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

Modulation of Cytokine and Cytokine Receptor/Antagonist by Treatment with Doxycycline and Tetracycline in Patients with Dengue Fever

Dengue virus infection can lead to dengue fever (DF) or dengue hemorrhagic fever (DHF). Disease severity has been linked to an increase in various cytokine levels. In this study, we evaluated the effectiveness of doxycycline and tetracycline to modulate serum levels of IL-6, IL-1B, and TNF and cytokine receptor/receptor antagonist TNF-R1 and IL-1RA in patients with DF or DHF. Hospitalized patients were randomized to receive standard supportive care or supportive care combined with doxycycline or tetracycline therapy. Serum cytokine and cytokine receptor/antagonist levels were determined at the onset of therapy and after 3 and 7 days. Cytokine and cytokine receptor/antagonist levels were substantially elevated at day 0. IL-6, IL-1β, and TNF remained at or above day 0 levels throughout the study period in untreated patients. Treatment with tetracycline or doxycycline resulted in a significant decline in cytokine levels. Similarly, IL-1RA and TNF-R1 serum concentrations were elevated at baseline and showed a moderate increase among untreated patients. Both drugs resulted in a significant rise in IL-1Ra levels by day 3 in patients. In contrast, treatment did not affect a similar result for TNF-R1. When compared to the control group, however, a significant rise post-treatment was seen upon intragroup analysis. Further analysis demonstrated that doxycycline was significantly more effective at modulating cytokine and cytokine receptor/antagonist levels than tetracycline

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%

Population fluctuation of Diaphorina citri Kuwayama (Hemiptera: Liviidae) and survey of some natural enemies in Ecuador

Diaphorina citri detected in Ecuador for the first time in 2013, is an insect pest of global relevance. It is the main vector of the phloem-limited bacterium Candidatus Liberibacter asiaticus, the causal agent of Huanglongbing (HLB), a devastating disease of citrus trees. During the period from April 2016 - July 2017, population fluctuation studies and a search for natural enemies of D. citri were conducted on young shoots of orange jessamine, Murraya paniculata, and Citrus spp. The natural enemies of D. citri were collected in the Provinces of Guayas and Santa Elena, Ecuador. A total of 1660 specimens of predators belonging to five species were collected, consisting of three coccinellids, Cheilomenes sexmaculata, the most abundant species (39.9%, P <0.05), followed by Cycloneda sanguinea (15.8%), and Paraneda pallidula guticollis (4.1%) (Coleoptera: Coccinellidae), an assassin bug, Zelus sp. (Hemiptera: Reduviidae) (17.8%), and the lacewing Ceraeochrysa sp. (Neuroptera: Chrysopidae) (22.4%). The parasitoid wasp Tamarixia radiata also was found, reaching a parasitization rate of 90% of the psyllid nymphs. This study represents the first report of P. pallidula guticollis feeding on D. citri. The diversity of natural enemies and the high level of parasitism detected suggest the importance of natural enemies as biological control agents of this important phytophagous insect pest. The natural control by these beneficial insects would make unnecessary the applications of chemical insecticides that are carried out in Ecuador for the control of this insect, especially at this moment when the HLB causing bacterium has not been reported in Ecuador.Diaphorina citri, especie detectada en Ecuador por primera vez en 2013, es una plaga de relevancia mundial debido a que es el principal vector de la bacteria Candidatus Liberibacter asiaticus, agente causal del Huanglongbing (HLB), una devastadora enfermedad de los cítricos. Durante el período abril 2016 – julio 2017, se realizaron estudios de fluctuación poblacional e inventario de enemigos naturales de D. citri en brotes jóvenes de azahar de la India, Murraya paniculata y citricos, Citrus spp. Los enemigos naturales fueron colectados en las provincias de Guayas y Santa Elena, Ecuador. Se colectaron un total de 1660 especímenes pertenecientes a cinco especies, entre estos, tres coccinélidos, Cheilomenes sexmaculata, la especie más abundante (39,9%, P<0,05), seguido por Cycloneda sanguinea (15,8%) y Paraneda pallidula guticollis 4,1% (Coleoptera: Coccinellidae), una chinche depredadora, Zelus sp. (Hemiptera: Reduviidae) (17,8%) y la crisopa Ceraeochrysa sp. (Neuroptera: Chrysopidae) (22,4%). La avispita parasítica Tamarixia radiata también fue encontrada, alcanzando un porcentaje de parasitismo del 90% en las ninfas de psílido. Este estudio representa el primer reporte de P. pallidula guticollis alimentándose de D. citri. La diversidad de enemigos naturales y el alto nivel de parasitismo detectado sugieren la importancia de los enemigos naturales como agentes de control biológico de esta importante plaga. El control natural existente haría innecesarias las aplicaciones de insecticidas químicos que se llevan a cabo en el Ecuador para el control de este insecto, especialmente en este momento que el HLB no se ha encontrado en Ecuador.Gerencia de Comunicación Institucional, DG SICyP, INTAFil: Chavez, Y. Ministerio de Agricultura y Ganadería; EcuadorFil: Castro, C. Investigador independiente; EcuadorFil: González, Guillermo F. Investigador independiente; ChileFil: Castro, Jessenia. Universidad Técnica de Manabí. Facultad de Ingeniería Agronómica; EcuadorFil: Peñarrieta Bravo, Soraya. Universidad Técnica de Manabí. Facultad de Ingeniería Agronómica; EcuadorFil: Perez-Almeida, Iris. Universidad ECOTEC. Facultad de Ingenierías. Carrera de Ingeniería Agrónoma; EcuadorFil: Chirinos, Dorys Terezinha. Universidad Técnica de Manabí. Facultad de Ingeniería Agronómica; EcuadorFil: Kondo Rodríguez, Demian Takumasa. Corporación colombiana de investigación agropecuaria AGROSAVIA. Centro de Investigación Palmira; Colombi

Morphological and genetic diversity of the Balearic lizard,Podarcis lilfordi(Gunther, 1874): Is it relevant to its conservation?

