Development of Flow Injection Spectrofluorimetric Detection System for the Determination of Homocysteine

In this work, a new simple and sensitive flow injection method is developed for the determination of homocysteine with spectrofluorimetric detection technique. This method is based on the oxidation of homocysteine with Tl (III) in acidic media, producing fluorescence reagent, TlCl₃^2- (λ_ex = 237 nm, λ_em = 419 nm). The effects of chemical parameters (including pH of the solutions, the buffer, Tl (III) and potassium chloride concentrations), instrumental parameters (such as flow rate of the solutions, reaction coil length, and sample loop volume) and temperature on the fluorescence intensity as an analytical signal are studied and optimized. In the optimum conditions of the above variables, homocysteine can be determined in the range 4.0 × 10^-7–40.0 × 10^-6 M with the LDR from 4.0 × 10^-7 to 25.0 × 10^-6 M. The detection limit (with S/N = 3) is 6.0 × 10^-8 M of homocysteine and precision for the injection of 5.0, 10.0 and 15.0 μM of homocysteine are 0.8%, 1.5% and 2.5% (n = 10) respectively. The rate of analysis is 90 samples per hour. The influence of potential interfering substances, including amino acids and carbohydrates is also studied. The proposed method has been successfully used for the determination of homocysteine in the real sample (blood serum and tap water) matrix.     

Determination of Ofloxacin using a Highly Selective Photo Probe Based on the Enhancement of the Luminescence Intensity of Eu3+—Ofloxacin Complex in Pharmaceutical and Serum Samples

A rapid, simple and sensitive spectrofluorimetric method for determination of trace amount of ofloxacin was developed. At pH 5.1 the ofloxacin enhances the luminescence intensity of the Eu³⁺ ion in Eu³⁺- ofloxacin complex at λ_ex = 365 nm. The produced luminescence intensity of Eu³⁺-ofloxacin complex was in proportional to the concentration of ofloxacin. The working range for the determination of ofloxacin was 5.0 × 10^-9–5.0 × 10^-6 mol L^-1 with lower detection limit (LOD) and quantitative detection limit (QDL) of 3 × 10^-9 and 9 × 10^-9 mol L^-1, respectively. The enhancement mechanism of the luminescence intensity in the Eu³⁺-ofloxacin system has been also explained. The method revealed good selectivity for ofloxacin in the presence of coexisting substances and used successfully for the assay of ofloxacin in pharmaceutical preparations and serum. A comparison with other standard methods was also discussed.     

Plasma-based nitrogen tail pulse shutter for CO2-TEA lidar dial systems

This paper presents the construction, use and characterisation of a laser-induced sealed plasma shutter to clip off the nitrogen pulse tail of a CO₂-TEA laser-based lidar dial system. Investigation of the optimum gas filling pressure, temporal profile of the clipped pulse, and the laser threshold power intensities to achieve ionisation growth and breakdown in helium, argon, and nitrogen are also presented. Values of these power density thresholds lie between 3×10¹¹ W cm^-2–5×10¹² W cm^-2, 2×10¹¹ W cm^-2–2×10¹² W cm^-2 and 3×10¹³ W cm^-2–2×10¹⁴ W cm^-2 for helium, argon, and nitrogen, respectively. The range resolution attainable with the present clipped pulses is 15 m, which is 30 times better than that readily obtained with the nitrogen-tailed pulses. Field measurements of the lidar returns with the clipped pulse from a co-operative target are presented. Received: 27 December 1999 / Revised version: 11 February 2000 / Published online: 27 April 2000     

Spectrofluorimetric Assessment of Doxycycline Hydrochloride in Pharmaceutical Tablets and Serum Sample Based on the Enhancement of the Luminescence Intensity of the Optical Sensor Sm<Superscript>3+</Superscript> Ion

