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PubMed2004

Preparation, characterization, and condensation of copper tellurolate clusters in the pores of periodic mesoporous silica MCM-41.

The copper-tellurolate cluster [(Cu(6)(TePh)(6)(PPh(2)Et)(5)] has been loaded into the pores of MCM-41 by solid-state impregnation techniques. It was found that the best loading conditions are 110 degrees C and 10(-)(3) Torr static vacuum. The resulting material was analyzed by powder X-ray diffraction (PXRD), nitrogen adsorption isotherms, thermogravimetric analysis (TGA), (31)P CP MAS NMR spectroscopy, and TEM. It was observed that loading is accompanied by loss of the phosphine shell, with retention of the copper-tellurium core. Condensation of the impregnated material may proceed thermally or photochemically. Thermal condensation results in the formation of Cu(2)Te nanoparticles as demonstrated by PXRD, and TEM data suggests that the process has taken place inside the pores of MCM-41. Photochemical condensation yields larger metal-chalcogen clusters in the pores as suggested by the result of UV-vis diffuse reflectance spectroscopy and TEM measurements.

Journal Article↗

PubMed2001

Photochemical cycling of iron in the surface ocean mediated by microbial iron(III)-binding ligands.

Iron is a limiting nutrient for primary production in large areas of the oceans. Dissolved iron(III) in the upper oceans occurs almost entirely in the form of complexes with strong organic ligands presumed to be of biological origin. Although the importance of organic ligands to aquatic iron cycling is becoming clear, the mechanism by which they are involved in this process remains uncertain. Here we report observations of photochemical reactions involving Fe(III) bound to siderophores--high-affinity iron(III) ligands produced by bacteria to facilitate iron acquisition. We show that photolysis of Fe(III)-siderophore complexes leads to the formation of lower-affinity Fe(III) ligands and the reduction of Fe(III), increasing the availability of siderophore-bound iron for uptake by planktonic assemblages. These photochemical reactions are mediated by the alpha-hydroxy acid moiety, a group which has generally been found to be present in the marine siderophores that have been characterized. We suggest that Fe(III)-binding ligands can enhance the photolytic production of reactive iron species in the euphotic zone and so influence iron availability in aquatic systems.

Bacteria↗

PubMed2005

Photochemical hydrosilylation of 11-undecenyltriethylammonium bromide with hydrogen-terminated Si surfaces for the development of robust microcantilever sensors for Cr(VI).

We report a novel approach to the design and development of microcantilever sensors in which photochemical hydrosilylation is used to modify the microcantilever surface. This process enables individual microcantilevers in multicantilever array chips to be modified separately by focusing the activating UV light sequentially on each particular cantilever. Photochemical hydrosilylation of 11-undecenyltriethylammonium bromide with hydrogen-terminated silicon microcantilever surfaces was carried out to yield a robust quaternary ammonium terminated organic monolayer suitable for chromate detection. The surface functionalities retain their affinity toward Cr(VI), and the organic monolayer is dense enough to generate significant surface stress upon subsequent adsorption of chromate ions from aqueous solutions.

Letter↗

PubMed2003

Photocatalytic processes with tungsten oxygen anion clusters.

Polyoxometalates (POM) have a rich and promising photochemical behavior. Upon illumination at the O M CT band (i.e., in UV and near-visible area) become powerful oxidizing reagents able to oxidize various organic compounds. In the process POM undergo stepwise reduction accumulating electrons that can be subsequently delivered, via thermal reactions to a variety of oxidants. This way a great variety of organic compounds are oxidized and indeed mineralize to CO2, H2O and inorganic anions and several organic and inorganic compounds can be reduced via a photocatalytic process in which POM serve as electron relays. Thus, in principle, POM can serve as decontamination photocatalysts of aquatic media removing both organic pollutants and metal ions. Under special conditions controlled photocatalytic reactions have been reported. In addition the reduction precipitation of metal ions mediated by POM may lead to formation of metal nanoparticles in which POM serve as reducing reagents and stabilizers.

