Fluorescence Properties of Twenty Fluorescein Derivatives: Lifetime,Quantum Yield,Absorption and Emission Spectra

The fluorescence lifetime (τ_f), emission quantum yield (Φ_f), absorption and emission spectral data of 20 fluorescein derivatives were measured under the same conditions by using time-correlated single photon counting, steady state fluorescence and absorption methods to get comparable data. Based on the results, the factors and mechanism that control the fluorescence properties of the fluorescein dyes are discussed. Both Φ_f and τ_f are remarkably dependent on the substitution on either xanthene or phenyl rings, but their ratio (Φ_f/τ_f), i.e. rate constant of radiation process, is a constant value (0.20?×?10⁹ s^?1). The rate constant of nonradiation process, on the other hand, is varied with both the structure and the solvent used.     

二卤代荧光素衍生物的荧光性能调控

用紫外可见吸收光谱、稳态/瞬态荧光光谱和单线态氧捕捉等方法分别测量了荧光素钠及4,5位-二卤代荧光素钠（FLX₂,X=H,Cl,Br,I）的电子吸收光谱、荧光光谱、荧光量子效率（Φ_f）、荧光寿命（τ_f）和单线态氧量子产率（Φ_Δ）,并与荧光素钠的相应性质进行了比较。对应于X=H,Cl,Br,I,FLX₂的Φ_f值分别为0.92、0.96、0.69、0.16;τ_f值分别为4.16、4.72、3.50、0.80ns;Φ_Δ值分别为0.0034、0.049、0.30、0.68。随着氯、溴、碘原子量增大,相应的Φ_f和τ_f值并非顺序减小,Φ_Δ值逐渐增大,只用重原子效应不能解释二卤代荧光素的荧光和光敏性质变化,而结合分子内光诱导电子转移就能较好的解释实验结果。     

胶束辅助的酞菁给体-碳纳米管受体超分子自组装及光诱导长寿命电荷分离态

利用十二烷基硫酸钠(SDS)阴离子胶束能够稳定分散单壁碳纳米管(SWCNT)和解聚富集四磺酸锌酞菁(ZnPcS₄)的能力, 组装了ZnPcS₄-SWCNT的电子给体-受体对来模拟光合作用的原初电子转移过程. 用稳态和时间分辨荧光法研究了相应的给体-受体分子间和分子内的光诱导电子转移速率, 用激光闪光光解技术检测了生成的电荷分离态. ZnPcS₄-SWCNT的电子给体-受体组装体在707 nm处出现了基态特征吸收峰, 但是复合体不产生荧光, 这主要归因于有效的分子内光诱导电子转移过程. 瞬态吸收光谱检测到相应的离子对, 动力学衰减结果表明, 电荷分离态的寿命长达42 μs. 这一长寿命电荷分离态的形成, 主要是因为ZnPcS₄是良电子给体(低氧化电位), SWCNT是好的电子受体, 使得三重态电子转移能够发生, 生成三重态电荷分离态.     

Interaction-based non-local damage model for failure in quasi-brittle materials

The purpose of this paper is to present a new macroscopic approach to describe the evolving non-local interactions which are produced at the mesoscale during damage and failure in quasi-brittle materials. A new-integral type non-local model is provided where the weight function is directly built from these interactions, and therefore takes into account their evolution during the material failure intrinsically.     

Photophysics of Halogenated Fluoresceins: Involvement of Both Intramolecular Electron Transfer and Heavy Atom Effect in the Deactivation of Excited States

The fluorescence quantum yield (Φ_f), fluorescence lifetime (τ_f), intersystem crossing quantum yield (Φ_isc) and redox potentials of seven halogenated fluoresceins in their dianion forms were measured and compared in methanol to get a deep insight into the effect of halogeno atoms on their photophysics. It is found that the heavy atom effect alone cannot explain the experimental results, as (1) Φ_f for chlorinated dyes exceeds that of fluorescein and close to unity, (2) the sum of Φ_f and Φ_isc for brominated and iodinated xanthene dyes is remarkably less than unity. The observations can be rationalized by the involvement of intramolecular photoinduced electron transfer, in which the benzoate acts as the electron donor while the xanthene moiety is the acceptor. The more negative reduction potential of excited singlet state for chlorinated fluoresceins results in their much smaller k_et, and hence higher Φ_f.     