A simple and sensitive spectrofluorimetric method for determination of trace amount of doxycycline hydrochloride (DC) in pharmaceutical tablets and serum samples was developed. In ammonia buffer solution of pH 8.9 the doxycycline hydrochloride can remarkably enhance the luminescence intensity of the Sm³⁺ ion in Sm³⁺- DC complex at λ_ex = 400 nm. The produced luminescence intensity of Sm³⁺- DC complex in DMSO is in proportion to the concentration of DC and used as optical sensor for its determination. The dynamic range for the determination of DC is 1 × 10⁻⁸ – 5 × 10⁻⁶ mol L⁻¹ and in case of quantum yield calculations is 7 × 10⁻⁹ – 5 × 10⁻⁶ mol L⁻¹ with detection limit of 6.5 × 10⁻¹⁰ mol L⁻¹. The enhancement mechanism of the luminescence intensity in the Sm³⁺- DC system has been also discussed. A comparison with other spectrofluorimetric methods for tetracycline derivatives in which Eu³⁺ ion is used instead of Sm³⁺ ion is also studied.     

Polarization effect in langasite crystals

The variation of the resonance frequency of piezoelectric resonators subjected to a constant electric field is demonstrated with longitudinal vibrations in La₃Ga₅SiO₁₄ (langasite) crystal rods at temperatures between −60 and +80°C. For the rods whose longtudinal axis makes angle α with the crystal axis in the plane of the axes and [0001], the change in the frequency is proportional to the field strength and depends on α. For a field of ±1.5 × 10⁶ V/m and α = 15°, the relative change in the frequency is ±120 × 10⁻⁶. It is shown that La₃Ga₅SiO₁₄ crystals offer a set of physical parameters that makes them promising for electrically controlled acoustoelectronic devices and for devices based on nonlinear interaction between acoustic waves.     

Resonance photoacoustic spectroscopy and gas analysis of gaseous flow at reduced pressure

The results of theoretical and experimental studies of sensitivity of a resonant photoacoustic Helmholtz resonator detector for gas flowing through a photoacoustic cell under reduced pressure are presented. The measurements of the sensitivity and ultimate sensitivity of the differential photoacoustic cell were performed with a near-IR room-temperature diode laser using the well-known H₂O absorption line (12496.1056 cm^-1) as a reference. The measured value of the sensitivity (6–17 Pa W m^-1) is in satisfactory agreement with the calculated one, which equals 6–35 Pa W m^-1. The obtained value of the ultimate sensitivity ((3–5)×10^-7 W m^-1 Hz^-1/2) provides measurements of the concentration of molecules at the ppb–ppm level. Received: 19 April 2001 / Revised version: 18 September 2001 / Published online: 7 November 2001     

Structure,thermal properties,conductivity and electrochemical stability of di-urethanesil hybrids doped with LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>

Variable chain length di-urethane cross-linked poly(oxyethylene) (POE)/siloxane hybrid networks were prepared by application of a sol-gel strategy. These materials, designated as di-urethanesils (represented as d-Ut(Y′), where Y′ indicates the average molecular weight of the polymer segment), were doped with lithium triflate (LiCF₃SO₃). The two host hybrid matrices used, d-Ut(300) and d-Ut(600), incorporate POE chains with approximately 6 and 13 (OCH₂CH₂) repeat units, respectively. All the samples studied, with compositions ∞ > n ≥ 1 (where n is the molar ratio of (OCH₂CH₂) repeat units per Li⁺), are entirely amorphous. The di-urethanesils are thermally stable up to at least 200 °C. At room temperature the conductivity maxima of the d-Ut(300)- and d-Ut(600)-based di-urethanesil families are located at n = 1 (approximately 2.0 × 10⁻⁶ and 7.4 × 10⁻⁵ Scm⁻¹, respectively). At about 100 °C, both these samples also exhibit the highest conductivity of the two electrolyte systems (approximately 1.6 × 10⁻⁴ and 1.0 × 10⁻³ Scm⁻¹, respectively). The d-Ut(600)-based xerogel with n = 1 displays excellent redox stability.     

