SPECTROCSOPIC STUDIES OF PURINES—III. PROPERTIES OF PURINES SUBSTITUTED AT THE SIXTH AND NINTH POSITIONS*

Abstract— We have investigated the effects of solvent and pH on the absorption and emission propertied of various 6- and 9-substituted purines as a means of examining the nature of the directed not only at deteriming the relative energies of (π,π*) and (π,π*) states, but in particular, at examining the nature and energies of the two lowest-lying (π,π*) states. For examplem, the attachment of a methyl or ribosyl group to the N9 of purine does not change the relative energies of the lowest-lying (π,π*) and (π,π*) states; thus, the latter is the singlet of lowest energy. However, the lowest singles in derivatives formed by substitution at C6 are(π,π*) states—i.e. there is no long-wavelength tail in the absorption spectra and florescence is comparable in intensity to phosphorescence. Further the absence of emission from neutaral adenine at room temperature is due to temperature quenching. Both lowest (π–π*) transtions. are contained under a common envelope and cannot be resolved in the absorption spectra. The shoulder observed in some of these compounds on the long-wavelength slope of absorption envelope is vibrational in nature. Consideration of the effects of solvents on absorption and the analysis of luminescence spectra make it possible to locate the relative position of these (π–π*) transitions within the common envelope. In compounds with an -H on N9 and a free (aza) N1 (e.g. adenine, anionic hupoxanthine) the weaker, solvent-sensitive (W) band has a higher energy then the more intense, solvent-insensitive (S) band. When N1 is protonated, (e.g., in hypoxanthine or cationic adenine) and/or when methyl or ribosyl is substituted at N9, the order of these bands is inverted due ot a red shift of the W band. This shift is most apparent in the 9-substituted hypoxanthines, where in non-polar solvents the W band can be readily resolved in the absoption spectra. This inversion results in a red shift of both fluorescence and phophorescence and an increase of the P/F ratio. When chlorine or iodine is attached at C6 only phosphorescence having a very short lifetime appears due to heavy atom enhancement of single—triplet transitions.     

SPECTROSCOPIC STUDIES ON THE STRUCTURES OF RETINOCHROME and METARETINOCHROME*

Abstract– Spectroscopic measurements of retinochrome and the related photoproduct, metaretino-chrome, were carried out to determine the conformation of the retinal and the protein. Absorption spectra with fourth derivatives indicate that the tryptophan residues are located in a hydrophobic core and that the environment around these residues does not change after light irradiation. Circular dichroism measurements indicate that retinochrome has a high helical content which is not altered by the conversion of retinochrome to metaretinochrome. Fourier transform infrared difference spectra demonstrate that retinochrome has the all-trans retinal and metaretinochrome has the 11-CM retinal. Retinochrome has an absorption due to amino acid residue(s) which changes in metaretinochrome. This work demonstrates that conformational changes are not induced during the conversion but the electrical charge(s) of the protein are changed by irradiation.     

THE BEHAVIOR OF DYE-MUCOPOLYSACCHARIDE COMPLEXES—I. SPECTROSCOPIC STUDIES OF THE SYSTEM CHONDROITIN SULFATE A-ACRIDINE ORANGE

Abstract —Absorption, fluorescence, and circular dichroism (CD) spectra have been obtained for a mucopolysaccharide—cationic dye complex. The dye acridine orange exhibits a blue shift in its absorption maximum and a red shift in its fluorescence maximum when mixed with chondroitin sulfate A in aqueous solution. The spectral shifts of the dye appear to be reversed by addition of salt, divalent cations being more effective than monovalent cations. The complex exhibits induced optical activity in the visible absorption spectrum of acridine orange. The biphasic nature of the CD curve is compatible with interpretations involving chromophore coupling.     

