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A B S T R A C TThe aim of this work was to determine the effect of temperature on the formation of acrylamide in cocoa beans during drying treatment by an experimental and computational study, in order to assess the presence of this neoformed compound from postharvest stage. The computational study was conducted on the reaction between fructose, glyoxal from glucose, and on asparagine at the M06-2X/6-31þG(d,p) level, under cocoa bean drying conditions at 323.15 to 343.15 K. The proposed reaction for acrylamide formation consisted of seven steps, which required to progress a via cyclic transition state of the four members. In addition, step III (decarboxylation) was considered to be the rate-determining step. Glucose followed an E1-like elimination and fructose exhibited an E1cb-like elimination. Computational model showed that the reaction of acrylamide formation was favored by fructose rather than glucose.The content of reducing sugars, asparagine and acrylamide in fermented and dried cocoa from two subregions of Antioquia-Colombia, as well as roasted cocoa, were evaluated by UHPLC-C-CAD and UHPLC-QqQ. The concentrations of monosaccharides measured at the end of the fermentation and drying process of cocoa nibs showed greater decreases in the levels of fructose as compared to glucose, supporting the main model hypothesis. Acrylamide formation only occurred in Bajo Cauca due to the presence of both precursors and fast drying time (72 h). Finally, it was possible to find the conditions to which acrylamide can be formed from the drying process and not only from roasting, information that can be used for future control strategies.

The nature of bonding along the gas-phase thermal decomposition of 1-chlorohexane to produce 1-hexene and hydrogen chloride has been examined at the DFT M05-2X/6-311+G(d,p) level of theory. Based on results both from energetical and topological analysis of the electron localization function (ELF), we propose to rationalize the experimental available results not in terms of a decomposition via a four-membered cyclic transition structure (TS), but properly as a two stage one step reaction mechanism featuring a slightly asynchronous process associated to the catalytic planar reaction center at the TS. In this context, the first electronic stage corresponds to the ‫ܥ‬ ఋା ••• ‫݈ܥ‬ ఋି bond cleavage, which take place on the activation path earlier the transition structure be reached. There is no evidence of a Cl-C bond at the TS configuration. The second stage, associated to the top of the energy barrier, includes the TS and extends beyond on the deactivation pathway towards the products. The existence of both bonding and nonbonding non covalent interactions (NCI) are also revealed for the first time for the TS configuration. 17 47 to point -9 along the IRC reaction pathway. Arbitrarily the second stage concerning main electronic changes will be associated to points -9 to +9. Both stages refer to regions where key electronic changes driving the transformation take place. Note that from point -34 to point -5, the population associated to the disynaptic basin V(C α ,C β ) increases from 1.99e to 2.20e, whereas the population integrated in the disynaptic protonated basin V(H β ,C β ) decreases from 1.98e to 1.72e. The attractor corresponding to the forming double bond localizes out of the line connecting the carbon center cores. This topology for the C  -C  region remains unchanged until point 12 in region g. At the top of the energy barrier, within the entire interval IRC=(-0.97962,+0.97971), i.e., point -9 to point 9, we observe an isolated electron localization region integrating to 7.64e which is associated to the migrating chlorine center. This picture, on the top of the barrier, corresponds to a lonely chlorine atom bearing an electronic charge of -0.64 while evolving to the encounter of the H β center.Thereafter, within the tiny region d four valence monosynaptic basins V(Cl) associated to the negatively charged chlorine center adopt a tetrahedral conformation, with an increasing in the population from 7.64e to 7.70e. In this region the valence basins populations for V(C α ,C β ) and V(H β ,C β ) varies from 2.41e to 2.34e, and from 1.81e to 1.51e, respectively. The migrating chlorine center develops thus a maximum charge of -0.71 at the transition structure (point 0). ELF picture of bonding reveals that activation events are mainly associated to conformational changes in preparation of the reaction center (region a), followed by the breaking of the Cl-C α bond (regions b and c), and the start of the migration of H  atom with the associated bonding changes at C α -C β -H β moiety (regions c and d). Regarding t...

