Production and decay of subcritical nuclei in a solid solution

The decay of “subcritical” nuclei in a solid solution has been revealed in the investigation of the CuCl phase nucleation kinetics in glass. As soon as “supercritical” nuclei with an average radius R = 1.1 nm are created at 500°C, a sharp temperature increase up to 650°C transforms most nuclei created in the first annealing stage into “subcritical” ones, and this results in the decay of 80% of the nuclei in 5 min, while the remaining 20% of the nuclei grow in size to 2.4 nm. Their growth provides a sixfold increase in the CuCl phase growth rate against that in conventional annealing at 650°C. The kinetic dependences of the nucleation parameters—the amount of the phase and the average radius and concentration of the particles—were determined by the intrinsic absorption spectra of the CuCl nanocrystals. The critical radius of the CuCl nanomelt at 650°C has been estimated as 1.3 nm and the evaporation heat of the CuCl phase molecules in glass, as 13 kJ/mol. It is shown that multistage annealing makes it possible not only to control the parameters of the particles of the new phase, but also to determine the critical parameters of the initial nucleation stage.     

Interaction of a New Fluorescent Probe with DNA and its Use in Determination of DNA

In this paper we reported a metal complex 1-Zn (2,5-di-[2-(3,5-bis(2-pyridylmethyl)amine-4-hydroxy-phenyl)-ethylene]-pyrazine-Zn) as a fluorescent probe sensing DNA. The result of the competitive experiment of the probe with ethidium bromide (EB) to bind DNA, absorption spectral change and polarization change in the presence and absence of DNA revealed that interaction between the probe and DNA was via intercalation. Ionic strength experiment showed the existence of electrostatic interaction as well. Scatchard plots also confirmed the combined binding modes. The fluorescence enhancement of the probe was ascribed to highly hydrophobic environment when it bound the macromolecules such as DNA, RNA or denatured DNA. The binding constant between the probe and DNA was estimated as 3.13 × 10⁷ mol⁻¹ L. The emission intensity increase was proportional to the concentration of DNA. Based on this, the probe was used to determine the concentration of calf thymus DNA (ct-DNA). The corresponding linear response ranged from 2.50 × 10⁻⁷ to 4.75 × 10⁻⁶ mol L⁻¹, and detection limit was 1.93 × 10⁻⁸ mol L⁻¹ for ct-DNA.     

Free carrier concentration and conductivity in chlorine doped lead telluride

Plasma resonance in the IR reflection spectra is used to measure the concentration and relaxation time of free charge carriers along with the conductivity in PbTe_{1 − x} Cl _x solid solutions. It is found that with increasing the chlorine concentration, the electron concentration and conductivity increase and reach saturation at x = 0.03 (n = 5.5 × 10¹⁹ cm⁻³, σ = 3750 Ohm⁻¹ · cm⁻¹). The relaxation time decreases with increasing the chlorine concentration and reaches the minimum value of 2.2 × 10⁻¹⁴ s at x = 0.03; then, it almost does not change.     

Quasi-simultaneous detection of CH2O and CH by cavity ring-down absorption and laser-induced fluorescence in a methane/air low-pressure flame

The combination of two-dimensional, planar laser-induced fluorescence (PLIF) and cavity ring-down (CRD) absorption spectroscopy is applied to map quantitatively the spatial distributions of CH₂O and CH in a methane/air flame at 25 Torr. Both species are detected in the same spectral region using the overlapping CH₂O A ¹ A ₂ -X ¹ A ₁ 4₁ ⁰ and CH B-X(1,0 )bands. The combination of diagnostic techniques exploits the spatial resolution of LIF and the quantitative CRD absorption measure of column density. The spatially resolved PLIF provides the distribution of absorbers and line-of-sight CRD absorption the absolute number density needed for quantitative concentration images. The peak CH₂O concentration is (3.5±1.4 )×10¹⁴ cm^-3, or 1450±550 ppm at 1000 K. The lack of precise absorption cross-section data produces these large error limits. Although a flame model predicts lower amounts, these large uncertainties limit this measurement’susefulness as a test of the flame chemistry. Received: 24 April 2001 / Revised version: 10 July 2001 / Published online: 10 October 2001     

