Silyl and siloxanediyl cyclopentadienyl titanium and zirconium complexes: synthesis and reactivity. X-ray molecular structure of [Zr{η5-C5H4SiMe2(μ-OH)}(μ-Cl)Cl2]2

Chloro(dimethyl)silyl-η5-cyclopentadienyl group 4 metal complexes of the type [M(η5-C5H4Cl)Cl3] (Full-size image (<1 K)) react with thallium salts Tl(C5H4R) (R = H, SiMe3) to give mixed dicyclopentadienyl derivatives [M(η5-C5H4R)(η5-C5H4SiMe2Cl)Cl2], (M = Ti, R = H 3, R = SiMe34; M = Zr, R = H 5, R = SiMe36) in high yield. Hydrolysis of complexes 3 and 4 affords the dinuclear complexes [Ti(η5-C5H4R)Cl2]2{μ-[(η5-C5H4SiMe2)2O]}] [R = H 7, R = SiMe38) containing a siloxanyl bridge, by elimination of two equivalents of HCl. Reactions of complexes 1 with hydroxo containing reagents such as anhydrous LiOH and SiPh2(OH)2 give the derivatives [Ti(η5-C5H4SiMe2Cl)Cl2]2(μ-O)], 9 and Ti[μ-(η5-C5H4SiMe2OSiPh2-η1-O)]Cl2, 10 identified by analytical, spectrometric and spectroscopic data. Treatment of analogous complex 2 with water produces the dimeric monocyclopentadienyl zirconium trichloride adduct [Zr(η5-C5H4SiMe2OH)Cl3]2, 11. Compound 11 has been characterized by X-ray crystallography.Universidad de AlcaláConsejería de Educación de la Comunidad de Madri

Diastereoselective insertion of isocyanide into the alkyl metal bond of methylbenz[e]indenyl ansa-zirconocene complexes

Alkylation of ansa-zirconocene [Zr{(η5-C5H5)SiMe2(MBI)}Cl2] (MBI = η5-2-Me−C13H7) with MgRCl gave the dimethyl complex [Zr{(η5-C5H5)SiMe2(MBI)}Me2], but unresolvable mixtures containing mono-alkylated compounds were obtained when bulkier alkyls were used. However pure dialkyl complexes [Zr{(η5-C5H5)SiMe2(MBI)}R2] (R = CH2Ph, CH2SiMe3) were easily obtained using K(CH2Ph) and Li(CH2SiMe3) as alkylating agents. Diastereoselective insertion into the MBI-unprotected Zr−R bond was observed when all of these dialkyl complexes were treated with 2,6-xylyl isocyanide to give the iminoacyl compounds [Zr{(η5-C5H5)SiMe2(MBI)}R{CR[η2-N-(2,6-xylyl)]}] (R = Me, CH2Ph, CH2SiMe3). All of the new complexes were characterized by NMR spectroscopy and the X-ray molecular structures of the dibenzyl and the imino-benzyl compounds were determined. The catalytic activity for ethene polymerization and ethene/1-hexene copolymerization of the dichloro zirconocenes [Zr{(η5-C5H5)EMe2(MBI)}Cl2] (E = C, Si), activated with methylalumoxane (MAO), was measured.Repsol-YP

Reactivity of chlorodimethylsilyl-η5-cyclopentadienyltrichlorotitanium\ud with nitrogen based donors. X-ray molecular structure of\ud [Ti{η5-C5H4SiMe2[η1-N(2,6-Me2C6H3)]}Cl2]

