Influence of Vibrational Excitation of Triplet Molecules of Anthraquinone on the Photochemical Processes in Gas Mixtures with Amines

By the quenching of the delayed fluorescence (DF) of anthraquinone vapors by aliphatic amines (diethylamine, dibutylamine, cyclohexylamine) and pyridine the photoinduced processes proceeding with the participation of vibrationally excited triplet molecules of anthraquinone have been investigated. The DF quenchingrate constants K _q varying from 1·10⁶ sec^–1·torr^–1 in mixtures with diethylamine to 7·10³ sec^–1·torr^–1 in mixtures with pyridine have been estimated. A correlation between the values of K _q and the ionization potentials of foreign gases confirming the important role of interactions with charge transfer in the quenching of triplet molecules in the gas phase has been established. The influence of other relaxation processes on the DF quenching is considered. It is shown that the intermolecular vibrational relaxation in the T ₁ triplet state leading to the establishment of relaxation equilibrium at a vibrational temperature T _vib considerably increasing the medium temperature is the fastest process among the biomolecular processes (rate constants K _col ^V > 10⁶ sec^–1·torr^–1 > K _q). The values of T _vib and the vibrational energies E _vib of the triplet molecules after the energy exchange in the collisional complex have been estimated. It has been concluded that the photochemical reaction yield is determined by the intermolecular processes proceeding in the T ₁ state at a vibrational equilibrium characterized by high values of T _vib. The influence of E _vib of triplet molecules on the DF quenching rates at a photoinduced electron transfer is considered.     

Influence of Temperature on Photoinduced Reactions of Organic Molecules in the Gas Phase

The influence of temperature on the rate constants of photoinduced intermolecular electron transfer, representing the first stage of photoinduced reactions, has been investigated based on analysis of the quenching of fluorescence of carbazole vapor by halomethanes (CHCl₃, CH₂Br₂, CCl₄, CHBr₃) and delayed fluorescence of benzophenone and anthraquinone vapors by aliphatic amines (diethylamine, dibutylamine, cyclohexylamine, triethylamine) and pyridine. It has been established that the rate constants of photoinduced electron transfer in different donor-acceptor pairs in the gas phase can increase or decrease with increase in the temperature from 433 to 623 K. The energies of activation and enthalpy of the fluorescence-quenching process have been determined. The interrelation between the rate constants of fluorescence quenching k _q and the free energy of electron transfer G _ET has been analyzed with account for the mean vibrational energy <E _vib> of the interacting molecules. It is shown that positive and negative temperature dependences k _q(T) are characteristic, respectively, of the regions of normal (k _ET increases with decrease in G _ET) and inverted (k _ET decreases with decrease in G _ET) changes in the rate constants caused by an increase in the exothermicity of the photoinduced electron transfer process.     

Spectral-Luminescence Characteristics of Carbazole, Dibenzofuran, and Dinaphthofuran in the Gas Phase in Excitation by Electrons and Photons

The spectra of electron-energy loss, the excitation functions, and the fluorescence spectra in excitation of carbazole, dibenzofuran, and dinaphthofuran by monoenergetic beams of electrons of different energies are determined. The singlet-triplet transitions S ₀–T ₁ and the singlet-singlet transitions up to S ₀–S ₇ are recorded, which covers the region 2–11 eV. In the spectra of electron-energy loss, bands that refer to the n^ast and ^* transitions are identified. The replacement of the heteroatom of nitrogen by the atom of oxygen in the five-membered ring has no substantial effect on the spectra of electron-energy loss.     

Photophysical Processes in the Vapor of Carbazole

The characteristics of the rapid and retarded fluorescence of the vapor of carbazole excited by the radiation of a nitrogen laser are studied. The dependences of the intensity and rate of decay of the retarded fluorescence on the exciting-radiation intensity, the temperature, and the pressure of the vapor and foreign gases are used to determine the predominant mechanisms of relaxation of triplet molecules. It is shown that the decay of the retarded luminescence is governed by the competition between the processes of triplet-triplet annihilation that lead to the emission of annihilation retarded fluorescence and intercombination conversion of the triplet molecules to the ground electronic state. The characteristic times of these processes and the lifetimes of the triplet state in the vapor _T are evaluated; the temperature dependence of _T is analyzed in a wide interval of temperatures (77–573 K). It is inferred that in all aggregative states, the reduction in _T with increase in the temperature has a common nature and reflects an increase in the rate of intercombination transition T ₁ — S ₀ with increase in the content of vibrational energy.     

