Photophysical aspects of single-molecule detection by two-photon excitation with consideration of sequential pulsed illumination.

An important goal in single molecule fluorescence correlation spectroscopy is the theoretical simulation of the fluorescence signal stemming from individual molecules and its autocorrelation function. The simulation approaches developed up to now are based exclusively on continuous-wave (cw) illumination and consequently on cw-excitation. However, this approximation is no longer valid in the case of two-photon excitation, for which pulsed illumination is usually employed. We present a novel theoretical model for the simulation of the fluorescence signal of single molecules and its autocorrelation function with consideration of the time dependence of the excitation flux and thus of all illumination-dependent photoprocesses: two-photon excitation, induced emission and photobleaching. Further important characteristics of our approach are the consideration of the dependence of the photobleaching rate on illumination and the low intersystem-crossing rates of the studied coumarins. Moreover, using our approach, we can predict quantitatively the effect of the laser pulse width on the fluorescence signal of a molecule, that is, the contributions of the photobleaching and saturation effects, and thus we can calculate the optimal laser pulse width. The theoretical autocorrelation functions were fitted to the experimental data, and we could ascertain a good agreement between the resulting and the expected parameters. The most important parameter is the photobleaching constant sigma, the cross section of the transition Sn<--S1, which characterises the photostability of the molecules independent of the experimental conditions. Its value is 1.7 x 10(-23) cm2 for coumarin 153 and 5 x 10(-23) cm2 for coumarin 314.     

炭气凝胶及其有机气凝胶前驱体的研究进展

介绍了炭气凝胶及其有机气凝胶前驱体的发展概况，着重总结了制备工艺条件(如催化剂及其浓度、反应物总浓度、反应物配比、溶剂、反应温度及时间、超临界干燥工艺条件和炭化工艺条件等)对有机气凝胶及其相应炭气凝胶中孔网络结构的影响，综述了中孔网络结构改性研究的进展．     

Time-resolved spectroscopy of long-path fluorescence and scattering for measuring total absorption of fluids

Optical methods are appropriate tools to detect organic micro-pollutants in fluids. A new technique is introduced which uses the decay of interaction processes like fluorescence and elastically scattered radiation by a fluid. Principally two different parameters are determined:

1. (i) the decay-time of the conventional interaction τ_C, which occurs at relatively short path-lengths of the incidence beam in the fluid, and

2. (ii) the decay-time τ_MP of the multi-path-saturation interaction originating at long path-lengths, e.g. in multi-path-reflection cuvettes, where the incidence beam is fully absorbed by the fluid.

A relation between the decay-time and the absorption coefficient of a fluid is theoretically derived. A simple preliminary experiment is performed considering distilled water polluted with non-fluorescent azobenzene and fluorescent quinine-sulphate. A nitrogen laser has been used to generate the fluorescence and scattering signals. The reciprocal value of the difference between the decay-time of the multi-path and conventional signals, 1/(τ_MP − τ_C), yields the total absorption coefficient directly. In comparison to the conventional absorption technique the decay-time method is characterized by a higher sensitivity.     

Imide-siloxane block copolymer/silica hybrid membranes: preparation, characterization and gas separation properties

Imide-siloxane block copolymer/silica hybrid membranes with covalent bonds were prepared via sol–gel reaction. The structural informations of these hybrid membranes were obtained by using Fourier transform-infrared spectrometry (FT-IR), ²⁹Si nuclear magnetic resonance (²⁹Si NMR), XPS and thermogravimetric analysis (TGA). The gas separation properties of the hybrid membranes were also investigated in terms of organosiloxane (PDMS) or silica content at various temperatures. In the hybrids, the addition of PDMS phase increased the permeabilities of gases such as He, CO₂, O₂, and N₂, indicating that the gas transport occurred mainly through rubbery organic matrix. Meanwhile, the PDMS phase contributed the decreased gas selectivities to nitrogen but the reduction in selectivities was very small in comparison with other siloxane containing polymeric membranes. This might be due to the restriction of chain mobility by the existence of inorganic component such as silica network in the hybrids. Additionally, the increase of silica content in these hybrid membranes considerably retarded the falling-off of gas selectivity at elevated temperature. The increase of silica content in hybrid membranes resulted in well-formed silica networks and hence these inorganic components restricted the plasticization of organic matrix by the thermal segmental motion of organic components, leading to preventing the large decrease of the gas selectivity.     

