NO分子A2Σ→X2Π双光子激光感生荧光光谱

以Nd∶YAG激光器抽运光学参变振荡器 /光学参变放大器做为激发源 ,得到了NO分子在 2 2 0～ 35 0nm波长范围内的双光子激光诱导荧光光谱 ,并将其归属于A2 Σ(ν′ =0 )→X2 Π(ν″ =1～ 8)跃迁 ,用最小二乘法拟合获得NO分子X2 Π态振动常量″ωe =(190 4 .7± 7.3)cm-1,″ωe ″xe =(14 .2± 1.2 )cm-1,″ωe″ye=- (0 .0 2 18± 0 .0 0 91)cm-1,及平衡位置的力常量k =(1.5 99± 0 .0 12 )× 10 3 N·m-1。计算了所得跃迁谱带的弗兰克康登因子及相对荧光强度 ,结果与实验观测值相符。这可为用激光诱导荧光光谱技术探测大气污染物NO分子提供理论及实验参考     

Crystal Structure of a Linear Ag(Ⅰ) Complex with Niflumic Acid and Its Fluorescent Property

A novel Ag(Ⅰ) complex AgH(Nifa)2 1 (C26H17AgF6N4O4, Mr = 671.31) was synthe- sized through hydrothermal reaction of Ag2SO4 and Niflumic acid (HNifa), and characterized by single-crystal X-ray determination, IR and fluorescent spectra. Crystal data for 1: monoclinic, space group C2/c, with a = 9.5446(16), b = 12.3203(16), c = 21.056 (3) (A), β = 98.075(2)o, V = 2451.5(6) (A)3, T = 293(2) K, Z = 4, Dc = 1.819 g/cm3, F(000) = 1336, μ = 0.912 mm-1, S = 1.001, (Δρ)min = -0.849, the final R = 0.0391 and wR = 0.1286. The local geometry around the central metal Ag(Ⅰ) ion is linear. Two carboxylic acids of neighboring ligands sharing one hydrogen atom by two hydro- gen bonds result in the formation of an infinite hydrogen-bonded chain. Solid-state fluorescence of 1 at room temperature shows that the maximal emission peak occurs in 439 nm.     

Synthesis and optical properties of fluorene‐based polymers incorporating organosilicon unit

The synthesis and optical properties of polymers bearing the repeating unit of terfluorene and various organosilicon groups were investigated. Polymers with high molecular weight and good solubility could be obtained by Suzuki coupling polymerization from silylene‐containing fluorene‐based dibromo monomers and 9,9‐dihexylfluorene‐2,7‐bis(trimethyleneborate). From UV spectra of polymers bearing acyclic silylene bridge, the organosilicon units not only interrupted a π‐conjugation but also contributed to an electronic communication between connected fluorenes. The emission maximum wavelengths (ca. 400 nm) blue‐shifted when compared with that of polyfluorene (418 nm) and the fluorescence quantum yields were considerably high (>0.82) in the CHCl₃ solution. On the other hand, rather broad emission was observed at 480 nm and the fluorescence quantum yield was quite low (0.004) in the solution‐state PL spectrum of tetraphenylsilole‐containing polymer. The polymer emitted visible green light in the spin‐coated film. The fluorescence peak intensity at 486 nm gradually decreased when the film was illuminated with the UV light of 359 nm in air. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4786–4794, 2007     

An integrated phase-resolved fluorescence imaging system with sub-nanosecond lifetime resolution

In this paper, a novel configuration of an integrated phase-resolved (PR) fingerprint fluorescence imaging system is proposed and implemented. In this integrated PR imaging system, a current modulated 402 nm dual diode laser is proposed to be the light source, to obtain both high laser power and easy modulability. To estimate the lifetime resolution of this PR imaging system, a novel method of using distance-selective suppression of fluorescence signals from two identical fluorescing samples is proposed. Detailed theoretical and experimental analyses are presented. The experimental results demonstrate that this integrated PR imaging system has a lifetime resolution of 0.1 ns. Fingerprint detection experiments are also carried out using this system with latent fingerprints deposited on substrates of aluminum foil and currency.     

