Effect of hydrophobicity of cationic carbocyanine dyes DiOC<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> on their binding to anionic surfactant micelles

The interaction of a series of cationic dialkyloxacarbocyanine perchlorate (DiOC _n ) dyes of different degrees of hydrophobicity with micelles of an anionic surfactant, sodium dodecylsulfate (SDS), has been studied spectrophotometrically in aqueous solutions. The Benesi–Hildebrand equation was used to calculate binding constants (K _b ) of the dyes to surfactant micelles, the fraction of dye bound to the micelles (f _mic ), and the standard free-energy change (ΔG ⁰) for the transfer of dye from the aqueous to micellar phase. It has been shown that the interaction of oppositely charged dye molecules and surfactant micelles is controlled by both electrostatic and hydrophobic interactions. A small increase in dye hydrophobicity due to lengthening of the hydrocarbon radical has been shown to cause an abrupt nonlinear increase of the fmic value. This points to a key role of hydrophobic interactions in the binding of dye molecules with the micelles.     

Quantum-chemical study of effect of conjugation on structure and spectral properties of C105 sensitizing dye

The structure and spectral properties of two organic ruthenium complexes used as sensitizing dyes for solar batteries (well-known N3 dye and its selenophene-conjugated analogue C105 ([Ru(bpy)(bpysef)(COOH)₂(NCS)₂] (bpy = 2,2′-bipyridine, bpysef = 4,4′-bis(5-hexylselenophene-2-yl)2,2′-bipyridine)) are comparatively studied within the density functional method. It is shown that the conjugation of the bipyridine ligand with selenophene affects the electronic structure of the C105 dye. A multilevel model for interpreting the electronic spectra of dyes is proposed based on the analysis of the shapes of molecular orbitals. The nature of the absorption bands of these ruthenium complexes in the region of 300–800 nm is explained. It is found that, in the polar acetonitrile solvent, these dyes are negatively solvatochromic, which agrees with the current classical views on the effect of the solvent on the shape of electronic absorption spectra of related compounds.     

Determination of the Constants of Binding of Acridine Dyes with Micelles of Sodium Dodecyl Sulfate Using the Quenching of Delayed Fluorescence by Heavy Atoms

The constants of binding dye molecules with the micelles of sodium dodecyl sulfate are determined using quenching of delayed fluorescence of acridine dyes by sodium iodide in aqueous–micellar solutions. Kinetic equations have been composed that describe the processes of deactivation of the excited states of dyes. By solving these equations at the concentration of the quencher sodium iodide corresponding to the minimum lifetime of triplet states and at the concentration of micelles corresponding to the least value of the delayed fluorescence quenching rate constants, we obtained the constants of binding dyes with micelles equal to 1.3·10⁷, 2.9·10⁷, and 3.1·10⁷ M^–1 for trypaflavine, acridine orange, and acridine yellow, respectively. We calculated the rate constants of quenching of the triplet states of the molecules of dyes by iodide ions (I ^–) that decreased in transition from trypaflavine to acridine orange and acridine yellow.     

RF exciplex halogen source of UV radiation on an argon-xenon-chlorine mixture

An exciplex halogen source of UV radiation that is excited by an rf transverse discharge is studied experimentally. The active medium of the source is an Ar-Xe-Cl₂ mixture kept at a low pressure (100–1000 Pa), and its working spectral range is 220–450 nm. The radiation spectrum contains 235 nm XeCl(D-X), 257 nm Cl₂(D′-A′), 306 nm XeCl(B-X), 390 nm XeCl(C-A), and 430 nm XeCl(B-A) lines. The results of optimization of the UV power as a function of the pressure, Ar-Xe-Cl₂ mixture composition, and excitation power are reported.     

Lineshapes of the even mp1/2 5n(p′/f′) autoionizing resonances of Ar, Kr and Xe

The even parity mp_1/2 ⁵np^′ and mp_1/2 ⁵nf^′ autoionizing resonances of Ar, Kr, and Xe (m=3,4,5) were investigated experimentally and theoretically by one-photon excitation from lower-lying intermediate levels. In particular, high resolution measurements for the Ar(nf^′), Kr(12p^′,8f^′), and Xe(8p^′) resonances are reported; lineshape parameters for these resonances have been derived by a Fano-type analysis, thus yielding reduced resonance widths. The experimental spectra and the resonance parameters are compared with theoretical calculations which are based on the configuration interaction Pauli–Fock approach including core polarization. The measured and calculated lineshapes are in good agreement. In addition, theoretical predictions are presented for other resonances, which have not yet been observed experimentally, and some systematic trends are elucidated.     

