Singlet-Singlet Electronic Excitation Energy Transfer in a Bichromophore Cooled in a Supersonic Jet

The fluorescence excitation spectra and polarization of the fluorescence of a bichromophore cooled in a supersonic jet are measured. The bichromophore consists of 2,5-diphenyloxazole (PPO) and 1-(5′-phenyl-1′, 3′-oxazole-2′-yl)-4-(5′-phenyl-1′,3′,4′-oxadiazole-2′-yl)-benzene (POPDP) connected by the methylene bridge -(CH₂)-. Based on the analysis of these components and theoretical calculations, it has been proven that the total intramolecular singlet-singlet transfer of the energy of electronic excitation from the energy donor PPO to the acceptor POPDP occurs in a time of 10⁻¹² sec. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 460–463, July–August, 2005.     

Luminescence characteristics of new substituted coumarins

Fluorescence spectra at 298 and 77 K and phosphorescence spectra at 77 K have been measured for five new compounds. Fluorescence and phosphorescence quantum yields have been measured by comparison with a standard (8-methoxypsoralen). Phosphorescence lifetimes at 77 K have been found for 2-hydrazyl-3,4-cyclopentyl-14,14-dimethylpryanocoumarin (1.60 msec); 2-hydrazyl-3,4-cyclohexyl-7-methoxycoumarin (1.35); 3,4-phenyl-4′,5′-cyclohexylpsoralen (2.50); 4′-methyl-3,4-cycloheptylpsoralen (1.10); and 4′,5′-dimethyl-3,4-cyclohexylpsoralen (1.25). The basic channel of energy deactivation for 3,4-phenyl-4′,5′-cyclohexylpsoralen; 4′-methyl-3,4-cycloheptylpsoralen; and 4′,5′-dimethyl-3,4-cyclohexylpsoralen is radiative transfer. Energies of the lowest excited triplet states have been calculated using an INDO/S quantum-chemical method.     

Synthesis of Novel Eu(III) Luminescent Probe Based on 9- Acridinecarboxylic Acid Skelton for Sensing of ds-DNA

Eu(III)-9-acridinecarboxylate (9-ACA) complex was synthesized and characterized by elemental analysis, conductivity measurement, IR spectroscopy, thermal analysis, mass spectroscopy, ¹H-NMR, fluorescence and ultraviolet spectra. The results indicated that the composition of this complex is [Eu(III)-(9-ACA)₂(NCS)(C₂H₅OH)₂] 2.5 H₂O and the oxygen of the carbonyl group coordinated to Eu(III). The interaction between the complex with nucleotides guanosine 5′- monophosphate (5′-GMP), adenosine 5′-diphosphates (5′-ADP), inosine (5′-IMP) and CT-DNA was studied by fluorescence spectroscopy. The fluorescence intensity of Eu(III)-9-acridinecarboxylate complex was enhanced with the addition of CT-DNA. The effect of pH values on the fluorescence intensity of Eu(III) complex was investigated. Under experimental conditions, the linear range was 9–50 ng mL⁻¹ for calf thymus DNA (CT- DNA) and the corresponding detection limit was 5 ng mL⁻¹. The results showed that Eu(III)-(9-ACA)₂ complex binds to CT-DNA with stability constant of 2.41 × 10⁴ M .     

Laser induced long-lived emission spectra of laser dyes in rigid glasses at 77 K

Phosphorescence decay of 3-(2′-N-methylbenzimidazolyl)-7-N, N-diethylaminocoumarin; 2,3,5,6-1H, 4H-tetrahydro-8-methylquinolizino-〈9, 9a, 1-gh〉 coumarin; 2,3,5,6-1H, 4H-tetrahydro-8-trifluormethylquinolizino-〈9,9a,1-gh〉 coumarin; 9(10H)-acridone; 9-aminocridine hydrochloride, 1-hydrate and 2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3, 4-oxadiazole dyes in EPA glass at 77 K have been recorded using N₂ laser. The results were used to determine lifetimes. Emission intensities from the first two dyes have been examined in relation to dye concentration and excitation intensity. The results are discussed.     

