Chemiluminescence of the Reaction System Ce(IV) - Non-Steroidal Anti-Inflammatory Drugs Containing Europium(III) Ions and its Application to the Determination of Naproxen in Pharmaceutical Preparations and Urine

The chemiluminescence (CL) of oxidation of non-steroidal anti-inflammatory drugs (NSAIDs) by Ce(IV) ions, was recorded in the presence and absence europium(III) ions, in solution of pH ~ 4 of solution. Kinetic curves and CL emission spectra of the all studied systems were discussed. CL of measurable intensity was observed in the Ce(IV)–NP–Eu(III) reaction system only in acidic solutions. The CL spectrum rcegistered for this system shows emission bands, typical of Eu(III) ions, with maximum at λ ~ 600 nm. The chemiluminescent method, based on Eu(III) emission in reaction system of NP-Ce(IV)–Eu(III) in acid solution was therefore used for the determination of naproxen in mixture of non-steroidal anti-inflammatory drugs.     

光泽精化学发光体系的研究与应用

对光泽精化学发光体系的动力学性质、荧光光谱、化学发光光谱及化学发光机理进行研究和探讨。详细研究了光泽精 - H2 O2 - Co( )流动注射化学发光体系的最佳分析条件。结果表明 ,当光泽精 (L c)为 2 .5×10 - 5mol/L、H2 O2 为 0 .5 mol/L、Na OH为 0 .4 mol/L、CTMAB为 2 .0× 10 - 5mol/L时 ,测定 Co( )的校准曲线线性范围为 0 .0 5— 2 0 0μg/m L ,检出限为 0 .0 1μg/m L。对 10μg/m L Co( )连续测定 7次 ,相对标准偏差为 1.7%。     

三唑磷-鲁米诺-H2O2发光体系的研究与应用

研究了碱性介质中三唑磷-鲁米诺-H2O2体系的化学发光特征,建立了三唑磷流动注射化学发光分析方法,并对反应机理进行了探讨.研究了三唑磷-鲁米诺-H2O2体系的化学发光反应动力学,考察了pH、流速、鲁米诺-H2O2配比等因素对化学发光的影响.在最佳条件下,过氧化氢HOO-负离子可能与三唑磷的磷原子反应生成磷的过氧化合自由基,与鲁米诺作用使得体系化学发光得到增强,3s内达到了最大值;应用于三唑磷的测定,在1.0×10-8-1.0×10-5g/mL范围内呈良好的线性关系,检出限(S/N=3)为6.7×10-9g/mL;测定蔬菜样品,三唑磷浓度分别为1.0-5.0μg/mL时,测定回收率为82.3%-108.6%,测定偏差为1.6%-4.7%.     

New sonochemiluminescence involving solvated electron in Ce(III)/Ce(IV) solutions

The moving single-bubble sonoluminescence of Ce³⁺ in water and ethylene glycol solutions of CeCl₃ and (NH₄)₂Ce(NO₃)₆ was studied. As found, a significant part of intensity of the luminescence (100% with cerium concentration less than 10^–4 M) is due to the sonochemiluminescence. A key reaction of sonochemiluminescence is the Ce⁴⁺ reduction by a solvated (or hydrated in water) electron: Ce⁴⁺ + e_s (e_aq) → *Ce³⁺. Solvated electrons are formed in a solution via electrons ejection from a low-temperature plasma periodically generated in deformable moving bubble at acoustic vibrations. Reactions of heterolytic dissociation of solvents make up the source of electrons in the plasma. In aqueous CeCl₃ solutions, the Ce⁴⁺ ion is formed at the oxidation of Ce³⁺ by OH radical. The latter species originates from homolytic dissociation of water in the plasma of the bubble, also penetrating from the moving bubble into the solution. The sonochemiluminescence in cerium trichloride solutions are quenched by the Br⁻ (acceptor of OH) and H⁺ ions (acceptor of e_aq). In water and ethylene glycol solutions of (NH₄)₂Ce(NO₃)₆, the sonochemiluminescence also quenched by the H⁺ ion. The sonochemiluminescence in CeCl₃ solutions is registered at [Ce³⁺] ≥ 10^–5 M. Then the sonochemiluminescence intensity increases with the cerium ion concentration and reaches the saturation plateau at 10^–2 M. It was shown that sonophotoluminescence (re-emission of light of bubble plasma emitters by cerium ions) also contributes to the luminescence of Ce³⁺ in solutions with [Ce³⁺] ≥ 10^–4 M. If the cerium concentration is more than 10^–2 M, a third source contributes to luminescence, viz., the collisional excitation of Ce³⁺ ions penetrating into the moving bubble.     

