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PubMed2001

Studies of all-trans-retinal as a photooxidizing agent.

The photophysical properties of all-trans-retinal (RAL) have been extensively studied because of the importance of the retinoids in the visual process. However, little information is available regarding the participation of RAL in photochemical transformations such as photoxidation. RAL is one of several native chromophores that have been suggested to act as photosensitizers of damage in the human retina, and this damage would likely occur through oxidative pathways. Time-resolved and steady state techniques have been used to examine the photoreactivity of RAL toward several suitable substrates. The lifetime of the RAL triplet excited state is observed to decrease with increasing concentration of the well-known electron and hydrogen atom donors, 2,3,5,6-tetramethyl-1,4-phenylenediamine (DAD), hydroquinone (HQ), methylhydroquinone (MHQ), 2,3-dimethylhydroquinone (DMHQ) and trimethylhydroquinone (TMHQ), although the bimolecular rate constants for the reaction are much less than that of diffusion controlled (2.9 x 10(7) M-1 s-1, 1.2 x 10(5) M-1 s-1, 1.2 x 10(5) M-1 s-1, 1.5 x 10(5) M-1 s-1 and 1.6 x 10(6) M-1 s-1, for DAD, HQ, MHQ, DMHQ and TMHQ, respectively). In the presence of the donors, new absorptions grow concomitant with the decay of the triplet excited state, and for DAD and TMHQ, the observed spectra are similar to the spectra of p-phenylenediamine and TMHQ radicals. Irradiation of RAL in argon-saturated methanol results in fairly efficient photobleaching of RAL and in the formation of two new compounds having absorption spectra that are shifted below 300 nm. Irradiation of RAL in argon-saturated acetonitrile also results in photobleaching of RAL, but the reaction proceeds at a slower rate.

Humans↗

PubMed2005

The efficacy of ozone as a pre- and post-treatment option for UASB-treated food processing wastewaters.

The efficiency of ozone as a pre- and post-treatment to UASB treatment was investigated, followed by a study into UASB reactor performance with ozonated wastewater as substrate. Combinations of pre- and/or post-ozonation with UASB treatment gave better results than ozonation or UASB alone and COD reductions of 53.0-98.9% were achieved for treatment of canning and winery wastewaters. A UASB reactor was fed with pre-ozonated cannery wastewater for over 70 d. COD removal improved from between 58.8 and 64.4% to between 85.3 and 91.8% after pre-ozonated substrate feed commenced. Subsequent increases in organic loading rate (OLR) from 2.4 to 3.4 kgCOD m(-3) x d(-1) did not affect reactor performance. By including a final post-ozonation treatment to this UASB effluent a total COD reduction of 99.2% was achieved.

Anaerobiosis↗

PubMed1975

A mathematical model of phytochrome - the receptor of photomorphogenetic processes in plants.

A mathematical model of the phytochrome pigment system is considered, the parameters of which are determined by solving the problem of identification on the basis of the dynamic characteristics of the photoreceptor obtained experimentally. The model is based on two photochemical and four dark reactions occurring in the phytochrome system. A study of the model permitted establishing the dynamics of processes in the photoreceptor and determining the relation between the behavior of the active form of phytochrome and the intensity and spectral distribution of light. The results of the investigation allows explaining of the high-energy reaction of photomorphogenesis as a consequence of the dynamics of phytochrome processes.

Darkness↗

PubMed2001

3'-nitrophenylpropyloxycarbonyl (NPPOC) protecting groups for high-fidelity automated 5' --> 3' photochemical DNA synthesis.

[structure: see text]. The most powerful DNA microarrays would be prepared by photolithography with free 3'-ends that could be processed enzymatically. A photoremovable group that could be removed in quantitative yield would ensure high purity of the synthesized probes. We have developed new pyrimidine building blocks for 5' --> 3' DNA synthesis with high cycle yields using the NPPOC (3'-nitrophenylpropyloxycarbonyl) protecting group. These phosphoramidites were proved in automated photochemical DNA synthesis on a modified synthesizer.

Automation↗

PubMed1996

Biochemical evaluation of photolabile precursors of choline and of carbamylcholine for potential time-resolved crystallographic studies on cholinesterases.