Use of PM6 quantum-chemical calculations in studying the properties of antioxidants in the biological environment

The energies of formation, enthalpies, and entropies of the conformers of 1-(carboxy)-1-(N-methylamide)-2-(3′,5′-di-tert-butyl)-4-hydroxyphenyl)-propionic acid and sodium and potassium 1-(carboxy)-1-(N-methylamide)-2-(3′,5′-di-tert-butyl)-4-hydroxyphenyl)-propionates are calculated by quantum-chemical methods in the PM6 approximation. A doubling of signals in the ¹H NMR spectrum of the first conformer is observed, which merge into singlets when the compound is heated. Changes in the structure of the conformers and donor-acceptor complexes (solvates) occur with the preservation of the metal-ligand coordination bond. Calculations of the characteristics of 1-(carboxy)-1-(N-methylamide)-2-(3′,5′-di-tert-butyl)-4-hydroxyphenyl)-propionic acid and sodium and potassium 1-(carboxy)-1-(N-methylamide)-2-(3′,5′-di-tert-butyl)-4-hydroxyphenyl)-propionates in the PM6 approximation make it possible to predict the structure and properties of the solvated structures. The energies of homolysis of the H-O bond D _(OH) are calculated, and a linear dependence of the antioxidant activity on D _(OH) for the structures of the studied compounds is demonstrated. The results make it possible to predict the properties of antioxidants in the biological environment.     

Photophysical parameters for potential vapour-phase dye-laser media

The fundamental photophysical parameters of the organic scintillators, anthracene, 9, 10 dimethyl antracene (DMA), 9, 10 diphenyl anthracene (DPA), 2-(1-napthyl)-5-phenyloxazole (α-NPO) and 2, 2′-p-phenyl bis (5-phenyloxazole) (POPOP), were investigated in the liquid and vapour phases. Their ground state, triplet-triplet and fluorescence spectra were determined and accurate extinction coefficients obtained. Photodecomposition of POPOP vapour under 337 nm excitation was investigated in detail and a photodecomposition quantum yield of 1.1×10⁻² obtained at 568 K. The POPOP triplet state in the vapour phase is quenched by the addition of 1, 3, 5, 7 cyclo-octatetraene and a quenching rate constant of 2.9×10¹⁰ M⁻¹ s⁻¹ was determined.     

A new polymeric material for optical switching

′ -(2^′′,4^′′,6^′′-trichlorophenazoamino)-phenazo-4-nitrobenzene, was studied. Large nonresonant optical nonlinearity (χ⁽³⁾≥10^-28 C⁴m/J³ or 10^-9 esu) and fast response time (t<20 ps) were measured by forward degenerate four-wave mixing experiment. Optical bistable behavior in a quasi-waveguide interferometer with the thin film of the material was observed. The potential of the material for optical switching was evaluated. Received: 20 July 1998/Revised version: 11 September 1998     

New Luminescent Bioprobes Eu(lll)-phloroglucinol Derivatives and Their Spectrofluorimetric, Electrochemical Interactions with Nucleotides and DNA

Two new ligands derived from phloroglucinol 2-{[(4-methoxy benzoyl ) oxy ] } methyl benzoic acid[L1] and 2-{[(4-methyl benzoyl )oxy] methyl} benzoic acid[L2] were synthesized. The solid complex Eu(III)-L2 has been synthesised and characterized by elemental analysis ,UV and IR spectra. The reaction of Eu(III) with the two synthesized ligands has been investigated in I = 0.1 mol dm^-3 p-toluene sulfonate by cyclic voltammetry and square wave voltammetry. The reaction of Eu (III)–L1 and Eu (III)–L2 binary complexes with nucleotide 5′-AMP , 5′-ADP ,5′-ATP , 5′- GMP , 5′-IMP , and 5′-CMP has been investigated using UV, fluorescence and electrochemical methods. The experimental conditions were selected such that self-association of the nucleotides and their complexes was negligibly small, that is, the monomeric complexes were studied. The interaction of the Eu(III)–L1 or L 2 solid complexes with calf-thymus DNA has been investigated by fluorescence and electrochemical methods including cyclic voltammetery(CV) ,differential pulse polarography (DPP) and square wave voltammetry (SWV) on a glassy carbon electrode. The fluorescence intensity of Eu(III)-L2 complex was enhanced with the addition of DNA. Under optimal conditions in phosphate buffer pH 7.0 at 25 °C the linear range is 3–20 μM for calf thymus DNA (CT–DNA) and the corresponding determination limit is 1.8 μM.     