Investigation of excited-state proton transfer in 3-hydroxyflavone molecules

The dual fluorescence spectra of 3-hydroxyflavone molecules excited by electromagnetic radiation in the region of the S ₁ and S ₂ absorption bands in the temperature region of 20–80°C are studied using the dynamic quenching of the excited state. An analysis of the fluorescence parameters shows that heating the solution from room temperature to 60°C increases the proton transfer rate by a factor of 1.24 in the case of standard excitation into the main absorption band and even stronger (by a factor of 6.9) in the case of excitation into the second absorption band. The presence of a quencher reduces the yield of the two emission bands and noticeably increases the proton transfer rate, by a factor of 1.16 at room temperature and by a factor of 1.25 at 80°C. Upon excitation into the second singlet band, the transfer rate increases even more (especially at higher temperatures), by a factors of 1.24 and 3.5 for the same temperatures. The temperature dependences of the transfer rate constant allowed us to estimate the activation energies of the proton transfer reaction under different physical conditions and reach conclusions about the mechanism by which this reaction proceeds. It is found that the proton transfer activation energy decreases from 500 to 360 cm⁻¹ when measured in temperature ranges of 20–40 and 20–60°C. The introduction of a quencher with a concentration of 5 × 10⁻³ M increases the activation barrier to 534 and 471 cm⁻¹ in the same temperature ranges.     

Effect of sulphuric–nitric acid mixture composition on surface chemistry and structural evolution of liquid‐phase oxidised carbon nanotubes

Liquid phase functionalisation of carbon nanotubes is carried out via a H₂SO₄ + HNO₃ mixture, and the effect of the sulphuric to nitric acid volume ratio (1:3–3:1) is systematically investigated by means of complementary techniques, observing the expected progressive downgrade of the crystalline quality, along with the increase of oxygenated functionality concentration. In addition, in contrast with common expectations, the results obtained demonstrate that the concentration of carboxylic groups (acids and anhydrides) never exceeds that of all other functionalities (lactones, phenols, quinones/carbonyls and sulphonic groups) introduced by chemical oxidation. Only by using equal volumes of sulphuric and nitric acids the concentrations of carboxylic and non‐carboxylic groups become comparable. Raman analysis reveals that a change in the sample homogeneity accompanies the variations of the relative proportions of the various oxygenated groups, by the typology of which the vibration modes of carbon pairs and carbon rings appear to be affected to different extents. Copyright © 2012 John Wiley & Sons, Ltd.     

The special features of the luminescence and light resistance of europium complexes and their mixtures with lanthanum complexes in polymethyl methacrylate

The kinetics of luminescence and transformation of short-lived products of the photolysis of europium and lanthanum complexes with thenoyltrifluoroacetone and 1,10-phenanthroline and their mixtures in polymethyl methacrylate films was studied by the nanosecond laser photolysis method with recording both light emission and absorption. Fast (535 and 585 nm, ⁵ D ₁ → ⁷ F ₀, ⁷ F ₃, decay time 0.7 μs) and slow (613 nm, ⁵ D ₀ → ⁷ F ₂, luminescence rise and decay times 0.7 μs and 0.5 ms, respectively) luminescence was studied. Induced absorption with a maximum at 600 nm and decay time ∼3 ms was observed; this absorption was assigned to triplet states of the deprotonated form of thenoyltrifluoroacetone. The dependences of luminescence intensity on the concentration of the components in a mixture of complexes were analyzed, and synergistic effects of luminescence strengthening were estimated. The kinetics of a decrease in luminescence intensity during photolysis was studied. Possible mechanisms of a decrease in the relative initial process rate and an increase in the quasi-stationary value of relative luminescence intensity as the concentration of complexes in the polymer increased were discussed.     

