Mössbauer and infrared spectroscopic studies of novel mixed valence states in cobaltous ferrocyanides and ferricyanides

Novel mixed valence states have been obtained by the treatment of cobaltous ferrocyanides (Co⁺²Fe^II) and ferricyanides (Co⁺²Fe^III) in an ozone flow. The CN stretching bands occur at 2085 cm^–1 for Co⁺²Fe^II and at 2160 cm^–1 for Co⁺²Fe^III. After the ozonization process of Co⁺²Fe^II, an intense band approximately at 2125 cm^–1 is detected. This intermediate band must correspond to a mixed valence state of the type: Fe^II–CN–Co²⁺–NC–Fe^III Mössbauer spectra recorded in situ during the ozonization of Co⁺²Fe^II show the presence of two components: a doublet with isomer shift and quadrupole splitting values close to the cobalti ferricyanide and a very broad line for the mixed valence state. From the Mössbauer and infrared spectra of the aged samples of the Co⁺²Fe^II after ozonization, a relaxation process to the initial state of the samples is observed but the mixed valence state is stable.     

Time reversal for infinite-dimensional diffusions

Summary In this paper we analize the reversibility of the diffusion property for the solution of certain infinite-dimensional systems of stochastic differential equations. Necessary and sufficient conditions ensuring this reversibility are given. The proofs use the techniques of the stochastic calculus of variations.This work was partly done when the first author was visiting the Centre de Recerca Matemàtica at Barcelona     

Validation of the thermodynamic model of inorganic arsenic in non polluted river waters of the Basque country (Spain)

The thermodynamic model of inorganic arsenic was validated by comparing the predicted As(III) concentration with the experimentally determined one in several river waters samples of the Basque Country (Spain) collected in two sampling campaigns: spring and autumn 2000. This model takes into account the acid-base equilibria of As(III) and As(V) together with the redox equilibria between the H₃AsO₃ and H₃AsO₄ species. A correct prediction of As(III) concentration requires the knowledge of the total concentration of arsenic, pH, redox potential (referred to hydrogen electrode), and ionic strength values of the solution. The estimation of the activity coefficients of the arsenic species was performed by means of the Modified Bromley’s Methodology (MBM).In order to perform the experimental As(III) determination, an analytical method was implemented by using an ion exchange separation of As(III)/As(V) on a continuous FIA-IE-HG-AAS system. The total arsenic concentration was determined together with total concentration of the main alkaline or alkaline-earth metals and anions in the natural waters. Temperature compensated measurements of the pH and redox potentials were made in-situ at the sampling sites.For both seasonal campaigns, the agreement between predicted and experimental As(III) is really high for those samples belonging to non polluted river waters.     

Application of molecular absorption properties of horseradish peroxidase for self-indicating enzymatic interactions and analytical methods

In this paper an in depth study is presented of the use of the horseradish peroxidase (HRP) enzyme as a self-indicating biorecognition reagent in UV-vis molecular absorption spectrometry. The HRP/H2O2 reaction mechanism in the absence of an external substrate has been clarified, and the interaction between HRP and glucose oxidase (GOx) has been studied. It has been demonstrated that GOx can act as a substrate of HRP; in both cases the kinetic constants have been obtained and mathematical models have been developed. Second, the HRP/H2O2 reaction is used to follow a H2O2-producing enzymatic reaction, the glucose reaction with GOx being used as a model. As an application of this, two methodologies have been proposed for glucose determination: with or without previous incubation of glucose with GOx. In both cases mathematical models relating HRP absorbance changes to glucose concentration have been developed and tested; both methods have been optimized, analytically characterized, and tested for glucose determination in samples. The methodology described could be applied to other heme-proteins and to other H2O2-producing enzymatic reactions. The models permit the reaction constants to be calculated. From the analytical chemistry point of view the models allow the prediction of the method sensitivity for other analytes involved in this type of reaction if the kinetic constants are known and can be used in the design of optical sensors.     

Mechanism of the grafting of organosilanes on mineral surfaces. IV. Phenylderivatives of sepiolite and poly (organosiloxanes)

Grafting reactions of phenyl groups on silica substrates using as reagents various phenylsilanes with variable distances between the silicon atoms and the aromatic ring by 0, 1, and 2 methylene groups [Si–(CH₂) _n –C₆H₅] were studied. Two different silicates have been selected as source of silica: sepiolite and tetraethyl-orthosilicate (TEOS). Sulfonic- and nitro-derivatives prepared from these phenyl compounds by electrophilic substitution reactions, have been obtained. The mechanism of these processes has been studied in relation to the number of methylene separating groups belonging to the starting reagents. The characterization of such systems has been achieved by XRD,²⁹Si and¹³C NMR/MAS, IR, and laser microprobe mass spectrometry.Parts I, II and III published in this Journal (1978) 256:135–139, (1979) 257:178–181 and (1985) 263:1025–1030