Anions↗

PubMed2004

In vitro evaluation of COM.TEC apheresis platelet concentrates using a preparation set and pathogen inactivation over a storage period of five days.

The aim of the present study was to evaluate in vitro data on platelets collected by apheresis, processed on a preparation set followed by photochemical treatment (PCT). Fifteen single-donor platelet concentrates (PCs) were collected by apheresis (COM.TEC blood cell separator, Fresenius, Bad Homburg, Germany). The platelets were transferred to the preparation set and plasma was removed after centrifugation to resuspend the platelets in approximately 37% plasma and 63% platelet additive solution InterSol. PCT was done by exposing the platelets to amotosalen HCl followed by illumination with ultraviolet light. Blood cell counts and in vitro PLT function were measured up to 5 days. An average of 3.44 +/- 0.28 x 10(11) platelets were collected in a product volume of 351 +/- 21 mL. Plasma removal resulted in a mean platelet loss of 7.8%. After PCT, a progressive decrease in platelet function was observed. LDH level rose through storage (171 +/- 81 U/L) to levels approximating LDH levels observed post-collection (180 +/- 103 U/L). There was a gradual decrease of the platelets to respond to hypotonic shock response from 90 +/- 9 % post-plasma reduction to 48 +/- 16% at day 5. All PLT units met the European requirements for leukoreduction and the pH limit of 6.8 up to day 5 post-collection. The new preparation set was capable of producing platelet units meeting the requirements for PCT. Despite differences observed in in vitro platelet function parameters, PLTs at storage day 5 fit the German and European guidelines.

Blood Component Removal↗

PubMed1984

Spatial dissipative structures formed by spontaneous molecular aggregation at interfaces.

Interfacial processes as well as formation of dissipative structures have been suggested to play a key role in early pre-biotic evolutionary stages, mainly due to the ability of such processes to induce aggregation and spatial structuring. In this context we would like to draw attention to our recent findings regarding a remarkably wide collection of interfacial chemical reactions which form dissipative spatial structures. Three types of interfacial processes were found to yield this phenomenon: photochemical oxidations at liquid/air and liquid/liquid interfaces; gas/solution reactions; and reactions at membrane surfaces. The phenomenon we describe is the first major example of a network of chemical reactions that develop into macroscopic far-from-equilibrium concentration patterns.

Aniline Compounds↗

PubMed1988

Atmospheric ozone: formation and effects on vegetation.

Ozone (O(3)) is present both in the troposphere and the stratosphere. Troposphere O(3) is predominantly produced by photochemical reactions involving precursors generated by natural processes and to a much larger extent by man's activities. There is evidence for a trend towards increasing tropospheric O(3) concentrations. However, tropospheric O(3) is known to account for only 10% of the vertical O(3) column above the earth's surface. The stratosphere accounts for an additional 90% of the O(3) column. There is evidence to suggest that there are losses in the stratospheric O(3) due to the updraft of O(3) destroying pollutants generated by both natural processes and by human activity. Such a loss in stratospheric O(3) can result in alterations of incidence in the ultraviolet (UV) radiation to the earth's surface. Tropospheric O(3) is known to be highly phytotoxic. Appropriate exposures to O(3) can result in both acute (symptomatic) and chronic (changes in growth, yield or productivity and quality) effects. Chronic effects are of great concern in terms of both crops and forests. A number of experimental techniques are available to evaluate the chronic effects of O(3) on plants. There are limitations attached to the use of these techniques. However, results obtained, with such techniques are valuable if interpreted in the appropriate context. Among all field evaluation techniques, open-top chambers are the most frequently used method for evaluating the chronic effects of O(3) on crops. The National Crop Loss Assessment Program (NCLAN) of the United States is the largest such effort. However, given the limitations of the open-top chambers and the experimental aspects of NCLAN, its results must be interpreted with caution. On the other hand, acute effects can be evaluated with less complexity through the use of biological indicator plants. The numerical modelling of such effects are also far less complicated than establishing numerical cause and effects relationships for chronic effects. Confounding the acute or chronic responses of plants to O(3), is the presence of other kinds and forms of pollutants in the ambient atmosphere and the incidence of pathogens and pests. The resulting complex interactions and joint effects on plants are poorly understood. Future research must address these issues. In the final analysis we have re-emphasized the fact that plant health is the product of its interaction with the physical and chemical climatology and pathogens and pests. What we have described in this context is the importance of tropospheric O(3) within the chemical climatology of our environment and its effects on vegetation.