Synthesis of highly fluorescent and thio-linkers stabilize gold quantum dots and nano clusters in DMF for bio-labeling

This study demonstrates a one versus two-step synthesis of fluorescent gold quantum dots (F-AuQDs) and nano clusters (F-AuNCs) functionalized with thiolated organic linkers using reduction of gold precursor in N,N′-dimethylformamide in 1 h of reaction. The F-AuQDs and F-AuNCs show fluorescence emission at 425 ± 5 nm upon excitation at 345 ± 5 nm of wavelength, with good water solubility and stability. Five different thiolated organic binary linkers consisting of various functional groups including: carboxylic acid, hydroxyl, and aromatic amine, were conjugated with the F-AuQDs and F-AuNCs. The formation mechanism and functionalization of the F-AuQDs and F-AuNCs was characterized using UV–vis absorption spectra, UV–vis light, fluorescent emission spectra, pH, TEM, and FTIR. The fluorescence emission of the F-AuQDs and F-AuNCs is greatly dependent on the thio-linker. This novel one-step approach provides facile and fast synthesis of F-AuQDs and F-AuNCs over the two-step method, with less than 5 h of reaction and workup compared to more than 28 h of reaction for the two-step approach. These thio-linker functionalized F-AuQDs and F-AuNCs have a wide application in fluorescent labeling of biomolecules, optical devices, imaging, energy transfer, and biosensing.     

Methodology for temperature measurements in water vapor using wavelength-modulation tunable diode laser absorption spectrometry in the telecom C-band

A methodology based upon wavelength modulation and two-line thermometry for assessment of gas temperature by tunable diode laser absorption spectroscopy utilizing a standard tunable distributed feedback (DFB) diode laser working in the telecom C-band has been developed. Due to the high density of water lines in this wavelength region at elevated temperatures the methodology does not make use of two individual lines, but rather two groups of lines. The two groups identified have been found to have favorable properties for accurate temperature assessment in the 200–1000°C range, primarily a separation that is within a single DFB laser scan (∼20 GHz), an adequate linestrength, and sufficient difference in temperature dependence; the ratio of the peak values of the 2f-wm-signals, R, was found to increase monotonically with temperature, T, with a relative sensitivity, (ΔR/R)/(ΔT/T), above or around unity for most of the pertinent temperature range. The standard deviation of a temperature measurement with a 1 s integration time was found to be below 0.3%. It is shown that the temperature assessment has virtually no dependence on water concentration but a weak dependence on modulation amplitude.     

Optical,nanostructural, and biophysical properties of Zn-induced changes in human erythrocyte membranes

We studied changes in the surface of erythrocyte membranes exposed to the action of zinc sulfate in the concentration range of 0.1–2.0 mM/l using methods of light scattering, spectrofluorimetry, and atomic force microscopy. Using the spectrofluorimetry method, we revealed a dose-dependent increase in the fluorescence intensity of a fluorescamine probe incorporated into erythrocyte membranes modified by zinc ions, which is indicative of an increase in the level of NH₂ groups on the cell surface. Using atomic force microscopy, we revealed changes in the surface topography of erythrocyte membranes exposed to the action of zinc sulfate in the concentration range of 0.1–2.0 mM/l. By performing a correlation analysis, we revealed that the correlation length of the autocorrelation function of the erythrocyte surface irregularity profile directly related to the fluorescence intensity of fluorescamine incorporated into erythrocyte membranes (r = 0.9, p < 0.05) modified by zinc ions. We showed that, in the zinc sulfate concentration range of 0.1–2.0 mM/l, zinc oxides form in erythrocyte membranes, which is confirmed by the appearance of an absorption band at 330–340 nm and by an increase in the light scattering. At more considerable concentrations, we identified absorption bands characteristic of zinc protein complexes in erythrocyte membranes. A considerable decrease in the elongation of the scattering indicatrix of erythrocyte membranes caused by luminescence correlates with the content of zinc proteins. Polarization measurements confirm the enhancement of the aggregation of protein complexes observed by the atomic force microscopy method. The proposed complex approach can be used in studies on the action of various abiotic factors on biological cells.     

Photoluminescence ofn-GaAs at transparent Schottky contacts

Near-bandgap photoluminescence at 300 K of a Se-dopedn-GaAs crystal withn=4.8·10¹⁶ cm⁻³ was measured at a transparent CrAu−GaAs Schottky contact. The dependence of the luminescence intensity on the applied reverse voltage was recorded. Both the doping concentration and absorption coefficients above bandgap are determined.     