苝分子低聚体的形成及其光谱性质

探讨了苝分子低聚体的形成条件和影响因素,这些低聚体与晶核形成紧密相关.用荧光光谱和吸收光谱法研究了不同的水含量和苝浓度对聚集的影响,低聚体属于具有光活性的J型,能发红光.计算得到低聚体的聚集数为9,平衡常数数量级较大.     

The Fluorescence Properties of Three Rhodamine Dye Analogues: Acridine Red,Pyronin Y and Pyronin B

The fluorescence spectra, fluorescence quantum yield, and fluorescence lifetime of Acridine Red (AR), Pyronin Y (PYY), and Pyronin B (PYB) in aqueous and organic solvents were measured by steady state fluorescence, time-correlated single photon counting, and electronic absorption methods. The rate constants of radiation and non radiation process (k_f and k_ic) were calculated to elucidate the structural effect on the fluorescence mechanism. The data for each compound are compared with that of the corresponding rhodamine dye. AR showed significant longer lifetime and higher quantum yield than PYY and PYB, because the alkyls on N atom enhance the internal conversion (IC), the longer the alkyl the faster the IC. However, the structural variation does not alter the rate constant of radiation process (k_f) but does change k_ic significantly. The phenyl in Rhodamine B or Rhodamine 6G shows only a slight effect on the fluorescence properties. Ethanol is the solvent in which all five compounds exhibit longest lifetime and highest fluorescence quantum yield.     

水溶性酞菁类光敏剂的合成及其光谱性质研究

以3-硝基邻苯二甲腈与3-巯基-1-丙磺酸钠为原料,在醋酸盐存在下通过四环化合成了三种带四个3-磺基丙基磺酰基的水溶性酞菁。利用紫外-可见吸收光谱,荧光光谱等对其光谱性质进行了测量,并计算了其荧光量子产率和单线态氧量子产率。引入吸电子基团所合成的水溶性酞菁与ZnPc相比,其荧光发射光谱的形状并未改变,但其最大荧光发射波长均发生10 nm以上的红移。三种水溶性酞菁中锌酞菁的荧光量子产率最高,铜酞菁的荧光量子产率最低;它们在水溶液中的荧光呈双指数衰减,这可归结为激发态质子化或去质子化的结果。单线态氧量子产率锌酞菁最大,空心酞菁次之,铜酞菁最小。光谱分析结果表明,合成的锌酞菁和空心酞菁具有高的单线态氧量子产率和高的光稳定性,有望用作光动力治疗和光免疫治疗的光敏剂。     

二卤代荧光素衍生物的荧光性能调控

用紫外可见吸收光谱、稳态/瞬态荧光光谱和单线态氧捕捉等方法分别测量了荧光素钠及4,5位-二卤代荧光素钠(FLX2,X=H,Cl,Br,I)的电子吸收光谱、荧光光谱、荧光量子效率(Φf)、荧光寿命(τf)和单线态氧量子产率(ΦΔ),并与荧光素钠的相应性质进行了比较。对应于X=H,Cl,Br,I,FLX2的Φf值分别为0.92、0.96、0.69、0.16;τf值分别为4.16、4.72、3.50、0.80 ns;ΦΔ值分别为0.003 4、0.049、0.30、0.68。随着氯、溴、碘原子量增大,相应的Φf和τf值并非顺序减小,ΦΔ值逐渐增大,只用重原子效应不能解释二卤代荧光素的荧光和光敏性质变化,而结合分子内光诱导电子转移就能较好的解释实验结果。     

荧光素-纳米二氧化钛表面复合及光诱导电子转移

本文研究了中性条件下TiO2纳米粒子与双阴离子态荧光素F2-的结合能力,发现所形成的复合物与文献报道的强酸性条件下TiO2-质子化荧光素H3F+复合物相比,结构与性能均很不同,F2--TiO2复合物吸收光谱红移30 nm以上且发射荧光。用UV-vis吸收光谱测定了复合物的结合常数、用稳态和瞬态荧光光谱测定了复合物的荧光效率和寿命分别为0.14和1.08 ns,与相应自由态F2-的测定值0.92和4.68 ns相比,复合物荧光效率和寿命都有很大的降低,这是由于复合物内部光诱导电子转移所致,因这一电子转移是热力学上非常有利的过程,其自由能变化达1.1 eV。光致电子转移的速率常数为7.1×108s-1,是其它竞争过程的3倍以上,复合物内光诱导电子转移效率达77%。