Electrosorption of Os(III)-complex at single-wall carbon nanotubes immobilized on a glassy carbon electrode: application to nanomolar detection of bromate, periodate and iodate

A simple procedure was developed to prepare a glassy carbon electrode modified with single-wall carbon nanotubes (SWCNTs) and Os(III)-complex. The glassy carbon (GC) electrode modified with CNTs was immersed into Os(III)-complex solution (direct deposition) for a short period of time (60 s). 1,4,8,12-Tetraazacyclotetradecane osmium(III) chloride, (Os(III)LCl₂)·ClO₄, irreversibly and strongly adsorbed on SWCNTs immobilized on the surface of GC electrode. Cyclic voltammograms of the Os(III)-complex-incorporated-SWCNTs indicate a pair of well defined and nearly reversible redox couple with surface confined characteristic at wide pH range (1-8). The surface coverage (Γ) and charge transfer rate constant (k_s) of the immobilized Os-complex on SWCNTs were 3.07 × 10⁻⁹ mol cm⁻², 5.5 (±0.2) s⁻¹, 2.94 × 10⁻⁹ mol cm⁻², 7.3 (±0.3) s⁻¹ at buffer solution with pH 2 and 7, respectively, indicate high loading ability of SWCNTs for Os(III) complex and great facilitation of the electron transfer between electroactive redox center and carbon nanotubes immobilized on the electrode surface. Modified electrodes showed higher electrocatalytic activity toward reduction of BrO₃⁻, IO₃⁻ and IO₄⁻ in acidic solutions. The catalytic rate constants for catalytic reduction bromate, periodate and iodate were 3.79 (±0.2) × 10³, 7.32 (±0.2) × 10³ and 1.75 (±0.2) × 10³ M⁻¹ s ⁻¹, respectively. The hydrodynamic amperometry of rotating modified electrode at constant potential (0.3 V) was used for nanomolar detection of selected analytes. Excellent electrochemical reversibility of the redox couple, good reproducibility, high stability, low detection limit, long life time, fast amperometric response time, wide linear concentration range, technical simplicity and possibility of rapid preparation are great advantage of this sensor.     

Peroxyoxalate chemiluminescence of 1,4-dihydroxy-3-methyl-thioxanthone and quenching effect of β-cyclodextrin

The chemiluminescence generated from the reaction of bis(2,4,6-trichlorophenyl) oxalate (TCPO), hydrogen peroxide and 1,4-dihydroxy-3-methyl-thioxanthone (DMT) was investigated. Effects of reacting components, solvent and concentrations of TCPO, sodium salicylate, hydrogen peroxide and DMT were studied and their optimal values were determined. In addition, the influences of β-Cyclodextrin (β-CD) on the peroxyoxalate chemiluminescence (PO-CL) system of DMT were examined at optimized condition. The results showed that the presence of β-CD causes both enhancing and quenching effects on PO-CL system of DMT based upon its concentration. The Stern–Volmer quenching constant (K _q) was evaluated as 2.32?×?10⁴?M^?1 (R ^2?= 0.991) by creating a linear regression plot on experimentally obtained data. This study resulted in satisfactorily determination of β-CD in the range 5.0?×?10^?6 to 1.0?×?10^?4?M.     

Synthesis and Characterization of Alkyl‐Imidazolium‐Based Periodic Mesoporous Organosilicas: A Versatile Host for the Immobilization of Perruthenate (RuO4−) in the Aerobic Oxidation of Alcohols

The preparation and characterization of a set of periodic mesoporous organosilicas (PMOs) that contain different fractions of 1,3‐bis(3‐trimethoxysilylpropyl)imidazolium chloride (BTMSPI) groups uniformly distributed in the silica mesoporous framework is described. The mesoporous structure of the materials was characterized by powder X‐ray diffraction, transmission electron microscopy, and N₂ adsorption–desorption analysis. The presence of propyl imidazolium groups in the silica framework of the materials was also characterized by solid‐state NMR spectroscopy and diffuse‐reflectance Fourier‐transform infrared spectroscopy. The effect of the BTMSPI concentration in the initial solutions on the structural properties (including morphology) of the final materials was also examined. The total organic content of the PMOs was measured by elemental analysis, whereas their thermal stability was determined by thermogravimetric analysis. Among the described materials, it was found that PMO with 10 % imidazolium content is an effective host for the immobilization of perruthenate through an ion‐exchange protocol. The resulting Ru@PI‐10 was then employed as a recyclable catalyst in the highly efficient aerobic oxidation of various types of alcohols.     

