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PubMed1988

Combination cytotoxic chemotherapy with cisplatin or doxorubicin and photodynamic therapy in murine tumors.

This study was designed to evaluate the interaction of photodynamic therapy (PDT) and chemotherapy in an animal model. PDT is based on the interaction of hematoporphyrin derivative and red light of the appropriate wavelength (630 nm) and intensity. Two tumor models were utilized: C3H/Km mice bearing the RIF-1 tumor and BALB/c mice bearing the EMT-6 tumor. Tumor-bearing mice were treated with either cisplatin (DDP), doxorubicin (ADM), PDT, or a combination of drug and PDT. It was demonstrated that the RIF-1 tumor was sensitive to DDP and insensitive to both PDT and ADM. There was no additional antitumor effect when either drug was combined with PDT. The EMT-6 tumor was moderately sensitive to PDT and mildly sensitive to both DDP and ADM. Although the addition of DDP did not potentiate tumor destruction, the addition of ADM significantly enhanced the effect of PDT (P = .01). The enhanced activity of the combination of PDT and ADM appeared to be the result of increased activity of ADM alone, when illuminated with red (630 nm) light. This potentiation may be due to a photochemical process or may be secondary to the mild hyperthermia generated by illumination with the laser. This study demonstrates that PDT combined with cytotoxic chemotherapy is well tolerated in these animals and that certain combinations of PDT and chemotherapy may result in an enhanced tumoricidal effect.

Animals↗

PubMed1984

Nucleotide sequence of the gene for the P680 chlorophyll alpha apoprotein of the photosystem II reaction center from spinach.

The DNA sequence of 2210 nucleotides including the gene for the "51 kd" chlorophyll alpha-conjugated thylakoid membrane protein associated with the photosystem II reaction center of spinach has been determined. This protein is functionally identical with the P680 chlorophyll alpha apoprotein that catalyses the primary light-induced photochemical processes of photosystem II (Camm, E.L. and Green, B.R. (1983) Biochim. Biophys. Acta 724 291-293). The only large open reading frame in the sequence consists of 508 triplets encoding a protein of molecular mass of 56,246 kd. The deduced amino acid sequence shows clustering of hydrophobic residues into seven core regions which probably traverse the membrane, and a large hydrophilic domain of about 200 amino acids interspersed between span VI and VII. Potential transcription promotor and terminator signals flanking the structural gene show prokaryotic-like features. Seven discrete RNA species ranging in size from 2.0 to over 5.0 kilobases display complementarity to apoprotein coding sequences implying that the region can be polycistronically transcribed. The primary transcript includes information for at least two further genes coding for subunits of the cytochrome b/f complex.

Amino Acid Sequence↗

PubMed1999

Interactive effects of leaf age and self-shading on leaf structure, photosynthetic capacity and chlorophyll fluorescence in the rain forest tree, Dryobalanops aromatica.

In the tropical canopy tree, Dryobalanops aromatica Gaertn. f., upper-canopy leaves (UL) develop under sunlit conditions but are subjected to self-shading within the crown as they age. In contrast, lower-canopy leaves (LL) are exposed to uniform dim light conditions throughout their life span. By comparing leaf morphology and physiology of UL and LL, variations in leaf characteristics were related to leaf age and self-shading. Mass-based chlorophyll (chl) concentration and the chlorophyll/nitrogen (chl/N) ratio were lower and the chl a/b ratio was higher in UL than in LL. In UL, the chl/N ratio gradually increased and the chl a/b ratio gradually decreased with leaf aging, whereas these ratios remained unchanged with leaf age in LL. The effective quantum yield of photosystem II (PSII) (DeltaF/F(m)') at a given irradiance remained unchanged with leaf age in LL, whereas DeltaF/F(m)' changed with leaf age in UL. These data indicate N reallocation within the leaves from carbon fixation components to light harvesting components and a dynamic regulation of photochemical processes of PSII in response to increased self-shading of UL. Despite the difference in light environment with leaf age between UL and LL, maximum photosynthetic rates and nitrogen-use efficiency decreased with leaf aging in both UL and LL. Constancy in the chl/N ratio with leaf age in LL indicated that the decrease in photosynthetic capacity was caused by effects other than shading, such as leaf aging. We conclude that N reallocation and acclimation of PSII to self-shading occurred even in mature leaves, whereas the change in photosynthetic capacity with leaf age was more conservative.

