UPON THE OPTIMAL GRAPHICAL REPRESENTATION OF FLASH DATA FROM PHOTOCHEMICAL SYSTEMS OBEYING FIRST ORDER KINETICS

Abstract— It is recommended that plots of absorbance change vs. log time be considered as a way to represent many decades of flash spectroscopy data when several separate decays are present. The values of the rate constants k , for the decays are easily revealed by nearly linear portions of the plots centered near t _j= k ⁻¹_j, which are inflection points in the graphs. The amplitudes of the decays are easily seen because they are proportional to the slopes of the linear portions of the plots. Such plots introduce no spurious singularities and they are easy to construct using semi-log paper. Examples, including one from bacteriorhodopsin, are presented. A simple mathematical proof of these features is provided.     

微载体糖基化修饰及培养基中添加果糖对大鼠原代肝细胞体外培养的影响

采用对大孔壳聚糖微载体进行糖基化修饰和培养基中添加果糖两种方式考察了果糖对原代大鼠肝细胞体外培养的影响。结果显示,肝细胞在果糖修饰大孔微载体上聚集生长,形态良好,保持了较高的白蛋白分泌和尿素合成活性,表明果糖修饰大孔壳聚糖微载体是较理想的细胞培养支架材料。培养基中加入果糖,肝细胞乳酸脱氢酶泄漏明显降低,白蛋白分泌与尿素合成活性进一步提高,显示有利于受损细胞功能的恢复。     

FLASH PHOTOLYSIS OF TRYPTOPHAN AND N-ACETYL-L-TRYPTOPHANAMIDE; THE EFFECT OF BROMIDE ON TRANSIENT YIELDS

Abstract— Electronic spectra of indoles are very sensitive to solvents. These solvent effects are particularly pronounced in the case of the fluorescence spectra of indoles. In order to elucidate the solvent band shifts during the relaxation of the excited states, particularly in polar solvents, the dipole moments of the excited singlet states have been estimated from the data of solvent-dependent Stokes shifts. In addition to indole, indole-5-carboxylic acid, indole-3-carboxylic acid, indole-2-carboxylic acid, 5-cyano- and 5-bromo-indoles have been investigated. All indoles showed a substantial increase in dipole moment upon excitation to the emitting state. These results are generally consistent with the Pariser-Parr-Pople SCF MO calculations.     

PHYTOCHROME-MEDIATED PHOTOTROPISM AND DIFFERENT DICHROIC ORIENTATION OF Pr AND Pfr IN PROTONEMATA OF THE FERN ADIANTUM CAPILLUS-VENERIS L.

Abstract— Single-celled protonemata of Adiantum capillus-veneris were cultured under continuous red light for 6 days and then in the dark for 15 h. Brief local exposure of a flank (5 times 20 /mi) of the subapical region of a protonema to a microbeam of red light effectively induced a phototropic response toward the irradiated side. The degree of the response was dependent upon the fluence of the red light. Red/far-red reversibility was typically observed in this photoreaction, showing that phytochrome was the photo-receptive pigment. When the flank was irradiated with a microbeam of linearly polarized red and far-red light, red light with an electrical vector parallel to the cell surface was most effective. However, the far-red light effect was most prominent when its electrical vector was normal to the cell surface. These polarized light effects indicate the different dichroic orientation of P_r (red-light-absorbing form of phytochrome) and P_r (far-red-light-absorbing form of phytochrome) at the cell flank.     

有机磷化合物中取代基电负性对P=O及P=S振动频率的影响

1.有机磷化合物的P=O频率在1160-1400厘米^-1,P=S频率在540-750厘米^-1.这些频率都因取代基不同而变化很大,随取代基电负性增大,频率也显著提高.2.P=O频率与取代基电负性和∑x之间呈良好的直线关系,其经验公式可写为υ_P=0=37.5∑x+950.1 利用这式,如果知道某一分子的P=O频率,就可求其取代基的电负性.3.P=O频率的移位主要是由于取代基诱导效应的作用,使P=O键的力常数发生变化而引起.4.P=S频率的移位较为复杂.除取代基的诱导效应外,当与P=S键直接相联的是第三或第四周期的硫、氯或溴原子时,这些原子还可能对P=S键产生另一效应,足以提高P=S键强度.     

