CORRELATION OF UVC AND UVB CYTOTOXICITY WITH THE INDUCTION OF SPECIFIC PHOTOPRODUCTS IN T-LYMPHOCYTES AND FIBROBLASTS FROM NORMAL HUMAN DONORS

Abstract— By using specific monoclonal antibodies in situ and a computer-assisted image analysis system we have determined the relative induction of cyclobutane dimers, (6–4) photoproducts and Dewar isomers in human mononuclear cells and fibroblasts following irradiation with UVC, broad-spectrum UVB and narrow-spectrum UVB. The lamps produced these lesions in different proportions, with broad-spectrum UVB inducing a greater combined yield of (6–4) photoproducts and Dewar isomers per cyclobutane dimer than UVC or narrow-spectrum UVB. The relative induction ratios of (6–4) photoproducts compared to cyclobutane dimers were 0.15, 0.21 and 0.10 following irradiation with UVC, broad- or narrow-spectrum UVB, respectively. Although Dewar isomers were induced by UVC, their relative rate of formation compared to cyclobutane dimers was significantly greater after irradiation with either broad-spectrum or narrow-spectrum UVB. These values were 0.001, 0.07 and 0.07, respectively. With each lamp source, we have determined the survival of normal human T-lymphocytes and fibroblasts at fiuences, which induce equivalent yields of cyclobutane dimers, (6–4) photoproducts or (6–4) photoproducts plus Dewar isomers. Killing of fibroblasts appears to be associated with (6–4) photoproduct formation, whereas killing of T-lymphocytes seems to be mediated by combined (6–4) plus Dewar yields. These results emphasize the need to study the biological effects of UVB because cellular responses may be different from those following UVC irradiation.     

Melting points and enthalpies of fusion of anthracene and its heteroatomic counterparts

Anthracene is a common byproduct of incomplete combustion of fossil fuels and other anthropogenic sources. Its heteroatomic counterparts, including 9-bromoanthracene, 1,5-dibromoanthracene, 9,10-dibromoanthracene, 2-chloroanthracene, 9,10-dichloroanthracene, 9-anthraldehyde, 2-anthracenecarboxylic acid, 9-anthracenecarboxylic acid, and anthraquinone, are formed through various mechanistic pathways during the combustion process. We use a differential scanning calorimeter to measure the melting points and enthalpies of fusion of these compounds. As expected, we find no correlation between molecular mass and melting point and enthalpy of fusion—rather the type, number and position of the heteroatoms substituted on the parent molecule all influence its fusion thermodynamics. A wide range of melting points is noted for the same substituents(s) at different carbon positions. This suggests that intermolecular forces, such as hydrogen bonding and steric repulsion, are significantly impacted by the position of the substituents on the linear anthracene parent molecular. In addition, different substituents at the same position further suggest that the electronegativity/polarity of a given atom strongly influences the observed fusion behavior.     

Robust partial least squares regression—part III,outlier analysis and application studies

This paper is the third part of the work on robust partial least squares (RPLS) regression. The paper focuses on implementation issues for outlier detection and diagnosis. Furthermore, the paper introduces a numerically more efficient algorithm for determining the Stahel–Donoho estimator (SDE). This has been identified as a potential drawback of the new proposed RPLS algorithm, detailed in Part II of this work. Finally, a total of three application studies are presented which involve data recorded from (i) a calibration experiment (similar number of variables/observations), (ii) a distillation process for purifying benzene (considerably more observations than variables) and (iii) an experiment of a multi‐component concentration determination using Raman spectroscopy (considerably more variables than observations). Copyright © 2008 John Wiley & Sons, Ltd.     

Photocrosslinking of G‐Quadruplex‐Forming Sequences found in Human Promoters

While is it well known that human telomeric DNA sequences can adopt G‐quadruplex structures, some promoters sequences have also been found to form G‐quadruplexes, and over 40% of promoters contain putative G‐quadruplex‐forming sequences. Because UV light has been shown to crosslink human telomeric G‐quadruplexes by cyclobutane pyrimidine dimer (CPD) formation between T's on adjacent loops, UV light might also be able to photocrosslink G‐quadruplexes in promoters. To investigate this possibility, 15 potentially UV‐crosslinkable G‐quadruplex‐forming sequences found in a search of human DNA promoters were UVB irradiated in vitro, and three were confirmed to have formed nonadjacent CPDs by mass spectrometry. In addition to nonadjacent T=T CPDs found in human telomeric DNA, a nonadjacent T=U CPD was discovered that presumably arose from deamination of a nonadjacent T=C CPD. Analysis of the three sequences by circular dichroism, melting temperature analysis and chemical footprinting confirmed the presence of G‐quadruplexes that could explain the formation of the nonadjacent CPDs. The formation of nonadjacent CPDs from the sequences in vitro suggests that they might be useful probes for the presence of non‐B DNA structures, such as G‐quadruplexes, in vivo, and if they were to form in vivo, might also have significant biological consequences.     

