PHOTOLYSIS OF POLYRIBOBROMOURIDYLIC ACID

Abstract— Photolysis of polyribobromouridylic acid with 313 nm light at neutral pH caused extensive debromination and a loss of A₂₈₀ (280–nm absorbance) without comparable increase in A₂₆₀. At an exposure of 190μE/cm ² , strand breakage occurred on the average of one break every 170 BrU residues. Little if any pyrimidine hydrate was produced. Exhaustive RNase hydrolysis of photolysed polymer gave a mixture of mononucleotides and oligonucleotides. The mononucleotide fraction was found to be composed of unaltered BrUMP and contained little if any UMP. Irradiation of the polymer at alkaline pH caused little or no debromination or spectral change.     

FLASH PHOTOLYSIS STUDIES OF OROTIC ACID

Abstract— The triplet state of orotic acid has been studied by flash photolysis. The rate for dimerization has been observed to vary from 2 × 10⁹ M ^-1 sec^-1 at pH 1 where both the triplet and ground state molecules are neutral, to under 10⁸ M^-1 sec^-1 above pH 9 where both the triplet and ground state molecules are doubly ionized. The p K of the triplet state has been measured as 4.6. The rate of oxygen quenching for the triplet is 2–3 × 10⁹ M^-1 sec^-1 while the rate of radiationless decay in solution is 0.73 × 10⁴ sec^-1. The triplet absorption spectra have been measured for the two ionic forms of the triplet.     

用吸收光谱法测定鎓盐光解生成酸的量子产率

近年来,鎓盐化合物,如碘鎓盐、硫鎓盐和氧鎓盐等,作为光引发剂在酸催化微电子器件加工技术中得到了广泛的应用。我们曾对它们的稳态和瞬态光解及机理进行过比较详细的研究,也发现它们在光解时能以不同途径生成很强的无机酸(Bronsted酸),进而可引发单体阳离子聚合或高分子薄膜的交联等。很显然,在这一工作中准确测定它们光解时生成酸的量子产率将与微电子器件加工中光刻质量(如分辨率等)密切相关。在过去的工作中,一般采用酸碱滴定法困,即用氢氧化钠,氢氧化钾水溶液测定嗡盐光解生成酸的量子产率,但由于嗡盐在水中溶解度不很理想,因而结果往往不能重复,测定的酸量子产率误差较大,如Pappas用此法测得的三苯基硫嗡盐在254 nm光解生成酸量子产率为0.74,误差在正负20%。     

PHOTOLYSIS OF NITRATE ESTERS—II. SOLUTION PHOTOLYSIS OF ARALKYL NITRATE ESTERS: KINETICS, ESR SPECTRA, AND PHOTOPRODUCTS

Abstract— Irradiation of benzyl nitrate, meso- and dl-hydrobenzoin dinitrates, and cis- and trans -1,2-acenaphthenediol dinitrates in benzene solutions 0.02M in nitrato groups at 265–313 mp decomposed the esters with a quantum yield of 0.4±0.2 in reasonable agreement with earlier work on the gas-phase photolysis of ethyl nitrate. An important primary process was ArRCHONO₂+h v ArRCHO +NO₂, although ArRCHONO₂+h v ArRCHONO + O was not excluded. In secondary reactions solvent benzene was oxidized and nitrated, aldehydes were formed from the nitrate esters, and nitric oxide was evolved. The higher quantum yields of the photodecomposition in ethanol (0.8±0.3) and ether (3±1) solutions were interpreted in terms of a charge-transfer state similar to that found with nitroalkanes in these solvents. Acetaldehyde was produced in a rapid secondary reaction in alcohol solutions at 25° and at 77° K, NO₂ was identified as an intermediate from the ESR spectrum. No stereospecificity was detected in a comparison of rates, photoproducts, and ESR spectra for the stereoisomers. The overall results indicated inter- rather than intramolecular migration of oxy-nitrogen groups in secondary reactions. An apparently new, long-lived, oxynitrogen radical was detected in benzene solutions of nitric oxide and nitrate esters irradiated at 25°.     

PHOTOSENSITIZATION BY METHOTREXATE PHOTOPRODUCTS

Abstract— Photoproducts induced upon excitation of methotrexate by UV light have been separated by ion exchange chromatography. They include 2,4-diamino-6-pteridinecarboxylic acid, 2,4-diamino-6-pteridine-carboxaldehyde and other unidentified pteridine derivatives. The same photoproducts can be also formed upon photodynamic reaction using hematoporphyrin as photosensitizer. In oxygen saturated aqueous solutions (pH∼7), methotrexate photoproducts sensitize the oxidation of histidine and tryptophan by UV light by a process involving singlet oxygen. In aqueous solutions containing albumin or in human serum, the same photoproducts are formed from free methotrexate but not from albumin-bound methotrexate. In the latter case the results may suggest that methotrexate covalently binds to albumin upon excitation with UV light either in absence or in presence of oxygen. These results could explain the photosensitization accompanying cancer chemotherapy with high dose methotrexate and also the synergistic effects of PUVA + low dose methotrexate in psoriasis therapy.     

