SYNTHESIS AND CHARACTERIZATION OF WATER-SOLUBLE BLOCK COPOLYMERS WITH AN END-TAGGED NAPHTHALENE PROBE

Water-soluble A-B block copolymers of 2-perfluoroethyl-2-oxazoline or 2-pentyl-2-oxazoline as hydrophobic monomers and 2-methyl-2-oxazoline as hydrophilic monomer were prepared by means of the living cationic ring-opening polymerization. The polymerization was initiated with N-methyl-2-(1-naphthyl)-2-oxazolinium trifluoromethanesulfonate as fluorescence label followed by sequential addition of the hydrophobic and the hydrophilic monomer. The polymerization was monitored by ¹H NMR spectroscopy and gel permeation chromatography (GPC) measurements. The results revealed that fluorophilic block copolymers can be prepared by this method while lipohilic block copolymers are not accessible by this monomer sequence. Micelle formation of the fluorophilic block copolymers in aqueous solution was studied by means of steady-state fluorescence spectroscopy which confirmed strong intermolecular excimer formation of the terminal bounded naphthalene moiety. In chloroform as a good solvent for both blocks, only monomer fluorescence could be observed.     

PHOTOINTERACTION OF BENZOPHENONE TRIPLET WITH LYSOZYME

The quenching of the benzophenone triplet by lysozyme and its constituent amino acids in aqueous solutions have been studied. Native lysozyme quenches the benzophenone triplet with a high rate constant, 4 x 10(9) M-1 s-1. The quenching process takes place with production of significant amounts of free ketyl radicals, phi ketyl = 0.56, but with a very low benzophenone consumption yield (0.022). The consumption yield is considerably smaller than that observed for the free amino acids. This difference can be explained in terms of a dominant back hydrogen transfer to the protein in the disproportionation of the free radicals produced. Reduced and carboxymethylated lysozyme shows a higher quenching rate (7.8 x 10(9) M-1 s-1) and a larger benzophenone consumption yield (0.07). The deactivation of the benzophenone triplet by the native protein leads to its inactivation, with a quantum yield of 0.01. Tryptophan and arginine residues are destroyed with a quantum yield of 0.01. In the modified enzyme tyrosine and methionine groups are also consumed.     

用正电子素探测叶绿素三线激发态浓度的变化

测量了在不同光强下叶绿素环已烷溶液(77 K)和酒精溶液(296 K)的正电子湮没寿命谱。提出正电子素光磁湮没模型以解释实验事实。在77 K固化的叶绿素环已烷溶液中, 正电子湮没寿命谱长寿命组分的湮没参数I_2和Λ_2随光强变化而呈现规律性变化, 表明可利用正电子素光磁猝灭效应来追踪光敏剂分子三线激发态浓度的变化。     

ZSM-5沸石膜的吸附表征

The framework and thickness of synthesized ZSM-5 membranes were characterized using static and dynamic adsorption methods. It is shown that the adsorptive properties of the membranes are the same as ZSM-5 zeolite, the average thickness of the membranes was 13 μm calculated from the adsorptive ability, which matched very well with the result measured by scanning electron micrograph. The results also shown that zeolite membranes have greated adsorptive ability than zeolite powders. The high Si/Al rate zeolite membranes have selective ability on ethanol/water, and this interpreted the separation of ethanol-water mixtures with the membranes.     

某些香豆素酮类化合物三重态最低能级特性的判别

芳酮类敏化剂的最低激发三重态的特性对其光还原反应的能力往往起着决定性的作用。本文通过对五种香豆素酮类化合物发射光谱行为的研究,明确了它们激发三重态(T₁)的特性,指出化合物3-苯甲酰基香豆素、对苯二甲酰基二香豆素和3,3-二香豆素甲酮的T₁态主要为n,n^*特性,而3-呋喃甲酰基香豆素及3-噻吩甲酰基香豆素的T₁态具有n,n^*和π,π^*混合的特性。     

