Experimental and Computational Study of the Thermal Decomposition of 3‐Methyl‐3‐buten‐1‐ol in m‐Xylene Solution

An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s^?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol^?1)·T^?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH₃ group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition.     

Structural and Kinetic Aspects of Blood Plasma Protein Adsorption on the Surface of Hydrophobic Polymers

Abstract

Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood.     

Removal efficiency of 75Se, 51Cr and 60Co from tidal water by mangrove sediments from Sepetiba Bay (SE Brazil)

Mangrove sediment cores sampled from Sepetiba Bay (SE Brazil) were covered with tidal water spiked with ⁷⁵Se, ⁵¹Cr and ⁶⁰Co to evaluate the removal efficiency of these radiotracers by underlying sediments. Variable time-evolution trends were observed along 115 h experiments, with significant differences between removal efficiencies of all radiotracers observed only after 70 h (⁵¹Cr > ⁶⁰Co > ⁷⁵Se). After an event of ⁶⁰Co release back to overlying water, there was a general trend of lower ⁶⁰Co removal than observed for other radiotracers during the period from 20 to 54 h. After this event, alternated periods of higher ⁶⁰Co and higher ⁷⁵Se removal trends were observed, attributed to behavioural differences expected for such anionic and cationic radiotracers. While ⁷⁵Se and ⁵¹Cr showed uniform time-evolution curves, as typically found in the literature for most radiotracers, ⁶⁰Co removal rates presented oscillations, probably due to sensitivity to changes in redox conditions within underlying sediments. Results evidenced the role of mangrove sediments as trace element sinks, which have implications for coastal water quality and for possible uses of such sediments in wastewater treatment systems.     

Multivariate analysis in provenance studies: Cerrillos obsidians case, Peru

We present the preliminary results of a provenance study of obsidians samples from Cerrillos (ca. 800–100 b.c.) using Mössbauer Spectroscopy. The Cerrillos archaeological site, located in the Upper Ica Valley, Peru, is the only Paracas ceremonial center excavated so far. The archaeological data collected suggest the existence of a complex social and economic organization on the south coast of Peru. Provenance research of obsidian provides valuable information about the selection of lithic resources by our ancestors and eventually about the existence of communication routes and exchange networks. We characterized 18 obsidian artifacts samples by Mössbauer spectroscopy from Cerrillos. The spectra, recorded at room temperature using different velocities, are mainly composed of broad asymmetric doublets due to the superposition of at least two quadrupole doublets corresponding to Fe²⁺ in two different sites (species A and B), one weak Fe³⁺ doublet (specie C) and magnetic components associated to the presence of small particles of magnetite. Multivariate statistical analysis of the Mössbauer data (hyperfine parameters) allows to defined two main groups of obsidians, reflecting different geographical origins.     

Non-destructive analysis of inorganic impurities in Brazilian coals by epithermal neutron activation

Twenty-two elements were identified and determined in different Brazilian coal samples by an epithermal neutron activation technique developed by the authors. The detection limits and the uncertainties of the results show that the technique can be used for routine analysis. The analysis of the complex gamma-ray spectra and the evaluation of the interfering activities are discussed in detail.     

Provenance study of obsidians from the archaeological site of La Maná (Ecuador) by electron spin resonance (ESR), SQUID magnetometry and 57Fe Mössbauer spectroscopy

Obsidians from major Ecuadorian sources (outcrops) were analyzed by electron spin resonance, SQUID magnetometry and ⁵⁷Fe Mössbauer spectroscopy. If the last technique allows to discriminate obsidians from the Quiscatola source, an association of ESR with SQUID magnetometry permits to differentiate obsidians from the sources of Cotopaxi volcano, from the Quiscatola and Mullumica-Callejones sources of the Chacana caldera and to infer that the 12 analyzed obsidians from the pre-Hispanic site of La Maná come from the Mullumica-Callejones source.     

Potential energy surface determinations for nonrigid molecules: Application to acetone

In the present work, the problem of the determination of the potential energy surface for nonrigid molecules is examined in the case of the double rotation of the methyl groups in acetone. From the symmetry adapted functional form for the potential, the minimum number of configurations to be calculated is deduced in order to have a reliable surface. With this consideration in mind, the potential energy surface of acetone is determined in some Hartree–Fock semiempirical (CNDO /2) and ab initio procedures with different standard basis sets. In addition, ab initio calculations are performed using different sets of floating Gaussian functions in order to introduce some polarization effects in the wave function. Finally, the influence of the electronic correlation effects in the barrier height, and the role of the possible relaxation of the structure during the rotation is discussed.