Radiolytic formation of Ce(IV) in aqueous solutions of Ce(III) chelates with aminopolycarboxylic acids

Gamma -radiolysis of alkaline solutions of Ce(III) chelates with aminopolycarboxylic acids of different sizes like ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA) and iminodiacetic acid (IDA) revealed that OH radicals selectively attack the ligands probably due to a molecular kinetic effect rather than a steric one. The low G (CH₂O) values are ascribed to the reaction of CH₂O with H₂O₂.     

Magnetoresistivity of the Kondo-system (La,Ce)B6

The electrical resistivity of the Kondo system (La, Ce)B₆ has been measured in longitudinal and transversal magnetic fields up to 6 Tesla in the temperature range 0.04–20K. Corresponding to the strong increase of the resistivity with decreasing temperature the alloys show a very large negative magnetoresistivity with a Kondo temperatureT _K =1.05K and a Kondo magnetic fieldB _K =1.1 Tesla. The observed anisotropy of the resistivity due to the magnetic field direction cannot be explained well by existing theories.     

Determination of Total Antioxidant Capacity by a New Spectrofluorometric Method Based on Ce(IV) Reduction: Ce(III) Fluorescence Probe for CERAC Assay

A Ce(IV)-based reducing capacity (CERAC) assay was developed to measure the total antioxidant capacity (TAC) of foods, in which Ce(IV) would selectively oxidize antioxidant compounds but not citric acid and reducing sugars which are not classified as antioxidants. The method is based on the electron-transfer (ET) reaction between Ce(IV) ion and antioxidants in optimized acidic sulphate medium (i.e., 0.3 M H₂SO₄ and 0.7 M Na₂SO₄) and subsequent determination of the produced Ce(III) ions by a fluorometric method. The fluorescent product, Ce(III), exhibited strong fluorescence at 360 nm with an excitation wavelength of 256 nm, the fluorescence intensity being correlated to antioxidant power of the original sample. The linear concentration range for most antioxidants was quite wide, e.g., 5.0 × 10⁻⁷–1.0 × 10⁻⁵ M for quercetin. The developed procedure was successfully applied to the TAC assay of antioxidant compounds such as trolox, quercetin, gallic acid, ascorbic acid, catechin, naringin, naringenin, caffeic acid, ferulic acid, glutathione, and cysteine. The proposed method was reproducible, additive in terms of TAC values of constituents of complex mixtures, and the trolox equivalent antioxidant capacities (TEAC coefficients) of the tested antioxidant compounds gave good correlations with those found by reference methods such as ABTS and CUPRAC.     

Sensitive Determination of Carbohydrates by Fluorimetric Method with Ce(IV) and Sodium Triphosphate

A new simple and sensitive fluorimetric method for the determination of carbohydrates is described. The method is based on the reaction between carbohydrates and Ce(IV) in the presence of sulfuric acid. All the reductive carbohydrates can be detected indirectly by the fluorescence of Ce(III) produced. The addition of sodium triphate enhances the sensitivity of the method by more than 10-folds. Under optimum conditions, an excellent linear relationship was obtained between the fluorescence intensity and the concentration of carbohydrates. The limits of detection lie in the range of 9.3 x 10(-10) - 1.3 x 10(-9) mol/L. As compared to the normal fluorimetric method, the proposed method is faster and more sensitive.     

Investigation of the hyperfine structure of Ta I-lines (IV)

The hyperfine structure of about 200 lines of the neutral tantalum atom was investigated by means of Doppler limited laser spectroscopy. From the spectra we have deduced the magnetic hyperfine interaction constants A and the electric quadrupole interaction constants B of 8 levels with even parity and 81 levels with odd parity. Further, we have discovered 24 new levels of even parity and 11 new levels of odd parity.     

