Imidazolium-based ionic liquid derivative/Cu<Superscript>II</Superscript> complexes as efficient catalysts of the lucigenin chemiluminescence system and its application to H<Subscript>2</Subscript>O<Subscript>2</Subscript> and glucose detection

The effects of six synthetic imidazolium-based ionic liquids (ILs) on the Cu^II-catalyzed chemiluminescence of lucigenin (Luc-CL) in the pH range 6.0–11 were investigated. Preliminary experiments found that the CL emission was strongly enhanced or inhibited in the presence of the ILs. The degree of enhancement or inhibition of the CL intensity in the presence of each IL was related to the molecular structure of the IL, the medium used, and the pH. The maximum enhancement of the CL intensity was observed at pH 9.0 (amplification factor?=?443). This decrease in the pH at which maximum CL enhancement occurred and the substantial signal amplification of the Luc-CL may be related to a strong interaction between Cu^II and the imidazolium ring of superior ILs at this pH. Additionally, the formation of IL microdomains in semi-aqueous media permitted more solubility of the product yielded by the Luc-CL reaction (N-methylacridone), which could increase the CL intensity. To obtain consistent data on the catalytic efficiency of Cu^II in the presence of various ILs as well as the corresponding CL emission intensities, fluorescence quantum yields (Φ _F) of lucigenin were measured under the same conditions. Comparison of the data pointed to the mechanism that controls the properties of Luc-CL in the presence of the Cu^II/IL complexes. Based on the catalytic effect of the Cu^II/IL complex and the measurement of the enzymatically generated H₂O₂, a novel, simple, and sensitive CL method for determining glucose with a detection limit (LoD) of 6.5 μM was developed. Moreover, this method was satisfactorily applied to the determination of glucose in human serum and urine samples.

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Graphical Abstract The lucigenin chemiluminescence assay for H₂O₂ and glucose using imidazolium–based ionic liquid derivatives/Cu^II complexes as efficient catalysts at pH 9.0

     

Kinetics of the oxidation of diethyl sulfide in the B(OH)<Subscript>3</Subscript>-H<Subscript>2</Subscript>O<Subscript>2</Subscript>/H<Subscript>2</Subscript>O system

Data obtained for the kinetics of oxidation of diethyl sulfide (Et₂S) by hydrogen peroxide in aqueous solution catalyzed by boric acid indicate that monoperoxoborates B(O₂H)(OH) ₃ ⁻ and diperoxoborates B(O₂H)₂(OH) ₂ ⁻ are the active species. The rates of the reactions of Et₂S with B(O₂H)(OH) ₃ ⁻ and B(O₂H)₂(OH) ₂ ⁻ are 2.5 and 100 times greater than with H₂O₂. __________ Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 1, pp. 38–42, January–February, 2007.     

Magnetic carbon nitride nanocomposites as enhanced peroxidase mimetics for use in colorimetric bioassays,and their application to the determination of H<Subscript>2</Subscript>O<Subscript>2</Subscript> and glucose

Graphite-like carbon nitride ? Fe₃O₄ magnetic nanocomposites were synthesized by a chemical co-precipitation method. The nanocomposites were characterized by transmission electron microscopy, X-ray diffraction, FTIR spectroscopy, X-ray photoelectron spectroscopy and magnetization hysteresis loops. The nanocomposites exhibit enhanced peroxidase-like activity (compared to that of graphite-like carbon nitride or Fe₃O₄ NPs). More specifically, they are capable of catalyzing the oxidation of different peroxidase substrates (such as TMB, ABTS or OPD) by H₂O₂ to produce the typical color reactions (blue, green or orange). The nanocomposites retain their magnetic properties and can be separated by an external magnet. On the basis of these findings, a highly sensitive and selective method was applied to the determination of H₂O₂ and glucose (by using glucose oxidase). It was successfully applied to the determination of glucose in (spiked) human serum. Compared to other nanomaterial-based peroxidase mimetics, the one described here provides distinctly higher sensitivity for both H₂O₂ and glucose, with detection limits as low as 0.3 μM and 0.25 μM, respectively.

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Graphical abstract The magnetic carbon nitride nanocomposite exhibits enhanced peroxidase-like activity that is much larger than that of graphite-like carbon nitride or Fe₃O₄ NPs alone. This finding was applied to design a highly sensitive and selective colorimetric assay for H₂O₂ and glucose.