Acetylcholinesterase and butyrylcholinesterase both rapidly hydrolyze the neurotransmitter acetylcholine. The unusual three-dimensional structure of acetylcholinesterase, in which the active site is located at the bottom of a deep and narrow gorge, raises cogent questions concerning traffic of the substrate, acetylcholine, and the products, choline and acetate, to and from the active site. Time-resolved crystallography offers a promising experimental approach to investigate this issue but requires a suitable triggering mechanism to ensure efficient and synchronized initiation of the dynamic process being monitored. Here we characterize the properties of two photolabile triggers which may serve as tools in time-resolved crystallographic studies of the cholinesterases. These compounds are 2-nitrobenzyl derivatives of choline and of carbamylcholine, which generate choline and carbamylcholine, respectively, upon photochemical fragmentation. Both photolabile compounds are reversible inhibitors, which bind at the active sites of acetylcholinesterase and butyrylcholinesterase with inhibition constants in the micromolar range, and both photofragmentation processes occur rapidly and with a high quantum yield, without substantial photochemical damage to the enzymes. Photolysis both of acetylcholinesterase and of butyrylcholinesterase, complexed with a 2-nitrobenzyl derivative of choline, resulted in regeneration of enzymic activity. Photolysis of acetylcholinesterase complexed with the 2-nitrobenzyl derivative of carbamylcholine led to time-dependent inactivation, resulting from carbamylation of acetylcholinesterase, which could be reversed upon dilution, due to decarbamylation. Both sets of experiments demonstrated release of choline within the active site. In the former case, choline was produced photochemically at the active site. In the latter case, choline was generated enzymatically, within the active site, concomitantly with carbamylation of the acetylcholinesterase. The two photolabile compounds may thus serve as complementary probes for time-resolved studies of the route of product release from the active sites of the cholinesterases.

Acetylcholinesterase↗

PubMed2000

Proton and hydrogen currents in photosynthetic water oxidation.

The photosynthetic processes that lead to water oxidation involve an evolution in time from photon dynamics to photochemically-driven electron transfer to coupled electron/proton chemistry. The redox-active tyrosine, Y(Z), is the component at which the proton currents necessary for water oxidation are switched on. The thermodynamic and kinetic implications of this function for Y(Z) are discussed. These considerations also provide insight into the related roles of Y(Z) in preserving the high photochemical quantum efficiency in Photosystem II (PSII) and of conserving the highly oxidizing conditions generated by the photochemistry in the PSII reaction center. The oxidation of Y(Z) by P(680)(+) can be described well by a treatment that invokes proton coupling within the context of non-adiabatic electron transfer. The reduction of Y(.)(Z), however, appears to proceed by an adiabatic process that may have hydrogen-atom transfer character.

Electron Transport↗

PubMed2006

In vitro evaluation of Haemonetics MCS+ apheresis platelet concentrates treated with photochemical pathogen inactivation following plasma volume reduction using the INTERCEPT Preparation Set.

Pathogen inactivation using the INTERCEPT Blood System requires platelet resuspension in InterSol and reduced plasma. Platelets in plasma collected on the Haemonetics MCS+ were processed on the INTERCEPT Preparation Set for plasma volume reduction and addition of InterSol. The use of the Preparation Set resulted in a mean platelet loss of 5.6 +/- 3.4%. Subsequent photochemical treatment (PCT) with amotosalen and ultraviolet A light, and 7 days of storage, resulted in acceptable changes for platelet swirling, lactate, lactate dehydrogenase (LDH), platelet factor-4 (PF4), p-selectin, glycoprotein V (GpV), pO2, pCO2, tumour necrosis factor-alpha (TNF-alpha) and interleukin-8 (IL-8). All platelet units processed with the Preparation Set and PCT met European requirements for leucoreduction and pH values.

Blood Platelets↗

PubMed1987

Proton concentration jumps and generation of transmembrane pH-gradients by photolysis of 4-formyl-6-methoxy-3-nitrophenoxyacetic acid.

