溶剂对三苯二噁嗪化合物荧光性能的影响

本文测试了两个三苯二(口恶)嗪化合物在18种溶剂中的电子吸收光谱和荧光发射光谱。计算了这些化合物的荧光量子产率。发现化合物的荧光光谱的ν_max^F与溶剂的(n²-1)/(2n²+1)和E_T(30)以及化合物的荧光光谱的Stokes位移△ν_s与溶剂的E_T(30)均存在着良好的线性关系。醇类溶剂与溶质间的氢键作用以及含卤素溶剂的“外部重原子效应”导致化合物的荧光量子产率明显减小。     

THE FLUORESCENCE OF ADENINE. THE EFFECTS OF SOLVENT AND TEMPERATURE ON THE QUANTUM YIELD

Abstract— To investigate the mechanism of the solvent and thermal quenching of fluorescence, the absolute fluorescence quantum yield of adenine has been determined in several alcoholic glasses as a function of the concentration (10^-5-10^-4M) and temperature (77°-298°K). The yield is independent of the concentration but increases with decreasing temperature and increasing bulk cohesion and rigidity of the solvent.
The environmental effects on the yield are attributed to radiationless electronic relaxation processes caused by solute-solvent interaction. Increasing the temperature and decreasing the intra-solvent cohesion cause increases in the interaction and therefore accelerate the relaxation. The rate determining step behaves like a diffusion in the limit of low viscosity.     

SOLVENT EFFECTS ON TRIPLET-STATE BACTERIOCHLOROPHYLL a AS DETECTED BY TRANSIENT RAMAN SPECTROSCOPY AND THE ENVIRONMENT OF BACTERIOCHLOROPHYLL a IN THE LIGHT-HARVESTING COMPLEX OF Rhodobacter sphaeroides R26

The frequency of BChl that was bound to the light-harvesting complex (LHC) of Rhodobacter sphaeroides R26 was found to be 1598 cm^-1, a result which suggests that a pair of BChl molecules form a dimer in the LHC in the T₁ state.     

SOLVENT EFFECTS ON THE PHOTOPHYSICAL PROPERTIES OF DIBUCAINE: A QUINOLINE ANALOGUE

Abstract— Emission and absorption spectra of neutral, monocation and dication dibucaine were recorded in hydrocarbon and hydroxylic solvents. The spectral analysis indicates that the lowest electronic states of dibucaine originate from the quinoline analogue in the molecule. The fluorescence and phosphorescence emission of neutral dibucaine in all solvents at 77 K are best assigned as resulting from ¹ n ,π* and ³π,π*, respectively, whereas those of both monocation and dication dibucaines are found to have ¹π,π* and ³π,π*. The monocation and neutral dibucaines in ethanol solutions were shown to give identical emission spectral properties, indicating that dibucaine-HCl in ethanol is H⁺ dissociative; this was confirmed by FT-IR studies. The possible explanations for the deprotonation of dibucaine-HCl in ethanol environments are discussed.     

竹红菌甲素荧光光谱的环境效应

竹红菌甲素(简称HA)是从竹红菌中提取的一种光敏色素,属于苝醌的衍生物,它对许多皮肤病都有显著的光疗作用。最近发现HA能杀死肿瘤细胞并富集在肿瘤组织处(傅乃武未发表的结果),虽然刘景瑤等管对它的荧光光谱作过研究,但还有许多问题有待于进一步的探讨。本文详细研究了环境对HA荧光光谱的影响,这有助于了解不同环境中激发态HA的性质,进而弄清竹红菌的光疗机制。     

