Bimetallic M-Cu (M = Ag, Au, Ni) Nanoparticles Supported on γAl2O3-CeO2 Synthesized by a Redox Method Applied in Wet Oxidation of Phenol in Aqueous Solution and Petroleum Refinery Wastewater.

Three bimetallic catalysts of the type M-Cu with M = Ag, Au and Ni supports were successfully prepared by a two-step synthesized method using Cu/Al2O3-CeO2 as the base monometallic catalyst. The nanocatalysts were characterized using X-ray diffraction (XRD), temperature-programmed reduction of H2 (H2-TPR), N2 adsorption-desorption, scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy with diffuse reflectance (DR-UV-Vis) techniques. This synthesized methodology allowed a close interaction between two metals on the support surface; therefore, it could have synthesized an efficient transition-noble mixture bimetallic nanostructure. Alloy formation through bimetallic nanoparticles (BNPs) of AgCuAlCe and AuCuAlCe was demonstrated by DR-UV-Vis, EDS, TEM and H2-TPR. Furthermore, in the case of AgCuAlCe and AuCuAlCe, improvements were observed in their reducibility, in contrast to NiCuAlCe. The addition of a noble metal over the monometallic copper-based catalyst drastically improved the phenol mineralization. The higher activity and selectivity to CO2 of the bimetallic gold-copper- and silver-copper-supported catalysts can be attributed to the alloy compound formation and the synergetic effect of the M-Cu interaction. Petroleum Refinery Wastewater (PRW) had a complex composition that affected the applied single CWAO treatment, rendering it inefficient.

Effects of Ground Cover Management on Insect Predators and Pests in a Mediterranean Vineyard.

Conservative techniques, such as ground cover management, could help promote viticulture sustainability, which is a goal of conservation biological control, by providing shelter and food sources for predatory insects. A field experiment was conducted in a Mediterranean vineyard to evaluate ground cover management impacts on predatory insect and potential grapevine pest abundance and diversity, both on the ground and in the grapevine canopy. Three different ground cover management techniques (tillage, spontaneous cover and flower-driven cover) were tested for two years (2016 and 2017). Overall, the ground cover management significantly affected the abundance of important epigeal predators, of which carabids, forficulids and staphylinids were the most captured. The carabid abundances under both the cover crop treatments were found to be approximately three times higher compared with that under the tillage treatment. In contrast, the canopy insect abundance in the vineyard was similar among the treatments for both the predators and the potential grapevine pest species. These results indicate that cover crop vegetation can be used in vineyards to enhance predatory insect abundance and may improve agroecosystem resilience.

Estado nutricional y coordinación motriz global en escolares de primaria de la Región de Murcia, España / Nutritional state and global motor coordination in primary school children in the Region of Murcia, Spain

Los objetivos del estudio fueron: 1) analizar las diferencias en la coordinación motriz según el estado nutricional (EN) y 2) examinar las diferencias en las variables antropométricas utilizadas para establecer el EN según la coordinación motriz. Diseño de estudio descriptivo-transversal. Participaron 157 escolares de 6-9 años de edad (Región de Murcia, España). Se empleó el índice de masa corporal (IMC) para establecer el EN (normopeso vs. sobrepeso-obesidad). La coordinación motriz se midió con el test GRAMI-2 calculando un índice de coordinación motriz (ICM). Se categorizó a los participantes según el ICM (< P50 vs. ≥ P50). Las diferencias entre grupos se analizaron con las pruebas U Mann-Whitney y Chi-cuadrado. Los niños con valores ICM ≥ P50 presentaron un menor IMC (p = .017). En las niñas no se detectaron diferencias significativas en el IMC según el ICM. Los niños con valores ICM ≥ P50 mostraron mayor prevalencia de normopeso (p = .003). Las niñas con valores ICM < P50 tuvieron mayor prevalencia de normopeso (p = .024). Los niños normopeso tuvieron mejor rendimiento en el test GRAMI-2 (p entre .05 y < .001), a excepción del lanzamiento de balón. Las niñas con sobrepeso-obesidad tuvieron mejor rendimiento en lanzamiento de balón (p = .006). Se encontró menor IMC en los niños con mejor coordinación motriz. No se observaron estas diferencias en las niñas. Los niños normopeso tienen mejor coordinación motriz. En las niñas no se observaron diferencias en la coordinación motriz según el EN, a excepción del lanzamiento de peso(AU)