     

Application of the chemiluminescence system composed of silicon-doped carbon dots,iron(II) and K<Subscript>2</Subscript>S<Subscript>2</Subscript>O<Subscript>8</Subscript> to the determination of norfloxacin

The authors describe a new chemiluminescence (CL) system composed of Si-doped carbon dots (Si-CDs), Fe(II) ions, and K₂S₂O₈. The Si-CDs were prepared by a hydrothermal method and characterized by fluorescence spectra, transmission electron microscopy, energy-dispersive X-ray and FTIR spectroscopy. The weak CL of the Fe(II)-K₂S₂O₈ reaction is found to be intensified by a factor of ~125 in the presence of Si-CDs. The possible mechanism for CL and its enhancement was studied by recording fluorescence and CL spectra and by investigating the effect of some radical scavengers. It is found that norfloxacin exerts a strong enhancing effect on the CL intensity of the system. This finding was employed to design a CL-based norfloxacin assay that works in the 5.0 to 300 μg L^?1 concentration range, with a limit of detection (3 σ) of 1.5 μg L^?1. The method was applied to the determination of therapeutic levels of norfloxacin in spiked human plasma and gave satisfactory results.

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Graphical Abstract Schematic of the new chemiluminescence system. It consists of silica-doped carbon dots, Fe(II) ions and K₂S₂O₈ and was applied to the determination of norfloxacin which exerts a strong enhancement effect.

     

Hydrogen generation from H<Subscript>2</Subscript>O/H<Subscript>2</Subscript>O<Subscript>2</Subscript>/MnWO<Subscript>4</Subscript> system

Hydrogen gas as a clear energy resource was found to be largely bubbled from a H₂O/H₂O₂/MnWO₄ system. MnWO₄ powder was fabricated by an aqueous reaction method. The powder was characterized with X-ray diffraction (XRD), transmission electron microscope (TEM), and X-ray photoelectron spectrometry (XPS). The efficiency of the hydrogen generation increases with an increase in initial pH in the appropriate range, H₂O₂ proportion, MnWO₄ proportion, and intensity of light resource. Calcining at 400 °C for 1 h can make the MnWO₄ powder synthesized by an aqueous reaction more effective for H₂ generation and more stable in higher initial pH. The MnWO₄ catalyst shows a long-term stability for photocatalytic H₂ generation. A mechanism was suggested for the hydrogen generation from the H₂O/H₂O₂/MnWO₄ system together with XPS analysis.     

Determination of nanomolar lead (II) using H<Subscript>2</Subscript>O<Subscript>2</Subscript>-oxidized activated carbon modified electrode

The virgin activated carbon (AC) was oxidized by 30% H₂O₂ under the ultrasonic condition for 6 h (denoted as AC-6). The electrochemical response of Pb²⁺ at the AC-6 modified paste electrode was investigated, suggesting that AC-6 shows much higher accumulation efficiency to trace levels of Pb²⁺. Based on this, a sensitive and convenient electrochemical method was developed for the determination of Pb²⁺ utilizing the excellent properties of AC-6. In pH 3.6 HAc-NaAc buffer, Pb²⁺ was easily accumulate at the surface of AC-6 modified paste electrode, then reduced to Pb at −1.20 V. During the following anodic sweep, the reduced Pb was oxidized and resulted in an oxidation stripping peak at −0.58 V. The stripping peak current is proportional to the concentration of Pb²⁺ over the range from the 8.0 × 10⁻⁹ to 2.0 × 10⁻⁶ mol l⁻¹, and the limit of detection is as low as 2.0 × 10⁻⁹ mol l⁻¹. Finally, this newly-developed method was successfully employed to determine Pb²⁺ in water samples.     

Physicochemical properties of KOH-H<Subscript>2</Subscript>O<Subscript>2</Subscript>-H<Subscript>2</Subscript>O solutions

Density, viscosity, and surface tension of KOH-H₂O₂-H₂O solutions used to synthesize potassium superoxide in sprayer apparatus were studied with various relative amounts of the components in the temperature range 0–30°C. Analytical dependences of the above-mentioned quantities on temperature and solvent (water) content of the system were found.     

Glassy carbon electrode modified with hemin and new melamine compounds for H<Subscript>2</Subscript>O<Subscript>2</Subscript> amperometric detection

In an attempt to increase the stability and efficiency of hemin-modified electrodes, the present work reports the preparation of a new modified glassy carbon electrode obtained by immobilization of hemin (Hm) on the electrode surface together with a new N-substituted melamine (2,4,6-triamino-1,3,5-triazine) based G-2 dendrimer comprising p-aminophenol as peripheral unit (Den) or with one of its analogues, a melamine G-0 dimer (Dim). Basic structural features, able to determine intimate relationships between Hm and Dim (or Den) at room temperature in solid state, were evidenced with the use of vibrational analysis carried out by FT-IR. This method revealed contacts between Hm and Dim or Den respectively as H-bond interactions, proton-interchange, and π-π stacking interactions. The new modified electrodes were characterized by cyclic voltammetry and electrochemical impedance spectroscopy and tested for amperometric detection of H₂O₂. In this purpose, GC/Hm-Dim electrode exhibited better catalytic properties than GC/Hm-Den electrode, but lower stability.     

