A new amperometric H<Subscript>2</Subscript>O<Subscript>2</Subscript> biosensor based on nanocomposite films of chitosan–MWNTs,hemoglobin, and silver nanoparticles

A new H₂O₂ biosensor was fabricated on the basis of nanocomposite films of hemoglobin (Hb), silver nanoparticles (AgNPs), and multiwalled carbon nanotubes (MWNTs)–chitosan (Chit) dispersed solution immobilized on glassy carbon electrode (GCE). The immobilized Hb displayed a pair of well-defined and reversible redox peaks with a formal potential (E ^θ′) of −22.5 mV in 0.1 M pH 7.0 phosphate buffer solution. The apparent heterogeneous electron transfer rate constants (k _s) in the Chit–MWNTs film was evaluated as 2.58 s⁻¹ according to Laviron’s equation. The surface concentration (Γ*) of the electroactive Hb in the Chit–MWNTs film was estimated to be (2.48 ± 0.25) × 10⁻⁹ mol cm⁻². Meanwhile, the Chit–MWNTs/Hb/AgNPs/GCE demonstrated excellently electrocatalytical ability to H₂O₂. Its apparent Michaelis–Menten constant (K _M^app) for H₂O₂ was 0.0032 mM, showing a good affinity. Under optimal conditions, the biosensors could be used for the determination of H₂O₂ ranging from 6.25 × 10⁻⁶ to 9.30 × 10⁻⁵ mol L⁻¹ with a detection limit of 3.47 × 10⁻⁷ mol L⁻¹ (S/N = 3). Furthermore, the biosensor possessed rapid response to H₂O₂ and good stability, selectivity, and reproducibility.     

Thermoelectric power and electrochemical studies on CdI<Subscript>2</Subscript>–Ag<Subscript>2</Subscript>O–V<Subscript>2</Subscript>O<Subscript>5</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript> system

A quaternary super-ion-conducting system, 20CdI₂ − 80[xAg₂O − y(0.7V₂O₅ − 0.3B₂O₃)] where 1 ≤ x/y ≤ 3, has been prepared by melt quenching technique. The electrical conductivity measured was the order of 10⁻⁴  S/cm at room temperature. The values of silver-ion transport number obtained by electromotive force technique are nearly unity. The thermoelectric power and electrochemical studies were done on the CdI₂–Ag₂O–V₂O₅–B₂O₃ system. The discharge and polarization characteristics were examined for different cathodes to evaluate the utility of these cells as power sources for low energy applications.     

Thermal studies of ZnO–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–TeO<Subscript>2</Subscript> glasses

The effect of TeO₂ additions on the thermal behaviour of zinc borophosphate glasses were studied in the compositional series (100 − x)[0.5ZnO–0.1B₂O₃–0.4P₂O₅]–xTeO₂ by differential scanning calorimetry, thermodilatometry and heating microscopy thermal analysis. The addition of TeO₂ to the starting borophosphate glass resulted in a linear increase of glass transition temperature and dilatometric softening temperature, whereas the thermal expansion coefficient decreased. Most of glasses crystallize under heating within the temperature range of 440–640 °C. The crystallization temperature steeply decreases with increasing TeO₂ content. The lowest tendency towards crystallization was observed for the glasses containing 50 and 60 mol% TeO₂. X-ray diffraction analysis showed that major compounds formed by annealing of the glasses were Zn₂P₂O₇, BPO₄ and α-TeO₂. Annealing of the powdered 50ZnO–10B₂O₃–40P₂O₅ glass leads at first to the formation of an unknown crystalline phase, which is gradually transformed to Zn₂P₂O₇ and BPO₄ during subsequent heating.     

