Electronic spectral and photophysical properties of some p-phenylenevinylene oligomers in solution and thin films

A comprehensive photophysical and spectroscopic study of a new class of p-phenylenevinylene oligomers (PPV-trimers) possessing different alkyl and alkyloxy sidechain substituents and different end groups (aldehyde, CC, phenylene and anthracene units) was undertaken in solution at room temperature (293 K), low temperature (77 K) and in thin films. The study comprises absorption, emission and triplet–triplet absorption spectra, together with quantitative measurements of quantum yields (fluorescence, intersystem crossing, internal conversion and singlet oxygen formation) and lifetimes. The data allow the determination of rate constants for all decay processes. From these, several conclusions could be drawn. Changing from alkyl to alkyloxy substituents does not change fluorescence and internal conversion yields but decreases the (already small) intersystem crossing yield. The introduction of anthracene at the terminal ends of the PPV-trimers leads to the lowest fluorescence yield reported in this study. Of particular importance is the fact that the fluorescence quantum yields in films are of the same order of magnitude as those in solution, which suggests the potential for use of these oligomers for light-emitting device applications. With one of the alkyloxy derivatives, a more detailed study of the early part of the fluorescence decay was made, and it was found that upon excitation a fast conformational relaxation process of the initially excited oligomer occurs, leading to a more planar conjugation segment.     

Competition in the bioreactor with general quadratic yields when one competitor produces a toxin

Microorganisms produce toxins against its competitors sometimes, and variable yields are useful to explain the observed oscillatory behavior in the reactor. In this paper, a model with general quadric yields of competition in the bioreactor of two competitors for a single nutrient where one of the competitors can produce toxin against its opponent, is proposed. We analyze the asymptotic behavior of the model in terms of the relevant parameters. The conditions of the three dimensional Hopf bifurcation, and the existence of limit cycles in the nutrient-organism phase plane are obtained.     

Effects of Halogen Substitution on Naphthazarin Tautomerism in the Ground and Excited States

5,8-Hihydroxyl-1,4-naphthazarin was taken as a model compound to explore the effect of halogen substitution on intramolecular proton transfer process. Calculations indicate that the substitution in the R2- and R4-positions far away from the active region has much weaker influence on the IPT process than that in the R1-and R3-positions. IPT barriers for substitution in the R1-position are higher than that of parent molecule. However, it is quite reverse for substitution in the R3-position. The IPT process is a proton transfer process coupled with charge separation and coulombic interaction would be dominant during this process. As for naphthazarin, halogen substitution would decrease the quantum yields of O2 but increase those of 1O2.     

The mechanism of nitrite formation in the radiation-induced oxidation of ammonia in aerated aqueous solutions

The mechanism of the radiation-induced conversion of ammonia to nitrites and nitrates in aerated aqueous solutions has been studied. The formation of the pernitrite ion, O=N-O-O^–, was detected at pH 10.5. The kinetics of its formation and decay were studied, andk _form was estimated at (2.3±0.2)·10⁷ L mol^–1 s^–1. The course of decay obeys first-order kinetics; the rate constant decreases at higher pH. Radiochemical yields of pernitrite, nitrite and nitrate at various pH and initial NH₃ concentrations were determined. A mechanism of ammonia oxidation in aqueous solution is proposed.Translated fromIzyestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 280–283, February, 1993.     

Synthesis and photochromic properties of novel yellow developing photochromic compounds

Two 1-thiazolyl-2-thienylcyclopentene derivatives, 1a and 2a, and a 1-thiazolyl-2-vinylcyclopentene derivative 3a have been synthesized in an attempt to obtain photochromic compounds which change the color from colorless to yellow, and have low photocycloreversion quantum yields and high absorption coefficients of the colored isomers. All of these compounds underwent reversible photochromic reactions. Compounds 1a and 2a in toluene solutions changed the color upon 313 nm light irradiation from colorless to orange and pink, in which absorption maxima were observed at 494 nm (ε=10,000 M⁻¹ cm⁻¹) and 525 nm (ε=8500 M⁻¹ cm⁻¹), respectively. On the other hand, the colorless toluene solution of 3a turned yellow upon irradiation with 313 nm light, in which the absorption maximum was observed at 416 nm (ε=17,100 M⁻¹ cm⁻¹). The photocyclization/cycloreversion quantum yields of 3 were 0.19 and 0.0014, respectively. The conversion from the open- to the closed-ring isomer of 3 in the photostationary state under irradiation with 313 nm light was close to 100%.     

