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PubMedDate not supplied

Comparison by PAM fluorometry of photosynthetic activity of nine marine phytoplankton grown under identical conditions.

The photosynthetic activity of marine phytoplankton from five algal classes (Phaeodactylum tricornutum, Skeletonema costatum, Thalassiosira oceanica, Thalassiosira weissflogii, Dunaliella tertiolecta, Mantoniella squamata, Emiliania huxleyi, Pavlova lutheri and Heterosigma akashiwo) was investigated under identical growth conditions to determine interspecies differences. Primary photochemistry and electron transport capacity of individual species were examined by pulse amplitude-modulated (PAM) fluorescence. Although few differences were found in maximal photosystem II (PSII) photochemical efficiency between various species, large differences were noticed in their PSII-photosystem I (PSI) electron transport activity. We found that species such as T. oceanica and M. squamata have much lower photochemical activity than H. akashiwo. It appeared that processes involved in electron transport activity were more susceptible to change during algal evolution compared with the primary photochemical act close to PSII. Large variations in the nonphotochemical energy dissipation event among species were also observed. Light energy required to saturate photosynthesis was very different between species. We have shown that M. squamata and H. akashiwo required higher light energy (>1300 micromol m(-2) s(-1)) to saturate photosynthesis compared with S. costatum and E. huxleyi (ca 280 micromol m(-2) s(-1)). These differences were interpreted to be the result of variations in the size of light-harvesting complexes associated with PSII. These disparities in photosynthetic activity might modulate algal community structure in the natural environment where light energy is highly variable. Our results suggest that for an accurate evaluation of primary productivity from fluorescence measurements, it is essential to know the species composition of the algal community and the individual photosynthetic capacity related to the major phytoplankton species present in the natural phytoplankton assemblage.

Electron Transport↗

PubMed2005

Oxidation of Fe(II) in rainwater.

Photochemically produced Fe(II) is oxidized within hours under environmentally realistic conditions in rainwater. The diurnal variation between photochemical production and reoxidation of Fe(II) observed in our laboratory accurately mimics the behavior of ferrous iron observed in field studies where the highest concentrations of dissolved Fe(ll) occur in afternoon rain during the period of maximum sunlight intensity followed by gradually decreasing concentrations eventually returning to early morning pre-light values. The experimental work presented here, along with the results of kinetics studies done by others, suggests thatthe primary process responsible for the decline in photochemically produced Fe(II) concentrations is oxidation by hydrogen peroxide. This reaction is first order with respect to both the concentrations of Fe(II) and H2O2. The second-order rate constant determined for six different authentic rain samples varied over an order of magnitude and was always less than or equal to the rate constant determined for this reaction in simple acidic solutions. Oxidation of photochemically produced ferrous iron by other oxidants including molecular oxygen, ozone, hydroxyl radical, hydroperoxyl/superoxide radical, and hexavalent chromium were found to be insignificant under the conditions present in rainwater. This study shows that Fe(II) occurs as at least two different chemical species in rain; photochemically produced Fe(II) that is oxidized over time periods of hours, and a background Fe(II) that is protected against oxidation, perhaps by organic complexation, and is stable against oxidation for days. Because the rate of oxidation of photochemically produced Fe(II) does not increase with increasing rainwater pH, the speciation of this more labile form of Fe(II) is also not controlled by simple hydrolysis reactions.

Chromium↗

PubMed2005

A multi-mode-driven molecular shuttle: photochemically and thermally reactive azobenzene rotaxanes.