Investigations of the excitation energy transport mechanism in donor-acceptor systems

Measurements of fluorescence quantum yield _D/_oD of Na-fluorescein (donor; D) versus concentration of rhodamine B (acceptor; A) in viscous solutions have been carried out. The donor concentration in these solutions was as follows:C _D=2·10^–2 M (system I), 1.5·10^–2 M (II), 10^–2 M (III), 3·10^–3 M (IV), and 5·10^–5 M (V). The experimental results have been compared with current theories of nonradiative electronic energy transfer (NEET). In the case of very strong migration (systems I, II, and III), a significant influence of correlations (between configurations of D and A molecules in the surroundings of successively excited donors) on quantum yield _D/_oD has been determined. Experimental values have been found to be clearly higher in comparison with those predicted theoretically. The influence of possible factors on the decrease in the effectiveness of excitation energy transport to traps-acceptors in systems of very strong migration has been discussed.Dedicated to Professor A. Kawski on the occasion of his 65th birthday.     

Quantum Efficiency of Photooxidation of Porphyrins by Halomethanes in Solutions

The quantum yields of photooxidation of porphyrins, chlorophyll a, and –carotene in diethyl ether in the presence of different concentrations of CCl₄ in irradiation into the S ₀ S ₁ absorption bands are determined. The quantum yields for deoxygenated solutions are in the range (0.001–4.200)·10^–3. In the presence of oxygen, the quantum yield is increased by more than an order of magnitude and is related to the formation of the peroxyl radical CCl₃O₂ . It is shown that in the initial stage of the photochemical reaction, an electron from the excited molecules of tetrapyrrole pigments in the S ₁ state is transferred to the molecules of halogen derivatives of methane.     

Determination of the Probability of Intermolecular Energy Transfer of the Triplet State of a Number of Tetrapyrrole Molecules in Liquid Solutions

The quenching of the triplet state of a number of Pd porphyrins and chlorophyll a by other complexes of porphyrins with Pd and Fe in liquid solutions was investigated with the use of pulsed photoexcitation. It is shown that the experimental data are consistent with the results of a kinetic analysis of the mechanism of quenching of the triplet state through the formation of excited complexes of interacting molecules. On the basis of analytical and experimental data, the probability values of intermolecular tripletstate energy transfer have been determined: K _ET = 2·10⁴3·10⁵ sec^–1. A conclusion about the character of the excited complexes has been drawn; in particular, the distance between the molecules in the complexes has been estimated to be 5 .     

Quenching of perylene fluorescence by Co2+ ions in dipalmitoylphosphatidylcholine (DPPC) vesicles

We report the fluorescence quenching of perylene by CoCl₂·6H₂O in small unilamellar DPPC vesicles via energy transfer. At the probe-to-lipid ratio of 1200 and quencher to lipid ratios of 12.51, donor-donor energy transfer between clustered perylene molecules was observed as well as energy transfer from the perylene molecules to cobalt ions bothabove andbelow the main phase transition temperature of the lipid. The fluorescence quenching of perylene by CoCl₂·6H₂O in the lipid gel state is shown to be well described by Förster long-range energy transfer when both donor-donor and donor-acceptor energy transfer are considered. In the liquid crystalline phase diffusion of the molecules is described as well as energy transfer. The interaction radiusR ₀ for energy transfer from perylene to Co²⁺ is found to be 13.4±1.1 Å in the gel phase at 303 K, in good agreement with the theoretical value forR ₀ of 13.9 Å. In the liquid crystalline phase at 323 K the lower value obtained forR ₀, 11.3±1.6 Å, is attributed to saturation of the Co²⁺ ions at the interfacial region of the bilayer. A diffusion coefficient of (1.06±0.15)×10^–6 cm² s^–1 is obtained for perylene-cobalt diffusion in the liquid crystalline phase at 323K.     

Pitfalls in the Use of Common Luminescent Probes for Oxidative and Nitrosative Stress