Proton concentration gradients across membranes are important for many biological energy transducing processes. The kinetics of proton dependent processes can be studied by pH-jump methods in which protons are photochemically released. In the following we describe the synthesis and the properties of photolabile 4-formyl-6-methoxy-3-nitrophenoxyacetic acid, a 'caged proton'. The synthesis is based on vanillin, which is alkylated with chloroacetic acid to give a carboxylic acid (pK = 2.72). In a second step a nitro group ortho to the formyl group is introduced. Photochemical proton release occurs by a reaction mechanism analogous to the well known photochemical formation of 2-nitrosobenzoic acid from 2-nitrobenzaldehyde. The pK values of the photoproduct are 0.75 and 2.76, respectively, thus allowing the use of the compound in a wide pH-range. The quantum yield is 0.18, lower than in the case of the 2-nitrobenzaldehyde/2-nitrosobenzoic acid system (phi = 0.5). The release of the proton in a flash photolysis experiment occurs within less than 1 microseconds. The spectrum of photolabile compound has absorption maxima at 263 nm and 345 nm, respectively. Its permeability across a lipid bilayer membrane is very low (permeability coefficient Pd approximately equal to 10(-9) cm.s-1 at pH 8) so that transmembrane proton concentration gradients can be generated.

Glycolates↗

PubMed2003

Environmental impact of highway construction and repair materials on surface and ground waters. Case study: crumb rubber asphalt concrete.

The practice of incorporating certain waste products into highway construction and repair materials (CRMs) has become more popular. These practices have prompted the National Academy of Science, National Cooperative Highway Research Program (NCHRP) to research the possible impacts of these CRMs on the quality of surface and ground waters. State department of transportations (DOTs) are currently experimenting with use of ground tire rubber ( crumb rubber) in bituminous construction and as a crack sealer. Crumb rubber asphalt concrete (CR-AC) leachates contain a mixture of organic and metallic contaminants. Benzothiazole and 2(3H)-benzothiazolone (organic compounds used in tire rubber manufacturing) and the metals mercury and aluminum were leached in potentially harmful concentrations (exceeding toxic concentrations for aquatic toxicity tests). CR-AC leachate exhibited moderate to high toxicity for algae ( Selenastrum capriconutum) and moderate toxicity for water fleas ( Daphnia magna). Benzothiazole was readily removed from CR-AC leachate by the environmental processes of soil sorption, volatilization, and biodegradation. Metals, which do not volatilize or photochemically or biologically degrade, were removed from the leachate by soil sorption. Contaminants from CR-AC leachates are thus degraded or retarded in their transport through nearby soils and ground waters.

Animals↗

PubMed1996

Energy transfer reactions involving carotenoids: quenching of chlorophyll fluorescence.

Carotenoids have a key role in photosynthesis in photosynthetic systems, transferring excitation energy to chlorophyll (Chl) during light harvesting. These pigments also protect the photosynthetic apparatus from photodamage by quenching the Chl triplet state and singlet oxygen. In addition, in higher plants and some algae, a number of xanthophylls also have the ability to deactivate excited Chl under conditions of excess excitation via the operation of the xanthophyll cycle (violaxanthin<-->antheraxanthin<-->zeaxanthin or diadinoxanthin<-->diatoxanthin). The formation of zexanthin (or diatoxanthin) can be clearly correlated with the non-photochemical quenching of Chl fluorescence, and is now recognized as a major photoprotective process in higher plants and a number of algal genera. The interconversion of these xanthophylls in response to a changing light environment alters the extent of their carbon-carbon double bond conjugation, which, in turn, affects the excited state energies and lifetimes of the carotenoids and may also alter their structure/conformation and hydrophobicity. The possible roles of these photophysical and physicochemical changes in the mechanism(s) of xanthophyll-mediated energy dissipation via quenching of Chl fluorescence are discussed.

Carotenoids↗

PubMed1985

Reactivities of tyrosine, histidine, tryptophan, and methionine in radical pair formation in flavin triplet induced protein nuclear magnetic polarization.

