Method of immobilization of carboxymethyl-dextran affects resistance to tissue and cell colonization

Coatings from carboxymethylated dextrans (CMDs) were fabricated, analyzed by XPS, and investigated for their ability to inhibit corneal epithelial tissue outgrowth and bovine corneal epithelial cell attachment and growth. CMDs with differing degrees of carboxymethyl substitution and various molecular weights were synthesized by the solution reaction of dextrans with bromoacetic acid under different reactant ratios. The CMD compounds thus obtained were attached onto aminated surfaces produced in two ways: by the plasma deposition of a coating from n-heptylamine vapour, and by the plasma deposition of an acetaldehyde coating onto whose surface aldehyde groups the polyamine compounds polylysine, polyethyleneimine and polyallylamine were immobilized to provide platforms for CMD immobilization. XPS spectra showed that the latter route produced thicker coatings than the former approach. CMD molecules attached directly onto the plasma-fabricated amine surface supported some tissue migration; the extent of carboxymethyl substitution and the molecular weight of the CMDs had little influence. For CMDs immobilized via polyamine spacers, on the other hand, tissue outgrowth was completely inhibited, and again there were no discernible effects from the extent of carboxymethyl substitution and the molecular weight of the CMDs. In assays involving cell attachment and growth, analogous observations were found. Thus, the mode of immobilization of these polysaccharide coatings is the dominant factor in their anti-fouling performance, suggesting that optimization of the architecture of polysaccharide coatings may be an important factor for maximizing their cell-repellent abilities.     

Surface tension of quantum fluids from molecular simulations

We present the first molecular simulations of the vapor-liquid surface tension of quantum liquids. The path integral formalism of Feynman was used to account for the quantum mechanical behavior of both the liquid and the vapor. A replica-data parallel algorithm was implemented to achieve good parallel performance of the simulation code on at least 32 processors. We have computed the surface tension and the vapor-liquid phase diagram of pure hydrogen over the temperature range 18-30 K and pure deuterium from 19 to 34 K. The simulation results for surface tension and vapor-liquid orthobaric densities are in very good agreement with experimental data. We have computed the interfacial properties of hydrogen-deuterium mixtures over the entire concentration range at 20.4 and 24 K. The calculated equilibrium compositions of the mixtures are in excellent agreement with experimental data. The computed mixture surface tension shows negative deviations from ideal solution behavior, in agreement with experimental data and predictions from Prigogine's theory. The magnitude of the deviations at 20.4 K are substantially larger from simulations and from theory than from experiments. We conclude that the experimentally measured mixture surface tension values are systematically too high. Analysis of the concentration profiles in the interfacial region shows that the nonideal behavior can be described entirely by segregation of H(2) to the interface, indicating that H(2) acts as a surfactant in H(2)-D(2) mixtures.     

A comparison of SCF-Xα and extended Hückel methods for metal clusters

A comparison of some results from Xα-scattered wave (Xα-SW) and extended Hückel (EH) calculations for metal clusters is given. It is found that small clusters of atoms (≈ 13 atoms) using the Xα-SW method reproduce many of the features of the electronic structure of the bulk metals, whereas this is not the case for the same clusters using the EH method. A more systematic approach to EH parametrizations is suggested in order to make this method a more viable approach to treating metal clusters.     

A new protecting group for the exocyclic amino groups of nucleosides

A new protecting group has been developed for the exocyclic amino groups of nucleosides that occur in DNA. 3-Phenyl-[{N-(2-trimethylsilyl-ethoxycarbonyl)-2-amino}]-propanoic acid used as the protective agent.     

A post-Hartree-Fock model of intermolecular interactions

Intermolecular interactions are of great importance in chemistry but are difficult to model accurately with computational methods. In particular, Hartree-Fock and standard density-functional approximations do not include the physics necessary to properly describe dispersion. These methods are sometimes corrected to account for dispersion by adding a pairwise C6R6 term, with C6 dispersion coefficients dependent on the atoms involved. We present a post-Hartree-Fock model in which C6 coefficients are generated by the instantaneous dipole moment of the exchange hole. This model relies on occupied orbitals only, and involves only one, universal, empirical parameter to limit the dispersion energy at small interatomic separations. The model is extensively tested on isotropic C6 coefficients of 178 intermolecular pairs. It is also applied to the calculation of the geometries and binding energies of 20 intermolecular complexes involving dispersion, dipole-induced dipole, dipole-dipole, and hydrogen-bonding interactions, with remarkably good results.     