Application of EPR spectroscopy to examination of gentamicin and kanamycin binding to DOPA-melanin

Electron paramagnetic resonance (EPR) spectroscopy was applied to measure the influence of two aminoglycoside antibiotics: gentamicin and kanamycin on free radical propertis of DOPA-melanin. DOPA-melanin was formed by oxidative polymerization of 3,4-dihydroxyphenylalanine. Different concentrations of gentamicin and kanamycin (from 1·10⁻⁴ to 1·10⁻² M) were used. o-Semiquinone free radicals with ag factor of 2.0043 were found in all studied melanin samples. Their concentrations in the DOPA-melanin-drug complexes were higher than in DOPA-melanin, and increased with the increase of gentamicin and kanamycin concentration. A single EPR line of the analyzed samples (ΔB _pp, 0.48-0.52 mT) indicates that aminoglycoside antibiotics do not create a new type of free radicals in DOPA-melanin. Microwave saturation behavior of the experimental lines indicates the homogeneous broadening of resonance absorption curves for DOPA-melanin and its complexes with aminoglycosides. The EPR lines saturate at low microwave powers. Slow spin-lattice relaxation processes were characteristic for all studied melanin samples.     

Two-photon—induced fluorescence and electronic structure of substituted dicyanomethylene pyrans in solutions under femtosecond excitation

The method of two-quantum etalon is used to determine the two-photon absorption cross sections of eight dicyanomethylene (DCM) pyran dyes (DCM derivatives). Measurements of two-photon absorption of femtosecond Ti: sapphire-laser (λ = 800 nm, τ = 100 fs, and f = 89 MHz) radiation have been carried out. The nature of nonlinear excitation has been confirmed by the dependence of the fluorescence intensity on the excitation radiation intensity, which is close to a square-law one. Based on the measured two-photon absorption cross sections, the sizes of delocalized π-electronic clouds of DCM dye molecules with different substitutes are estimated in solvents with different polarity parameters. It is demonstrated that an increase in the polarity parameter of the solvent causes the two-photon absorption cross sections and sizes of delocalized π-electronic clouds of DCM, DCM-doa, DCM-17, DCM-5M, and DCM-11 dyes to increase. It is demonstrated that the size of the delocalized π-electronic cloud and the quantum fluorescence yield of the DCM-ul dye decrease with increasing polarity of the solvent despite the growth of the two-photon absorption cross section. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 69–73, November, 2005.     

Vibrational spectra of an LiNO3–(CH3)2SO2 system

Raman and IR absorption spectra were studied and molecular relaxation characteristics of vibrations of the anion and solvent were calculated for an xLiNO₃–(1 – x)(CH₃)₂SO₂ system (x = 0.1, 0.2, 0.3, 0.4 M). It was found that it is impossible to increase the concentration of free ions involved in charge transfer in such a system by either increasing the temperature or changing the concentration composition in the studied range of x.     

Fundamental noise sources in a high-sensitivity two-tone frequency modulation spectrometer and detection of CO2 at 1.6 μm and 2 μm

2 , and its sensitivity is 7(2)×10^-8 in a 1-Hz bandwidth. The corresponding minimum detectable concentration of CO₂ in air has been estimated to be 1 ppm · m. This opens the possibility of a detection at ppb levels at 2 μm, where a two orders of magnitude increase in the CO₂ absorption signal is demonstrated. Received: 06 April 1998/Revised version: 02 July 1998     

Long-term evolution of photoinduced light absorption in C60 films

It is found that photoinduced absorption in the energy range 0.6–2.1 eV in C₆₀ films grown by the same method can differ by a factor of 100. This change is attributable a 10⁶-fold increase in the relaxation time τ of electron-hole photoexcitations after working with the films for several months. It is established that the bimolecular recombination mechanism for photoexcitations (triplet excitons and polarons), which is typical of as-prepared and partially aged films, is superseded in fully aged films by thermally activated tunneling of localized photoexcitations. An investigation of the film transmission spectra in the photon energy range 0.2–5.0 eV shows that the long-time variations of the optical properties are associated with a decrease in the concentration of defects forming shallow tails of the density of states. An abrupt decrease of the relaxation time τ and the photoinduced absorption is observed in both types of films at T⩾80 K. Fiz. Tverd. Tela (St. Petersburg) 39, 1303–1309 (July 1997)     