A Novel Fluorescent Cesium Ion-Selective Optode Membrane based on 15-Crown-5-Anthracene

An optode system based on a plasticized polymer membrane containing cesium ion-selective fluoroionophore and lipophilic anions for the determination of cesium ions has been developed. In this work, 15-crown-5 derivative including anthracene was used as a fluoroionophore. Emission intensity of the optode membrane incorporating 15-crown-5-anthracene was measured at 500 nm with excitation at 360 nm in the presence of Tris-HCl buffer solution. Under optimum experimental condition, the relative fluorescence intensity was linear with the concentration of cesium ion in the range of 1.0 × 10^-4 M to 1.0 × 10^-1 M and the detection limit was obtained 4.2 × 10^-5 M, as defined by LOD = 3 × S_b/m (where S_b=standard deviation of blank signal and, m=slope of the calibration curve). The effect of pH of sample solution on the fluorescent response, the selectivity, response time and reproducibility of the optode membrane were also discussed. The fluorescent optode system shows a high selectivity and sensitivity for cesium ion with respect to other cations such as K⁺, Na⁺ and Li⁺.     

Spectrofluorimetric Assessment of Chlorzoxazone and Ibuprofen in Pharmaceutical Formulations by using Eu-Tetracycline HCl Optical Sensor Doped in Sol–Gel Matrix

A novel, simple, sensitive and selective spectrofluorimetric method was developed for the determination of trace amounts of chlorzoxazone and Ibuprofen in pharmaceutical tablets using optical sensor Eu-Tetracycline HCl doped in sol–gel matrix. The chlorzoxazone or Ibuprofen can remarkably enhance the luminescence intensity of Eu-Tetracycline HCl complex doped in a sol–gel matrix in dimethylformamide (DMF) at pH 9.7 and 6.3, respectively, λ_ex = 400 nm. The enhancing of luminescence intensity peak of Eu-Tetracycline HCl complex at 617 nm is proportional to the concentration of chlorzoxazone or Ibuprofen a result that suggested profitable application as a simple optical sensor for chlorzoxazone or Ibuprofen assessment. The dynamic ranges found for the determination of chlorzoxazone and Ibuprofen concentration are 5 × 10⁻⁹–1 × 10⁻⁴ and 1 × 10⁻⁸–7 × 10⁻⁵ mol L⁻¹, and the limit of detection (LOD) and quantitation limit of detection (LOQ) are 3.1 × 10⁻¹⁰ , 9.6 × 10⁻¹⁰ and 5.6 × 10⁻¹⁰, 1.7 × 10⁻⁹ mol L⁻¹, respectively.     

Electrochemical study of P(VDF-HFP)/PMMA blended polymer electrolyte with high-temperature stability for polymer lithium secondary batteries

In the present study, a kind of solid polymer electrolyte (SPE) based on poly(vinylidene difluoride-co-hexafluoropropylene)/poly(methyl methacrylate) blends was prepared by a casting method to solve the safety problem of lithium secondary batteries. Owing to being plasticized with a room temperature ionic liquid, N-butyl-N′-methyl-imidiazolium hexafluorophosphate, the obtained SPE shows a thermal decomposition temperature over 300°C and an ionic conductivity close to 10⁻³ S cm⁻¹. The SPE-3 sample, in which the weight of two polymers is equivalent, possesses an ionic conductivity of 0.45 × 10⁻³ S cm⁻¹ at 25°C and presents an electrochemical window of 4.43 V. The ionic conductivity of the SPE-3 is as high as 1.73 × 10⁻³ S cm⁻¹ at 75°C approaching to that of liquid electrolyte. The electrochemical performances of the Li/LiFePO₄ cells confirmed its feasibility in lithium secondary batteries.     

Study of Enhanced Chemiluminescence of Diperiodatocuprate (III) on 1,10-Phenanthroline/Hydrogen Peroxide/Cetyltrimethylammonium Bromide System

In the paper, a chemiluminescence (CL) system was developed based on the catalytical effect of diperiodatocuprate (III) (DPC) on the 1,10-phenanthroline (phen)/hydrogen peroxide (H₂O₂) in the presence of cetyltrimethylammonium bromide (CTAB). The effects of experimental conditions were investigated. Meanwhile the increase of CL intensity of the DPC/phen/H₂O₂/CTAB system is proportional to the concentration of phen in the range of low concentration. The linear range of the calibration curve is 5.0 × 10⁻⁹–1.0 × 10⁻⁶ mol L⁻¹, and the corresponding detection limit is 1.9 × 10⁻⁹ mol L⁻¹. The effects of phenolic compounds (PCs) on the system were investigated. Hydroquinone was used as an example to investigate the application of the CL system to the determination of PCs. The quenched CL intensity is linearly related to the logarithm of concentration of hydroquinone. The linear range of the calibration curve is 2.5 × 10⁻⁹–1.0 × 10⁻⁵ g mL⁻¹, and the corresponding detection limit is 1.8 × 10⁻⁹ g mL⁻¹. This phen and hydroquinone can be synchronously determined. The method was applied to the determination of hydroquinone in water samples and the recoveries were from 92% to 106%.     