Journal Article↗

PubMed1998

Soft X-ray photochemistry beamline at SPring-8.

Design and construction of a soft X-ray beamline at SPring-8 is reported. The beamline utilizes high-quality linearly polarized soft X-rays obtainable from a figure-8 undulator for the study of photophysical and photochemical processes of atoms, molecules and surfaces in the inner-shell excitation region. It consists of two experimental stations, a photochemistry station and a chemical vapour deposition (CVD) station. A high-resolution grating monochromator is installed at the photochemistry station, while the intense undispersed undulator radiation is used at the CVD station. Unique features of the experimental chambers and of the analysis and characterization systems are described along with those of the monochromator.

Journal Article↗

PubMed1991

Quantum yields for the cyclization and configurational isomerization of 4E,15Z-bilirubin.

Extraction of a solution of bilirubin configurational isomers in chloroform with an aqueous solution of human serum albumin was found to remove selectively the 4Z,15E-isomer. This phenomenon was used to develop a method for the purification of the 4E,15Z-isomer of bilirubin. The quantum yield for the cyclization and configurational isomerization of the 4E,15Z-isomer bound to a molar excess of human serum albumin was measured at 450 and 510 nm. The quantum yield for cyclization to form lumirubin was 0.12 and 0.19 at 450 and 510 nm, respectively. The quantum yield for configurational isomerization to form 4Z,15Z-bilirubin was 0.03 and 0.05 at 450 and 510 nm. An analysis of previously published data on the quantum yield for the formation of lumirubin from 4Z, 15Z-bilirubin bound to human serum albumin suggests that all of the formation of lumirubin may occur via consecutive photochemical processes with the 4E,15Z-isomer as an intermediate.

Bilirubin↗

PubMed1995

Novel therapeutic and diagnostic applications of hypocrellins and hypericins.

Hypocrellins and hypericins, structurally related plant pigments isolated from Hypocrella bambuase and Hypericum respectively, are known photodynamic agents. This review summarizes certain significant advances in the photophysics, photochemistry and photobiology of these pigments in the last 2 years and discusses their prospects as novel therapeutic and diagnostic agents in the future. Recently, certain unique properties of hypocrellins and hypericins have been explored for a variety of therapeutic and diagnostic applications. In particular, substantial progress has been made in both anticancer and antiviral applications (especially anti-human immunodeficiency virus). The promising anticancer and antiviral results obtained both in vitro and in vivo have led to intensive investigation into their photo-physical and photochemical processes, especially kinetic studies of their intramolecular proton transfer. These compounds offer the potential for a highly sensitive fluorescent redox sensor for investigation of a variety of cellular events. The biomedical advances of hypocrellins and hypericins have been further promoted by significant progress in their chemical synthesis and the recent commercialization of hypocrellins A and B and hypericin.

Animals↗

PubMed1996

The photochemistry of the retinoids as studied by steady-state and pulsed methods.

The retina and retinal pigment epithelium contain a number of retinoids in a metabolic pathway that eventually forms the visual pigments. This study investigates the photochemistry of those retinoids that may contribute to light-induced damage to the retina. These include retinal (RAL), retinol (ROL), retinylpalmitate (ROLpal) and the protonated Schiff-base of retinal (RALsb). Their photochemistry was followed by both EPR spin-trapping techniques and the direct detection of singlet oxygen via its luminescence at 1270 nm. Irradiation (> 300 nm) of RAL, ROL in methanol (MeOH) or RALpal in dimethylformamide, produces free radicals from both solvents. Illumination of RALsb in MeOH containing NADH with light above 400 nm (and even above 455 nm) generates the superoxide radical. We also determined that the quantum yields for singlet oxygen sensitization by RAL, ROL or RALpal in MeOH are 0.05, 0.03 and < 0.01, respectively. These values are at least 75% less than those previously found using chemical methods. These observations indicate that a major photochemical process for these retinoids may be an electron (or hydrogen) process that will lead to radical products, and that the singlet oxygen mechanism is of relatively minor importance in protic solvents. These results may explain the action spectra obtained from light-induced damage to the retina.