This paper reports the reactivity of [Ti(η5-C5H4SiMe2Cl)Cl3], 1 towards nitrogen based donor reagents. Complex 1 reacts with lithium benzamidinato Li[PhC(NSiMe3)2] to afford [Ti(η5-C5H4SiMe2Cl){PhC(NSiMe3)2}Cl2] 2 and with lithium amide LiNMe2 to produce [Ti(η5-C5H4SiMe2NMe2)(NMe2)3] 3. The latter compound was converted into the dihalide derivatives [Ti(η5-C5H4SiMe2NMe2)(NMe2)X2] [X=Cl (4) and Br (5)] by reaction with SiMe3X (X=Cl or Br, respectively). The constrained geometry derivatives [Ti{η5-C5H4SiMe2(η1-NR)}Cl2] (R=C6H56, 2,6-Me2C6H37 and 2-Me-6-iPr-C6H38) have been synthesized by treatment of 1 with the corresponding primary aryl amines H2NR. Complex 7 was readily converted into the dialkyl and diamido compounds [Ti{η5-C5H4SiMe2[η1-N(C6H3Me2)]}X2] (X=Me (9), CH2Ph (10), CH2SiMe3 (11) or NMe2 (13)) by metathesis using Grignard or organolithium reagents and into the monoalkyl derivative [Ti{η5-C5H4SiMe2[η1-N(C6H3Me2)]}MeCl] (12) by reaction with AlMe3. The molecular structure of complex 7 [Ti{(η5-C5H4SiMe2[η1-N(2,6-Me2C6H3)]}Cl2] was established by X-ray crystallography.We are grateful to the DGICYT (Project PB-92-0178-C) and University of Alcalá for financial support of this research

Plant Metabolites in Plant Defense Against Pathogens

Medicinal plants are widely used worldwide to treat various diseases. Its widespread use is due in part to the cultural acceptance of traditional medicine in different regions of the world, as well as its effectiveness in treating various diseases. Many of its active substances or secondary metabolites are formed to a response of various situations that generate stress in their habitat, such as sudden changes in environmental temperature, humidity, rain, drought, and infections by phytopathogens (fungi, bacteria, viruses, nematodes, protozoa). The production of these secondary metabolites is a mechanism of defense of plants. In this context, the objective of this chapter is to study the secondary metabolites of medicinal plants that could have a promising application in the control of different phytopathogens in crops of agricultural and economic interest

Synthesis and reactivity of new silyl substituted monocyclopentadienyl zirconium complexes. X-ray molecular structure of [Zr{η5-C5H4(SiMe2CH2Ph)}(CH2Ph)3]

Synthesis and reactivity of new silyl substituted monocyclopentadienyl zirconium complexes. X-ray molecular structure of [Zr{η5-C5H4(SiMe2CH2Ph)}(CH2Ph)3]We are grateful to the DGICYT (Project PB-92-0178-C) and University of Alcalá for the financial support of this research

Networking of differentially expressed genes in human cancer cells resistant to methotrexate

BACKGROUND: The need for an integrated view of data obtained from high-throughput technologies gave rise to network analyses. These are especially useful to rationalize how external perturbations propagate through the expression of genes. To address this issue in the case of drug resistance, we constructed biological association networks of genes differentially expressed in cell lines resistant to methotrexate (MTX). METHODS: Seven cell lines representative of different types of cancer, including colon cancer (HT29 and Caco2), breast cancer (MCF-7 and MDA-MB-468), pancreatic cancer (MIA PaCa-2), erythroblastic leukemia (K562) and osteosarcoma (Saos-2), were used. The differential expression pattern between sensitive and MTX-resistant cells was determined by whole human genome microarrays and analyzed with the GeneSpring GX software package. Genes deregulated in common between the different cancer cell lines served to generate biological association networks using the Pathway Architect software. RESULTS: Dikkopf homolog-1 (DKK1) is a highly interconnected node in the network generated with genes in common between the two colon cancer cell lines, and functional validations of this target using small interfering RNAs (siRNAs) showed a chemosensitization toward MTX. Members of the UDP-glucuronosyltransferase 1A (UGT1A) family formed a network of genes differentially expressed in the two breast cancer cell lines. siRNA treatment against UGT1A also showed an increase in MTX sensitivity. Eukaryotic translation elongation factor 1 alpha 1 (EEF1A1) was overexpressed among the pancreatic cancer, leukemia and osteosarcoma cell lines, and siRNA treatment against EEF1A1 produced a chemosensitization toward MTX. CONCLUSIONS: Biological association networks identified DKK1, UGT1As and EEF1A1 as important gene nodes in MTX-resistance. Treatments using siRNA technology against these three genes showed chemosensitization toward MTX

