Synthesis, characterization of a new carbonylated zirconium metallocene using a dichloro-zirconocene derived from partially alkylated s-indacene

Indexación: ScieloThis work describes the synthesis and characterization of new organometallic species, an unprecedented mononuclear zirconium complex bearing a tetraalkylated s-indacene ligand, and secondly, its respective dicarbonyl complex obtained by reduction with Mg/HgCl2. Theoretical calculations of these two compounds were carried out to gain further understanding of these novel molecular systems.http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072009000300014&lng=es&nrm=is

Theoretical and experimental SERS study of thiocarbonyl compounds adsorbed on metal nanoparticles

Thiocarbonyl compounds have been reported to exhibit interesting biological and pharmacological properties but they are many often characterized by their toxicological effects. However the chemistry of thiobenzoic acid (TBA) and thiobenzamide (TB) has not been fully studied yet. Some of the biological studies of TBA are related to the tautomerism of thiocarboxylic acids and the important role that the -C(=O)-S and -C(=S)-O functional groups play in the catalytic activities of enzymes such as cysteine or serine proteases.1 From a chemical point of view, thiocarboxylates are an interesting type of molecules having two different donor atoms, a soft sulfur donor atom and a hard oxygen donor one. The presence of these unlike groups can lead to the bonding with metal surfaces. Likewise the interaction of thiobenzamide and their derivatives with metals is of great interest because both the sulfur and nitrogen atoms are also able to coordinate with the surface. Therefore the high affinity of these molecules for metal surfaces makes them suitable SERS target adsorbates. Taking advantage of the fact that SERS spectroscopy is both surface selective and highly sensitive we have attempted to determine the molecular structure of TBA and TB once they are adsorbed on the metal. The main objective of this work is focussed on discussing the observed vibrational wavenumber shifts of TBA and TB upon adsorption on silver nanoparticles. In this work the SERS substrates have been prepared by using different colloidal silver solutions according to the method described by Creighton et al.2 and Leopold and Lendl.3 The analysis of the vibrational wavenumbers shifts of the Raman and SERS spectra allow us to know the adsorption process (Figure 1). In the case of TBA, the wavenumber of the SERS band assigned to (C=O) vibrational mode shows an important blue shift up to 40 cm-1 with respect to the Raman whereas the (C-S) band undergoes a red shift up to 40 cm-1. These results suggest a unidentate coordination of TBA to the silver surface through the sulfur atom. On the other hand, the SERS band assigned in the case of TB to Amide III (mainly (CN)) exhibits a significant blueshift up to 41 cm-1, and the SERS band assigned to Amide I (mainly (CS)) shows a red shift up to 11 cm-1. These wavenumber shifts indicate that TB interacts to the silver surface through the sulfur atom. Interestingly, in previous SERS studies of pyridinecarboxamides and benzamide we have observed that some SERS bands assigned to 1;ring, Amide I (mainly (C=O)) and Amide III (mainly C-N)) show wavenumber shifts of +50, -50 and +10 cm-1, respectively, which were attributed to the deprotonation of carboxamide group.4,5 Finally, in order to verify experimental results DFT calculations have been carried out for different silver complexes of TBA and TB concluding that the unidentate coordination is the most likely interaction of both of them.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech

Characterization of a putative grapevine Zn transporter, VvZIP3, suggests its involvement in early reproductive development in Vitis vinifera L

Gonzalez, E (reprint author), Univ Talca, Inst Biol Vegetal & Biotecnol, Talca, Chile.Background: Zinc (Zn) deficiency is one of the most widespread mineral nutritional problems that affect normal development in plants. Because Zn cannot passively diffuse across cell membranes, it must be transported into intracellular compartments for all biological processes where Zn is required. Several members of the Zinc-regulated transporters, Iron-regulated transporter-like Protein (ZIP) gene family have been characterized in plants, and have shown to be involved in metal uptake and transport. This study describes the first putative Zn transporter in grapevine. Unravelling its function may explain an important symptom of Zn deficiency in grapevines, which is the production of clusters with fewer and usually smaller berries than normal. Results: We identified and characterized a putative Zn transporter from berries of Vitis vinifera L., named VvZIP3. Compared to other members of the ZIP family identified in the Vitis vinifera L. genome, VvZIP3 is mainly expressed in reproductive tissue - specifically in developing flowers - which correlates with the high Zn accumulation in these organs. Contrary to this, the low expression of VvZIP3 in parthenocarpic berries shows a relationship with the lower Zn accumulation in this tissue than in normal seeded berries where its expression is induced by Zn. The predicted protein sequence indicates strong similarity with several members of the ZIP family from Arabidopsis thaliana and other species. Moreover, VvZIP3 complemented the growth defect of a yeast Zn-uptake mutant, ZHY3, and is localized in the plasma membrane of plant cells, suggesting that VvZIP3 has the function of a Zn uptake transporter. Conclusions: Our results suggest that VvZIP3 encodes a putative plasma membrane Zn transporter protein member of the ZIP gene family that might play a role in Zn uptake and distribution during the early reproductive development in Vitis vinifera L., indicating that the availability of this micronutrient may be relevant for reproductive development