空间因素对敏化剂性质的影响

本文介绍了一种新的敏化剂cis-(NCS)₂-bis(2,2′-bipyridyl-3,3′-dicar-boxylate)ruthenium(Ⅱ)的合成,测定了它的吸收光谱及氧化还原电位,并将这种染料吸附到具有大比表面的TiO₂纳晶电极上测量它的光电转换效率。另外,参照文献分别合成出cis-(NCS)₂-bis(2,2′-bipyrdyl-4,4′-or 5,5′-dicarboxylate)Ru(Ⅱ)染料,测定它们的光电及光物理性质并以此为依据讨论了空间因素对敏化剂性质的影响。     

两种不同光谱类型的R-藻红蛋白的荧光性质研究

红藻中的R-藻红蛋白(R-PE)依照其吸收光谱可分为两种不同的光谱类型,即“双峰型”和“三峰型”。本文通过对不同pH条件下的R-PE的荧光光谱及荧光寿命的研究,发现“三峰型”R-PE的pH稳定范围较“双峰型”R-PE大。在R-PE浓度对荧光光谱的影响实验中,随着蛋白浓度的增加,荧光峰位置逐渐红移。荧光寿命逐渐增大,荧光强度先行增加而后减弱。用碘离子对其荧光进行猝灭,随着碘离子浓度的增大,荧光强度逐渐降低,荧光寿命逐渐缩短,并服从Stem-Volmer规则。     

THE Py SCALE OF SOLVENT POLARITIES. SOLVENT EFFECTS ON THE VIBRONIC FINE STRUCTURE OF PYRENE FLUORESCENCE and EMPIRICAL CORRELATIONS WITH ET and Y VALUES

Abstract— Pyrene fluorescence spectra have been run in 62 solvents of widely differing solvent polarity. As has been noted previously, the intensity ratio of the first (the 0–0 band) and third bands in vibronic fine structure of these spectra are very sensitive to solvent polarity. These I ₁/ I ₃ values, however, are not sensitive to hydrogen bonding aspects of solvent-solute interactions. Correlations are reported with Winstein's Y values and with Dimrotb's E _T values. On this basis the I ₁/ I ₃ values for pyrene fluorescence are suggested as the basis for a new empirical scale of solvent polarity, called the Py scale, which offers certain conveniences over other scales of solvent polarity.     

ZnO纳米粒子的光物理性质──微量水对荧光的影响

ZnO不仅是极其重要的半导体材料,而且还广泛用做化学反应的催化剂,光催化剂和光电转换材料。近年来,ZnO纳米粒子的制备和应用得到了广泛的研究,但许多问题并不十分清楚。譬如,对ZnO颗粒的可见荧光的发生机制就众说纷纭。Henglein等认为ZnO可见荧光由ZnO颗粒表面的阴离子空位引起,而Bahnemann等却认为可见荧光由被捕获的光生电子向被捕获的空穴越迁而引起。本文通过微量水对ZnO超微粒的荧光的影响的研究,进一步阐明ZnO荧光的产生机理。结果支持了Bahnemann的观点。     

SOLVENT EFFECTS ON THE ELECTRONIC ABSORPTION AND FLUORESCENCE SPECTRA OF INDOLE-4-CARBOXYLIC ACID: PROTOTROPIC EQUILIBRIA IN AQUEOUS SOLUTIONS

Abstract— The absorption and fluorescence spectra of indole-4-carboxylic acid in various solvents have indicated that the -COOH group is more planar with respect to the indole ring in the first excited singlet state (S₁) than in the ground (S₀) state. Relatively large Stokes' shifts indicate that polarisability and dipole moment of the molecule are increased predominantly upon excitation. Prototropic reactions in the S₀ and S₁ states are the same. The -COO^- and -COOH+₂ groups are not coplanar in the S₀, but coplanar in the S₁ state. pH-dependent fluorescence spectra have revealed that both protonation and deprotonation of the -COOH group increase the basicity of the molecule upon excitation.     