Diterpenes↗

PubMed1997

Transmembrane signaling mediated by water in bovine rhodopsin.

Unhydrated air-dried films of rhodopsin from bovine rod outer segment membranes do not produce its active state, metarhodopsin II. In order to reveal requirements for its formation, we studied changes in H-bonding of water, peptide carbonyl and carboxylic acid in the photochemical reactions by means of difference Fourier transform infrared spectroscopy, under both hydrated and unhydrated conditions. A water molecule near Glu113, which undergoes H-bonding change in bathorhodopsin, remained in the unhydrated film, but with a weaker H-bonding state than in the hydrated film. The other water molecules, which shfit in lumirhodopsin and metarhodopsin I as well as in bathorhodopsin of the hydrated film, were not observed in the unhydrated film. Effects of the dehydration were detected in all the C=O stretching vibrations of the peptide backbone and of Asp83 in the formation of bathorhodopsin. The C=O stretching band of Asp83 of lumirhodopsin and metarhodopsin I is intensified in the unhydrated film. We propose that structural changes at the intradiscal site in the interaction between the Schiff base and Glu113 affect water molecules, the peptide backbone, Asp83 and Glu122 in helices B and C through consecutive photochemical processes to metarhodopsin II.

Animals↗

PubMed2006

Organic globules in the Tagish Lake meteorite: remnants of the protosolar disk.

Coordinated transmission electron microscopy and isotopic measurements of organic globules in the Tagish Lake meteorite shows that they have elevated ratios of nitrogen-15 to nitrogen-14 (1.2 to 2 times terrestrial) and of deuterium to hydrogen (2.5 to 9 times terrestrial). These isotopic anomalies are indicative of mass fractionation during chemical reactions at extremely low temperatures (10 to 20 kelvin), characteristic of cold molecular clouds and the outer protosolar disk. The globules probably originated as organic ice coatings on preexisting grains that were photochemically processed into refractory organic matter. The globules resemble cometary carbon, hydrogen, oxygen, and nitrogen (CHON) particles, suggesting that such grains were important constituents of the solar system starting materials.

Carbon↗

PubMed1976

Theory of photochemical reactions.

Although the great number of electronic states available to an excited molecule might seem to preclude a coherent picture of photochemical reaction mechanisms, it is possible to bring out some basic features common to a great many reactions. The electronic states of the primary diradical intermediates, surface crossings, topicity, and avoided surface crossings have been shown to be essential components of the electronic theory of photochemical reactions. Diradicals have four important electronic states. Knowing these states, and making a simple electron count, it is possible to draw state correlation diagrams. Some diagrams show a typical surface crossing of the ground singlet state with the lowest (singlet, triplet) pair of excited states, with clear-cut consequences of quantum yields under various conditions. In other reactions the surfaces stay apart. The critical discriminating feature that determines the type of correlation diagram is the topicity. Photochemical reactions can be classified according to topicity, which is useful in interpreting their mechanisms (53). Avoided surface crossings can also be classified into different types. Figure 7, which illustrates the interplay of a covalent and an ionic surface responsible for photochemical electron transfer, is a typical multidimensional representation of a photochemical reaction. The chemical behavior of the excited zwitterionic states of common intermediates, such as twisted ethylene or diallyl, reflects the quantum mechanical nature of photochemical processes. In these states, for perfectly symmetric systems, charge oscillates back and forth between two symmetry-equivalent sites. Slight geometric perturbations can create a sudden polarization of the excited molecule, with localization of almost a full charge at one end of the molecule. A photon is transformed into an electrical signal thanks to an appropriate molecular distortion. Nature may have used this simple process in the N-retinylidene visual chromophore to trigger an electrical response to vision.

Electron Transport↗

PubMed1967

Mutagenesis by near-visible light.

Mutants resistant to bacter iophage T5 were produced both in continuous and in stationary cultures of Escherichia coli by near-visible light, 320 to 400 millimicrons, at rates greatly exceeding spontaneous rates in the ab sence of light. Aerobic mutation rates were about twice anaerobic rates, which shows that mutations were induced in either of at least two different proces ses. Mutations induced by near-visible light involve different photochemical processes than those induced by ul traviolet light.

