Characteristic features of carbazole phosphorescence quenching by benzophenone molecules in toluene at 77 K

We have studied the characteristic features of carbazole phosphorescence quenching by benzophenone in toluene at 77 K. We have shown that the decrease in the relative phosphorescence intensity for carbazole (energy donor) by a greater factor than we see for the relative change in its decay time is due to the fact that a change in the phosphorescence decay time occurs only for carbazole molecules participating in triplet-triplet energy transfer, while the substantial decrease in the phosphorescence intensity for carbazole with no change in the phosphorescence decay time is connected with quenching of its singlet states. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 554–556, July–August, 2006.     

Bimolecular quenching of fluorescence and interaction between excited molecules in solution

Bimolecular quenching of fluorescence was observed for fluoranthene, coronene and 3,4-benzophenanthrene in 1,2,4-trichlorobenzene or tetrahydrofuran solution, and the rate constant of the process was determined at various temperatures between room temperature (295 K) and 77 K. The bimolecular quenching rate constant was found to be a little smaller than that for a diffusion-controlled process in a fluid solvent. From the temperature dependence of the rate constant the quenching was found to be due to the long-range interaction which is enhanced by diffusion of the excited molecules in fluid media.     

Migration-Accelerated Quenching of Triplet Excitations of Organic Molecules in Toluene at 77 K

The influence of the organic molecule (naphthalene, acenaphthene, and benzophenone) concentration in toluene at 77 K on the phosphorescence parameters of degassed and non-degassed solutions is studied for organic molecule concentrations ranging from 0.025 to 0.8 M. The migration-accelerated quenching of triplet excitations of naphthalene and acenaphthene by oxygen molecules is established. A conclusion is drawn that this quenching mechanism can be one of the main reasons for the influence of the concentration on the phosphorescence parameters of impurity centers in non-degassed solid solutions of organic compounds at 77 K.     

Isothermal bulk modulus of solid xenon for zero pressure at 4.2 K, 65 K and 77 K

An interferometric method has been used to measure the isothermal bulk modulus (the reciprocal of the compressibility) of solid xenon at zero pressure for several temperatures. It is the first time that an elastic constant of this substance has been measured at a temperature below 10 K. The smoothed results are (37.9 ± 0.5) kbars at 4.2 K, (29.6 ± 0.5) kbars at 65.6 K, and (28.2 ± 0.5) kbars at 77 K.     

Depletion of singlet and triplet states of 1-amino-5, 6, 7, 8-tetrahydronaphthalene due to external heavy-atom perturbation

Summary Quenching of luminescence of 1-amino-5, 6, 7, 8-tetrahydronaphthalene (ATHN) in nonpolar and polar solvents at 300 K and 77 K by the chloroalkanes carbon tetrachloride (CCl₄), methyl chloroform (CH₃CCl₃), chloroform (CHCl₃) and methylene chloride (CH₂Cl₂) is reported. Different photophysical parameters at 77 K of unperturbed and perturbed fluorescer ATHN in ternary solutions are determined. The bimolecular dynamic fluorescence quenching rate constant (K _q) increases with the electron affinity (EA) of the quenchers and a linear correlation exists between lnK _q and EA. The quenching depends on polarity of solvents. The quenching is ascribed to contact CT exciplex formed between chloroalkanes and excited singlet ATHN.

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Riassunto Si riporta lo spegnimento di luminescenza dell' l-amino-5, 6, 7, 8-tetraidronaftalene (ATHN) in solventi non polari e polari a 300 K e 77 K mediante i cloroalcani tetracloruro di metilene (CH₂Cl₂). Si determinano diversi parametri fotofisici a 77 K di ATHN fluorescente perturbato e non perturbato in soluzioni ternarie. La constante (K _q) del valore di smorzamento di fluorescenza dinamico bimolecolare aumenta con l'affinità elettronica (EA) degli spegnitori ed esiste una correlazione lineare tra lnK _q ed EA. Lo spegnimento dipende dalla polarità dei solventi. Lo spegnimento è attribuito all'exciplex CT di contatto formato tra cloroalcani e ATHN a singoletti eccitati.

