Síntesis y caracterización de óxidos mixtos precursores de bronces tetragonales de W de potencial actividad en la oxidación de difenilsulfuro

Fases de heteropolioxometalatos (HPOM), a base de heteropolitungstatos complejos derivados de tipo Keggin de la serie [M4(H2O)2(PW9O34)2]10- (PWM) con M(II) = Cu y su precursor Na8H(PW9O34) (PW9), se han modificado químicamente mediante reacción hidrotermal, con iones Nb y V en el gel de síntesis, dando lugar a la formación de materiales del tipo (KNaCu)xP0.11WV0,2NbOx y (Na)xPWV0,2NbOx. Tanto los materiales de síntesis como los tratados a 500ºC (en atmosfera de N2) son pseudocristalinos (que tras tratamiento a 800º C, conduce a una estructura típica de bronce tetragonal). Los materiales tratados térmicamente a 500ºC se han caracterizado y estudiado como catalizadores en la oxidación parcial de difenilsulfuro. Los resultados catalíticos se han comparado con los obtenidos con los HPOM de partida, observándose que los bronces metálicos presentan una mayor actividad catalítica (con una drástica disminución del tiempo de reacción) y un marcado aumento de la selectividad a difenil-sulfona.Phases based on complex heteropolytungstates (HPOM), derived from series Keggin type [M4 (H2O)2 (PW9O34)2] 10-(PWM) with M(II) = Cu and its precursor Na8H (PW9O34) (PW9), have been chemically modified by hydrothermal reaction, with Nb and V ions in the synthesis gel, giving place materials as (KNaCu)xP0.11WV0,2NbOx and (Na)xPWV0,2NbOx. The as-synthesized and the heat-treated at 500ºC (in N2) are pseudocrystalline (although they are transformed to tetragonal bronze after heattreatment at 800ºC). The samples heat-treated at 500ºC have been characterized and tested in the partial oxidation of diphenylsulfide. The catalytic results have been compared to those achieved over pure HPOM. It has been observed that these metal oxides bronzes show a higher both catalytic activity (with a drastic reduction of the reaction time) and selectivity to diphenyl-sulfone

NiO diluted in high surface area TiO2 as efficient catalysts for the oxidative dehydrogenation of ethane

[EN] Catalysts consisting of NiO diluted in high surface area TiO2 can be as efficient in the oxidative dehydrogenation of ethane as the most selective NiO-promoted catalysts reported previously in the literature. By selecting the titania matrix and the NiO loading, yields to ethylene over 40% have been obtained. In the present article, three different titanium oxides (TiO2) have been employed as supports or diluters of nickel oxide and have been tested in the oxidative dehydrogenation of ethane to ethylene. All TiO2 used present anatase as the main crystalline phase and different surface areas of 11,55 and 85 m(2) g(-1). It has been observed that by selecting an appropriate nickel loading and the titanium oxide extremely high selectivity towards ethylene can be obtained. Thus, nickel oxide supported on TiO2 with high surface areas (i.e. 55 and 85 m(2) g(-1)) have resulted to give the best catalytic performance although the optimal nickel loading is different for each case. The optimal catalyst has been obtained for NiO-loadings up to 5-10 theoretical monolayers regardless of the TiO2 employed. Free TiO2 is inactive whereas unsupported NiO is active and unselective (forming mainly carbon dioxide) and, therefore, unmodified NiO particles have to be avoided in order to obtain the optimal catalytic performance. The use of low surface area titania (11 m(2) g(-1)) have led to the lowest selectivity to olefin due to the presence of an excess of free NiO particles. (C) 2017 Elsevier B.V. All rights reserved.The authors would like to acknowledge the DGICYT in Spain CTQ2012-37925-C03-2, CTQ2015-68951-C3-1-R, CTQ2015-68951-C3-3-R and SEV-2012-0267 Projects for financial support. D.D. also thanks Severo Ochoa Excellence fellowship (SVP-2014-068669). We also thank the University of Valencia (UV-INV-AE-16-484416 project) and SCSIE-UV for assistanceSanchis, R.; Delgado-Muñoz, D.; Agouram, S.; Soriano Rodríguez, MD.; Vázquez, MI.; Rodriguez-Castellon, E.; Solsona, B.... (2017). NiO diluted in high surface area TiO2 as efficient catalysts for the oxidative dehydrogenation of ethane. Applied Catalysis A General. 536:18-26. https://doi.org/10.1016/j.apcata.2017.02.012S182653