Production management model through MPS and line balancing to reduce the non-fulfillment of orders in lingerie clothing MSEs in Peru

The focus of this research is to establish control and planning management in the sewing production process of lingerie clothing to better prepare companies for demand growth. The lack of improvement tools in this sector, the lack of staff training and a lack of quality culture has led to companies, especially MYPES, not being able to meet the established delivery times and non-fulfillment of orders with the customers, which represents 80% of dissatisfied orders due to the limited production capacity and non-productive time in the plant. This problem is due to limited production capacity, deficient production planning, and lack of materials. In order to solve this problem, industrial engineering tools were used. The application of these tools improved production from 79% to 95%

Tuning the electronic and magnetic properties of 2D g-GaN by H adsorption: An ab-initio study

We have theoretically studied the structural, electronic and magnetic properties of the hydrogen adsorption on a honeycomb gallium-nitride two-dimensional monolayer (2D g-GaN). Results indicate that the band gap energy can be systematically tuned by the hydrogen coverage on the 2D g-GaN in the diluted limit. In addition, a total magnetic moment can be induced in the 2D g-GaN by hydrogen adsorption due to s-p interaction and band structure effects. Although hydrogen adsorption on top of nitrogen atoms shows the most stable energy in the 2D g-GaN, the most stable ferromagnetism -with a nonzero magnetic moment-is obtained when hydrogen is adsorbed on top of Ga atoms. These results indicate that H adatoms on the 2D g-GaN systems could be a potential candidate for future spintronic applications

Study of different mathematical approaches in determining the dynamic rating of overhead power lines and a comparison with real time monitoring data

Electricity generation is changing as new, renewable and smaller generation facilities are created, and classic topologies have to accommodate this distributed generation. These changes lead to the creation of smart grids in which advanced generation, information and communication technologies are needed. Information metering is important, and one of the most important grid parameters to be measured and controlled is the temperature of overhead conductors due to their relation to the maximum allowable sag of the line. The temperature and current of an overhead conductor and the weather conditions surrounding the cable are measured every 8 min for more than a year. With these data, the accuracies of the different algorithms presented in the standards (CIGRE TB601 and IEEE 738) are studied by implementing them in MATLAB®. The use of precise measurements of solar radiation and low wind speeds with ultrasonic anemometers, improves the accuracy of the estimated temperature compared with the real measured conductor temperature. Additionally, using dynamic algorithms instead of assuming a steady state analysis increases the accuracy. However, an equilibrium between the accuracy and mathematical complexity should be obtained depending on the specific needs.This work was supported by the Spanish Government under the R+D initiative INNPACTO with reference IPT-2011-1447-920000 and Spanish R+D initiative with reference ENE2013-42720-

Efeito de doses de fosforo e fontes de potassio na produtividade e qualidade comercial da batata (Solanum tuberosum, L., cv. Achat).

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Frequency of rare mutations and common genetic variations in severe hypertriglyceridemia in the general population of Spain

Background: Hypertriglyceridemia (HTG) is a common complex metabolic trait that results of the accumulation of relatively common genetic variants in combination with other modifier genes and environmental factors resulting in increased plasma triglyceride (TG) levels. The majority of severe primary hypertriglyceridemias is diagnosed in adulthood and their molecular bases have not been fully defined yet. The prevalence of HTG is highly variable among populations, possibly caused by differences in environmental factors and genetic background. However, the prevalence of very high TG and the frequency of rare mutations causing HTG in a whole non-selected population have not been previously studied. Methods: The total of 23, 310 subjects over 18 years from a primary care-district in a middle-class area of Zaragoza (Spain) with TG >500 mg/dL were selected to establish HTG prevalence. Those affected of primary HTG were considered for further genetic analisys. The promoters, coding regions and exon-intron boundaries of LPL, LMF1, APOC2, APOA5, APOE and GPIHBP1 genes were sequenced. The frequency of rare variants identified was studied in 90 controls. Results: One hundred ninety-four subjects (1.04 %) had HTG and 90 subjects (46.4 %) met the inclusion criteria for primary HTG. In this subgroup, nine patients (12.3 %) were carriers of 7 rare variants in LPL, LMF1, APOA5, GPIHBP1 or APOE genes. Three of these mutations are described for the first time in this work. The presence of a rare pathogenic mutation did not confer a differential phenotype or a higher family history of HTG. Conclusion: The prevalence of rare mutations in candidate genes in subjects with primary HTG is low. The low frequency of rare mutations, the absence of a more severe phenotype or the dominant transmission of the HTG would not suggest the use of genetic analysis in the clinical practice in this population