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PubMed2000

Chlorophyll fluorescence quenching in isolated light harvesting complexes induced by zeaxanthin.

Non-photochemical quenching of chlorophyll fluorescence in plants occurs in the light harvesting antenna of photosystem II and is regulated by the xanthophyll cycle. A new in vitro model for this process has been developed. Purified light harvesting complexes above the detergent critical micelle concentration have a stable high fluorescence yield but a rapidly inducible fluorescence quenching occurs upon addition of zeaxanthin. Violaxanthin was without effect, lutein and antheraxanthin induced a marginal response, whereas the violaxanthin analogue, auroxanthin, induced strong quenching. Quenching was not caused by aggregation of the complexes but was accompanied by a spectral broadening and red shift, indicating a zeaxanthin-dependent alteration in the chlorophyll environment.

Chlorophyll↗
PubMed2000

Contrasting effects of excess ferritin expression on the iron-mediated oxidative stress induced by tert-butyl hydroperoxide or ultraviolet-A in human fibroblasts and keratinocytes.

Iron and/or ferritin accumulation are known to occur under pathological conditions in many inflammatory skin diseases or in human skin chronically exposed to UV light. Under such conditions, ferritin is believed to play an effective protective role in accommodating and 'deactivating' excess 'free' iron produced by the inflammatory process or the UV illumination. The present study compares the relationship between ferritin over-expression and effects of an oxidative stress induced chemically by tert-butyl hydroperoxide or photochemically by UV-A radiation. As shown by immunoassay, cultured MRC 5 and HS 68 fibroblasts treated for at least one day with transferrin or overnight with non-toxic concentrations of the ferric nitrilotriacetate complex express up to 10 times more ferritin than untreated cells, whereas a five-fold increase is obtained with NCTC 2544 keratinocytes. In all cases a parallel increase in soluble cellular iron is measured by inductive plasma emission spectroscopy. The superoxide dismutase and catalase activities and total glutathione levels are not modified by the iron treatment, whereas a transient increase in the Se-dependent glutathione peroxidase activity of keratinocytes is observed after a short incubation with the iron complex. In keratinocytes and fibroblasts, ferritin over-expression after iron treatment markedly inhibits lipid peroxidation but, paradoxically, not the mortality induced by tert-butyl hydroperoxide. In contrast, this excess ferritin does not protect cells from both the peroxidation and mortality induced by moderate doses (30 J/cm2) of UV-A radiation. As a consequence, protection against oxidative damage by excess ferritin synthesis clearly depends on the nature of the oxidative stress on cell targets and it seems to be of lesser importance in the case of photochemically induced oxidation.

Catalase↗
PubMed2001

State-of-the-art chamber facility for studying atmospheric aerosol chemistry.

A state-of-the-art chamber facility is described for investigation of atmospheric aerosol chemistry. Dual 28 m3 FEP Teflon film chambers are used to simulate atmospheric conditions in which aerosol formation may occur. This facility provides the flexibility to investigate dark, single oxidant reactions as well as full photochemical simulations. This paper discusses the environmental control implemented as well as the gas-phase and aerosol-phase instrumentation used to monitor atmospheric aerosol formation and growth. Physical processes occurring in the chamber and procedures for estimating secondary organic aerosol formation during reaction are described. Aerosol formation and evolution protocols at varying relative humidity conditions are presented.

Aerosols↗
PubMed2006

Synthesis, photochemistry, and electrochemistry of single-wall carbon nanotubes with pendent pyridyl groups and of their metal complexes with zinc porphyrin. Comparison with pyridyl-bearing fullerenes.

A soluble, functionalized Py-SWNT has been synthesized and characterized by solution (1)H and (13)C NMR, FT-Raman, and electron microscopy. Experimental data indicate that Py-SWNT has short tubes with pentyl esters at the tips and pyridyl isoxazolino units along the walls. The synthesis of Py-SWNT is based on a 1,3-dipolar cycloaddition of a nitrile oxide on the SWNT walls, similar to 1,3-dipolar cycloadditions that are common for fullerene functionalization. The resulting Py-SWNT forms a complex with a zinc porphyrin (ZnPor) in a way similar to that reported for pyridyl-functionalized [60]-fullerenes. Formation of this metal-ligand complex was firmly established by a detailed electrochemical study. However, in contrast to the behavior observed for the ZnPor/Py-C(60) complex, photochemical excitation of the complex between ZnPor/Py-SWNT does not lead to electron transfer with the generation of charge-separated states. Fluorescence and laser flash studies indicate that the main process is energy transfer from the singlet ZnPor excited state to the Py-SWNT with observation of emission from Py-SWNT. Triplet ZnPor excited-state quenching by Py-SWNT is only observed in polar solvents such as DMF, but not in benzonitrile.