HgCl (B-X) Chemiluminescence from Alkali Atom - HgCl2 Reactions

Laser action on the B²Σ⁺ _1/2 → X²Σ⁺ _1/2 band of HgCl at 557.6 nm (v′=0→v″=22) has previously been achieved under a variety of electronic and optical excitation mechanisms. This letter describes a chemical mechanism for producing excited HgCl. We report on the gas phase reaction between alkali atoms (K, Rb, and Cs) and HgCl₂ which produces HgCl (B-X) emission.     

Investigation of (3He,3He)- and (3He,t)-reactions on10B,11B and13C

The³He-elastic scattering and the (³He,t)-reactions on¹⁰B,¹¹B and¹³C were studied. Excitation functions for the reactions¹⁰B(³He,t)¹⁰C and¹¹B(³He,t)¹¹C were measured at incident energies between 11 and 17 MeV. All angular distributions were taken at 14 MeV³He-energy. From an optical model analysis of the³He-elastic scattering data the parameters of the optical potentials were determined. Best fits were obtained using surface peaked potentials. The (³He,t)-reactions were interpreted in terms of a microscopic model, which, in general, gave a good account of the data. Corrections due to nonlocality effects were included in the calculations. A satisfactory agreement of the predicted and the measured cross sections required an effective nucleon-nucleon interaction of the Yukawa form (α^?1=1.2 fm). Using a Serber exchange mixture the isospindependent- and the spin-isopin-dependent strength parameters of the potential were deduced to beVτ=21.4±2.3 MeV andV _{σ τ}=19.5 ± 2.7 MeV, respectively.     

1-(6-硝基-2-苯并噻唑)-3-(4-硝基苯)-三氮烯与铜显色反应的研究及应用

在TritonX-100表面活性剂存在下,pH为10.0-11.0的Na2B4O7-NaOH缓冲溶液中,1-(6-硝基-2-苯并噻唑)-3-(4-硝基苯)-三氮烯(NBTNPT)与铜生成2:1配合物。配合物的最大负吸收峰是540nm,表观摩尔吸光系数为1.15×105L·mol-1·cm-1。Cu2 的质量浓度在0-360μg/L符合比耳定律。测定铝合金样品中的微量铜,结果满意。     

Spectral components that form UV absorption spectrum of Ce3+ and Ce(IV) valence states in matrix of photothermorefractive glasses

We have measured the UV absorption spectra of photothermorefractive glasses of the system Na₂O-ZnO-Al₂O₃-NaF-SiO₂ doped by cerium oxide in the range of (2.8–5.0) × 10⁴ cm⁻¹ (360–200 nm). The spectra have been processed by the method of dispersion analysis based on the analytical convolution model for the complex dielectric function of glasses. We show that the absorption band centered at 3.3 × 10⁴ cm⁻¹ (∼303 nm) that is attributed to the transition 2F _5/2 → 5d in the Ce³⁺ ion, is an envelope of three spectral components. The broad absorption range (3.5–4.7) × 10⁴ cm⁻¹ (200–270 nm) that is commonly interpreted as a charge transfer band of the Ce(IV) valence state, is an envelope of at least three spectral components.     

溴化镧闪烁体探测器性能及应用研究

LaBr3(Ce)探测器是一种新型闪烁体探测器,具有高光产额,高探测效率,高时间和空间分辨率,高能量分辨率,温度特性良好,抗辐射性能良好,操作简便等优点.从2001年以来,该探测器得到了迅速的研究和应用.LaBr3(Ce)探测器在核共振荧光检测、瞬发γ中子活化分析、爆炸物检测、核医学成像、环境辐射监测、空间辐射探测等方面的应用研究中取得了非常良好的效果.该探测器表现出优于以往用于这些领域的探测器的性能(例如NaI(Tl)探测器、BGO探测器、HPGe探测器等).介绍了LaBr3(Ce)探测器的性能及其应用研究进展,对代表性文献进行了简析和综述,阐明了其良好的应用前景.     

