Development of Macrocyclics based Electrochemical Sensors

Electroanalytical techniques represent a class of powerful and versatile analytical method which is based on the electrical properties of a solution of the analyte when it is made part of an electrochemical cell. They offer high sensitivity, accuracy, precision and a large linear dynamic range. The cost of instrumentation is relatively low compared to other instrumental methods of analysis. Many solid state electrochemical sensors have been commercialised nowadays. Potentiometry is a very simple electroanalytical technique with extraordinary analytical capabilities. Since valinomycin was introduced as an ionophore for K+, Ion Selective Electrodes have become one of the best studied and understood analytical devices. It can be used for the determination of substances ranging from simple inorganic ions to complex organic molecules. It is a very attractive option owing to the wide range of applications and ease of the use of the instruments employed. They also possess the advantages of short response time, high selectivity and very low detection limits. Moreover, analysis by these electrodes is non-destructive and adaptable to small sample volumes. It has become a standard technique for medical researchers, biologists, geologists and environmental specialists. This thesis presents the synthesis and characterisation of five ionophores. Based on these ionophores, nine potentiometric sensors are fabricated for the determination of ions such as Pb2+, Mn2+, Ni2+, Cu2+ and Sal- ion (Salicylate ion). The electrochemical characterisation and analytical application studies of the developed sensors are also described. The thesis is divided into eight chapters

Low temperature preparation of ceria solid solutions doubly doped with rare-earth and alkali-earth and their properties as solid oxide fuel cells

A series of solid electrolytes, (Ce(0.8)Ln(0.2))(1 - x)MxO2 - delta(Ln = La, Nd, Sm, Gd, M:Alkali-earth), were prepared by amorphous citrate gel method. XRD patterns indicate that a pure fluorite phase is formed at 800 degreesC. The electrical conductivity and the AC impedance spectra were measured. XPS spectra show that the oxygen vacancies increase owing to the MO doping, which results in the increase of the oxygen ionic transport number and conductivity. The performance of ceria-based solid electrolyte is improved. The effects of rare-earth and alkali-earth ions on the electricity were discussed. The open-circuit voltages and maximum power density of planar solid oxide fuel cell using (Ce0.8Sm0.2)(1 - 0.05)Ca0.05O2 - delta as electrolyte are 0.86 V and 33 mW . cm(-2), respectively.

Preparation of polyacrylonitrile–natural polymer composite precursors for carbon fiber using ionic liquid co solvent solutions

We report on the use of ionic liquid co-solvents in the preparation of polyacrylonitrile–natural polymer carbon fibers as low cost environmentally friendly alternatives to conventional carbon fibers precursors and processing solvents. We have characterized the structure properties of the new composites as a function of dissolving solvent using solid state NMR, DSC, FTIR and TGA. We show that the dissolving solvent plays a significant role in the properties of the new composites, we also find that the incorporation of the natural polymer additive impacts the thermal transition temperatures for the PAN

Effect of citrate ions on the electrochemical behaviour of low-carbon steel in borate buffer solutions

The electrochemical behaviour of cold-rolled low carbon steel was studied on both active and passive potential regions in borate buffer solutions with and without the addition of sodium citrate (NaCit). In the active region anodic charges increased significantly and RCT values decreased with citrate, due to the formation of soluble complexes. In the passive potential region the film formed at +0.4 V in borate buffer solution with and without 0.010 M NaCit is probably enriched by Fe3O4 oxide, while films formed at +0.8 V are probably enriched by gamma-Fe2O3. The equivalent circuit [R-s(R(CT)Q)] fitted all experimental impedance data. (C) 2003 Elsevier Ltd. All rights reserved.