Search for solar axions emitted in the M1-transition of 7Li* with Borexino CTF

Results of background measurements with a prototype of the Borexino detector were used to search for 478 keV solar axions emitted in the M1-transitions of ⁷Li^*. The Compton conversion of axion to a photon A+e→e+γ, axioelectric effect A+e+Z→e+Z, decay of axion in two photons A→2γ and Primakoff conversion on nuclei A+Z→γ+Z are considered. The upper limit on constants of interaction of axion with electrons, photons and nucleons – g_Aeg_AN≤(1.0–2.4)×10^-10 at m_A≤450 keV and g_Aγg_AN≤5×10^-9 GeV^-1 at m_A≤10 keV are obtained (90%c.l.). For heavy axions with mass at 100<m_A<400 keV the limits g_Ae<(0.7–2.0)×10^-8 and g_Aγ<10^-9–10^-8 are obtained in assumption that g_AN depends on m_A as for KSVZ axion model. These limits are stronger than obtained in previous laboratory-based experiments using nuclear reactor and artificial radioactive sources. PACS 14.80.Mz; 29.40.Mc; 26.65.+t     

New Fluorescent Antitumour Cisplatin Analogue Complexes. Study of the Characteristics of their Binding to DNA by Flow Injection Analysis

The flow injection technique is applied to study the binding to DNA of new platinum complexes—E₁: ethylenediaminechlorocholylglycinateplatinum(II): [PtCl(CG)(en)], C₅₄H₉₂O₁₂Pt and E₂: ethylenediaminebischolylglycinateplatinum(II): [Pt(CG)₂(en)], C₂₈H₅₀ClN₃O₆Pt—derived from cisplatin in which the exchangeable ligands were replaced by bile acids, such that these anticancer drugs have less toxicity and less resistance is developed towards them. Both compounds are fluorescent and their fluorescence is enhanced when they form adducts with DNA, a property that is extremely useful for monitoring the cytotoxic activity and their mechanisms of action. The binding parameters to DNA of E₁ [apparent intrinsic binding constant K_E1: (11.2 ± 0.4) × 10³ M⁻¹ and maximum number of binding sites per nucleotide, n _E1: 0.121 ± 2 × 10⁻³) and E₂ (K_E2: 9.2 ± 0.7) × 10³ M⁻¹ and n _E2 0.098 ± 2 × 10⁻³] were determined following the Scatchard method and the type of binding was studied experimentally through the modifications introduced by each of the compounds into the ethidium bromide–DNA bond.     

Transparent conducting antimony-doped tin oxide films deposited on flexible substrates by r.f. magnetron-sputtering

Transparent conducting antimony-doped tin oxide (SnO₂:Sb) films were deposited on organic substrates by r.f. magnetron-sputtering. Polycrystalline films with a resistivity of ≈ 6.5×10^-3 Ω cm, a carrier concentration of≈ 1.2×10²⁰ cm^-3 and a Hall mobility of ≈ 9.7 cm² v^-1 s^-1 were obtained. The average transmittance of these films reached 85% in the wavelength range of the visible spectrum. Received: 20 April 2001 / Accepted: 23 July 2001 / Published online: 17 October 2001     

Strain dependence of the piezoelectric polarization of z-cut lithium niobate

Measurements of the piezoelectric polarization of z-cut lithium niobate are accomplished for dynamic compressive strains of from 8.9 × 10^?4 to 6 × 10^?3. Values for the linear piezoelectric constant, $\text{e}$₃₃ and its strain derivative are determined. The logarithmic strain derivatives of the longitudinal piezoelectric constants of x-cut quartz and z-cut lithium niobate are found to be approximately equal.     