Journal Article↗

PubMed2005

Control of the light harvesting function of chloroplast membranes: the LHCII-aggregation model for non-photochemical quenching.

Dissipation of excess excitation energy within the photosystem II light-harvesting antenna (LHCII) by non-photochemical quenching (NPQ) is an important photoprotective process in plants. An update to a hypothesis for the mechanism of NPQ [FEBS Letters 292, 1991] is presented. The impact of recent advances in understanding the structure, organisation and photophysics of LHCII is assessed. We show possible locations of the predicted regulatory and quenching pigment-binding sites in the structural model of the major LHCII. We suggest that NPQ is a highly regulated concerted response of the organised thylakoid macrostructure, which can include different mechanisms and sites at different times.

Allosteric Site↗

PubMed1999

Artificial senescence of bovine retinal pigment epithelial cells induced by near-ultraviolet in vitro.

RPE cells irradiated by near-ultraviolet (NUV) were characterized at cellular, biochemical and molecular levels in order to determine whether light-induced RPE changes contribute to the senescence of RPE cells in vitro. Biochemical and molecular parameters of cellular senescence were studied by using both bovine RPE cells at confluence repeatedly irradiated by NUV (peaking at 365 nm) and RPE cells at different levels of population doubling (PDL). After repeated NUV irradiation, RPE proliferation was markedly suppressed. In parallel, the BrdU index significantly reduced to a minimum level, similar to RPE cells undergoing multiple population doublings. NUV irradiation resulted in a decrease in cellular alkali-soluble melanin and an increase in lipofuscin-like fluorophores. The lipofuscin-like fluorophores, isolated from RPE cells exposing repeated NUV irradiation, represented a gradual hyperchromic change and red-shift, reaching the wavelength maxima (560-572 nm), at excitation wavelength of 365 nm, a typical range of 'age pigment'. These phenomena were substantially eliminated in oxygen-free conditions. Both the NUV-irradiated RPE cells and RPE cells at 20 Pd expressed 4 to 8-fold and 2 to 4-fold less PEDF and TIMP-3 genes, respectively. As result of experiments using chronic photochemical treatment, RPE cells represented several characteristics of cellular senescence. In addition to alterations of the melanin/lipofuscin system, DNA synthesis was greatly suppressed in NUV-irradiated RPE cells, indicating replicative senescence. The phenomena of downregulation of the possible senescence markers imply that photochemical reactions of RPE cells accelerate the process of RPE senescence.

Animals↗

PubMed2002

Quantitative cavities and reactivity in stages of crystal lattices: mechanistic and exploratory organic photochemistry.