B<Subscript>2</Subscript>O<Subscript>3</Subscript> additives on sintering and microwave dielectric behaviors of Mg<Subscript>4</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics synthesized through the aqueous sol–gel Process

The relationships between the sintering temperatures and the microwave dielectric properties of (1−x)Mg₄Nb₂O₉-xB₂O₃ (x = 0.5–10 wt. %) compounds were investigated by the sol–gel method in order to reduce the sintering temperature in this study. A suitable amount of B₂O₃ doping was effective in allowing low sintering temperatures without a little detrimental effect on these dielectric properties of the Mg₄Nb₂O₉ compounds. The variations in the dielectric constant (ε _r ) and the quality factor (Q·f) of the Mg₄Nb₂O₉ compounds depended on the amount of B₂O₃ doping and the sintering temperature. As a result, a ε _r value of ~12.8 and a Q·f value of ~142,570 GHz were obtained when the Mg₄Nb₂O₉ compound with x = 3% was sintered at 1,200 °C for 4 h. The temperature coefficient of resonant frequency (τ _f ) of the 3%-B₂O₃ doping Mg₄Nb₂O₉ compound slightly changed from −33 to −48 ppm/°C with an increased sintering temperature.     

Calorimetric studies on 2TeO<Subscript>2</Subscript>–V<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Glasses of the composition 2TeO₂–V₂O₅ were fabricated via the conventional melt-quenching technique. The amorphous and the glassy nature of the as-quenched samples were confirmed by X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC), respectively. The glass transition and crystallization parameters were evaluated under non-isothermal conditions using DSC. X-ray diffraction studies confirmed the presence of partially oriented crystallites in the heat-treated glasses. Kauzmann temperature (lower bound for the kinetically observed glass transition) was deduced from the heating rate dependent glass transition and crystallization temperatures.     

Study on Bi—Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocomposite prepared via mechanochemical processing

In this work Bi-Fe₃O₄ nanocomposite was synthesized by room temperature milling of Bi₂O₃ and Fe powders using a planetary ball mill in air. The synthesis reaction proceeds with increase in milling time and is finished by about 4 h. The XRD pattern of the as-milled powder shows that the main phases are Bi and Fe₃O₄ without any extra phases. The average crystallite sizes of the constituents have been determined by Scherrer’s formula and they were 22 and 18 nm for Bi and Fe₃O₄ respectively. This was also confirmed by Transmission Electron Microscopy (TEM). Magnetic hysteresis loops at room temperature were recorded using a vibrating sample magnetometer (VSM). A tow-probe method was used to measure resistivity variation of the nanocomposite as a function of magnetic filed and temperature. We have observed a room temperature magnetoresistance (ρ₀ — ρ _H )/ρ₀ as large as 17% in a magnetic field of 1 T.     

Effects of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> on the crystallization and structure of CaO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> glass ceramics

Radiation-induced degradation of the weakly and strongly 4-vinylpyridine basic ion exchange resins by gamma radiolysis was investigated in the presence of air and liquid water. This study is focused on evaluating the radiolytic gases (H₂, CO, CO₂ and CH₄) and liquid products (water-solute TOC and NH₄ ⁺). The weakly basic resin yielded lower amounts of H₂ and CO and higher amounts of CO₂ than those of the strongly basic resin. Moreover, the strong basic resin tended to yield greater amounts of NH₄ ⁺. Resins were characterized by the FTIR spectroscopy technique and the results showed that the resins structures are relatively stable.     

Formation of solid solutions of multiferroics in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Nd<Subscript>2</Subscript>O<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The sequence of phases appearance during the formation of Bi_1–xNd_xFeO₃ solid solutions in powder oxides mixtures of bismuth, neodymium, and iron has been determined. It has been shown that the closeness of the reaction mixture composition to that of the individual compound (BiFeO₃ or NdFeO₃) is essential for the realization of the series of phase transformations yielding solid solutions of multiferroics Bi_1–xNd_xFeO₃ as the final product, due to the prevalence of various interphase contacts in the starting reaction zone.     

Distribution of niobium and lanthanum between two immiscible melts in the system LaPO<Subscript>4</Subscript>–SiO<Subscript>2</Subscript>–NaF–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

The system LaPO₄–SiO₂–NaF–Nb₂O₅–Fe₂O₃ is characterized by immiscibility fields in the liquid state region. Addition of iron expands fields of immiscibility of melts and decreases the temperature of their coexistence. A fraction of 87–90% of niobium is extracted into iron silicate melt, and 92–98% of lanthanum is extracted into phosphate salt melt.     

