Spectral-luminescent properties of condensation products of 8-aminoquinoline,aromatic aldehydes,and dimedone

Hydrobenzophenanthrolinone derivatives were synthesized by three-component condensation of 8-aminoquinoline, aromatic aldehydes, and dimedone. The structures of the obtained substances were confirmed by NMR and IR spectroscopy and mass spectrometry. Spectral-luminescent investigations of the synthesized compounds showed that they were characterized by high oscillator strengths for allowed electronic transitions S _n ← S ₀ (n = 1–3). Low fluorescence quantum yields in EtOH (Φ_fl ~ 10^–4–10^–3) and an increase of the Φfl values in toluene (~10^–2) at room temperature and with lowering the temperature to 77 K (Φ_fl ~ 10^–1) for a number of the compounds under study were satisfactorily explained within the framework of Marcus theory.     

Electronic deactivation and energy transfer in doped oligophenylenevinylene nanoparticles

Suspensions of oligophenylenevinylene (nPV) nanoparticles withn = 2 vinylene units are doped with nPVs of longer chainlengths,n = 3–5. Absorption and fluorescence spectroscopy and steady-state and time-resolved fluorescence anisotropy measurements are used to determine the photo-physical properties of the suspensions. Undoped nanoparticles form highly oriented H-aggregates with low fluorescence quantum yields (Φ_F ≈ 0.1). Introduction of bulky substituents into the particle constituting molecules perturbs the intermolecular orientation. Upon doping, efficient energy transfer to the dopants is found, changing the color and leading to enhancement of the fluorescence quantum yields up to Φ_F = 0.6. The intermolecular orientation is not changed upon doping.     

Fluorescence spectroscopy of potential electroluminescent materials: Substituent effects on DSB and segmented PPV derivatives

The absorption and fluorescence of substituted distyrylbenzene (DSB) derivatives and segmented poly(phenylene vinylene) (PPV) derivatives are characterized by long-wavelength absorption maxima and absorption coefficients of λ_a = 380–450 nm, ε = 20,000–60,000 M⁻¹ cm¹ and fluorescence maxima, quantum yields, and decay times of λ_r = 440–530 nm, Φ_f = 0.2–0.9, and Τ = 0.8–2.5 ns, respectively. Alkoxy substituents at the central phenylene ring of DSB groups increase the bathochromic shift in the spectra in comparison to DSB, without a significant decrease in the high DSB fluorescence quantum yield. Both phenyl and cyano substitutions at the vinylene bridge lead to a further bathochromic shift of the fluorescence and a decrease in the quantum yield to ca. 0.4. The DSB derivatives and the related segmented PPV derivatives show nearly the same absorption spectra, fluorescence spectra, and radiative rate constantsk _f= Φ_f/Τ, indicating the efficacy of the segmentation of the polymer chain. The radiative rate constants determined by the Φ_f and Τ values and by the Strickler/Berg formula are in reasonable agreement. This supports the possibility of interpreting the properties of the polymers in terms of their DSB units. The decrease in the emission anisotropy can be ascribed to multistep energy transfer processes between different oriented segments.     

Luminescence of oxotetrahydrobenzo[c]phenanthridine in polar and nonpolar solvents: Inversion of the energy levels of the Sππ* and Tnπ* states

The spectral-luminescent properties and electronic-level structure of a derivative of oxotetrahydrobenzo[c]phenanthridine—3,3-dimethyl-1,2,3,4-tetrahydrobenzo[c]phenanthridine-1-one (DTP)—in polar and nonpolar solutions are studied by the luminescence and picosecond spectroscopy techniques at 293 and 77 K. It is shown that DTP exhibits ππp* fluorescence only in polar proton-containing methanol, ethanol, and n-propanol and that this fluorescence is associated with a chromophore + alcohol complex. Solutions of DTP in n-propanol and the nonpolar mixture methylcyclohexane + toluene (6:1) at 77 K display ππp* phosphorescence with a quantum yield Φ_Ph=0.1, a lifetime τ_Ph=1.9 s, and a frequency of the 0-0 transition equal to 21550 cm⁻¹. The fact that DTP fluorescence is absent in aprotic solvents and exists in alcohols is explained by the inversion of the energy levels of the S _ππ* and T _n π* states, as a result of which the energy level of the fluorescing S _ππ* state in alcohol becomes the lowest. The picosecond spectra and kinetics of the inducedS _n (ππ*) ← S ₁(π π*) and T _k (ππ*) ← T ₁(ππ*) absorption made it possible to estimate the lifetime of the S ₁(ππ*) state of DTP in n-propanol at 293 K (20±10 ps) and the position of the triplet-triplet absorption peak (495 nm). __________ Translated from Optika i Spektroskopiya, Vol. 94, No. 6, 2003, pp. 993–998. Original Russian Text Copyright ? 2003 by Bondarev, Knyukshto, Tikhomirov, Pyrko.     

