PHOTOISOMERIZATION OF SIXTEEN ISOMERS OF RETINAL. INITIAL PRODUCT DISTRIBUTION IN DIRECT AND SENSITIZED IRRADIATION. PHOTOCHEMISTRY OF POLYENES 31*

Abstract— Initial product distributions of all 16 geometric isomers of retinal in hexane solutions have been determined. With direct irradiation, the product ratios are characterized by a preference for isomerization at the 13,14-bond. In particular, all isomers containing the 13-cis geometry give the corresponding 13-trans isomer as the major product. Preference for one-photon-one-bond isomerization was also noted, although a substantial amount of the all-trans isomer was detected for all poly-cis, 13-trans isomers. In sensitized irradiation, the initial mixture shows extensive one-photon-two(or multiple)-bond isomerization to the corresponding unhindered isomers. In cases of hindered isomers, multiple-bond isomerized products are dominant. The different results are accountable by the different shapes of the excited state potential curves for singlet and triplet states.     

SYNTHETIC CAROTENOIDS, NOVEL POLYENE POLYKETONES AND NEW CAPSORUBIN ISOMERS AS EFFICIENT QUENCHERS OF SINGLET MOLECULAR OXYGEN

Novel synthetic polyene polyketones and new synthetic capsorubin isomers were examined for their ability to quench singlet molecular oxygen (1O2) generated by the thermodissociation of the endoperoxide of 3,3'-(1,4-naphthylene) dipropionate (NDPO2). C28-polyene-tetrone (1) exhibits the highest physical quenching rate constant with 1O2 (kq = 16 x 10(9) M-1 s-1). For comparison, the rate constant for the most efficient biological carotenoid, lycopene (3) is kq = 9 x 10(9) M-1 s-1 and that of beta-carotene (5) kq = 5 x 10(9) M-1 s-1. The presence of two oxalyl chromophores at the ends of the polyene chain seems to enhance the 1O2 quenching ability in the C28-polyene-tetrone (1). C28-polyene-tetrone-diacetal (2) (kq = 9 x 10(9) M-1 s-1) and C40-epiisocapsorubin (4) (kq = 8 x 10(9) M-1 s-1) also have high 1O2 quenching abilities. Two carotenoids from plants, phytoene and phytofluene, were much less efficient, kq values being below 10(7) M-1 s-1. Due to the very high singlet oxygen quenching abilities, C28-polyene-tetrone (1), C28-polyene-tetrone-diacetal (2) and C40-epiisocapsorubin (4) may have potential use in preventing 1O2-induced damage in biological and non-biological systems.     

PREPARATION AND PURIFICATION OF SCHIFF BASE AND PROTONATED SCHIFF BASE FROM 9-CIS-RETINAL

A modified method for preparation and purification of Schiff base and protonated Schiff base from 9-cis-retinal has been suggested. Reaction took place in chloroform phase and purification was conducted by using water to remove the excess solvent, base and acid.     

SYNTHESIS, MOLECULAR STRUCTURE, SPECTRA AND ELECTROCHEMISTRY OF TWO GEOMETRIC ISOMERS OF TETRAKIS(2-ANILINOPYRIDINATO) DIRHODIUM*

Two gemetric isomers of new dirhodium complex, Rh_2(ap)_4(ap=2-anilinopyridinato),have been synthesixed and isolated. The isomers were characterized by a single-crystal X-ray diffraction analysis. They are 4,0 gemeter (compound 1) and 2,2 trans geometer (compound 2).The radical cations of 1and 2are ESR active. The ESR spectrum of 1+ions, reports that the order of g value is g_⊥>g_e>∥,and the value of g is split into doublet at 77K. This result is consistent with a calculation of the self-consistent-charge discrete variational method. It is shown conclusively that the odd electron is localized on one rhodium. ion with no bound axial ligand, thus giving the first example of true Rh(Ⅱ )—Rh(Ⅲ) complex. The ESR spectrum of 2+ shows g split into a 1:2:1 trilet .In addition, cyclic voltammetry and ESCA of two isomers were detrmined and analyxed. The results indicate that Rh_2(ap)_4 is not only chemically reactive but also sensitive to photochemical oxidation, thus having a wide application in future.     