Glass Formation in the Ternary System La<Subscript>2</Subscript>O<Subscript>3</Subscript>–As<Subscript>2</Subscript>S<Subscript>3</Subscript>–Er<Subscript>2</Subscript>O<Subscript>3</Subscript>

The boundaries of the glass formation region in the ternary system La₂O₃–As₂S₃–Er₂O₃ were found. Transparent glass of composition (La₂O₃)_0.03(As₂S₃)0.90(Er₂O₃)0.07 was studied by X-ray photoelectron and Raman spectroscopy. The intensities of the bands characterizing As–S, La–O, and Er–O bonds increased, and these bands were shifted toward higher energies. This was due to an increase in the covalence of these bonds and probably due to the formation of new bonds in the glasses. Samples in the glass formation region are resistant at 300 K to air, water, and organic solvents.     

Thermal properties of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>–PbO–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glass system

Thermal behavior of xGa₂O₃–(50 − x)PbO–50P₂O₅ (x = 0, 10, 20, and 30 mol.% Ga₂O₃) and xGa₂O₃–(70 − x)PbO–30P₂O₅ (x = 0, 10, 20, 30, and 40 mol.% Ga₂O₃) glassy materials were studied by thermo-mechanical analysis (TMA) and differential thermal analysis (DTA). Replacement of PbO for Ga₂O₃ is accompanied by increasing glass-transition temperature (263 ≤ T _g/°C ≤ 535), deformation temperature (363 ≤ T _d/°C ≤ 672), crystallization temperature (396 ≤ T _c/°C ≤ 640) and decreasing of coefficient of thermal expansion (5.1 ≤ CTE/ppm K⁻¹ ≤ 16.7). Values of Hruby parameter were determined (0.1 ≤ K _H ≤ 1.3). The thermal stability of prepared glasses increases with increasing of concentration of Ga₂O₃.     

A magnetic CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> nanocomposite fabricated by the sol-gel method for electrocatalytic oxidation and determination of L-cysteine

Magnetic CoFe₂O₄/SiO₂ spinel-type nanocomposites have been fabricated by a sol-gel method in the presence of various acids. Their structural, morphological and magnetic properties were characterized by XRD, SEM, TEM, FTIR, VSM and EDX which revealed that they are formed in the presence of all precursors. TEM analysis indicates homogeneous and porous spherical morphology with nanosize grains 10–20 nm in diameter in the presence of salicylic acid. Electrochemical sensor application of nanocrystalline CoFe₂O₄/SiO₂ synthesized by salicylic acid for determination of L-cysteine was investigated using differential pulse voltammetry (DPV) and cyclic voltammetry (CV). DPV indicates that the sensor shows remarkable sensitivity for the determination of L-Cys. The response of a glassy carbon electrode modified with CoFe₂O₄/SiO₂ is linear in the 0.02–425 μM L-Cys concentration range, with a 0.20 μM detection limit (at an S/N ratio of 3). The electrode produces a negligible current response for tryptophan, glutamic acid and citric acid at the working potential applied (+0.748 V vs Ag/AgCl). The electrode is reliable, simple, rapidly prepared, precise, and the method does not require extensive sample treatment.

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Graphical abstract A CoFe₂O₄/SiO₂ magnetic nanocomposite was synthesized by a sol-gel auto combustion method in the presence of various acids as precursors. A highly sensitive electrochemical sensor was fabricated for determination of trace amount of L-cysteine using a glassy carbon electrode modified with the nanocomposite.

     

Novel sol–gel method for preparation of high concentration ε-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> nanocomposite

ε-Fe₂O₃/SiO₂ nanocomposite was prepared by novel solgel method using single precursor for both nanoparticles and matrix. This method allows to prepare the samples free of α-Fe₂O₃ with 40% of Fe₂O₃ in SiO₂. Nanoparticles of 12 nm diameter were obtained by annealing at 1,000 °C. The samples were characterized by powder X-ray diffraction and transmission electron microscopy. Mössbauer spectroscopy identified ε-Fe₂O₃ as the only magnetically ordered phase at room temperature. Magnetic measurements revealed progressive necking of hysteresis loops measured at 300 and 2 K. In both cases the intrinsic coercivity reaches only 0.25 T. Measurements up to 14 T shows monotonous decreasing trend of saturated magnetization with increasing temperature.     

