The Infestation of Olive Fruits by Bactrocera oleae (Rossi) Modifies the Expression of Key Genes in the Biosynthesis of Volatile and Phenolic Compounds and Alters the Composition of Virgin Olive Oil

Bactrocera oleae, the olive fruit fly, is one of the most important pests affecting the olive fruit, causing serious quantitative and qualitative damage to olive oil production. In this study, the changes induced by B. oleae infestation in the biosynthesis of volatile and phenolic compounds in olive (cvs. Picual, Manzanilla, and Hojiblanca) have been analyzed. Despite cultivar differences, the oils obtained from infested fruits showed a significant increase in the content of certain volatile compounds such as (E)-hex-2-enal, ethanol, ethyl acetate, and β-ocimene and a drastic decrease of the phenolic contents. The impact of those changes on the inferred quality of the oils has been studied. In parallel, the changes induced by the attack of the olive fly on the expression of some key genes in the biosynthesis of volatile and phenolic compounds, such as lipoxygenase, β-glucosidase, and polyphenol oxidase, have been analyzed. The strong induction of a new olive polyphenol oxidase gene (OePPO2) explains the reduction of phenolic content in the oils obtained from infested fruits and suggest the existence of a PPO-mediated oxidative defense system in olives.     

Autoacceleration and inhibition: Free volume. Epoxy-amine kinetics

The epoxy-diamine cure process was studied. We found that the mechanism can be described in three steps: (i) initiation up to 20–25% of conversion. (ii) autoacceleration and (iii) inhibition. It has been observed that after the initiation there is a clear autoacceleration effect which has been explained in terms of free volume, considerations: the volume occupied by the products of reaction diminishes the available volume increasing the “local concentration” of the reactants and therefore the rate of reaction. The reaction was followed by FTIR (near infrared) as the main technique. We used a purified epoxy resin as well as phenyl glycidyl ether cured with m-xylenediamine. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1001–1016, 1998     

Enthalpy relaxation in polymethyl(α-n-alkyl)acrylates: Effect of length of alkyl chain

In this work, we have investigated by DSC the structural relaxation of amorphous polymethyl(α-n-alkyl)acrylates in which it is possible to change the length of the alkyl chain. We have evaluated the Narayanaswamy parameter, x, which controls the relative contribution of temperature and of structure to the relaxation time, the apparent activation energy, Δh*, and the nonexponentiality parameter, β, of the stretched exponential response function. The results suggest that x increases while Δh* decreases and β remains constant as the length of the side chain increases. This allows us to comment on the effect of chemical modification on the relaxation kinetics. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 583–593, 1998     

Optimal Control of Uniformly Heated Granular Fluids in Linear Response

We present a detailed analytical investigation of the optimal control of uniformly heated granular gases in the linear regime. The intensity of the stochastic driving is therefore assumed to be bounded between two values that are close, which limits the possible values of the granular temperature to a correspondingly small interval. Specifically, we are interested in minimising the connection time between the non-equilibrium steady states (NESSs) for two different values of the granular temperature by controlling the time dependence of the driving intensity. The closeness of the initial and target NESSs make it possible to linearise the evolution equations and rigorously—from a mathematical point of view—prove that the optimal controls are of bang-bang type, with only one switching in the first Sonine approximation. We also look into the dependence of the optimal connection time on the bounds of the driving intensity. Moreover, the limits of validity of the linear regime are investigated.     

The effect of chain architecture on “sharkskin” of metallocene polyethylenes

Dynamic viscoelastic and extrusion capillary results of metallocene based polyethylenes are analyzed. Three samples show very high viscosities at low frequencies and large relaxation times, which is a symptom of the presence of small amounts of long chain branching (LCB). A linear correlation is found between the sharkskin dynamics (periodicity) and a characteristic entanglement‐disentanglement time. It is found that this correlation does not hold for samples suspected of LCB.     

A Path Integral Molecular Dynamics Simulation of a Harpoon-Type Redox Reaction in a Helium Nanodroplet

We present path integral molecular dynamics (PIMD) calculations of an electron transfer from a heliophobic Cs2 dimer in its (3Σu) state, located on the surface of a He droplet, to a heliophilic, fully immersed C60 molecule. Supported by electron ionization mass spectroscopy measurements (Renzler et al., J. Chem. Phys. 2016, 145, 181101), this spatially quenched reaction was characterized as a harpoon-type or long-range electron transfer in a previous high-level ab initio study (de Lara-Castells et al., J. Phys. Chem. Lett. 2017, 8, 4284). To go beyond the static approach, classical and quantum PIMD simulations are performed at 2 K, slightly below the critical temperature for helium superfluidity (2.172 K). Calculations are executed in the NVT ensemble as well as the NVE ensemble to provide insights into real-time dynamics. A droplet size of 2090 atoms is assumed to study the impact of spatial hindrance on reactivity. By changing the number of beads in the PIMD simulations, the impact of quantization can be studied in greater detail and without an implicit assumption of superfluidity. We find that the reaction probability increases with higher levels of quantization. Our findings confirm earlier, static predictions of a rotational motion of the Cs2 dimer upon reacting with the fullerene, involving a substantial displacement of helium. However, it also raises the new question of whether the interacting species are driven out-of-equilibrium after impurity uptake, since reactivity is strongly quenched if a full thermal equilibration is assumed. More generally, our work points towards a novel mechanism for long-range electron transfer through an interplay between nuclear quantum delocalization within the confining medium and delocalized electronic dispersion forces acting on the two reactants.