Syntheses and configurations of some heterocyclic amidoximes. X-Ray crystal structure of 3-phenyl-5,6-dihydro-2(1H)-pyrazinone-O-methyloxime

O-Methyl-α-ketophenylacetohydroximoyl chloride ( 1 ) was prepared by the reaction of O-methyl-α-methoxyphenylacetohydroximoyl chloride ( 5 ) with N-bromosuccinimide and concentrated hydrobromic acid. Reaction of 1 with ethylenediamine gave 3-phenyl-5,6-dihydro-2(1H)-pyrazinone-O-methyloxime ( 6 ). 3-Phenyl-5,6-cyclohexano-5,6-dihydro-2(1H)-pyrazininone-O-methyloxime ( 7 ) was prepared by reaction of 1 with trans-1,2-diaminocyclohexane. The X-ray structure of 6 has been determined. The crystals are orthorhombic, space group Pbca with a = 10.264(3), b = 18.262(4), c = 23.530(4)Å, V = 4411(2)ų, and Z = 16. The structure, which was refined to R = 0.038 using 1652 observed reflections, shows the amidoxime moiety to be the Z configuration. Reaction of benzohydroximoyl chloride with aziridine gave (Z)-aziridinylbenzaldoxime ( 16a ). Ultraviolet irradiation of a benzene solution of 16a gave a mixture of the Z and E isomers 16a and 16b . The E isomer 16b underwent thermal isomerization to 16a at 100°. Reaction of 16a with dimethyl sulfate in sodium hydroxide solution gave (Z)-O-methylaziridinylbenzaldoxime ( 17a ). Photoisomerization of a hexane solution of 17a gave a mixture of the Z and E isomers 17a and 17b which were separated by preparative glc. The isomers 17a and 17b are resistant to thermal Z = E isomerization. The mechanisms of thermal isomerization of benzamidoximes are discussed.     

Reduction of nitric oxide,nitrous acid and nitrogen dioxide at platinum electrodes in acidic solutions: Review and new voltammetric results

The literature concerning the chemical and electrochemical reactions of nitric oxide, nitrous acid and nitrogen dioxide in aqueous solutions is reviewed briefly, with emphasis on electrochemical reductions at platinum electrodes in acidic solutions. The voltammetric behavior of NO and NO₂ at a Pt electrode in perchloric acid is virtually identical to that for HNO₂ and this is explained on the basis of a common electroactive precursor concluded to be NO⁺. Three cathodic waves are obtained for acidic solutions of NO, HNO₂ and NO₂. The first two waves correspond to reduction of NO⁺ to NO and N₂O₃ to NO, respectively. The presence of N₂O₃ results from decomposition of the parent compounds. The presence of Br^- or Cl^- in acidic solutions of the title compounds promotes the voltammetric reductions at lower H⁺ concentrations. This probably results from formation of electroactive nitrosyl halides.     

Advantages to Conversion of Lattice Heat Capacity to Cv in the Resolution of Excess Properties The Ln2S3's as an example

This paper represents a fitting (modeling) of the temperature dependence of the Komada-Westrum characteristic temperature for those γ-, δ- and ε-phase lanthanide sesquisulfides for which the total heat capacities, including internal degrees of freedom (e.g., Schottky and magnetic contributions), were connected to the residue of only lattice vibrations yielding lattice heat-capacity contributions. These characteristic temperatures (θ_KW) at 298.15 K are seen to behave smoothly (nearly linearly) as a function of (cationic) atomic number within the region of stability of each phase as does the density. The trends between the phases also show some consistency but not predictability of one from the other. This revised version was published online in July 2006 with corrections to the Cover Date.     

Synthesis of mixed metal decaosmium carbido clusters: The X-ray structures of the monoanions [Os10C(CO)24Cu(NCMe)]− and [Os10C(CO)24AuPPh3]−

The high nuclearity mixed metal cluster monoanions [Os₁₀C(CO)₂₄Cu(NCMe)]^? (I) and [Os₁₀C(CO)₂₄AuPPh₃]^? (II) have been obtained by reaction of the carbido-dianion [Os₁₀C(CO)₂₄]^2? (III) with one equivalent of [Cu(NCMe)₄] [BF₄] and Ph₃PAuCl, respectively, in CH₂Cl₂. X-ray analysis of the [PPh₃Me]⁺ salts of I and II show that the Cu and Au ligands have added to capping tetrahedra of the dianion III in μ₃- and μ₂-bridging positions, respectively.