Spectroscopic characteristics of erbiumand ytterbium-activated laser media

Judd–Ofelt parameters (Ω₂ = 5.09∙10^–20, Ω₄ = 0.92∙10^–20, and Ω₆ = 0.63∙10^–20 cm²) and oscillator strengths of fundamental optical transitions involved in lasing at wavelength 1.54 μm have been calculated for borosilicophosphate glass co-activated with Er³⁺ and Tb³⁺ ions based on experimental luminescence and absorption spectra and refractive indices. The results were used to determine the emission (6∙10^–23 cm²) and absorption (5∙10^–21 cm²) cross sections for λ = 1.54 μm and the gain cross section as a function of inverse population levels.     

Influence of local excitation of octupolar Oligophenylenevinylenes on their dipole moments

Absorption and fluorescence spectra of octupolar centrosymmetric oligophenylenevinylene dyes (E,E)-bis[2-(4-hexyloxyphenyl)ethenyl]-(E,E)-3,6-bis-[2-(4-N,N-dipropylaminophenyl)ethenyl]pyrazine and (E,E,E,E)-2,3,5,6- tetra-[2-(4-hexyloxyphenyl)ethenyl]pyrazine were measured in various solvents. An electro-optical absorption method was used to determine their dipole moments as μ _g  = 6.1∙10^–30 and 3.4∙10^–30 C∙m in the equilibrium ground state and the increased values ∆ ^a μ = 11.9∙10^–30 and 8.2∙10^–30 C∙m upon excitation into a Franck–Condon state. Quantum-chemical calculations showed that the molecules had non-planar configurations. The π,π-conjugated system was localized on the most planar part of the molecule that was responsible for light absorption in the range 300–450 nm due to a change in the geometry of the molecules in the ground state. Localized excitation of the molecules caused their dipole moments ∆ ^a μ to change significantly.     

Development and validation spectroscopic methods for the determination of lomefloxacin in bulk and pharmaceutical formulations

Four simple, sensitive spectrophotometric and spectrofluorimetric methods (A-D) for the determination of antibacterial drug lomefloxacin (LMFX) in pharmaceutical formulations have been developed. Method A is based on formation of ternary complex between Pd(II), eosin and LMFX in the presence of methyl cellulose as surfactant and acetate-HCl buffer pH 4.0. Spectrophotometrically, under the optimum conditions, the ternary complex showed absorption maximum at 530 nm. Methods B and C are based on redox reaction between LMFX and KMnO₄ in acid and alkaline media. In indirect spectrophotometry method B the drug solution is treated with a known excess of KMnO₄ in H₂SO₄ medium and subsequent determination of unreacted oxidant by reacting it with safronine O in the same medium at λ_max = 520 nm. Direct spectrophotometry method C involves treating the alkaline solution of LMFX with KMnO4 and measuring the bluish green product at 604 nm. Method D is based on the chelation of LMFX with Zr(IV) to produce fluorescent chelate. At the optimum reaction conditions, the drug-metal chelate showed excitation maxima at 280 nm and emission maxima at 443 nm. The optimum experimental parameters for the reactions have been studied. The validity of the described procedures was assessed. Statistical analysis of the results has been carried out revealing high accuracy and good precision. The proposed methods were successfully applied for the determination of the selected drug in pharmaceutical preparations with good recoveries.     

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.     

Spectrophotometric determination of ofloxacin in pharmaceuticals by redox reaction

Two simple spectrophotometric methods have been developed to analyze ofloxacin (OFX) in pharmaceuticals. The methods are based on the oxidation of OFX by a measured excess of cerium(IV) sulfate in H₂SO₄ medium. This was followed by the determination of the unreacted oxidant by reacting it with either p-toluidine (p-TD) and measuring the absorbance at 525 nm (method A) or o-dianisidine (o-DA) and measuring the absorbance at 470 nm (method B). In both methods, the amount of cerium(IV) sulfate reacted corresponds to the amount of OFX. Calibration graphs were linear over the ranges of 0–120 and 0–4 g/ml OFX for methods A and B, respectively. The calculated molar absorptivity (2.34⋅10³ and 5.99⋅10⁴), Sandell sensitivity, and limit of quantification for the methods are reported. The intra-day precision (%RSD) and accuracy (%RE) were < 8.0 and ≤ 4.0%, respectively, and the inter-day RSD and RE values were within 5 and 4.0%, respectively. The applicability of the methods was demonstrated by determining OFX in tablets with an accuracy (%RE) of < 3% and precision (%RSD) of ≤2.65%. The accuracy of the methods was further ascertained by recovery experiments via a standard-addition procedure.     