碱金属、碱土金属氯化物对稀土谱线强度的影响

本文研究了碱金属、碱土金属氯化物载体对稀土谱线强度的影响。实验结果表明,加入这些载体后,由于等离子区稀土原子数增加,能大大提高稀土谱线强度,其效果原子线大于离子线,所用载体中以选用NaCl、KCl、CsCl为宜。     

ELECTRONICALLY EXCITED SPECIES IN THE PEROXIDASE CATALYZED OXIDATION OF INDOLEACETIC ACID. EFFECT UPON DNA AND RNA

Abstract— The electronically excited species generated in the peroxidase (oxidase) catalyzed oxidation of the plant hormone indole-3-acetic acid is an excited state of indole-3-carboxaldehyde.
The chemiexcited species is able to induce in DNA the same alterations as observed with light or with enzyme-generated triplet acetone. The chemiexcited species can also alter r-RNA.     

具有负泊松比效应的聚烯烃共混物

实验证实用共混法制备的特殊聚烯烃共混物是一种拉伸膨胀材料 (Auxetic) ,测试发现共混物具有明显的负泊松比效应 ,所获得的最稳定体系可以获得 -1 4的泊松比值 ,比目前文献报道的数据减小了 2 0 0 %.采用SEM观察了共混体物拉伸前后的微观结构 ,推断负泊松比效应的产生是由于材料内部发生了空化作用的结果 ,与提出的理论模型基本一致     

PHOTOSELECTION AND TRANSIENT LINEAR DICHROISM WITH ORIENTED IMMOBILIZED PURPLE MEMBRANES: EVIDENCE FOR MOTION OF THE C(20)-METHYL GROUP OF THE CHROMOPHORE TOWARDS THE CYTOPLASMIC SIDE OF THE MEMBRANE*

Abstract— We have determined the transition dipole moment orientation of the chromophore during the photocycle of bacteriorhodopsin by photoselection and time-resolved linear dichroism experiments with samples of oriented immobilized purple membranes. This technique offers two important advantages over experiments with isotropic aqueous suspensions: (1) the depolarization due to the rotational diffusion of the membranes is eliminated, (2) the sensitivity for detecting the orientation of the transition dipole moment of intermediates is greatly increased. The appropriate equations for the analysis of time-resolved linear dichroism experiments with samples of oriented immobilized membranes will be presented. In the transition from the ground state of bacteriorhodopsin to the M-intermediate, the transition dipole moment tilts out of the plane of the membrane by about 3°. On the basis of current structural information on the plane of the chromophore and the orientation of its C(19) and C(20) methyl groups, a tilt of the transition dipole moment into the plane of the membrane would have been expected if it is assumed that the orientation of the conjugated polyene chain from C(5) to C(13) is the same in both states. The experimental result may be explained by an 11° tilt of the C(5) to C(13) part of the chain out of the plane of the membrane with the C(20) methyl group moving towards the cytoplasmic side of the membrane by about 1.7 Å and the cyclohexene ring staying fixed. This interpretation is supported by recent neutron diffraction experiments on the chromophore position in the M-intermediate.     

EFFECT OF SPATIAL NON-UNIFORMITY OF ILLUMINATION IN NON-LINEAR INTENSITY-DEPENDENT PHOTO PHYSICAL EXPERIMENTS. APPLICATION TO SOME FLUORESCENCE YIELD MEASUREMENTS IN PHOTOSYNTHETIC SYSTEMS

The spatial non-uniformity of a light beam must be taken into account in interpreting phenomena which depend on the light intensity in a non-linear manner. Omission of this effect may lead to incorrect values of parameters obtained from a fitting of theoretical curves, which describe the dependence of a given phenomenon on light intensity, to the experimental data. The effect of spatial non-uniformity of excitation light beams is illustrated utilizing non-linear intensity-dependent fluorescence phenomena in photosvnthetic svstems and a Gaussian light beam profile.     

EFFECT OF THE BROMINE ATOM UPON THE DISSOCIATION CONSTANTS OF BROMOPYRIDINES,BROMOQUINOLINES AND 4-BROMOISOQUINOLINE IN THEIR LOWEST EXCITED SINGLET AND TRIPLET STATES*