Thioflavin T Displays Enhanced Fluorescence Selectively Inside Anionic Micelles and Mammalian Cells

Thioflavin T (ThT) has been widely employed to detect amyloid fibrils in tissues and recently in presence of SDS micelles. However, the contribution of membranes or micelles to ThT fluorescence has never been investigated. In this paper, we show for the first time that the anionic micellar microenvironment of SDS has a profound impact on the absorption and fluorescence spectra of ThT in sharp contrast to cationic (CTAB) and neutral micelles (Triton X-100 & Tween 20). Unlike CTAB or Triton X-100 or Tween 20 micelles, formation of SDS micelles shifts the λ_max for ThT absorption from 412 nm in buffer to 428 nm inside the micelle, with a 28% increase in the peak molar absorptivity and a ∼13 fold increase in ThT fluorescence (λ_max = 489 nm). Extending these observations to cell plasma membranes, we show that ThT can quickly enter and appear selectively fluorescent inside mammalian cells like BHK21 and HT29, against a dark background owing to negligible fluorescence from free ThT in aqueous medium. The above results suggest that ThT can be a useful probe for live cell imaging and for selectively labeling micelles on the basis of the charge in the polar headgroup. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

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.     

Spectroscopic Study of the Interaction of Styrylcyanine Dyes Sbo,Sil and Their Derivatives with Bovine Serum Albumin

The spectral-luminescent characteristics of newly synthesized styrylcyanine dyes on the base of dyes Sbo ((E)-2-(4-(dimethylamino)styryl)-3-methylbenzo[d]oxazol-3-ium iodide) and Sil ((E)-2-(4-(dimethylamino)styryl)-1,3,3-trimethyl-3H-indolium perchlorate) in aqueous solutions without and in the presence of bovine serum albumin (BSA) were studied. It was established that the absorption spectra of dyes Tol-6, Dbo-10 and Dil-10 with increasing amount of BSA appear new bands with λ_max = 505 nm, λ_max = 512 nm and λ_max = 566 nm, respectively, whose intensity increases in proportion to the amount of albumin. The intensity of the glow of the main band of fluorescence in the presence of BSA sharply increases. The binding constant (K) and the number of binding sites (N) of studied dyes with BSA were determined. The dependence of binding constants with BSA on the dipole moment of dye molecules was determined, which indicates that besides electrostatic forces of attraction between molecules styrylcyanine dyes with BSA, hydrophobic interactions are essential.     

Photophysical and Analyte Sensing Properties of Cyclometalated Ir(III) Complexes

The synthesis of some heteroleptic, cyclometalated iridium(III) complexes is described. The utility of these [Ir(ppy)₂(N-N)]Cl (ppy = 2-phenylpyridine and N-N = substituted bipyridine, biquinoline, or phenanthroline) complexes as luminescence-based sensors is assessed. The emission intensity of an Ir(III) complex featuring the 3,3′-H_ndcbpy ligand (H_ndcbpy = dicarboxylic acid-2,2′-bipyridine; n = 0,1,2 to indicate deprotonated, mono- and diprotonated species, respectively) is seen to increase in the presence of Pb(II). Insight into the structure and analyte-sensing capability is achieved by X-ray crystallography in conjunction with computational modeling. Complexes incorporating carboxylic acid-functionalized bipyridine and biquinoline as the polypyridyl ligand show pH sensitivity while similar phenanthroline complexes do not.     

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.     

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.     

Lattice mechanical properties of noble and transition metals

A model pseudopotential depending on an effective core radius but otherwise parameter free is used to study the interatomic interactions, phonon dispersion curves (inq and r-space analysis), phonon density of states, mode Grüneisen parameters, dynamical elastic constants (C ₁₁,C ₁₂ andC ₄₄), bulk modulus (B), shear modulus (C′), deviation from Cauchy relation (C ₁₂–C ₄₄), Poisson’s ratio (σ), Young’s modulus (Y), behavior of phonon frequencies in the elastic limit independent of the direction (Y ₁), limiting value in the [110] direction (Y ₂), degree of elastic anisotropy (A), maximum frequencyω _max, mean frequency 〈ω〉, 〈ω ²〉^1/2=(〈ω〉/〈ω ⁻¹〉)^1/2, fundamental frequency 〈ω ²〉, and propagation velocities of the elastic constants in Cu, Ag, Au, Ni, Pd, and Pt. The contribution of s-like electrons is calculated in the second-order perturbation theory for the model potential while that of d-like electrons is taken into account by introducing repulsive short-range Born-Mayer like term. Very recently proposed screening function due to Sarkar et al. has been used to obtain the screened form factor. The theoretical results are compared with experimental findings wherever possible. A good agreement between theoretical investigations and experimental findings has proved the ability of our model potential for predicting a large number of physical properties of transition metals.     

