竹红菌甲素敏化嘌呤和嘧啶碱的光氧化作用及其影响因素

本工作利用光吸收和高效液相色谱(HPLC)技术研究了甲素对DNA分子中四种碱基A、G、C和T光氧化的敏化作用,发现在反应体系的pH为9.0、甲素浓度为3×10~(-5)mol/L、光照40分钟时,G和T紫外吸收明显降低;HPLC分析发现甲素敏化的G光氧化体系比对照体系多出现一组分峰(滞留时间0.927分钟),该峰用475nm波长检测比260nm波长检测灵敏。根据反应机制推测是G环破裂产物。在反应条件固定时,甲素敏化G的光氧化作用受pH、光照时间及甲素浓度影响极大。单线态氧淬灭剂——叠氮钠浓度在40—110mmol/L可部分抑制甲素敏化G的光氧化作用,>110mmol/L时反应完全被阻断,提示甲素对G光氧化的敏化作用主要通过单线态氧(~1O_2)即Ⅱ型机制起作用。本文还讨论了G光氧化的可能途径。     

长白山常绿针叶树越冬期间光合能力的抑制

在长白山地区以红皮云杉、樟子松为材料,研究其冬季光合能力的变化,探讨了除红松外的其它针叶树是否在冬季也存在光合抑制以及遮荫是否可减轻抑制等问题,结果表明,红皮云杉、樟子松有与红松相似的冬季光合抑制,但程度较轻;遮荫对减轻光合抑制非常有效,可以推测,在长白山地区或冬季气候与之相似的地区,常绿针叶树在冬季均可能表现光合抑制,遭受冬季光氧化伤害,并且其释放的ＣＯ２（光越强,释放量越大）是空气中ＣＯ２含量     

Specific Deprotonation Reactions of the Pyrimidine Radical Cation Resulting from the Menadione Mediated Photosensitization of 2′-Deoxycytidine

Menadione(2-methyl-1, 4-naphthoquinone) was shown to sensitize 2′-deoxycytidine to near ultraviolet light according to two main mechanisms. Reaction of a water molecule with the initially photo-induced pyrimidine radical cation and subsequent addition of molecular oxygen leads to the preponderant formation of the four cis and trans diastereoisomers of 5,6-dihydroxy-5,6-dihydro-2′-deoxyuridine. Pyrimidine ring opening and rearrangement products are also generated through the intermediate 6-hydroxy-5,6-dihydro-2′-deoxyurid-5-yl radical. The competitive deprotonation reaction of the radical cation is likely to involve two sites. Loss of an amino group proton is the likely initial event to explain the formation of 2′-deoxyuridine which is resistant to further photooxidation. The second deprotonation reaction involves the osidic carbon C(1′). The resulting radical will further react with oxygen leading to the release of free cytosine with concomitant formation of 2-deoxy-D-ribono-1,4-lactone. This reaction which is not prevented by hydroxyl radical scavengers constitutes to our knowledge the first example of a pyrimidine radical which is able to initiate selective intramolecular reaction at position 1 within the sugar moiety.     

C3和C4植物叶片对光氧化响应的日变化

田间生长的C3植物花生和C4植物玉米分别于晴天上午9：00、中午12：00、下午15：00取样。中午12：00花生叶片的Fv／Fm较早上9：见下降16％,出现了光抑制现象,玉米叶片的Fv／Fm则未下降。不同时间取样的花生和玉米叶片经甲基紫精（MV） 强光的人为光氧化处理,叶绿素和类胡萝卜素出现不同程度的氧化降解,中午12：00降解幅度最大,15时降幅最小。植物叶片的抗氧化能力与其SOD活性相关,而与PEPCase的活性没有明显的相关性。光氧化处理后,花生和玉米的叶绿素荧光参数FV／Fm、qp、pSII都下降,花生在12：00的降幅最小,玉米的降幅最大。光氧化引起花生的qN和热耗散系数（KD）上升,玉米则都下降．结果显示C3植物花生和C4植物玉米对光氧化的响应可能存在不同的机制。     

