …
Biomimetic oxygen reduction by cofacial porphyrins at a liquid-liquid interface.
2012
Oxygen reduction catalyzed by cofacial metalloporphyrins at the 1,2-dichlorobenzene−water interface was studied with two lipophilic electron donors of similar driving force, 1,1'-dimethylferrocene (DMFc) and tetrathiafulvalene (TTF). The reaction produces mainly water and some hydrogen peroxide, but the mediator has a significant effect on the selectivity, as DMFc and the porphyrins themselves catalyze the decomposition and the further reduction of hydrogen peroxide. Density functional theory calculations indicate that the biscobaltporphyr- in, 4,5-bis(5-(2,8,13,17-tetraethyl-3,7,12,18-tetramethylporphyrinyl))-9,9-dimethylxanthene, Co2(DPX), actually catalyzes oxygen reduction to hydrogen p…
A Ser residue influences the structure and stability of a Pro-kinked transmembrane helix dimer
2012
AbstractWhen localized adjacent to a Pro-kink, Thr and Ser residues can form hydrogen bonds between their polar hydroxyl group and a backbone carbonyl oxygen and thereby modulate the actual bending angle of a distorted transmembrane α-helix. We have used the homo-dimeric transmembrane cytochrome b559′ to analyze the potential role of a highly conserved Ser residue for assembly and stabilization of transmembrane proteins. Mutation of the conserved Ser residue to Ala resulted in altered heme binding properties and in increased stability of the holo-protein, most likely by tolerating subtle structural rearrangements upon heme binding. The results suggest a crucial impact of an intrahelical Ser…
Conformational investigation of alpha,beta-dehydropeptides. XIII. Conformational properties of N-acetyl-alpha,beta-dehydrovaline N',N'-dimethylamide.
2004
The crystal structure of Ac-DeltaVal-NMe(2) (DeltaVal = alpha,beta-dehydrovaline) was determined by X-ray crystallography. The found angles phi = -60 degrees and psi = 125 degrees correspond exactly to the respective values of the (i + 1)th residue in idealised beta-turn II/VIa. Ab initio/DFT studies revealed that the molecule adopts the angle psi restricted only to about |130 degrees | and very readily attains the angle phi = about -50 degrees. This is in line with its solid-state conformation. Taken together, these data suggest that the DeltaVal residue combined with a C-terminal tertiary amide is a good candidate at the (i + 1)th position in a type II/VIa beta-turn.