Optical Activity of Spin-Forbidden Electronic Transitions in Metal Complexes from Time-Dependent Density Functional Theory with Spin-Orbit Coupling

The calculation of magnetic transition dipole moments and rotatory strengths was implemented at the zeroth-order regular approximation (ZORA) two-component relativistic time-dependent density functional theory (TDDFT) level. The circular dichroism of the spin-forbidden ligand-field transitions of tris(ethylenediamine)cobalt(III) computed in this way agrees very well with available measurements. Phosphorescence dissymmetry factors and the corresponding lifetimes are evaluated for three N-heterocyclic-carbene-based iridium complexes, two of which contain helicene moieties, and for two platinahelicenes. The agreement with experimental data is satisfactory. The calculations reproduce the signs and order of magnitude of , and the large variations of phosphorescence lifetimes among the systems. The electron spin contribution to the magnetic transition dipole moment is shown to be important in all of the computations.     

Absolute configuration of C76 from optical rotatory dispersion.

The absolute configuration of C76 has been determined as (+)589-(fC)-C76 , for the first time, by comparing the experimental and predicted optical rotatory dispersion (ORD) patterns. The experimental ORD pattern was derived from the experimental electronic circular dichroism (ECD) spectrum using the Kramers-Kronig (KK) transform. The theoretical ORD spectra were calculated in the resonant region using linear response theory, and also using the KK transform of the theoretical ECD spectrum, at different theoretical levels, namely BHLYP/6-31G*, B3LYP/6-31G*, BLYP/6-31G*, and HF/6-31G*. Good agreement noted between experimental and predicted spectra allows for an unambiguous determination of the absolute configuration.     

SOME FURTHER CONSIDERATIONS ON THE USE OF REPAIR-DEFECTIVE ORGANISMS AS BIOLOGICAL DOSIMETERS FOR BROAD-BAND ULTRAVIOLET RADIATION SOURCES

Abstract— The extreme variation in biological effectiveness of the various components of solar ultraviolet radiation (solar UV) which reaches the earth's surface, especially photons of wavelengths between 295 and 330 nm, makes the dosimetry of solar UV a complex and, as yet, unresolved problem. A proper weighting of the various components of solar UV would permit expression of expsoure as a single parameter (dose). Weighting could compensate for the variations in composition of solar UV which might occur during exposure or the differences in sources of UV radiations; weighting would permit comparison of exposures at various locations on the earth and extrapolation of laboratory observations to field situations where wavelength composition might be rather different. Various radiation-sensitive microorganisms have been proposed as biological dosimeters. Biological dosimeters automatically weight the subcomponents of solar UV differently than a purely physical irradiance meter. We have examined the available evidence regarding the weighting which repair-defective mutants provide in comparison with response of a number of wild-type organisms and would caution investigators that, for broad-band UV sources, especially those with significant biological actions through the range of 300–330 nm, repair-sensitive mutants may improperly weight the components, leading to errors of dosimetry and thus to possible errors of interpretation of results of solar UV exposure of wild-type organisms     

Counterion dependent dye aggregates: nanorods and nanorings of tetra(p-carboxyphenyl)porphyrin

Atomic force microscopy (AFM) of porphyrin aggregates formed on silica from acidic aqueous solution is used to investigate the basis for the previously reported counterion dependence of the optical spectra of aggregates of H(2)TCPP(2+), the diacid form of tetra(p-carboxyphenyl)porphyrin (TCPP). Resonance light scattering confirms the presence of excitonically coupled porphyrin aggregates in solutions of H(2)TCPP(2+) in both aqueous HCl and HNO(3). Aggregates formed in aqueous HNO(3) solutions show resonance light scattering (RLS) at wavelengths within both the H and J aggregate absorption bands and are imaged on the surface of silica as nanorods about 3 to 4 nm in height. H(2)TCPP(2+) aggregates in aqueous HCl solution exhibit RLS when excited within the blue-shifted Soret band (H band) and produce AFM images on silica of ring-shaped structures ranging from about 200 to 2000 nm in diameter. Fluorescence excitation and emission spectra reveal quenching of the Q-band emission in the aggregates at a pH less than 1 and confirm the existence of a single species, assigned to a dimer, at a pH just above 1. The morphology of the nanostructures as revealed by AFM provides insight into the structural basis for the counterion-dependent optical properties of H(2)TCPP(2+) aggregates.     

Propriétés électriques des gels aqueux d'amphiphile

Summary This paper deals with the calculation of electrical conductivity in soap-water-systems. Two models are discussed and compared with experimental data.

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Zusammenfassung In der vorliegenden Arbeit werden zwei Modelle zur Berechnung der Leitf?higkeit in Seifen-Wasser-Mischungen beschrieben und mit experimentellen Daten verglichen.

     

Biotinyl-Glucose-6-Phosphate Dehydrogenase Preparation,Kinetics, and Modulation by Avidin

The kinetics of free glucose-6-phosphate dehydrogenase (G-6-PDH), biotinylated G-6-PDH, and biotinylated G-6-PDH complexed with avidin were investigated. The kinetics of the free enzyme were consistent with a sequential rather than a ping-pong mechanism. The kinetics of the biotinylated enzyme were similar to that of the free enzyme, but the kinetic constants were different; theK _m value for NADP was halved, whereas theK _m for G-6-P decreased only slightly. In the presence of avidin, theK _m of biotinylated G-6-PDH for G-6-P nearly doubled whereas theK _m for NADP did not change significantly. Avidin complexed with biotinylated G-6-PDH inhibited the enzyme from acting. Based upon these reactions, it was possible to devise assays for either free biotin or free avidin using biotinylated G-6-PDH as the indicator enzyme. Concentrations of biotin between 40 and 60 mg/mL, or of 25–95 Μg/mL of avidin could be measured within 2 min through the use of biotinylated G-6-PDH.     

PHOTOMOVEMENT, PIGMENTATION AND UV-B SENSITIVITY IN PLANARIA

Four differently pigmented species of planarians were examined for UV-B (Λ= 320 280 nm) tolerance and ability to delect and avoid UV-B-exposed areas. It was found that lighter-pigmented species are more UV sensitive and that movement out of the UV-B is directly related to UV sensitivity. Three species showed positioning preference corresponding to their pigmentation; the darker the species, the less avoidance of UV-B. The white (unpigmented) species showed exceptional and very sensitive behavior.