TRIPLET STATES OF CAROTENOIDS FROM PHOTOSYNTHETIC BACTERIA STUDIED BY NANOSECOND ULTRAVIOLET AND ELECTRON PULSE IRRADIATION

Abstract— Absorptions of the triplet excited states of five carotenoids (15,15'-ds phytoene, all- trans phytoene, C-carotene, spheroidene and spirilloxanthin), extracted from the photosynthetic bacteria Rhodopseudomonas spheroides and Rhodospirillum rubrum, have been detected in solution using pulse radiolysis and laser flash photolysis. Triplet lifetimes, extinction coefficients, lowest energy levels and quantum efficiencies of formation have been determined. Comparison of the carotenoid triplet energy levels with that of O₂('Δ_g) suggests that spirilloxanthin, spheroidene and possibly alsoζ-carotene, would be expected to protect against photodynamic action caused by O₂ ('Δ_g), but not cis or trans phytoene. The S → T intersystem crossing efficiences of all five polyenes were found to be low, being a few per cent or less. In their protective role these triplet states can only therefore be effectively reached via energy transfer from another triplet, except in the case of O₂ ('Δ_g). The low crossover efficiencies also mean that light absorbed by such carotenoids in their possible role as accessory pigments would not be wasted in crossing over to the triplet state.     

DEPENDENCE OF THE TRIPLET YIELD ON EXCITATION ENERGY IN ALL-TRANS AND 11-CIS RETINAL*

Abstract. The triplet-triplet absorption of all-trans and 11- cis retinal was measured as a function of the exciting radiation from 423 nm to 365 nm in a glass of 3-methylpentane at 77 K. This experiment was also accomplished with all-trans retinal in hexane at ambient temperature. The relative triplet formation quantum yields of all-trans and 11-cis retinal at 77 K were found to be independent (±10%) of the frequency of the exciting radiation. At room temperature we measured an increase in this relative quantum yield for all- trans retinal from 1.0 at 365 nm to 1.82 at 423 nm [Bensasson et al. (1975) measured an absolute quantum yield of 0.45 at 353 nm]. These results are used to evaluate previous interpretations for photophysical decay processes in all-trans retinal, and previous suggestions for wavelength dependent radiationless transitions are shown to be unacceptable. High energy excitation of 300 K solutions of all- trans retinal produce excited states that result in less efficient intersystem crossing. These states appear to be inaccessible in the 77 K matrices. We suggest that steric restrictions introduced by the retinal matrix interaction at 77 K are able to block this new internal conversion pathway back to the ground state.     

TWENTY-TWO CARBON HOMOLOGUE OF 11-CIS RETINAL. PHOTOPHYSICAL AND PHOTOCHEMICAL PROPERTIES

Abstract— Results concerning absorption-emission spectra and fluorescence quantum yields at 77 and 298K. triplet absorption spectra, and quantum yields of intersystem crossing and photoisomerization at 298 K, are presented for 11- cis β-apo-14'-carotenal (C₂₂-Ald), the immediate higher homologue of 11- cis retinal. The absorption spectra are characterized by two band-systems with maxima at 390–400 and 270–280 nm, respectively. Upon cooling from 298 to 77 K, the intensities of these two band-systems undergo changes in opposite directions indicating 12-s- cis: 12- s-trans conformational changes. No intermediate band-system analogous to the one located at 270–310 nm in cis retinals is observed for 11- cis C₂₂-Ald. In nonpolar hydrocarbon solvents (e. g. cyclohexane) at room temperature, quantum yields of fluorescence (0.01), intersystem crossing (0.6) and photoisomerization (0.4) are all quite pronounced. The photophysical and photochemical properties of 11- cis C₂₂-Ald are discussed in the light of similarities and dissimilarities with those of all- trans C₂₂-Ald and 11- cis retinal under comparable conditions.     