Bleaching of kraft cellulose by the ClO<Subscript>2</Subscript>-H<Subscript>2</Subscript>O<Subscript>2</Subscript> scheme

The influence of conditions of a two-stage treatment of deciduous and coniferous kraft cellulose (by the ClO₂-H₂O₂ scheme) on the degree of its delignification and bleaching was studied. The optimum ratio of reagents in each stage of the treatment was elucidated.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 10, 2004, pp. 1735–1738.Original Russian Text Copyright © 2004 by Shcherbakova, Demin.     

Determination of doxycycline in pharmaceuticals based on its degradation by Cu(II)/H<Subscript>2</Subscript>O<Subscript>2</Subscript> reagent in aqueous solution

The reaction between doxycycline, hydrogen peroxide and Cu(II) was investigated spectrophotometrically in aqueous solutions. The absorption spectra show that the degradation of antibiotic drug occurs in weak alkaline aqueous solutions. The kinetics of the reaction was studied by applying the initial-rate method and the relative rate constants were calculated at different temperatures. The kinetic-spectrophotometric method for the determination of doxycycline based on the kinetics of pseudo-first order reaction at 20°C is proposed. The effects of several molecules and ions usually present in pharmaceutical formulations were studied in order to assess their interference. The calibration graph was applied to the determination of doxycycline in capsule dosage form. The relative standard deviation was no greater than 3.80%. The results were compared to those obtained by the official HPLC method.     

Hydrothermal synthesis of nanosized and amorphous alumina in the ZrO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-H<Subscript>2</Subscript>O system

The reciprocal influence of components on the chemical and structural transformations in the ZrO₂-Al₂O₃-H₂O system during nanoparticle formation under hydrothermal conditions is considered. The possibility of formation of amorphous aluminum oxide under hydrothermal conditions is found as a result of the influence of zirconia nanoparticles on the crystallization.     

Sorption of phosphate and arsenate ions from solutions by sorbents of the system TiO<Subscript>2</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-H<Subscript>2</Subscript>O

Hydrated nanosize oxides of the system TiO₂-Fe₂O₃-Al₂O₃-H₂O were tested as sorbents for recovery of phosphate and arsenate ions from aqueous solutions in a wide range of pH values. The optimal compositions of the sorbents were found, their ion-exchange functions were studied, and limiting sorption capacities were determined.     

Phases in the system Tb<Subscript>2</Subscript>O<Subscript>3</Subscript>-SeO<Subscript>2</Subscript>-H<Subscript>2</Subscript>O at 100°C and their physicochemical study

Summary The solubility isotherm of the system Tb₂O₃-SeO₂-H₂O at 100° was studied. The compounds of the three-component system were identified by the Schreinemakers’ method as well as by chemical and X-ray phase analyses. Simultaneous TG and DTA analyses of all compounds of the system were made. The mechanism of thermal decomposition was described.     

Synthesis of peroxy-radical condensates from mixtures of H<Subscript>2</Subscript>+O<Subscript>2</Subscript>

One of the methods for the synthesis of peroxy-radical condensates is the condensation at liquid nitrogen temperature of an H₂+O₂ mixture dissociated in an electrical discharge at low pressure. Peroxy-radical condensates are thought to contain substantial quantities of higher hydrogen peroxides H₂O₃ and H₂O₄. The present work investigates the influence of experimental parameters on the synthesis of peroxy-radical condensates from an H₂+O₂ mixture, analyses the relevant literature, and recommends the optimal experimental conditions for the synthesis. The synthesis is carried out in a U-tube electrical discharge reactor (inner diameter ∼15 mm), immersed in liquid nitrogen, at rather low pressure (0.5–1 Torr). The maximum conversion of initial O₂ into higher hydrogen peroxides was observed at a composition of initial gas mixture of 66.7% H₂ + 33.3% O₂.     