The shuttling process of alpha-CyD in three rotaxanes (1-3) containing alpha-cyclodextrin (alpha-CyD) as a ring, azobenzene as a photoactive group, viologen as an energy barrier for slipping of the ring, and 2,4-dinitrobenzene as a stopper was investigated. The trans-cis photoisomerization of 1 by UV light irradiation occurred in both DMSO and water due to the movement of alpha-CyD toward the ethylene group, while the photoisomerization of 2 occurred in DMSO, but not in water. No photoisomerization was observed for 3 in both water and DMSO. The activation parameters of 1 and 1-ref in DMSO are subject to a compensation relation between deltaS(double dagger) and deltaH(double dagger); however, in water, the deltaS(double dagger) terms are not compensated by the deltaH(double dagger) terms. Alternating irradiation of the UV and visible lights resulted in a reversible change in the induced circular dichroism (ICD) bands of trans-1 and cis-1. In contrast, after the UV light irradiation, the ICD band of trans-2 decreased without the appearance of any bands of cis-2. The NMR spectra of 2 in DMSO showed coalescence of the split signals for the methylene and for the viologen protons due to the shuttling of alpha-CyD. Both the NOE differential spectra for cis-1 in water after UV light irradiation and 2 in DMSO after heating to 120 degrees C showed the negative NOE peaks assigned to interior protons of alpha-CyD, suggesting that alpha-CyD in cis-1 exists at the one ethylene moiety, and alpha-CyDs in cis-2 and 2 heated in DMSO exist at the propylene moieties.

Journal Article↗

PubMed1988

Plants and high temperature stress.

The effect of high temperature on higher plants is primarily on photosynthetic functions. The heat tolerance limit of leaves of higher plants coincides with (and appears to be determined by) the thermal sensitivity of primary photochemical reactions occurring in the thylakoid membrane system. Tolerance limits vary between genotypes, but are also subject to acclimation. Long-term acclimations can be superimposed upon fast adaptive adjustment of the thermal stability, occurring in the time range of a few hours. Light causes an increase in tolerance to heat, and this stabilization is related to the light-induced proton gradient. In addition to irreversible effects, high temperature may also cause large, reversible effects on the rate of photosynthesis. We report here some studies of photosynthetic gas exchange and chlorophyll fluorescence, designed to examine the energetic balance between photosynthetic carbon metabolism and light reactions during steady state photosynthesis with leaves of cotton plants at different temperatures. At temperatures exceeding the optimum for assimilation, but well below the tolerance limit, the feedback control of light reactions by carbon metabolism declines, as additional dissipative processes become important. Energy dissipated by photorespiration can exceed that consumed by CO2 assimilation, and a reversible, temperature-induced non-photochemical 'quenching' process, related to 'spillover' of excitation energy to photosystem 1, decreases the efficiency of photosystem 2 with increasing temperature. However, despite the overall decline in the 'potential quantum efficiency', our analysis indicates that CO2 assimilation may be limited, in part, at high temperature by an imbalance in the regulation of the carbon metabolism, which is reflected in a 'down-regulation' of the ribulose-1,5-bisphosphate carboxylase/oxygenase.

Adaptation, Physiological↗

PubMed2006

[The role of free radicals in the UV-induced skin damage. Photo-aging].

The natural (intrinsic) ageing of the skin is enhanced by environmental factors (extrinsic ageing). One of the most important exogenous factors is the solar UV exposure, which results in photo-aging. Besides this, epidemiological and experimental data show a rapid increase in the incidence of human skin cancers, which is also in relation to the increased sunlight exposure of the skin. In the background of these processes there are cell biological effects, photochemical reactions, membrane receptor changes, lipid- and protein modifications, DNA-damage induced by UV. The qualities and quantities of them are wavelength dependent. The UVB photons are absorbed mostly by the DNA of the epidermal keratinocytes, therefore this spectrum is more relevant for photocarcinogenesis. The effect of UVA-irradiation is mainly manifested in the induction of free radicals, which have not only DNA-damaging, but also immunomodulating effect, which also can influence on tumour development. Furthermore, the free radicals cause dermal connective tissue damage as well via activating transcription factors, inducing matrix metalloproteinases, diminishing the procollagen I and fibrillin-1 synthesis. These processes are augmented by mitochondrial DNA mutations, protein oxidation, apoptosis induction. Therefore the enzymes neutralising free radicals and antioxidant molecules, respectively, have an important role in the defence mechanisms. In the therapy of photo-aging the local retinoids lived up to expectations, but the clinical effectiveness of antioxidant vitamins is lower than expected. The most important factor in the prevention of the photo-aging and photocarcinogenesis is the sun protection at present.

Antioxidants↗

PubMed1992

Modified apolipoprotein pattern after irradiation of human high-density lipoproteins by ultraviolet B.

