Structural Investigation and Molecular Modeling Studies of Strobilurin-Based Fungicides Active against the Rice Blast Pathogen Pyricularia oryzae

The increasing emergence of fungicide-resistant pathogens requires urgent solutions for crop disease management. Here, we describe a structural investigation of new fungicides obtained by combining strobilurin and succinate dehydrogenase inhibitor pharmacophores. We identified compounds endowed with very good activity against wild-type Pyricularia oryzae, combined in some cases with promising activity against strobilurin-resistant strains. The first three-dimensional model of P. oryzae cytochrome bc1 complex containing azoxystrobin as a ligand was developed. The model was validated with a set of commercially available strobilurins, and it well explains both the resistance mechanism to strobilurins mediated by the mutation G143A and the activity of metyltetraprole against strobilurin-resistant strains. The obtained results shed light on the key recognition determinants of strobilurin-like derivatives in the cytochrome bc1 active site and will guide the further rational design of new fungicides able to overcome resistance caused by G143A mutation in the rice blast pathogen.     

Film Blowing of Biodegradable Polymer Nanocomposites for Agricultural Applications

Films for agricultural applications, such as greenhouses films or mulching films are generally made of polyolefins such as linear low-density polyethylene (LLDPE) or low-density polyethylene. However, the use of biodegradable and/or compostable polymers is increasing, which enjoy the additional advantage that they can be left on the site since a fine life would be gradually assimilated to the underlying soil. Nevertheless, biodegradable polymeric films often do not have suitable mechanical performances. In this work, biodegradable polymer-based nanocomposite films are prepared by film blowing and compared with traditional LLDPE based nanocomposites. In particular, a biodegradable polymer blend and two different inorganic nanofillers (an organo-modified clay and a calcium carbonate with a hydrophobic coating) are used for the preparation of the nanocomposites. A detailed investigation of obtained materials is performed through rheological, mechanical, and optical characterizations. Adding nanofillers led to an increase of rigidity and tear strength of blown films without negatively affecting their ductility.     

A new short-path distillation system applied to the reduction of cholesterol in butter and lard

A molecular distillation plant, built particularly to increase the separation efficiency and to obtain safer working conditions, was tested to remove cholesterol from anhydrous butter and lard. A preliminary experiment was carried out with butter to evaluate the fractionation obtained at temperatures between 190 and 250°C and residual pressures between 10⁻³ and 10⁻⁴ torr. A second experiment was carried out at 185°C and at the maximum operational vacuum, evaluating the fractionation achieved within a time scale between 30 and 180 min. Cholesterol was almost completely removed during the second hour with minimal loss of low-molecular weight triglycerides. An experiment was carried out with lard at 250°C and maximum achievable operational vacuum (10⁻⁴ Torr), lasting approximately 6 h, and cholesterol was removed almost completely during the second hour without significant modifications in the triglyceride composition. This situation remained constant throughout the duration of the test.     

Cable-direct-driven-robot (CDDR) with a 3-link passive serial support

Cable-direct-driven-robots (CDDRs) provided with a passive serial support represent an interesting and rising evolution of planar cable robots. The paper is devoted to present and analyze a novel CDDR robot. The robot consists in a fully actuated CDDR supported against loading normal to the motion plane with a 3-link passive planar serial manipulator. This hybrid structure combines positive features of both parallel and serial architectures, and prevents out-of-plane movements without the necessity for the robot to be supported on the motion plane. The adoption of a 3-link serial manipulator ensures a greater workspace area compared with similar structures that adopt a smaller number of links, and improves specific characteristics of their dynamics. Nevertheless undesired oscillations may occur since the serial manipulator is underconstrained. For this reason damping elements are inserted in the structure. Simulation examples are presented to demonstrate the novel CDDR concept and its dynamics. In addition, a strategy to select proper values of damping coefficients is presented.     

<Superscript>1</Superscript>H NMR characterization of milk lipids: A comparison between cow and buffalo milk

Characterization of the lipid fraction of raw cow and buffalo milk samples, collected in different breeding areas in Apulia, a region of southern Italy, were performed by means of ¹H NMR. The aim of this work was to establish whether FA composition data obtained by ¹H NMR can be used in the differentiation of buffalo and cow milk samples according to species. A complete assignment of the signals present in the spectrum was attempted by COSY, heteronuclear coherence spectra. Quantification of FA was carried out by inserting the integrals of particular peaks in suitable calculations. Multivariate statistical analysis, conducted on the results of the quantification, permitted buffalo and cow milks to be distinguished.     

Synthesis, fabrication and characterization of poly[3-3′(vinylcarbazole)] (PVK) Langmuir-Schaefer films

Poly[3-3′(vinylcarbazole)] (PVK) was synthetized with N-vinylcarbazole as monomer by oxidative polymerization with ferric chloride. The resulting polymer was then deposited on various solid supports by using Langmuir-Schaefer (LS) method. The pressure-area isotherm of PVK revealed the possibility of compact monolayer formation at air-water interface. Different layers of PVK were doped with iodine vapours. Both scanning probe microscopy and optical microscopy images indicated a good uniformity of the films. The morphology and the thickness of PVK films were investigated using atomic force microscopy. The voltammetric investigation of I₂ doped PVK showed a distinctive electrochemical behaviour. The photoinduced charge transfer across a donor/acceptor (D/A) hybrid interface provided an effective method to study the photoelectrochemical properties of the composite LS films.     