PHOTOBIOLOGY OF RNA BACTERIOPHAGES—I. ULTRAVIOLET INACTIVATION AND PHOTOREACTIVATION STUDIES*

Abstract— Biologically active f2-RNA, Obtained from bacteriophage f2, was inactivated by ultraviolet (u.v) light (2537 Å) with a quantum yield of 3.3 ± 0.3 times 10^-3 when assayed in the dark with protoplasts of an F- strain of E. coli k12. Assay under “black light” gave a quantum yield of 2.7 ± 0.5 times 10^-3 which was just enough lower to suggest that 17 per cent photorecovery of the u.v. lesions has taken place. Intact phage f2 was inactivated by u.v. radiation with a quantum yield of 0.7 ± 0.12 times 10^-3, Thus the whole phage is much less sensitive than the free RNA. No evidence of photorecovery was found in u.v.-irradiated RNA phage 7S assayed in its host Pseudomonas aeruginosa.     

THE COLORS OF FIREFLY BIOLUMINESCENCE—I. OPTIMIZATION MODEL*

Abstract— A model is developed for the optimization of signal-to-noise ratio for the detection of bioluminescence by fireflies during twilight. The relative degree of optimization is derived in terms of a dimensionless ratio, a biologically effective adaptation. The numerical values of this adaptation can be used to predict the sequence of adaptations of both visual spectral sensitivities and bioluminescence spectral emissions that result in the range of colors of bioluminescence of fireflics from green through yellow. It is shown that a narrowing of visual spectral sensitivity via a screening pigment pathway in order to discriminate against green ambient light is more efficient than a shift in visual spectral sensitivity via change in the opsin photoprotein. The model predicts that the range of wavelengths for the peak intensities of bioluminescence for North American fireflies should be between 550 and 580 nm and provides the physical basis for the observations that in general dark-active firefly species cmit green bioluminescence and twilight-active firefly species emit yellow bioluminescence.     

SOME FACTORS AFFECTING THE THERMOCHEMILUMINESCENCE OF CHLOROPHYLL

Abstract— The therrnochemiluminescence of the chloroplasts from normal lettuce seedlings is enhanced by the addition of β carotene but not by chlorophyll a .The thermochemiluminescence of chloroplasts from etiolated seedlings is enhanced by neither β carotene nor chlorophyll a .A variety of electron donors were substituted for β carotene in the mixtures with chlorophyll a .The most active were squalene, β carotene, vitamin A, and nerolidol.
The isoprene structure (-CH₂-CCH₃=CH-CH₂-) appears to be a necessary but not sufficient requirement for energy transfer during thermochemiluminescence.Changes in the absorption spectra indicate that both chlorophyll and carotene are destroyed during thermochemiluminescence.     

THE PHOTOCHEMISTRY OF RIBOFLAVIN—II. POLAROGRAPHIC STUDIES ON THE HYDROXYETHYL AND FORMYLMETHYL ANALOGS OF RIBOFLAVIN*

Abstract— The anaerobic photobleaching of 6, 7-dimethyl-9-(2′-hydroxyethyl)-isoalloxazine, 9-(2′-hydroxyethyl)-isoalloxazine and 6,7-dimethyl-9-(formylmethyl)-isoalloxazine have been compared. Polarographic and spectrophotometric techniques were used for rate studies. The methyl groups on the aromatic ring at the 6 and 7 positions affects the product distributtion in these simple flavins. Formylmethylflavin is postulated to undergo a bimolecular photoredox reaction which is novel to flavin photochemistry. It was demonstrated that there is a common type of leucoflavin formed during anaerobic photobleaching of riboflavin, formylmethylflavin and hydroxyethylflavin. This leucocompound also formed during the photoreduction of formylmethylflavin but not during the photoreduction of the other flavins.     