Dielectronic recombination rate coefficients for the Ni ${\sf I}$ isoelectronic sequence

Ab initio calculations of the total dielectronic recombination (DR) rate coefficients for thirteen ions along the NiI isoelectronic sequence in the ground state (Kr⁸⁺, Mo¹⁴⁺, Ag¹⁹⁺, Sn²²⁺, Xe²⁶⁺, Nd³²⁺, Gd³⁶⁺, Yb⁴²⁺, W⁴⁶⁺, Au⁵¹⁺, Pb⁵⁴⁺, At⁵⁷⁺, and U⁶⁴⁺) have been performed using the flexible atomic code. The level-by-level calculations are performed for evaluating the DR contributions through the relevant Cu-like autoionizing inner-shell excited 3l¹⁷4l^′n^′′l^′′ and 3l¹⁷5l^′n^′′l^′′ configuration complexes with n^′′ ≤15, which are associated with Δn=1 and Δn=2 core-excitations, respectively. The usual (n^′′)^-3 scaling law is found to be invalid for low-Z ions. A level-by-level extrapolation procedure is employed to obtain the contributions through higher n^′′ complexes. The decays to autoionizing levels followed possibly by radiative cascades could enlarge the rates at relatively high temperature by a factor up to about 23%. For the whole isoelectronic ions the contributions from 3s²3p⁶3d⁹ 4l^′n^′′l^′′ dominate the total DR rates while the contributions from the 3s²3p⁶3d⁹ 5l^′n^′′l^′′ configuration complexes are about 10-20% at relatively high temperature. On the basis of the calculated results, a general analytic formula for the total DR rate coefficients of all the ions with 36≤Z ≤92 along the NiI isoelectronic sequence is constructed. The comparisons of the rates obtained from the general formula with those from the detailed calculations show that the formula is of high precision, generally better than 3% accuracy for electron temperatures kT≥0.1E_I, where E_I is the ionization energy of the Cu-like ion. The present DR rates at temperature above 1.0E_I are larger than the previously published data by a factor above 30%. The commonly used semiempirical formula proposed by Burgess and modified by Merts may overestimate the rates at high temperature by a factor of about 2 for low-Z ions.     

New one-pot synthesis of spiro[furo[2,3-<Emphasis Type="Italic">d</Emphasis>]pyrimidine-6,5′-pyrimidine]pentaones and their sulfur analogues

Reaction of barbituric acid (BA), 1,3-dimethyl barbituric acid (DMBA) and 2-thiobarbituric acid (TBA) with cyanogen bromide and various aldehydes in presence of triethylamine afforded a new class of heterocyclic stable 5-alkyl and/or 5-aryl-1H, 1′H-spiro[furo[2,3-d]pyrimidine-6,5′-pyrimidine]2,2′,4,4′,6′(3H,3′H,5H)-pentaones which are dimeric forms of barbiturate (uracil and thiouracil derivatives) at 0 °C to ambient temperatures. Structure elucidation is proved by X-ray crystallography, ¹H NMR, ¹³C NMR, FT-IR, CHN and mass analyses techniques. Mechanisms of the formations are discussed.     

Measurement of vibrational energy transfer of OH (A2Σ+,v′=1→0) in low-pressure flames

2 Σ⁺) was measured in a low-pressure H₂/O₂ flame for three rotational levels of OH (v^′=1). Rate coefficients for collisions with H₂O and N₂ were determined. At 1600 K, k_VET (N₂) is (in 10^-11 cm³s^-1) 10.1±2, 6.1±1.8, and 3.8±1.3 for N^′=0, 5, and 13, respectively. The k_VET (H₂O) is <1.1±1.8. The k_Q (N₂) is <2.4±8 for both vibrational levels. The k_Q (H₂O) in v^′=1 is 59.1±6.5, 54.7±6.4, and 54.9±6.6 for N^′=0, 5, and 13, respectively, and, determined indirectly, 74.6±10.4, 70.6±10.3, and 63.4±7.3 for N^′=0, 5, and 13 in v^′=0. A multi-level model of OH population dynamics, which is being developed for the quantitative simulation of experimental LIF spectra, was extended to include VET. It was attempted to simulate state-to-state-specific VET coefficients for N₂ collisions. From these simulations it appears that angular momentum conservation does not determine the N dependence of the vibrational relaxation step. Received: 9 September 1996/Revised version: 6 January 1997     

