Free-electron molecular-orbital treatment of chalcone group of dyes

The position and intensity of the absorption bands of a number of chalcone dyes have been calculated on the basis of the free-electron molecular-orbital (FEMO ) theory. The three to four absorption maxima of the chalcones are calculated by assuming the molecule to consist of two parts. The hypothetical cleavage is affected at the site of C?O bond such that first and second part of the molecule contains six and eight π electrons, respectively. Each part is then treated as an independent entity and the absorption maxima obtained by the application of joint and continuity condition of Kuhn are in agreement with the experimental values. The perturbation energy correction due to the substituted functional groups with higher electronegativity than carbon have also been made in the absorption maxima. The oscillator strengths corresponding to the values of the absorption maxima have been obtained as well.     

Optical absorption of tetraphenylporphyrin thin films in UV-vis-NIR region

The optical absorption of thermally evaporated tetraphenylporphyrin (TPP) in the UV-vis-NIR region have been studied. The absorption spectra recorded in the UV-vis region for the as deposited and annealed films showed different absorption bands, namely the Soret(B) at region 360-490nm, Q-band region consist of four bands in the region 500-720nm and two other bands labeled N and M in UV region. The Soret band always shows its characteristic effect splitting in all the TPP thin films and the effect of annealing on the intensities of these components have been observed. The spectra of the infrared absorption allow characterization of vibrational modes for the powder, as deposited and annealed thin films. Some of the optical absorption parameters, namely molar extinction coefficient, varepsilon, half band width, Deltalambda, electronic dipole strength, q(2) and oscillator strength, f, of the principle optical transitions have also been evaluated.     

Submillimetre wave spectroscopy of 4-n-alkyl-4'-cyano biphenyl liquid crystals

The absorption coefficient of the 4-n-alkyl-4'-cyano biphenyls has been studied in the submillimetre wave range 50-220 cm^-1. Molecular processes which give rise to superimposed but distinct absorption bands are reported. These processes have been analysed using a multi-oscillator model for the observed absorption and are assigned to the Poley absorption as well as to intermolecular and intramolecular mechanisms. Spectra at temperatures in the range 20-70°C and of solutions in cyclohexane support the proposed assignments.     

Dipicolinate as acceptor in D-π-A chromophores: synthesis, characterization and fluorescence following single- and two-photon excitation

Three novel donor-π-acceptor type compounds with dipicolinate as acceptor have been synthesized. Their absorption, photoluminescence as well as their two-photon absorption properties have been investigated. Two of them show strong two-photon absorption and two-photon excited up-conversion fluorescence.     

Optical absorption of tetraphenylporphyrin thin films in UV-vis-NIR region

The optical absorption of thermally-evaporated tetraphenylporphyrin (TPP), in the UV-vis-NIR region has been studied. The absorption spectra recorded in the UV-vis region for the as-deposited and annealed films showed different absorption bands, namely the Soret, B, at region 360-490 nm, Q-band region consist of four bands in the region 500-720 nm and two other bands labeled N and M in UV region. The Soret band always shows splitting in all the TPP thin films and the effect of annealing on the intensities of these components have been observed. The spectra of the infrared absorption allow characterization of vibrational modes for the powder, as deposited and annealed thin films. Some of the optical absorption parameters, namely molar extinction coefficient (epsilon), half band width (Deltalambda), electronic dipole strength (q2), and oscillator strength (f), of the principal optical transitions have also been evaluated.     

Far-infrared studies of alkali-anthracene ion-pairs and triple-ions in solution

Solutions of the anthracene mono- and di-anion produced by reduction with alkali metals in tetrahydrofuran show absorption bands in the far-infrared region. These bands have been interpreted as arising from the vibration of ion-pairs and triple-ions. The corresponding force constants have been calculated using simple models. Some discussions is given of possible causes of the two absorption bands of the sodium-anthracene triple-ion.     

Binuclear complexes of Pt(II) with platinated 2-phenylbenzothiazole and bridged derivatives of pyridin- and benzothiazol-2-thiols

Binuclear complexes of Pt(II) cycloplatinated with 2-phenylbenzothiazole and bridging ligands have been shown to contain the Pt-Pt bond. The complexes have been studied by X-ray diffraction, ¹H NMR and electronic absorption spectroscopy, and electrochemical methods. The complexes cis-N_(bt),S-isomers with antisymmetric positions of the cyclometalated and the bridging ligands have been detected in the crystals as well as in the solutions. The low-wavelength absorption and luminescence of the complexes have been assigned to the metal-metal-ligand charge transfer. The two-electron oxidation and reduction waves in the voltamperograms are associated with the metal- and the ligand-centered processes, respectively.     