Stress-Induced Alteration of Chlorophyll Fluorescence Polarization and Spectrum in Leaves of <Emphasis Type="Italic">Alocasia macrorrhiza</Emphasis> L. Schott

The value of intrinsic chlorophyll fluorescence polarization, and the intensity in emission spectrum were investigated in leaf segments of Alocasia macrorrhiza under several stress conditions including different temperatures (25–50°C), various concentrations of NaCl (0–250 mM), methyl viologen (MV, 0–25 μM), SDS (0–1.0%) and NaHSO₃ (0–80 μM). Fluorescence emission spectrum of leaves at wavelength regions of 500–800 nm was monitored by excitation at 436 nm. The value of fluorescence polarization (P value), as result of energy transfer and mutual orientation between chlorophyll molecules, was determined by excitation at 436 nm and emission at 685 nm. The results showed that elevated temperature and concentrations of salt (NaCl), photooxidant (MV), surfactant (SDS) and simulated SO₂ (NaHSO₃) treatments all induced a reduction of fluorescence polarization to various degrees. However, alteration of the fluorescence spectrum and emission intensity of F₆₈₅ and F₇₃₁ depended on the individual treatment. Increase in temperature and concentration of NaHSO₃ enhanced fluorescence intensity mainly at F₆₈₅, while an increase in MV concentration led to a decrease at both F₆₈₅ and F₇₃₁. On the contrary, NaCl and SDS did not cause remarkable change in fluorescence spectrum. Among different treatments, the negative correlation between polarization and fluorescence intensity was found with NaHSO₃ treatments only. We concluded that P value being measured with intrinsic chlorophyll fluorescence as probe in leaves is a susceptible indicator responding to changes in environmental conditions. The alteration of P value and fluorescence intensity might not always be shown a functional relation pattern. The possible reasons of differed response to various treatments were discussed.     

The transformation of <Emphasis Type="Italic">n</Emphasis>-alkanes on H-forms of zeolites under supercritical conditions

The skeleton isomerization of n-butane, n-hexane, and n-heptane was studied under supercritical conditions on H-forms of zeolites mordenite, beta, and ZSM-5 over the temperature and pressure ranges 260–450°C and 80–130 atm. The isomerization of n-hexane and n-heptane was accompanied by side processes such as oligomerization and cracking. The selectivity of formation of branched isomers of these hydrocarbons did not exceed 70 and 30%, respectively. The catalyst with the most stable operation was pentasil ZSM-5, but the selectivity of formation of branched isomers on it did not exceed 30% even at 260–280°C and decreased to 3% as the reaction temperature increased to 400–450°C. The fraction of aromatization products was then more than 15%. A study of the influence of C₆–C₇ n-alkane additives on the isomerization of n-pentane on mordenite in the H-form under supercritical conditions at 260°C and 120 atm showed that a gradual decrease in the activity of this catalyst in the isomerization of n-pentane was related to the formation of heavier hydrocarbons.     

Superconducting transition temperature in mercury HTSC-cuprates under hydrostatic pressure

A study is made of the properties of the homologous series of mercury HTSC-cuprates HgBa₂Ca_n−1Cu_nO_2n +2+δ with n=1–8. Experiments are conducted under pressure for samples with n=1–5. The Hg-1223 and Hg-1234 phases were synthesized using a controlled high pressure chamber. The oxygen content of an initial mixture corresponding to the Hg-1234 phase was varied by changing the composition of the initial BaO/BaO₂ oxides. The dependence of the superconducting transition temperature T _c on the lattice constant a (and, therefore, on the oxygen content) and of T _c ^max and dT _c ^max /dp on n are convex upward up to n=4, 5. The maximum values always correspond to the Hg-1223 phase. Experimental T _c ^max (n) curves for the phases with n=1–6 and dT _c ^max /dp curves for n=1–5 are compared with Anderson’s theory (the so-called RVB model). A general analysis of these results indicates that the mercury cuprates have an ideal structure for HTSC. The Hg-1223 phase is the “champion” in this ideal structure and the critical temperature corresponding to this phase (T _c =135 K) is the highest at atmospheric pressure. Zh. éksp. Teor. Fiz. 113, 1474–1483 (April 1998)     