Are Traditional Lima Bean (Phaseolus lunatus L.) Landraces Valuable to Cope with Climate Change? Effects of Drought on Growth and Biochemical Stress Markers

[EN] Agrobiodiversity and adaptability to environmental changes derived from global warming are challenges for the future of agriculture. In this sense, landraces often have high levels of genetic variation, tightly connected with the changing environmental conditions of a territory. The genus Phaseolus, with five domesticated species, is one of the most important sources of proteins, carbohydrates and micronutrients in various countries. This study aimed to compare the adaptation capacity to drought, in the vegetative growth phase, of a commercial cultivar and two landraces traditionally cultivated in the Mediterranean basin of Phaseolus lunatus (Lima bean). Growth and biochemical responses of the analysed genotypes to different water¿deficit treatments were evaluated and compared. In addition, the effectiveness of the voltammetric method for evaluating stress levels in cultivated plants was tested. The studied parameters revealed that P. lunatus is a drought tolerant species, showing similar results for the three cultivars. However, contrary to what was expected from the germination phase results, the commercial variety Peru showed some better responses under water stress conditions. Finally, the voltammetric method proved to be a good and fast tool for assessing oxidative stress in cultivated plants, showing results in agreement with total phenolic compounds and total flavonoid fluctuations.Martínez-Nieto, MI.; González-Orenga, S.; Soriano, P.; Prieto-Mossi, J.; Larrea, E.; Doménech-Carbó, A.; Tofei, AM.... (2022). Are Traditional Lima Bean (Phaseolus lunatus L.) Landraces Valuable to Cope with Climate Change? Effects of Drought on Growth and Biochemical Stress Markers. Agronomy. 12(7):1-20. https://doi.org/10.3390/agronomy1207171512012

Total oxidation of VOCs on mesoporous iron oxide catalysts: soft chemistry route versus hard template method

[EN] A comparative study on the total oxidation of volatile organic compounds, VOCs, on mesoporous iron oxide catalysts prepared by soft chemistry route versus those achieved by hard template methodThe authors would like to acknowledge the DGICYT in Spain (CTQ2012-37925-C03-1, CTQ2012-37925-C03-2, CTQ2012-37925-C03-3 and CTQ2012-37984-C02-01) and FEDER for financial support. We also thank the University of Valencia and SCSIE-UV for assistance.Solsona Espriu, BE.; Garcia, T.; Sanchis Martinez, R.; Soriano Rodríguez, MD.; Moreno, M.; Rodríguez-Castellon, E.; Agouram, S.... (2016). Total oxidation of VOCs on mesoporous iron oxide catalysts: soft chemistry route versus hard template method. The Chemical Engineering Journal and the Biochemical Engineering Journal. 290:273-281. https://doi.org/10.1016/j.cej.2015.12.109S27328129

Actigraphic Sleep and Dietary Macronutrient Intake in Children Aged 6-9 Years Old: A Pilot Study

The objective of this study was to examine the relationship between different sleep parameters and energy and macronutrient intake in school-aged children. A total of 203 children 6 to 9 years of age participated in this cross-sectional study. Anthropometric measurements were taken first. Diet was assessed with 3-day food logs and sleep was measured with a questionnaire on sleep quality and a wrist actigraph worn for at least 7 days. A decrease of 165.45 kcal was observed per each additional hour of sleep during the week (β (95% CI) = −165.45 (−274.01, −56.88); p = 0.003). This relationship was also observed for fat (β (95% CI) = −11.14 (−18.44, −3.84); p = 0.003) and protein (β (95% CI) = −13.27 (−22.52, −4.02); p = 0.005). An increase in weekend sleep efficiencies for those under the recommended threshold of 85% also had a similar association with energy (β (95% CI) = −847.43 (−1566.77, 128.09); p = 0.021) and carbohydrate (β (95% CI) = −83.96 (−161.76, −6.15); p = 0.035)) intake. An increase in habitual sleep variability was related with a slight increase in protein intake (β (95% CI) = 0.32 (0.031, 0.62); p = 0.031). Children who slept less had a higher energy intake, especially from fat and protein and those who presented inefficient sleep had a higher carbohydrate intake. Strategies to enhance sleep quality and quantity combined with dietary recommendations could help to improve energy and macronutrient intake levels in children

