Synthesis,characterization and applications of polysiloxane networks with immobilized pyrogallol ligands

A porous, solid insoluble polysiloxane‐immobilized ligand system bearing pyrogallol active sites of the general formula P? (CH₂)₃? NH(CH₂)₃OC₆H₃(OH)₂ (where P represents [Si? O]_n siloxane network) has been prepared by the reaction of 3‐aminopropylpolysiloxane with 1,3‐dibromopropane followed by the reaction with pyrogallol. ¹³C CP‐MAS NMR and X‐ray photoelectron spectroscopy confirmed that the pyrogallol is chemically bonded to the siloxane backbone. Thermal analysis showed that the ligand system is stable under nitrogen at relatively high temperature. The polysiloxane–pyrogallol ligand system exhibits high potential for the uptake of the metal ions (Fe³⁺, Co²⁺, Ni²⁺ and Cu²⁺). Complexation of the pyrogallol ligand system for the metal ions at the optimum conditions was found to be in the order Fe³⁺ > Cu²⁺ > Ni²⁺ > Co²⁺. Copyright © 2005 John Wiley & Sons, Ltd.     

Sol–gel encapsulation of cresol red in presence of surfactants

Cresol Red (CR) pH indicator was encapsulated into silica network using the sol–gel process. Transparent monolithic disks of entrapped CR were obtained in the presence of cetyl trimethyl ammonium bromide (CTAB) or dodecyl dimethyl amino oxide (Genaminox LA,GLA) alkyl hydroxyethyl dimethyl ammonium chloride (HY, R = 12–14) and TX-100 surfactants. UV/VIS spectra showed that the encapsulated CR retains its structure in terms of its response to pH. At the neutral conditions it is found that the HY surfactant is considered as proton donor as favor the cationic form of the indicator, while CTAB surfactant favor the neutral, however GLA surfactant, the anionic form of CR is more favored because GLA has a zwitterionic head. The surfactant GLA with TEOS has shifted the equilibrium to the ionized form of CR due to the electrostatic interaction between the surfactant and the CR anion. Therefore their pH range is dependent on the nature of a surfactant used. It is found that the HY surfactant is more efficient as far as loading of CR is concern and it widened the working pH range.     

Behavoir of Trapped Bromothymol Blue into Sol-Gel Matrix in Presence of CTAB

Encapsulation of bromothymol blue (BTB) into a polysiloxane network was prepared using sol-gel method without using a catalyst. The co-entrappment of the bromothymol blue (BTB) and surfactant cetyltrimethyl ammonium bromide (CTAB) was used to modify the properties of the sol-gel matrixes which may provide a highly porous materials and made the polysiloxane network an excellent host for sensing molecules. Monolithic disks of trapped BTB were obtained with no leaching. Polarized light microscopy shows that a almost unique particle sizes distributions were formed. The immobilized BTB shows a response for various pH solutions, the feature of absorption spectra of the immobilized BTB was almost the same as that of the solutions.     

Potentiometric Titration of Na2HAsO4, NaPO3, Na4P2O7, and their Binary Mixtures in NaNO3 Melt at 350°C Using a Novel Solid State Glass/TiO2 as pH Indicator Electrode

A solid‐state glass/TiO₂ electrode was fabricated using a transparent conductive titanium oxide film on a glass substrate. The coating of the glass substrate was achieved by a novel simple chemical vapor deposition (CVD) procedure. This electrode can be used as an indicator electrode in potentiometric acid‐base titration. This electrode behaves reversibly and responds to the oxide ion concentration in molten NaNO₃ · Na₂HAsO₄, NaPO₃, Na₄P₂O₇, and their binary mixtures were potentiometrically titrated with Na₂O₂ as titrants in molten NaNO₃ at 350°C, using the above mentioned indicator electrode.     

Nineteen-membered pentaazamacrocyclic complexes bearing tetraamide groups

A new series of CoII, NiII, CuII and ZnII complexes incorporating pentaazamacrocyclic ligands has been prepared via the template condensation of o-aminobenzoic acid with succinic or phthalic acids in the presence of diethylenetriamine. The overall geometry and mode of bonding have been deduced on the basis of elemental analyses, i.r., 1H-n.m.r., e.p.r. and u.v.-vis. spectral studies, and conductivity and magnetic susceptibility measurements. An octahedral geometry is proposed for all the complexes, where five coordination sites are occupied by the macrocyclic nitrogens and the sixth by an anion.     

Development of a Novel Solid‐State pH Sensor Electrode Based on Titanium Oxide Thin Film as an Indicator Electrode in Potentiometric Acid‐Base Titrations in Fused NaNO3 at 350°C

A solid‐state pH sensor was fabricated using a transparent conductive titanium oxide film on a glass substrate. The coating of the glass substrate was achieved by a novel simple chemical vapor deposition (CVD) procedure. The sensor slope was found to increase as the temperature of the solution was increased. The performance of the sensor was investigated in the pH range from 2.2 to 11.19. The E‐pH curve is linear with slope of 0.054 V at 298.15 K. This value is closed to the theoretical value 2.303RT/F (0.059 V at 298.15). The standard potential of this electrode, E°, is computed as 177.58 mV with respect to the SCE as reference electrode. Results obtained by the suggested sensor compares very well with conventional pH electrodes where the square of the correlation coefficient was 0.998. This electrode can be used as an indicator electrode in potentiometric acid‐base titration. This electrode behaves reversibly and responds to the oxide ion concentration in molten NaNO₃. K₂Cr₂O₇ was potentiometrically titrated with Na₂O₂ and K₂CO₃ as titrants in molten NaNO₃ at 350°C, using the above mentioned indicator electrodes. An acidity/basicity scale of the oxyanions was established in molten NaNO₃ at 350°C.     

Encapsulation of Bromothymol Blue into a Polysiloxane Network Matrix in Presence of Surfactants

Bromothymol blue (BTB) pH indicator was encapsulated into polysiloxane network using the sol-gel process. Transparent monolithic disks of entrapped BTB were obtained in the presence of cetyl trimethyl ammonium bromide (CTAB) or dodecyl dimethyl amino oxide (Genaminox LA, GLA) surfactant. Ultraviolet visible spectra showed that the encapsulated BTB retains its structure in terms of its response to pH. The kinetic studies reveal that there was a faster response to pH in the case of GLA surfactant than in the case of CTAB. It is found that the co-entrapment of cationic surfactant CTAB or zwitterionic surfactant GLA with TEOS has shifted the equilibrium of the BTB to the ionized form due to the electrostatic interaction between the surfactant and the BTB anion and therefore the base form becomes more pronounced (e.g., shift from yellow to red) than that of sol-gel matrix without surfactant.