Secondary ion emission from bismuth under bombardment with Bi m ? and Au m ? cluster ions

The mass spectra of secondary cluster ions Bi _n ⁺ (n = 1–9) from bismuth sputtered by (6–21) keV Au _m ⁻ (m = 1–9) and Bi _m ⁻ (m = 1–5) cluster ions have been investigated. New features of manifestation of dense nonlinear cascades and thermal spikes have been revealed. It is concluded that the thermal spike regime makes a significant contribution to the mechanism of formation of small cluster ions, containing up to seven atoms for a bismuth target.     

Luminescence Properties of Metal(II)-Diethyldithiocarbamate Chelate Complex Particles and Its Analytical Application

In a suitable pH buffer solutions, sodium diethyldithiocarbamate (DDTC) reacts with some divalence metal ions M(II) to form (M–DDTC) _n chelate complex nanoparticles, which exhibit different luminescence properties. There is a strongest luminescence peak at 470 nm for the Co(II)–DDTC system, three peaks at 330, 470, and 630 nm for the Cu(II)–DDTC system, three peaks at 420, 470, and 630 nm for the Cd(II)–DDTC system, four peaks at 350, 400, 435, and 470 nm for the Ni(II)–DDTC system, two peaks at 408 and 470 nm for the Pb(II)–DDTC system, two peaks at 415 and 470 nm for the Fe(II)–DDTC system. The different luminescence properties of (M–DDTC) _n chelate complex nanoparticles was explained. Under the optimal conditions, the luminescence intensity of (Co–DDTC) _n chelate complex nanoparticles at 470 nm (F _{470 nm}) is linear to Co(II) concentration in the range of 0.012–1.44 μg/mL. The detection limit is 0.0023 μg/mL. A novel luminescence method has been proposed for the determination of cobalt in Vitamin B₁₂ samples, with satisfactory results.     

All-electron scalar relativistic calculation on the interaction between nitric monoxide and small gold cluster

An all-electron scalar relativistic calculation on Au _n NO (n = 1–10) clusters has been performed by using density functional theory with the generalized gradient approximation at the PW91 level. The small gold cluster would like to bond with nitric and the nitric monoxide molecule prefers to occupy the on-top and single fold coordination site. The Au _n structures in all Au _n NO clusters are only distorted slightly and still keep the planar structures. With the bend of Au-N-O bond, the structures of Au _n NO clusters evolve from the 2D structure to 3D structure. The most favorable adsorption between small gold cluster and nitric monoxide molecule takes place in the case that nitric monoxide molecule is adsorbed onto an odd-numbered pure Au _n cluster and becomes odd-numbered Au _n NO cluster with even number of valence electrons. The scalar relativistic effect strengthens the Au–Au, Au–N interaction and weakens the N–O interaction, appearing as the shorter Au–Au, Au–N bond-length and the longer N–O bond-length. The differences between our work and previous work are believed to be the reflection of the scalar relativistic effect.     

Mobility–diffusivity relationship for heavily doped organic semiconductors

The relationship between the diffusivity D _n and the mobility μ _n of chemically doped organic n-type semiconductors exhibiting a disordered band structure is presented. These semiconductors have a Gaussian-type density of states. So, calculations have been performed to elucidate the dependence of D _n /μ _n on the various parameters of this Gaussian density of states. Y. Roichman and N. Tessler (Appl. Phys. Lett. 80:1948, 2002), and subsequently Peng et al. (Appl. Phys. A 86:225, 2007), conducted numerical simulations to study this diffusivity–mobility relationship in organic semiconductors. However, almost all other previous studies of the diffusivity–mobility relationship for inorganic semiconductors are based on Fermi–Dirac integrals. An analytical formulation has therefore been developed for the diffusivity/mobility relationship for organic semiconductors based on Fermi–Dirac integrals. The D _n /μ _n relationship is general enough to be applicable to both non-degenerate and degenerate organic semiconductors. It may be an important tool to study electrical transport in these semiconductors.     