Size-dependent phase transformation kinetics in nanocrystalline ZnS

Nanocrystalline ZnS was coarsened under hydrothermal conditions to investigate the effect of particle size on phase transformation kinetics. Although bulk wurtzite is metastable relative to sphalerite below 1020 degrees C at low pressure, sphalerite transforms to wurtzite at 225 degrees C in the hydrothermal experiments. This indicates that nanocrystalline wurtzite is stable at low temperature. High-resolution transmission electron microscope data indicate there are no pure wurtzite particles in the coarsened samples and that wurtzite only grows on the surface of coarsened sphalerite particles. Crystal growth of wurtzite stops when the diameter of the sphalerite-wurtzite interface reaches approximately 22 nm. We infer that crystal growth of wurtzite is kinetically controlled by the radius of the sphalerite-wurtzite interface. A new phase transformation kinetic model based on collective movement of atoms across the interface is developed to explain the experimental results.     

Molecular chemistry of consequence to renewable energy

Energy conversion cycles are aimed at driving unfavorable, small-molecule activation reactions with a photon harnessed directly by a transition-metal catalyst or indirectly by a transition-metal catalyst at the surface of a photovoltaic cell. The construction of such cycles confronts daunting challenges because they rely on chemical transformations not understood at the most basic levels. These transformations include multielectron transfer, proton-coupled electron transfer, and bond-breaking and -making reactions of energy-poor substrates. We have begun to explore these poorly understood areas of molecular science with transition-metal complexes that promote hydrogen production and oxygen bond-breaking and -making chemistry of consequence to water splitting.     

Palladium-catalyzed asymmetric phosphination: enantioselective synthesis of a p-chirogenic phosphine

The racemic secondary phosphine PH(Me)(Is) (1, Is = 2,4,6-(i-Pr)3C6H2) was coupled with PhI in the presence of NaOSiMe3 and the catalyst Pd((R,R)-Me-Duphos)(Ph)(I) (3) to give P(Ph)(Me)(Is) (2) in up to 78% ee. The intermediate phosphido complex Pd((R,R)-Me-Duphos)(Ph)(P(Me)(Is)) (5a,b) was observed as a mixture of diastereomers by low-temperature 31P NMR. The rate of interconversion of 5a,b by phosphorus inversion is greater than or equal to that of reductive elimination, which suggests that the enantiodetermining step occurs after Pd-P bond formation.     

Optical sensing of amine vapors with a series of tin compounds

Certain common Sn(2+) salts exhibit bright luminescence of various optical wavelengths upon excitation with 254 nm UV irradiation at room temperature. Light emission can be selectively quenched by exposure to low concentrations of amines, and can in some cases be regenerated with either a nitrogen purge or exposure to acid vapors, rendering the compounds useful for application in optical sensing arrays.     

Reversible, surface-controlled structure transformation in nanoparticles induced by an aggregation state

The structure of 3 nm ZnS nanoparticles differs from that of bulk ZnS and is shown to vary with the particle aggregation state. Dispersed or weakly aggregated nanoparticles in suspension have a more distorted internal structure than strongly aggregated nanoparticles. Reversible switching between distorted and crystalline structures can be induced by changing the aggregation state via slow drying and ultrasonic agitation. The transformation was analyzed using pair distribution function data from wide angle x-ray diffraction and the aggregation state monitored via small angle x-ray scattering. Molecular modeling provides insight into particle-particle interactions that induce the structural changes. The reversible nature also implies a low activation energy of nanoparticle transformation and indicates that distorted nanoparticles are not trapped in a metastable state.     

Photoluminescence of porous silicon surfaces stabilized through Lewis acid mediated hydrosilylation

Lewis acid mediated hydrosilylation on porous silicon surfaces permits facile incorporation of a wide variety of functionalities through stable silicon–carbon bonds. The surfaces demonstrate high chemical stability with respect to hydrofluoric acid and aqueous base. The effects of the covalently bound surface groups on photoluminescence have been investigated and it was noted that alkyl and alkenyl termination induced only small decreases in photoluminescence efficiency. Aromatic substituents conjugated through a vinyl group, however, bring about almost complete quenching of the observed photoluminescence, regardless of substitution with either electron withdrawing (chloride) or donating (methyl) functionalities. The photoluminescence fatigue of dodecyl terminated surfaces in air for 12–16 h periods has been monitored and compared to unfunctionalized porous silicon. In air, the photoluminescence of dodecyl terminated surfaces degrades faster than the unfunctionalized porous silicon but under inert atmosphere (nitrogen), the rate of photoluminescence fatigue is slow in both cases and approximately equivalent.