Terpyridine-Functionalized Calixarenes: Synthesis,Characterization and Anion Sensing Applications

Lanthanide complexes have been developed and are reported herein. These complexes were derived from a terpyridine-functionalized calix[4]arene ligand, chelated with Tb³⁺ and Eu³⁺. Synthesis of these complexes was achieved in two steps from a calix[4]arene derivative: (1) amide coupling of a calix[4]arene bearing carboxylic acid functionalities and (2) metallation with a lanthanide triflate salt. The ligand and its complexes were characterized by NMR (¹H and ¹³C), fluorescence and UV-vis spectroscopy as well as MS. The photophysical properties of these complexes were studied; high molar absorptivity values, modest quantum yields and luminescence lifetimes on the ms timescale were obtained. Anion binding results in a change in the photophysical properties of the complexes. The anion sensing ability of the Tb(III) complex was evaluated via visual detection, UV-vis and fluorescence studies. The sensor was found to be responsive towards a variety of anions, and large binding constants were obtained for the coordination of anions to the sensor.     

Engineering the Charge-Transfer State to Facilitate Spin–Orbit Charge Transfer Intersystem Crossing in Spirobis[anthracene]diones

Spiro conjugation has been proposed to dictate the efficiency of charge transfer, which could directly affect the spin–orbit charge transfer intersystem crossing (SOCT-ISC) process. However, this process has yet to be exemplified. Herein, we prepared three spirobis[anthracene]diones, in which two benzophenone moieties are locked in close proximity and differentially functionalized to fine-tune the charge transfer state. Its feasibility for SOCT-ISC was theoretically predicted, then experimentally evaluated. Through fine-tuning the spiro conjugation coupling and varying the solvent dielectric constants, ISC rate constants were engineered to vary in a dynamic range of three orders of magnitude, from 7.8×10⁸ s⁻¹ to 1.0×10¹¹ s⁻¹, which is the highest ISC rate reported for SOCT-ISC system to our knowledge. Our findings substantiate the key factors for effective SOCT-ISC and offer a new avenue for the rational design of heavy atom free triplet sensitizers.     

Systematics on fission fragment mass distribution of neutron induced 235U fission

Based on the neutron induced fission fragment mass distribution data up to neutron energy 20 MeV measured with the double kinetic energy method (KEM) and the radio active method (RAM), the systematics of fission fragment mass distribution was investigated by using 5 Gaussian model and the systematics parameters were obtained by fitting the experimental data. With the systematics, the yields of any mass A and at any energy in the region from 0 to 20 MeV of neutron energy can be calculated. The calculated results could well reproduce the experimental data measured with KEM, but show some systematical deviation from the data measured by RAM, which reflects some systematical deviations between the two kinds of measured data.The error of systematics yield was calculated in an exact error transformation way, including from the error of the experimental yield data to the error of the discrete parameters, then to the systematics parameters,and at last to the yield calculated with systematics.     

Fission fragment mass yields of Th to Rf even-even nuclei

Fission properties of the actinide nuclei are deduced from theoretical analysis. We investigate potential energy surfaces and fission barriers and predict the fission fragment mass yields of actinide isotopes. The results are compared with experimental data where available. The calculations were performed in the macroscopic-microscopic approximation with the Lublin-Strasbourg Drop (LSD) for the macroscopic part, and the microscopic energy corrections were evaluated in the Yukawa-folded potential. The Fourier nuclear shape parametrization is used to describe the nuclear shape, including the non-axial degree of freedom. The fission fragment mass yields of the nuclei considered are evaluated within a 3D collective model using the Born-Oppenheimer approximation.