Electrochemical immune bioassay for the antigen–antibody interaction based on [Fe(CN)<Subscript>6</Subscript>]<Superscript>4-/3-</Superscript> and [AuCl<Subscript>4</Subscript>]<Superscript>-</Superscript> ions-derivated biomimetic interface

A simple and sensitive electrochemical immune bioassay for the detection of hepatitis B surface antigen (HBsAg), as a model, was developed based on [Fe(CN)₆]^4-/3- and [AuCl₄]^- ions-derivated biomimetic interface in this study. A layer of [Fe(CN)₆]^4-/3- film (i.e., Prussian blue, PB) was initially electrodeposited onto a glassy carbon electrode, and then [AuCl₄]^- ions were reduced under the potentiostat to form gold nanoparticles on the PB film. Finally, hepatitis B surface antibody (HBsAb) was adsorbed onto the nanogold surface. The performance and factors influencing the immunosensor were assessed and optimized. The proposed immunosensor exhibits a specific response to HBsAg in the range of 2.13–314.3 ng∙ml^-1 with a detection limit of 0.42 ng∙ml^-1. In addition, the developed immunosensor shows high sensitivity, good reproducibility, and long-term stability. Importantly, the ions-derivated biomimetic interface could be further extended for the immobilization of other proteins and biocompound.     

Diffuse reflectance spectra of aluminum oxide micropowders,modified powders,and nanopowders and their changes upon electron irradiation

Comparative analysis of the diffuse reflectance spectra (300–2100 nm) and of the integrated absorption factor of coatings based on micropowders, nanopowders, and micropowders modified with Al₂O₃ nanopowders has been performed. In addition, the changes in the spectra resulting from electron irradiation of the powders with energies of 30 keV at a fluence of up to 3∙16 cm^–2 have been analyzed. It has been found that the diffuse reflectance decreases in order of coatings based on micro-powders, nano-powders and modified powders, while radiation resistance increases in order of coatings based on nano-powders, modified and micropowders.     

Laser-induced synthesis of BaMoO<Subscript>4</Subscript> nanocolloidal suspension and its optical properties

Pulsed laser ablation in a liquid phase was successfully employed to synthesize a barium molybdate (BaMoO₄) nanocolloidal suspension. The nanocolloidal suspension was composed of well-dispersed and horizontally assembled BaMoO₄ aggregates. The BaMoO₄ aggregates showed predominantly elliptically shaped nanorods with sizes between 100 and 200 nm. The preferential elliptical growth was rationalized from the viewpoint of the intrinsic structure of BaMoO₄. The optical properties of the prepared BaMoO₄ colloidal nanoparticles were investigated using Raman spectroscopy, UV–vis spectroscopy and photoluminescence (PL) spectrophotometry. The optical band gap was estimated by Tauc and Menth’s law. The PL emission feature was decomposed into several individual Gaussian components, which could be interpreted by a Jahn–Teller splitting effect on the [MoO₄]^2- tetrahedron of the BaMoO₄ colloidal nanoparticles. PACS  42.62.-b; 82.70.Dd; 78.55.Hx; 81.07.Wx     

Fluorimetric Determination of Some Sulfur Containing Compounds Through Complex Formation with Terbium (Tb<Superscript>+3</Superscript>) and Uranium (U<Superscript>+3</Superscript>)

Two simple, sensitive and specific fluorimetric methods have been developed for the determination of some sulphur containing compounds namely, Acetylcysteine (Ac), Carbocisteine (Cc) and Thioctic acid (Th) using terbium Tb⁺³ and uranium U⁺³ ions as fluorescent probes. The proposed methods involve the formation of a ternary complex with Tb⁺³ in presence of Tris-buffer method (I) and a binary complex with aqueous uranyl acetate solution method (II). The fluorescence quenching of Tb⁺³ at 510, 488 and 540 nm (λ_ex 250, 241 and 268 nm) and of uranyl acetate at 512 nm (λ_ex 240 nm) due to the complex formation was quantitatively measured for Ac, Cc and Th, respectively. The reaction conditions and the fluorescence spectral properties of the complexes have been investigated. Under the described conditions, the proposed methods were applicable over the concentration range (0.2–2.5 μg ml⁻¹), (1–4 μg ml⁻¹) and (0.5–3.5 μg ml⁻¹) with mean percentage recoveries 99.74±0.36, 99.70±0.52 and 99.43±0.23 for method (I) and (0.5–6 μg ml⁻¹), (0.5–5 μg ml⁻¹), and (1–6 μg ml⁻¹) with mean percentage recoveries 99.38±0.20, 99.82±0.28 and 99.93±0.32 for method (II), for the three cited drugs, respectively. The proposed methods were successfully applied for the determination of the studied compounds in bulk powders and in pharmaceutical formulations, as well as in presence of their related substances. The results obtained were found to be in agree statistically with those obtained by official and reported ones. The two methods were validated according to USP guidelines and also assessed by applying the standard addition technique.     

