Electronic Energy Transfer from Sinclet Molecular Oxygen to Carotenoids

Abstract

Aerated benzene solutions containing anthracene together with one of the carotenoids, β-carotene, β-apo-8′-carotenal, ethyl β-apo-8′-carotenate and canthaxanthin were subjected to laser photolysis. Under these conditions oxygen quenching of triplet anthracene produces the excited singlet state of molecular oxygen O₂? (¹δ_g) which in turn transfers energy to the carotenoid thereby yielding its triplet state, the absorption of which was monitored thereby confirming electronic energy transfer as the mechanism of quenching of O₂ ?(¹δ_g) by these carotenoids and enabling the bimolecular quenching constansts which vary from 1.2 – 1.45 × 10¹⁰ 1 mol^?1s^?1 to be measured.     

Intermolecular Electronic Energy Transfer in the Gas Phase

The kinetics of triplet-triplet energy transfer in the gas phase has been studied for various donor-acceptor pairs of aromatic hydrocarbons and ketones. For all the donor-acceptor pairs investigated the triplet-triplet energy transfer efficiencies are much lower than unity. The triplet triplet energy transfer was used to gain insight into the paths of intramolecular excitation energy degradation in benzophenone and anthraquinone vapours and to obtain sensitized anti-Stokes annihilation delayed fluorescence of vapours of anthracene and its derivatives.

The intermolecular triplet-triplet transfer (T-T transfer) of excitation energy and sensitized phosphorescence were first discovered in 1952 by Terenin and Yermolayev in organic solutions¹. Later these phenomena became known for liquid solutions², crystals³, and also for vapours^4-10. And though the nature of interactions underlying the T-T energy transfer phenomena in different aggregate states is the same, a number of specific features is observed in the vapour phase. The study of these processes makes it possible to obtain additional information on interacting molecules.     

Theory of Directed Electronic Energy Transfer

The migration of electronic energy between molecules or chromophores in molecular solids is a well-studied phenomenon. The ability to exert control over the directionality of this transfer, by a variety of methods involving applied electrical or optical fields, holds promise for advances in fields including nanoelectronics and energy harvesting materials. In this paper, we review in detail a number of methods for directing energy transfer, also identifying potential applications.     

钨-硅基红色荧光粉的制备及其能量传递

通过溶胶-凝胶技术制备了以稀土离子Eu3＋为激活剂的硅基发光材料,并考察了Na2WO4的掺杂对体系发光性能的影响。主要通过研究三维荧光光谱,荧光激发光谱和发射光谱,分析探讨了Na2WO4的掺入对发光中心Eu3＋发光性质的影响,结果发现,三维荧光光谱高斯图像充分表明了Na2WO4的掺杂有效地提高了Eu3＋的5D0→7F2特征跃迁。用荧光激发光谱图和发射光谱图进一步详细的表征了基质和Eu3＋的f→f跃迁及其强度变化情况。通过能级图、位形坐标图和敏化过程示意图等理论对这个影响的原因进行了进一步的说明和探讨。结果表明,O→W的电荷迁移带吸收了大量的能量,并有效地将能量传递给Eu3＋,促使发光中心的发光强度增大。但由于Na2WO4的掺杂还增加了硅基质的能量吸收而使整体材料的发光效率下降。     

水中振动能量的分子间转移

生命体通过接受光辐射可以获得所需的能量.光合作用将空气中的CO2和土壤中的NH+4结合成有机碳水化合物,从而促进了植物的生长.用红外线治疗仪照射人体的局部,可以增强微循环,从而起到舒筋活血的作用--光辐射通过耗散弛豫转化成热能, 并散布到周围的人体组织中.紫外光的光子能量很大,它足以将各种物质的电子激发到较高能态,从而可能造成生命体的损伤.     

Solvent Reorganization Energy and Electronic Coupling for Intramolecular Electron Transfer in Biphenyl-Acceptor Anion Radicals

基于非平衡溶剂化理论和连续介质模型修改了GAMESS中的相关程序,实现了电子转移溶剂重组能的数值计算. 采用修改后的程序计算得到了联苯-雄甾烷-萘和联苯-雄甾烷-菲这两个体系电子转移的溶剂重组能约为60 kJ/mol. 这个结果与实验拟合值符合的很好. 利用线性反应坐标与Koopmans定理计算了电子转移耦合矩阵元,结果与实验拟合值有可比性.     

碳量子点/罗丹明B分子复合体系中的能量和电子转移过程研究

本文采用荧光光谱结合稳态和瞬态吸收光谱技术,研究了碳量子点(CQDs)/罗丹明B(RhB)分子复合体系o-CQDs/RhB和m-CQDs/RhB中的能量转移和电子转移过程以及它们之间的关系. 研究发现在能量转移效率为73.2%的o-CQDs/RhB体系中,电子转移过程可以忽略;而在能量转移效率低于33.5%的m-CQDs/RhB体系中,电子转移过程则较为显著. 在这个由碳量子点和染料分子组成的典型复合体系中所揭示的能量转移与电子转移过程之间的内联关系,将为与激子猝灭相关的应用提供有用的视角.     