The objectives of the study were: 1) to analyze the differences in motor coordination according to nutritional status and 2) to examine the differences in anthropometric variables used to establish nutritional status according to motor coordination. Descriptive-cross-sectional study design. 157 schoolchildren aged 6-9 years (Region of Murcia, Spain) participated. The body mass index (BMI) was used to establish the nutritional status (normal weight vs. overweight-obesity). Motor coordination was measured with the GRAMI-2 test, calculating a motor coordination index (ICM). Participants were categorized according to the ICM (

Mathematical Models for Predicting Development of Orius majusculus (Heteroptera: Anthocoridae) and Its Applicability to Biological Control.

Complete development of Orius majusculus Reuter (Heteroptera: Anthocoridae) at nine constant temperatures, between 12 and 34°C, was evaluated under laboratory conditions. The maximum developmental period of 90.75 d occurred at 12°C, whereas the minimum of 11.34 d occurred at 30°C. From 30 to 34°C, the developmental period increased to 13.50 d. Between 21 and 33°C the survival rate was more than 80%. The optimal temperature when considering developmental rate and survival was between 24 and 30°C. At constant temperatures, four models were developed, one of which was linear and three nonlinear (Logan type III, Lactin, and Brière). All models were validated under field conditions and diel temperature variations. The values of the adjusted determination coefficients of the linear (>0.77) and nonlinear models (>0.93) were high. The thermal requirement for complete development, from egg to adult, was 284.5 degree-days (DD). In all nonlinear models, elevated levels of accuracy (≥90.31%) in field validation were also obtained, especially in the Brière model. With the results obtained herein, the optimization of O. majusculus mass rearing, its ideal use, and field management in biological control strategies can be improved.

Optimizing Nesidiocoris tenuis (Hemiptera: Miridae) as a biological control agent: mathematical models for predicting its development as a function of temperature.

For optimal application of Nesidiocoris tenuis as a biological control agent, adequate field management and programmed mass rearing are essential. Mathematical models are useful tools for predicting the temperature-dependent developmental rate of the predator. In this study, the linear model and nonlinear models Logan type III, Lactin and Brière were estimated at constant temperatures and validated at alternating temperatures and under field conditions. N. tenuis achieved complete development from egg to adult at constant temperatures between 15 and 35°C with high survivorship (>80%) in the range 18-32°C. The total developmental time decreased from a maximum at 15°C (76.74 d) to a minimum at 33°C (12.67 d) and after that, increased to 35°C (13.98 d). Linear and nonlinear developmental models all had high accuracy (R a 2 >0.86). The maximum developmental rate was obtained between 31.9°C (Logan type III and Brière model for N1) and 35.6°C (for the egg stage in the Brière model). Optimal survival and the highest developmental rate fell within the range 27-30°C. The field validation revealed that the Logan type III and Lactin models offered the best predictions (95.0 and 94.5%, respectively). The data obtained on developmental time and mortality at different temperatures are useful for mass rearing this predator, and the developmental models are valuable for using N. tenuis as a biological control agent.

Interaction between anions and cationic metal complexes containing tridentate ligands with exo-C-H groups: complex stability and hydrogen bonding.