Application of 3-methylbenzothiazolin-2-one hydrazone for the quantitative spectrophotometric determination of oxcarbazepine in pharmaceuticals with cerium(IV) and periodate

Two simple, sensitive, selective, accurate, and cost-effective spectrophotometric methods are described for the assay of oxcarbazepine (OXC) in bulk drug and in tablets. The methods are based on an oxidative coupling reaction involving OXC, 3-methylbenzothiazolin-2-one hydrazone (MBTH), and cerium(IV) sulfate at pH 4.28 ± 0.07 (method A) or sodium periodate at pH > 4.0 (method B) to form an orange colored product with an absorption maximum at 450 nm. Under optimized experimental conditions, the calibration graphs are linear over the ranges of 4–80 and 2–32 μg/ml for methods A and B, respectively, with correlation coefficient (r) values of 0.9984 and 0.9976. The apparent molar absorptivity values are 3.13⋅10³ and 9.13⋅10³ l/mol⋅cm for methods A and B, respectively. The other optical characteristics such as Sandell’s sensitivity, limits of detection (LOD) and quantification (LOQ) values are also reported. The accuracy and precision of the methods were evaluated based on intra-day and inter-day variations. The proposed methods were successfully applied to the determination of OXC in tablets: the results were comparable with the published data obtained using the reference method. The reaction stoichiometry of OXC with MBTH (1:1 in method A and 1:2 in method B) was also evaluated using the limiting logarithmic method, and a possible reaction pathway is presented for the both methods.     

Use of short-wavelength synchrotron radiation to measure luminescence quantum yield and the luminescence excitation spectrum of polymers

We describe an optical diagnostics module and the instrumental and methodological features of ultrahigh vacuum experiments investigating the optical characteristics of condensed media in the short-wavelength (hv ~ 3.5–25 eV) range of the spectrum of probing synchrotron radiation. We give a brief presentation of the results of an experimental determination of the spectral dependence of the luminescence quantum yield and the luminescence excitation spectrum of ablatable polymer dielectrics on the Kurchatov synchrotron radiation source at values of the probing radiation power density (I ₀ ~ 10¹² photons/cm²∙sec) that are below threshold for extended surface vaporization and a surface temperature of the condensed targets equal to 77–300 K.     

The absorption spectrum of radiation-colored SrCl2-Ce crystals

We investigate the spectra of the x-ray radiation-induced absorption of SrCl₂−Ce crystals over the spectral range 345–830 nm and their temperature transformations in the interval from 77 to 450 K. We found that radiative color centers are characterized by a complex spectrum of induced absorption that contains wide bands of photochromic PC (750, 519, 378 nm) and PC⁺ (620, 446, 340 nm) centers and quasi-linear bands of Ce²⁺ centers. The most significant thermal transformations of radiative color centers occur in the vicinity of the thermostimulated luminescence peak of 394 K, at which the holes of the PC⁺ centers recombine with the electrons of the Ce²⁺ centers. Ivan Franko L’vov State University, 8, Kirilla i Mefodiya St., L’vov 290005, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 4, pp. 545–547, July–August, 1997.     

Synthesis,spectroscopic, thermal and electrical conductivity studies of three charge transfer complexes formed between 1,3-di[(<Emphasis Type="Italic">E</Emphasis>)-1-(2-hydroxyphenyl)methylideneamino]-2-propanol Schiff base and different acceptors