Rare t-quark decays t → clj+lk? and t → c?jvk induced by doublets of scalar leptoquarks within the minimal four-color-symmetry model

The rare t-quark decays t → cl _j ⁺ l _k ⁻ and t → cṽ _j k _k induced by scalar-leptoquark doublets are considered within the minimal model involving four-color quark-lepton symmetry and the Higgs mechanism of quark and lepton mass splitting. The partial widths with respect to the decays being considered and the total widths Γ(t → cl ⁺′l ⁻) = Σ_j,k Γ(t → cl _j ⁺ l _k ⁻ ) and Γ(t → cl ⁺′l ⁻) = Σ_j,kΓ(t → cṽ _j v _k ) with respect to, respectively, the charged leptonic and neutrino modes are calculated. It is shown that, at scalar-leptoquark masses higher than the t-quark mass (m _S > m _t), the branching ratios for these modes are Br(t → cl ⁺′l ⁻) ≈ (3.5−0.4) × 10⁻⁵ and Br(t → cṽ′v) ≈ (7.1−0.8) × 10⁻⁵ at m _s = 180–250 GeV and an appropriate value of the leptoquark-mixing angle (sin β ≈ 0.2) and can increase for m _S < m _t to Br(t → cl ⁺′l ⁻) ≈ 0.03−0.002 and Br(t → cl ⁺′l ⁻) ≈ 0.46−0.05 for the charged mode at m _S = 150–170 GeV for sin β ≈ 1 and sin β ≈ 0.2, respectively. In the cases being considered, t-quark decays to pairs of charged leptons can be accessible to detection at LHC. In the last case, these decays could manifest themselves (for example, in dilepton events) at the Tevatron as well. Original Russian Text ? P.Yu. Popov, A.D. Smirnov, 2006, published in Yadernaya Fizika, 2006, Vol. 69, No. 6, pp. 1006–1016.     

The Susceptibility of Non-UV Fluorescent Membrane Dyes to Dynamical Properties of Lipid Membranes

Fluorescence spectroscopy and microscopy are powerful techniques to detect dynamic properties in artificial and natural lipid membrane systems. Unfortunately, most fluorescent dyes that sense dynamically relevant membrane parameters are UV sensitive. Their major disadvantage is a high susceptibility to fluorescence bleaching. Additionally, the risk for hazardous damages in biological components generally increases with decreasing excitation wavelength. Therefore the use of non-UV–sensitive membrane dyes would provide significant advantage, particularly for applications in fluorescence microscopy, which usually implies high local excitation intensities. We applied steady-state fluorescence spectroscopy techniques to several UV and non-UV membrane dyes to detect and compare dynamically relevant excitation and emission characteristics. Small unilamellar liposomes (composed of egg yolk phosphatidylcholine) served as a model system for biological membranes. The dynamic properties of the membranes were varied by two independent parameters: the intrinsic cholesterol content (0–50 mol%) and temperature (10–50°C). We tested four non-UV–sensitive membrane dyes: 9-diethylamino-5H-benzophenoxazine-5-one (Nile Red), 4-(dicyanovinyl)julolidine (DCVJ), N-(3-triethylammoniumpropyl)-4-(4-(dibutylamino)styryl) pyridinium dibromide (FM 4-64), and 1,1-dioctadecyl-3,3,3,3-tetramethylindocarbocyanine perchlorate (DiIC₁₈). We also tested three derivatives of DiIC₁₈: DiIC₁₆ and DiIC₁₂ differ in acyl chain length and Fast-DiIC₁₈ provides double bonds between hydrocarbon atoms. The spectral results were compared to established fluorescence characteristics of four UV membrane dyes: the anisotropy of 1-6-phenyl-1,3,5,-hexatrien (DPH), two derivatives of DPH (TMA-DPH and COO^–-DHP), and the generalized polarization of 6-dodecanoyl-2-dimethyl-aminonaphthalene (Laurdan). Our results indicate that the tested non-UV dyes do not reveal dynamically relevant membrane parameters in a direct manner. However, spectral characteristics make DiIC₁₈, Nile Red, and DCVJ promising probes for the microscopic detection of lateral lipid organization, an indirect indicator of membrane dynamics. In particular, DiIC₁₈ showed very selective shifts in the emission spectra at defined temperatures and cholesterol contents that have not been reported elsewhere.     