[Re(CO)3 ([9]aneS3 )][BAr'4 ] (1), prepared by reaction of ReBr(CO)5 , 1,4,7-trithiacyclononane ([9]aneS3 ) and NaBAr'4 , forms stable, soluble supramolecular adducts with chloride (2), bromide, methanosulfonate (3) and fluoride (4) anions. These new species were characterized by IR, NMR spectroscopy and, for 2 and 3, also by X-ray diffraction. The results of the solid state structure determinations indicate the formation of CH⋅⋅⋅X hydrogen bonds between the anion (X) and the exo-CH groups of the [9]aneS3 ligand, in accord with the relatively large shifts found by (1) H NMR spectroscopy in dichloromethane solution for those hydrogens. The stability of the chloride adduct contrasts with the lability of the [9]aneS3 ligand in allyldicarbonyl molybdenum complexes recently studied by us. With fluoride, in dichloromethane solution, a second, minor neutral dimeric species 5 is formed in addition to 4. In 4, the deprotonation of a CH group of the [9]aneS3 ligand, accompanied by CS bond cleavage and dimerization, afforded 5, featuring bridging thiolates. Compounds [Mo(η(3) -methallyl)(CO)2 (TpyN)][BAr'4 ] (6) and [Mo(η(3) -methallyl)(CO)2 (TpyCH)][BAr'4 ] (7) were synthesized by the reactions of [MoCl(η(3) -methallyl)(CO)2 (NCMe)2 ], NaBAr'4 and tris(2-pyridyl)amine (TpyN) or tris(2-pyridyl)methane (TpyCH) respectively, and characterized by IR and (1) H and (13) C NMR spectroscopy in solution, and by X-ray diffraction in the solid state. Compound 6 undergoes facile substitution of one of the 2-pyridyl groups by chloride, bromide, and methanosulfonate anions. Stable supramolecular adducts were formed between 7 and chloride, bromide, iodide, nitrate, and perrhenate anions. The solid state structures of these adducts (12-16) were determined by X-ray diffraction. Binding constants in dichloromethane were calculated from (1) H NMR titration data for all the new supramolecular adducts. The signal of the bridgehead CH group is the one that undergoes a more pronounced downfield shift when tetrabutylammonium chloride was added to 7, whereas smaller shifts were found for the 2-pyridyl C(3)H groups. In agreement, both types of CH groups form hydrogen bonds to the anions in the solid state structures.

1,3,5-Tris(thiocyanatomethyl)mesitylene as a ligand. Pseudooctahedral molybdenum, manganese, and rhenium carbonyl complexes and copper and silver dimers. copper-catalyzed carbene- and nitrene-transfer reactions.

New molybdenum(0), molybdenum(II), manganese(I), rhenium(I), silver(I), and copper(I) complexes with the 1,3,5-tris(thiocyanatomethyl)mesitylene [Ms(CH(2)SCN)(3)] ligand have been synthesized and characterized by IR, NMR, and by X-ray diffraction (except for the rhenium complex). The Ms(CH(2)SCN)(3) ligand coordinated with the molybdenum, manganese, and rhenium carbonyl fragments as a tripodal chelate. With copper and silver, dimeric dicationic species were obtained instead, with the Ms(CH(2)SCN)(3) ligand acting simultaneously as a bidentate chelate and bridge. The [{Cu(Ms(CH(2)SCN)(3))}(2)][BAr'(4)](2) (BAr'(4) = tetra(3,5-bis(trifluoromethyl)phenyl)borate) product is an excellent catalyst for cyclopropanation and aziridination of alkenes and cyclopropenation of alkynes by means of carbene- and nitrene-transfer reactions.

Synthesis of new copper(I) complexes with tris(2-pyridyl) ligands. Applications to carbene and nitrene transfer reactions.

New copper(I) complexes with tris(2-pyridyl)methane (TPC), tris(2-pyridyl)methoxymethane (TPM) and tris(2-pyridyl)amine (TPN) ligands have been synthesized and characterized, including structural determinations by X-ray diffraction of some examples. Their activity as catalysts in carbene and nitrene transfer reactions was studied.