In order to check the validity of several basic assumptions of protein photochemically induced nuclear polarization (protein photo-CIDNP), we have investigated the quenching processes of the dye triplets by the side chains of tyrosine, histidine, and tryptophan in a variety of molecular systems and environments. The quenching (H atom or electron transfer) is the generating process of the triplet electron-spin-correlated radical pair, the evolution of which gives rise to nuclear polarization. At pH 7 the quenching of 10-(carboxyethyl)flavin triplets by tyrosine and tryptophan is almost diffusion controlled. Quenching by histidine is slower. We have also investigated the slow quenching (by electron transfer) by the side chains of methionine and could show that quenching by cysteine S derivatives is negligible. Quenching by tyrosine and histidine peptides and by the tyrosines of the pancreatic trypsin inhibitor protein is slightly slower than by free side chains. Quenching is strongly viscosity controlled, to be expected of a process requiring bimolecular contact. Reactivity trends at high viscosities resemble those observed in fluid aqueous solutions. Activation energies of quenching by tyrosine, tryptophan, and histidine are similar. No difference could be detected in the mechanism of quenching by these side chains. No fast static quenching was observed that could compete with the diffusional process.

Flavins↗

PubMed2003

Anticipatory active-site motions and chromophore distortion prime photoreceptor PYP for light activation.

Protein photoreceptors use small-molecule cofactors called chromophores to detect light. Only under the influence of the receptors' active sites do these chromophores adopt spectral and photochemical properties that suit the receptors' functional requirements. This protein-induced change in chromophore properties is called photochemical tuning and is a prime example for the general--but poorly understood--process of chemical tuning through which proteins shape the reactivity of their active-site groups. Here we report the 0.82-A resolution X-ray structure of the bacterial light receptor photoactive yellow protein (PYP). The unusually precise structure reveals deviations from expected molecular geometries and anisotropic atomic displacements in the PYP active site. Our analysis of these deviations points directly to the intramolecular forces and active-site dynamics that tune the properties of PYP's chromophore to absorb blue light, suppress fluorescence, and favor the required light-driven double-bond isomerization.

Bacterial Proteins↗

PubMed2003

Application of nano TiO(2) towards polluted water treatment combined with electro-photochemical method.

A novel composite reactor was prepared and studied towards the degradation of organic pollutants in this work. In the reactor, a UV lamp was installed to provide energy to excite nano TiO(2), which served as photocatalyst, leading to the production of hole-electron pairs, and a three-electrode electrolysis system was used to accumulate H(2)O(2) which played an important role in the degradation process. The reactor was evaluated by the degradation process of rhodamine 6G (R-6G), and the data obtained in the experiments showed that the combination of the photochemical and electrochemical system raised the degradation rate of R-6G greatly; the working mechanism of the reactor was also discussed in the article. The prepared reactor was also utilized to treat polluted water from dyeing and printing process. After continuous treatment for 0.5h, chemical oxygen demand biochemical oxygen demand, quantity of bacteria and ammonia nitrogen of the polluted water were reduced by 93.9%, 87.6%, 99.9% and 67.5%, respectively, which indicated that the method used here could be used for effective organic dyes degradation.

Catalysis↗

PubMedDate not supplied

Studies on simulated ageing of paper by photochemical degradation.

The study of the ageing of two paper types was performed on monitoring it during a simulated process by means of the measure of the photocatalytic degradation of the paper cellulose. Such evaluation was possible due to the combined responses of a photosensor based on titanium dioxide in suspension, of an enzymatic biosensor based on superoxide dismutase (SOD), of a specific conductivity sensor and of an enzymatic biosensor based on glucose oxidase.

Biosensing Techniques↗

PubMed2006

Photochemical degradation of diethyl phthalate with UV/H2O2.

The decomposition of diethyl phthalate (DEP) in water using UV-H2O2 process was investigated in this paper. DEP cannot be effectively removed by UV radiation and H2O2 oxidation alone, while UV-H2O2 combination process proved to be effective and could degrade this compound completely. With initial concentration about 1.0mg/L, more than 98.6% of DEP can be removed at time of 60 min under intensity of UV radiation of 133.9 microW/cm2 and H2O2 dosage of 20mg/L. The effects of applied H2O2 dose, UV radiation intensity, water temperature and initial concentration of DEP on the degradation of DEP have been examined in this study. Degradation mechanisms of DEP with hydroxyl radicals oxidation also have been discussed. Removal rate of DEP was sensitive to the operational parameters. A simple kinetic model is proposed which confirms to pseudo-first order reaction. There is a linear relationship between rate constant k and UV intensity and H2O2 concentration.