Theoretical calculations at the M05‐2X/6‐31+G(d) level of theory have been carried out in order to explore the nature of the mechanism of the thermal decomposition reactions of the β‐hydroxy ketones, 4‐hydroxy‐2‐butanone, 4‐hydroxy‐2‐pentanone, and 4‐hydroxy‐2‐methyl‐2‐pentanone in gas phase and in m‐xylene solution. The mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state. A reasonable agreement between experimental and calculated activation parameters and rate constants has been obtained, the tertiary : secondary : primary alcohol rate constant ratio being calculated, at T = 503.15 K, as 5.9:4.7:1.0 in m‐xylene solution and 44.1:5.0:1.0 in the gas phase, compared with the experimental values, 3.7:1.3:1.0 and 13.5:3.2:1.0, respectively. The progress of the thermal decomposition reactions of β‐hydroxy ketones has been followed by means of the Wiberg bond indices. The lengthening of the O1–C2 bond with the initial migration of the H6 atom from O5 to O1 can be seen as the driving force for the studied reactions. Calculated synchronicity values indicate that the mechanisms correspond to concerted and highly synchronous processes. The transition states are “advanced”, nearer to the products than to the reactants. Copyright © 2012 John Wiley & Sons, Ltd.

The formation of polyacids in a glass-ionomer cement was computationally modeled. The polyacid modelled is an oligomer made up of three molecules: acrylic acid, itaconic acid and an additional molecule that acts as a spacer group between the previous two. Acryloyl and meta-acryloyl derivatives of some amino acids and related molecules such as N-vinyl pyrrolidone and Nvinyl caprolactam were used as spacer groups. Some of these molecules have been previously used experimentally as spacer groups. In this work the spacer behaviour of 15 different molecules was investigated. To our knowledge, this is the first computational attempt to model some promising molecules to be incorporated into glass-ionomer dental cements. The results revealed the best structural arrangement for the investigated molecules.

This paper describes cost-efficient, innovative and interoperable ocean passive acoustics sensors systems, developed within the European FP7 project NeXOS (Next generation Low-Cost Multifunctional Web Enabled Ocean Sensor Systems Empowering Marine, Maritime and Fisheries Management) These passive acoustic sensors consist of two low power, innovative digital hydrophone systems with embedded processing of acoustic data, A1 and A2, enabling real-time measurement of the underwater soundscape. An important part of the effort is focused on achieving greater dynamic range and effortless integration on autonomous platforms, such as gliders and profilers. A1 is a small standalone, compact, low power, low consumption digital hydrophone with embedded pre-processing of acoustic data, suitable for mobile platforms with limited autonomy and communication capability. A2 consists of four A1 digital hydrophones with Ethernet interface and one master unit for data processing, enabling real-time measurement of underwater noise and soundscape sources. In this work the real-time acoustic processing algorithms implemented for A1 and A2 are described, including computational load evaluations of the algorithms. The results obtained from the real time test done with the A2 assembly at OBSEA observatory collected during the verification phase of the project are presented.

This paper describes the development of costefficient, innovative and interoperable ocean passive acoustics sensors systems deployable from multiple platforms in the European FP7 project NeXOS (Next generation Low-Cost Multifunctional Web Enabled Ocean Sensor Systems Empowering Marine, Maritime and Fisheries Management). The objective of the NeXOS project is to develop cost-effective, innovative, and compact multifunctional sensor systems in ocean optics, ocean passive acoustics and for an Ecosystem Approach to Fisheries (EAF), which can be deployed from mobile and fixed platforms, with data services contributing to the GEOSS, the Marine Strategy Framework Directive (MSFD) and the Common Fisheries Policy of the European Union. Development of a new generation of multifunctional sensor systems is underway to address ocean monitoring challenges. The development of innovative hydrophones will focus on the pre and post-processing of acoustic information and improved transducer integration, reducing size and overall procurement and operations cost while increasing functionality. An important part of the effort will focus on the need for greater dynamic range and the integration on autonomous platforms, such as gliders and profilers.

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 CH 3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. C