Fragmentation of sputtered Si<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>O<Stack><Subscript><Emphasis Type="Italic">m</Emphasis></Subscript><Superscript>+</Superscript></Stack> clusters: Release kinetic and dissociation energies

The spectra of kinetic energies of positive Si _n O _m ⁺ cluster ions (n = 2–5, m = 2–7) have been measured using a double focusing ion microanalyzer with reverse geometry at instants 10⁻⁵ to 10⁻⁴ s after emission. The dissociation energies have been determined within the evaporative ensemble model and the theory of unimolecular decay reactions. The results obtained are compared with the binding energies of neutral Si _n O _m clusters.     

Theoretical study of small clusters of manganese-doped gallium oxide: Mn(GaO)n and Mn2(GaO)n with n?=?1?7

Structures, electronic and magnetic properties of Mn and Mn₂ doped stoichiometric (GaO) _n clusters with n = 1−7 are studied in the framework of density functional theory. Doping of a Mn atom is found to be energetically favorable in (GaO) _n clusters and the equilibrium configurations are found to be determined by the metal–oxygen interactions. Mn prefers to maximize the number of Mn–O bonds by selecting a Ga site in the cluster which increases its coordination with oxygen. Addition of a Mn atom in Mn(GaO) _n clusters results into the ground state to be either ferromagnetic or antiferromagnetic depending on the Mn coordination number and the Mn–Mn bond-length in the given Mn₂(GaO) _n cluster.     

Assessment of the possibility of determination of the electrophysical characteristics of CdxHg1–xTe p+–n-structures using differential hall measurements

The process of reconstuction of the distribution profile of hole concentration in the p ⁺–n structure by the method of differential Hall measurements upon implantation of ions As⁺ (Е = 190 keV, D = 3.10¹⁴ cm^-2, j = 0.025 μA/cm²) into epitaxial films Cd _x Hg_1–x Te for x ~ 0.2, with the initial electron concentration and mobility n = 10¹⁴ cm^-3 and μ = 2∙10⁵ cm²∙V^–1∙s^–1 is numerically simulated. The dependences of degree of reconstruction of the hole-concentration distribution profile on the depth of a shunting n-layer and magnitude of the magnetic field, at which the electrophysical parameters of the p ⁺–n structure are measured, are calculated. The dependence of the limiting magnetic field determining the magnetic-field range for measurements on the n-layer depth is found. It is shown that in calculations one should use the conduction values measured at the same magnetic fields as the Hall coefficients for determination of the holeconcentration distribution profile using the Petritz model.     

Carrier mobility in nonstoichiometric n-Bi2Te3−x Sex solid solutions

A study has been made of the thermoelectric and galvanomagnetic properties of n-Bi₂Te_3−x Se_x solid solutions (x=0.3 and 0.36) in the temperature range 80–300 K. The lowest carrier concentrations, (0.8–1)×10¹⁸ cm⁻³, were obtained by displacing the solid solution from the stoichiometric to a Te-rich composition. At such carrier concentrations, the second subband in the conduction band of n-Bi₂Te_3−x Se_x is not filled, which results in a growth of mobility because of the absence of interband scattering, and brings about an increase of thermoelectric efficiency in the 80–120-K range. Fiz. Tverd. Tela (St. Petersburg) 39, 483–487 (March 1997)     

Femtosecond photodissociation dynamics of HNO3 after exitation of the S3-state at 200 nm

The photodissociation dynamics of HNO₃ in the electronic S₃ (2 ¹ A ^′ ) state leading to the fragments OH and NO₂ was investigated in real time. HNO₃ was prepared either in a fluorescence cell at room temperature (LIF probing of OH) or rotationally cold in a molecular beam (probing of NO₂ by three-photon ionization). A 2 ¹ A ^′ lifetime of 60–80 fs could be obtained from the experimental results, indicating essentially barrierless dissociation. In addition, secondary dissociation of internally excited nascent fragments NO₂ ^* leading to products NO(X ² Π) and O(³ P) with a characteristic dissociation time of 2.3 ps was observed. This time is surprisingly long when compared with dissociation lifetimes of NO₂ from the literature, obtained after direct photoexcitation. The discrepancy is explained by differences in the preparation conditions of the dissociative state of NO₂. Received: 12 November 1999 / Published online: 13 July 2000     

