Electroanalysis at modified carbon-paste electrodes containing natural ionic polysaccharides

The strong affinity of natural ionic polysaccharides for certain metal ions is exploited in the design of a new class of voltammetric sensing devices. In particular, carbon-paste electrodes containing pectic and alginic acids are used for the nonelectrolytic collection and subsequent voltammetric determination of copper and lead, respectively. Cyclic and differential pulse voltammetry are used to quantify the accumulated ions. The response is characterized with respect to modifier loading, preconcentration period, metal concentration, reproducibility, possible interferences and other variables. Titrimetric experiments illustrate the potential of polysaccharide electrodes for speciation work. Preliminary data are also given for analogous measurements of copper at heparin-modified electrodes. Detection limits are 1 mug/ml and the relative standard deviation is 4.8%.     

The Complexation of Some Transition Metals by Acetoacetanilidehydrazo Ligands “Stability Constants”

Acid dissociation constants of acetoacetanilide abbreviated (AAA); Orthocarboxy-phenylhydrazoacetoacetanilide (o-CPHAAA); and orthocarboxy-phenylhydrazo-parachloro-acetoacetanilide (o-CPH-p-Cl-AAA) and chelate stability constants of the corresponding anions with Cu⁺², Ni⁺², CO⁺², Zn⁺², Mn⁺², and Cd⁺² ions are reported. The infra-red spectra of o-CPHAAA and o-CPH-p-Cl-AAA ligands and their chelates for copper and nickel are discussed.     

Epoxy-amine multimethacrylic prepolymers,kinetic and structural studies

Epoxy-amine methacrylated prepolymers are prepared in a 1-step synthesis by the reaction of Bisphenol A diglycidyl ether, glycidyl methacrylate, and different diamines. The adaptation of these reactions to production processes with a reduced reaction time requires a kinetic control and the use of efficient catalysts. The comparative kinetic treatment of the epoxy-amine reaction in the frame of Horie's and Rozenberg's kinetic schemes have been made. Cases where an efficient acid catalyst is used are also examined. Structural studies of these reactions established the occurrence of a Michael amine/double bond addition, when some amines are used. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of maleimide polymers with pendant pyrazole groups. IV. Copolymerization of pyrazole-modified maleimides with vinyl ethers

The synthesis of maleimides that have pyrazolic or bipyrazolic pendant groups is described. Their homopolymerization and their copolymerization with 2-chloroethyl vinyl ether (CEVE) is reported. The homopolymerizations of such maleimides were performed under various conditions and led to low molecular-weight polymers. However, alternating copolymers were obtained from CEVE as comonomers whatever the monomers feed compositions. A similar behavior was also observed for maleimides that do not exhibit any spacer, whereas for bulky vinyl ethers, random copolymers were produced. A comparison of the thermal behavior between these copolymers (glass transition temperatures, T_g, and decomposition temperatures) and other copolymers having different spacers between the nitrogenated cycles and the chain are related. Thus, an important decrease of T_g, was observed when C₃H₆CO₂CH₂ groups were used as the spacer instead of methylene groups. Moreover, the thermal weakness of these copolymers may come from the substituents of the vinyl ether and is discussed. © 1994 John Wiley & Sons, Inc.     

Synthesis of Some New Heterobicyclic Nitrogen Systems Bearing 7H‐1,2,4‐Triazolo[1,5‐d]tetrazol‐6‐yl Moiety for Biological Interest

Reaction of 6‐mercapto‐7H‐1,2,4‐triazolo[1,5‐d]tetrazole ( 1 ) wtih 1,2‐phenylenediamine afforded N‐{7H‐1,2,4‐triazolo[1,5‐d]tetrazol‐6‐yl}‐1,2‐phenylenediamine which was cyclized to benzimidazolyl‐1,2,4‐triazolo[1,5‐d]tetrazoles using various one‐carbon cyclizing agents. Also, the treatment of 1 with maleic anhydride or phthalic anhydride gave the corresponding thio derivatives followed by hydrazinolysis to afford the thio heterobicyclic systems. Former structures of the products have been established upon elemental and spectral analyses.     

Spectrophotometric determination of some drugs for osteoporosis

Three simple, accurate and sensitive spectrophotometric methods are developed for the determination of some new drugs for the treatment of osteoporosis: risedronate sodium (I), alendronate sodium (II) and etidronate disodium (III). The first method is based on the measurement of difference in absorbance (Delta A) of risedronate sodium in 0.01 mol l(-1) hydrochloric and 0.1 mol l(-1) sodium hydroxide at 262 nm. Beer's law is obeyed over a concentration range of 15-150 microg ml(-1) with mean recovery 99.75+/-1.22 and molar absorptivity (epsilon) 1.891 x 10(3). The second method is based on the reaction of the primary amino group of (II) with ninhydrin reagent in methanolic medium in the presence of 0.05 mol l(-1) sodium bicarbonate. The colored product is measured at 568 nm, and the linearity range is found to be 3.75-45 microg ml(-1) with mean recovery 99.77+/-0.73 and epsilon 9.425 x 10(3). The third method is based on oxidation of the three mentioned drugs with ceric (IV) sulphate in 0.5 mol l(-1) sulphuric acid at room temperature and subsequent measurement of the excess unreacted cerium (IV) sulphate at 320 nm. The method obeyed Beer's law over a concentration range of 2-24 microg ml(-1) for the three drugs with mean recovery 99.79+/-1.16, 99.73+/-1.38 and 99.86+/-1.13 and epsilon 14.427 x 10(3), 13.813 x 10(3) and 14.000 x 10(3) for drugs I, II, III respectively. The proposed methods were successfully applied for the determination of the studied drugs in bulk powder and in pharmaceutical formulations. The results were found to agree statistically with those obtained the reported methods. Furthermore, the methods were validated according to USP regulations and also assessed by applying the standard addition technique.     