ENVIRONMENTAL EFFECTS ON THE FLUORESCENCE OF TYROSINE AND ITS HOMOLOGUES

Abstract— In order to study the influence of the environment on the fluorescence of tyrosine the emission of tyrosine as well as of the related compounds p-cresol, O-methyltyrosine and phenylalanine in aqueous solutions of alcohol, dioxane, acetonitrile, dimethylformarnide, N- dimethylacetamide and acetic acid was measured. It was found that the quenching of the tyrosine fluorescence by —CONH and —COOH groups proceeds apparently by direct interaction with the excited aromatic ring. The phenolic OH group does not seem to be directly involved in the process although it contributes to the quenching, probably, by increasing the electronic charge density of the excited ring. The relevant quenching constants are presented.     

取向对物理老化的聚对苯二甲酸乙二酯纤维溶剂诱导结晶速率的影响

通过密度法、ＤＳＣ、力学性能测试等方法研究了物理老化对聚对苯二甲酸乙二酯（ＰＥＴ）纤维溶剂诱导结晶速率及结构的影响，并进一步探讨了取向程度对ＰＥＴ纤维物理老化过程的影响．发现在一定老化温度下，ＰＥＴ纤维的溶剂诱导结晶（ＳＩＮＣ）速率随老化时间的延长呈现先降低后升高的趋势；取向程度高的样品则经较短的老化时间即可出现这种情况．对上述现象用凝聚缠结的观点加以解释．     

ELECTRONIC EFFECTS ON THE FLUORESCENCE OF TYROSINE IN SMALL PEPTIDES

Abstract— It is shown for a series of tyrosine-derivatives and tyrosine-containing peptides that the amide group in combination with electron-withdrawing substituents quenches the fluorescence of the phenol moiety. The ammonium group has the strongest electron-withdrawing effect and thus the largest influence on the quenching rate. The peptide group itself does not quench the fluorescence. In a series of peptides with an increasing number of alanines the decreasing quenching efficiency or the peptide group due to the greater distance of the ammonium group is demonstrated. In tyrosine-containing di- and tripeptides a linear correlation between the ¹³C-NMR chemical shift δ of the C₂ atom of various aliphatic amino acids and the fluorescence-quenching constant confirms the hypothesis that electron-withdrawing and donating groups are modulating the fluorescence-quenching efficiency of the peptide group. In small peptides the fluorescence lifetime of tyrosine is characteristic for the neighboring amino acids. Using model substances the redox properties of a peptide group and the phenol ring were studied electrochemically. The highest occupied molecular orbital of the tyrosine (1.4 V vs saturated calomel electrode [SCE]) and the lowest unoccupied molecular orbital of the peptide group (-3.12 V vs SCE) have appropriate energies for a photoinduced electron transfer reaction. For solute-quenching experiments quencher molecules can be systematically selected.     

FLUORESCENCE YIELD PROPERTIES OF A FRACTION ENRICHED IN NEWLY SYNTHESIZED BACTERIOCHLOROPHYLL U-PROTEIN COMPLEXES FROM RHODOPSEUDOMONAS SPHAEROIDES

Abstract— A membrane fraction enriched in newly synthesized bacteriochlorophyll a-protein complexes was isolated from Rhodopseudomoms sphaeroides by rate-zone sedimentation. An examination of the fluorescence yield properties showed that the ratio of the maximal fluorescence emission near 910 nm (with all photochemical traps closed) to that of the initial fluorescence rise (with all traps open) was 2.2 compared to 2.9 in chromatophores. The spectrum for the variable portion of the fluorescence emission (the slow rise between the initial and maximal levels) was essentially the same in both fractions, but that observed for the initial rise in the newly synthesized material showed a greater fluorescence yield with a broad peak near 865 nm. This extra emission is thought to arise from the light-harvesting bacteriochlorophyll complex with an absorption maximum at 850 nm and suggests that this component is only partially connected to photosynthetic units. In contrast, the little extra emission observed at the longer wavelengths in this fraction indicated that energy is transferred more efficiently between the 875 nm antenna complex and photochemical reaction centers. The kinetics of the fluorescence rise suggest that photosynthetic units exist at separate sites in newly synthesized membrane regions.     