PHENYLATION OF PYRIDINE BY PHOTOLYSIS OF DIPHENYL SULFONE

Abstract

The photolysis of diphenyl sulfone in neat pyridine or pyridine diluted with the organic solvent, with a high-pressure mercury arc lamp, was studied. The presence of acetone in the reaction system remarkably promoted photochemical conversion of the sulfone. The isomer distribution ratios (β > α > γ) of phenylpyridines produced during the reaction were clearly different from those (α > β > γ) so far reported for a free-radical phenylation of pyridine. Benzenesulfinic acid produced in the reaction was separated from the product mixture and identified as its S-benzylthiuronium derivative.     

THE USE OF SPECIFIC RADIOIMMUNOASSAYS TO DETERMINE ACTION SPECTRA FOR THE PHOTOLYSIS OF (6-4) PHOTOPRODUCTS

Abstract. A radioimmunoassay (RIA) was developed which specifically detects a photoproduct produced by the near-UV photolysis of pyrimidine(6-4)pyrimidone photoproducts. This assay was used in conjunction with a previously characterized RIA which specifically detects (6-4) photoproducts to determine the relative efficiency of wavelengths between 265 and 435 nm for photolysing these lesions. The rate of loss of antibody-binding sites associated with (6-4) photoproducts correlates with the production of those associated with its photolysis product. Action spectra for both the loss of (6-4) photoproducts and the induction of the photolysis product parallel the absorption spectrum of the (6-4) photoproduct.     

有机锡化合物光解活泼自由基的ESR研究

本文用自旋捕捉技术与ESR相结合的方法,研究了六种有机锡化合物的光解反应历程。结果表明:有机锡化合物紫外光照时,碳-锡键发生均裂,产生碳中心和锡中心自由基。其中碳中心自由基易被捕捉剂α-苯基-N-特丁基氮氧化物(PBN)或2,3,5,6-四甲基亚硝基苯(ND)所捕获;而锡中心自由基可与菲醌形成稳定的环状加合物。由于环状加合物中配体的不同,产生的空间效应也不同,从而导致加合物中的未偶电子云密度发生变化,给出相异的ESR信号。     

SPECTROSCOPIC ANALYSIS OF BINARY AND TERNARY COPPER(II) COMPLEXES FORMED BY HISTIDINE AND GLUTAMIC ACID

Abstract

Ternary copper(II) complexes of the type [Cu(His)A] (HisH=L-histidine, A=glycinato, L-valinato, L-alaninato, L-threoninato, L-serinato, or L-asparaginato) and [Cu(Glu)B]^n- (GluH₂=L-glutamic acid, B=glycinato, L-alaninato, L-valinato (n=1) or an amino-acid with positively charged protonated side chain such as L-asparagine, L-lysine, or L-ornithine (n=0)) have been investigated in aqueous solution by means of ESR and absorption spectra. It is suggested that in the ternary species the histidinate ion adopts a histamine-like bonding mode giving rise to CuN₃O chromophores in the metal plane. Coordination in the bis-(glycine)-like mode is detected in the Glu-containing species. The spectral results have been used to postulate plausible structures for the bis-(histidinato)copper(II) complexes.     

示差脉冲极谱法测定铋-邻吡啶甲酸体系的络合物稳定常数

在5×10-5mol·L-1Bi(Ⅲ)溶液中,增加络合剂邻吡啶甲酸的浓度,用示差脉冲极谱法研究铋 邻吡啶甲酸体系。通过计算机分析程序求解体系的质量平衡方程及拟合试验络合物形成曲线,优化得到铋和邻吡啶甲酸形成的络合物BiL2+和BiL+2的稳定常数,分别为7.51±0.03和13.92±0.04。     

IN SITU GENERATION OF PSORALENS BY PHOTOLYSIS OF WATER-SOLDBLE PRECURSORS

Abstract— The poor water solubility of typical photochemotherapeutic psoralens restricts their utility in aqueous solutions and commonly requires the use of organic co-solvents in photobiological studies. This paper describes the preparation of readily water-soluble "pre-psoralens", (Z)-3-[5-(4,6-dimethoxy)benzofuranyl]propenoic acid (3) and (Z)-3-[5-(6,7-dimethoxy)benzofuranyl]propenoic acid (4), and their novel photocyclization in aqueous media to give 5-methoxypsoralen (5-MOP) and 8-methoxypsoralen (8-MOP), respectively. Quantum efficiencies, measured at 308 nm for the cyclization, are 12. 1 × 10^-3 for 3 → 5-MOP and 2.7 × 10^-3 for 4 → 8-MOP. 5-Methoxyisopsoralen (5-MOiP, 5) is a side product from the photolysis of 3. Photocross-linking of calf thymus DNA is effected when the "pre-psoralens" are irradiated with 308 or 355 nm (3 only) light.     