Electrochemical disk generation and ring identification of carbanions from organomercurials in acetonitrile

A rotating disk-ring electrode was used for study of a series of organomercury compounds R₂Hg, where R = CN, CF(NO₂)₂, C₆F₅, PhCC, p-NO₂C₆H₄OCC, PhSCH₂CC, PhCOCH₂, CH₂CN, CCl₂CCl, 2-phenyl-o-carboranyl. Reduction of these compounds at a Pt-disk in acetonitrile is a two-electron process and results in generation of the carbanion R^?. The carbanions generated at the disk interact with the solvent during their convective diffusion to the ring electrode where there may be oxidized. The main reaction in solution, shown using chromatography-mass spectrometry techniques, is acid-base interaction of carbanions with the solvent acetonitrile, which acts as a Brönsted acid. Reaching the ring, the carbanions may be oxidized at anodic potentials of the ring; oxidation potentials depend significantly on carbanion structure (e.g.+0.28 V (vs. SCE), for PhCC^? and +2.20 V for CN^?. It is shown that PK_a value of the carbanions do not correlate with the oxidation potentials, however, a linear correlation is observed between pK_a values and a special parameter called the efficiency coefficient.     

Physicochemical characterization of degradable thermosensitive polymeric micelles

Amphiphilic AB block copolymers consisting of thermosensitive poly(N-(2-hydroxypropyl) methacrylamide lactate) and poly(ethylene glycol), pHPMAmDL-b-PEG, were synthesized via a macroinitiator route. Dynamic light scattering measurements showed that these block copolymers form polymeric micelles in water with a size of around 50 nm by heating of an aqueous polymer solution from below to above the critical micelle temperature (cmt). The critical micelle concentration as well as the cmt decreased with increasing pHPMAmDL block lengths, which can be attributed to the greater hydrophobicity of the thermosensitive block with increasing molecular weight. Cryogenic transmission electron microscopy analysis revealed that the micelles have a spherical shape with a narrow size distribution. 1H NMR measurements in D2O showed that the intensity of the peaks of the protons from the pHPMAmDL block significantly decreased above the cmt, indicating that the thermosensitive blocks indeed form the solidlike core of the micelles. Static light scattering measurements demonstrated that pHPMAmDL-b-PEG micelles with relatively large pHPMAmDL blocks possess a highly packed core that is stabilized by a dense layer of swollen PEG chains. FT-IR analysis indicated that dehydration of amide bonds in the pHPMAmDL block occurs when the polymer dissolved in water is heated from below to above its cmt. The micelles were stable when an aqueous solution of micelles was incubated at 37 degrees C and at pH 5.0, where the hydrolysis rate of lactate side groups is minimized. On the other hand, at pH 9.0, where hydrolysis of the lactic acid side groups occurs, the micelles started to swell after 1.5 h of incubation and complete dissolution of micelles was observed after 4 h as a result of hydrophilization of the thermosensitive block. Fluorescence spectroscopy measurements with pyrene loaded in the hydrophobic core of the micelles showed that when these micelles were incubated at pH 8.6 and at 37 degrees C the microenvironment of pyrene became increasingly hydrated in time during this swelling phase. The results demonstrate the potential applicability of pHPMAmDL-b-PEG block copolymer micelles for the controlled delivery of hydrophobic drugs.     

New Clerodane Diterpenoids from Casearia membranacea

Bioassay‐guided fractionation of an AcOEt extract of Casearia membranacea resulted in the isolation of six new clerodane diterpenes, caseamembrins G–L ( 1 – 6 ). The structures of the new compounds, including their relative configurations, were established by an extensive study of their spectral data, especially 2D NMR. The cytotoxic activities of the isolated diterpenes against human oral epidermoid (KB), cervical epitheloid (Hela), and liver (Hep59T/VGH) carcinoma cell lines were investigated.     

The spectrophotometric and titrimetric determination of gold with ferroin as reagent

A spectrophotometric and a photometric titration method in a two-phase system for the determination of gold with ferroin is reported. Both methods are rapid and reproducible with an accuracy of ±1%. In the spectrophotometric determination Co²⁺, Cu²⁺, Ni²⁺ , Fe³⁺, Zn²⁺, Mn²⁺ and Cr³⁺ do not interfere with the determination of gold and Pt⁴⁺, Pd²⁺, Hg²⁺, Ir⁴⁺ and Os⁴⁺ can be tolerated up to a ratio of 1:1. The titrations can also be carried out in the presence of a number of diverse ions, e.g. Ni²⁺, Cu²⁺, Co²⁺, Fe³⁺, Zn²⁺, Cr³⁺, Mn²⁺, without interference; the platinum metals and Hg²⁺ cause interference but, by the use of the spectrophotometric procedure, this can be reduced.