Abstract— The lowest excited singlet-state dissociation constants (pK^S_a) of bromosubstituted pyridines, quinolines, and isoquinolines were determined from the pH-dependent shifts in their electronic absorption spectra. The lowest excited triplet-state dissociation constants (pK^T_a) of bromosubstituted quinolines and 4-bromoisoquinoline were obtained from the shifts of the 0–0 phosphorescence bands measured in rigid aqueous solution at 77 K. The pK^S_a values indicate that the basicity of these brominated nitrogen heterocycles is increased in the lowest excited singlet state by 2 to 10 orders of magnitude as compared with the ground state. The pK^T_a values are found to be significantly different from the corresponding ground-state pK_a values, indicating that the basicity of bromoquinolines is increased in the lowest excited triplet state by 1.7 to 3.0 pK units. The enhancement of the excited singlet-and triplet-state basicity of brominated nitrogen heterocycle derivatives as compared with the unsuhstituted parent compounds is attributed to the increased electron-donor conjugative interactions of the bromine atom pπ orbitals with π orbitals in the lowest excited singlet and triplet state.     

PRIMARY PROCESSES IN THE LASER FLASH PHOTOLYSIS AND PULSE RADIOLYSIS OF l-EPHEDRINE

Abstract— Transient absorption spectra produced by laser flash-photolysis of an aqueous solution of ephedrine have been measured under a variety of conditions. Ephedrine was found to photoionise via a biphotonic process. The apparent yield of photoionisation increases with lowering of pH, a value of 8.8 being found for the p K _a associated with this change. The cation radical absorption spectrum has been determined using the techniques of both pulse radiolysis and laser flash photolysis. The extinction coefficient of the cation at 295 nm was determined to be 1.37 × 10⁴ dm³ mol^-1 cm^-1 and 1.2 × 10⁴ dm³ mol-¹cm-¹ by the two techniques, respectively, at pH 11. It is also shown that the rate constant for electron abstraction by the azide radical to form the ephedrine cation is controlled by protonation of the amine group in the side chain. The ephedrine anion radical spectrum and its extinction coefficient at 305 nm were also determined. The excited states responsible for photoionisation and photodegradation are discussed.     

担体酸性对铂催化剂的表面性质和催化性能的电子调变效应

采用红外光谱法、竞争加氢反应法和程序升温脱附法等研究三种具有不同酸性的载体—γ-Al_2O_3, Al_2O_3-SiO_2和HY分子筛与铂的相互作用, 结果表明载体的酸性部位对铂原子具有吸电子作用, 使铂原子表现为缺电子状态; 酸性部位的酸强度越大吸电子的能力越强。酸性部位的这种电子效应使铂催化剂的甲苯加氢活性和抗硫中毒性能都增强。     

ELECTRON TRANSFER REACTIONS OCCURRING UPON LASER FLASH PHOTOLYSIS OF PHOSPHOLIPID BILAYER SYSTEMS CONTAINING CHLOROPHYLL,BENZOQUINONE AND CYTOCHROME c-I. NEGATIVELY-CHARGED VESICLES*

Abstract— In negatively-charged lipid bilayer vesicles prepared in deionized water from egg phosphatidylcholine and 25 mol % of α-eleostearic acid, and containing chlorophyll a, benzoquinone, and cytochrome c, primary electron transfer after a laser flash occurred principally from chlorophyll triplet to benzoquinone, and to a smaller extent from chlorophyll triplet to oxidized cytochrome c. Several secondary electron transfer reactions occurred subsequent to this. The most rapid of these was electron transfer from reduced cytochrome c, which was bound to the outer surface of the negatively-charged vesicle, to chlorophyll cation radical (k= 3.9 times 10³ s^-1). Subsequent to this, the cation radical was reduced by benzoquinone anion radical (k= 1.6 times 10² s^-1>) and bound oxidized cytochrome c was reduced by the remaining anion radical which was expelled into the aqueous phase by the negative charge on the vesicle surface. This latter reaction occurred at the membrane-solution interface with an observed rate constant (k= 60 s^-1) two orders of magnitude smaller than cytochrome oxidation. Net reduced cytochrome c was produced in this process. The reduced cytochrome c was slowly reoxidized by benzoquinone (k= 17 s^-1) and the system was returned to its original state. When the vesicle system was made slightly basic by adding tris(hydroxymethyl)aminomethane, the rates of both the reverse electron transfer between chlorophyll cation radical and benzoquinone anion radical (k= 5 times 10² s^-1) and the oxidation of reduced cytochrome c by chlorophyll cation radical (k= 9.4 times 10³ s^-1) were accelerated. The rate of reduction of oxidized cytochrome c by benzoquinone anion radical remained approximately the same.     