Kinetic study on solid state thermal degradation of epoxy nanocomposite containing Octasilane polyhedral oligomeric silsesquioxane

A nanocomposite based on epoxy and octasilane polyhedral oligomeric silsesquioxanes (Octasilane POSS) was synthesized and characterized. Thermal degradation kinetics of the epoxy system containing different concentrations of Octasilane POSS was studied by thermogravimetry analysis (TGA). The derivative thermogravimetry (DTG) curves showed a single stage decomposition process. Influence of both the Octasilane POSS concentration and heating rate on degradation characteristics was eliminated. The better thermal and morphological properties were obtained using a formulation containing 1 wt.% of Octasilane POSS. Using Kissinger's method, activation energy of the degradation process was determined to be 155.8 kJ/mol. This is in good agreement with that value determined by Flynn–Wall–Ozawa isoconversional approach. Based on 13 various model functions and the calculation procedures of Coats–Redfern, Van Krevelen, Horowits–Metzeger, and Criado et al. methods the degradation mechanism was found. It was concluded that the kinetics of thermal degradation obeys through a nucleation and growth mechanism described by Avrami–Erofeev equation (A₂). The homogeneous dispersion of Octasilane POSS in the polymer matrix was evidenced by SEM and XRD observations.     

Fabrication of a Sensitive Cholesterol Biosensor Based on Cobalt‐oxide Nanostructures Electrodeposited onto Glassy Carbon Electrode

Electrodeposited cobalt oxide (CoOx) nanomaterials are not only used for immobilization of cholesterol oxidase (ChOx) but also as electron transfer mediator for oxidation of H₂O₂ generated in the enzymatic reaction. Voltammetry and flow injection analysis (FIA) were used for determination of cholesterol. FIA determination of cholesterol with biosensors yielded a calibration curve with the following characteristics: linear range up to 50 μM, sensitivity of 43.5 nA μM^?1 cm^?2 and detection limit of 4.2 μM. The apparent Michaelis‐Menten constant and the response time of the biosensor are 0.49 mM and 15 s, respectively. This biosensor also exhibits good stability, reproducibility and long life time.     

Connected Domination Number of a Graph and its Complement

A set S of vertices in a graph G is a connected dominating set if every vertex not in S is adjacent to some vertex in S and the subgraph induced by S is connected. The connected domination number γ _c (G) is the minimum size of such a set. Let d^*(G)=min{d(G),d([`(G)])}{\delta^*(G)={\rm min}\{\delta(G),\delta({\overline{G}})\}} , where [`(G)]{{\overline{G}}} is the complement of G and δ(G) is the minimum vertex degree. We prove that when G and [`(G)]{{\overline{G}}} are both connected, g<sub>c</sub>(G)+g<sub>c</sub>([`(G)]) ￡ d^*(G)+4-(g_c(G)-3)(g_c([`(G)])-3){{\gamma_c}(G)+{\gamma_c}({\overline{G}})\le \delta^*(G)+4-({\gamma_c}(G)-3)({\gamma_c}({\overline{G}})-3)} . As a corollary, g<sub>c</sub>(G)+g<sub>c</sub>([`(G)]) ￡ \frac3n4{{\gamma_c}(G)+{\gamma_c}({\overline{G}})\le \frac{3n}{4}} when δ*(G) ≥ 3 and n ≥ 14, where G has n vertices. We also prove that g_c(G)+g_c([`(G)]) ￡ d<sup>*</sup>(G)+2{{\gamma_c}(G)+{\gamma_c}({\overline{G}})\le \delta^*(G)+2} when g<sub>c</sub>(G),g<sub>c</sub>([`(G)]) 3 4{{\gamma_c}(G),{\gamma_c}({\overline{G}})\ge 4} . This bound is sharp when δ*(G) = 6, and equality can only hold when δ*(G) = 6. Finally, we prove that g_c(G)g_c([`(G)]) ￡ 2n-4{{\gamma_c}(G){\gamma_c}({\overline{G}})\le 2n-4} when n ≥ 7, with equality only for paths and cycles.     

Laser-Induced Breakdown Spectroscopy Via the Spatially Resolved Technique Using Non-Gated Detector

We present a simple setup for laser-induced breakdown spectroscopy using the spatially resolved technique (SRLIBS). We show that, without any need for time-gated ICCD and pulse generator, the signal-to-background ratio is enhanced. We develop a homemade spectrograph with a movable slit located at its entrance to detect different parts of the plasma emission. For optimizing the position of the slit, we use the shadowgraphy technique to study the plasma expansion. In this low cost setup, with nanosecond laser pulses, we perform SRLIBS experiments on the plasma induced in air and iron. Our results show that the signal-to-background ratio for iron and air is enhanced up to 15 and 8 times, respectively.