PHOTOSENSITIZATION OF HUMAN DIPLOID CELL CULTURES BY INTRACELLULAR FLAVINS AND PROTECTION BY ANTIOXIDANTS

Abstract— The damaging effects of near ultraviolet and visible light on WI-38 human diploid lung fibroblasts were investigated. WI-38 cells in culture were killed by light doses ranging from 2 to 10 × 10³ W/m² h. There was an inverse correlation between culture age, i.e. population doubling level and photosensitivity. However, this effect could not be related to capacity for DNA synthesis and cell division.
Flavins were clearly implicated as endogenous photosensitizers, and antioxidants such as d, l -α-tocopherol (vitamin E), BHT and ascorbic acid were found to afford the cells protection from light damage. Furthermore, products of lipid peroxidation could be detected in cell homogenates irradiated in the presence of ribofiavin.     

Infrared spectrum and structure of the Hf(OH)4 molecule

Laser-ablated Hf atoms react with H2O2 and with H2 + O2 mixtures in solid argon to form the Hf(OH)2 and Hf(OH)4 molecules, which are identified from the effect of isotopic substitution on the matrix infrared spectra. Electronic structure calculations at the MP2 level varying all bond lengths and angles converge to nearly linear and tetrahedral molecules, respectively, and predict frequencies for these new product molecules and mixed isotopic substituted molecules of lower symmetry that are in excellent agreement with observed values, which confirms the identification of these hafnium hydroxide molecules. This work provides the first evidence for a metal tetrahydroxide molecule and shows that the metal atom reaction with H2O2 in excess argon can be used to form pure metal tetrahydroxide molecules, which are not stable in the solid state.     

Formation and characterization of the photochemically interconvertible side-on and end-on bonded dioxygen-iron dioxide complexes in solid argon

Two interconvertible iron dioxide-dioxygen complexes were prepared and characterized by matrix isolation infrared absorption spectroscopy as well as theoretical calculations. Iron atoms react with O2 to form the inserted FeO2 molecule in solid argon only upon UV-visible light irradiation. Annealing allows the dioxygen molecules to diffuse and to react with FeO2 and form the side-on and end-on bonded dioxygen-iron dioxide complexes, (eta2-O2)FeO2 and (eta1-O2)FeO2. The side-on bonded structure is a peroxide complex having a singlet ground state with a nonplanar C2v symmetry. The end-on bonded isomer is characterized to be a superoxide complex with a planar 3A' ' ground state. These two isomers are photoreversible, that is, near-infrared light (lambda > 850 nm) induces the conversion of the side-on bonded (eta2-O2)FeO2 complex to the end-on bonded (eta1-O2)FeO2 isomer and vice versa with red light irradiation (lambda > 600 nm).     

Electronic quenching of OH A 2Sigma+ radicals in single collision events with H2 and D2: a comprehensive quantum state distribution of the OH X 2Pi products

A pump-probe laser-induced fluorescence technique has been used to examine the nascent OH X (2)Pi product state distribution arising from non-reactive quenching of electronically excited OH A (2)Sigma(+) by molecular hydrogen and deuterium under single-collision conditions. The OH X (2)Pi products were detected in v'=0, 1 and 2; the distribution peaks in v'=0 and decreases monotonically with increasing vibrational excitation. In all vibrational levels probed, the OH X (2)Pi products are found to be highly rotationally excited, the distribution peaking at N'=15 when H(2) was used as the collision partner and N'=17 for D(2). A marked propensity for production of Pi(A') Lambda-doublet levels was observed, while both OH X (2)Pi spin-orbit manifolds were equally populated. These observations are interpreted as dynamical signatures of the nonadiabatic passage of the OH + H(2)/D(2) system through the seams of conical intersection that couple the excited state (2 (2)A') and ground state (1 (2)A') surfaces.     

The structure of ce-doped Bi2(MoO4)3 as determined by neutron profile refinement

The structure of Bi_1.8Ce_0.2(MoO₄)₃ has been refined with powder neutron diffraction data by the Rietveld method. The structure can be derived by severely distorting the scheelite structure (AMO₄) and is perhaps better written $\text{A}{}_{\mathrm{<mtext>2</mtext><mtext>3</mtext>}}\text{Ø}{}_{\mathrm{<mtext>1</mtext><mtext>3</mtext>}}\text{M}\text{O}{}_4$, where Ø = cation vacancy. Of the two bismuth atom sites, cerium preferentially occupies the more symmetric of the two (Bi(2) in the structure) with some cerium found in the scheelite subcell vacancies also. This site preference is understood by examining the symmetries of the two Bi sites. Crystal data: monoclinic, space group $\text{P2}{}_1\text{c}\text{, Z = 4, a = 7.697(2), b = 11.535(3), c = 11.944(3)}$, β = 115.19.     