INTERMEDIATES IN THE ROOM TEMPERATURE FLASH PHOTOLYSIS OF ADENINE AND SOME OF ITS DERIVATIVES

The transient absorption spectra of aqueous solutions of adenine, 2′-deoxyadenosine, 2′-deoxyadenosine-5′-phosphate and 2′-deoxyadenylyl-(3′-5′)-2′-deoxyadenosine have been determinated at different pH values using conventional flash photolysis. Reactives intermediates produced in the flash photolysis of these adenine derivatives present similar absorption regions: two higher intensity bands in the UV and 560–720 nm wavelength region and a third weaker band at 420–560 nm. On the basis of the effects produced by triplet quenchers and/or electron scavengers the bands have been assigned to hydrated electrons, radical cations, radical anions and/or neutral radicals resulting from neutralization reactions of the charged radicals. The results indicate that the bases photoionize via a triplet state under these conditions.     

THE LETHAL EFFECT OF LONGWAVE ULTRAVIOLET LIGHT AND PUVA. AN ANALYSIS BASED UPON HUMAN MESENCHYMAL CELLS IN VITRO

Abstract— The lethal effect of UVA and PUVA radiation was studied in cultures of fresh and mature monocytes. UVA radiation alone was shown to possess a lethal effect at doses which are attained in the dermis in vivo. The synergistic action of 8-methoxypsoralen and UVA radiation predominated in PUVA radiation, but again a residual effect of UVA alone was demonstrated mathematically. Mature cells were less sensitive than fresh monocytes.
Our results indicate that a monolayer culture of non-dividing, mesenchymal cells offers considerable advantages over in vivo systems as a model for the study of phototoxicity.     

ELECTRON TRANSFER REACTIONS OCCURRING UPON LASER FLASH PHOTOLYSIS OF PHOSPHOLIPID BILAYER SYSTEMS CONTAINING CHLOROPHYLL,BENZOQUINONE AND CYTOCHROME c-II. ELECTRICALLY NEUTRAL AND POSITIVELY-CHARGED VESICLES*

Abstract— The primary and secondary electron transfer reactions which occurred upon laser flash photolysis of electrically neutral and positively-charged lipid bilayer vesicles containing chlorophyll, benzoquinone and cytochrome c were determined by time-resolved difference spectral and kinetic measurements, and compared with previous results obtained with negatively-charged vesicles (Y. Fang and G. Tollin, Photochem. Photobiol. 1988). The extent to which oxidized cytochrome c could function as an electron acceptor from triplet state chlorophyll, and reduced cytochrome c could act as an electron donor to chlorophyll cation radical, decreased from negatively-charged to electrically neutral to positively-charged vesicles, in agreement with expectations based on changes in the ability of cytochrome c to bind to the bilayer. In all three types of vesicles, cytochrome c reduction by benzoquinone anion radical occurred in the aqueous phase.     

吐温-80对固定化脂肪酶催化酮基布洛芬氯乙酯对映体选择性水解反应的影响

酮基布洛芬为2-芳基丙酸类非甾体抗炎药的一种,其药效与立体构型有很大关系[1].生物法催化的动力学拆分是获得单一对映体酮基布洛芬的有效方法之一[2,3].最近,我们发现在利用皱褶假丝酵母(Candida rugosa)脂肪酶Lipase OF催化拆分酮基布洛芬氯乙酯时,向反应体系中加入非离子表面活性剂吐温-80,不仅可大幅度提高反应速度,而且更重要的是解决了原来Lipase OF选择性较差的问题,从而为酮基布洛芬的对映体拆分提供了一种新方法.     

固定化木瓜蛋白酶的制备和性质研究

多孔硅球固定化木瓜蛋白酶具有热增活性 .本文在前文研究的基础上 ,用载体交联法制备了甲壳胺固定化木瓜蛋白酶和纤维素固定化木瓜蛋白酶 .考察了固定化pH值、戊二醛浓度和给酶量对固定化木瓜蛋白酶活力的影响 .研究了固定化木瓜蛋白酶的性质 ,特别是热稳定性和耐热性 ,并与溶液酶和多孔硅球固定化木瓜蛋白酶进行了比较 .所制得的甲壳胺固定化木瓜蛋白酶和纤维素固定化木瓜蛋白酶的最适反应温度均达到了 80℃ ;90℃温育 1h后固定化酶的活力保持在 95 %以上 ;70℃温育处理 5h和 6h后固定化酶的活力也仍能保持在 90 %以上 .固定化木瓜蛋白酶的热稳定性和耐热性得到了显著提高