Lucigenin (LC²⁺, bis-N-methylacridinium) and 2,7-dichlorofluorescin (DCFH₂) are widely used as chemiluminescent or fluorescent probes for cellular oxidative stress, to reflect levels of superoxide (O₂ ^·–) and hydrogen peroxide, respectively. We report mechanistic studies that add to the growing evidence for the unsuitability of either probe except in very well-defined circumstances. The ability for lucigenin to generate superoxide via reduction of LC²⁺ to LC^·+ and redox cycling with oxygen depends on the reduction potential of the LC²⁺/LC^·+ couple. Redox equilibrium between LC^·+ and the redox indicator benzyl viologen is established in microseconds after generation of the radicals by pulse radiolysis and indicated E(LC²⁺/LC^·+) –0.28 V vs. NHE. Reaction of LC^·+ with O₂ to generate O₂ ^·– was also observed directly similarly, occurring in milliseconds, with a rate constant k 3 × 10⁶ M ^–1 s^–1. Quinones act as redox mediators in LC^·+/O₂ redox cycling. Oxidation of DCFH₂ to fluorescent DCF is not achieved by O₂ ^·– or H₂O₂, but NO₂ ^·) reacts rapidly: k 1 × 10⁷ M ^–1 s^–1. Oxidation by H₂O₂ requires a catalyst: cytochrome c (released into the cytosol in apoptosis) is very effective (even 10 nM). Fluorescence reflects catalyst level as much as O₂ ^·–) production.     

Detection of chlorinated hydrocarbons via Laser-atomization/Laser-induced fluorescence

Chlorinated hydrocarbons (CHC), photodissociated at 193 nm, are detected with high sensitivity by observing the atomic chlorine fragment via laser-induced fluorescence (LIF). Photofragment emission spectra from CH₃Cl, CH₂Cl₂, CHCl₃, CCl₄, C₂HCl₃, and C₂Cl₄ demonstrate that photofragment fluorescence and chemiluminescence are negligible in the region 700–800 nm where the 3p ⁴4p ⁴ S ⁰ 3p ⁴4s ⁴ P fluorescence from atomic chlorine is detected. There is also negligible interference for photodissociation in Ar, N₂, and air bath gases. Total CHC can be readily detected in air flows at mixing fractions less than 20 ppb and averaging times less than 1 minute. Techniques for considerable improvement in this detection limit are discussed.Supported by the NSF     

Nuclear orientation study of the decay of204BiFe

The decay of²⁰⁴Bi nuclei (I =6⁺, T_1/2=11·22 h) oriented in an iron host was investigated on the JINR low-temperature nuclear orientation facility SPIN. The orientation parameterB ₂=1·17 (6) was obtained from the analysis of six prominent E1 gamma-transitions. From the measured normalized intensities of the gamma-rays observed some 70 values of multipole mixing ratios for the gamma-transitions in²⁰⁴Pb nucleus were determined for the first time. The spins 6, 6, 5 and 4 could be uniquely assigned to the²⁰⁴Pb negative parity levels at 3891·5 keV, 3768·4 keV, 3301·5 keV and 2338·2 keV, respectively. The spin-parity assignments of the levels at 4183·8 keV, 4094·2 keV, 3782·0 keV, 2506·9 keV and 2065·1 keV were confirmed as 6^–, 6^–, 5^–, 5^– and 5⁺, respectively. For the level at 3105·1 keV spin-parity 5^– was suggested and spinparity 7^– of the level at 2696·4 keV was called in question. The possible placements of the gammatransitions 3 1351·7 keV and 1353·4 keV in the decay scheme is discussed. The reorientation parameters for the long-living levels at 2264·2 keV (T _1/2=0·45 s) and 1273·9 keV (T _1/2= =265 ns) were determined asG ₂=0·41 (14) andG ₂=0·60 (17), respectively. For the isomeric level at 2185·7 keV (T _1/2=67·2 min) the value ofG ₂=0·88 (49) was proposed.The authors would like to express their thanks to T. I. Kracíková and M. Trhlík for the valuable discussions in the course of the evaluation of the experimental data.     

Edge cathode luminescence of zinc-selenide single crystals at high levels of excitation

Investigating cathode-luminescence spectra over a broad range of temperature at high levels of excitation (G 10²⁷ cm^–3 · sec^–1) permits the establishment of the experimental conditions for the observation of a multiplasmon structure in studying electron-hole plasma of zinc-selenide single crystals.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 69–73, July, 1989.     

Manifestation of Intermolecular Interactions in the IR Spectra of 8-Azasteroids

We have investigated the intermolecular interactions of 8-aza-D-homogona-1,3,5(10),13-tetrane-12,17a-dione and 2,3-dimethoxy-8-azagone-1,3,5(10),13-tetran-12,17-dione with CHCl₃, binary solvents CHCl₃–CH₃OH, CCl₄–CHCl₃, and CCl₄–CH₃OH and also in the solid phase, which manifest themselves in the IR spectra. When the C=O groups of the studied 8-azasteroids form hydrogen bonding with the OH groups of alcohol, the frequencies (C=O) change insignificantly. We have found that they are higher than the corresponding frequencies in the IR absorption spectra of solid-phase samples, which is attributable not only to the effect of the medium but also to the possible shortened contacts of the C=O groups with the CH₃ and CH₂ groups of the molecules under study.     