X-ray photoelectron study of the interaction of H<Subscript>2</Subscript> and H<Subscript>2</Subscript>+O<Subscript>2</Subscript> mixtures on the Pt/MoO<Subscript>3</Subscript> model catalyst

The effects of H₂ and H₂ + O₂ gas mixtures of varying composition on the state of the surface of the Pt/MoO₃ model catalyst prepared by vacuum deposition of platinum on oxidized molybdenum foil were investigated by X-ray photoelectron spectroscopy (XPS) at room temperature and a pressure of 5–150 Torr. For samples with a large Pt/Mo ratio, the XP spectrum of large platinum particles showed that the effect of hydrogen-containing mixtures on the catalyst was accompanied by the reduction of molybdenum oxide. This effect results from the activation of molecular hydrogen due to the dissociation on platinum particles and subsequent spill-over of hydrogen atoms on the support. The effect was not observed at low platinum contents in the model catalyst (i.e., for small Pt particles). It is assumed for the catalyst that the loss of its hydrogen-activating ability is a consequence of the formation of platinum hydride. Possible participation of platinum hydride as intermediate in hydrogen oxidation to H₂O₂ is discussed.     

In-situ growth of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles on mesoporous carbon nanofibers: a new nanocomposite for nonenzymatic amperometric sensing of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

The paper describes a nonenzymatic amperometric H₂O₂ sensor that uses a nanocomposite consisting of Co₃O₄ nanoparticles (NPs) and mesoporous carbon nanofibers (Co₃O₄-MCNFs). The Co₃O₄ NPs were grown in situ on the MCNFs by a solvothermal procedure. The synergetic combination of the electrocatalytic activity of the Co₃O₄ NPs and the electrical conductivity of MCNFs as an immobilization matrix enhance the sensing ability of the hybrid nanostructure. The oxidation current, best measured at 0.2 V (vs. SCE) is linear in the 1 to 2580 μM H₂O₂ concentration range, with a 0.5 μM lower detection limit (at an S/N ratio of 3). The sensor is highly selective even in the presence of common electroactive interferents. It was applied to the determination of H₂O₂ in spiked milk samples.

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Graphical abstract Schematic of the synthesis of a nanocomposite consisting of Co₃O₄ nanoparticles (NPs) and mesoporous carbon nanofibers (Co₃O₄-MCNFs) by a solvothermal procedure. It was used as electrocatalyst for direct oxidation of H₂O₂.

     

Model of the catalytic reaction 2H<Subscript>2</Subscript> + O<Subscript>2</Subscript> → H<Subscript>2</Subscript>O with the participation of molecules in a precursor state

The absence of experimental evidence for the occurrence of the catalytic reaction 2H₂ + O₂ → 2H₂O on platinum in accordance with the Langmuir-Hinshelwood mechanism was established. It was found that the heterogeneous process can be described more adequately and its nature can be better understood with consideration for chemical transformations involving molecules in a precursor state in a model of the above reaction. The inverse kinetic problem was solved. It was found that the model in which an unambiguously specified set of rate constants for the elementary steps of the reaction was used provided an opportunity to describe experimental data obtained by various authors concerning the oxidation of hydrogen on platinum over the detonating gas pressure range 10^?3-10⁵ Pa. The signs of the occurrence of heterogeneous reactions by an adsorption mechanism were found.     

Solid solutions in the MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Coexisting solid solutions with spinel and corundum structure were synthesized at 1773 K and two pressures, 1 bar and 25 kbar. Samples were analyzed by electron microprobe analysis and X-ray powder diffraction. Pressure and temperature were shown to affect the properties of the solid solutions in different ways. Pressure governs the composition of the defect spinel Mg_1−xAl₂O₄, and temperature changes the cation distribution between coexisting phases. This allows one to separate the effects of cation exchange and magnetic contribution to the heat capacity in thermodynamic modeling. The defect spinel itself can form only because γ-Al₂O₃ exists, polymorph with spinel structure.     

Mechanism of the nanocrystals formation of the spinel structure in the MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-H<Subscript>2</Subscript>O system under the hydrothermal conditions

Using the method of hydrothermal synthesis,the nanoparticles of magnesium-aluminum spinel were obtained with a crystallite size of 40–50 nm. The sequence was determined of the chemical transformations under hydrothermal conditions of the initial magnesium-aluminum hydroxides obtained by co-precipitation, leading to the formation of nanoparticles MgAl₂O₄.     

Phase relations in the MgO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Phase relations in the MgO-Bi₂O₃-B₂O₃ system have been investigated by X-ray powder diffraction analysis and DTA. No ternary compounds have been found in the system. Quasi-binary sections have been the 600°C determined and isothermal section of the system has been constructed.