A sensitive chemiluminescence method for the determination of H2O2 in exhaled breath condensate

In this paper, a novel flow injection chemiluminescence (FI-CL) method is proposed for the determination of picomolar L(-1) levels of hydrogen peroxide (H(2)O(2)) in exhaled breath condensate (EBC). This method is based on the oxidation of a low concentration of luminol (10(-7) M) by H(2)O(2) at a low concentration level (< 10(-8) M) in an alkaline medium catalyzed by a complex, K(5)[Cu(HIO(6))(2)] (DPC), which is not interfered by other metal ions or horseradish peroxidase (HRP). Under the optimum conditions, H(2)O(2) was determined over the range of 1.0 x 10(-10) to 1.0 x 10(-8) mol L(-1) with a detection limit of (3sigma) of 4.1 x 10(-11) mol L(-1). The relative standard deviation (RSD) was 3.2% for 5 nmol L(-1) H(2)O(2) (n = 7). The proposed method offers the advantages of ultra-sensitivity, selectivity, simplicity and rapidity for H(2)O(2) determination. It was successfully applied to directly determine trace amounts of H(2)O(2) (nmol L(-1)) in human's EBC of both rheum and healthy volunteers. A statistically significant difference was found between patients with rheum (n = 11) and control subjects without rheum (n = 11).     

Green and blue electrochemically generated chemiluminescence from click chemistry--customizable iridium complexes

Cationic cyclometalated iridium complexes containing two anionic phenylpyridine (ppy) ligands and the neutral bidentate triazole-pyridine ligand, 2-(1-substituted-1H-1,2,3-triazol-4-yl)pyridine (pytl), were investigated. The complexes display a rich and reversible electrochemical behavior, upon investigations by cyclic voltammetry in strictly aprotic conditions, that couples with excellent emission quantum yields and long lifetimes of the excited states. Therefore, in organic media, all complexes have generated intense green electrochemiluminescence (ECL) through the so-called annihilation procedure and, importantly, a modulation of the emission energy (to blue) has been easily obtained by simple fluorination of the ppy ligand. Finally, taking advantage of their remarkable solubility in water, intense ECL was also obtained from aqueous buffer solutions using the co-reactant method, thus making all the investigated complexes highly promising for their effective use as ECL labels in bioanalytical applications.     

Dual reactivity of electrochemically generated 2-thiophenaldehyde anion-radicals

Conclusions The one-electron reduction of 2-thiophenaldehyde in DMF as the medium gives, besides the usual dimerization product of the pinacol type, also 5-(-thienyl)-2-acetoxymethylthiophenaldehyde, which is explained by the dual reactivity of the electrochemically generated anion-radicals.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1150–1153, May, 1981.     

H2-受体拮抗剂的流动注射-化学发光分析方法的研究

碱性介质中K3Fe（CN）6与H2-受体拮抗剂发生氧化-还原反应产生化学发光,罗丹明6G可显著增强其发光信号,且强度与药物浓度呈良好的线性关系。据此,建立了采用K3Fe（CN）6-罗丹明6G体系测定制剂中H2-受体拮抗剂的流动注射-化学发光分析方法。在优化的实验条件下,西咪替丁在1.0&#215;10^-9-7.0&#215;10^-5g/mL范围内呈良好的线性关系,检出限为8.6&#215;10^-10g/mL;盐酸雷尼替丁在1.0&#215;10^-9-5.0&#215;10^-5g/mL范围内呈线性关系,检出限为8.7&#215;10^-10g/mL;法莫替丁在5.0&#215;10^-9-7.0&#215;10^-5g/mL范围内呈线性关系,检出限为2.4&#215;10^-9g/mL。通过对浓度为1.0&#215;10^-6g/mL的3种H2-受体拮抗剂分别进行的11次平行测定,其RSD分别为4.0%,3.8%和2.9%。     

Turn-on fluorescence detection of H2O2 and TATP

Peroxide-based explosives, like triacetone triperoxide (TATP), are important targets for detection because of their broad use in improvised explosives but pose challenges. We report a highly sensitive turn-on fluorescence detection for H2O2 and organic peroxides, including TATP. The detection strategy relies on oxidative deboronation to unmask H2Salen, which subsequently binds Zn(2+) to form fluorescent Zn(Salen). Sensitivity is excellent, with detection limits below 10 nM for H2O2, TATP, and benzoyl peroxide. In addition, acid treatment is necessary to sense TATP, suggesting the potential to discriminate between H2O2 and TATP based upon minimal sample pretreatment.     