In continuing our research on solid-state organic photochemistry, we have been investigating the phenomenon of reactivity in stages. In this study we present new examples where the photochemical reactivity changes discontinuously at some point in the conversion. In these instances, the reaction course of the solid differs from that in solution. One example is the reaction of 2-methyl-4,4-diphenylcyclohexenone, where an unusual reaction course was encountered in the solid state; and, of two possible mechanisms, one was established by isotopic labeling. A second case is that of 4,5,5-triphenylcyclohexenone. The solid-state reaction of this enone was found to give a new photochemical transformation, the Type C rearrangement, a process that involves a delta to alpha aryl migration. In the case of 3-tert-butyl-5,5-diphenylcyclohexenone the Type C rearrangement occurred even in solution. The stage behavior was investigated using X-ray analysis and Quantum Mechanics/Molecular Mechanics computations. This permitted us to determine the sources and details of the stage phenomenon. The analysis revealed how a product molecule as a neighbor affects reactivity. The computations were employed to follow the course of a solid-state reaction from reactant through the succeeding stages. Additionally, the Delta-Density Analysis was utilized to ascertain the electronic nature of molecular changes. Besides product composition changing with extent of conversion, the reaction quantum yield was found to change as one stage gave way to a succeeding one.

Journal Article↗

PubMed2004

New Fluorescence Parameters for the Determination of QA Redox State and Excitation Energy Fluxes.

A number of useful photosynthetic parameters are commonly derived from saturation pulse-induced fluorescence analysis. We show, that qP, an estimate of the fraction of open centers, is based on a pure 'puddle' antenna model, where each Photosystem (PS) II center possesses its own independent antenna system. This parameter is incompatible with more realistic models of the photosynthetic unit, where reaction centers are connected by shared antenna, that is, the so-called 'lake' or 'connected units' models. We thus introduce a new parameter, qL, based on a Stern-Volmer approach using a lake model, which estimates the fraction of open PS II centers. We suggest that qL should be a useful parameter for terrestrial plants consistent with a high connectivity of PS II units, whereas some marine species with distinct antenna architecture, may require the use of more complex parameters based on intermediate models of the photosynthetic unit. Another useful parameter calculated from fluorescence analysis is ΦII, the yield of PS II. In contrast to qL, we show that the ΦII parameter can be derived from either a pure 'lake' or pure 'puddle' model, and is thus likely to be a robust parameter. The energy absorbed by PS II is divided between the fraction used in photochemistry, ΦII, and that lost non-photochemically. We introduce two additional parameters that can be used to estimate the flux of excitation energy into competing non-photochemical pathways, the yield induced by downregulatory processes, ΦNPQ, and the yield for other energy losses, ΦNO.

antenna↗

PubMed1980

Phototransduction in the fly compound eye exhibits temporal resonances and a pure time delay.

Photoreceptor cells in both vertebrates and invertebrates respond to a flash of light with a slow graded change in membrane potential, which is generally depolarising in invertebrates and hyperpolarising in vertebrates. Although some of the early photochemical and biochemical stages of the transduction process have been elucidated in both cases, these reactions are fast compared with the time course of the electrical response, which is typically hundreds of milliseconds long. To explain this slow response in the eye of Limulus, Fuortes and Hodgkin proposed a mechanism in which the light signal passes through a cascade of simple low pass filters. The model was later defined more specifically in terms of a chain of chemical reactions linked together through products and reactants, and has been used with small modifications and different numbers of stages to account for the behaviour of various vertebrate and invertebrate photoreceptors including the fly compound eye. I have now obtained evidence that phototransduction in the fly in small signal conditions involves underdamped resonance behaviour and a significant pure time delay, neither of which can be accounted for by the conventional cascade model.

Animals↗

PubMed1991

Photoinduced degradation of the D1 polypeptide in isolated reaction centers of photosystem II: evidence for an autoproteolytic process triggered by the oxidizing side of the photosystem.