The temperature dependences of electromechanical properties of PLZT ceramics

The mechanical and electrical properties in lanthanum modified lead zirconate-titanate ceramics of 5/50/50 and 10/50/50 were studied by mechanical loss Q ^{- 1}, Young's modulus E, electric permittivity ε and tangent of dielectric loss of angle tgδ measurements. The internal friction Q ^{- 1} and Young modulus E measured from 290 K to 600 K shows that Curie temperature T_C is located at 574 K and 435 K (1^st cycle of heating) respectively for ceramic samples 5/50/50 and 10/50/50. The movement of T_C in second cycle of heating to lower temperature (561 K for 5/50/50 and 420 K for 10/50/50) has been observed. Together with Q ^{- 1} and E measurements, temperature dependences of ε=f(T) and tgδ=f(T) were determinated in temperature range from 300 K to 730 K. The values of T_C obtained during ε and tgδ measurements were respectively: 560 K for 5/50/50 and 419 K for 10/50/50. These temperatures are almost as high as the temperatures obtained by internal friction Q ^{- 1} measurements in second cycle of heating. In ceramic sample 10/50/50 the additional maximum on internal friction Q ^{- 1} curve at the temperature 316 K was observed.     

Electric conductivity of siliconorganic polyhomoconjugated polymer films upon adsorption of volatile organic compounds

The electrophysical parameters of polyhomoconjugated organosilicon polymer films are studied, and variation of their conductivity under the action of water, toluene, and ammonia vapors is measured. Films 1–2 μm thick are prepared by the casting method from a solution of poly[2,2-dimethyl-2-sila-1,3-propylene-(4, 4′-biphenylene)]a (polymer I) and poly[2-n -butyl-2-phenyl-2-sila-1,3-propylene-(4, 4′-biphenylene)]a (polymer II). In the course of conductivity measurement, organic volatiles and water are adsorbed due to a stepwise rise in the pressure over the sample from 10⁻³ to 10⁻¹ Torr. The initial values of the resistivity of polymers I and II are estimated as 4 × 10⁹ Θ cm. Exposure of the films to organic volatile vapors and water vapor causes a reversible change in the conductivity of the films. For polymer-I films, the conductivity upon adsorption of ammonia, toluene, and water vapors exceeds the initial value by 150, 10, and 600 times, respectively. The sensitivity of polymer-II films is lower by a factor of 1.5–2.0. The time of conductivity variation as the vapors are injected and evacuated is within 10 and 30 s, respectively. The mechanisms of organic volatile and water adsorption on the surface of polyhomoconjugated organosilicon polymer films are compared with adsorption mechanisms on the surface of π-polyconjugated organic films.     

Synthesis,Characterization Luminiscence Studies and Microbial Activity of Ethylenediamine Ruthenium (II) Complexes with Dipyridophenazine Ligands

Three symmetric ligands 7-methyl dipyrido-[3,2-a;2′,3′-c]phenazine (dppz-CH₃), 7-nitro dipyrido-[3,2-a;2′,3′-c]phenazine (dppz-NO₂) and benzo[i]dipyrido-[3,2-a;2′,3′-c]phenazine (dppn) and their ruthenium(II) complexes [Ru(en)₂(L)][ClO₄]₂ (en= ethylenediamine), L= dppz-CH₃, dppz-NO₂ and dppn have been synthesized and characterized by IR, ¹H, ¹³C NMR and Mass spectra. The interactions of these complexes with calf thymus DNA have been investigated by spectrophotometric, spectrofluorimetric, circular dichroism, viscosity and thermal denaturation studies. As the planar extension of the intercalative ligand increases, the interaction of the complex with DNA increases, indicating that the size and shape of the intercalalative ligand has a marked effect on the strength of interaction. The plot of log K versus log [Na⁺] yield a slope of -1.26, -1.53, -1.60 for the complexes 1, 2 and 3 respectively. These three complexes have been found to promote the cleavage of plasmid pBR 322 DNA upon irradiation.     

Iron based carbon nanocomposites for electromagnetic wave absorber with wide bandwidth in GHz range

The electromagnetic wave absorption properties of resin compacts containing 40 vol. % composite powders of α-Fe/C(a), and Fe₃C/C(a) were characterized in a frequency range of 0.05–26.5 GHz, according to a conventional reflection/transmission technique. The real part (ε_r ^′) and the imaginary part (ε_r ^′′) of relative permittivity were constantly low in the 2–14 GHz (ε_r ^′= ∼12.4 and ε_r ^′′= ∼0.6) for α-Fe/C(a) resin composites, and in the 1–26.5 GHz (ε_r ^′= ∼9.6 and ε_r ^′′= ∼0.8) for Fe₃C/C(a) ones. The imaginary part (μ_r ^′′) of relative permeability exhibited wide peaks in the 1–9 GHz range for α-Fe/C(a), and in the 2–26.5 GHz range for Fe₃C/C(a) owing to their different magnetocrystalline anisotropy field values. Consequently, the resin compacts with 40 vol. % α-Fe/C(a), and Fe₃C/C(a) powders provided good electromagnetic wave absorption performances (reflection loss <-20 dB) in ranges of 4.3–8.2 GHz, and 9–26.5 GHz over absorber thicknesses of 1.8–3.3 mm, and 1.0–2.4 mm, respectively. PACS 76.50.+g; 61.46.+w; 75.50.Bb; 75.30.Gw; 75.20.En     