Search for the lepton-flavor-violating leptonic B(0)-->mu(+/-)tau(-/+) and B(0)-->e(+/-)tau(-/+)

We have searched a sample of 9.6 x 10(6) BB events for the lepton-flavor-violating leptonic B decays, B(0)-->mu(+/-)tau(-/+) and B(0)-->e(+/-)tau(-/+). The tau lepton was detected through the decay modes tau-->lnunu(-) , where l=e, mu. There is no indication of a signal, and we obtain the 90% confidence level upper limits B(B(0)-->mu(+/-)tau(-/+))<3.8 x 10(-5) and B(B(0)-->e(+/-)tau(-/+))<1.3 x 10(-4).     

Kondo effect and impurity-impurity interaction in (La,Ce)B6 alloys

Measurements of the magnetic susceptibility between 0.03 and 300 K and of the magnetization between 0.05 and 10K for magnetic fields up to 60kOe have been used to investigate effects from the interaction between the conduction electrons and local magnetic moments in (La_1–x Ce _x )B₆ alloys (0.0007x0.10). For Ce concentrationsx<0.006 the data show Kondo-type single impurity behavior at low temperatures with a transition from a magnetic to a non-magnetic regime of the Ce ions. In the magnetic regime the impurity susceptibility follows a Curie-Weiss law, and in the non-magnetic regime it varies withT ². An external magnetic field gradually restores the free-ion behavior of the Ce impurities. For more concentrated alloys interactions between the impurities are observed. The RKKY interaction strength derived is more than two orders of magnitude smaller than in the Kondo systemCuFe. Values of thes–f exchange integral,J, estimated from both the Kondo effect and the RKKY interactions are in good agreement. The relatively high Kondo temperature, in spite of a smallJ, can be explained by a density-of-states argument. The influence of crystal field excitation on the susceptibility is also discussed.     

Microwave-Triggered Metal-Enhanced Chemiluminescence (MT-MEC): Application to Ultra-fast and Ultra-sensitive Clinical Assays

In this rapid communication we describe a new approach to protein detection with chemiluminescence. By combining common practices in protein detection with chemiluminescence, microwave technology, and metal-enhanced chemiluminescence, we show that we can use low power microwaves to substantially increase enzymatic chemiluminescent reaction rates on metal substrates. As a result, we have found that we can in essence trigger chemiluminescence with low power microwave (Mw) pulses and ultimately, perform on-demand protein detection assays. Using microwave triggered metal-enhanced chemiluminescence (MT-MEC), we not only improve the sensitivity of immunoassays with enhanced signal-to-noise ratios, but we also show that we can accurately quantify protein concentrations by integrating the photon flux for discrete time intervals.     

Ultrasensitive Study of Gatifloxacin Based on Its Enhancing Effect on the Cerium (IV)-Sodium Hyposulfite Chemiluminescence Reaction in a Micellar Medium

A sensitive and rapid flow-injection chemiluminescence (CL) method has been developed for the determination of gatifloxacin in pharmaceutical preparations and biological samples. The method is based on the enhancing effect of gatifloxacin on CL emission generated by the interaction of Ce (IV) in sulphuric acid and sodium hyposulphite (Na(2)S(2)O(4)) sensitized by sodium dodecyl benzene sulfonate (SDBS). Strong CL emission was observed when gatifloxacin was injected into the Ce (IV) in sulphuric acid and Na(2)S(2)O(4) solution incorporated with SDBS in a flow-cell. Several experimental parameters affecting the CL reaction were investigated and optimized systematically. Under the optimum conditions, it was found that the CL intensity is proportional to the concentration of gatifloxacin in the range of 1.12 × 10(-11)-4.40 × 10(-9) g mL(-1) with a co-relation coefficient of 0.9994. The limit of detection was found to be 4.87 × 10(-12) g mL(-1) and the relative standard deviation (RSD, n=7) was 1.8% for 4 × 10(-8) g mL(-1) of GFLX. The proposed method offers higher sensitivity, wide linear range and better stability without requiring sophisticated instrumentation. Thus, the proposed method has been successfully applied to the determination of gatifloxacin in pharmaceuticals, serum and human urine.