Journal Article↗
PubMed2000

Electrophoretic assembly of colloidal crystals with optically tunable micropatterns

The production of materials with micrometre- and submicrometre-scale patterns is of importance in a range of applications, such as photonic materials, high-density magnetic data storage devices, microchip reactors and biosensors. One method of preparing such structures is through the assembly of colloidal particles. Micropatterned colloidal assemblies have been produced with lithographically patterned electrodes or micromoulds. Here we describe a different method that combines the well-known photochemical sensitivity of semiconductors with electric-field-induced assembly to create ordered arrays of micrometre-sized colloidal particles with tunable patterns. We show that light affects the assembly processes, and demonstrate how to produce patterns using electrophoretic deposition in the presence of an ultraviolet (UV) illumination motif. The distribution of current across an indium tin oxide (ITO) electrode can be altered by varying the illumination intensity: during the deposition process, this causes colloidal particles to be swept from darkened areas into lighted regions. Illumination also assists in immobilizing the particles on the electrode surface. Although the details of these processes are not well understood, the patterning effects of the UV light are discussed in terms of alterations in the current density that affects particle assembly on an ITO electrode.

Journal Article↗
PubMed2005

Fate of flavins in sensitized photodegradation of isohumulones and reduced derivatives: studies on formation of radicals via EPR combined with detailed product analyses.

Photodegradation of isohumulones accounts for formation of the lightstruck flavor in beer. The reactions involved are mediated by riboflavin, a natural photosensitizer present in beer in ppb quantities. The results of an investigation of this sensitized degradation process are presented herein. Product analyses and electron paramagnetic resonance spectroscopy, in steady-state as well as in time-resolved mode, offer extensive insight into the photophysical and photochemical details of the degradation mechanism. In contrast to energy transfer and Norrish type I alpha-cleavage reactions that take place on direct irradiation of isohumulones, the sensitization pathway proceeds via one-electron redox chemistry involving the excited triplet state of riboflavin and derivatives. The flavin semiquinone radical thus formed could be readily detected, either by steady state or by time-resolved electron paramagnetic resonance spectroscopy. Superimposed signals in the spectra revealed the presence of radical fragments derived from isohumulones or tetrahydroisohumulones, which, on recombination with riboflavin semiquinone radicals, produced stable reaction products that were identified by HPLC-MS. However, no superimposed signals were observed on sensitized irradiation of dihydroisohumulones.

Cyclopentanes↗
PubMed2005

Degradation of the main Photosystem II light-harvesting complex.

Many factors trigger the degradation of proteins, including changes in environmental conditions, genetic mutations, and limitations in the availability of cofactors. Despite the importance for viability, still very little is known about protein degradation and its regulation. The degradation of the most abundant membrane protein on Earth, the light-harvesting complex of Photosystem II (LHC II), is highly regulated under different environmental conditions, e.g. light stress, to prevent photochemical damage of the reaction center. However, despite major effort to identify the protease/proteases involved in the degradation of the apoproteins of LHC II the molecular details of this important process remain obscure. LHC II belongs to the family of chlorophyll a/b binding proteins (CAB proteins) and is located in the thylakoid membrane of the plant chloroplast. The results of biochemical experiments to isolate and characterize the protease degrading LHC II are summarized here and compared to our own recent finding indicating that a metalloprotease of the FtsH family is involved in this process.

Arabidopsis↗
PubMed2002

Effect of ozonation on the biological treatability of a textile mill effluent.

Ozonation applied prior to biological processes, has proved to be a very effective chemical treatment step mostly for colour removal when soluble dyes are used in textile finishing operations. Its impact on biological treatability however has not been fully evaluated yet. This study evaluates the effect of ozonation on the quality of wastewater from a textile mill involving bleaching and reactive dyeing of cotton and synthetic knit fabric. The effect of ozonation on COD fractionation and kinetic coefficients defining major biological processes is emphasised. The results indicate that the extent of ozone applied greatly affects the remaining organic carbon composition in the wastewater. The relative magnitude of different COD fractions varies as a function of the ozone dose. Ozonation does not however exert a measurable impact on the rate of major biological processes.