煤酸异构化制对苯二甲酸

进行了煤氧化产物煤酸（水溶酸WSA）钾在催化剂碳酸镉的存在下，异构化制对苯二甲酸(TPA)的研究。主要考察了催化剂用量、二氧化碳初压、反应温度和反应时间对TPA产率的影响。结果表明，在催化剂存在下煤酸可以转化成TPA。单独煤酸钾异构化时，较佳反应条件：温度430 ℃～450 ℃，压力4.0 MPa，催化剂CdCO3用量4%，反应时间2 h。煤酸钾与苯甲酸（BA）钾混合异构化时，较佳反应条件与单独煤酸钾时基本相同。单独煤酸钾在较佳条件下异构化时，粗TPA产率达34%左右，相当于根据其中有效成分苯多羧酸（BPCA）计算的理论产率的75%左右，选择性较好。煤酸钾加苯甲酸钾在较佳条件下异构化时,粗TPA产率可达68%，扣除假定BA自身岐化生成TPA理论产量之后，则煤酸的TPA产率高达70%，比煤酸单独异构化TPA产率(34%)高1倍。粗TPA经精制可得纯度99%以上的精TPA。     

INDUCTION OF PHOTOPRODUCTS IN SYNTHETIC POLYNUCLEOTIDES BY FAR AND NEAR ULTRAVIOLET RADIATION

Single and double-stranded polynucleotides of thymine and cytosine have been used to analyse the photoproducts produced by irradiation with far or near UV light. Reversed-phase high performance liquid chromatography was used to detect and quantify cyclobutane dimers and Pyr(6–4)Pyo adducts produced by 254 nm. At 320 nm 10-times less Thy(5–6)Thy dimers and one half the number of Cyt(5–6)Cyt dimers were induced; no Pyr(6–4)Pyo adducts were evident. HPLC has recently been applied to the isolation and characterization of various nucleic acid substituents and their UV-photoproducts. The relative retention times of pyrimidines and their UV photoproducts on HPLC reflect differences in the hydrophobicity of the compounds being separated. Hence, the more hydrophobic (less polar) a compound is, the greater its capacity to bind to the column and the greater its retention time; for T o T, C<>T and C<>C dimers this difference may result from variations in the number of methyl moieties (Cadet et al., 1983). The retention time of the compound also depends on its stereochemistry. Separation of the four stereoisomers of T<>T by HPLC shows that compounds which are molecular equivalents can be more or less accessible to the non-polar stationary phase depending on their conformation (Cadet, 1980). The relatively long retention times of the bipyrimidine photoadducts suggest a structural configuration which allows greater access to the hydrophobic moieties of the molecule. It is intriguing to consider that this difference in conformation may also be reflected in DNA–protein interactions such as binding by UV-endonucleases or antibodies directed against UV photodamage. Proteins can be used as sensitive probes for photoproduct induction and repair but an accurate evaluation of their specificity is required. It was the intent of this paper not only to compare the induction parameters for various dimers in pyrimidine homo-polymers but to provide controlled substrates which can be used to define the relative binding efficiencies of repair enzymes and antibodies for different types of photoproducts.     

PREBIOTIC FORMATION OF HIGHER MOLECULAR WEIGHT COMPOUNDS FROM THE PHOTOLYSIS OF AQUEOUS ACETIC ACID

In the study of chemical evolution, experiments simulating primitive earth conditions have shown that many compounds of biological significance can be produced from simple precursors. In an attempt to search for the origin of polycarboxylic acids, the UV irradiation of aqueous acetic acid was performed. Among the products detected were succinic, citric and malonic acids which are key compounds in metabolic pathways, suggesting that these compounds might have been formed on the primitive Earth prior to life itself.     

STRUCTURES OF THE BERGAMOTTIN PHOTOPRODUCTS

The extensive use of bergamot oil in perfumery and cosmetics led us to study the photoreactivity of 5-geranoxypsoralen (bergamottin), the major chromophore in this oil. Structure determination of the bergamottin photoproducts was achieved using extensive NMR techniques including two-dimensional NMR: ¹H-¹³C correlation by long-range coupling, ¹H-¹H correlation spectroscopy (COSY) and ¹H-¹H COSY phase sensitive (COSYPH). Bergaptol is formed according to the well-known fragmentation of allyl-aryl ethers. The other photoproducts arise from an intramolecular [2 + 2] photocycloaddition and appeared as an equimolecular mixture of diastereomeric cyclobutyl derivatives. The relative configurations were determined by nuclear Overhauser effect analysis. These structures were further corroborated by X-ray crystal analysis. The facile formation of an intramolecular cyclobutyl derivative in bergamottin might prevent the intermolecular cyclobutane adduct formation with pyrimidine DNA bases responsible, in part, for phototoxicity of psoralens.     