In vivo microbiological evaluation of the effect of biomechanical preparation of root canals using different irrigating solutions

The aim of this study was to evaluate the antimicrobial effect of biomechanical preparation using different irrigating solutions. Seventy-eight root canals from premolars of four dogs were used. After experimental induction of periapical lesions, the root canals were prepared using the following solutions for irrigation: Group 1) 2.5% sodium hypochlorite (NaOCl); Group 2) 2% chlorhexidine (CHX); Group 3) saline solution and Group 4) control group with no biomechanical preparation. The microbiological evaluation of the root canals was performed by counting the colony forming units (CFUs) using different culture mediums. Two absorbent paper cones were used in each root canal in order to collect the microbiological samples before, and thirty days after the biomechanical preparation. The culture plates were incubated in aerobic, anaerobic and microaerophilic environment. Statistical evaluation was carried out using analysis of variance, Tukey and Student tests. The results demonstrated that there was reduction in the number of microorganisms in the NaOCl and CHX groups (p<0.05). There was greater effectiveness in the chlorhexidine group. The group that used saline solution and the control group presented an increased number of microorganisms. It can be concluded that the use of antimicrobial irrigating solutions during biomechanical preparation promotes the reduction of endodontic microbiota. However, a considerable number of microorganisms were still observed.

Reagent chemicals and standards, with methods of assaying and testing them; also the preparation and standardization of volumetric solutions and extensive tables of equivalents,

Mode of access: Internet.

Preparation of bionanoparticles derived from Spirulina platensis and its application for Cr (VI) removal from aqueous solutions

Spirulina platensis nanoparticles were prepared by mechanical agitation and were applied to removal Cr (VI) from aqueous solutions. Nanoparticles preparation was function of stirring rate and contact time. In the optimal conditions, Cr (VI) removal by nanoparticles as a function of pH and initial ion concentration was carried out. The optimal conditions for preparation were 10,000 rpm and 20 min, and the nanoparticles presented mean diameter of 215.6 nm and polydispersity index of 0.151. The best conditions for Cr (VI) removal were at pH 4 and ion concentration of 250 mg L 1, and the Cr (VI) removal percentage was 99.1%.

In-situ carbon control in the preparation of precursors to boron carbide by a non-aqueous solution technique

Synthesis of high quality boron carbide (B4C) powders is achieved by carbothermal reduction of boron oxide (B2O3) from a condensed boric acid (H3BO3)/polyvinyl acetate (PVAc) product. Precursor solutions are prepared via free radical polymerisation of vinyl acetate (VA) monomer in methanol in the presence of dissolved H3BO3. A condensed product is then formed by flash evaporation under vacuum. As excess VA monomer is removed at the evaporation step, the polymerisation time is used to manage availability of carbon for reaction. This control of carbon facilitates dispersion of H3BO3 in solution due to the presence of residual VA monomer. B4C powders with very low residual carbon are formed at temperatures as low as 1,250 °C with a 4 hour residence time.

A simple method for large-scale preparation of chick embryo tRNA

A simple method for preparing bulk quantities of tRNA from chick embryo has been developed. In this method chick embryos were homogenized in a buffer of pH 4.5, followed by deproteinization with phenol. The aqueous layer was allowed to separate under gravity. The resulting aqueous layer, after two more phenol treatments, was directly passed through a DEAE-cellulose column and the tRNA eluted therefrom with 1 Image NaCl. The tRNA prepared by this method was as active as the one prepared at neutral pH.

Preparation of 50mm 3C-SiC/Si(111) as Substrates Suited for Ⅲ-Nitrides

50mm SiC films with high electrical uniformity are grown on Si(111) by a newly developed vertical low-pressure chemical vapor deposition (LPCVD) reactor.Both in-situ n- and p-type doping of 3C-SiC are achieved by intentional introduction of ammonia and boron into the precursor gases.The dependence of growth rate and surface morphology on the C/Si ratio and optimized growth conditions is obtained.The best electrical uniformity of 50mm 3C-SiC films obtained by non-contact sheet resistance measurement is ±2.58%.GaN films are grown atop the as-grown 3C-SiC/Si(111) layers using molecular beam epitaxy (MBE).The data of both X-ray diffraction and low temperature photoluminescence of GaN/3C-SiC/Si(111) show that 3C-SiC is an appropriate substrate or buffer layer for the growth of Ⅲ-nitrides on Si substrates with no cracks.

