THE QUENCHING OF EXCITED STATES OF HYPOCRELLIN A BY RARE EARTH IONS

The quenching processes of prompt and delayed fluorescence of hypocrellin A by rareearth ions were investigated. It is demonstrated that the prompt fluorescence of HA can bequenched efficiently by RE in methanol via a static quenching process including a groundstate complex formation. The thermally induced delayed fluorescence of HA can also bequenched effectively by complex formed, which quenching is of dynamic quenching behavior.The fluorescence quenching of HA in various micellar systems which protect the quenchingby the compartmentalization of micelles is discussed as well.     

螺吡喃激发态的反应活性

研究了6′-硝基-1,3,3-三甲基吲(口乃木)苯骈螺吡喃,Ⅰ,和6′-硝基-1-苯基-3,3-二甲基吲(口乃木)苯骈螺吡喃,Ⅱ,的光化学,Ⅰ的直接光解和敏化光解均得到份菁结构的光解产物Ⅲ,量子产率分别是0.42和0.32.Ⅱ直接光解时生成相应的有色光解产物Ⅳ,量子产率是0.40,氮杂蒽酮为敏化剂的敏化光解量子产率是0.58,无疑地,单线态和三线态均参予螺吡喃的发色反应,用这些结果和折算关系式得到,在Ⅰ的直接光解中,Ⅲ主要来自单线态,而在Ⅱ的直接光解中,Ⅳ主要来自三线态.从Ⅰ或Ⅱ的敏化联乙酰燐光实验中求得三线态参数.它们是:φ_ISC^Ⅰ＝0.11,φ_ISC^Ⅱ＝0.48;³K_dt^Ⅰ＝3×10⁴秒^-1,³K_dt^Ⅱ＝9×10⁴秒^-1,类似地,³K_r^Ⅰ＝0.12×10⁴秒^-1,³K_r^Ⅱ＝2.52×10⁴秒^-1,这样,³φ_r^Ⅰ值较小是由于³φ_ISC^Ⅰ值较小,而三线态寿命随结构变动不大.最后,取苯乙烯为模型,用它的电子能量与乙烯双键扭曲角度关系图推断出,来自单线态的双离子具有螺环构型,而来自三线态者具有平面状构型.     

配位体 SO_4~(2-)对激发态铀(Ⅵ)去活化的影响

近年来,随着激光、微弱信号测量以及瞬态测量技术等发展,对溶液中激发态离子的化学和物理行为的研究已日益受到人们的重视,激发态铀酰离子发光衰减的研究尤为活跃.Marcantonatos 等、Formosinho 等以及郑企克、王志麟等对高氯酸溶液中激发态铀酰离子的发光衰减过程进行了详细的研究.探讨了ClO_4~-溶液中pH 等对激发态铀酰离子的发光衰减的影响,观察到了一定的pH 条件下激发态铀(Ⅵ)的非单一指数衰减,并各自提出了不同的解释.值得提出的是,上述的一系列研究都是在高氯酸溶液中,其它体系中铀(Ⅵ)的发光哀减的研究进行得很少,报导则更少.1983年Joshi 等曾研究了80K 时SO_4~(2-)     

掺杂立方AgBr乳剂介电频谱的研究Ⅱ.Ⅰ-离子的影响

本文测定了用0.1—2.0mool%的I^-进行表面掺杂的单分散立方AgBr乳剂的介电吸收谱。经分析证实,在本实验掺杂浓度范围内,99%以上的I^-取代了AgBr微晶表面层晶格上的Br^-。随I^-掺杂量的增大,样品的介电吸收峰明显向高频方向位移。当掺杂量为1mol%时,样品的介电吸收峰频率已很接近纯AgI乳剂的介电吸收峰频率。继续增大掺杂量,则介电吸收峰不再向高频方向位移。 由上述结果可以看到,在连续相介质保持不变的条件下,由界面极化效应产生的介电吸收峰的形状和频率位置受分散相颗粒表面层物质的组成与结构影响很大。用I^-对AgBr微晶进行表面掺杂,可以使AgBr微晶的表面电导率明显增大。     

LASER FLASH PHOTOLYSIS STUDIES OF DNA-COMPLEXED ETHIDIUM BROMIDE

Abstract— Laser flash photolysis studies of DNA-complexed ethidium bromide were undertaken. We have observed a singlet-singlet (S₁-S_n) absorption process for DNA-complexed ethidium bromide. The observed lowest singlet excited state lifetime was 21 ± 2 ns. The molar difference extinction coefficient was measured to be 2.4 ± 0.4 × 10³M^-1 cm^-1 at 370 nm. The assignment of this transition was confirmed by time resolved fluorescence measurements.     

THE EFFECT OF LIGHT ON HALOGENATED SALICYLANILIDE IONS

Abstract— Irradiation of the anions of halogenated salicylanilides with near ultraviolet light causes the halogen atoms substituted in the 3– or 5– positions to be replaced by hydrogen. With 3, 5 substituted salicylanilides the halogen substituted on the 3 position is lost; 5-substituted bromosalicylanilides lose the 5-bromo substituent. 5-substituted chlorosali-cylanilides do not lose the 5-chloro substituent. A free radical mechanism for the reaction is suggested.     