THE TRIPLET STATE OF 8-METHOXYPSORALEN

Abstract— Transient absorption spectra produced by laser flash photolysis of an aqueous solution of 8-methoxypsoralen (8-MOP) have been studied. The biphotonic production of hydrated electrons and of the radical ions, 8-MOP ⁺ and 8-MOP^- is reported. The hydrated electron was found to react with ground state 8-MOP with k ˜ 3 × 10¹⁰ M ^-1 s^-1. In order to obtain a true triplet-triplet absorption spectrum. contributions from the radical ions were subtracted from the overall transient absorption. In addition, contributions from e^-_aq to the transient spectrum were removed by using N₂O, low laser intensity to minimize photoionization or by measuring the transient O.D. after the electron has decayed. These three methods each produced the same triplet-triplet spectrum which differs in the red region from previously reported spectra.     

不同晶粒大小ZSM－5的合成和表征

采用水热合成法，由不同途径合成出晶粒大小不同的几种ＺＳＭ－５分子筛，这几种分子筛具有大致相同的硅铝比．采用ＮＨ３－ＴＧ－ＴＰＤ，Ｐｙｒｉｄｉｎｅ－ＩＲ－ＴＰＤ表征其酸性，用ＸＰＳ表征其外表面的硅铝比（体相的硅铝比用元素原子吸收法测定）．研究结果表明，应用导向剂可以合成出要求的晶粒大小而且粒度均匀；加晶种的合成得不到较大的晶体，粒度亦不均匀．分子筛的晶粒大小对其酸性有一定的影响，一般来讲，小晶粒分子筛的酸量多．本文中大晶粒分子筛的硅铝比基本上是不均匀的．     

TRIPLET EXCITED STATE OF THE 4'5' PHOTOADDUCT OF PSORALEN AND THYMINE

Abstract— The triplet-triplet absorption spectrum of the 4'5' psoralen-thymine mono-adduct has been determined in water and methanol using the technique of laser flash photolysis. The extinction coefficient of the triplet was measured by the energy-transfer method with retinol triplet as standard, and used to determine the singlet → triplet intersystem crossing quantum yield for 353 nm excitation. Reaction rate constants for mono-adduct triplet with thymine and tryptophan were measured in water. Long-lived transient absorptions detected after quenching the mono-adduct triplet with thymine and tryptophan are assigned mainly to the corresponding mono-adduct radical anion, whose spectrum was established in separate pulse radiolysis studies of the mono-adduct in aqueous formate.
The significant singlet → triplet quantum yields found for the mono-adduct might be consistent with the involvement of triplet excited mono-adduct in DNA cross-link formation, as also may be the high reactivity obtained for the triplet with thymine. The initial quenching products observed resulted from a charge-transfer reaction.     

以聚醚为主链的含苯骈15-冠-5的聚合物冠醚的合成及其络合与催化性能

用羟甲基苯骈15-冠-5的钠盐与β-碘乙基缩水甘油醚-四氢呋喃共聚物进行反应合成了以聚醚为主链、侧链带苯骈15-冠-5的低聚物,它可以进一步与异氰酸酯反应而交联固化,制成不溶性颗粒状固体或具有较好弹性的胶片。研究了这种低聚物冠醚的络合与催化性能。它对Na~+、K~+均有较好的络合容量,作为相转移催化剂,在Wolff-Kishner反应和正溴辛烷的碘代反应中具有良好的催化活性。还改进了羟甲基苯骈15-冠-5的合成方法并提高了产率。     

用硫脲分子表面修饰的CdS纳米粒子的合成和表征

报道了用硫脲分子进行表面化学修饰的CdS纳米粒子的合成方法,并引入了AOT(磺基琥珀酸双-2-乙基己基酯钠盐)作为平衡反离子,进一步对CdS表面作了修饰,增加了CdS纳米粒子在有机溶剂中的稳定性和可分散性。我们还探讨了温度、浓度、pH等因素对合成的影响,并通过TEM、XRD、FT-IR等手段对产物结构进行了表征。所得微粒粒径为5 nm左右,呈球形,硫脲分子与CdS纳米粒子富Cd²⁺表面通过形成Cd-S配位键而修饰在粒子表面。这种表面修饰的CdS纳米粒子将在非线性光学及自组装方面具有优     

