Photodecomposition of several compounds commonly used as sunscreen agents

The photolysis reactions of three compounds commonly used as a sunscreen agents, Parsol 1789 (1-[4-(1,1-dimethylethyl)phenyl]-3-(4-methoxyphenyl)-1,3- propanedione), Oxybenzone ((2-hydroxy-4-methoxyphenyl)phenyl-methanone) and Padimate O (2-ethylhexyl-4-(dimethylamino)benzoate), were investigated to provide a chemical background to aid in the understanding of the photosensitization of the sunscreen agents. Photolysis was carried out in cyclohexane for 70–140 h using a mercury vapor lamp (450W) without excluding oxygen.

Irradation of Parsol 1789 in cyclohexane yielded tert-butylbenzene, p-tert-butylbenzoic acid and p-methoxybenzoic acid; products obtained from the combination of the sunscreen with the solvent included the cyclohexyl esters of p-methoxybenzoic acid, p-tert-butylbenzoic acid and methanoic acid; products obtained from the solvent included cyclohexanol, cyclohexanone and dicyclohexyl ether.

Irradiation of Oxybenzone in the cyclohexane for 100 h produced no detectable products by either gas or liquid chromatographic analysis. Oxybenzone was recovered unchanged and no products were observed from the photoinitiated reaction of oxygen with the solvent.

Irradiation of Padimate O in cyclohexane yielded the ethylhexyl esters of p-aminobenzoic acid, p-monomethylaminobenzoic acid and p-dimethylamino (o/m)-methylbenzoic acid, as well as products from the photoinitiated reaction of oxygen with the solvent.     

Magnetotransport and magnetic properties of InAs/Mn digital alloys

We have investigated the magnetic and magneto-transport properties of a systematic sequence of five InAs/Mn digital alloys grown by a combination of molecular beam epitaxy and atomic layer epitaxy. The samples consist of 30 periods of Mn fractional monolayers (ML) (0.17–0.5 ML) separated by 14 ML thick InAs spacer layers in a superlattice configuration. Four samples show n-type electrical conduction while the fifth (0.25 ML Mn) is p-type. Squid magnetization measurements performed on these samples show remnant magnetization above room temperature, which is apparently related to a second phase.     

Kinetics of the degradation of polystyrene in supercritical acetone

The kinetic analysis of the degradation of polystyrene (PS) in supercritical acetone has been studied using the nonisothermal weight loss technique with heating rates of 3, 5 and 7 °C/min. The weight loss data according to degradation temperature have been analyzed using the integral method based on Arrhenius form to obtain the kinetic parameters such as apparent activation energy and overall reaction order. The kinetic parameters obtained from this work were also compared with those of the thermal degradation of PS in nitrogen atmosphere. From this work, it was found that the activation energies of PS degradation in supercritical acetone were 73.3-200.7 kJ/mol and lower than those of the thermal degradation in nitrogen atmosphere.     

Chiral conflict. The effect of temperature on the helical sense of a polymer controlled by the competition between structurally different enantiomers: from dilute solution to the lyotropic liquid crystal state

Helical polymers appended with paired structurally different enantiomers, which have opposing helical sense preferences, yield a new kind of relationship between optical activity and temperature, and also reveal unusual details of the nature of chiral interactions. Consistent with a statistical physical theory developed for these experiments, the proportion of the competing chiral groups, determined by synthesis, fixes the compensation temperature at which the helical senses are equally populated. The lyotropic liquid crystal state formed by these polymers yields therefore a nematic state at any chosen temperature over a very wide range, with a cholesteric state arising with tightening pitch as temperature deviates from this point. Far from the nematic temperature, the pitch reaches the nanometer scale and therefore the reflection of visible light. Before crossing zero at the nematic temperature, the optical activity becomes so large that it may be observed with the unaided eye through crossed polarizers.     

Mesocellular polymer foams with unprecedented uniform large mesopores and high surface areas

Mesocellular polymer foams with uniform approximately 17 nm cellular pores were fabricated using mesocellular silica foams as inorganic templates. The mesocellular polymer foams have high surface areas up to approximately 600 m(2)g(-1) and pore volumes of 1.6 cm(3)g(-1).     