Chromatography, Gas↗

PubMedDate not supplied

A study of the spatiotemporal health impacts of ozone exposure.

Exposure analysis and mapping of spatiotemporal pollutants in relation to their health effects are important challenges facing environmental health scientists and integrated assessment modellers. In this work, a methodological framework is discussed to study the impact of spatiotemporal ozone (O3) exposure distributions on the health of human populations. The framework, however, is very general and can be used to study various other pollutants. The spatiotemporal analysis starts with exposure distributions producing the input to pollutokinetic (or toxicokinetic) laws which are linked to effect models which, in turn, are integrated with relationships that describe how effects are distributed across populations. Important characteristics of the environmental health framework are holisticity and stochasticity. Holisticity emphasizes the functional relationships between composite space/time O3 maps, pollutokinetic models of burden on target organs and tissues, and health effects. These relationships offer a meaningful physical interpretation of the exposure and biological processes that affect human exposure. Stochasticity involves the rigorous representation of natural uncertainties and biological variations in terms of spatiotemporal random fields. The stochastic perspective introduces a deeper epistemological understanding in the development of improved models of spatiotemporal human exposure analysis and mapping. Also, it explicitly determines the knowledge bases available and develops logically plausible rules and standards for data processing and human exposure map construction. The proposed approach allows the horizontal integration among sciences related to the human exposure problem that leads to accurate and informative spatiotemporal maps of O3 exposure and effect distributions and an integrative analysis of the whole risk case. By processing a variety of knowledge bases, the spatiotemporal analysis can bring together several sciences which are all relevant to the aspect of human exposure reality that is examined.

Body Burden↗

PubMed2006

Very strong UV-A light temporally separates the photoinhibition of photosystem II into light-induced inactivation and repair.

When organisms that perform oxygenic photosynthesis are exposed to strong visible or UV light, inactivation of photosystem II (PSII) occurs. However, such organisms are able rapidly to repair the photoinactivated PSII. The phenomenon of photoinactivation and repair is known as photoinhibition. Under normal laboratory conditions, the rate of repair is similar to or faster than the rate of photoinactivation, preventing the detailed analysis of photoinactivation and repair as separate processes. We report here that, using strong UV-A light from a laser, we were able to analyze separately the photoinactivation and repair of photosystem II in the cyanobacterium Synechocystis sp. PCC 6803. Very strong UV-A light at 364 nm and a photon flux density of 2600 micromol photons m(-2) s(-1) inactivated the oxygen-evolving machinery and the photochemical reaction center of PSII within 1 or 2 min before the first step in the repair process, namely, the degradation of the D1 protein, occurred. During subsequent incubation of cells in weak visible light, the activity of PSII recovered fully within 30 min and this process depended on protein synthesis. During subsequent incubation of cells in darkness for 60 min, the D1 protein of the photoinactivated PSII was degraded. Further incubation in weak visible light resulted in the rapid restoration of the activity of PSII. These observations suggest that very strong UV-A light is a useful tool for the analysis of the repair of PSII after photoinactivation.

Darkness↗

PubMed1987

[Spectrophotometric research on the photochemical isomerization of the polyene macrolide antibiotic levorin A2].

Photochemical (cis-trans) isomerization of levorin A2 under the effect of light at wave lengths of 313 and 365 nm (excitation of the polyenic system and p-aminobenzoylene respectively) was studied. In case of the polyenic system excitation the reaction was reversible and the process quantum yield was extremely low while the use of light at the wave length of 313 nm as photochemical activator resulted in increasing the quantum yield by two orders. In this case triplet-triplet transfer of energy took place. A calculation procedure is recommended for quantitative determination of the quantum yield of levorin isomerization including direct and reverse reactions. The procedure may be used in study of other objects with similar mechanisms of phototransformation.

Antifungal Agents↗