Correlations in 11B NMR spectra of dihalo derivatives of bis(1,2-dicarbollyl)cobalt(III)

In the ¹¹B NMR spectra of dihalo derivatives of bis(dicarbollyl)cobalt(III), we have identified a correlation between the ¹¹B NMR chemical shifts of substituted boron atoms and boron atoms found in other positions on the carborane skeleton. We have observed an increased shielding effect for fluorine atoms (compared with other halogens), manifested in an upfield shift of the ¹¹B NMR signals for antipodal and trans boron atoms. For the fluorine-containing compound Bu₄N⁺ [8,8′-F₂-3,3′-Co(1,2-C₂B₉H₁₀)₂]⁻, we propose the following sequence of electron density transfer: B(8) → {B(6) and B(10)} → B(4, 7). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 547–549 (cont.), July–August, 2006.     

Theoretical investigation of the local lattice structure of Mn 2+ ion doped in tetragonal K 2ZnF 4 crystal

The complete energy matrices for a d⁵configuration ion in a tetragonal ligand-field has been constructed on the basis of the complete set of basis of d⁵configuration (252 dimension), and the relationship between the low-symmetry EPR parameters b₂ ⁰ ,b₄ ⁰ and the local distortion parameters has been established based on the complete energy matrices. As an application, we have studied the EPR parameters and the local lattice structure of Mn²⁺ ion doped in tetragonal K₂ZnF₄ system. The calculation indicated that the local lattice structure around a tetragonal Mn²⁺ ion center has an expansion distortion. Simultaneously, the local lattice structure parameters R₁ =2.0727 ?, R₂ =2.0801 ? at room temperature (295 K) and R₁ ^′ = 2.0439 ?, R₂ ^′ =2.05478 ? at low temperature (4.2 K) are determined.     

Structure and Luminescence Properties of Monomeric and Dimeric Re(I) Complexes with Dicarboxylic Acid-2,2′-Bipyridine Ligands

The luminescence properties of Re(I) complexes incorporating the dcbpy ligand (dcbpy = n,n′-dicarboxylic acid-2,2′-bipyridine; n = 3, 4) were investigated as well as their utility as Pb²⁺ sensors. An unusual binuclear complex of the 3,3′- species was isolated. The emission intensity and lifetime for all complexes were found to be highly temperature-dependent, with quantum yields and lifetimes dramatically greater at 77 K than at room temperature. The monomeric 3,3′-dcbpy Re(I) complex demonstrates nearly 1:1 binding with Pb²⁺. The effect of this lead binding on the emission intensity is great, but the low quantum yields allow only for detection of the metal at the micromolar level. The binding of Pb²⁺ to the 4,4′-dcbpy complex is modeled and the interaction is demonstrated to involve two binding sites.     

Influence of heterojunction interface on exciplex emission from organic light-emitting diodes under electric fields

In this paper, electroluminescence from organic light-emitting diodes based on 2-(4^′-biphenyl)-5-(4^′′-tert-butylphenyl)-1,3,4-oxadiazole (PBD) and N,N^′-diphenyl-N,N^′-bis(3-methylphenyl)-(1,1^′-biphenyl)-4,4^′-diamine (TPD) is reported. Based on the exciplex emission from the TPD/PBD interface under high electric fields, the influence of the TPD/PBD interface on exciplex emission was investigated by increasing the number of TPD/PBD interfaces while keeping both the total thickness of the TPD layer and the PBD layer constant in the multiple quantum-wells (MQW) device ITO/TPD/[PBD/TPD]_n/PBD/Al (n is the well number that was varied from 0 to 3). Our experimental data shows that exciplex emission can be enhanced by suitably increasing the well number of this kind of MQW-like device. PACS 78.60.Fi; 78.55.Kz; 73.61.Ph