When the isolated D1/D2/cytochrome b559 complex was exposed to bright light, a distinctive pattern of D1 polypeptide fragments was observed under both aerobic and anaerobic conditions. The major degradation product had an apparent molecular mass of 24 kDa, while other fragments were detected at 17, 14, and 10 kDa by immunoblotting. This pattern was observed when the electron acceptors 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone or silicomolybdate were present during illumination. It is known that these conditions stabilize P680+ chlorophyll and bring about the photooxidation and destruction of pigments in the reaction center, particularly chlorophyll absorbing at 670 nm and beta-carotene. When P680+ was not allowed to accumulate, either by omission of an electron acceptor or by addition of both an electron donor (Mn2+) and an acceptor, no breakdown fragments were observed. In the former case, however, some degradation of the D1 and D2 polypeptides did occur. Under conditions that gave rise to the characteristic D1 breakdown pattern, the D2 polypeptide was also degraded to specific fragments detected at about 29 and 21 kDa by immunoblotting. The results indicate that the photoinduced degradation of D1 (and D2) does not involve exogenous proteases but is most likely an autoproteolytic process. Moreover, our data indicate that the photochemical damage giving rise to D1 and D2 degradation occurs on the oxidizing rather than the reducing side of photosystem II and involves photooxidation of the accessory pigments. The results are discussed in terms of D1 and D2 turnover and photoinhibition.

Electrophoresis, Polyacrylamide Gel↗

PubMed1980

Role of lipids in functions of photosynthetic membranes revealed by treatment with lipolytic acyl hydrolase.

1. Thylakoid membranes and subchloroplast particles I and II enriched in photosystem I and photosystem II, respectively, were treated with a potato lipolytic acyl hydrolase. 2. In the thylakoid membrane fraction, this treatment inhibited electron flows involving both photosystems and the associated photophosphorylations. However, electron flows involving either photosystem I or photosystem II were still preserved. The treatment of thylakoid membranes by lipolytic acyl hydrolase brought about a temporal convergence of different events such as maximal activity of reduced dichloroindophenol-supported electron flows, complete inhibition of photophosphorylations and electron transport activities through photosystem II + I, onset of the decay N,N,N',N-tetramethyl-rho-phenylenediamine-supported activity of photosystem activity and of the stimulation of photosystem activity (from reduced dichloroindophenol to NADP+ by exogenous plastocyanin. 3. Lipolytic acyl hydrolase catalyzed a limited hydrolysis of each lipid but in a stepwise manner, the galactolipids being attacked before the ionic lipids. The extent of the hydrolysis was not more than 50% for each lipid. Most of the hydrolytic process occurred before any significant change in photochemical activities could be observed. 4. In subchloroplast particles I, a treatment by lipolytic acyl hydrolase did not greatly affect the electron transport whilst lipid hydrolysis was almost complete. 5. In subchloroplast particles II, neither the electron flow activities nor lipid content were significantly altered by lipolytic acyl hydrolase. 6. The sites of lipolytic acyl hydrolase action appeared to be localized between plastoquinones and P700. It is suggested that it is not possible to establish a quantitative and/or temporal correlation between the extent of lipid hydrolysis and the inhibition of photochemical activities. 7. The profile of the hydrolysis of lipids in thylakoid membranes suggests that ionic lipids are less accessible to lipolytic acyl hydrolase than galactolipids.

Chloroplasts↗

PubMed1992

Hoechst 33258 photosensitization of 5-iododeoxyuridine-substituted DNA to 365 nm light: dependence of dehalogenation on the dye-to-nucleotide ratio.

DNA containing 5-iododeoxyuridine substituted at levels ranging from 1 to 24% was irradiated at 365 nm in the presence of various amounts of the Hoechst dye 33258. The subsequent loss of iodine was measured by following the loss of radioactive iodine (125I) from filter immobilized DNA subjected to repeated washings. A plot of the photochemical cross section (sigma B) for this process as a function of r, the molar ratio of dye added per nucleotide present, shows a maximum at r = 0.04 to 0.06, followed by a decrease with increasing dye-to-phosphate ratios to give a minimum at r = 0.5. Increasing the amounts of dye further results in sigma B reaching a second maximum at r greater than or equal to 1, after which it levels off. An attempt was made to interpret these results in terms of the binding models currently employed for analyzing binding of Hoechst dye to DNA. Chain breaks as measured in alkali were also measured and found to be enhanced by the dye; the ratio of breaks per iodine loss was 0.9.