An Adaptive and Optimized Switching Observer for Sensorless Control of an Electromagnetic Valve Actuator in Camless Internal Combustion Engines

In this paper, the design and operation of a special electromagnetic actuator as a variable engine valve actuator are presented. Further, this paper describes a feasible approximated velocity switching estimator based on measurements of current and input voltage to achieve sensorless control. The proposed concept allows a reduced‐order observer to be conceived and yields a specific control strategy with an acceptable performance. In general, this approach represents a viable strategy to build reduced‐order observers for estimating the velocity of systems through the measurement of input current and voltage. The robustness of the velocity tracking is explored using a minimum variance approach. The effect of the noise is minimized, and the position can be achieved through an adaptive and optimized structure by combining this particular velocity estimator and an observer based on the electromechanical system. Position control is achieved through an inversion of the model. This approach avoids a more complex structure for the observer and yields an acceptable performance as well as eliminating bulky position‐sensor systems. In addition, a control strategy is presented and discussed. Computer simulations of the sensorless control structure are presented in which the positive effects of the observer with optimized parameter setting are visible in the closed‐loop control.     

Electrochemical characterization of 8-hydroxyquinoline-5-sulphonate/aluminium(III) aqueous solutions

8-Hydroxyquinoline-5-sulphonate/Al(III) aqueous solutions were studied both by potentiometric titrations and voltammetric measurements, in order to obtain the number, the stoichiometry and the stability constants of the complexes formed at equilibrium, and to evaluate the redox and (electro)kinetic properties of the free ligand and of the metal/ligand complexes. The complexes formed in 0.2 m (Na)Cl aqueous solution (stability log beta values ± standard deviation) are AlL⁺ (8.95 ± 0.05), AlL₂⁻ (17.43 ± 0.03) and AlL₃³⁻ (24.58 ± 0.05), where “L” denotes the free ligand in the completely deprotonated form (L²⁻, pK_a1 = 3.910 ± 0.008, pK_a2 = 8.319 ± 0.004). AlL₃³⁻ is the predominant Al(III) species in a very wide range of pH, metal and ligand concentrations and metal-to-ligand ratios. The free ligand shows an oxidation wave at 0.62 V versus SCE. The proposed oxidation mechanism includes a first reversible one-electron oxidation of the ligand, followed by a coupling reaction and by a second reversible one-electron oxidation, and finally by a decomposition reaction. The addition of Al(III) lowers the intensity of the oxidation wave due to the formation of the redox-inactive complex AlL₃³⁻. A residual low signal was attributed to the free ligand produced by the complex dissociation, AlL₃³⁻ = AlL₂⁻ + L²⁻. All the kinetic parameters involved in the ligand oxidation and in the complex disruption were calculated on the basis of the agreement between experimental and simulated linear sweep and cyclic voltammetries. Correctness of the mechanisms proposed was further confirmed “a posteriori” by the agreement between potentiometric and linear sweep voltammetric results. The low residual signal observed in the presence of fully formed complex was attributed to the free ligand produced by the complex dissociation, having a kinetic constant estimated 0.2 s⁻¹.     

Domain-specific discrete event modelling and simulation using graph transformation

Graph transformation is being increasingly used to express the semantics of domain-specific visual languages since its graphical nature makes rules intuitive. However, many application domains require an explicit handling of time to accurately represent the behaviour of a real system and to obtain useful simulation metrics to measure throughputs, utilization times and average delays. Inspired by the vast knowledge and experience accumulated by the discrete event simulation community, we propose a novel way of adding explicit time to graph transformation rules. In particular, we take the event scheduling discrete simulation world view and provide rules with the ability to schedule the occurrence of other rules in the future. Hence, our work combines standard, efficient techniques for discrete event simulation (based on the handling of a future event set) and the intuitive, visual nature of graph transformation. Moreover, we show how our formalism can be used to give semantics to other timed approaches and provide an implementation on top of the rewriting logic system Maude.     

Long-term cyclability of nanostructured LiFePO4

Amorphous LiFePO₄ was obtained by lithiation of FePO₄ synthesized by spontaneous precipitation from equimolar aqueous solutions of Fe(NH₄)₂(SO₄)₂·6H₂O and NH₄H₂PO₄, using hydrogen peroxide as oxidizing agent. Nano-crystalline LiFePO₄ was obtained by heating amorphous nano-sized LiFePO₄ for different periods of time. The materials were characterized by TG, DTA, X-ray powder diffraction, scanning electron microscopy (SEM) and BET. All materials showed very good electrochemical performance in terms of energy and power density. Upon cycling, a capacity fading affected the materials, thus reducing the electrochemical performance. Nevertheless, the fading decreased upon cycling and after the 200th cycle the cell was able to cycle for more than 500 cycles without further fading.