BIOCHEMICAL FACTORS AFFECTING THE QUANTUM EFFICIENCY OF HYDROGEN PRODUCTION BY MEMBRANES OF GREEN PHOTOSYNTHETIC BACTERIA*

Abstract— Photohydrogen production, 200-700 μmol H₂ h^?1 (mg bacteriochlorophyll a)^?1 has been obtained in a system containing unit membrane vesicles (Complex I) from the green photosynthetic bacterium Chiorobium limicola f. thiosulfatophilum, ascorbate, N,N,N′,N′-tetramethyl-p-phenylene-diamine, dithioerythritol, an oxygen scavenging mixture, either methyl viologen (MV) or clostridial ferredoxin (CPS Fd) as electron carrier, and either CPS hydrogenase or platinum asbestos as catalyst. All components are necessary for maximum activity, and spinach Fd cannot be substituted for CPS Fd. Higher rates of photohydrogen production are obtained using MV or CPS Fd with hydrogenase than with MV and Pt asbestos. The highest quantum efficiencies (7–10% at 0.2–0.9 mW absorbed light and over 20% at lower light) were obtained with CPS Fd, hydrogenase and non-saturating 812 nm light. With saturating white light, however, rates of photohydrogen production varied relatively little among the various combinations of electron carrier and catalyst tested. The reaction rate is unaffected by 0.03% Triton X-100, and is insensitive to treatment with antimycin a or m-chloro-carbonyl cyanide phenylhydrazone. This indicates that neither electron flow through an endogenous cyclic chain, nor maintenance of a proton gradient are involved in this process.     

meso-苯基四苯并卟啉锌的合成和光谱性能的研究

四苯并叶琳(TBP)及其金属配合物是一类新型的光敏性分子,其0-0跃迁出现在λ_max大于630nm的红光区,在光功能材料方面显示出良好的应用前景^[1-2].虽然有关meso-四取代四苯并叶琳金属配合物的合成及其光谱性能的研究已有多篇报道^[3-8],但报道方法的产率较低(最高达15%^[7],有关的光谱性能的报道也不一致^[3-5]。     

FLASH PHOTOLYSIS-ELECTRON SPIN RESONANCE STUDIES OF THE DYNAMICS OF PHOTOSYSTEM I IN GREEN-PLANT PHOTOSYNTHESIS—II. INTACT AND BROKEN SPINACH CHLOROPLASTS*

Abstract —The transient oxidation and subsequent reduction of P700⁺ in spinach chloroplasts has been monitored by flash photolysis-electron spin resonance spectroscopy in the presence of various donors and acceptors. In general, the results obtained correlate well with results on Photosystem I subchloroplast particles, with two major differences. For Type A and B intact chloroplasts in the presence of 3-(3, 4-dichlorophenyl)-1, 1-dimethylurea (DCMU), the electron acceptor methyl viologen has no effect on the decay kinetics. This phenomenon is interpreted in terms of a functioning cyclic electron flow path around Photosystem I. Also, the photoresponse of Signal I depends on the length of the photolyzing flash. This is interpreted in terms of the existence of a primary electron donor to P700⁺ with a transfer time of ? 10 μs.     

STUDIES ON THE TRIPLET EXCITED STATE OF 4-THIOURIDINE

Abstract— The absorption spectra, lifetimes, extinction coefficients and intersystem crossing quantum yields of the lowest triplet T ₁ of 4-thiouridine have been determined both in acetonitrile and in water. An ordering of ^1,3(n,π)* and ^1,3(π,π)* states is suggested. Triplet quenching rate constants with various pyrimidine bases or amino acids are reported.     

有机元素分析中影响燃烧过程的因素

燃烧过程是有机元素分析中十分重要而又较难把握的一个步骤。本文介绍了有机元素分析中影响燃烧过程的因素及控制方法。     

影响重氮片影像颜色的因素

本文探讨了重氮片的主要组份——偶合剂、重氮化合物和成膜剂对重氮片颜色的影响.试验结果说明:不同芳核结构的偶合剂以及在重氮盐中引入不同芳核和取代基对重氮片的影像颜色影响较大,另外,重氮片所用的成膜剂对其影像颜色也有影响.     