Coloring Agents↗
PubMed2004

Applications of advanced oxidation processes: present and future.

The use of advanced oxidation processes (AOPs) to remove pollutants in various water treatment applications has been the subject of study for around 30 years. Most of the available processes (Fenton reagent, O3 under basic conditions, O3/H2O2, O3/UV, O3/solid catalyst, H2O2/M(n+), H2O2/UV, photo-assisted Fenton, H2O2/solid catalyst, H2O2/NaClO, TiO2/UV etc.) have been investigated in depth and a considerable body of knowledge has been built up about the reactivity of many pollutants. Various industrial applications have been developed, including ones for ground remediation (TCE, PCE), the removal of pesticides from drinking water, the removal of formaldehyde and phenol from industrial waste water and a reduction in COD from industrial waste water. The development of such AOP applications has been stimulated by increasingly stringent regulations, the pollution of water resources through agricultural and industrial activities and the requirement that industry meet effluent discharge standards. Nevertheless, it is difficult to obtain an accurate picture of the use of AOPs and its exact position in the range of water treatment processes has not been determined to date. The purpose of this overview is to discuss those processes and provide an indication of future trends.

Hydrogen Peroxide↗
PubMed1998

Free radicals in primary photobiological processes.

Formation of a semiquinone free radical derived from chlorophyll in the reaction of photoreduction has been discovered by A. A. Krasnovsky, Sr. in 1953. This review consider the results obtained in the author's laboratory, concerning the participation of free radicals in photochemical reactions under UV-irradiation of aromatic amino acids, proteins, and lipids, as well as in the reactions of chemiluminescence (CL) in the protein and chlorophyll-containing systems. Free radicals are the very first products of photochemical reactions in all systems studied. The back reactions of radicals are accompanied with photon emission. From the point of view of the molecular energetics, the radiativeless electronic transition in molecules is the most probable event, the transition triplet level is less probable, and the transition to the singlet excited level is virtually impossible. This may explain the low quantum yield of CL, similarity of CL and phosphorescence (rather than fluorescence) spectrum of the reaction products, low quantum yield of CL, and its high temperature coefficient.

Chlorophyll↗
PubMed2004

Kinetic control of surface patterning by laser-induced photochemical deposition in liquid solutions. II. Experimental investigations.

We experimentally analyze the real-time formation of periodic surface patterning resulting from laser-driven photochemical deposition in liquid solutions. Using photochemical deposition of chromium hydroxide layers driven by a continuous Ar+ laser wave in a potassium chromate solution, we analyze the kinetic formation of three different types of patterning: dot array, periodic line writing, and holographic grating formed by interfering beams. Results are also presented for both flat and curved substrates. In each case, the deposit growth laws are measured and they show the emergence of scaling regimes that are predicted by our model [Phys. Rev. E 69, 051605 (2004)]]. Data taken from literature are also confronted to the model. The observed agreement suggests that a unified picture of the processes involved for photodeposition driven by a one-photon absorption can be devised, whatever the initial photosensitive medium is. This kinetic control of photodeposition, associated to the versatility in monitoring the geometry of laser/medium interaction and the flexibility in deposited materials by various photochemical reactions, offers a valuable level of development in substrate patterning for lithographic or holographic applications.

Journal Article↗
PubMed2001

Modeling the formation of secondary organic aerosol. 1. Application of theoretical principles to measurements obtained in the alpha-pinene/, beta-pinene/, sabinene/, delta3-carene/, and cyclohexane/ozone systems.