Modifying additives affect the properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system

The effects caused by modifying additives, namely nonionic surfactants (Tween 80 and Neonol AF 9-6) and oxides (B₂O₃ and HfO₂), on the rheology, film formation, and phase formation in the yttrium aluminum silicate system prepared by sol–gel technology were studied. The effect of 1 wt % HfO₂ additions on the activation energy of crystallization was studied.     

Multicomponent systems LiCl–LiBr–Li<Subscript>2</Subscript>SO<Subscript>4</Subscript> and LiCl–LiBr–Li<Subscript>2</Subscript>SO<Subscript>4</Subscript>–Li<Subscript>2</Subscript>MoO<Subscript>4</Subscript>

Phase equilibria in the LiCl–LiBr–Li₂SO₄ ternary system and the LiCl–LiBr–Li₂SO₄–Li₂MoO₄ quaternary system were studied by differential thermal analysis. The compositions and temperatures of minima in the ternary and quaternary systems were determined to be (31.2 mol % LiCl, 46.8 mol % LiBr, 22.0 mol % Li₂SO₄, 460°C) and (25.2 mol % LiCl, 30.2 mol % LiBr, 14.6 mol % Li₂SO₄, 30.0 mol % Li₂MoO₄, 411°C), respectively.     

Characterization of gold supported on Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–CuO–Mn<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts obtained by thermal decomposition of aerosols

The purpose of this work was to employ the differential thermal analysis (DTA) technique to compare variations in the collapse energy of the zeolite Y crystalline structure in a fresh catalyst and in the same catalyst impregnated with nickel and vanadium. A small exothermic signal in the DTA curve at 950–1150 °C indicated the collapse of the crystalline structure. The areas of the exothermic signals in the DTA curves of the two samples indicated a reduction in the curve of the metal impregnated catalyst. These results were compared with X-ray data, leading to the conclusion that metal impregnation affects the zeolite Y crystalline structure and that the DTA technique is a potentially useful tool for measuring the integrity of zeolite Y in catalysts.     

Structural and Temperature Dependent Electrical Conductivity Properties of Dy<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sm<Subscript>2</Subscript>O<Subscript>3</Subscript> CO-Doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>

In the present work, Dy₂O₃ and Sm₂O₃ double-doped Bi₂O₃-based materials are synthesized by exploiting the solid-state synthesis method. The structural and temperature dependent electrical properties of these ternary ceramic samples, which are candidate materials for solid oxide fuel cell (SOFCs) electrolyte, are determined by means of a powder X-ray diffractometer (XRD), the four point-probe method (FPPM), and the thermal-gravimetry/differential thermal analysis (TG/DTA). As a result of the XRD measurements, the fluorite-type fcc δ-phase with a stable structure is obtained for higher values of the dopant oxide material, which are the samples with the maximum content of fixed 20% Dy₂O₃ and 15% and 20% Sm₂O₃. The samples with the stable δ-phase structure have higher conductivities. The highest electrical conductivity is found for the (Bi₂O₃)0.6(Dy₂O₃)_0.2(Sm₂O₃)_0.2 sample, which was 2.5×10^–2 (Ohm cm)^–1 at 750 °C. The activation energies are also calculated from the Arrhenius charts, which were determined from the FPPM measurements. The lowest activation energy is found as 0.85 eV for the sample with the highest electrical conductivity.     

Synthesis and properties of γ-Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> solid solutions

The textural and structural properties of mixed oxides Ga₂O₃–Al₂O₃, obtained via impregnating γ-Al₂O₃ with a solution of Ga(NO₃)₃ and subsequent heat treatment, are studied. According to the results from X-ray powder diffraction, gallium ions are incorporated into the structure of aluminum oxide to form a solid solution of spinel-type γ-Ga₂O₃–Al₂O₃ up to a Ga₂O₃ content of 50 wt % of the total weight of the sample, accompanied by a reduction in the specific surface area, volume, and average pore diameter. It is concluded that when the Ga₂O₃ content exceeds 50 wt %, the β-Ga₂O₃ phase is observed along with γ-Ga₂O₃–Al₂O₃ solid solution. ⁷¹Ga and ²⁷Al NMR spectroscopy shows that gallium replaces aluminum atoms from the tetrahedral position to the octahedral coordination in the structure of γ-Ga₂O₃–Al₂O₃.