SPECTROSCOPIC STUDIES OF CUTANEOUS PHOTOSENSITIZING AGENTS—XL PHOTOLYSIS OF CHLORPROMAZINE METABOLITES: A SPIN-TRAPPING STUDY

Abstract. The photochemistry of chlorpromazine (CPZ) and its metabolites, 7-hydroxychlorpromazine (7OHCPZ), desmethylchlorpromazine (DCPZ), didesmethylchlorpromazine (DDCPZ) and chlorpromazine sulfoxide (CPZSO) was studied by the spin trapping technique with 2-methyl-2-nitrosopropane and 5,5-dimethyl-l-pyrroline-N-oxide. 7-Hydroxychlorpromazine generated hydroxyl radicals when excited at 330 nm under either anaerobic or aerobic conditions. 7-Hydroxychlorpromazine, DCPZ and DDCPZ all underwent dechlorination upon photoexcitation which was enhanced in the absence of air. Chlorpromazine sulfoxide did not undergo photodechlorination but instead generated a high yield of the hydroxyl radical. A comparison among CPZ and its derivatives shows that the yield of the photodechlorinated product is directly related to the degree of phototoxicity. This suggests photodechlorination is an important factor in the phototoxicity of CPZ and its metabolites.     

DYNAMICS OF EXCITED FLAVOPROTEINS—PICOSECOND LASER PHOTOLYSIS STUDIES

Abstract— Molecular mechanism of fluorescence quenching of flavins in flavodoxin from Desulfovibrio vulgaris , strain Miyazaki, and riboflavin binding protein from egg white has been investigated by means of picosecond laser photolysis technique. In the case of flavodoxin, a transient absorption band characteristic of the non-fluorescent exciplex formed by electron transfer from indole to excited flavins in model systems has been observed around 600 nm at the delay time of 33 ps from exciting ps pulse pulse width, 25 ps). In the case of riboflavin binding protein, the transient absorption spectra were different from those of flavin-indole exciplex and rather similar to the spectra of the model system of flavin-phenol. These results suggest that tryptophan residue exists near the isoalloxazine nucleus in flavodoxin, and in riboflavin binding protein, tyrosine residue exists near the flavin. Direct measurements of the ultrafast process of the electron transfer in flavoproteins as developed here could provide useful information for elucidating protein dynamics, associated with redox reaction, in the picosecond time region.     

SPECTRAL CHARACTERISTICS OF THE EXCITED STATES OF THE PRODUCT OF THE CHEMILUMINESCENCE OF LUMINOL*

Abstract— In dimethylsulfoxide the emission spectrum of luminol chemiluminescence is red-shifted by 300 cm^-1 from the photoexcited fluorescence of the product 3-aminophthalate dianion, while in aqueous solvent the two spectra are identical. The spectral properties of the product dianion have been measured in aqueous solvent and in a number of aprotic solvents, both at room temperature and at 77°K. The ground states and the excited states from which emissions are observed are characterized. Two alternatives are presented to explain the aprotic emission spectra.     

SPECTROSCOPIC STUDIES OF CUTANEOUS PHOTOSENSITIZING AGENTS–XVI. ISPERSE BLUE 35

The photochemistry (Type I and II) of the phototoxic textile dye Disperse Blue (DB-35) and its purified components has been studied using electron spin resonance in conjunction with spin trapping technique and the direct detection of singlet oxygen (1O2) luminescence. The main components of DB-35 (which is synthesized by the successive nitration, reduction and methylation of 1,8-dihydroxy-anthraquinone) were separated by HPLC and identified by mass spectrometry and 2-D NMR as 4,5-diamino-1,8-dihydroxyanthraquinone (4,5-DDHAQ; 62% of total dye) and 2,7-diamino-1,8-dihydroxyanthraquinone (2,7-DDHAQ; 31% of total dye). Minor components included 2,5-diamino-1,8-dihydroxyanthraquinone (2,5-DDHAQ) and a monomethylated derivative of either 4,5-DDHAQ or 2,7-DDHAQ. Irradiation (624 nm) of 4,5-DDHAQ and 2,7-DDHAQ in dimethylsulfoxide resulted in the generation of superoxide which was trapped by 5,5-dimethyl-1-pyrroline-N-oxide (DMPO). Visible light irradiation of the components in ethanol generated 1O2 with the yields decreasing in the following order: 4,5-DDHAQ greater than 2,5-DDHAQ greater than 2,7-DDHAQ. These findings indicate that upon irradiation by visible light DB-35 can generate active oxygen species which may be responsible for the photocontact dermatitis caused by this dye.     