Phenotypic, molecular characterization, antimicrobial susceptibility and draft genome sequence of Corynebacterium argentoratense strains isolated from clinical samples

During a 12-year period we isolated five Corynebacterium argentoratense strains identified by phenotypic methods, including the use of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF) and 16S rRNA gene sequencing. In addition, antimicrobial susceptibility was determined, and genome sequencing for the detection of antibiotic resistance genes was performed. The organisms were isolated from blood and throat cultures and could be identified by all methods used. All strains were resistant to cotrimoxazole, and resistance to β-lactams was partly present. Two strains were resistant to erythromycin and clindamycin. The draft genome sequences of theses isolates revealed the presence of the erm(X) resistance gene that is embedded in the genetic structure of the transposable element Tn5423. Although rarely reported as a human pathogen, C. argentoratense can be involved in bacteraemia and probably in other infections. Our results also show that horizontal transfer of genes responsible for antibiotic resistance is occurring in this species.Supported in part by the Gerencia Regional de Salud, Junta de Castilla y León, Spain (research project GRS 698/A/2011

On the Origin of the Spontaneous Formation of Nanocavities in Hexagonal Bronzes (W,V)O3

[EN] Hexagonal (W,V)O3−x oxides of high thermal stability have been synthesized hydrothermally through the intermediate products Nax(W,V)O3·zH2O and (NH4)0.33−x(W,V)O3−y. The obtained crystals show nanostructured surface via the formation of a dense population of polyhedral nanocavities self-distributed along particular crystallographic directions. Nanocavities present a regular size that ranges from 5 to 10 nm in both length and width. The synthesis process involves a significant topotactic relationship between the as-synthesized product and the desired final product and this relationship is suggested as the origin of the observed surface nanostructure. The comparison of our results with observations in different solids has allowed us to suggest that the formation of nanocavities is an extensive spontaneous process when materials are obtained by the chemical reactions of solids leading to products with defined crystallographic orientation with respect to the original compound. The characterization provides evidence regarding the potential relevance of nanocavities in the functional properties of the resulting solids.Authors acknowledge the financial support from DGICYT in Spain through projects MAT2010-19837-C06-05 and CTQ2012-37925-C03-1. Authors are also grateful to the Centro de Microscopia Electronica (UCM) for facilities.García-González, E.; Soriano Rodríguez, MD.; Urones-Garrote, E.; López Nieto, JM. (2014). On the Origin of the Spontaneous Formation of Nanocavities in Hexagonal Bronzes (W,V)O3. Dalton Transactions. 43:14644-14652. https://doi.org/10.1039/C4DT01465KS14644146524