DNA, Bacterial↗

PubMed2000

Photochemistry. Twist and fluoresce.

Catalytic antibodies, or artificial enzymes, act as catalysts by lowering the energy of the transition state of a reaction. In his Perspective, Brauman highlights the study by Simeonov et al., who have applied similar principles to photochemical processes and shown that intense fluorescence can be achieved. The approach provides a way of measuring internal molecular motion within the antibody on a very fast time scale. Fluorescent antibodies may find applications in immunochemistry, histological assays, and genomic studies.

Antibodies, Catalytic↗

PubMed1985

Photochemical and microbial degradation of 2,4,5-trichloroaniline in a freshwater lake.

Surface waters from a eutrophic lake in northern Georgia were incubated with C-labeled 2,4,5-trichloroaniline to study the disappearance of the parent compound and production of CO(2). There was no degradation of the compound in the dark. Under 12 h of sunlight and 12 h of darkness, 28% of the trichloroaniline was degraded in both poisoned and untreated samples. Mineralization after 24 h in poisoned and untreated lake water was 5.5 and 6.8%, respectively. Thus, 81% of the mineralization was attributable to photochemical processes, and 19% was attributable to microbial processes. Most biological mineralization was due to microbes of bacterial size (<1.0 mum). Approximately 90% of the trichloroaniline bioaccumulated was associated with organisms larger than 1.0 mum, e.g., algae. When algae were removed by filtration, the amount of trichloroaniline mineralized increased to 9.4%, compared with 6.8% in the presence of algae. The excretion of organic compounds by algae may have inhibited bacterial mineralization of photoproducts.

Journal Article↗

PubMed2000

Reduced enzymatic antioxidative defense in deep-sea fish.

Oxygen, while being an obligate fuel for aerobic life, has been shown to be toxic through its deleterious reactive species, which can cause oxidative stress and lead ultimately to cell and organism death. In marine organisms, reactive oxygen species (ROS), such as the superoxide anion and hydrogen peroxide, are generated within respiring cells and tissues and also by photochemical processes in sea water. Considering both the reduced metabolic rate of nektonic organisms thriving in the deep sea and the physico-chemical conditions of this dark, poorly oxygenated environment, the meso- and bathypelagic waters of the oceans might be considered as refuges against oxidative dangers. This hypothesis prompted us to investigate the activities of the three essential enzymes (superoxide dismutase, SOD; catalase, CAT; glutathione peroxidase, GPX) constitutive of the antioxidative arsenal of cells in the tissues of 16 species of meso- and bathypelagic fishes occurring between the surface and a depth of 1300 m. While enzymatic activities were detected in all tissues from all species, the levels of SOD and GPX decreased in parallel with the exponential reduction in the metabolic activity as estimated by citrate synthase activity. In contrast, CAT was affected neither by the metabolic activity nor by the depth of occurrence of the fishes. High levels of metabolic and antioxidative enzymes were detected in the light organs of bioluminescent species. The adjustment of the activity of SOD and GPX to the decreased metabolic activity associated with deep-sea living suggests that these antioxidative defense mechanisms are used primarily against metabolically produced ROS, whereas the maintenance of CAT activity throughout all depths could be indicative of another role. The possible reasons for the occurrence of such a reduced antioxidative arsenal in deep-sea species are discussed.

Anaerobiosis↗

PubMed2002

H-vinyl conical intersections for dienes: a mechanism for the photochemical hula twists.

The potential role of "H-vinyl" conical intersections in a photochemical process known as the hula twist has been evaluated. The H-vinyl conical intersections of butadiene are explored with complete active space self-consistent field calculations, and proposals about the geometries involved in the hula-twist mechanism are discussed and contrasted with the conventional one-bond flip mechanism of cis-trans isomerization.

Journal Article↗

PubMed2003

Metallophthalocyanines photosensitize the breakdown of (hydro)peroxides in solution to yield hydroxyl or alkoxyl and peroxyl free radicals via different interaction pathways.