Charge-transfer complexes (CTC) resulting from interactions of 1,3-di[(E)-1-(2-hydroxyphenyl) methylideneamino]-2-propanol Schiff base with some acceptors such as iodine (I₂), bromine (Br2), and picric acid (PiA) have been isolated in the solid state in a chloroform solvent at room temperature. Based on elemental analysis, UV-Vis, infrared, and ¹H NMR spectra, and thermogravimetric analysis (TG/DTG) of the solid CTC, [(Schiff)(I₂)] (1), [(Schiff)(Br₂)] complexes with a ratio of 1:1 and [(Schiff)(PiA)₃] complexes with 1:3 have been prepared. In the picric acid complex, infrared and ¹H NMR spectroscopic data indicate that the charge-transfer interaction is associated with a hydrogen bonding, whereas the iodine and bromine complexes were interpreted in terms of the formation of dative ion pairs [Schiff⁺, I₂^∙−] and [Schiff⁺, Br₂^∙−], respectively. Kinetic parameters were obtained for each stage of thermal degradation of the CT complexes using Coats–Redfern and Horowitz–Metzger methods. DC electrical properties as a function of temperature of these charge transfer complexes have been studied.     

Luminescence of europium and ytterbium ions in strontium hexaborate

We have studied the luminescent properties of Eu^2+/3+ and Yb²⁺ ions in strontium hexaborate SrB₆O₁₀ for excitation in the 120–400 nm region. The luminescence spectra of Ln²⁺ ions in SrB₆O₁₀ consist of overlapping bands in the 370–520 nm region, due to 5d → 4f transitions at several nonequivalent centers. In the excitation spectra, besides the bands associated with 4f → 5d transitions in the Ln²⁺ ions, we also observe a band in the 135–160 nm region due to the transitions O(2p) → B(2s,2p) within the borate anions. The luminescence of the Eu³⁺ ions is excited most efficiently in the region of the Eu³⁺ charge transfer band (λ_max = 226 nm). The results obtained are compared with data for Ln in other strontium borates. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 770–774, November–December, 2006.     

Optical Flow-Through Sensor for the Determination of Norfloxacin Based on Emission of KMnO<Subscript>4</Subscript>–Na<Subscript>2</Subscript>SO<Subscript>3</Subscript>–Tb<Superscript>3+</Superscript> System

A simple and selective method to determine norfloxacin using an optical flow-through sensor has been developed. The present sensor was prepared by packing anionic ion exchange resin in a glass tube, followed by introducing KMnO₄ solution to the glass tube for immobilization on resin. The optical sensor is based on the emission intensity from the Tb(III) solution sensitized by norfloxacin. The excitation of norfloxacin occurred by the chemiluminescence from the reaction of KMnO₄ and Na₂SO₄ solutions. The effects of pH, concentration of Tb(III) ion, KMnO₄ and Na₂SO₄ solutions and flow rate of the norfloxacin solution on the chemiluminescence intensity were studied to find the optimum experimental conditions. The emission intensity increased linearly with increasing norfloxacin concentration from 1.0 × 10⁻³ to 1.0 × 10⁻⁸ M and the detection limit (3σ) was 8.7 × 10⁻⁹. The applicability of the present method was demonstrated by determination of norfloxacin in various pharmaceutical preparations and serum sample.     

High-contrast and high-efficiency top-emitting organic light-emitting devices

The reflection properties of top-emitting organic light-emitting devices with different electrodes and organic layers were calculated. The results guided the fabrication of a high-contrast device: Au/copper phthalocyanine (CuPc: 35 nm)/N,N’-bis-(1-naphthyl)-N,N’diphenyl-1,1’ biphenyl-4,4’diamine (NPB: 15 nm)/tris(8-hydroxyquinoline) aluminum (Alq₃: 50 nm)/Sm (35 nm)/Alq₃ (65 nm). The device has a contrast ratio of 8.3:1 at a luminance of 300 cd/m² under 1000 lx ambient light, and a maximum luminance and efficiency of 5000 cd/m² and 4.14 cd/A, respectively. The high contrast is attributed to the moderate reflection of Au at 380–550 nm, low reflection of Sm in the visible range, and high absorption of CuPc at 600–700 nm. PACS 85.60.Jb; 78.20.Ci; 78.40.-q     

Spectrofluorimetric Methods for the Determination of Gemifloxacin in Tablets and Spiked Plasma Samples

Two new, sensitive and selective spectrofluorimetric methods have been developed for the determination of gemifloxacin (GFX) in tablets and spiked plasma samples. Gemifloxacin, as a primary amine compound, reacts with 7-chloro-4-nitrobenzofurazon (NBD-Cl) (for method A) and fluorescamine (for method B) which are a highly sensitive fluorogenic reagents used in many investigations. For method A, the reaction product was measured spectrofluorimetrically at 516 nm with excitation at 451 nm. The reaction proceeded quantitatively at pH 8.5, 80 °C in 7 min. For method B, the method was based on the reaction between GFX and fluorescamine in borate buffer solution of pH 8.5 to give highly fluorescent derivatives that were measured at 481 nm using an excitation wavelength of 351 nm. The fluorescence intensity was directly proportional to the concentration over the range 40–200 ng mL⁻¹ and 100–1,200 ng mL⁻¹ for method A and B, respectively. Successful applications of the developed methods, for the drug determination in pharmaceutical preparations and spiked plasma samples, were performed.     