Electronic absorption spectra of benzoquinone and its hydroxy substituents and effect of solvents on their spectra

The electronic absorption spectra of 1,4-benzoquinone (BQ) and its 2,5-dihydroxy and tetrahydroxy derivatives have been studied in detail. The interpretation of the electronic bands is made on the basis of PPP and CNDO calculations. It is found that the pi --> pi* transitions are well predicted by the PPP method. The predictions of the CNDO method are however superior both in their accuracy as well as ability to predict the n --> pi* transitions. The effect of solvents on the electronic absorption bands have also been investigated in detail. Linear correlations are found between the solvent's dielectric constant and wavelength of the absorption bands. The solvent shifts are explained on the basis of the polarities of the solute and solvent molecules as well as due to hydrogen bonding.     

Synthesis and study of fluorescent properties of benzothiazolylthieno-thiophene derivatives

A number of benzothiazolylthienothiophenes have been synthesized. Spectral studies have revealed that all these compounds have fluorescent properties that depend on their structure. Dependence of absorption and fluorescence bands positions on the nature of substituents have been established. Increase of the electron-withdrawing nature of substituents led to bathochromic shift of the absorption and fluorescence bands as well as to decrease of the fluorescence intensity.     

Many-particle spectra and nonlinear polarizabilities of crystals (peculiarities of two-photon absorption)

An expression has been found for the frequency and polarization dependence of the two-photon absorption in the many-particle spectral region (vibronic and two-phonon spectra) of centrosymmetric crystals. The peculiarities of one-photon and two-photon absorption have been compared and the conclusions drawn have been correlated with some experimental results on two-photon absorption.     

Synthesis, fluorescence and two-photon absorption properties of multichromophoric boron-dipyrromethene fluorophores for two-photon-excited fluorescence applications

The synthesis and the characterization of new multichromophoric boron-dipyrromethene dyes are described. Their absorption, photoluminescence as well as their two-photon absorption properties have been investigated. This work shows that assembling several dyes in conjugated multichromophoric structures is a promising strategy for improving the two-photon absorption properties of such fluorophores in the NIR region while retaining their excellent photoluminescence properties.     

Synthesis and two-photon absorption of triphenylbenzene-cored dendritic chromophores

The synthesis and the characterization of triphenylbenzene-cored dendrimers of first- and second-generation are described. Their absorption, photoluminescence as well as their two-photon absorption properties have been investigated and compared to a quadrupolar counterpart. These molecules combine wide transparency in the visible range and high two-photon absorption cross-sections that increase with the generation, making these dendrimers promising systems for optical power limiting applications.     

Two-photon absorption of [2.2]paracyclophane derivatives in solution: a theoretical investigation

The two-photon absorption of a class of [2.2]paracyclophane derivatives has been studied using quadratic response and density functional theories. For the molecules investigated, several effects influencing the two-photon absorption spectra have been investigated, such as side-chain elongation, hydrogen bonding, the use of ionic species, and solvent effects, the latter described by the polarizable continuum model. The calculations have been carried out using a recent parallel implementation of the polarizable continuum model in the DALTON code. Special attention is given to those aspects that could explain the large solvent effect on the two-photon absorption cross sections observed experimentally for this class of compounds.     

Design, synthesis, characterization, luminescence and non-linear optical (NLO) properties of multinuclear platinum(II) alkynyl complexes

A series of luminescent multinuclear platinum(II) alkynyl complexes containing triethynylbenzene or 1,4-bis(3,5-diethynylphenyl)buta-1,3-diyne as cores has been successfully synthesized and characterized. The electronic absorption, emission, nanosecond transient absorption and electrochemical properties of these complexes have been reported. These complexes show long-lived emissions in degassed benzene solution and in alcoholic glass at 77 K. Moreover, they are found to exhibit two-photon absorption (2PA) and two-photon induced luminescence (TPIL) properties, and their two-photon absorption cross-sections have been determined to be 6-191 GM upon excitation at 720 nm. Through a systematic comparison, it has been found that tetra- and hexanuclear platinum(II) complexes show better 2PA and TPIL properties than their di- and trinuclear counterparts.     

Study of the thermal oxidation of polyolefins—III: Pressure and temperature dependence of the rate of oxygen absorption

The kinetics of oxygen absorption by high pressure polyethylene (PE) have been studied between 8 and 650 torr oxygen pressure and in the temperature range 140 to 180°. The mechanism of thermal oxidation has been described and the equation for the rate of oxygen absorption has been derived. The rate equation has been studied in the initial stage and at points of the maximum rate of oxygen absorption. Some rate constant combinations (characteristic of the process) and their temperature dependence have been determined from experimental data. The pressure dependence of the initial and maximum rates of oxygen absorption, in the pressure range investigated, is well described by the proposed mechanism.     