Secondary organic aerosol (SOA) forms in the atmosphere when volatile parent compounds are oxidized to form low-volatility products that condense to yield organic particulate matter (PM). Under conditions of intense photochemical smog, from 40 to 80% of the particulate organic carbon can be secondary in origin. Because describing multicomponent condensation requires a compound-by-compound identification and quantification of the condensable compounds, the complexity of ambient SOA has made it difficult to test the ability of existing gas/particle (G/P) partitioning theory to predict SOA formation in urban air. This paper examines that ability using G/P data from past laboratory chamber experiments carried out with five parent hydrocarbons (HCs) (four monoterpenes at 308 K and cyclohexene at 298 K) in which significant fractions (61-100%) of the total mass of SOA formed from those HCs were identified and quantified by compound. The model calculations were based on a matrix representation of the multicomponent, SOA G/P distribution process. The governing equations were solved by an iterative method. Input data forthe model included (i) deltaHC (microg m(-3)), the amount of reacted parent hydrocarbon; (ii) the alpha values that give the total concentration T (gas + particle phase, ng m(-3)) values for each product i according to Ti = 10(3) alphaideltaHC; (iii) estimates of the pure compound liquid vapor pressure pL(degrees) values (at the reaction temperature) for the products; and (iv) UNIFAC parameters for estimating activity coefficients in the SOA phase for the products as a function of SOA composition. The model predicts the total amount Mo (microg m(-3)) of organic aerosol that will form from the reaction of deltaHC, the total aerosol yield Y(= Mo/deltaHC), and the compound-by-compound yield values Yi. An impediment in applying the model is the lack of literature data on PL(degrees) values for the compounds of interest or even on pL(degrees) values for other, similarly low-volatility compounds. This was overcome in part by using the G/P data from the alpha-pinene and cyclohexene experiments to determine pL(degrees) values for use (along with a set of 14 other independent polar compounds) in calculating UNIFAC vapor pressure parameters that were, in turn, used to estimate all of the needed pL(degrees) values. The significant degree of resultant circularity in the calculations for alpha-pinene and cyclohexene helped lead to the good agreement that was found between the Yi values predicted by the model, and those measured experimentally for those two compounds. However, the model was also able to predict the aerosol yield values from beta-pinene, sabinene, and delta3-carene, for which there was significatly less circularity in the calculations, thereby providing evidence supporting the idea that given the correct input information, SOA formation can in fact be accurately modeled as a multicomponent condensation process.

Aerosols↗
PubMed2000

Suppression of proteasome C2 contralateral to ischemic lesions in rat brain.

Functional as well as structural reorganization takes place in the surrounding and remote brain areas after focal ischemic lesions. In particular, reactive or regenerative processes have been described to occur in the contralateral hemisphere. We used mRNA differential display to gain more insight into the molecular mechanisms underlying this type of neuronal plasticity. Circumscribed unilateral infarcts consistently affecting the forelimb area of the primary motor cortex were induced photochemically in adult male Wistar rats. The lesion produced significant behavioral asymmetry with subsequent partial recovery within 1 week. Cloning the genes with altered expression profiles identified the 20S proteasome subunit C2 as a gene whose expression level is decreased in contralateral homotopic cortex. Semiquantitative reverse transcription-polymerase chain reaction (RT-PCR) revealed approximately twofold lower proteasome C2 mRNA levels in the lesion group as compared with the sham-operated group. The proteasome serves as the central enzyme of non-lysosomal protein degradation. It is responsible for intracellular protein turnover and is critically involved in a variety of regulation processes, such as cell cycle, metabolism and differentiation. Our results suggest that proteasome activity may play also a role in contralateral cortical plasticity occurring after focal cerebral ischemia.

Animals↗
PubMed2000

Kinetic stabilization of the [1.1]paracyclophane system: isolation and X-ray structural analysis of a [1.1]paracyclophane derivative and its interconversion with the transannular adduct.

Intentionally designed kinetic stabilization of the [1.1]paracyclophane skeleton has been achieved by multiple substitution of the aromatic rings with trimethylsilylmethyl and N,N-dimethyl-carbamoyl groups, which serve to shield the proximate bridgehead carbon atoms sterically from access by other reagents. The bis(Dewar benzene) precursor (1a) has been prepared in essentially the same manner as previous derivatives--starting from the photocycloaddition of 1,4-bis(trimethylsilyl)-2-butyne to octa-hydroindacene-1,5-dione--except for a few critical modifications described in the text. Substituted [1.1]paracyclophane (2a), photochemically generated from the precursor, is indefinitely stable at 50 degrees C and suffers decomposition only by 8 % after 2 h at 100 degrees C in degassed n-decane, demonstrating its greatly improved kinetic stability compared to previous [1.1]paracyclophanes. Since 2a undergoes efficient photochemical transformation into the transannular addition product 3a, irradiation of la tends to produce a mixture of products consisting mainly of 3a. Compound 3a, however, reverts thermally to 2a in a process of half life 40 min at 55 degrees C; the activation parameters for this process are deltaH(not equal to)= 21.1 +/- 0.8 kcalmol(-1) and deltaS(not equal to) = -10.5 +/- 2.6 cal K(-1)mol(-1). Thus, on heating 3a in benzene and cooling the resultant solution, 2a is obtained as orange-red crystals. X-ray crystallographic analysis of 2a reveals benzene rings bent to the highest degree ever reported for a paracyclophane, with their face-to-face arrangement in unusually close proximity. The shortest nonbonding interatomic distance is 2.376 A; less than the sum of the van der Waals radii by more than 1.0A. The generation of related substituted [1.1]paracyclophanes and their kinetic stabilities are also reported.