A LASER FLASH PHOTOLYSIS STUDY OF THE NATURE OF FLAVIN MONONUCLEOTIDE TRIPLET STATES AND THE REACTIONS OF THE NEUTRAL FORM WITH AMINO ACIDS

Abstract— Primary photochemical processes in aqueous solution have been characterised for FMN. The influence of pH on these processes is attributed to protonation of the neutral triplet and not to the presence of a dimeric species as postulated earlier. Second order rate constants for reaction between the neutral triplet and some naturally occurring amino acids are reported.     

THE EFFECT OF COORDINATING LIGANDS ON THE TRIPLET STATE OF CHLOROPHYLL

Under laser excitation at 457.9 and 514.5 nm, a frozen solution of chlorophyll a in n -octane displays fluorescence peak maxima at 2K that may be assigned to two distinct monomeric chlorophyll species. Using zero-field fluorescence-detected magnetic resonance the triplet state properties of the two chlorophyll species have been assigned to the monoligated and biligated chlorophyll monomer in which water serves as the ligand coordinated to the magnesium metal center. These triplet state properties for chlorophyll in solution are then utilized in interpreting triplet state results for in vivo chlorophylls associated with the light harvesting chlorophyll protein complex. It is shown that the triplet state data are consistent with attachment of the chlorophyll molecule to the protein site with a single ligand coordinated to the chlorophyll metal center.     

DECAY KINETICS OF THE TRIPLET EXCITED STATE OF LUMIFLAVIN

Abstract— The rate of decay of the triplet state of lumiflavin in deaerated phosphate buffer at pH 6.9, has been studied using the flash photolysis technique, at various concentrations and flash energies. The decay of the transient appears as a mixture of first and second order processes, the relative importance of which depends on the experimental conditions.
The following competitive reactions have been found to explain the course of the reaction of the triplet excited state of lumiflavin.     

PHOTOHEMOLYSIS OF HUMAN ERYTHROCYTES LABELED IN BAND 3 WITH EOSIN-ISOTHIOCYANATE

Eosin-isothiocyanate (EYNCS) is 50 to 100 times more effective in sensitizing delayed photo-hemolysis of human erythrocytes than is eosin when matched for absorbance in the reaction medium. These dyes are equally efficient in generating singlet oxygen, a potent membrane oxidant. When cells are treated with sensitizer and washed extensively prior to illumination, EYNCS phototoxicity persists, while that of eosin is lost. SDS-gel electrophoresis of membranes from EYNCS-exposed cells shows a large fluorescence signal coincident with band 3 protein that is abolished by pretreatment with H₂DIDS, the inhibitor of anion exchange by band 3. This treatment reduces the photohemolytic potency of EYNCS by over 90%. The marked enhancement of photohemolytic activity upon binding sensitizer to band 3 implicates band 3 itself as a site of photodamage leading to lysis.     

ANTHRALIN-DERIVED TRANSIENTS–I. THE TRIPLET STATE AND THE PRODUCTS OF ITS REACTION WITH OXYGEN IN BENZENE

Direct laser excitation in benzene of 1,8-dihydroxy-9-anthrone (anthralin) does not lead to transient species with lifetimes in the nanosecond time regime or longer. The triplet state has been produced in benzene by pulse radiolysis and characterised in terms of its absorption spectrum (lambda max 560 nm), natural lifetime (11 microseconds), self-quenching properties (kmicrosecond = 2.6 x 10(7) l mol-1 s-1) and triplet energy (234 kJ mol-1). There is no tendency in the non-polar medium for production of either the triplet or ground state in a tautomeric form. The observed triplet state reacts with oxygen with a typical rate constant, 2.2 x 10(9) l mol-1 s-1. The products of this reaction are singlet oxygen (approximately 64%) and the anthralin radical (approximately 14%).