The ultraviolet B-induced destruction of tryptophan residues and lipid peroxidation of high-density lipoproteins is accompanied by the immediate and marked structural modification of the apolipoproteins, as revealed by SDS-polyacrylamide gel electrophoresis and immunoblot with specific monoclonal antibodies. Formation of several polymers of apolipoprotein A-I, apolipoprotein A-II or both apolipoproteins occurred, although apolipoprotein A-II did not contain any Trp residue. These results suggest that initial photochemical damage can be transferred via intramacromolecular processes to other sites within the same apolipoprotein and by intermacromolecular reactions from apolipoprotein A-I to other apolipoproteins. In both cases, lipid peroxidation enhances the propagation of the initial photochemical damage. The physiological significance of this work is discussed with respect to the low-light doses required for the alterations of the high-density lipoproteins.

Apolipoprotein A-I↗

PubMed2002

Population dynamics in vibrational modes during non-Born-Oppenheimer processes: CARS spectroscopy used as a mode-selective filter.

The coupling of specific nuclear and electronic degrees of freedom of a molecular system during non-radiative electronic transitions plays a central role in photochemistry and photobiology. This breakdown of the Born-Oppenheimer approximation during processes such as internal conversion determines the mechanism and product distribution of photochemical reactions and is responsible for the high efficiency of photobiological processes. In order to explore this phenomena in beta-carotene, a molecule that plays a primary role as an auxiliary light-harvesting pigment in photosynthesis, a spectroscopic method was employed that allows for the individual vibrational modes to be monitored selectively within the dynamics of an internal conversion process. This spectroscopic technique employs an initial pump laser to excite the molecule into an excited electronic state and resolves the subsequent relaxation process by interrogating the system with a time-delayed, coherent anti-Stokes Raman process (CARS), which acts as a mode-selective filter for observing the population flow within specific vibrational modes with a time resolution in the femtosecond regime.

Journal Article↗

PubMed2000

[Photochemical immobilization--a new approach to surface modification of medical polymer materials].

The present paper reviews the approach of surface modification of medical polymer materials-photochemical immobilization. The approach is dramatically different from any other surface modification process available for medical materials. The topics include the principle of photochemical immobilization, the fundamental classification photoreactive groups and the typical applications of photochemical surface modification.

Biocompatible Materials↗

PubMed1964

RAT ELECTRORETINOGRAM: EVIDENCE FOR SEPARATE PROCESSES GOVERNING B-WAVE LATENCY AND AMPLITUDE.

Studies of the simultaneous changes in the latency and amplitude of the b-wave of the rat electroretinogram (ERG) under three different conditions of adaptation show that the latency is primarily a function of the absolute stimulus intensity, being only slightly affected by conditions that strongly reduce the amplitude. This implies that the latency and the amplitude are determined by two independent processes, with the latency-process more closely linked to the initial photochemical events. Furthermore, the different adaptation conditions have surprisingly similar effects on the shape and amplitude of the electroretinogram, which suggests that they all produce only one type of variation in the amplitudedetermining process.

Acclimatization↗

PubMedDate not supplied

Reducing the infectivity of blood components--what we have learned.

The safety of the nation's blood supply has improved over the last several years as a result of more intensive donor screening and viral testing. Concurrently, there has been more judicious use of blood components. Although the risk is small, transmission of blood borne viruses, bacteria and parasites can occur. Investigators have studied a myriad of processes for pathogen depletion and/or inactivation, including the use of chemicals, extended storage, filtration, heating, irradiation, photochemicals and washing. Pasteurization, methylene blue and solvent-detergent processes have been introduced in parts of Europe for improving the safety of plasma used for transfusion. The FDA is reviewing a license application for the solvent-detergent process. For red cells, use of highly efficient leukodepletion filters is believed to be equivalent to antibody testing for the prevention of CMV disease transmission. Otherwise, no successful treatments have yet been identified for red cells or platelets. Several photochemicals, which may be useful for treating these components, are being studied. However, there appear to be trade-offs between the extent of pathogen inactivation, platelet or red cell damage, and genotoxicity. These as well as other biological parameters and operational issues will need to be further evaluated before implementation can be considered.