Aims: To characterize the genetic and morphological diversification of the endangered Balearic lizard Podarcis lilfordi and to assess the relevance of this diversity, and how it is described, to conservation measures. Location: This study covers all the populations of the Balearic lizard, Podarcis lilfordi, present in its range of distribution at coastal islets of Menorca, Mallorca and Cabrera Archipelago. Methods: We analysed genetic and morphological variation across the 43 known extant populations of the Balearic lizard, using mitochondrial and nuclear markers. We examined morphometric and scalation characters using, in some cases, phylogenetically independent contrasts. We also incorporated the study of dorsal coloration and dorsal colour pattern including the analysis of melanism in several populations. Results: We detected clear genetic divergence between Menorcan populations and populations from Mallorca and Cabrera, in both nuclear and mtDNA markers, but genetic divergence is relatively low among different insular populations within these groups. In contrast, morphological divergence was substantial both between Menorcan and remaining populations and within these groups. Morphological traits, such as dorsal coloration, body size and the number and size of scales, seemed to be linked with differences in climatic conditions between populations. In addition, some traits, as melanism, showed a strong phylogenetic signal. Main conclusions: The morphological and genetic diversity of the Balearic lizard is incongruent with the subspecies described in the classical taxonomic literature. Moreover, current populations differ not only in some genetic and morphological features, but also in several ecological and ethological characteristics, in many cases unique to one population. Based on our results, we propose abandoning the use of subspecies to describe the extraordinary morphological diversity of the Balearic lizard and its replacement with the concept of evolutionary significant units (ESUs). ESUs are particularly suitable to describe and recognize such diversity and, especially, to ensure the continuity of the evolutionary process

Methionine adenosyltransferase S-nitrosylation is regulated by the basic and acidic amino acids surrounding the target thiol

S-Adenosylmethionine serves as the methyl donor for many biological methylation reactions and provides the propylamine group for the synthesis of polyamines. S-Adenosylmethionine is synthesized from methionine and ATP by the enzyme methionine adenosyltransferase. The cellular factors regulating S-adenosylmethionine synthesis have not been well defined. Here we show that in rat hepatocytes S-nitrosoglutathione monoethyl ester, a cell-permeable nitric oxide donor, markedly reduces cellular S-adenosylmethionine content via inactivation of methionine adenosyltransferase by S-nitrosylation. Removal of the nitric oxide donor from the incubation medium leads to the denitrosylation and reactivation of methionine adenosyltransferase and to the rapid recovery of cellular S-adenosylmethionine levels. Nitric oxide inactivates methionine adenosyltransferase via S-nitrosylation of cysteine 121. Replacement of the acidic (aspartate 355) or basic (arginine 357 and arginine 363) amino acids located in the vicinity of cysteine 121 by serine leads to a marked reduction in the ability of nitric oxide to S-nitrosylate and inactivate hepatic methionine adenosyltransferase. These results indicate that protein S-nitrosylation is regulated by the basic and acidic amino acids surrounding the target cysteine

Significance of calcium: its correlation with red and white muscle contraction, fatigue and potential

According to the predominant types of muscle fibers in an individual, they will have the ability to perform different types of exercises (both aerobic and anaerobic). To comprehend the mechanism of muscle fibers, which can act in diverse ways, enhancing either resistance or power, it is essential to examine the significance of calcium. Calcium plays a crucial role in both red and white muscle fibers. The release of calcium in white (fast-twitch) muscle fibers is significantly greater and faster, resulting in increased energy consumption, facilitating explosive physical activities. Conversely, in red (slow-twitch) muscle fibers, the release of calcium occurs in smaller amounts and over a prolonged period, leading to sustained energy consumption. The characteristics of contraction in red fibers enable endurance activities. A reduction in the amount of calcium results in diminished muscle contractile capacity, known as fatigue. The primary contributing factor, as previously mentioned, is the decline in calcium, but factors such as lactic acid and the dephosphorylation of the myosin head also contribute to its onset

The Large Aperture GRB Observatory

The Large Aperture GRB Observatory (LAGO) is aiming at the detection of the high energy (around 100 GeV) component of Gamma Ray Bursts, using the single particle technique in arrays of Water Cherenkov Detectors (WCD) in high mountain sites (Chacaltaya, Bolivia, 5300 m a.s.l., Pico Espejo, Venezuela, 4750 m a.s.l., Sierra Negra, Mexico, 4650 m a.s.l). WCD at high altitude offer a unique possibility of detecting low gamma fluxes in the 10 GeV - 1 TeV range. The status of the Observatory and data collected from 2007 to date will be presented.Comment: 4 pages, proceeding of 31st ICRC 200