A Titration Microcalorimetric Study of the Effects of Halide Counterions on Vesicle-Forming Aggregation in Aqueous Solution of Branched-Chain Alkylpyridinium Surfactants

Titration microcalorimetry is used to study the influences of iodide, bromide, and chloride counterions on the aggregation of vesicle-forming 1-methyl-4-(2-pentylheptyl)pyridinium halide surfactants. Formation of vesicles by these surfactants was characterised using transmission electron microscopy. When the counterion is changed at 303 K through the series iodide, bromide, to chloride, the critical vesicular concentration (cvc) increases and the enthalpy of vesicle formation changes from exo- to endothermic. With increase in temperature to 333 K, vesicle formation becomes strongly exothermic. Increasing the temperature leads to a decrease in enthalpy and entropy of vesicle formation for all three surfactants. However the standard Gibbs energy for vesicle formation is, perhaps surprisingly, largely unaffected by an increase in temperature, as a consequence of a compensating change in both standard entropy and standard enthalpy of vesicle formation. Interestingly, standard isobaric heat capacities of vesicle formation are negative, large in magnitude but not strikingly dependent on the counterion. We conclude that the driving force for vesicle formation can be understood in terms of overlap of the thermally labile hydrophobic hydration shells of the alkyl chains. Copyright 2000 Academic Press.     

Effects of Adsorbed Polyaniline on Redox Process on MoO3 Surface

The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press.     

Mass spectrometry of transition-metal π-complexes. III—a study of an iron-coordinated tautomer of phenol

A study of the fragmentation of the \documentclass{article}\pagestyle{empty}\begin{document}$ \left[{\left({{\rm C}_{\rm 6} {\rm H}_{\rm 6} {\rm O}} \right){\rm Fe}} \right]_{}^{_.^ + } $\end{document} ion formed from two different precursors suggests that the ions adopt different structures over that part of the energy distribution giving rise to decomposition in the ion source.     

Ethane adsorption in slit-shaped micropores: influence of molecule orientation on adsorption capacity

Adsorption of ethane in a slit shaped micropore system has been studied by Monte Carlo molecular simulation by considering this hydrocarbon as a two interacting sites molecule. Ethane adsorption in pore sizes from 0.41 to 1.66 nm was simulated at 303 K. Microscopic characteristics of the adsorbed phase have been studied for pores of different size, comparing two density profiles: the molecule centre of mass profile and the molecular interaction site profile. Averaged angle distribution of molecule positions with respect to the slit plane across the pore width has been also obtained by simulation. These results were related to ethane molecule packing efficiency, which is also related to the adsorption capacity in terms of the adsorbed phase density. Packing efficiency presents an oscillation shape as the result of the adsorbate disorder inside the pore. Pressure influence on the adsorption has been studied by following pore filling by simulation. When pore condensation takes place and for pressures above condensation, fluid-fluid interactions are determinant in molecule disorder observed between the two adsorbed layers.     

Qsar Models for Predicting the Acute Toxicity of Selected Organic Chemicals with Diverse Structures to Aquatic Non-Vertebrates and Humans

Abstract

The linear and non-linear relationships of acute toxicity (as determined on five aquatic non-vertebrates and humans) to molecular structure have been investigated on 38 structurally-diverse chemicals. The compounds selected are the organic chemicals from the 50 priority chemicals prescribed by the Multicentre Evaluation of In Vitro Cytotoxicity (MEIC) programme. The models used for the evaluations are the best combination of physico-chemical properties that could be obtained so far for each organism, using the partial least squares projection to latent structures (PLS) regression method and backpropagated neural networks (BPN). Non-linear models, whether derived from PLS regression or backpropagated neural networks, appear to be better than linear models for describing the relationship between acute toxicity and molecular structure. BPN models, in turn, outperform non-linear models obtained from PLS regression. The predictive power of BPN models for the crustacean test species are better than the model for humans (based on human lethal concentration). The physico-chemical properties found to be important to predict both human acute toxicity and the toxicity to aquatic non-vertebrates are the n?octanol water partition coefficient (Pow) and heat of formation (HF). Aside from the two former properties, the contribution of parameters that reflect size and electronic properties of the molecule to the model is also high, but the type of physico-chemical properties differs from one model to another. In all of the best BPN models, some of the principal component analysis (PCA) scores of the ¹³C-NMR spectrum, with electron withdrawing/accepting capacity (LUMO, HOMO and IP) are molecular size/volume (VDW or MS1) parameters are relevant. The chemical deviating from the QSAR models include non-pesticides as well as some of the pesticides tested. The latter type of chemical fits in a number of the QSAR models. Outliers for one species may be different from those of other test organisms.     

