Non-linear density dependence of rotational line-broadening of HCl in dense argon

The rotational far-infrared spectra of HCl in argon at densities between 100 and 480 amagat and T = 162.5 K are presented. The observed density dependence of the width of the different rotational lines is non-linear and differs for high- and low-frequency lines. An Enskog correction to the collision frequency in the dense gas fails to account for the density dependence of the high rotational lines. It is argued that the many-body character of the relaxation mechanism should be taken into account. Comparison with the results of MD calculations on argon indicates that such an approach may explain the observed density dependence.     

Excitation energies of pi-conjugated oligomers within time-dependent current-density-functional theory

We study the pi*<--pi singlet excitations of the pi-conjugated oligomers of polyacetylene, polydiacetylene, polybutatriene, polythiophene, poly(para-phenylene vinylene), and the lowest singlet excitations of the hydrogen chain. For this we used time-dependent current-density-functional theory within the Vignale-Kohn and adiabatic local density approximations. By studying the dependence of the excitation spectrum on the chain length we conclude that the reduction of the static polarizability when using the Vignale-Kohn functional has two origins. First, the excitation energies of transitions with a large transition dipole are shifted upward. Second, the character of the transition between the lowest occupied and highest unoccupied molecular orbitals and the oscillator strength of the lowest transition within the adiabatic local density approximation is transferred to higher transitions. The lowest transitions that have a considerable oscillator strength obtained with the Vignale-Kohn functional have excitation energies that are in most cases in better agreement with available reference data than the adiabatic local density approximation.     

Miscibility of small colloidal spheres with large polymers in good solvent

Nearly athermal colloid-polymer mixtures were studied in the "protein limit." A fluid-fluid transition was observed in mixtures of stearyl-alcohol-coated silica particles and large polystyrene coils in toluene. The ratios of the polymer radius of gyration to the particle radii were q=4.1 and q=5.2. The binodal curves and the critical points were determined. Turbidity measurements and analysis for one set of particles allowed the systems to be mapped onto hard sphere-polymer mixtures. A comparison with recent predictions for the miscibility of model mixtures shows that the experimental binodals lie between the two extreme results for ideal and interacting polymers. The critical colloid volume fraction is also found to decrease with increasing size ratios.     

Microstructural investigation of monoglyceride-water coagel systems by NMR and CryoSEM

Monoglyceride coagels consist of a network of plate-like crystals and are formed from a swollen gel state (alpha-gel). In order to resolve the transition mechanism, coagels were prepared with monoglycerides that differ in fatty acid composition (monomyristate and palmitate/stearate, respectively). Rheology provided information on kinetics of coagel formation and the strength of the resulting crystal network. From NMR measurements, the surface-to-volume ratio, tortuosity, and dimensionality of the network were obtained. These findings were in line with qualitative and quantitative structural information obtained from CryoSEM. As a model for the behaviour of non-monoglyceride species, the dynamics of (perdeuterated) palmitic acid was monitored in both alpha-gels and coagels. The experimental data support a two-stage mechanism. In the first stage, two-dimensional separation of D- and L-isomers in the monoglyceride bilayers of the alpha-gel occurs. This process depends primarily on lateral diffusion rate of the monoglycerides. Palmitic acid can be accommodated in the alpha-gel bilayer, but in the coagels it is separated into relative mobile and mechanically weak junction zones between the crystal plates. In the second stage of coagel formation, the crystal plates also grow in the third dimension. Both monoglyceride type and concentration determine the kinetics of this process.     

Synthesis and Conformational Behavior of Rhodium(I) Metallohosts Derived from Diphenylglycoluril

The design and synthesis of molecules containing both a substrate-binding cavity and a nearby catalytically active metal center is a useful approach to the development of synthetic systems that function according to the principles of enzymes. To this end the receptor molecule 2a, derived from diphenylglycoluril, was functionalized with triaryl phosphite ligands to give the receptor ligand 2d. Exchange reactions of 2d with (diketonate)Rh(CO)(2), (diketone = acetylacetone, dibenzoylmethane, or dipivaloylmethane) led to the formation of the metallohosts 3a-c, respectively. The properties and conformational behavior of these metal complexes were studied by NMR techniques. Reaction of compounds 3 with H(2) in the presence of a small excess of additional triphenyl phosphite yields the rhodium(I) hydride complex 5. The metallohosts are capable of binding dihydroxybenzene guests in their cavities by hydrogen bonding and pi-pi stacking interactions. On binding a substrate the conformational behavior of hosts 3a-c was affected considerably.     