Time-resolved Stark effect in rapidly varying fields

The cycle-averaged ac Stark effect associated with the ^[ A _]2Σ⁺v^′=2?^[ X _]2Π1/2v^′=0 two-photon absorption of NO at intensities between 7.7 and 15.2 TW cm^-2 has been characterized in real time through a synergic combination of bichromatic laser experiments and quantum-dynamics calculations. Measurements of the fluorescence emitted by the Rydberg ^[ A _]2Σ⁺v^′=2 level as a function of time between Stark and probe components of a bichromatic field exhibit a characteristic evolution in temporal peak structure with Stark-field intensity, which is interpreted in terms of a time-dependent Floquet analysis of the laser–matter interaction. The experimental observations are consistent with a dynamic Stark shift of Δε_s(ω₁,ω₂)≤0.23 eV of the optical transition at these intensities. Received: 18 January 2002 / Revised version: 6 March 2002 / Published online: 24 April 2002     

Investigation of carrier injection mechanism in small molecular organic light emitting device with a mixed single organic layer

Injection properties of electrons and holes in a mixed single layer organic light emitting device with mixed small molecules tris-(8-hydroxy-quinoline) aluminum (Alq₃), 2,5-bis(6′-(2′,2″-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole (PyPySPyPy), 4′-bis[N-(1-napthyl)-N-phenyl-amino]biphenyl (α-NPD), and 5,6,11,12-tetraphenylnaphthacene (rubrene) were investigated using Au/MoO₃ as hole and Al alloy as electron injection electrodes. On the basis of measuring the temperature dependence of currents through the interface between the electrodes and the mixed single organic layer, the carrier injection mechanism was primarily ascribed to the Schottky thermionic emission with the barrier height of 0.25 eV for holes and 0.67 eV for electrons. By adding the dopant material rubrene and the electron transport material PyPySPyPy into the mixed single layer, the barrier height of electrons could be reduced. The interfacial state analysis demonstrated that the electron barrier height was also dependent on the interfacial conditions of the device.     

Centrality dependence of pseudorapidity distributions of baryons in heavy ion collisions at RHIC

The energy and centrality independence of the limiting fragmentation for produced mesons have been used to extract the reduced pseudorapidity (η′ = η − η _beam ) distributions of charged baryons at forward rapidity. The distribution crosses at η′ ≈ = −1 suggesting the prominence of beam protons above that rapidity. The loss of beam rapidity has been extracted which has been found to increase with centrality.     

Dielectric properties of BiMg1/2Ti1/2O3 and BiMg1/2Zr1/2O3 perovskite ceramics with elimination of the contribution for direct current conductivity

A technique for analysis of the electric modulus spectrum of dielectric ceramics based on the elimination of the direct current conductivity (σ _dc ) contribution has been developed. Expressions are given for the real (M′ _ac ) and imaginary (M′′ _ac ) parts of the complex electrical modulus related only to the dielectric polarization and not containing the contribution of σ _dc . The frequency dependence of M′′ _ac and the M′′ _ac – M′ _ac diagram for BiMg_1/2Ti_1/2O₃ and BiMg_1/2Zr_1/2O₃ perovskite ceramics are analyzed.     

Source of far and vacuum ultraviolet radiation based on a transverse high-frequency discharge

We present the results of an investigation of a short-wavelength radiation source (Δλ = 130–350 nm) with excitation by a transverse high-frequency (f = 1.76 MHz) discharge based on a mixture of argon and chlorine (p = 100–500 Pa). We have studied the spectral characteristics of the plasma, the oscilloscope traces of the voltage, the current and emission of the discharge, the dependence of the power of the emission on the electrical power of the discharge, and also the pressure and partial composition of the Ar/Cl₂ mixture. The UV-VUV source emits in a system of broadened and overlapping ArCl(B/X), Cl₂(D′/A′), and Cl**₂ molecular bands. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 5, pp. 648–651, September–October, 2007.     

Effect of annealing on structure and magnetic properties of Fe-N and Fe-Ti-N thin films

The structure and magnetic properties of Fe-N and Fe-Ti-N films have been studied as a function of annealing temperature T_a with a transmission electron microscope and a vibrating sample magnetometer. The as-prepared Fe-N films consist of the γ^′-Fe₄N and α^′′-Fe₁₆N₂ phases, and the Fe-Ti-N films are composed of the γ^′-Fe₄N, α^′′-Fe₁₆N₂, and TiN phases. The structural changes with annealing temperature in the Fe-N films are distinct. The α^′′-Fe₁₆N₂ decomposes into α+γ^′ phases in the Fe-N film annealed at about 300 °C, and it disappears in the film annealed at 350 °C. Annealing of the Fe-Ti-N films shows no structural changes between room temperature (RT) and 500 °C. The saturation magnetization 4πM_S and coercivity H_c of the Fe-N films change drastically with the annealing temperature T_a, whereas those of the Fe-Ti-N films do not change with T_a up to 500 °C. These results indicate that the additon of Ti may improve the thermal stability of Fe-N films. Recieved: 6 Juli 1998 / Accepted: 19 Oktober 1998 / Published online: 10 March 1999