Determination of the Concentration of Electrons in the Laser Plasma of Helium

The dependence of the Stark width of the spectral line of He II P 468.6 nm on the electron concentration in the laser plasma of helium for the range of electron densities N _e = (1–10)·10²³ m^–3 and electron temperatures of the order of 60 kK has been measured. The results obtained correspond well to Griem's theoretical data. An empirical relation is suggested which makes it possible to reliably determine the electron concentration from measured halfwidths in the investigated range of N _e.     

Inclusive production of φ-mesons in neutron-proton interaction at 30–70 GeV/c

A signal of the-K⁺K^– decays has been observed in neutron-hydrogen interactions at energies of 30–70 GeV in an experiment using the BIS-2 spectrometer. The longitudinal momentum spectrum in the forward region,x _F<0·1 atp _T<1 GeV/c, can be well described by a power law dependence (1–x _F)^N withN=4·28±0·42. Thep _T ² -spectrum has been parametrized by the exp(–Bp _T ² ) law with the exponentB=(3·02±0·55) (GeV/c)^–2. The extrapolation of the measured cross section to the full kinematic region yields a value of (220±85) b in agreement with measurements from the proton beams.     

Electrical properties of p-type ZnGeP2 irradiated by H+ ions

The properties of p-type ZnGeP₂ [p₀=(5–10)·10¹⁰ cm^–3, ₀=(2–5)·10^–7 (·cm)^–1], irradiated with H⁺ ions [E=5 MeV, T_irr=300 K, D=(1·10¹²–1.7·10¹⁶) cm^–2] are studied. An increase in the resistivity (to gr_max - 5·10¹¹ ·cm) and subsequent reduction in for large currents of H⁺ ions ( - 9·10⁸ ·cm for D - 1.7·10¹⁶ cm^–2), is observed in irradiated crystals. The resistivity of irradiated p-type ZnGeP₂ is found to be very sensitive to hydrostatic pressure [(4–5)·10^–5 bar^–1]. The annealing of radiation defects in the temperature interval (20–600) °C is examined.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 91–93, October, 1991.     

The effect of low-temperature electron irradiation on the transition temperature of YBa2Cu3O7−δ superconductors

Measurements of the complex susceptibility =–i of electron-irradiated YBa₂Cu₃O_7– show a strong influence of the electron irradiation dose, ·t on the transition temperatureT _c . For irradiation doses of ·t=2.2·10¹⁹ e^–/cm² we find a damage rate of T _c /(·t)=–1.6·10^–19 K/(e^–/cm²). It is assumed that the decrease ofT _c is mainly a bulk effect due to the production of atomic defects like vacancies and interstitials in the Cu–O–Cu chains and in the basal planes of the unit cells.     

The Dependence of Benzo-15-Crown-5 Ether-Containing Oligo Paraphenylene Vinylene (CE-OPV) Emission Upon Complexation with Metal Ions in Solution

The effects of metal salts (NaCl, CaCl₂·2H₂O, EuCl₃·6H₂O and Eu(OAc)₃) on the steady state and time resolved fluorescence behaviour of poly(para phenylene vinylene) oligomers containing benzo-15-crown-5 ether units (CE-OPV) have been investigated. The presence of EuCl₃ causes a significant (8–9 fold) increase in the fluorescence emission intensity of the OPV segments, as compared to pure CE-OPV, in 99:1 methanol/chloroform solution and a small (9 nm) red shift in the emission maximum. The presence of Na⁺ or Ca²⁺ results in less marked increases in fluorescence intensity compared to Eu³⁺. In the presence of Eu³⁺ and Na⁺, the fluorescence intensity increases approximately linearly with metal ion concentration up to a metal ion/CE-OPV molar ratio of 10. The emission enhancement is not related to a simple 1:1 (CE-OPV:metal ion) complex formation process. In contrast, in acetonitrile, CE-OPV shows complex fluorescence quenching behaviour as a function of EuCl₃ concentration. This solvent dependence suggests that the emission changes with metal concentration are related to the formation of charge-transferred complexes. The marked changes in fluorescence quantum yield of the PPV backbone due to complexation with metal ions makes CE-OPV a sensitive fluorescent probe for metal ions, or may be exploited for improving the quantum yield of PPV-based devices.