Spectroscopic investigation of the plasma of a high-current diffuse discharge in He/Ar/CF2Cl2(CCl4) mixtures

Survey emission spectra in the region of 190–600 nm and time and service-life characteristics of a transverse nanosecond discharge in He/Ar/CF₂Cl₂(CCl₄) mixtures at a pressure of 10–100 kPa are investigated. In the emission spectra, excited products of the decomposition of freons—C₂(A−X), CN(B−X), Cl ₂ ^* , C^*, Cl^*, and Cl^+*— and the emission of ArF at λ=193 nm are revealed. The emissions of Cl ₂ ^* at λ=258 nm and ArF at λ=193 nm were the most intense. The discharge in the He/Ar/CF₂Cl₂ mixture is a multiwave emission source with λ=258 nm Cl ₂ ^* 193 nm ArF, and probably, 175 nm Arcl. It is of interest for applications in UV-VUV-range pulse photometry. The duration of the emission on Cl ₂ ^* , ArF, ArI, ClI, and ClII transitions in the discharge in the Ar/CF₂Cl₂ mixture (P=10–20 kPa) was 200–300 nsec. With adding He and increasing pressure to 100 kPa the duration of the emission decreased by a factor of 1.5–2. The basic mechanisms of the formation of Cl₂, ArF, and CN(B) molecules in the transverse-discharge plasma are considered. Uzhgorod State University, 46, Pidgirna Str., Uzhgorod, 294000, Ukraine. Translated from Zhurnal. Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 241–246, March–April, 1999.     

Simultaneous determination of aluminum (III) and iron (III) by first-derivative spectrophotometry in alloys

A highly sensitive and selective first-derivative spectrophotometric method has been developed for the determination of aluminum and iron in mixtures. The method is based on the formation of the binary complexes of aluminum and iron with Alizarin yellow R (AYR) 5-[4-nitrophenylazo]salicylic acid at pH 2.0 with molar absorptivity of 1.1∙10⁴ l⋅mol^–1⋅cm^–1. A zero-crossing technique is found suitable for the direct measurement of the first derivative value at the specified wavelength, so aluminum and iron were thus determined in the ranges 1.3–5.4 μg/ml and 1.1–8.3 μg/ml, respectively, in the presence of both components. The detection limits were found to be 1.4 ng/ml for aluminum and 2.8 ng/ml for iron. The relative standard deviations were in all cases less than 1.5%. The proposed method was successfully applied for the simultaneous determination of aluminum and iron in certified reference aluminum samples.     

Near IR laser light visualizators using nonlinear GaSe and other layered crystallites

Two methods of preparation of the devices for visualization of pulsed and continuous near-IR (near infrared) are described and the results of conversion of pulsed and continuous IR (800–1360 nm) laser radiation into the visible range of spectra (400–680 nm) by using a transparent substrate covered with the particles (including nanoparticles) of effective nonlinear materials of GaSe _x S_{1 − x} (0.2 ≤ x ≤ 0.8) are presented. Converted light can be detected in transmission or reflection geometry as a visible spot corresponding to the real size of the incident laser beam. Developed device structures can be used for checking if the laser is working or not, for optical adjustment, for visualization of distribution of laser radiation over the cross of the beam and for investigation of the content of the laser radiation. Low energy (power density) limit for visualization of the IR laser pulses with 2–3 ps duration for these device structures are: between 4.6–2.1 μJ (3 × 10⁻⁴−1 × 10⁻⁴ W/cm²) at 1200 nm; between 8.4–2.6 μJ (4.7 × 10⁻⁴−1.5 × 10⁻⁴ W/cm²) at 1300 nm; between 14.4–8.1 μJ (8.2 × 10⁻⁴–4.6 × 10⁻⁴ W/cm²) at 1360 nm. Threshold damage density is more than 10 MW/cm² at λ = 1060 nm, pulse duration τ = 35 ps. The results are compared with commercially existing laser light visualizators.