Photophysics and nonlinear absorption of peripheral-substituted zinc phthalocyanines

The photophysical properties, such as the UV-vis absorption spectra, triplet transient difference absorption spectra, triplet excited-state extinction coefficients, quantum yields of the triplet excited state, and lifetimes of the triplet excited state, of 10 novel zinc phthalocyanine derivatives with mono- or tetraperipheral substituents have been systematically investigated in DMSO solution. All these complexes exhibit a wide optical window in the visible spectral range and display long triplet excited-state lifetimes (140-240 mus). It has been found that the complexes with tetrasubstituents at the alpha-positions exhibit a bathochromic shift in their UV-vis absorption spectra, fluorescence spectra, and triplet transient difference absorption spectra and have larger triplet excited-state absorption coefficients. The nonlinear absorption of these complexes has been investigated using the Z-scan technique. It is revealed that all complexes exhibit a strong reverse saturable absorption at 532 nm for nanosecond and picosecond laser pulses. The excited-state absorption cross sections were determined through a theoretical fitting of the experimental data using a five-band model. The complexes with tetrasubstituents at the alpha-positions exhibit larger ratios of triplet excited-state absorption to ground-state absorption cross sections (sigma T/sigma g) than the other complexes. In addition, the wavelength-dependent nonlinear absorption of these complexes was studied in the range of 470-550 nm with picosecond laser pulses. All complexes exhibit reverse saturable absorption in a broad visible spectral range for picosecond laser pulses. Finally, the nonlinear transmission behavior of these complexes for nanosecond laser pulses was demonstrated at 532 nm. All complexes, and especially the four alpha-tetrasubstituted complexes, exhibit stronger reverse saturable absorption than unsubstituted zinc phthalocyanines due to the larger ratio of their excited-state absorption cross sections to their respective ground-state absorption cross sections.     

Optimization of the determination of selenium in marine samples by atomic absorption spectrometry: Comparison of a flameless graphite furnace atomic absorption system with a hydride generation atomic absorption system

A comparison has been made between a graphite furnace system based on nickel as a matrix stabilizing metal and an automated hydride generation system with a heated quartz cell. The effect of nickel as a matrix modifier was studied in pure selenite solutions as well as in biological matrixes by different charring temperatures. The suppression effect of different acids on the response of the analyte is reported and discussed. The use of an electrically heated quartz tube as an alternative to the argon hydrogen flame method unproved the selenium determination by hydride generation atomic absorption. The effect of hydrochloric acid to secure quantitative formation of selenium (IV) and the interference of copper in the response measurements have been studied. Further a comparison has been made between three different digestion procedures when the hydride generation atomic absorption system was applied. The results of the graphite furnace atomic absorption and the hydride generation atomic absorption were found to be equally accurate, but the graphite furnace technique gave better reproducibility.     

用催化氧化法从水溶液中制备Tb(Ⅳ)水合氧化物及其性质的研究

有关水溶液中Pr(Ⅳ)和Tb(Ⅳ)化合物的制得虽曾有过报道,但往往是有争议的。近年来,苏联学者报道了水溶液中Pr(Ⅳ)和Tb(Ⅳ)与不饱和杂多酸形成络合物的研究。顾翼东等用"带同氧化"法从近中性溶液中获得了Pr(Ⅳ)和Ce(Ⅳ)的杂多核氧化物。     

Encapsulation of norharmane in cyclodextrin: formation of 1:1 and 1:2 inclusion complexes

Steady state absorption and fluorometric techniques have been used to investigate the photophysics of norharmane (NHM), a bioactive fluorophore, in aqueous as well as aqueous cyclodextrin (CD) environments. The absorption and steady state fluorescence spectral studies reveal the formation of two types of inclusion complexes between the fluorophore and beta-cyclodextrin (beta-CD) depending on the relative population of the two. The stoichiometries and association constants of these complexes have been determined monitoring the fluorescence data. alpha-and gamma-cyclodextrin (alpha-CD, gamma-CD) do not have appreciable effect on the spectral pattern of the fluorophore. The differential fluorimetric behavior of NHM in different CD environments has been rationalized from the variation of the relative dimensions of the probe and the CD cavities.     

DNA as a template for synthesis of fluorescent gold nanoclusters

Water-soluble blue-emitting gold nanoclusters have been synthesized using dsDNA as a template without any additional reducing agent. The features of the formed nanoclusters have been revealed by fluorescence and electronic absorption spectroscopy as well as transmission electron microscopy. The prepared gold nanoclusters have been highly stable at physiological pH without any further modification.