A simple and general method for the synthesis of multicomponent Na2V6O16.3H2O single-crystal nanobelts

Multicomponent Na2V6O16.3H2O (barnesite) single-crystalline nanobelts were synthesized by a direct reaction-crystallization growth of bulk V2O5 and NaF powders under hydrothermal treatment without using any templates or catalysts. This new strategy could be extended to prepare other one-dimensional multicomponent nanomaterials including ammonium, alkali-metal or alkali-earth metal vanadium oxide bronzes and other transition metal oxyfluorides. This is an efficient and mild solution method with clear advantages over the traditional high-temperature approach for the large-scale production of 1D multicomponent nanomaterials. The applicability of this approach toward the preparation of other inorganic systems, such as tungstates and molybdates, will be explored.     

Photometric detection of cyclodextrins in liquid chromatography by using iodine generated electrochemically in-situ

A method has been developed for photometric detection of cyclodextrins (CD) in liquid chromatography using iodine (I₂) generated electrochemically in-situ. Iodide ion in the mobile phase was electrochemically oxidized to I₂ which was subsequently reacted with I^–, in an electrochemical flow cell, forming I₃^–. The absorbance of I₃^– was found to be greatly enhanced when CD were present in the mobile phase. The absorbance enhancement was caused by the change in the mole fraction of I₃^–, because of the inclusion reaction of I₃^– with CD. On the basis of this phenomenon, CD were detected by means of a photodiode-array UV–visible detector positioned downstream of the electrochemical flow cell. The signals were found to be linearly dependent on CD concentration. Because the formation constants of I₃^– with CD decrease in the order -CD>-CD>-CD, -CD was most detectable by the method. Detection limits were 1.0 mol L^–1 for -CD, 65 mol L^–1 for monoG1--CD, 100 mol L^–1 for -CD, and 200 mol L^–1 for -CD.     

A new staining method for the detection of activities of H2O2-producing oxidases on gels and blots using cerium and 3,3'-diaminobenzidine.

Cerium chloride (CeCl3) was used to trap the hydrogen peroxide generated by several oxidases on native gels and blots. The pale yellow color of cerium perhydroxide formed is converted to a brown-black precipitate by the subsequent reaction with 3,3'-diaminobenzidine. The suitability of this method for the detection of the activity of several oxidases on gels and on blots under nondenaturing conditions, employing different electrophoretic systems and resolving techniques, is demonstrated. Moreover, this method has proven to be highly suitable for the assessment of the substrate and stereospecificity of oxidases, the determination of their molecular weights, and the isoelectric points of isoforms.     

Layer-by-layer assembly of porphyrin/layered double hydroxide ultrathin film and its electrocatalytic behavior for H2O2

The ordered ultrathin film based on iron(III) porphyrin and Co–Al layered double hydroxide (Co–Al LDH) nanosheets has been fabricated via the layer-by-layer (LBL) method. The film modified electrode demonstrates a couple of well-defined reversible redox peaks attributed to Co(III)/Co(II), with iron(III) porphyrin serving as an efficient mediator for facilitating the electron transfer. Furthermore, it exhibits excellent electrocatalytic behavior for H₂O₂ with a wide linear range of response, high sensitivity and low detection limit.     

Deuterium exchange in the systems of H2O+/H2O and H3O+/H2O

The reactions of H₂O⁺, H₃O⁺, D₂O⁺, and D₃O⁺ with neutral H₂O and D₂O were studied by tandem mass spectrometry. The H₂O⁺ and D₂O⁺ ion reactions exhibited multiple channels, including charge transfer, proton transfer (or hydrogen atom abstraction), and isotopic exchange. The H₃O⁺ and D₃O⁺ ion reactions exhibited only isotope exchange. The variation in the abundances of all ions involved in the reactions was measured over a neutral pressure range from 0 to 2 × 10⁻⁵ Torr. A reaction scheme was chosen, which consisted of a sequence of charge transfer, proton transfer, and isotopic exchange reactions. Exact solutions to two groups of simultaneous differential equations were determined; one group started with the reaction of ionized water, and the other group started with the reactions of protonated water. A nonlinear least-squares regression technique was used to determine the rate coefficients of the individual reactions in the schemes from the ion abundance data. Branching ratios and relative rate coefficients were also determined in this manner.A delta chi-squared analysis of the results of the model fitted to the experimental data indicated that the kinetic information about the primary isotopic exchange processes is statistically the most significant. The errors in the derived values of the kinetic information of subsequent channels increased rapidly. Data from previously published selected ion flow tube (SIFT) study were analyzed in the same manner. Rigorous statistical analysis showed that the statistical isotope scrambling model was unable to explain either the SIFT or the tandem mass spectrometry data. This study shows that statistical analysis can be utilized to assess the validity of possible models in explaining experimentally observed kinetic behaviors.     