Tungsten-niobium oxide bronzes: a bulk and surface structural study

[EN] Materials from the WO3-Nb2O5 system, presenting bronze-type crystal structures, display outstanding functional properties for several applications as thermoelectric materials, lithium-ion battery electrodes, or catalysts. In this work, a series of W-Nb-O oxide bronzes have been synthesized by the hydrothermal method (with Nb/(W + Nb) ratios in the range of 0-1). A combination of bulk and surface characterisation techniques has been applied to get further insights into: (i) the effect of thermal treatments on as-prepared materials and (ii) the surface chemical nature of W-Nb-O oxide bronzes. Thermal treatments promote the following structural changes: (i) loss of emerging long-range order and (ii) the elimination of NH4+ and H2O species from the structural channels of the as-synthesized materials. It has been observed that W-Nb-O bronzes with Nb at% of ca. 50% are able to retain a long-range order after heat-treatments, which is attributed to the presence of a Cs-0.5[W2.5Nb2.5O14]-type structure. Increasing amounts of Nb 5T in the materials (i) promote a phase transition to pseudocrystalline phases ordered along the c-axis; (ii) stabilize surface W s. species (elucidated by XPS); and (iii) increase the proportion of surface Lewis acid sites (as determined by the FTIR of adsorbed CO). Results suggest that pseudocrystalline oxides (with a Nb at% >= 50%) are closely related to NbO2 pentagonal bipyramid-containing structures. The stabilisation of Lewis acid sites on these pseudocrystalline materials leads to a higher yield of heavy compounds, at the expense of acrolein formation, in the gas-phase dehydration of glycerol.The authors would like to acknowledge the Ministerio de Ciencia, Innovacion y Universidades in Spain for the financial support (RTI2018-099668-B-C21 and SEV-2016-0683 projects), and the Electron Microscopy Service at Universitat Politecnica de Valencia for providing facilities and technical support. D. D. also thanks Severo Ochoa Excellence Program for his fellowship (SVP-2014-068669).Delgado-Muñoz, D.; Concepción Heydorn, P.; Trunschke, A.; López Nieto, JM. (2020). Tungsten-niobium oxide bronzes: a bulk and surface structural study. Dalton Transactions. 49(38):13282-13293. https://doi.org/10.1039/d0dt02058cS13282132934938D. J. M. Bevan and P.Hagenmuller , Non-Stoichiometric Compounds , Pergamon , 1973Quan, H., Gao, Y., & Wang, W. (2020). 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Optimizing both catalyst preparation and catalytic behaviour for the oxidative dehydrogenation of ethane of Ni-Sn-O catalysts

[EN] Bulk Ni-Sn-O catalysts have been synthesized, tested in the oxidative dehydrogenation of ethane and characterized by several physicochemical techniques. The catalysts have been prepared by evaporation of the corresponding salts using several additives in the synthesis gel, i.e. ammonium hydroxide, nitric acid, glyoxylic acid or oxalic acid, in the synthesis gel. The catalysts were finally calcined at 500 degrees C in air. Important changes in the catalytic behaviour have been observed depending on the additive. In fact, an important improvement in the catalytic performance is observed especially when some additives, such as glyoxylic or oxalic acid, are used. Thus the productivity to ethylene multiplies by 6 compared to the reference Ni-Sn-O catalyst if appropriate templates are used, and this is the result of an improvement in both the catalytic activity and the selectivity to ethylene. This improved performance has been explained in terms of the decrease of the crystallite size (and the increase in the surface area of catalyst) as well as the modification of the lattice parameter of nickel oxide.The authors would like to acknowledge the DGICYT in Spain (CTQ2015-68951-C3-1-R and CTQ2012-37925-C03-2) for financial support. We also thank the University of Valencia and SCSIE-UV for assistanceSolsona Espriu, BE.; López Nieto, JM.; Agouram, S.; Soriano Rodríguez, MD.; Dejoz, A.; Vázquez, MI.; Concepción Heydorn, P. (2016). Optimizing both catalyst preparation and catalytic behaviour for the oxidative dehydrogenation of ethane of Ni-Sn-O catalysts. Topics in Catalysis. 59(17-18):1564-1572. https://doi.org/10.1007/s11244-016-0674-zS156415725917-18Heracleous E, Lee AF, Wilson K, Lemonidou AA (2005) J Catal 231:159–171Heracleous E, Lemonidou AA (2006) J Catal 237:162–174Savova B, Loridant S, Filkova D, Millet JMM (2010) Appl Catal A 390:148–157Heracleous E, Lemonidou AA (2010) J Catal 270:67–75Solsona B, Nieto JML, Concepcion P, Dejoz A, Ivars F, Vazquez MI (2011) J Catal 280:28–39Skoufa Z, Heracleous E, Lemonidou AA (2012) Catal Today 192:169–176Zhu H, Ould-Chikh S, Anjum DH, Sun M, Biausque G, Basset JM, Caps V (2012) J Catal 285:292–303Skoufa Z, Heracleous E, Lemonidou AA (2012) Chem Eng Sci 84:48–56Zhu H, Rosenfeld DC, Anjum DH, Caps V, Basset JM (2015) ChemSusChem 8:1254–1263Heracleous E, Lemonidou AA (2015) J Catal 322:118–129Solsona B, Concepcion P, Demicol B, Hernandez S, Delgado JJ, Calvino JJ, Nieto JML (2012) J Catal 295:104–114Nieto JML, Solsona B, Grasselli RK, Concepción P (2014) Top Catal 57:1248–1255Popescu I, Skoufa Z, Heracleous E, Lemonidou AA, Marcu IC (2015) PCCP 17:8138–8147Zhang X, Gong Y, Yu G, Xie Y (2002) J Mol Catal A 180:293–298Popescu I, Skoufa Z, Heracleous E, Lemonidou A, Marcu I-C (2015) Phys Chem Chem Phys 17:8138–8147Nakamura KI, Miyake T, Konishi T, Suzuki T (2006) J Mol Catal A 260:144–151Solsona B, Dejoz AM, Vazquez MI, Ivars F, Nieto JML (2009) Top Catal 52:751–757Bortolozzi JP, Gutierrez LB, Ulla MA (2013) Appl Catal A 452:179–188Takeguchi T, Furukawa S, Inoue M (2001) J Catal 202:14–24Richardson JT, Turk B, Twigg MV (1996) Appl Catal 148:97–112Biju V, Khadar MA (2002) J Nanopart Res 4:247–253Van Veenendaal MA, Sawatzky GA (1993) Phys Rev Lett 70:2459–2462Vedrine JC, Hollinger G, Duc TM (1978) J Phys Chem 82:1515–1520Salagre P, Fierro JLG, Medina F, Sueiras JE (1996) J Mol Catal A 106:125–13