LIGHT INDUCED ISOMERISATION, AT ACIDIC pH, INITIATES HYDROLYSIS OF BACTERIORHODOPSIN TO BACTERIO-OPSIN AND 9-CIS-RETINAL

Abstract— Bacteriorhodopsin (BR) from the purple membrane of Haiobacterium halobium contains covalently bound retinal in the 13- cis and all- trans configurations. Several forms of bacteriorhodopsin are known, with different absorption maxima which are designated as BRλ_max (nm). At acidic pH, BR605 is formed from BR560. The following sequence of reactions was found, which is initiated by irradiation of BR605 with red light:

An all- trans /13- cis to 9- cis isomerisation occurs in the light induced reaction BR605 ∼ BR500. BR500 seems to contain covalently bound retinal, whereas BR390 contains free retinal. By irradiation with light, BR500, BR450 and BR390 can be reconverted to BR560.     

ELECTRON SPIN RESONANCE OF MELANIN FROM HAIR. EFFECTS OF TEMPERATURE, pH AND LIGHT IRRADIATION

Abstract— The variation with temperature, pH and light of the ESR signal of hydrated melanin powders from Japanese black hair has been studied. An explanation of the results is proposed on the basis of quinhydrone type complexes and of acid-base equilibria of melanin and its semiquinone radicals. During exposure to light of wavelengths 254–600 nm, both stable and unstable radicals have been observed. The action spectrum for the formation of stable melanin radicals has been determined.     

PREPARATION AND PROPERTIES OF NEW VISUAL PIGMENT ANALOGUES FROM 5,6-DIHYDRORETINAL AND CATTLE OPSIN*

Abstract— On irradiation of all-trans 5,6-dihydroretinal (I), two opsin-active isomers are formed. Both these isomers (believed to be the 11-cis and 9-cis isomers) individually couple with cattle opsin to form complexes which have maximal absorption at 465 nm. These complexes satisfy all the established criteria characteristic of synthetic visual pigments.     

CHLOROPHYLL CATABOLISM. PART 3. STRUCTURE ELUCIDATION AND PARTIAL SYNTHESIS OF A NEW RED BILIN DERIVATIVE FROM Chlorella protothecoides*

The structure of a new red pigment produced during the “bleaching” of Chlorella protorhecoides cells has been elucidated by analytical methods as well as by in vitro isomerization into the new compound of a synthetic sample of a previously characteriLed chlorophyll a catabolite.     

STUDIES ON THE INTERRELATIONSHIP AMONG THE INTENSITY OF A RAMAN MARKER BAND OF CAROTENOIDS, POLYENE CHAIN STRUCTURE, AND EFFICIENCY OF THE ENERGY TRANSFER FROM CAROTENOIDS TO BACTERIOCHLOROPHYLL IN PHOTOSYNTHETIC BACTERIA

Abstract Resonance Raman spectroscopy was used to study the polyene-chain structure of carotenoids in light-harvesting pigment-protein complexes from purple photosynthetic bacteria. When major carotenoids of Rhodobacter sphaeroides were incorporated into the light-harvesting complexes of Chromatium vinosum , they showed a relatively intense Raman band at 965 cm^-1 arising from the CH out-of-plane wagging modes of the polyene chain. This result was almost the same as that for the intrinsic carotenoids in Chromatium vinosum , but completely different from that for the intrinsic carotenoids in Rhodobacter sphaeroides . On the other hand, the intrinsic carotenoids of Chromatium vinosum lost the intensity of the 965 cm^-1 Raman band upon protein denaturation. These results support the view that the intensity of the 965 cm^-1 Raman band reflects distortion of the polyene chain, independent of its chemical structure. The polyene-chain distortion is affected by the apoprotein to which carotenoids are bound. The distortion of the polyene chain is correlated with a decrease in the efficiency of the energy transfer from carotenoids to bacteriochlorophyll.     