THE EFFECTS OF AGGREGATION ON THE FLUORESCENCE and THE TRIPLET STATE YIELD OF HEMATOPORPHYRIN

Abstract— The fluorescence and triplet state yields of hematoporphyrin have been measured in wuter/methanol mixtures. There is a closely linked response of these yields to aggregation of the hematoporphyrin molecule. The monomer, which is the principal species present at high methanol content, has a triplet state yield of 0.91 and a fluorescence yield of 0.09. By contrast, hematoporphyrin solutions with a high water content containing aggregates have lower fluorescence and triplet state yields, e.g. 0.018 and 0.56, respectively, in water. Static, singlet state quenching in some of the aggregates is responsible for the reduced fluorescence yield. The results also show that in addition to these aggregates there are other types of aggregates where there is an increased singlet to ground state radiative transition probability, resulting from the interaction between transition dipoles in adjacent molecules.     

溶液pH值对聚邻甲苯胺电化学性质的影响

本文报道了溶液pH值对聚邻甲本胺电化学性质的影响。研究结果表明,电化学合成的聚邻甲苯胺的循环伏安曲线、氧化电位、膜的颜色、充放电容量、紫外可见光谱以及氧化还原活性都受到溶液pH的影响。在低pH值的溶液中,随着扫描电位的变化,聚邻甲苯胺膜的颜色可逆地变化,而在pH4.13的溶液中进行扫描时,膜的颜色不变化,电化学活性也消失。     

炭黑结合橡胶对天然橡胶性能的影响

本文研究了天然橡胶(NR)与五种不同类型炭黑的结合橡胶对其混炼胶的应力-应变、流变性质等的影响。结果表明,NR与炭黑的结合橡胶量随炭黑结构和表面积增加而增加。结合橡胶的增加使NR在低剪切下的本体粘度、弹性恢复性和强度增加,塑性和粘着性降低;在高剪切下流动性变差,挤出物收缩则有所下降。此外,结合橡胶的增加也增加了硫化胶的交联度,因此模量、硬度和耐磨性提高,抗张强度和伸长率却有所下降。     

SOLVENT AND TEMPERATURE EFFECTS ON THE EXCITED SINGLET STATE ABSORPTION OF DIPHENYLBUTADIENE

Nanosecond excited state absorption spectra of all-trans-1,4-diphenyl-1,3-butadiene (DPB) and a rigid s-cis DPB analog, 1,4-diphenyl-1,3-cyclopentadiene, were obtained in several hydrocarbon solvents at room temperature and low temperatures. Analysis of the excited state absorption spectra of these two molecules suggests the presence of excited state s-cis rotamers in DPB at room temperature.     

SOLVENT EFFECTS ON THE TAUTOMERIZATION OF 5'-DEOXYPYRIDOXAL. A PHOTOPHYSICAL STUDY

Abstract— Absorption and fluorescence spectra of 5'-deoxypyridoxal (DPL) in various pure solvents and mixtures were recorded both at room temperature and over the range10–65°C. The areas under the absorption bands were analyzed to obtain the mole fraction (f_N, f_z) of two tautomers (the zwitterionic, Z, and neutral, N, forms) in the ground state. The following spectral parameters were determined from the fluorescence spectra: Stokes shift (Δ v ), fluorescence quantum yield of the neutral form (Q_N), fluorescence ratio of the neutral to the zwitterionic form (ø_N/ø_Z) and the rate constant of tautomerization ( k ₁) from Z to N in the excited state. Some of these parameters (f_N, Δ v , Q_N, k ₁) were found to depend on the proton donor character of the solvent, whereas others (ø_N/ø_Z) depended on its dipole moment. Thus, the absorption and fluorescence spectra of DPL allow one to obtain information on the polarity and the concentration of –OH groups on its environment.