Preparation of Microporous Membranes by Swift Heavy Ion Irradiation and Impedance Characterization

Polypropylene (PP) microporous membranes were successfully prepared by swift heavy ion irradiation and track-etching. Polypropylene foils were irradiated with Au-197 ions of kinetic energy 11.4 MeV.u(-1) (total energy of 2245.8 MeV) and fluence 1x10(8) ions.cm(-2) at normal incidence. The damaged regions produced by the gold ions along the trajectories were etched in H2SO4 and K2Cr2O7 solutions leading to the formation of cylindrical pores in the membranes. The pore diameters of the PP microporous membranes increased from 380 to 1610 nm as the etching time increased from 5 to 30 min. The surface and cross-section morphologies of the porous membranes were characterized by scanning electron microscopy (SEM). The micropores in the membranes were found to be cylindrical in shape, homogeneous in distribution, and equal in size. Some mathematical relations of the porosity of the PP microporous membranes were established by analytic derivation. The microporous membranes were used in lithium-ion batteries to measure their properties as separators. The electrical conductivity of the porous membrane immersed in liquid electrolyte was found to be comparable to that of commercial separators by electrochemical impedance spectroscopy (EIS). The results showed that the porosity and electrical conductivity were dependent on the ion fluence and etching time. By adjusting these two factors, microporous membranes with good porosity and electrical conductivity were made that met the requirements for commercial use.

Preparation of Mn substituted La-hexaaluminate catalysts by using supercritical drying

LaMnxAl12-xO19 catalysts were prepared from NH4OH and metal nitrates solutions. Supercritical drying (SCD) and conventional oven drying (CD) methods were used to extract the water in the hydrogel. The effects of drying methods on properties of the catalysts were investigated by means of TEM, N-2-adsorption, thermogravimetry (TG)-differential thermal analysis (DTA) and X-ray diffraction. SCD method is beneficial to maintain high surface area and improving catalytic activity for methane combustion of the catalyst. The specific surface area and pore volume of LaMn1Al11O19 catalyst prepared by SCD method are 28 m(2)/g and 0.23 cm(3)/g, respectively, and the ignition of methane could be carried out at 450degreesC. However, those of the CD catalyst prepared from the same precursor are 15 m(2)/g, 0.11 cm(3)/g and 530 degreesC, respectively. Suitable Mn content (0 less than or equal to x less than or equal to 2) could promote the formation of LaMnAl11O19 hexaaluminate, while further addition of Mn (2 less than or equal to x less than or equal to 6) cause the formation of LaMnO3. (C) 2003 Elsevier B.V All rights reserved.

Nucleobase-metal hybrid materials: Preparation of submicrometer-scale, spherical colloidal particles of adenine-gold(III) via a supramolecular hierarchical self-assembly approach

We report a simple and effective supramolecular route for facile synthesis of submicrometer-scale, hierarchically self-assembled spherical colloidal particles of adenine - gold(III) hybrid materials at room temperature. Simple mixture of the precursor aqueous solutions of adenine and HAuCl4 at room temperature could result in spontaneous formation of the hybrid colloidal particles. Optimization of the experimental conditions could yield uniform-sized, self-assembled products at 1:4 molar ration of adenine to HAuCl4. Transmission electron microscopy results reveal the formation of hierarchical self-assembled structure of the as-prepared colloidal particles. Concentration dependence, ratio dependence, time dependence, and kinetic measurements have been investigated. Moreover, spectroscopic evidence [i.e., Fourier transform infrared (FTIR) and UV-vis spectra and wide-angle X-ray scattering data] of the interaction motives causing the formation of the colloidal particles is also presented.

Preparation of CeO2-ZrO2 ceramic fibers by electrospinning

Electrospinning was employed to fabricate polymer-ceramic composite fibers from solutions containing poly(vinyl pyrrolidone) (PVP), Ce(NO3)(3)(.)6H(2)O and ZrOCl2-8H(2)O. Upon firing the composite fibers at 1000 degrees C, Ce(0.67)Zr(0.33)O(2)fibers with diameters ranging from 0.4 to 2 mu m were synthesized. These fibers exhibit strong resistance to sintering. They still have specific surface area around 11.8 m(2)/g after being heated at 1000 degrees C for 6 h.