Blood↗

PubMed2005

Understanding of the mode of action of Fe(III)-EDDHA as iron chlorosis corrector based on its photochemical and redox behavior.

The very low reduction potential of the chelate Fe(III)-EDDHA (EDDHA = ethylenediamine N,N'-bis(2-hydroxy)phenylacetic acid) makes it unreactive in photochemically or chemically induced electron transfer processes. The lack of reactivity of this complex toward light invalidates photodegradation as an alternative mechanism for environmental elimination. However, in spite of its low reduction potential, the biological reduction of Fe(III)-EDDHA is very effective. Based on electrochemical measurements, it is proposed that Fe(III)-EDDHA itself is not the substrate of the enzyme ferric chelate reductase. Likely, at the more acidic pH in the vicinity of the roots, the ferric chelate in a closed form (FeL-) could generate a vacant coordination site that leads to an open hexacoordinate species (FeHL) where the reduction of the metal by the enzyme takes place.

Journal Article↗

PubMed1980

Influence of recC and uvrD on ultraviolet-induced mutation to valine resistance in E. coli K12.

The production of mutants in E. coli exposed to ultraviolet light is initiated by photochemical reactions, and completed by metabolic processes controlled by recA and other genes. Ultraviolet-induced mutagenesis to valine resistance was measured in cells carrying recC, uvrD, or both recC and uvrD. The spontaneous and UV-induced mutagenesis was slightly greater in those carrying uvrD, as compared to recC or wild-type. At low doses, UV mutagenesis in the recC uvrD double mutant was greater than in either recC or wild-type, and was comparable to that in the uvrD strain, although this double mutant was very UV-sensitive and showed poor survival at doses above 2 J/m2.

Dose-Response Relationship, Radiation↗

PubMed2006

Degradation of bisphenol A in aqueous solution by H2O2-assisted photoelectrocatalytic oxidation.

A series of titanium dioxide (TiO(2)/Ti) film electrodes were prepared from titanium (Ti) metal mesh by an improved anodic oxidation process and were further modified by photochemically depositing gold (Au) on the TiO(2) film surface as Au-TiO(2)/Ti film electrodes. The morphological characteristics, crystal structure and photoelectroreactivity of both the TiO(2)/Ti and Au-TiO(2)/Ti electrodes were studied. The experiments confirmed that the gold modification of TiO(2) film could enhance the efficiency of e(-)/h(+) separation on the TiO(2) conduction band and resulted in the higher photocatalytic (PC) and photoelectrocatalytic (PEC) activity under UV or visible illumination. To further enhance the TiO(2) PEC reaction, a reticulated vitreous carbon (RVC) electrode was applied in the same reaction system as the cathode to electrically generate H(2)O(2) in the aqueous solution. The experiments demonstrated that such a H(2)O(2)-assisted TiO(2) PEC reaction system could achieve a much better performance of BPA degradation in aqueous solution due to an interactive effect among TiO(2), Au, and H(2)O(2). It may have good potential for application in water and wastewater treatment in the future.

Benzhydryl Compounds↗

PubMed1994

Kinetics of relaxation from rigor of permeabilized fast-twitch skeletal fibers from the rabbit using a novel caged ATP and apyrase.

The complex time course of tension decay was investigated in fast-twitch permeabilized rabbit muscle fibers when they were relaxed from the rigor state using photochemical generation of ATP. A novel caged ATP compound, the P3-3',5'-dimethoxybenzoin ester of ATP (DMB-caged ATP), as well as the P3-1-(2-nitrophenyl)ethyl ester of ATP (NPE-caged ATP), have been used. DMB-caged ATP photolyzes at least three orders of magnitude more rapidly than NPE-caged ATP. The role of ADP on relaxation kinetics from rigor was examined by using apyrase to remove ADP from the rigor muscle solutions. The presence of Pi-sensitive states was investigated from the effect of Pi on relaxation. Rigor tension was varied enabling the influence of tension on the relaxation to be examined. The time course of relaxation was faster with DMB-caged ATP compared with NPE-caged ATP for concentrations of ATP released by photolysis greater than 0.7 mM. Most of the complexity in the relaxation tension records was caused by ADP. In the absence of ADP, tension decayed monotonically after photochemical release of ATP in a process whose rate was unaffected by Pi. In the presence of ADP, relaxation was more complex and tension passed through a maximum. A model invoking cooperative interactions involving ADP-containing myosin heads provides a reasonable description of the data.

