Reorientational relaxation and rotational–translational coupling in water clusters in a d.c. external electric field

Molecular dynamics simulations have been carried out for small water clusters (N=16, 32, 64) in a d.c. electric field at T=200 K. It was shown that for relatively weak fields, there was a significant decrease of reorientational and structural relaxation times for all cluster sizes examined. Regarding the molecular reorientational motions, in the strong field regime, a decoupling of tumbling and spinning librations was observed. Reorientational relaxation times of the dipole and vector joining the two hydrogen atoms were found to follow different relaxation laws, with the former decreasing and the latter increasing with electric field increase. These trends were qualitatively explained by invoking the Debye model with field-dependent friction for dipole librations and the symmetric double-well for spinning rotations on a plane perpendicular to the field axis. Finally, the interdependence of the reorientation on the translational modes of the cluster was indicated, with the translationally slow molecules being rotationally slow as well and vice versa.     

Polyamide Layer Chromatography. VIII. Preparation of Polyamide Layer on Poly(ethylene terephthalate) Film and its Application to Aromatic Nitro Compounds

Poly(ethylene terephthalate) film was used as supporter for preparation of polyamide layer. The most convenient method of preparation was described. This layer can be cut into any size and its sensitivity is higher than the glass plate supported layer. Twenty aromatic nitro compounds were used to show the behavior of polyester film based polyamide layer.     

Antihydrophobic solvent effects: an experimental probe for the hydrophobic contribution to enzyme-inhibitor binding

The hydrophobic component to the binding affinities of one acyclic phosphinate (4) and three macrocyclic phosphonamidate inhibitors (1-3) to the zinc peptidase thermolysin was probed by varying the solvent composition. Increasing the percentage of ethanol in the buffer solution over the range 0-9% increases the inhibition constants, K(i), by up to an order of magnitude. This approach represents an experimental method for distinguishing solvation from conformational or other effects on protein-ligand binding. The size of the "antihydrophobic effect" is correlated with the amount of hydrophobic surface area sequestered from solvent on association of the inhibitor and enzyme, although it is attenuated from that calculated from the surface tension of ethanol-water mixtures. The results are consistent with the Lum-Chandler-Weeks explanation for the size dependence of the hydrophobic effect.     

Determination of degree of conversion as a function of depth of a photo-initiated dental restoration composite—III application to commercial Prodigy Condensable™

In this third work, we evaluated the degree of conversion (DC) versus depth of dental filling composite named Prodigy Condensable™ using infrared spectroscopy. Confirming previous results, there was a gradual reduction of DC with increasing depth but the composite exhibited extreme values of DC, an upper value (45.9%) on the surface and a lower one (6.1%) at a depth of 5 mm. The composite presented the worst performance among materials studied. The composite formulation was 80% of inorganic fillers and BisfenolA/dimethacrylate (BisGMA) (18%)/triethyleneglycoldimethacrylate (TEGDMA) (2.0%) as monomers. As stated before, type/ratio/viscosity of monomers and type, amount, size and size distribution of fillers all together had an important role in the cure reaction contributing to the final performance of the composite.     

Liquid chromatography-diode array detection-electrospray ionisation mass spectrometry/nuclear magnetic resonance analyses of the anti-hyperglycemic flavonoid extract of Genista tenera. Structure elucidation of a flavonoid-C-glycoside

The anti-hyperglycemic flavonoid extract obtained from Genista tenera was first studied by liquid chromatography (LC)-diode array detection (DAD) which showed the presence of two major compounds. One of them was identified as genistein-7-O-glucoside. Luteolin-7-O-glucoside was detected as a minor constituent, while luteolin-7,3'-di-O-glucoside and rutin were found in trace amounts. LC-DAD-ESI-MS and NMR were used to confirm the structure of these compounds and allowed the elucidation of the structure of the unknown major compound, which is the flavonoid 5,7,4'-trihydroxyisoflavone-8-C-glucoside.     

A catalytic asymmetric method for the synthesis of gamma-unsaturated beta-amino acid derivatives

Catalytic enantioselective synthesis of beta-amino acid derivatives is an area of intense interest, due to the importance of these compounds as components in pharmaceutical agents and peptidomimetics. In this report, we present the first catalytic enantioselective method for the synthesis of gamma-unsaturated beta-amino acids and their corresponding 1,3-amino alcohol derivatives. This methodology takes advantage of a highly enantioselective vinylzinc addition to an aldehyde to set chirality. The resulting allylic alcohols are then transformed into the corresponding allylic amines via Overman's [3,3]-sigmatropic imidate rearrangement, and subsequent one-pot deprotection-oxidation of a pendant oxygen leads to the gamma-unsaturated beta-amino acid derivatives of high enantiopurity.     

Deorthogonalization of atomic originals in the CNDO approach

The procedure for deorthogonalization (D) of atomic orbitals in the semiempirical CNDO approach is reviewed. For comparative studies, CNDO/2, CNDO/2D, and STO -3G calculations of molecular dipole moments and Mulliken populations are carried out on 35 prototype molecules containing H, C, N, O, and F atoms. The calculated values are assessed on the basis of how well they agree with experimental trends, chemical bonding theories, and ab initio molecular orbital (MO) values. Results of analyses indicate that the CNDO/2D values for dipole moments are in reasonable agreement with experimental values, and those for net atomic charges and electron populations bear greater resemblance to the ab initio (STO -3G and 6-31G**) values than the original CNDO/2 values. These findings, together with those of previous investigators, demonstrate unequivocally the advantages of incorporating deorthogonalization into routine CNDO/2 or INDO calculations as a means to obtain reasonable estimates of charge distributions.     

Enhancement of phosphoprotein analysis using a fluorescent affinity tag and mass spectrometry

A fluorescent affinity tag (FAT) was synthesized and was utilized to selectively modify phosphorylated serine and threonine residues via beta-elimination and Michael addition chemistries in a 'one-step' reaction. This labeling technique was used for covalent modification of both phosphoproteins and phosphopeptides, allowing identification of these molecular species by fluorescence imaging after solution- or gel-based separation methods. In addition to the strong fluorescence of the rhodamine tag, a commercially available antibody can be used to enrich low-abundance post-labeled phosphopeptides present in complex mixtures. Application of this methodology to phosphorylation-site mapping has been evaluated for a phosphoprotein standard, bovine beta-casein. Initial results demonstrated low femtomole detection limits after fluorescence image analysis of FAT-labeled proteins or peptides.     

Understanding the role of stereoelectronic effects in determining collagen stability. 2. A quantum mechanical/molecular mechanical study of (Proline-Proline-Glycine)(n) polypeptides

The importance of vicinal and long-range interresidue effects in determining the stability of the collagen triple helix has been investigated by quantum mechanical (QM) and molecular mechanical (MM) computations on suitable model polypeptides, taking into account solvent effects by the polarizable continuum model (PCM). At the QM level, the PII conformation corresponds to an energy minimum for pentapeptide analogues incorporating the sequence Gly-Pro-Pro-Gly, irrespective of the down or up puckering of the pyrrolidine ring. However, our computations indicate that the alternation of down and up prolines characterizing collagen and collagen-like peptides is not due to an intrinsic preference of the Pro-Pro-Gly sequence. This result is confirmed by MM computations of longer polypeptides. Next, MM computations on model triple helices show that a better packing is obtained for specific values of backbone dihedrals, which, in turn, favor the alternation of down and up prolines along each chain.     

Rational Krylov methods for fractional diffusion problems on graphs

BIT Numerical Mathematics - In this paper we propose a method to compute the solution to the fractional diffusion equation on directed networks, which can be expressed in terms of the graph...