Bisbenzimidazole↗

PubMed1980

Photosensitization by drugs: photolysis of some chlorine-containing drugs.

Irradiation with ultraviolet light of chlorpromazine, prochlorperazine, frusemide or hydrochlorothiazide in either aqueous or methanol solution yielded free chloride ion. Potentiometric methods were used to detect one mol of chloride ion produced per mol of drug irradiated in deoxygenated solution, with a concomitant equimolar appearance of hydrogen ion. Saturation of the solutions with oxygen strongly inhibited the photolysis reaction in methanol but only partially inhibited the production of Cl- and H+ in aqueous solution. The oxidation of 2,5-dimethylfuran is photosensitized by these drugs more effectively in methanol compared with aqueous solution. The photochemical behaviour is consistent with a photodissociative process occurring predominantly in methanol while photoionization predominates in aqueous media. No chloride ion was detected after extended irradiation of chlortetracycline, demeclocycline, chlordiazepoxide and hexachlorophane. The photolability of the chlorine in the compounds tested correlated with their ability to photosensitize oxidation by the Type I (free radical) mechanism.

Chemistry, Pharmaceutical↗

PubMedDate not supplied

Plaque removal and thrombus dissolution with the photoacoustic energy of pulsed-wave lasers-biotissue interactions and their clinical manifestations.

Pulsed-wave lasers ablate atherosclerotic plaque and dissolve coronary thrombus by emission of photoacoustic energy initiating photomechanical, photochemical and photothermal transformation. The newly discovered process of 'inertially confined ablation' ascribes to pressure generation and plaque vaporization during lasing. Tremendous pressure within the lased plaque and gas bubble formation account for adverse clinical manifestations such as perforations, acute vessel closure and dissections. Pulsed-wave lasers can be applied for selected patients with lesions considered 'nonideal' for balloon angioplasty who present with acute ischemic syndromes. Due to strong optical absorption by thrombi in the ultraviolet (excimer), visible (dye), and mid-infrared (holmium) wavelengths, these lasers can also dissolve clots and therefore serve as an emerging option in patients with complicated acute myocardial infarction who fail to respond to thrombolytic drugs and exhibit thrombotic lesions deemed unsuitable for standard balloon angioplasty.

Acoustics↗

PubMed2005

Regulation of tissue factor-induced coagulation and platelet aggregation in flowing whole blood.

Photochemically induced thrombosis (a thrombin-dependent process) was measured in rats treated with moderate doses of anticoagulants, but which appeared to be unchanged. We considered the possibility that platelet-inhibiting agents, which also indirectly inhibit coagulation, would act as more potent antithrombotic agents. Inhibitors used as such were prostaglandin E1 (PGE1), which elevates cyclic AMP levels, and the P2Y12 ADP-receptor antagonist, AR-C69931MX. Effects of these agents were investigated in an ex vivo model system, in which whole blood under coagulant conditions was perfused over fibrinogen at defined wall shear rate. Perfusion of blood (rat or human) in the presence of tissue factor resulted in deposition of activated platelets and subsequent aggregate formation, along with exposure of procoagulant phosphatidylserine (PS) on the platelet surface and formation of fibrin fibers. In the presence of PGE1 aggregation was completely inhibited, but platelet adhesion and PS exposure were only party reduced, while fibrin formation was hardly affected. Treatment with AR-C69931MX caused similar, but less complete effects. These results indicate that in tissue factor-triggered blood under conditions of flow: (i) the platelet procoagulant response is independent of aggregate formation; (ii) the platelet-inhibiting effect of PGE1 and AR-C69931MX is sufficient to suppress aggregation, but not platelet adhesion and coagulation. These platelet inhibitors thus maintain their aggregation-inhibiting effect at sites of thrombin formation.

Adenosine Monophosphate↗