RESPIRATION RESPONSES OF A polA1 AND A tif-1 MUTANT OF ESCHERICHIA COLI TO FAR-ULTRAVIOLET IRRADIATION*

Abstract— Cessation of respiration in Escherichia coli 60min after far-ultraviolet (254 nm) irradiation is dependent upon the recA and lexA gene products and is regulated by cyclic 3′,5′-adenosine monophosphate (cAMP) and its receptor protein. Respiration responses to UV irradiation were studied in two E. coli B/r mutants, polA1 and tif-1, both of which express other rec/lex functions (such as mutagenesis) after UV irradiation. The cells were grown on glycerol minimal medium supplemented with required amino acids. After receiving a relatively high UV fluence, the polA1 mutant, deficient in DNA polymer-ase I, showed a respiration shutoff response like the wild type cells. 5-Fluorouracil and rifampin, an inhibitor of initiation of RNA synthesis, did not prevent respiration shutoff in the mutant cells as they did in the wild type cells. Thus, RNA synthesis is not necessary for cessation of respiration in polA1 cells and the process is not an induced one. At lower fluences which did not shut off respiration of polA1 cells, cAMP did not cause a more complete shutoff as it did for the wild type cells. The tif-1 mutant has a modified recA protein, and when unirradiated cells are incubated at 42°C they form filaments, mutate, and show other rec/lex responses. This mutant did not shut off its respiration at either 30 or 42°C, and the response was not modified by cAMP. An E. coli K12 strain, W3110, was also tested for its respiration response to UV. At 52J/m² respiration did not shut off and cAMP had no effect.     

ISOLATION AND STRUCTURE OF RANAMARGARIN,A NEW TACHYKININ FROM THE SKIN OF CHINESE FROG Rana margaratae

A new tetradecapeptide, ranamargarin, has been isolated by Sep-Pak C_(18) and HPLC from methanol extracts of the skin of the Chinese frogRana margaratae. The sequence of the peptide is: Asp-Asp-Ala-Ser-Asp-Arg-Ala-Lys-Lys-Phe-Tyr-Gly-Leu-Met-NH_2. This structure has been confirmed by synthesis. The peptide is the largest among the amphibian tachykinins and its N-terminal amino acids are quite different from those of the other tachykinins. The formation of the sulfoxide and peak-splitting of ranamargarin during purification procedures are briefly discussed.     

CRYSTAL AND MOLECULAR STRUCTURE OF A NEW DITERPENE DERIVATIVE FROM SOFT CORAL

<正> Introduction. The crystal and molecular structure of an acetylated derivative of a new diterpene from soft coral (Clavularia sp.) has been determined by X-ray crystal structure analysis.     

ULTRAVIOLET IRRADIATION OF POTATO VIRUS X, ITS RNA, AND A HYBRID VIRUS PARTICLE: PHOTOREACTIVATION, KINETIC ISOTOPE EFFECTS, AND QUANTUM YIELD OF INACTIVATION*

Abstract— Studies have been made of the inactivation of potato virus X (PVX), free PVX-RNA, and a phenotypically mixed virus particle composed of PVX-RNA and tobacco mosiac virus (U-1 strain) protein (PVX_RNA: TMV_PRO) by ultraviolet radiation of 254, 280 and 302 nm wavelengths. Rate constants and quantum yields of inactivation have been determined under conditions of photoreactivation and non-photoreactivation in H₂O and D₂O. The ratios of the rate constants in H₂O to those in D₂O obtained for PVX-RNA were greater than unity at the above three wavelengths, as was the case for PVX at 254 and 302 nm. The ratios of the rate constants were, within experimental error, equal to unity for PVX_RNA:TMV_PRO at all three wavelengths and for PVX at 280 nm. It is concluded that, in contrast to the situation observed with TMV and PVX_RNA:TMV_PRO, the behavior of the intact PVX viron upon irradiation closely approximates the behavior of free RNA in solution, on the basis of quantum yields of inactivation, photoreactivated sector, and the ratio of kinetic isotope effects in H₂O and D₂O.     