     

Properties of erbium luminescence in bulk crystals of silicon carbide

The infrared luminescence of Er³⁺ ions has been studied in bulk crystals of silicon carbide 6H-SiC doped with erbium in the process of their growth. The erbium centers of different symmetry in the crystals are revealed by the EPR technique. A number of intense luminescence bands of erbium ions are observed at a wavelength of about 1.54 μm. The luminescence can be excited by the light with quantum energies above and below the band gap of SiC. It is found that the luminescence exhibits unusual temperature behavior: as the temperature increases, the luminescence intensity abruptly rises starting with 77 K, passes through a maximum at ∼240 K, and, in the vicinity of ∼400 K, decreases down to the values observed at 77 K. The activation energies for the flare-up and quenching of the Er³⁺ luminescence are estimated at E _A ≈130 and ≈350 meV, respectively. The mechanisms of the flare-up and quenching of the Er³⁺ luminescence in SiC are discussed. __________ Translated from Fizika Tverdogo Tela, Vol. 42, No. 5, 2000, pp. 809–815. Original Russian Text Copyright ? 2000 by Babunts, Vetrov, Il’in, Mokhov, Romanov, Khramtsov, Baranov.     

Index matching far-infrared method for measuring the static dielectric constant of PbTe

An index-matching far-infrared reflectance technique has been used to measure the PbTe static “bare phonon” dielectric constant with great precision. Values obtained are 414 at 300 K and 801 at 77 K. This technique applies to many systems in which large low-frequency front-surface reflectivity makes conventional techniques insensitive.     

7-羟基香豆素与三种芳香族氨基酸作用的荧光光谱研究

运用荧光光谱和紫外光谱研究7-羟基香豆素UBM分别与色氨酸Trp,酪氨酸Tyr和苯丙氨酸Phe三种芳香族氨基酸的相互作用。结果表明在模拟人体生理条件下,UMB能引起上述氨基酸发生荧光猝灭,最大猝灭波长依次为347,303和282 nm,猝灭机制均为静态猝灭,相互之间均以摩尔比1：1形成了复合物,且得到两种温度下UMB与Trp,Tyr和Phe反应的表观平衡常数K_c分别为298.15 K时2.993×106,7.858×104和1.186×103 L·mol-1,310.15 K时2.702×104,1.063×105和8.352×103 L·mol-1。热力学函数变化表明UMB与以上三种氨基酸结合作用较强,其中UMB-Trp相互作用力是氢键或范德华力,UMB-Tyr和UMB-Phe相互作用主要以疏水作用为主,同时都可能存在偶极-偶极之间的相互作用。     

Effects of non-equilibrium polar optic phonons and the band non-parabolicity on small signal high-frequency hot electrons ac mobility in narrow gap semiconductors in high magnetic fields

The small signal high-frequency ac mobility of hot electrons in n-HgCdTe in the extreme quantum limit at low and high temperatures have been calculated considering the non-equilibrium phonon distribution as well as the thermal phonon distribution .The energy loss rate has been calculated considering only optical phonon scattering while the momentum loss rate has been calculated considering acoustic phonon scattering and piezoelectric scattering together with polar optical phonon scattering and separately considering only the polar optical scattering. The results have been discussed and compared. It has been observed that at 20 K, the normalized mobility considering all the three scattering mechanisms differs appreciably from that considering only the polar optical phonon scattering. However, at 77 K, there is no difference in the normalized mobility. This establishes the fact that at higher temperature, the effect of acoustic phonon scattering and piezoelectric coupling is negligible, compared to the polar optical phonon scattering. So the ac mobility considering only polar optical phonon scattering has been studied at 77 and 20 K. The ac mobility is found to remain constant up to 100 GHz and thereafter it started decreasing at higher frequencies at 77 K whereas the ac mobility reduces at much lower frequencies at lower temperature at lower field. The non-parabolicity of the band structure enhances the normalized mobility.     