TEH PHOTO-OXIDATION OF SIMPLE N-ALKYL ANILINES STUDIED BY FLASH PHOTOLYSIS

Abstract— The flash-initiated photo-oxidation of six simple N-alkyl tertiary, secondary and primary anilines was studied in aqueous solution by kinetic spectroscopy. Two transient species were observed with the tertiary anilines, but only one "transient" was observed with the secondary and primary anilines. Where possible, the kinetics of formation and decay of these transients was studied in detail. The formation of highly coloured products was observed on flashing the anilines in air-saturated solution and the variation of their colour with the pH of the solution was noted. Preliminary observations on the nature of possible blue products from the tertiary anilines were made. The results for thwe tertiary anilines are interpreted in terms of the mechanism previously for the photo-oxidation of HEMA.     

MODIFICATION OF POLYETHYLENE BY in situ FORMED SODIUM ACRYLATE

To improve the water tree resistance of PE, linear low-density polyethylene （LLDPE） was compounded with sodium acrylate （NaAA） for in situ polymerization, in which NaAA was fbrmed through the neutralization of acrylic acid （AA） with sodium hydroxide （NaOH） before adding dicumyl peroxide （DCP） to initiate the in situ graft polymerization and homo polymerization. A series of LLDPE/NaAA compounds were investigated for their water absorption ratio （WAR） measurement, water treeing, mechanical and dielectric properties. The results strongly suggest that NaAA can improve the water tree resistance of LLDPE. In addition, the LLDPE/NaAA compounds possess satisfactory mechanical properties and dielectric properties. Characterization of LLDPE/NaAA compounds by using Fourier transform infrared spectrometry （FTIR） suggests that the neutralization and polymerization reaction could be achieved effectively. Using adequate DCP content is the key factor for controlling the polymerization of NaAA with precise conversion ratio.     

STRUCTURE OF A THYMINE-THYMINE ADDUCT FORMED BY MENADIONE PHOTOSENSITIZATION

Abstract— The structure of one of the dithymine adducts formed by near-UV photosensitization of aqueous oxygenated thymine in the presence of 2-methyl- 1, 4-naphthoquinone is reported. The compound, 6'β-hydroxy-5'β-1 - [5-methylpyrimidinyl- 2,4-dione]-5'-6'-dihydrothymine has one thymine ring (ring I) linked through the 1-nitrogen atom to the C5' atom of a second thymine, which has been hydroxylated af C6' (ring II). Crystals are monoclinic, space group 12/c, and the structure was refined to R_obs= 0.036 for 2072 unique reflections with intensities I greater than 2.33(I). Ring I is planar, whereas ring II is not. Ring I and the OH group on ring II are cis to ring II. The planar ring I and the OH group are attached, respectively, in an equatorial and axial manner to ring II (which is in the sofa conformation). The planar rings I of close-lying pairs of molecules stack parallel to each other. The structure is held together by a hydrogen-bonding system consisting of the water molecules, the NH groups, two of the C=O groups and the OH group. The chemical formula and relative configurations at C5' and C6 are established by this analysis.     

PREFERENTIAL INHIBITION OF NUCLEOSOME ASSEMBLY BY ULTRAVIOLET-INDUCED (6-4)PHOTOPRODUCTS

We reconstituted nucleosomes in vitro using two kinds of damaged pBR322 plasmid DNA carrying cyclobutane pyrimidine dimers (CPD) or (6-4)photoproducts. The results indicate that nucleosome assembly is inhibited preferentially by (6-4)photoproducts compared with CPD, suggesting that the regions carrying (6-4)photoproducts retain their nucleosome-free form, i.e. linker-like conformation until completion of the repair processes.     

INTRAMOLECULAR TRAPPING OF THE NITRENE GENERATED BY PHOTOLYSIS OF S,S-DIPHENYL N-ACYLSULFILIMINE

Abstract

Various N-acyldiphenylsulfilimines (1a-k) were found to undergo photolysis in argon atmosphere, to afford the corresponding isocyanates, diphenyl sulfide and diphenyl disulfide. Attempts to trap intramolecularly the acylnitrene with olefinic linkage or sulfide afforded small amounts of the trapped products, whereas photolysis of N-mesitoyldiphenyl-sulfilimine (Ia) afforded a C–H inserted product of the nitrene in a substantial yield together with the isocyanate. Benzophenone-sensitized photolysis of Ia indicates that the nitrene generated is a singlet species.