Alternative antifouling biocides

In response to increasing scientific evidence on the toxicity and occurrence of organotin residues from antifouling paints in the aquatic environment, the use of triorganotin antifouling products was banned on boats of less than 25 m length in many countries during 1987. The use of tributyltin (TBT) products on small boats was superseded by products based on copper, containing organic booster biocides to improve the efficacy of the formulation. Available information and evidence on the occurrence, fate and toxicity of these biocides is reviewed. It is concluded that increased copper concentrations in the aquatic environment, due to the increased use of copper‐based antifoulants, do not have significant effects on marine ecosystems. However, lack of validated analytical methods, limited monitoring data, and very little information about the fate and toxicity of the booster biocides in the aquatic environment, make accurate risk assessments in relation to these compounds difficult. Copyright © 1999 John Wiley & Sons, Ltd.     

The Crystal Structure of a Potassium Channel— A New Era in the Chemistry of Biological Signaling

The similarity to crown ethers is apparent when the arrangement of the oxygen atoms of the carbonyl groups of the protein backbone in the structure of the potassium channel (see schematic drawing of a section of the structure) found in the bacterium Streptomyces lividans is considered. This particular part of the channel pore acts as the selectivity filter, with the permeability of the channel for K⁺ being as much as 10 000 times greater than for the Na⁺ ion. In fact, in this area of the structure two K⁺ ions are located, a feature that enables high flux through the channel.     

Frequency and effects of teachers'' voice problems

This study compared the frequency and effects of voice symptomsin teachers to a group of individuals employed in other occupations. Teachers were more likely to report having a voice problem (15 vs. 6%), having 10 specific voice symptoms, and having 5 symptoms of physical discomfort. They averaged almost 2 symptoms compared with none for nonteachers. Likewise, teachers were more likely to perceive that a voice problem would adversely affect their future career options, had done so in the past, and was limiting their current job performance. Over 20% of teachers but none of the nonteachers had missed any days of work due to a voice problem. These findings suggest that teaching is a high-risk occupation for voice disorders and that this health problem may have significant work-related and economic effects.     

Laser Excitation Matrix-Isolation Spectroscopy

Perhaps the most significant recent development in the field of matrix isolation spectroscopy has proven to be the laser-Raman matrix technique. Infrared absorption and Raman scattering spectroscopic methods provide complementary information on vibrational data for the large body of interesting molecular species which require matrix synthesis and stabilization. The laser-excitation technique offers several advantages over the IR experiment: (1) the possibility of obtaining new chemical species by laser photolysis, (2) the observation of resonance Raman spectra which provide harmonic and anharmonic vibrational constants from overtone bands, and (3) the possible observation of fluorescence from new chemical species. Specific experimental examples of complementary IR and Raman studies, laser photolysis, resonance-Raman, and flouorescence spectra are discussed.     

The electronic absorption and magnetic circular dichroism spectra of IrBr6 2- in several host crystals

The absorption and magnetic circular dichroism (M.C.D.) spectrum of the IrBr₆ ^2- ion at room and liquid helium temperature has been studied in the host crystals (NH₄)₂SnBr₆, K₂SnBr₆ and (C₂H₅NH₃)₂SnBr₆ in the region ～11 000–21 000 cm^-1. An interpretation of the spectrum is presented which differs significantly from those suggested previously. In order of increasing energy the allowed bands are assigned to the following ligand-to-metal charge-transfer transitions: E_g ″(² T _2g )→ U_u ′(² T _1u ) (13–14 000 cm^-1), E_g ″(² T _2g )→ E_u ″(² T _2u ) (16 800 cm^-1), and E_g ″(² T _2g )→ U_u ′(² T _2u ) (～ 18 300 cm^-1). Both our absorption and M.C.D. data strongly suggest a Jahn-Teller splitting of the U_u ′(² T _1u ) state but contradict a previous suggestion of such a splitting of the U_u ′(² T _2u ) state. Consideration of σ—π mixing in the t _1u (π + σ) molecular orbital suggests that the ～17 300 cm^-1 band arises from the orbitally-forbidden E_g ″(² T _2g )→ E_u ′(² T _1u ) transition. Bands in the 11 000–13 000 cm^-1 region are assigned to parity-forbidden charge-transfer transitions to states generated by the t _1g (π)→ t _2g excitation. The fine structure seen at liquid helium temperature in K₂SnBr₆ : Ir⁴⁺ both in the 14 500 cm^-1 band and overlying the E_g ″→ U_u ′(² T _2u ) band appears to be associated with parity-forbidden transitions.