Electronic and Structural Properties of Highly Aluminum Ion Doped TiO2 Nanoparticles: A Combined Experimental and Theoretical Study

This study presents the experimental and theoretical study of highly internally Al‐doped TiO₂ nanoparticles. Two synthesis methods were used and detailed characterization was performed. There were differences in the doping and the crystallinity, but the nanoparticles synthesized with the different methods share common features. Anatase to rutile transformation occurred at higher temperatures with Al doping. X‐ray photoelectron spectroscopy showed the generation of oxygen vacancies, which is an interesting feature in photocatalysis. In turn, the band‐gap energy and the valence band did not change appreciably. Periodic density functional calculations were performed to model the experimentally doped structures, the formation of the oxygen vacancies, and the band gap. Calculation of the density of states confirmed the experimental band‐gap energies. The theoretical results confirmed the presence of Ti⁴⁺ and Al³⁺. The charge density study and electron localization function analysis indicated that the inclusion of Al in the anatase structure resulted in a strengthening of the Ti?O bonds around the vacancy.     

Influence of pH on the binding of diphenylmethylenepiperidines by 5-HT2B receptors in rat stomach fundus

Cyproheptadine is one of the compounds exhibiting the highest activity at 5-HT2B receptors. In a previous work we analysed the relevance of the amino group in diphenylmethylenepiperidines (DPMP), which are open cyproheptadine analogues. Only compounds containing N-H or N-methyl motifs, showed significant 5-HT2B activity. Surprisingly, the corresponding quaternary ammonium salt demonstrated a total lack of activity. Therefore, the question arises whether protonation favours the interaction of these compounds with 5-HT2B receptors. Consequently, we studied the protonation influence (by varying the pH of the medium) on the antagonism of serotonin by some cyproheptadine analogues in rat stomach fundus. The main results were: 1) N-protonation increases the activity of DPMPs. 2) Alkaline pH facilitates the occurrence of a non-surmountable antagonism. 3) The contrast between the activity of protonated DPMPs and the lack of activity of the corresponding quaternary ammonium cation, suggests either that the latter is prevented from acting by steric hindrance, or that the mechanism by which protonation may increase the activity depends not only on the charge of the proton, but also on its ability to form hydrogen bonds.     

Characterization of the Suzuki phase in doped alkali halides by Raman spectroscopy

The symmetries and frequencies of the Raman active modes of the Suzuki phase in the systems 6NaCl:CdCl₂; and 6NaCl:MnCl₂, have been calculated. Three of the four peaks allowed by symmetry (A_1g and 2F_g) agree to within 25% in position with the experimental values presented here and with other experimental results. The fourth peak (E_g) seems to be associated with a very soft mode, which explains why this peak has not been observed. The features of the Raman spectrum depend mainly upon the chlorine ions.     

Microstructure–conductivity relationship in Gd- and Sm-doped ceria-based electrolytes prepared by the acrylamide sol–gel-related method

We have prepared pure electrolytes of Ce_0.8Gd_0.2O_1.9 (CGO) and Ce_0.8Sm_0.2O_1.9 (CSO), useful for SOFCs, by a sol–gel-related technique like the acrylamide method. This method consists of preparing a solution from the single oxides followed by gelation. Then, the combustion or decomposition of the organic molecules is initiated, producing nanometric calcined powders of the above-mentioned compounds. Thermal treatments were optimized in order to obtain good electrochemical properties of the electrolytes. We have observed that the synthesis temperature to obtain the pure phase is lower for the sol–gel samples than for the pellets prepared by solid-state reaction, and the final density is higher. The microstructure and composition of the powders were characterized by TEM, SEM, and EDX analysis. The electrical properties of the electrolytes were measured by impedance spectroscopy at different temperatures and oxygen partial pressures.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003