Pyrophosphate Selective Recognition in Aqueous Solution Based on Fluorescence Enhancement of a New Aluminium Complex

A novel and simple fluorescence enhancement method for selective pyrophosphate(PPi) sensing was proposed based on a 1:1 metal complex formation between bis(8-hydroxy quinoline-5-solphonat) chloride aluminum(III) (Al(QS)₂Cl), (L) and PPi in aqueous solution. The linear response range covers a concentration range of 1.6 × 10⁻⁷ to 1.0 × 10⁻⁵ mol/L of PPi and the detection limit of 2.3 × 10⁻⁸ mol/L. The association constant of L-PPi complex was calculated 2.6 × 10⁵ L/mol. L was found to show selectively and sensitively fluorescence enhancement toward PPi over than I₃^-, NO₃^-, CN⁻, CO₃²⁻, Br⁻, Cl⁻, F⁻, H₂PO4⁻ and SO₄²⁻, which was attributed to higher stability of inorganic complex between pyrophosphate and L.     

Application of photothermal deflection spectroscopy for the determination of iron(II) with ferrozine with sorption preconcentration on Silufol

Photothermal deflection spectroscopy was applied for selective detection of the intensely coloured iron(II) chelate with ferrozine on Silufol plates. The linearity range was 1×10^-11 - 6×10^-8 mol cm^-2 of chelate at the plate surface, which corresponded to 1×10^-9 - 4×10^-6 M of chelate in solution. The limits of detection and quantification are 8×10^-12 and 20×10^-12 mol cm^-2 at the plate from 15 μL of test solution (0.5 nM and 1.5 nM in solution, respectively), which corresponded to n ×10^-18 mol absolute amounts of the chelate at the detection zone.     

Double spin asymmetry in exclusive ρ0 muoproduction at COMPASS

The longitudinal double spin asymmetry A₁ ^ρ for exclusive leptoproduction of ρ⁰ mesons, μ+N→μ+N+ρ, is studied using the COMPASS 2002 and 2003 data. The measured reaction is incoherent exclusive ρ⁰ production on polarised deuterons. The Q² and x dependence of A₁ ^ρ is presented in a wide kinematical range, 3×10^-3<Q²< 7 (GeV/c)² and 5×10^-5<x<0.05. The results presented are the first measurements of A₁ ^ρ at small Q² (Q²< 0.1 (GeV/c)²) and small x (x<3×10^-3). The asymmetry is in general compatible with zero in the whole kinematical range. PACS 13.60.Le; 13.88.+e     

Spectrofluorimetric Assessment of Hydrochlorothiazide Using Optical Sensor Nano-Composite Terbium Ion Doped in Sol-Gel Matrix

A new, simple, sensitive and selective spectrofluorimetric method for the determination of Hydrochlorothiazide was developed in acetonitrile at pH 6.2. The Hydrochlorothiazide can remarkably enhance the luminescence intensity of the Tb³⁺ ion doped in sol–gel matrix at λ_ex = 370 nm. The intensity of the emission band of Tb³⁺ ion doped in sol–gel matrix was increased due to the energy transfer from the triplet excited state of Hydrochlorothiazide to (⁵D₄) excited energy state of Tb³ ion. The enhancement of the emission band of Tb³⁺ ion doped in sol–gel matrix at (⁵D₄→⁷ F₅) 545 nm was directly proportion to the concentration of Hydrochlorothiazide with a dynamic ranges of 5.0 × 10⁻¹⁰—5.0 × 10⁻⁶ mol L⁻¹ and detection limit of 2.2 × 10⁻¹¹ mol L⁻¹.     

Cilostazol determination by the enhancement of the green emission of Tb3+ optical sensor

The efficiency of excited-state interaction between Tb³⁺ and the industrial product Cilostazol (CIL) has been studied in different solvents. High luminescence intensity peak at 545 nm of terbium complex in acetonitrile was obtained. The photophysical properties of the green emissive Tb³⁺ complex have been elucidated, the terbium was used as optical sensor for the assessment of CIL in the pharmaceutical tablets and body fluids at pH 3.1 and λ_ex = 320 nm with a concentration range 1.0 × 10⁻⁹–1.0 × 10⁻⁶ mol L⁻¹ of CIL, correlation coefficient of 0.998 and detection limit of 7.5 × 10⁻¹⁰ mol L⁻¹.