Large-scale synthesis of TiO2 nanorods via nonhydrolytic sol-gel ester elimination reaction and their application to photocatalytic inactivation of E. coli

A simple method of synthesizing a large quantity of TiO(2) nanorods was developed. A nonhydrolytic sol-gel reaction between titanium(IV) isopropoxide and oleic acid at 270 degrees C generated 3.4 nm (diameter) x 38 nm (length) sized TiO(2) nanocrystals. The transmission electron microscopic image showed that the particles have a uniform diameter distribution. X-ray diffraction and selected-area electron diffraction patterns combined with high-resolution transmission electron microscopic image showed that the TiO(2) nanorods are highly crystalline anatase crystal structure grown along the [001] direction. The diameters of the TiO(2) nanorods were controlled by adding 1-hexadecylamine to the reaction mixture as a cosurfactant. TiO(2) nanorods with average sizes of 2.7 nm x 28 nm, 2.2 nm x 32 nm, and 2.0 nm x 39 nm were obtained using 1, 5, and 10 mmol of 1-hexadecylamine, respectively. The optical absorption spectrum of the TiO(2) nanorods exhibited that the band gap of the nanorods was 3.33 eV at room temperature, which is 130 meV larger than that of bulk anatase (3.2 eV), demonstrating the quantum confinement effect. Oleic acid coordinated on the nanorod surface was removed by the reduction of the carboxyl group of oleic acid, and the Brunauer-Emmett-Teller surface area of the resulting naked TiO(2) nanorods was 198 m(2)/g. The naked TiO(2) nanorods exhibited higher photocatalytic activity than the P-25 photocatalyst for the photocatalytic inactivation of E. coli.     

Functional involvement of src and focal adhesion kinase in a CD99 splice variant-induced motility of human breast cancer cells

Earlier report showed that expression of a splice variant of CD99 transmembrane protein increases invasive ability of human breast cancer cells. Cell motility was also significantly enhanced by the CD99 splice variant expression. In an effort to identify the cellular components that mediate a signal transduction pathway triggered by the CD99 splice variant, known signal path inhibitors were examined for their effects on the motility of the CD99 splice variant-transfected MDA-MB-231 breast cancer cells. Phenylarsine oxide, an inhibitor of phosphatase specific for focal adhesion kinase, and PP1, an inhibitor of src kinase family, significantly suppressed motility of the cells. Among different types of src transfectant clones generated, kinase-negative mutant src transfectant cells were 80% less motile than the mock cells transfected with an empty-vector, while v-src and c-src transfectants exhibited cell motility levels at or slightly above the mock transfectant. These results suggest that src and focal adhesion kinase mediate the intracellular signaling pathway of a CD99 splice variant for the induction of motility of human breast cancer cells.     

Characterization and epitope mapping of two monoclonal antibodies against human CD99

CD99 plays a critical role in the diapedesis of monocytes, T cell differentiation, and the transport of MHC molecules. Engagement of CD99 by agonistic monoclonal antibodies has been reported to trigger multifactorial events including T cell activation as well as cell-cell adhesion during hematopoietic cell differentiation. In this study, to identify the functional domains participating in the cellular events, we mapped the epitopes of CD99, which are recognized by two agonistic CD99 monoclonal antibodies, DN16 and YG32. Using recombinant fusion proteins of GST with whole or parts of CD99, we found that both antibodies interact with CD99 molecules independently of sugar moieties. DN16 mAb detected a linear epitope located in the amino terminal region of CD99 while YG32 mAb bound another linear epitope in the center of the extracellular domain. To confirm that the identified epitopes of CD99 are actually recognized by the two mAbs, we showed the presence of physical interaction between the mAbs and the fusion proteins or synthetic peptides containing the corresponding epitopes using surface plasmon resonance analyses. The dissociation constants of DN16 and YG32 mAbs for the antigen were calculated as 1.27 x 10(-7) and 7.08 x 10(-9) M, respectively. These studies will help understand the functional domains and the subsequent signaling mechanism of CD99.     

Ligand to ligand charge transfer in (hydrotris(pyrazolyl)borato)(triphenylarsine)copper(I)

Emission and UV-vis absorption spectra of (hydrotris(pyrazolyl)borato)(triphenylarsine)copper(I), (CuTpAsPh3), (hydrotris(pyrazolyl)borato)(triethylamine)copper(I), (CuTpNEt3), and (hydrotris(pyrazolyl)borato)(triphenylphosphine)copper(I), (CuTpPPh3), are reported. The spectra of the arsine complex contain low-energy bands (with a band maximum at 16,500 cm(-1) in emission and a weak shoulder centered at about 25,000 cm(-1) in absorption) that are not present in the corresponding spectra of the amine or phosphine complexes. The lowest energy electronic transition is assigned to ligand to ligand charge transfer (LLCT) with some contribution from the metal. This assignment is consistent with PM3(tm) molecular orbital calculations that show the HOMO to consist primarily of pi orbitals on the Tp ligand (with some metal orbital character) and the LUMO to be primarily antibonding orbitals on the AsPh3 ligand (also with some metal orbital character). The absorption shoulder shows a strong negative solvatochromism, indicative of a reversal or rotation of electric dipole upon excitation, and consistent with a LLCT. The trends in the energies of the electronic transitions and the role of the metal on the LLCT are discussed.