Titanium silicalite-1 zeolite microparticles for enzymeless H2O2 detection

In this communication, we demonstrate for the first time that titanium silicalite-1 zeolite microparticles (TSZMs) can effectively catalyze the reduction of H(2)O(2), leading to an enzymeless H(2)O(2) sensor with a linear detection range from 100 μM to 40 mM (r = 0.994) and a detection limit of 0.5 μM at a signal-to-noise ratio of 3.     

Singlet oxygen generated from the decomposition of peroxymonocarbonate and its observation with chemiluminescence method

The decomposition of peroxymonocarbonate (HCO(4)(-)) has been investigated by flow-injection chemiluminescence (CL) method. An ultraweak CL was observed during mixing the bicarbonate and hydrogen peroxide solution in organic cosolvent. An appropriate amount of fluorescent organic compounds, such as dichlorofluorescein (DCF), was added to the HCO(4)(-) solution, a strong CL was recorded. Based on studies of the spectrum of fluorescence, CL and UV-vis spectra, electron spin trapping (ESR) technique, mass spectra (MS) and comparison with H(2)O(2)/hypochlorite (ClO(-)) and H(2)O(2)/molybdate (MoO(4)(-)) systems, the CL mechanism was proposed. The reaction is initiated by unimolecular homolysis of the peroxo O-O bond in HO-OCOO(-) molecule. It was suggested that the bond rearrangement within radicals yield superoxide ion (O(2)(*-)). The interaction of superoxide ion with perhydroxyl radical produces singlet oxygen ((1)O(2)). The energy transfers from singlet oxygen to DCF forming an excited energy acceptor (DCF*). Luminescence (lambda(max)=509 nm) was emitted during the relaxation of the energy acceptor to the ground state.     

H2O2 triggered sol-gel transition used for visual detection of glucose

A new approach for the visual detection of glucose based on a H(2)O(2) triggered sol-gel transition in combination with modified gold nanoparticles is reported.     

Cu2+-H2O2-罗丹明B-西咪替丁化学发光体系的研究

在弱碱性的多聚磷酸钠介质中,二价铜离子、过氧化氢和染料罗丹明B混合可以产生较强的化学发光,西咪替丁对此发光有较强的抑制作用,其抑制发光强度与西咪替丁P43的质量浓度在5.0-1000μg.L-1范围内呈良好的线性关系,基于此,结合流动注射技术,建立了一种直接测定西咪替丁的化学发展发光新方法。该方法具有较高的灵敏度,检出限为2.2μg.L-1(IUPAC),对500μg.L-1西咪替丁平行测定11次,其相对标准偏差为2.1%。该方法已成功用于西咪替丁胶囊和针剂含量的测定。     

Factors affecting the catalytic epoxidation of olefins by iron porphyrin complexes and H2O2 in protic solvents

The catalytic epoxidation of cyclohexene by iron(III) porphyrin complexes and H2O2 has been investigated in alcohol solvents to understand factors affecting the catalyst activity in protic solvents. The yields of cyclohexene oxide and the Fe(III/II) reduction potentials of iron porphyrin complexes were significantly affected by the protic solvents, and there was a close correlation between the product yields and the reduction potentials of the iron porphyrin catalysts. The role of alcohol solvents was proposed to control the electronic nature of iron porphyrin complexes that determines the catalyst activity in the epoxidation of olefins by H2O2. We have also demonstrated that an electron-deficient iron porphyrin complex can catalyze the epoxidation of olefins by H2O2 under conditions of limiting substrate with high conversion efficiency in a solvent mixture of CH3OH and CH2Cl2.