SPECTROSCOPIC STUDIES OF CUTANEOUS PHOTOSENSITIZING AGENTS—IX. A SPIN TRAPPING STUDY OF THE PHOTOLYSIS OF AMIODARONE AND DESETHYLAMIODARONE

The photolysis of amiodarone (AM) and its major metabolite mono-N-desethylamiodarone (DEA), has been studied by absorption spectroscopy, electron spin resonance spectroscopy (spin trapping) and oxygraph measurements. Changes in the absorption spectrum of both AM and DEA upon UV irradiation indicate that both drugs undergo deiodination. Spin trapping experiments with 2-methyl-2-nitrosopropane (MNP), α-phenyl-N- tert -butyl-nitrone (PBN) and 5.5-dimethyl-1-pyrroline-N-oxide (DMPO) suggest the formation of an aryl radical from AM during UV irradiation. Amiodarone also undergoes photoionization. Under aerobic conditions the photoelectron is scavenged by oxygen to give superoxide, which is trapped by DMPO. Oxygraph measurements further confirmed the consumption of oxygen and the generation of superoxide during the irradiation of aqueous solutions of AM. Deiodination, photoionization and superoxide formation were all observed at wavelengths as low as 335 nm, suggesting that some or all of these processes may be involved in AM-induced photosensitivity. The aryl radical derived from AM during UV irradiation abstracted a hydrogen atom from suitable donors (ethanol, glutathione, cysteine, linoleic acid). Reaction of the dienyl radical derived from linoleic acid would yield the corresponding peroxy radical thereby initiating lipid peroxidation. This would explain the deposition of lipofuscin, a pigment formed from the products of lipid peroxidation, in the skin of patients receiving AM.     

SPECTROSCOPIC STUDIES OF CUTANEOUS PHOTOSENSITIZING AGENTS. XVII. BENZANTHRONE

The photochemistry of benzanthrone (7H-benz[de]-anthracene-7-one) has been studied using electron paramagnetic resonance (EPR) in conjunction with the spin trapping technique and the direct detection of singlet molecular oxygen luminescence. Irradiation (lambda ex = 394 nm) of benzanthrone (BA) in aerated ethanol, dimethylsulfoxide or benzene resulted in the generation of superoxide (O2-.) which was trapped by 5,5-dimethyl-1-pyrroline-N-oxide. The ethoxy radical was also detected in ethanol. Photolysis of BA in deaerated basic ethanol led to the formation of BA anion radical, BA-., which was detected directly by ESR. This radical anion decayed back to BA with a unimolecular rate constant of 1.5 x 10(-3) s-1. The 1O2 quantum yields (lambda ex greater than 345 nm) for BA in ethanol, 90% ethanol and basic ethanol (0.1N NaOH) were 0.89, 0.88 and 0.28 respectively relative to Rose Bengal. The lower yield of 1O2 in basic ethanol may be attributable to the reaction of oxygen with BA-. (which is generated in higher yield at alkaline pH) to give O2-.. These findings suggest that on exposure to light BA can generate active oxygen species which may be responsible for the photocontact dermatitis caused by BA in industrial workers exposed to this chemical.     

STUDY ON THE FACTORS AFFECTING REDUCTION CAPACITIES OF ACTIVATED CARBON FIBERS

1. INTRODUCTION The discharge of effluent containing precious metal ions, which comes from electroplating, mining, smelting, and other industries, not only contaminate the environment where people live, but also cause the waste of natural resources. From…