Measurements of electrical conductivity in solid bromine and iodine

Measurements of the electrical conductivity were performed with bromine and iodine in the liquid and the solid states, both containing low concentrations of the corresponding halide ions. In bromine the specific conductivity increases dramatically upon solidification and in iodine it changes only slightly. In both systems the conductivity in the solid is rather high, with remarkably low temperature coefficients, pointing to an unusual mechanism of conduction (of the Grotthuss type) requiring very little movement of the heavy nuclei while the charge is transferred. In mixtures of bromine with a small amount of nitrobenzene (NB) an equivalent conductivity as high as 12 cm² mol^?1 Ω^?1 was observed at ?25°C. In iodine the specific conductivity reached a value of about 0.01 Ω^?1 cm^?1 at 100°C. The energy of activation for conduction in bromine down to ?40°C was found to be about 23 kJ mol^?1, increasing sharply below this temperature. In iodine, values of about 21–27 kJ mol^?1 were observed over the whole temperature range measured.     

Dual Fluorescence and Photoprototropic Characteristics of 2-Aminodiphenylsulphone-β-Cyclodextrin Inclusion Complex

The absorption and fluorescence spectral characteristics of 2-aminodiphenylsulphone (2ADPS) have been investigated in the presence of β-cyclodextrin (β-CDx) in water. Dual emission is observed upon the complexation of 2ADPS in β-CDx. The stoichiometry of the host:guest inclusion complex is found to be 2:1. Steady state and time-resolved fluorescence spectral analysis support the formation of 2:1 complex between β-CDx and 2ADPS. The large enhancement in fluorescence intensity of twisted intramolecular charge transfer (TICT) band in aqueous β-CDx solution is due to the decrease in non-radiative processes. The ground and the excited state pK_a values for the monocation-neutral equilibrium of 2ADPS in β-CDx are found to be different from the pK_a values in aqueous solution. In the presence of β-CDx, 2ADPS is found to be less basic in the ground and the excited states.     

Coordination-based gold nanoparticle layers

Gold nanoparticle (NP) mono- and multilayers were constructed on gold surfaces using coordination chemistry. Hydrophilic Au NPs (6.4 nm average core diameter), capped with a monolayer of 6-mercaptohexanol, were modified by partial substitution of bishydroxamic acid disulfide ligand molecules into their capping layer. A monolayer of the ligand-modified Au NPs was assembled via coordination with Zr4+ ions onto a semitransparent Au substrate (15 nm Au, evaporated on silanized glass and annealed) precoated with a self-assembled monolayer of the bishydroxamate disulfide ligand. Layer-by-layer construction of NP multilayers was achieved by alternate binding of Zr4+ ions and ligand-modified NPs onto the first NP layer. Characterization by atomic force microscopy (AFM), ellipsometry, wettability, transmission UV-vis spectroscopy, and cross-sectional transmission electron microscopy showed regular growth of NP layers, with a similar NP density in successive layers and gradually increased roughness. The use of coordination chemistry enables convenient step-by-step assembly of different ligand-possessing components to obtain elaborate structures. This is demonstrated by introducing nanometer-scale vertical spacing between a NP layer and the gold surface, using a coordination-based organic multilayer. Electrical characterization of the NP films was carried out using conductive AFM, emphasizing the barrier properties of the organic spacer multilayer. The results exhibit the potential of coordination self-assembly in achieving highly controlled composite nanostructures comprising molecules, NPs, and other ligand-derivatized components.     

Iron(III) and iron(IV) corroles: synthesis,spectroscopy, structures,and no indications for corrole radicals

A delicate control of reaction conditions allows the isolation of several distinctively different iron complexes of tris(pentafluorophenyl)- and tris(2,6-dichlorophenyl)corrole. As long as coordinating ligands are present, the iron(III) complexes are stable in solution. Otherwise they are aerobically oxidized to either mononuclear chloroiron(IV) or dinuclear (mu-oxo)iron(IV) complexes, in acidic and basic solutions, respectively (the latter holds only for tris(pentafluorophenyl)corrole). When treated with NaNO(2), the mononuclear chloroiron(IV) corroles are efficiently converted into diamagnetic iron nitrosyl complexes. The low- and intermediate-spin iron(III), iron nitrosyl, and chloroiron(IV) corroles were fully characterized by a combination of spectroscopic methods and X-ray crystallography. There was no indication for an open-shell corrole in any of the complexes.     

syn,Anti isomerization of 5,5′-Bis-5H-dibenzo[a,d]cyclohepten-5-ylidene

syn-5,5-Bis-5H-dibenzo[a,d]cyclohepten-5-ylidene (2syn), an overcrowded bistricyclic aromatic ene with central seven-membered rings, undergoes a thermal isomerization to the anti stereoisomer (2anti) at elevated temperatures, with G _inv (174°C)=36.4 kcal/mole. The high-energy barrier for syn anti isomerization of2 is compared with the corresponding inversion barrier of 5H-dibenzo[a,d]cycloheptene derivatives and interpreted in terms of a lower degree of overcrowding in2 relative to bistricyclic enes (1) with central five- and six-membered rings. The overcrowding features of2syn,2anti, and theiranti-10,11,10,11-tetrahydro derivative (3) is analyzed, and a mechanism for the syn anti isomerization of 2 is proposed.     

High-temperature analyticity in classical lattice systems

We prove analyticity of the correlation functions for classical lattice systems, including continuous-spin systems, at high temperatures and in strong external fields. For systems whose configuration spaces are homogeneous spaces for compact groups (e.g. Ising, plane rotator and classical Heisenberg models), improved estimates on the region of analyticity are obtained by generalizing an integral equation of Gruber and Merlini. Exponential cluster properties are also obtained for such systems with a finite-range interaction.     

Generic triviality of phase diagrams in spaces of long-range interactions

We show that interactions with multiple translation-invariant equilibrium states form a very thin set in spaces of long-range interactions of classical or quantum lattice systems. For example, generic finite-dimensional subspaces do not intersect this set. This constitutes a severe violation of the Gibbs Phase Rule.Research supported by NSERC grant A-4015     

TRANSITORY UV RESISTANCE DURING GERMINATION OF UV-SENSITIVE SPORES PRODUCED BY A MUTANT OF Bacillus cereus 569

Abstract— A mutant of Bacillus cereus 569, isolated by us and designated 2422 is unable to excise cyclobutane-type dimers and spore-specific photoproducts from the DNA of UV-irradiated vegetative cells and dormant spores. The deficiency in the excision repair mechanism was found to be at the post-incision step in the exonuclease-mediated removal of the photoproducts. During germination, the mutant B. cereus 2422 exhibits UV-resistance and an efficient photoproduct removal which is followed by DNA repair synthesis. The data presented indicate the existence of germinative excision repair in B. cereus 569.