Fluorescence emission and enhanced photochemical stability of Zn-5-triethyl ammonium methyl salicylidene ortho-phenylendiiminate interacting with native DNA

The photophysical and photochemical properties of the cationic Zn^II complex of 5-triethyl ammonium methyl salicylidene ortho-phenylendiimine (ZnL²⁺) interacting with native DNA were investigated by steady state and time-resolved fluorescence spectroscopies. Experimental results indicate that, in the presence of DNA, ZnL²⁺ is efficiently protected from a photochemical process, which occurs when it is in the free state dispersed in aqueous solution. The analysis of the absorption and emission spectra of ZnL²⁺, both stored in the dark and after exposure to tungsten lamp light for 24 h, corroborated by quantum chemical calculations, allowed us to point out that ZnL²⁺ undergoes a photoinduced two-electron oxidation process. According to this picture, the protective action of DNA toward the intercalated ZnL²⁺ was attributed to an effective inhibition of the ZnL²⁺ photooxidation. In this context, it can be considered that DNA-intercalated ZnL²⁺ is located in a region more hydrophobic than that sensed in the bulk water solvent. Moreover, by a thorough analysis of steady state and time-resolved fluorescence spectra, the interaction process can be consistently explained in terms of a complete intercalation of the complex molecules and that the polarity of the environment sensed by intercalated ZnL²⁺ is comprised between that of methanol and ethanol.     

Photooxidation of wetland and riverine dissolved organic matter: altered copper complexation and organic composition

In natural waters, the uptake of transition metals such as copper (Cu) by aquatic biota depends on the activity of the free cupric ion ({Cu²⁺}) rather than on total Cu concentration. Thus, an important ecological function of dissolved organic matter (DOM) in aquatic ecosystems is Cu–DOM complexation, which greatly decreases the {Cu²⁺}. However, Cu bioavailability is greatly modified by source and environmental history of DOM because DOM affinity for Cu varies by orders of magnitude among DOM sources; moreover, DOM is photochemically unstable. During 72-h irradiation experiments at intensities approximating sunlight with DOM from a palustrine wetland and a third-order river, we investigated photooxidative effects on DOM complexation of Cu as well as spectral and chemical changes in DOM that might explain altered Cu complexation. Irradiation decreased Cu complexation by riverine DOM, but unexpectedly increased Cu complexation by wetland DOM, resulting in 150% greater {Cu²⁺} in riverine DOM at the same dissolved organic carbon concentrations. The specific ultraviolet absorption (SUVa) and humic substances tracked photochemical changes in the conditional stability constants of Cu–DOM complexes, suggesting that the aromaticity of DOM influences its affinity for Cu. Carbonyl concentration in ¹³C nuclear magnetic resonance spectra (¹³C-NMR) covaried directly with Cu binding-site densities in DOM. However, no aspect of Cu–DOM complexation consistently covaried with fluorophores (i.e., the fluorescence index) or low molecular weight organic acids. Our results suggest that global increases in UV radiation will affect Cu–DOM complexation and subsequent Cu toxicity depending on light regime as well as DOM source. Handling editor: K. Martens     

光氧化条件下碳代谢中间产物与光合电子传递对PSⅡ光化学活性的调节作用

在MV和强光的光氧化条件下研究外加光合碳代谢中间产物、光呼吸C2酸和光合电子传递抑制剂等对菠菜叶绿体PSⅡ光化学活性的调节作用。结果表明,光氧化条件下外加“RuBP再生系统”和乙醇酸钠可提高qP和Φpsu,而R5P、DHAP和HCO3^-可提高qN,显示其对光氧化下叶绿体PSⅡ活性有一定程度的保护作用。其他外加化合物3-PGA、3-GAP、HPMS、DCMU、DBMIB、Ant A、短杆菌肽D等则对以叶绿素荧光参数表示的光化学活性和氧电极测定的全链电子传递速率表现抑制效应。据此认为在叶绿体水平上阻断或改变光合电子流的流向,更改光合碳还原和光呼吸代谢物浓度,皆可直接或间接影响光氧化下PSⅡ的光化学活性,其作用因不同化合物而异。     

