Surface analysis of new chlorpromazinium plastic membrane electrodes.

New chlorpromazinium (Cp) plastic membrane electrodes of the conventional type were constructed and characterized. They are based on incorporation of Cp-reineckate (CpRn) ion pair, Cp-phosphotungstate (Cp3PT), or Cp-phosphomolybdate (Cp3PM) ion associate into poly(vinyl chloride) membrane. The electrodes exhibited calibration graph slopes of 49.83, 52.87, and 61.30 mV/Cp concentration decade over life spans of 1, 5, and 3 days, respectively. All electrodes proved to be selective for Cp and have been applied to the assay of a pharmaceutical preparation. Energy dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), as well as scanning electron microscopy (SEM) showed that the limitation of the lifetime of the electrodes is attributed to leaching of the ion exchanger from the membrane into the test solution in addition to deformation of the surface.

Complexes of vitamin B6XX: equilibrium and mechanistic studies of the reaction of pyridoxal-5'-phosphate with pyridoxamine-5'-phosphate in the presence of copper(II).

The interaction of Cu(II) with pyridoxamine-5'-phosphate (PMP) and pyridoxal-5'-phosphate (PLP) was studied potentiometrically. The titration data were assessed by MINIQUAD program. Several protonated and nonprotonated complexes have been found to exist in solution. The reaction of PLP with Cu(II)-PMP has been studied kinetically, using the stopped-flow technique. Two rate steps have been observed. The first step has been attributed to the formation of a Schiff's base metal complex. The second step may be due to the formation of a ternary complex formation. A mechanism was suggested.

Complexes of hydroxamates. V: Equilibrium and kinetics of the formation of the binary and ternary complexes involved in the nickel(II)-histidinehydroxamic acid-pyridoxal system.

Equilibrium-based computer models utilizing SUPERQUAD program were made to determine the formation constants of the binary complexes of Ni(II) with histidine-hydroxamic acid (HX) from pH-metric titration data at 25 degrees C and I = 0.15 M NaCl. The species were monomeric in the pH range 3.0-8.0. The mechanism of their complex formation was determined using the stopped flow technique under the same experimental conditions of the equilibrium study. It has been concluded that Ni2+ and NiOH- were the active species in the complex formation reactions. Moreover, the reaction of HX with pyridoxal (PL) was studied in the absence of metal-ions by polarographic and spectrophotometric techniques at pH greater than or equal to 5.0. No rates were observed by using the stopped-flow methods. The formation constants for the binary system (HX-PL) and the ternary system (Ni(II)-HX-PL) were also determined by the same program applied on data obtained from pH metric titration at 25 degrees C and I = 0.15 M NaCl. Ternary complex formation involving PL and the species of the Ni(II)-HX system was also investigated kinetically in the pH range of 6.5-10.5. Several rate steps have been observed which have been interpreted qualitatively in terms of sequence of processes involving the condensation of aldehydic form of PL with amino moiety of HX. A comparison with other pertinent systems is also discussed.