Adenosine Diphosphate↗

PubMedDate not supplied

Reversible photocontrol of peptide helix content: adjusting thermal stability of the cis state.

Cross-linking reagents based on an azobenzene core can be used to reversibly photoregulate secondary structure when introduced as intramolecular bridges in peptides and proteins. Photoisomerization of the azobenzene core in the trans to cis direction is triggered by photon absorption but isomerization from cis to trans occurs thermally as well as photochemically. The rate of the thermal process effectively determines the half-life of the cis form as well as the extent to which the trans form can be recovered. We designed and characterized a series of methanethiosulfonate (MTS)-bearing thiol-reactive azo-benzene-based cross-linkers. These cross-linkers are shown to permit photoregulation of helix content in a test peptide with half-lives for the cis conformation ranging from 11 s to 43 h at 25 degrees C. The cross-linkers described here thus broaden the range of reagents available for reversible photocontrol of peptide and protein conformation.

Cross-Linking Reagents↗

PubMed2006

Molecular spectroscopy: complexity of excited-state dynamics in DNA.

Absorption of ultraviolet light by DNA is known to lead to carcinogenic mutations, but the processes between photon absorption and the photochemical reactions are poorly understood. In their study of the excited-stated dynamics of model DNA helices using femtosecond transient absorption spectroscopy, Crespo-Hernández et al. observe that the picosecond component of the transient signals recorded for the adenine-thymine oligonucleotide (dA)18.(dT)18 is close to that for (dA)18, but quite different from that for (dAdT)9.(dAdT)9; from this observation, they conclude that excimer formation limits excitation energy to one strand at a time. Here we use time-resolved fluorescence spectroscopy to probe the excited-state dynamics, which reveals the complexity of these systems and indicates that the interpretation of Crespo-Hernández et al. is an oversimplification. We also comment on the pertinence of separating base stacking and base pairing in excited-state dynamics of double helices and question the authors' assignment of the long-lived signal component found for (dA)18.(dT)18 to adenine excimers.

Adenine↗

PubMed2006

Contrasting photochemical and thermal reactivity of Ru(CO)2(PPh3)(dppe) towards hydrogen rationalised by parahydrogen NMR and DFT studies.

The synthesis, characterisation and thermal and photochemical reactivity of Ru(CO)2(PPh3)(dppe) 1 towards hydrogen are described. Compound proved to exist in both fac (major) and mer forms in solution. Under thermal conditions, PPh3 is lost from 1 in the major reaction pathway and the known complex Ru(CO)2(dppe)(H)2 2 is formed. Photochemically, CO loss is the dominant process, leading to the alternative dihydride Ru(CO)(PPh3)(dppe)(H)2 3. The major isomer of 3, viz. 3a, contains hydride ligands that are trans to CO and trans to one of the phosphorus atoms of the dppe ligand but a second isomer, 3b, where both hydride ligands are trans to distinct phosphines, is also formed. On the NMR timescale, no interconversion of 3a and 3b was observed, although hydride site interchange is evident with activation parameters of DeltaH(double dagger) = 95 +/- 6 kJ mol(-1) and DeltaS(double dagger) = 26 +/- 17 J K(-1) mol(-1). Density functional theory confirms that the observed species are the most stable isomeric forms, and suggests that hydride exchange occurs via a transition state featuring an eta2-coordinated H2 unit.

Journal Article↗

PubMed1992

A proposed function for spermine and spermidine: protection of replicating DNA against damage by singlet oxygen.

Like all aliphatic amines, the polyamines spermine and spermidine are physical quenchers of singlet molecular oxygen (1O2*). The rate constants of these processes were determined in vitro with photochemically generated 1O2* and the hydrocarbon rubrene as substrate, in pyridine. At millimolar concentration, spermine and spermidine should quench 1O2* in vivo and prevent it from damaging DNA. It is proposed that a biological function of polyamines is the protection of replicating DNA against oxidative damage.

DNA↗