Photooxidative damage to plastids affects the abundance of nitrate-reductase mRNA in mustard cotyledons

It was found previously that in the mustard (Sinapis alba L.) seedling (Schuster et al. 1989, Planta 177, 74–83) the action of nitrate and phytochrome on the appearance of cytosolic nitrate reductase (NR) is abolished if the plastids are damaged by photooxidation. In the present study this finding has been corroborated by the following results: (i) the appearance and disappearance of NR activity are strictly correlated with the appearance and disappearance of immunoresponsive NR protein; (ii) the appearance of NR correlates with the appearance of translatable NR mRNA; (iii) photodestruction of the plastids strongly reduces the level of NR mRNA. It is concluded that the dependence of the NR level on the state of the plastids can be detected at the level of its mRNA and is not attributable to an inactivation of the enzyme.Abbreviations NR nitrate reductase (EC 1.6.6.1) This research was supported by a grant from the Deutsche Forschungsgemeinschaft. We are greatly indebted to Dr. Ann Oaks (University of Guelph, Ontario, Canada) for the gift of antiserum.     

Minireview: Versatile Melatonin: A Pervasive Molecule Serves Various Functions in Signaling and Protection

Melatonin, which is able to enter all tissues and all compartments of the cell, acts in a highly pleiotropic fashion. Some melatonin effects are mediated by membrane receptors, others are receptor independent. Melatonin is produced in the pineal gland and various extrapineal organs of vertebrates, but is also found in invertebrates, angiosperms, and unicells. In mammals, melatonin elicits various secondary humoral responses, e.g., in the immune system via interleukin-4 and other cytokines and in the brain by modulation of NO formation. Melatonin is also a powerful radical scavenger, terminating free radical reaction chains initiated by photooxidants, hydroxyl or peroxyl radicals. The protective potency of this indoleamine is demonstrated by various experiments.     

Developmental changes in antioxidant metabolites, enzymes, and pigments in fruit exocarp of four tomato (Lycopersicon esculentum Mill.) genotypes: β-carotene, high pigment-1, ripening inhibitor, and ‘Rutgers’

In surface cell layers of fleshy fruit, antioxidants must limit photooxidative reactions that generate reactive oxygen species (ROS) in high light. Our objective was to measure changes in the concentrations of antioxidant metabolites and pigments, and the activities of enzymes of the Mehler-peroxidase, ascorbate-glutathione cycle in fruit exocarp tissue under non-stress conditions of the following fruit-specific tomato (Lycopersicon esculentum Mill.=Solanum lycopersicum) mutants and their parent: (1) beta-carotene (B), (2) high pigment (hp-1), (3) ripening inhibitor (rin), and (4) the nearly isogenic wild-type 'Rutgers'. Developmental variables included days after anthesis (DAA) and fruit surface color. The highest total ascorbic acid (AsA) concentration was in the exocarp of immature green fruit of hp-1, being 32% higher than 'Rutgers'. The hp-1 mutant also had the highest chlorophyll and total carotenoid concentrations, comprised mostly of lycopene in red ripe fruit; whereas, beta-carotene comprised 90% of the carotenoids in B. Although enzyme activities varied within genotype, they generally increased with development, then decreased as fruit maturity was reached, being coupled with AsA and glutathione (GSH) concentrations. In all mutants, dark-green (DG) exocarp had more chlorophyll and protein, higher concentrations of reduced AsA and GSH, and usually lower enzyme activities than light-green (LG) exocarp taken from the same fruit.