TS及PTS聚合过程的介电性质研究

测量了TS的介电常数与温度的关系,在160K和203K附近观察到异常;同时也跟踪测量了TS在固态聚合过程中介电常数与聚合度的关系,发现在聚合初期,介电常数先是下降,当聚合度高于30％时,介电常数迅速上升。我们认为这些变化与侧链极性基团和碳链π电子的行为有关,并对此进行了定性的讨论。 关键词：     

Dislocation mobility in silver chloride

Stress relaxation test has been used as an indirect method for determination of the velocity-stress exponent for dislocation motion in AgCl single crystals in the temperature range 77 to 423 K. The stress dependence of the velocity-stress exponent has been estimated. A large effect of quenching on the value of the exponent has been found.We wish to thank Dr. F.Vávra for supplying the specimens.     

光谱法研究芹菜素与牛血清白蛋白的相互作用

在模拟人体的生理条件下（pH=7.40,Tris-HCl）,采用荧光光谱研究了牛血清白蛋白与芹菜素的相互作用。研究结果表明牛血清白蛋白与较小浓度的芹菜素间的相互作用属于静态猝灭过程;随着芹菜素浓度的增加,与牛血清白蛋白间的相互作用为静态猝灭和动态猝灭共同作用,但仍以静态猝灭为主。进一步求出了在287K和310K温度条件下静态猝灭的猝灭常数,由求得的热力学参数,证明了芹菜素与牛血清白蛋白之间主要依靠静电引力结合,采用同步荧光光谱技术探讨了芹菜素对牛血清白蛋白构象的影响。     

Photoinduced Electron Transfer From Carbazole to Halomethanes in a Gas Phase

Intermolecular photoinduced electron transfer (PET) in a gas phase was studied using carbazole vapor fluorescence quenching by halomethanes (CHCl₃, CH₂Br₂, CCl₄, CHBr₃). The fluorescence quenching rate constants k _q changing from 2.3·10⁵ sec^–1·torr^–1 in mixtures with CHCl₃ to 4.6·10⁶ sec^–1·torr^–1 in mixtures with CHBr₃ at a constant temperature of 403 K were estimated. The dependence of the carbazole fluorescence decay rates in the presence of halomethanes on the free energy change G during transfer of the electron from carbazole to halomethanes is considered. It is suggested to take into account the influence of the vibrational energy of the carbazole molecule E _vib and its temperature changes in estimation of the G values. The differences between PET in the gas and liquid phases were analyzed. It is found that for mixtures with CCl₄ and CHBr₃ the negative temperature dependence of k _q is observed, when the decay rates and efficiencies of the intermolecular PET decreased with temperature increase in the range 403–573 K, i.e. these mixtures the electron transfer is not a barrier-restricted process.     

Energy transfer in perylene-doped polyvinyl carbazole

Time resolved spectroscopy and fluorescence decay time measurements have been made on thin films of amorphous polyvinyl carbazole (PVK). The value obtained for the excimer fluorescence decay time in the undoped sample is less than that reported previously and a wavelength dependent double exponential decay is observed, which has been seen before only at low temperatures. The observed quenching of the excimer fluorescence decay times in the doped samples is evidence of direct energy transfer from excimers to perylene which is inconsistent with the model of energy transfer by exciton diffusion proposed to explain intensity quenching data. Several models for energy transfer in PVK are discussed and it is shown that the only model which predicts the observed time resolved spectroscopy results requires a long range resonant interaction strength much greater than that obtained theoretically. Several possible reasons for this are discussed.     

Hydrogen bonding,polarity and matrix effects on the spectroscopic and photophysical properties of some N- and 3-substituted derivatives of carbazoles

Fluorescence spectra and photophysical properties of N-cyano and N-carboethoxy carbazole derivatives have been compared to the equivalent 3-substituted compounds in fluid polar and unpolar solutions and in a low temperature rigid matrix at 77 K. The 3-carboethoxy derivatives have been shown to form an excited state complex (exciplex) with ethanol in fluid solutions. On the other hand the photophysical properties of the N-substituted derivatives are much affected by the solvent polarity in fluid solutions in that the radiationless decay rate constants show a marked increase in these media. A tentative explanation has been given in terms of the relative energy gap existing between the ¹L_b and the ¹L_a states of these molecules.     