Rearrangement during cyclisation of some 3-(2-pyrrolyl) propionic acids and related compounds

Cyclisation of the title compounds leads to mixtures of the expected 4H-cyclopental[b]pyrrol-4-ones (1), the corresponding 6-ones (3) by a single rearrangement, and the cyclopenta[c]pyrrol-4-ones (4) by a double rearrangement, the proportions depending upon the substituents.The ¹H NMR spectra of 2-methyl-4H-cyctopenta[b]thiophen-6-one (3f) shows 6J long range $\text{CH}{}_3\text{CH}{}_2$ coupling, but this is absent in the corresponding pyrroles (3c,d). The ¹³C spectra of 1 and 3 cannot be interpreted on the basis of substituent chemical shifts in pyrroles and thiophens, and are clearly -CH = CH-X (X = NMe, NPh, S) bridged derivatives of cyclopent-2-enone.     

Calculation of harmonic force constants,vibrational frequencies and integrated intensities of some organic molecules using the MINDO—Forces method

The harmonic force constants, vibrational frequencies and integrated intensity ratios of CH₂, H₂O, CH₂O, C₂H₂, CO₂, HCN, CH₃, CH₄, and C₂H₄ have been calculated using the MINDO—FORCES program and the Pulay method for the calculation of the molecular force constants. The results obtained are in general quite satisfactory when compared with available literature values. The results are, however, not as satisfactory in case of molecules containing heteroatoms, due to the neglect of some dipolar repulsion integrals for the heteroatoms by the MINDO/3 method. Calculated integrated intensities for CH₃ and C₂H₄ agree well with experimental results. The calculated integrated intensities for other molecules are obtained for the first time and no comparison with published data is therefore possible.Part of the M.Sc. Thesis of K. H. A. 1978.     

Spectroscopic Interrogation of Layer-by-layer Assembled Films of Conjugated Polyelectrolytes

Layer-by-layer fluorescent conjugated polyelectrolyte films have been studied. The photoluminescence of conjugate polyelectrolytes was observed to be highly tunable during this film assembly process. Efficient photoinduced electron transfer from thus prepared highly luminescent film to a natural electron-transfer protein cytochrome c has also been observed.     

有机分子与聚电解质静电吸附成膜特性研究

选取多种有机分子及聚电解质，采用静电吸附自组装法制备了聚电解质，聚电解质、聚电解质，有机分子、有机分子，有机分子的复合薄膜，讨论了这些体系的静电吸附成膜特性及其成膜机理．     

过渡金属配合物催化剂及其分子设计构思的发展与相互作用

讨论了某些不对称合成和α－烯烃定向配位聚合及α－烯烃氢甲酰化的过渡金属配合物向络合催化剂的发展与催化剂分子设计构思的发展及相互促进作用，并藉以说明过渡金属配合物定向络合物催化剂的分子设计已具备向计算机辅助设计发展的科学基础。     

1,3,3—三甲基—2—[β—（5—取代苯基—2—呋喃基）乙烯基]—3H—吲哚盐的合成

1,3,3- 三甲基-2-[β-(4-取代苯基)乙烯基]-3H-吲哚盐是熟知的聚甲川型染料,常由费歇尔碱与芳香醛制备,也可由该碱的季铵盐一步合成。但这些方法往往需要使用较昂贵的溶剂,有的尚未分出染料纯品.近年来这类染料获得许多新的用途,如作光敏电照相记录材料和电照相增感剂等.本文考察了碘化1,2,3,3-四甲基-3H-吲哚(Ⅰ)与5-取