ROLE OF CAROTENOIDS IN PROTECTING CHLOROPHYLL FROM PHOTODESTRUCTION—II. STUDIES ON THE EFFECT OF FOUR MODIFIERS OF THE ALBINO cl1 MUTANT OF MAIZE*

Abstract— By combining independent, dominant, niodifier genes of the albino cl₁ mutant it is possible to produce a spectrum of phenotypes ranging from normal green to albino. Analysis of plastid pigments reveals that the albino possesses the ability to produce as much or more chlorophyll than normal siblings and that this ability is not impaired by the presence of the modifier genes. The modifiers do influence, however, the amount of carotene and xanthophyll the plants produced. The level of the three plastid pigments (chlorophyll, carotene and xanthophyll) vary simultaneously and, in most modified phenotypes, occur in approximately the same concentrations relative to their normal siblings. Since chlorophyll production appears to be normal in these mutants, it is suggested that the modifier genes do not directly influence the concentration of this pigment. Rather, the ultimate amount of chlorophyll will not rise above that which can be protected from photodestruction by the carotenoid levels determined by the various modifier genotypes.     

ISOLATION AND STRUCTURE DETERMINATION OF LAMIOPHLOMICL C,A NEW HIGHLY OXYGENATED IRIDOID FROM LAMIOPHLOMIS ROTATA

A new highly oxygenated iridoid, lamiophlomiol C, was isolated from theroots of Lamiophlomis rotata and its structure was elucidated by spectrosoopic techniquesand X-ray diffraction.     

ULTRAVIOLET IRRADIATION OF NUCLEIC ACIDS COMPLEXED WITH HEAVY ATOMS-II. PHOSPHORESCENCE AND PHOTODIMERIZATION OF DNA COMPLEXED WITH Ag*

Abstract— We have studied the luminescence (at 77°K) and photochemistry (at 298°K) of a variety of polynucleotides complexed with Ag⁺. In all cases we observed that Ag⁺ induces a 'heavy atom effect' as indicated by quenching of fluorescence, enhancement of phosphorescence, and reduction of triplet lifetimes. The enhancement by Ag⁺ of the phosphorescence intensity of poly (dT) and DNA paralleled a 20-fold enhancement of the rate of thymine dimerization. These results suggest a possible triplet precursor for thymine dimerization in Ag⁺ complexes. Dimers were also made with a variety of triplet sensitizers, and Ag⁺ increased the dimer yield two- to four-fold, depending on the sensitizer used.     

ENERGY TRANSFER AND CYTOCHROME FUNCTION IN A NEW TYPE OF PHOTOSYNTHETIC BACTERIUM*

Abstract— The excitation spectrum for bacteriochlorophyll b fluorescence at 1027 mμ in Rhodopseudomonas sp. NHTC 133 indicates that the efficiency of energy transfer from caro-tenoid to bacteriochlorophyll b is between 27 and 28 %.
Light-induced absorbancy changes in anaerobic whole cells indicated the oxidation of three c -type cytochromes (C-550. 5, C-553, C-558) and one b -type cytochrome or cytochromoid C (C-560). At low light intensities C-553 is the main cytochrome oxidized, while at high light intensities mainly C-558 is oxidized in addition to C-553. The light responses of the heme proteins appear to be similar to those observed previously in purple and green photo-synthetic bacteria. No light-induced shifts in carotenoid absorption bands were detected.
In bacterial extracts C-553 and C-558 are bound to the chromatophores, while C-550. 5 is soluble.