Interactions of organic peroxides (R'OOR) and hydroperoxides (R'OOH), including H2O2, with excited triplet and singlet state metallophthalocyanines (MPc, M = Zn, Al) have been studied by T-T absorption decay and fluorescence quenching. The ensuing photochemical processes result in decomposition of (hydro)peroxides as assessed by photo-EPR (electron paramagnetic resonance) and spin trapping. In argon-saturated apolar solutions and low MPc concentrations, alkoxyl free radicals (*OR) were identified as the primary products of (hydro)peroxide breakdown. Similarly, photosensitized decomposition of symmetric disulfides results in the formation of sulfur-centered radicals. In air-free aqueous solutions, ROOH photosensitization always gave rise to a mixture of hydroxyl and peroxyl radical (*OOR) adducts in varying molar ratios. At high MPc concentrations, both in polar and in apolar solutions, the most abundant products of ROOH decomposition were identified as *OOR. This indicates a change in the predominant interaction pathway, most likely mediated by MPc exciplexes and involving H-atom abstraction from ROOH by MPc-cation radicals. The prevalence of MPc singlet vs. triplet state interactions was confirmed by the much higher singlet quenching rate constants (log kq up to 9.5; vs. log kT < or = 4.5). In contrast to the triplet quenching, singlet quenching rates were found to depend on the (hydro)peroxide structure, following closely the trend of varying *OR yields for different substrates. Thermodynamic calculations were performed to correlate experimental results with models for electronic energy and charge transfer processes in agreement with the Marcus theory (Rhem and Weller approximation) and Savéant's model for a concerted dissociative electron transfer mechanism.

Electron Spin Resonance Spectroscopy↗

PubMedDate not supplied

Surface retention and photochemical reactivity of the diphenylether herbicide oxyfluorfen.

The photochemical behavior of oxyfluorfen [2-chloro-1-(3-etoxy-4-nitrophenoxy)-4-(trifluoromethyl) benzene] on two Greek soils was investigated. Soils were sampled from Nea Malgara and Preveza regions, characterized by a different organic matter content. Soils were spiked with the diphenyl-ether herbicide and irradiation experiments were performed either in the laboratory with a solar simulator (xenon lamp) or outside, under natural sunlight irradiation; other soil samples were kept in the dark to control the retention reaction. Kinetic parameters of both retention and photochemical reactions were calculated using zero-, first- and second- (Langmuir-Hinshelwood) order equations, and best fit was checked through statistical analysis. The soil behaviors were qualitatively similar but quantitatively different, with the soil sampled from the Nea Malgara region much more sorbent as compared with Preveza soil. All studied reactions followed second-order kinetics and photochemical reactions were influenced by retaining capability of the soils. The contributions of the photochemical processes to the global dissipation rates were also calculated. Two main metabolites were identified as 2-chloro-1-(3-ethoxy-4-hydroxyphenoxy)-4-(trifluoromethyl)benzene and 2-chloro-1- (3-hydroxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene.

Environmental Monitoring↗

PubMedDate not supplied

[Effects of low intensity laser (632.8 nm) and ultraviolet radiation on spectral properties and functional activity of human ceruloplasmin].

Photoinduced changes of human ceruloplasmin (hCp) under laser and ultraviolet (UV) radiation have been studied. A complex character of hCp spectral modifications points to a different degree of the protein molecule folding. After the influence of UV radiation (240-390 nm) in a dose range 906-4530 J/m2 the decrease of oxidase hCp activity was registered. These changes are thought to be connected with modification of the conformation of hCp active centre or copper reduction that was confirmed by the decrease of optical density at 610 nm. An inactivation constant (kf = 3.8 x 10(-4) 1/s) and a photoinactivation quantum yield (1.4 x 10(-4)) were calculated. Kinetic dependencies of o-phenilen-diamine oxidation by intact and UV-modified glycoprotein do not correspond to Michaelis-Menten equation. UV radiation in a dose range 151-4530 J/m2 induced increasing of ceruloplasmin superoxiddismutase activity. The influence of He-Ne laser radiation (1.3 mW; lambda = 632.8 nm, exposure time from 1 up to 30 min) leads to the raise of the hCp functional activity; superoxiddismutase activity changes more significantly. Possible photophysical and photochemical processes in hCp molecule, leading to photomodification and changes of protein functional activity have been represented on the scheme.

Ceruloplasmin↗