Kinetics and mechanism of H+(aq)-assisted aquation of [Cr(N3)(S-pdtra)]− and [Cr(N3(edtrp)]−ions

Two new complex anions, [Cr(N3)(S-pdtra)]– and [Cr(N3)(edtrp)]–, were obtained in solution by N3–/HN3 anation of the aqua analogues (S-pdtra = S-propane-1,2-diamine-N,N,N-triacetate, edtrp = ethylenediamine-N,N,N-tripropionate). Aquation of these species in acidic media leads to the same geometrical isomers as those used for the synthesis. The aquation rate is strongly dependent upon [H] and is substantially higher in D2O than in H2O. Protonation of the coordinated azide was not observed spectrophotometrically. The rate law and activation parameters have been determined and discussed.     

Kinetics and mechanism of aquation of [Cr(NCS)(edtrp)]-, [Cr(NCS)(R-pdtrp)]-, [Cr(edtrp)(NCSHg)]+ and [Cr(R-pdtrp) (NCSHg)]+ complexes. Unexpected rate retardation in strongly acidic media for NCS- ligand release

Three new complex ions, [Cr(NCS)(R-pdtrp)]^-, [Cr(R-pdtrp)(NCSHg)]⁺ and [Cr(edtrp)(NCSHg)]⁺, that are derivatives of the trans-equatorial isomers of [Cr(R-pdtrp)(H₂O)]⁰ and [Cr(edtrp)(H₂O)]⁰ (edtrp= ethylenediamine-N,N,N-tripropionate, R-pdtrp= R-propane-1,2-diamine-N,N,N-tripropionate) have been obtained and characterized in solution. Rate constants and activation parameters, including, in two cases, volumes of activation, have been determined. Rate retardation for NCS^- ligand release has been observed with increasing acidity within the pH 0–2 range. The mechanism of the reactions has been discussed.     

Comparison of modifiers for determination of arsenic, antimony and selenium by atomic absorption spectrometry with atomization in graphite tube or hydride generation and in-situ preconcentration in graphite tube

The study was performed to compare the effect of magnesium modifier (magnesium nitrate) with that of other modifiers (palladium nitrate and nickel nitrate) in determination of arsenic, antimony and selenium by atomic absorption spectroscopy with atomization in a graphite tube, with generation of hydrides and in situ preconcentration in a graphite tube. The assumed criterion of a modifier performance was the magnitude of the analytical signal. It was found that in determinations with atomization in a graphite furnace the effects of all these modifiers were comparable, while in those with hydride generation and in situ preconcentration in a graphite tube the magnesium modifier showed poorer performance (25% decrease of the analytical signal). In determinations of arsenic and selenium the analytical signal obtained with magnesium salt as a modifier was comparable with those obtained in the presence of all other modifiers.     

Comparative Action Spectrum for Ultraviolet Light Killing of Mouse Melanocytes from Different Genetic Coat Color Backgrounds

The photobiology of mouse melanocyte lines with different pigment genotypes was studied by measuring colony-forming ability after irradiation. The cell lines were wild-type black (melan-a) and the mutants brown (melan-b) and albino (melan-c). Four lamps emitting various UV wavelengths were used. These were germicidal (UVC, 200–280 Dm), 82.3% output at 254 nm, TL01 (UVB, 280–320 nm), 64.2% at 310–311 nm, FS20, broadband with peak output at 312 nm and Alisun-S (UVA, 320–400 nm), broadband with peak output at 350–354 nm. Appropriate filtration reduced the contaminating UVC to nonlethal levels for the longer waverange lamps. Wild-type melan-a was resistant to UVC and UVA compared to the other two cell lines, but the differences were small. The melan-c cell line was more resistant to UVB and markedly more resistant to FS20 than the pigmented lines. With the exception of FS20 responses, melan-b was more sensitive than melan-a to killing by the various UV lamps. There were more pyrimidine dimers (cyclobutane dimers and 6–4 photoproducts) produced in melan-a than in melan-c cells by UVC, UVB and FS20 lamps. Unlike melan-c, melan-a and melan-b showed a strong free radical signal of melanin character with a detectable contribution of pheomelanin-like centers. The contribution of pheome-lanin was higher in melan-b than in melan-a, while the total melanin content in these two cell lines was comparable. The abundant melanin granules of wild-type melan-a melanocytes were well melanized and ellipsoidal, whereas those of melan-b melanocytes tended to be spherical. In the albino line (melan-c) the melanocytes contained only early-stage melanosomes, all of which were devoid of melanin. The results indicate that pigment does not protect against direct effect DNA damage in the form of pyrimidine dimers nor does it necessarily protect against cell death. High pigment content is not very protective against killing by UVC and UVA, and it may photosensitize in UVB the very wavelength range that is of greatest concern with respect to the rising incidence in skin cancer, especially melanoma. It is clear from these studies that, in pigment cells, monochromatic results cannot predict polychromatic responses and that cell death from solar irradiations is a complex phenomenon that depends on more than DNA damage.     

Multipoint laser Doppler vibrometry using holographic optical elements and a CMOS digital camera

A laser Doppler vibrometer (LDV) is described in which holographic optical elements are used to provide the interferometer reference and object illumination beams. A complementary metal-oxide semiconductor camera, incorporating a digital signal processor, is used to carry out real-time signal processing of the interferometer output to allow multipoint LDV to be implemented.     

Soluble Flavanthrone Derivatives: Synthesis,Characterization, and Application to Organic Light‐Emitting Diodes

Simple modification of benzo[h]benz[5,6]acridino[2,1,9,8‐klmna]acridine‐8,16‐dione, an old and almost‐forgotten vat dye, by reduction of its carbonyl groups and subsequent O‐alkylation, yields solution‐processable, electroactive, conjugated compounds of the periazaacene type, suitable for the use in organic electronics. Their electrochemically determined ionization potential and electron affinity of about 5.2 and ?3.2 eV, respectively, are essentially independent of the length of the alkoxyl substituent and in good agreement with DFT calculations. The crystal structure of 8,16‐dioctyloxybenzo[h]benz[5,6]acridino[2,1,9,8‐klmna]acridine ( FC‐8 ), the most promising compound, was solved. It crystallizes in space group P and forms π‐stacked columns held together in the 3D structure by dispersion forces, mainly between interdigitated alkyl chains. Molecules of FC‐8 have a strong tendency to self‐organize in monolayers deposited on a highly oriented pyrolytic graphite surface, as observed by STM. 8,16‐Dialkoxybenzo[h]benz[5,6]acridino[2,1,9,8‐klmna]acridines are highly luminescent, and all have photoluminescence quantum yields of about 80 %. They show efficient electroluminescence, and can be used as guest molecules with a 4,4′‐bis(N‐carbazolyl)‐1,1′‐biphenyl host in guest/host‐type organic light‐emitting diodes. The best fabricated diodes showed a luminance of about 1900 cd m^?12, a luminance efficiency of about 3 cd A^?1, and external quantum efficiencies exceeding 0.9 %.     

Crystal structure and mesogenic behaviour of a new fluorene derivative: 9,9‐dimethyl‐2,7‐bis(4‐pentylphenyl)‐9H‐fluorene

The title compound, C₃₇H₄₂, is a new mesogenic compound containing the fluorene moiety. It exhibits enantiotropic nematic liquid crystalline behaviour with melting at 125 °C and isotropization at 175 °C. The crystallographically independent unit contains two molecules oriented face‐to‐edge with respect to each other. The two molecules have nearly the same conformation of the bis‐phenyl fluorene moiety. The molecular packing in the crystal phase is nematic‐like.