Transfer ionization in isocharge sequence ion and Ne collisions

The dependence of the ratio R1 for transfer ionization to single capture for Cq+, Nq+, Oq+, Neq+ ions on Ne target upon the electronic structure of the projectile is studied. For Aq+-Ne collisions the ratio R1 decreases as the atomic number Z of the projectile increases for q=4,5,6,7 sequences which provides strong evidence for the increase of the binding energy of the target valence electron after single electron capture. The increase in binding energy depends both upon the atomic number of the projectile and the target atom.     

氰化给体中分子间相互作用促进的全小分子光伏混合物的超快电子转移

氰基取代被认为是优化全小分子有机太阳能电池性能的可行方法. 然而,氰基取代对太阳能电池中电荷产生动力学的影响仍未得到探索. 本文光谱研究表明,在全小分子太阳能电池中,氰化给体中增强的分子间电荷转移相互作用会显著促进共混物中的电子转移. 实验发现,在氰基取代给体中,分子间相互作用引起的离域激发,在混合物中会进行超快电子转移. 相比之下,在没有氰基取代的给体中剩余的局域激发态,并没有积极参与电荷分离. 此发现很好地解释了为何氰化取代给体的共混物器件的性能会得到提升,表明可以通过调控分子间相互作用、来优化全小分子器件性能.     

Enhancing the Emission of Polydiacetylene Sensing Materials Through Fluorophore Addition and Energy Transfer

Enhancement of the environmentally responsive fluorescent properties of polydiacetylene (PDA) by combination with lipophilic fluorophores was demonstrated and properties of the PDA/fluorophore systems were explored. Liposomes containing PDA and fluorophores exhibited enhanced Stokes shift and increase in emission as a result of energy transfer from PDA to fluorophore. The effects of fluorophore variation, degree of PDA polymerization and diyne placement in the diacetylene lipid tails on the emission enhancement were studied. It was determined that signal generation was optimized at a relatively low extent of PDA polymerization with the optimal degree of polymerization dependent on the other parameters. Energy transfer was used as a tool to detect fluorophore exchange between polymerized and unpolymerized liposomes and to study the effects of fluorophore structure on exchange from unpolymerized to PDA liposomes. Fluorophores that locate at the aqueous interface with alkyl anchors were slow to transfer while fluorophores that partition into the alkyl regions of the liposomes transfer quickly.     

表面增强能量转移效应的研究

通过分析2、2′菁染料水溶液、银胶体以及2、2′菁染料吸附于银胶表面时的吸收光谱得知,2、2′菁染料吸附于银胶表面时,有J聚集体出现,通过分析基频及高阶线性Raman光谱,证实了一些低波数的Raman信号是由J聚集体产生的,从而进一步证实了吸附于银胶表面的2、2′菁染料以单体和J聚集体形式共存.同时,由吸收光谱还可以看出,2、2′菁染料分子及其J聚集体分子的吸收带都处于银胶吸收带的半高宽范围内,满足共振条件,当用不同激发波长(514.5 nm和488 nm)的光激发吸附于银胶表面的2、2′菁染料时,观察到了J聚集体的敏化荧光,而用此激发光激发2、2′菁染料水溶液时,就没有观察到J聚集体的敏化荧光,从而说明了银胶表面的存在,加速了单体2、2′菁染料分子与其J聚集体分子之间的能量转移速率.     

苯硝化反应中电子转移反应重组能的计算

提出了重组能的量子化学算法 ,在用CISD/6 31G基组水平上 ,得到苯硝化反应中反应物及过渡态的结构 .并计算了各自交换电子转移反应以及交叉电子转移反应的重组能 ,同实验重组能进行了比较 .计算用了Gaus sian 94程序 .从重组能的角度分析了苯硝化反应 .结果表明 ,对于NO2 + +NO2 →NO2 +NO2 + 的自交换电子转移反应 ,重组能较大 ,结论为 :在芳烃硝化反应中 ,存在以NO2 + 为氧化剂的电子转移步骤的可能性很小 ,而从动力学的角度上 ,用NO+ 作反应的氧化剂更有可能 .     

双掺杂聚合物电致发光中能量传递的光谱分析

将两种荧光染料掺杂到有机聚合物中,制作了双掺杂的电致发光器件ITO/PVK:TPB:Rubrene/LiF/Al, 得到了聚合物与两种荧光染料之间的阶梯式的能量传递。当PVK作为能量给体,Rubrene为能量受体时,能量传递不是很有效。但通过研究共掺杂体系的发光性质,发现辅助染料TPB的加入,作为能量传递的桥梁,提高了能量传递的效率,从而增加了器件的色纯度。     