Journal Article↗
PubMed2006

Experimental and theoretical investigations of the sulfite-based polyoxometalate cluster redox series: alpha- and beta-[Mo(18)O(54)(SO(3))(2)](4-/5-/6-).

The synthesis, isolation and structural characterization of the sulfite polyoxomolybdate clusters alpha-(D(3h))(C(20)H(44)N)(4){alpha-[Mo(18)O(54)(SO(3))(2)]}CH(3)CN and beta-(D(3d))(C(20)H(44)N)(4){beta-[Mo(18)O(54)(SO(3))(2)]}CH(3)CN is presented. Voltammetric studies in acetonitrile (0.1 M Hx(4)NClO(4), Hx(4)N=tetra-n-hexylammonium) reveal the presence of an extensive series of six one-electron reduction processes for both isomers. Under conditions of bulk electrolysis, the initial [Mo(18)O(54)(SO(3))(2)](4-/5-) and [Mo(18)O(54)(SO(3))(2)](5-/6-) processes produce stable [Mo(18)O(54)(SO(3))(2)](5-) and [Mo(18)O(54)(SO(3))(2)](6-) species, respectively, and the same reduced species may be produced by photochemical reduction. Spectroelectrochemical data imply that retention of structural form results upon reduction, so that both alpha and beta isomers are available at each of the 4-, 5-, and 6-redox levels. However, the alpha isomer is the thermodynamically favored species in both the one- and two-electron-reduced states, with beta-->alpha isomerization being detected in both cases on long time scales (days). EPR spectra also imply that increasing localization of the unpaired electron occurs over the alpha- and beta-[Mo(18)O(54)(SO(3))(2)](5-) frameworks as the temperature approaches 2 K where the EPR spectra show orthorhombic symmetry with different g and hyperfine values for the alpha and beta isomers. Theoretical studies support the observation that it is easier to reduce the alpha cluster than the beta form and also provide insight into the driving force for beta-->alpha isomerization in the reduced state. Data are compared with that obtained for the well studied alpha-[Mo(18)O(54)(SO(4))(2))](4-) sulfate cluster.

Journal Article↗
PubMed2006

Investigation of a new approach to decompose two potent greenhouse gases: photoreduction of SF(6) and SF(5)CF(3) in the presence of acetone.

In this paper, we addressed the utilization of photochemical method as an innovative technology for the destruction and removal of two potent greenhouse gases, SF(6) and SF(5)CF(3). The destruction and removal efficiency (DRE) of the process was determined as a function of excitation wavelength, irradiation time, initial ratio of acetone to SF(5)X (X represented F or CF(3)), initial SF(5)X concentration, additive oxygen and water vapor concentration. A complete removal was achieved by a radiation period of 55min and 120min for SF(6)-CH(3)COCH(3) system and SF(5)CF(3)-CH(3)COCH(3) system respectively under 184.9nm irradiation. Extra addition of water vapor can enhance DRE by approximately 6% points in both systems. Further studies with GC/MS and FT-IR proved that no hazardous products such as S(2)F(10), SO(2)F(2), SOF(2), SOF(4) were generated in this process.

Acetone↗
PubMed2001

Temperature-dependent photochemistry of 1,3-diphenylpropenes. The di-pi-methane reaction revisited.

The temperature-dependent photochemical behavior of 1,3-diphenylpropene and several of its 3-substituted derivatives has been investigated over a wide temperature range. The singlet state is found to decay via two unactivated processes, fluorescence and intersystem crossing, and two activated processes, trans,cis isomerization and phenyl-vinyl bridging. The latter activated process yields a diradical intermediate which partitions between ground-state reactant and formation of the di-pi-methane rearrangement product. Kinetic modeling of temperature-dependent singlet decay times and quantum yields of fluorescence, isomerization, di-pi-methane rearrangement, and nonradiative decay provides rate constants and activation parameters for each of the primary and secondary processes. Substituents at the 3-position are found to have little effect on the electronic spectra or unactivated fluorescence and intersystem crossing pathways. However, they do effect the activated primary and secondary processes. Thus, the product ratios are highly temperature dependent.

Journal Article↗