Sex Identification of in vitro Plants of Carica papaya L. MSXJ Hybrid through Molecular Markers

Objective: To identify the sex in vitro plants of the MSXJ hybrid papaya (Carica papaya L.) obtained via somatic organogenesis, using molecular markers SCAR type. Design/methodology/approach: Plants of the MSXJ hybrid papaya with eight months of age and during the fruiting stage were collected at the municipality of Cotaxtla, Veracruz. They were superficially disinfected, with plenty of running water, detergent for 30 minutes, 70% alcohol was added for one minute, 30% commercial chlorine for another 30 minutes and rinsed with sterile distilled water. Subsequently the meristems were grown under a MS medium, and after 30 days a subculture was performed. The extraction of DNA was performed using the Doyle and Doyle method. The PCR was done by the Deputy et al. method, and initiators T1, T12 and W11 were used. Results: Initiator T1 was positive control. Initiators T12 and W11 allowed the amplification of fragments identifying hermaphrodite, female and male plants, while the T12 and W11 initiators were specific to hermaphrodite plants. Study limitations/implications: Papaya producers know the genus of plants three months after planting. Sexuality in papaya plants cannot be differentiated until the flowering step. Findings/conclusions: the implementation of molecular markers could facilitate large-scale plant selection, reducing costs, maintenance time and the elimination of plants with unwanted sex.Objective: To identify the sex of in vitro plants of papaya (Carica papaya L.) MSXJhybrid obtained via somatic organogenesis, through SCAR type molecular markers. Design/Methodology/Approach: Eight-month old MSXJ papaya hybrid plants in thefructification stage were collected in Cotaxtla, Veracruz, Mexico. They weresuperficially disinfected with abundant running water, detergent during 30 min, andthen alcohol at 70% was added for one minute, commercial chlorine at 30% for 30min, and they were rinsed with sterile distilled water; then the meristems werecultivated in MS medium and after 30 d a subculture was made. The DNA extractionwas made with the CTAB method, and the DNA PCR was done with the Deputy et al.(2002) method, and the primers T1, T12 and W11 were used.Results: The T1 primer was the positive control and the T12 and W11 primersallowed the amplification of fragments that identify hermaphrodite, feminine and maleplants, while the T12 and W11 primers were specific for hermaphrodite plants.Study Limitations/Implications: It is required to standardize the method for it to beinexpensive.Findings/Conclusions: The sexuality of papaya plants can be differentiated until thestage of flowering, which is why the implementation of molecular markers wouldfacilitate plant selection if it is implemented at a large scale. Costs, maintenance timeand elimination of plants of unwanted sex are reduced this way