碱性介质中茜素黄R与牛血清白蛋白作用的荧光法研究

在碱性条件下,采用荧光光谱法研究了茜素黄R(alizarin yellow R, AYR)与牛血清白蛋白(BSA)结合反应的光谱特征。研究表明,pH 11.00,激发波长为393 nm时,BSA的发射峰位于641 nm,且AYR对BSA有较强的荧光猝灭作用,AYR在BSA分子上荧光敏感部位有五个结合位点;由温度对AYR-BSA体系荧光猝灭速率的影响和动态猝灭常数K_SV以及静态猝灭结合常数K_LB的计算得出,AYR对BSA内源荧光的猝灭机制属于形成BSA-AYR复合物的静态猝灭,荧光猝灭常数为1.6×104 L·mol-1;由反应前后热力学函数ΔHθ＜0,ΔSθ＜0以及AYR对BSA-CBBG(CBBG-考马斯亮蓝G)体系具有荧光猝灭作用推出,茜素黄R与牛血清白蛋白之间的作用力主要是氢键和范德华力。     

Effect of pH on the fluorescence and phosphorescence spectra of indolecarboxylic acids. Evidence for the existence of a singlet excited-state indole acid dianion

Room-temperature electronic absorption, fluorescence, and low-temperature (77 K) phosphorescence spectra of a series of indolecarboxylic acids have been measured in predominantly aqueous solutions at pH 1.2, 7.0, 12.5, and in 5 N NaOH. The ¹L_a and ¹L_b π, π ¹ states have been assigned to the electronic transitions for all the compounds under study. The quenching of fluorescence, the appearance of a new fluorescence emission band, red-shifted by 40 nm, in very alkaline media, and the disappearance of the indole carboxylate short-wavelength band have been attributed to the formation of an excited singlet-state indolate carboxylate (dianion) stabilized by hydrogen bonding with the solvent. The existence of two successive excited singlet-state prototropic equilibria is discussed.     

Photocapacitance quenching effect for “oxygen” in GaAs

New experimental data about the persistent photocapacitance quenching observed at 77 K in GaAs are reported. The effect is demonstrated to arise on the so-called oxygen centre in this material. Thermal annealing is described. The results are interpreted assuming that the O centre when filled with an electron has two possible states: the stable one and a metastable state with a large lattice relaxation.     

水杨酸与牛血清蛋白相互作用的荧光光谱研究

应用荧光光谱研究了水杨酸与牛血清蛋白 (BSA)分子间的相互作用。研究表明 :水杨酸对BSA内源荧光的猝灭机制属于形成化合物所引起的静态猝灭 ,猝灭常数Ksv 为 1 0 97× 10 4 (mol·L- 1 ) - 1 ;水杨酸与BSA反应的结合常数为 7 377× 10 4 ,结合位点数为 1,当水杨酸浓度较低 (摩尔比小于 1∶1)时 ,它与Trp残基或其附近基团结合但并不引起Trp残基微环境的改变 ;根据F rster非辐射能量转移理论 ,计算了授体 受体间的结合距离和能量转移效率     

Mechanism of infrared stimulation and quenching in ZnS: Cu,Al Phosphors

To investigate the mechanism of the stimulation and quenching of the green luminescence in ZnS: Cu, Al phosphors by infrared (IR) light of 0.7–1.5 μm, stimulation and quenching spectra, IR effects on time-resolved emission spectra, and IR-induced photoconductivity are measured at 4.2 K, 77 K, and room temperature. Both the stimulation and quenching are caused by the IR transitions ascribed to excited copper acceptors. It is concluded that the stimulation is induced by the process in which holes produced by IR light migrate among copper acceptors, so that the statistical distribution of the intrapair separations of excited copper-aluminum pairs are changed to shorter distances. It is found that at low temperatures the holes migrate from one copper acceptor to another without being thermally released to the valence band. It is confirmed that the quenching is caused by the recombination of holes released to the valence band with electrons in the conduction band via some kind of nonradiative recombination centers.