EXCITED STATES OF BILIRUBIN

Abstract— The excited states of bilirubin (BR) in a variety of environments have been studied by 347 nm laser flash photolysis. Quantum yields of formation of triplet BR have been shown to be less than 0.005 in solution in water ( p H 9–11), methanolic ammonia, 10% aqueous mulgofen and in cetyl trimethyl-ammonium bromide. In benzene the quantum yield was 0.01 although this diminished to less than 0.005 on addition of triethylamine. Permanent products are formed with benzene and with 1% methanolic ammonia. With BR in HSA a transient decaying with k = 3.5 × 10⁵ s^-1 is formed by a monophotonic process together with a permanent product. Neither species is affected by oxygen or by iodide ion. Both originate from BR molecules in the strongest binding site in the HSA. The yields of both species are unaffected by salt but are temperature dependent. The decay of the transient is strongly temperature dependent corresponding to an activation energy of about 50–60 kj mol^-1. If this transient is a triplet it is formed with a quantum yield of 0.13 ± 0.01. The relevance of these results to an understanding of the photo therapeutic process is discussed.     

烯丙基溴对钼体系催化聚合丁二烯的影响

本文探讨了烯丙基溴对钼体系催化丁二烯聚合的影响。烯丙基溴降低了聚丁二烯的分子量而提高了1,2-链节和间同构型的含量。由于分子构造发生了变化,提高了聚丁二烯玻璃化转变温度和呈现出一定程度的结晶。加烯丙基溴体系的聚丁二烯的屈服强度比不加溴的大,两者对[η]作图,出现二条平行的直线。分子量对生胶挤出破裂的影响比分子量分布的大。硫化胶的力学机械性能比较好。     

H_5~+的几何构型及电子激发态研究

本文使用组态相互作用(CI)与多组态自洽场(MCSCF)相结合的方法,对H_5~+进行了研究。得到H_5~+为H_3~+·H_2复合体的新构型,属C_2点群。且给出了H_5~+的电子激发态能量。     

分子离子NO+激发态的势能函数

100公里以上的大气分子离子主要为NO~+。它的辐射特点及它与电子、原子或分子的相互作用,对于理解大气的化学过程具有特别重要的意义。为了研究这些过程,确定NO~+分子离子基态及其各个激发态的分子势能函数是非常重要的。精确的X~1Σ~+,A~1Ⅱ和a~3∑~+势能曲线已发表;基于光电子谱的研究发现了NO~+的其它激发态,但对于这些激发态的研究尤其是势能函数的研究不多。本文研究并导出NO~+的基态和10个激发态的势能函数。     

COMPLEX FORMATION BETWEEN ETHIDIUM BROMIDE AND THE NUCLEOTIDES AMP AND GMP

Abstract— The antimicrobial drug ethidium bromide (EB) has been found to form molecular complexes with nucleotides, the strongest being those with the purines AMP and GMP. For the EB-AMP and EB-GMP complexes (which we characterized) the values of the ground-state association constant have been found to be 100 and 103 M ^-1, respectively. The fluorescence of the drug is enhanced when complexed to AMP, GMP, and TMP by about 60, 30 and 10%, respectively, whereas it is quenched by about 20% when complexed to CMP. Fluorescence enhancement analysis has yielded the values of 1.1 × 10¹⁰ and 0.7 × 10¹⁰ M ^-1 s^-1 for the excited-state rate constant of complex formation with the former two nucleotides, respectively. About one out of two collisions between an excited EB molecule and an AMP or GMP molecule results in complex formation. The potential implications of these findings for the EB-DNA interaction are discussed.     

高分子链对激发态芳烃和胺相互作用的影响

本文研究了在激发状态下芳烃(受体)和脂肪胺(给体)的相互作用以及高分子链在其中的影响。结果表明,高分子胺与不带高分子链的胺相比,其对激发态芳烃的淬灭速度和形成激基复合物的能力都强得多,并且激基复合物光谱发生明显红移。     

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.     

DETECTION OF PORPHYRIN EXCITED STATES IN THE INTACT BOVINE LENS

Previous steady state and time resolved spectroscopic studies on porphyrins have shown that the triplet lifetimes of those sensitizers that bind to lens proteins are lengthened by several orders of magnitude. Presented here is an extension of this experiment to measure these transients in an intact bovine lens. As demonstrated by steady state fluorescence spectroscopy and flash photolysis, mesotetra (p-sulfonatophenyl)porphyrin (TPPS) binds to lens proteins. In air-saturated aqueous solution, TPPS has a triplet lifetime of 2 microseconds. In an intact bovine lens the triplet state decayed via biexponential kinetics with lifetimes of 0.16 and 1.6 microseconds. In addition to a lengthening of the lifetime there was a red shift in the triplet transient spectra of 10-20 nm of the porphyrin in the intact lenses.     

THE TRIPLET EXCITED STATES OF BILIVERDIN AND BILIVERDIN DIMETHYL ESTER

Abstract— The triplet states of biliverdin and biliverdin dimethyl ester have been generated using pulse radiolysis excitation. Biliverdin triplet was formed by energy transfer from biphenyl triplet in acetone, absorbed throughout the wavelength range studied (380–1000 nm) and had a half-life of 11.7μs under the cpnditions chosen. Biliverdin dimethyl ester triplet was formed by energy transfer from biphenyl triplet in benzene, likewise absorbed throughout the wavelength range studied (360–1000 nm) and had a half-life of 6.7μs under the conditions used. Both biliverdin and biliverdin dimethyl ester efficiently quench anthracene, naphthacene, but not μ-carotene, triplet states. On the other hand. neither μ-carotene nor oxygen were found to quench the triplet states of biliverdin or biliverdin dimethyl ester. Estimates or limits for the rate constants of all these quenching reactions were obtained. These reactivities suggest that the triplet levels of both biliverdin and biliverdin dimethyl ester lie around 90 kJ mol^-1. The triplet energy transfer rate from bilirubin to biliverdin dimethyl ester in benzene was measured to be 1.9 × 10⁹ M^-1 s^-1. The singlet-triplet intersystem crossing efficiencies of both molecules were very low, limits of 0.004 and 0.001 being found for biliverdin and biliverdin dimethyl ester, respectively, using 347 nm laser excitation.