介质势垒放电(DBD)等离子体中NO荧光发射谱研究

利用介质阻挡放电 (DBD)等离子体技术对大气污染物NO分子进行了光谱研究 ,得到了低气压条件下放电等离子体在 2 1 0～ 2 80nm光谱范围内的荧光发射谱。该谱明显的表现为双峰结构 ,谱线均成对出现 ,强度分布符合Frank Condon原理 ,且最大峰值位置出现在 2 36nm处 ,将该组谱线归属为NO分子的A2 ΣA →X2 Π1 / 2 ,2 / 3 跃迁。荧光产生过程为 :基态NO分子与高能电子发生非弹性碰撞被激发至激发态A2 Σ 后自发跃迁回基态同时辐射出荧光。通过测量等离子体中NO分子和N2 分子 337nm谱线强度随时间的变化关系 ,初步证实了放电等离子体中存在的NO分子的分解机制为 :e NO→N O e,N NO→N2 O ,O NO→NO2 hν。     

含Eu3+离子的Na2O-K2 O-SiO2-Al2O3系统玻璃的制备及其变温发射光谱与结构特性

通过高温熔融法制备了含Eu^3 离子的Na2O-K2O-SiO2-Al2O3系统玻璃。在488nm波长光的激发下，系统地研究了上述玻璃从77K到700K温度范围的变温发光特征。发现总的荧光强度首先随温度的升高而大幅度升高，然后随温度的升高而减少，用声子辅助吸收与热激活过程及温度淬灭效应定性地解释了上述强度的变化，同时测量与分析了Eu^3 离子的晶格场参量。结果表明，Eu^3 离子与氧离子的距离随着温度升高而变短，而Eu^3 离子的配位数不随温度而变化。     

Calcium imaging using fluorescence lifetimes and long-wavelength probes

We describe imaging of calcium concentrations using the long-wavelength Ca²⁺ indicators, Calcium Green, Orange, and Crimson. The lifetimes of these probes were measured using the frequency-domain method and were found to increase from 50% to severalfold in response to calcium. The two-dimensional images of the calcium concentration were obtained using a new apparatus for fluorescence lifetime imaging (FLIM). We also describe procedures to correct for the position-dependent frequency response of the gain-modulated image intensifier used in the FLIM apparatus. Importantly, the FLIM method does not require the probe to display shifts in the excitation or emission spectra. Using the FLIM method, calcium imaging is possible using probes which display changes in lifetime in response to calcium. Consequently, calcium imaging is possible with excitation wavelengths ranging from 488 to as long as 620 nm, where autofluorescence and/or photochemical damage is minimal. These probes are also suitable for calcium measurements of single cells using lifetime-based flow cytometry.     

Cover Picture: QM/MM Car‐Parrinello Molecular Dynamics Study of the Solvent Effects on the Ground State and on the First Excited Singlet State of Acetone in Water (ChemPhysChem 11/2003)

The cover picture shows …?‥the solvent effect of water upon the lowest‐lying singlet excitation in acetone. The transition, which involves the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO), is blue‐shifted in water (sol) with respect to the gas phase (vac), since the HOMO is stronger stabilized in water than the LUMO. The authors calculate the absorption and fluorescence spectra of acetone in water with a hybrid Car–Parrinello quantum chemical/classical molecular dynamics approach and investigate the influence of the solvent. The lower part of the picture shows the excitation energy during a simulation. One configuration with a very high excitation energy (three hydrogen bonds, short C?O bond) and one configuration with a very low excitation energy (two hydrogen bonds, long C?O bond) are shown in detail. Find out more in the article by Rothlisberger and co‐workers on pages pp. 1177–1182.     

Two photon-induced fluorescence intensity and anisotropy decays of diphenylhexatriene in solvents and lipid bilayers

We measured the fluorescence intensity and anisotropy decays of 1,6-diphenyl-1,3,5-hexatriene (DPH)-labeled membranes resulting from simultaneous two-photon excitation of fluorescence. Comparison of these two-photon data with the more usual one-photon measurements revealed that DPH displayed identical intensity decays, anisotropy decays, and order parameters for one- and two-photon excitation. While the anisotropy data are numerically distinct, they can be compared by use of the factor 10/7, which accounts for the two-photon versus one-photon photoselection. The increased time 0 anisotropy of DPH can result in increased resolution of complex anisotropy decays. Global analysis of the one- and two-photon data reveals consistency with a single apparent angle between the absorption and the emission oscillators. The global anisotropy analysis also suggests that, except for the photoselection factor, the anisotropy decays are the same for one-and two-photon excitation. This ideal behavior of DPH as a two-photon absorber, and its high two-photon cross section, makes DPH a potential probe for confocal two-photon microscopy and other systems where it is advantageous to use long-wavelength (680- to 760-nm) excitation.