Energy Transfer from the Aminophthalate Dianion to Fluorescein

Energy transfer from the excited aminophthalate dianion species to fluorescein at pH 8.32 (Tris-HCl buffer) was studied. The excited aminophthalate dianion species was obtained either by excitation with UV radiation (330 nm), with fluorescence emission, or by the well-known chemical reaction luminol-hydrogen peroxide in an alkaline medium, with chemiluminescent emission, both with _max at 425 nm. The influence of Co²⁺ and Mg²⁺ on fluorescence and chemiluminescence (CL) was studied. It was found that at low concentrations (10^–7–10^–9 M), these ions do not modify the fluorescein fluorescence, however, the CL is strong affected. The effect of the concentration of these elements, which exert an influence on CL even at a high dilution (nanomolar concentration), was determined. In the case of Co²⁺ the prooxidant character is stronger than in the case of Mg²⁺, and therefore the CL enhancer effect is higher. Compared to the system without catalyst, their presence ensures stronger, prolonged, and stable light emission. The emission spectra, in the presence of fluorescein, show two bands with maxima at 425 and 520 nm, the second one being specific to fluorescein emission. The intensity of aminophthalate dianion luminescence is lower and the duration shorter in the presence of fluorescein. The influence of Co²⁺ and Mg²⁺ catalyst and fluorescein concentration on the energy transfer process was studied. The efficiency of the energy transfer process for these two situations (fluorescence and CL) was compared. An attempt was made to replace hydrogen peroxide with superoxide anion (solubilized by means of crown ether) and its effect upon the energy transfer process was observed.     

Electron Energy Function Distribution in Hollow Cathode Discharge at Resonant Irradiation

Abstract

The behaviour of electron energy function distribution in hollow cathode discharge at resonant light irradiation is analyzed. The function is calculated for energies near and higher than the energy excitation ?₁ of the hellium metastable levels. It turns out that the electron energy function distribution is essentially influenced in the vicinity of point ?₁.     

A Theory of Electronic Energy Transfer in Complex Molecular Systems

The Förster theory for energy transfer is critically reviewed in the context of the present-day theory of nonradiative transitions, and the fundamental tenets of the Förster theory are shown to be erroneous. A new theory of electronic energy transfer is constructed taking into account the electronic transition theory. The intermolecular interaction between donor and acceptor molecules is assumed to perturb electron states of isolated molecules before the donor-molecule excitation. A distinguishing characteristic of the intermolecular interaction is spatial delocalization of the wave functions of electron states of the interacting molecules. It is this fact that has made it possible to realize ordinary photophysical processes between electron states of various molecules in a bimolecular system. In the experiments under study, the result of the intermolecular nonradiative photoprocess is given as evidence of electronic energy transfer from the donor molecule to the acceptor molecule.     

PSⅡ颗粒二聚体中类胡萝卜素向反应中心传能研究

运用瞬态荧光光谱技术在77 K低温下对PSⅡ颗粒复合物中类胡萝卜素（Car）分子的能量传递过程进行研究, 通过不同激发波长473 nm, 481 nm, 507 nm选择性激发PSⅡ颗粒复合物中色素分子, 得到PSⅡ颗粒二聚体中关于Car能量传递的三组时间组分：16.6 ps, 130~183 ps, 217~249 ps. 其中16.6 ps反映了LHCⅡ中的Car分子将能量通过中间体Cars、Chls分子传递到Chl639的过程; 130~183 ps为核心天线中的β-Car分子向RC的能量传递时间; 217~249 ps为LHCⅡ中Car481通过中间Chla分子向RC的传能时间.     

核黄素与蒽酮衍生物之间的能量传递现象的研究

依据Förster的能量传递理论,研究了核黄素和蒽酮衍生物之间的能量转移。研究结果表明：核黄素与蒽酮衍生物之间存在着显著的能量转移,而且二者的能量转移效率受加热温度、加热时间和质量配比的影响;核黄素与蒽酮衍生物最佳质量比为1∶3;随着加热温度和加热时间的增大,能量转移效率减小。     

Detection and Characterization of Membrane Microheterogeneity by Resonance Energy Transfer

The application of resonance energy transfer (RET) in the study of heterogeneity in membrane systems is described. Useful formalisms for monophasic and biphasic systems are presented, together with quantitative studies. Evidence for reduction of dimensionality, probe segregation, and microdomain sizes in these systems is discussed. Selected examples of multicomponent systems (natural membranes or model systems including proteins) are also referred, as well as recent work using RET under the microscope.     

Energy transfer process in CaSO4:Tb,Ce phosphor

Thermoluminescence (TL) and photoluminescence studies have been carried out on CaSO₄:Tb, CaSO₄:Ce and CaSO₄:Tb,Ce phosphors with the aim of studying energy transfer process in the CaSO₄:Tb,Ce phosphor. CaSO₄:Tb,Ce shows TL peaks at 150, 220, 320 and 400°C. Changes in Tb and Ce concentrations influence the relative heights of these glow peaks. Co-doping with 0.1 mol% of Ce in CaSO₄:Tb enhances the sensitivity of 320^oC TL peak by a factor of 15. Fluorescence results show that there is energy transfer from Ce to Tb ion. The defect centres formed in CaSO₄:Tb,Ce phosphor are studied using electron spin resonance technique. The 320^oC glow peak correlates with a centre (SO₃⁻radical) with g-values: g_||=2.0061 and g_⊥=2.0026.