Recent Result of Muon Catalyzed t–t Fusion at RIKEN-RAL

We have measured X-rays and neutrons associated with the muon catalyzed t–t fusion process at the RIKEN-RAL Muon facility. In the X-ray measurement, we observed K_α and K_β X-rays originating from the muon sticking process in muon catalyzed t–t fusion, and obtained the K_α X-ray yield and the K_β/K_α intensity ratio. An average recoil energy of the (μ⁻α) atoms in a solid T₂ medium was determined from the observed Doppler broadening width of the K_α X-ray line. The obtained t–t fusion neutron has shown an exponential time spectrum with a single component and a continuous energy spectrum with a maximum energy of 9 MeV. We have determined the t–t fusion neutron yield, the t–t fusion cycling rate and the muon sticking probability from the neutron data. The obtained maximum neutron energy is a very peculiar value from the view point of the reaction Q value (11.33 MeV) with the three-particle decay mode at the exit channel: t + t → α + n + n + Q. The obtained neutron energy distribution was analyzed by a simple model with two neutron energy components; reasonable agreement has been obtained, suggesting a strong (n–α) correlation in the exit channel of the t–t muon catalyzed fusion reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Preparation and characterization of p–n heterojunction photocatalyst p-CuBi2O4/n-TiO2 with high photocatalytic activity under visible and UV light irradiation

In this article, the p-type CuBi₂O₄ powder was prepared by the solid-state reaction method. The p–n heterojunction photocatalyst p-CuBi₂O₄/n-TiO₂ was prepared by ball milling. The photocatalyst was characterized by X-ray powder diffraction (XRD), UV–Vis diffuse reflectance spectroscopy, scanning electron microscopy (SEM), and photoluminescence emission spectra. The photocatalytic activity of the photocatalyst was evaluated by photocatalytic reduction of Cr₂O₇ ²⁻ and photocatalytic oxidation of methyl orange (MO). The results showed that the photocatalytic activity of the p–n heterojunction photocatalyst p-CuBi₂O₄/n-TiO₂ was much higher than that of TiO₂ and the mixture of p-CuBi₂O₄–n-TiO₂ without ball milling under visible and UV light irradiation. The optimal percentage of doped p-CuBi₂O₄ is 20 wt%. Compared with pure TiO₂, the photoabsorption wavelength range of the photocatalyst is extended greatly toward visible light and improves the utilization of the total spectrum. The effect of ball milling time on the photocatalytic activity of the photocatalyst was also investigated. The optimum ball milling time is 6 h. The mechanisms of influence of p-CuBi₂O₄ on the photocatalytic activity of p-CuBi₂O₄/n-TiO₂ were also discussed by the p–n junction principle and the valance band theory.     

CORAL: QSPR models for solubility of [C60] and [C70] fullerene derivatives

Quantitative structure–property relationships (QSPRs) between the molecular structure of [C₆₀] and [C₇₀] fullerene derivatives and their solubility in chlorobenzene (mg/mL) have been established by means of CORAL (CORrelations And Logic) freeware. The CORAL models are based on representation of the molecular structure by simplified molecular input line entry system (SMILES). Three random splits into the training and the external validation sets have been examined. The ranges of statistical characteristics of these models are as follows: n = 18, r ² = 0.748–0.815, s = 15.1 –17.5 (mg/mL), F = 47–71 (training set); n = 9, r ² = 0.806–0.936, s = 12.5–17.5 (mg/mL), F = 29–103 (validation set).     

Asymptotic Behavior of the Magnetization Near Critical and Tricritical Points via Ginzburg–Landau Polynomials

The purpose of this paper is to prove connections among the asymptotic behavior of the magnetization, the structure of the phase transitions, and a class of polynomials that we call the Ginzburg–Landau polynomials. The model under study is a mean-field version of a lattice spin model due to Blume and Capel. It is defined by a probability distribution that depends on the parameters β and K, which represent, respectively, the inverse temperature and the interaction strength. Our main focus is on the asymptotic behavior of the magnetization m(β _n ,K _n ) for appropriate sequences (β _n ,K _n ) that converge to a second-order point or to the tricritical point of the model and that lie inside various subsets of the phase-coexistence region. The main result states that as (β _n ,K _n ) converges to one of these points (β,K), . In this formula γ is a positive constant, and is the unique positive, global minimum point of a certain polynomial g. We call g the Ginzburg–Landau polynomial because of its close connection with the Ginzburg–Landau phenomenology of critical phenomena. For each sequence the structure of the set of global minimum points of the associated Ginzburg–Landau polynomial mirrors the structure of the set of global minimum points of the free-energy functional in the region through which (β _n ,K _n ) passes and thus reflects the phase-transition structure of the model in that region. This paper makes rigorous the predictions of the Ginzburg–Landau phenomenology of critical phenomena and the tricritical scaling theory for the mean-field Blume–Capel model.