Energy spectrum and phase transitions in C70 fullerite crystals at high pressure

Measurements have been made of the Raman, optical absorption, and luminescence spectra of single crystals and pellets of the fullerite C₇₀ at T=300 K and at pressures up to 12 GPa. The baric shift dω/dP and the Grüneisen parameters of the Raman-active intramolecular phonon modes have been determined. It has been established that the d ω/dP value for certain phonon modes abruptly changes at pressures of P ₁≈2 GPa and P ₂≈5.5 GPa, as do the half-widths of the Raman lines. These features in the Raman spectrum are associated with phase transitions at high pressure. The baric shifts of the absorption and luminescence edges of C₇₀ crystals have been determined and are −0.12 eV/GPa and −0.11 eV/GPa, respectively, for absorption and luminescence. The baric shift of the absorption edge decreases significantly with increasing pressure and is −0.03 eV/GPa at 10 GPa. These data have been used to determine the deformation potential of the fullerite C₇₀, which is about 2.1±0.1 eV. Zh. éksp. Teor. Fiz. 111, 262–273 (January 1997)     

Linear and nonlinear optical absorption coefficients in inverse parabolic quantum wells under static external electric field

In the present theoretical study, the linear and third-order nonlinear optical absorption coefficients have been calculated in GaAs/Ga_1−x Al _x As inverse parabolic quantum wells (single and double) subjected to an external electric field. Our calculations are based on the potential morphing method in the effective mass approximation. The systematic theoretical investigation contains results with all possible combinations of the involved parameters, as quantum well width, quantum barrier width, Al concentration at each well center and magnitude of the external electric field. Our results indicate that in most cases investigated, the increase of the electric field blue-shifts the peak positions of the total absorption coefficient. In all cases studied it became apparent that the incident optical intensity considerably affects the total absorption coefficient.     

Optical absorption in layered MnGaInS<Subscript>4</Subscript> single crystals

Optical absorption in MnGaInS₄ single crystals has been studied. Direct and indirect optical transitions are found to occur in the range of photon energies of 2.37–2.74 eV and in the temperature range of 83–270 K. The temperature dependence of the band gap has been determined; its temperature coefficients E _gd and E _gi are −5.06 × 10⁻⁴ and −5.35 × 10⁻⁴ eV/K, respectively. MnGaInS4 single crystals exhibit anisotropy in polarized light at the absorption edge; the nature of this anisotropy is explained.     

Wavelength Dependant Quenching of 2,5-Diphenyloxazole Fluorescence by Nucleotides

The quenching of 2,5-diphenyloxazole (PPO) fluorescence by nucleotides has been investigated by electronic absorption and steady state fluorescence spectra. Five purine nucleotides AMP, ADP, ATP, GMP and dGMP, one pyrimidine nucleotide UMP and one dinucleotide NAD have been employed in the present study. Electronic absorption studies indicate that there is no ground state complexation between the nucleotides and PPO. The quenching of PPO fluorescence was investigated at two different wavelengths. When excited at 304 nm, the λ _max of PPO, the fluorescence spectra of PPO is quenched following Stern–Volmer kinetics. The quenching ability of nucleotides are in the order NAD > AMP > ADP > GMP > dGMP > UMP. The K _SV and k _q values obtained indicate that AMP is a better quencher of PPO fluorescence than GMP, which is contrary to commonly observed pattern. The quenching is found to be dynamic in nature. However, when excited at 260 nm, the absorption maximum of the nucleotides, the fluorescence intensity of PPO is reduced with increase in the concentration of the nucleotide. This is attributed to the primary inner filter effect arising due to the absorption of the incident radiation by the nucleotides. Thus the inner filter effect phenomenon can be employed to assay the non-fluorescent molecules by fluorimetry.