The solid state and solution chemistry of dichlorobis(α-picoline)-cobalt(II)

Summary The thermal decomposition of [CoCl₂(-pic)₂] was investigated over the 108°C to 222°C range and the Intennediates CoCl₂(-pic) (s) and CoCl₂ (s) were observed, with the evolution of (-pic) (g). Quantitative thermodynamic and kinetic data were obtained by performing dynamic and isothermal studies on the complex Additional thermodynamic data were obtained by studying the CoCl₂/-pic system in acetone. The effect of the methylsubstituent on the metal-donor-N bond as well as on the thermodynamic quantities were discussed.     

S-4-methylphenyl-o,o-bis[1-benzotriazolyl] phosphorothioate: a versatile phosphorylating agent

The phosphorylating agent obtained by treatment of S-4-methylphenyl phosphorodichloridothioate with 1-hydroxybenzotriazole can not only be applied for the introduction of polyphosphate functions at the terminal ends of nucleic acids, but also for the formation of 3′-5′-phosphotriester linkages.     

PROFLAVINE MEDIATED PHOTOINACTIVATION OFBACTERIOPHAGE φX174 AND ITS ISOLATED DNA: EFFECTS OF AGENTS MODIFYING VARIOUS PHOTOCHEMICAL PATHWAYS

Abstract. Thiols and disulfides protect both φX174 phage and its isolated DNA from the lethal action of proflavine plus light. The protective ability of these compounds appears to be attributed to the -SH or the -S-S- group and the property to interact with the proflavine-phage DNA complex. The phage inactivation efficiency per proflavine bound to DNA is reduced by 50 to 30% upon addition of cysteine or cystamine. Substances that affect the lifetime of singlet oxygen modify the rate of phage photoinactivation in the presence of proflavine; the inactivation rate is decreased by N^-₃ and increased by D₂O. Irradiation under N₂ atmosphere markedly decreases the phage photosensitization by proflavine. Irradiation with monochromatic light of 440 nm is less efficient than irradiation with light of 440 nm plus 360 nm, and the difference is more pronounced in N₂ than in air. These results are discussed in relation to various possible photochemical pathways.     

Tuning of the alpha-terthiophene radical cation coupling reaction using mixed micelles with varying charge density.

The photophysics and photochemistry of alpha-terthiophene (alphaT), compartmentalized in mixed nonionic/anionic micelles, have been investigated with focus on the influence of the micellar surface charge density on the formation of the radical coupling product alpha-hexathiophene (alphaH). By varying the ratio of nonionic-to-anionic surfactants, and assuming ideal mixing, the charge density of the mixed micelles was varied. From Poisson-Boltzmann calculations, performed using the cell model, the electrostatic potential and the counterion activity were estimated as a function of the distance from the micellar surface. Upon excitation, the triplet state of alphaT is formed, from which the alphaT radical cation can be formed by absorption of a second photon. The radical cation can form alphaH if it encounters another alphaT radical cation. Under the experimental conditions used, this implies that the alphaH formation only occurs if the compartmentalized radical cation is able to migrate from its host micelle to another micelle, either via the surrounding bulk or by fusion of two micelles followed by mixing of their contents before micellar fission. The formation yield of the radical cation depends on the charge density of the mixed micelle; a lower charge density, that is, an increased amount of nonionic surfactant, lowers the yield. The yield of the coupling product alphaH, however, does not follow the same trend. A maximum yield of alphaH is found at intermediate nonionic surfactant molar ratios. This behavior is understood in terms of the Poisson-Boltzmann simulation results and by comparing charge-density changes as a function of molar fraction with the changes in counterion activity. The alphaH yield is a result of the balance between an increased possibility of radical cation bulk migration and a lowered electrostatic stabilization of the radical.