Knigth's Move in the Periodic Table, From Copper to Platinum, Novel Antitumor Mixed Chelate Copper Compounds, Casiopeinas, Evaluated by an in Vitro Human and Murine Cancer Cell Line Panel

We synthesized a novel anticancer agents based on mixed chelate copper (II) complexes, named Casiopeínas® has of general formula [Cu(N-N)(N-O)H2O]NO3 (where, N-N = diimines as 1,10- phenanthroline, 2,2-bipyridine, or substituted and N-O=aminoeidate or [Cu(N-N)(O-O)H2O]NO3 (where NN= diimines as 10-phenanthroline, 2,2-bipyridine or substituted Casiopeínas I, II, IV, V, VI, VII VIII and O-O=acetylacetonate, salicylaldehidate Casiopínas III). We evaluated the in vitro antitumor activity using a human cancer cell panel and some nurine cancer cells. Eleven Casiopeinas are evaluated in order to acquire some structure-activity correlations and some monodentated Casiopeinäs analogues; cisplatinum was used as control drug. The 50% growth inhibition observed is, in all cases reach with concentrations of Casiopeina's 10 or 100 times lower than cisplatinum. In a previous work we reported the induction of apoptosis by Casiopeina II. The results indicate that Casiopeinass are a promising new anticancer drug candidates to be developed further toward clinical trials

Heterosis y aptitud combinatoria para producción y calidad de forraje en seis poblaciones de maíz

Six corn populations drawn from outstanding forage quality germplasm, and 15 of their direct crosses were assessed in four sites located between 1,117 and 1,932 m asl. The purpose of the present study was to determine general and specific combining ability and mid parent heterosis for whole plant dry matter (TDM), ear dry matter (EDM), stover dry matter (SDM), in vitro dry matter digestibility (IVDMD), neutral detergent fiber content (NDF) and crude protein (CP). Populations showed significant differences for all dry matter yield characteristics, but not for forage quality, while crosses showed differences for EDM and IVDMD. General combining ability effects (GCA) were high and significant only for TDM, while specific combining ability effects (SCA) were significant for IVDMD. Population P3 had the highest GCA for TDM (0.66 t ha-1) and P5F for EDM (0.49 t ha-1). Early cross P1*P2 had the highest heterosis for TDM (17.6 %) and highly significant SCA effects for both TDM and IVDMD (1.48 t ha-1 and 22.6 g kg-1, respectively), while crosses P2*P5F, P1*P4 and P1*P6F had high mid parent heterosis for EDM, with values ranging from 18.6 % to 26.2 %. None of the crosses showed mid parent heterosis for forage traits of importance.Seis poblaciones de maíz derivadas de fuentes de germoplasma sobresalientes por sus cualidades forrajeras y sus 15 cruzas directas se evaluaron en cuatro localidades entre 1,117 y 1,932 m sobre el nivel del mar. El objetivo fue determinar la aptitud combinatoria general y específica, y la heterosis media para variables de producción: materia seca total (MST), de elote (MSEL) y de rastrojo (MSRAS) y variables de calidad del forraje: digestibilidad in vitro de la materia seca (DIVMS), contenido de fibra detergente neutro (FDN) y proteína cruda (PC). Las poblaciones difirieron significativamente en las tres variables de producción, pero no en calidad forrajera, en cambio las cruzas difirieron en producción de MSEL y en DIVMS. Los efectos de aptitud combinatoria general (ACG) fueron significativos sólo para MST y MSEL, mientras que los efectos de aptitud combinatoria específica (ACE), lo fueron adicionalmente para DIVMS. La población P3 tuvo la mayor ACG para MST (0.66 t ha-1), y la población P5F para MSEL (0.49 t ha-1). La cruza precoz P1xP2 presentó la heterosis media más alta para MST con 17.6 % y efectos positivos y significativos de ACE para MST y DIVMS con valores de 1.48 t ha-1 y 22.6 g kg-1. En cambio, las cruzas P2xP5F, P1xP4 y P1xP6F tuvieron los valores de heterosis más altos para MSEL con valores de 18.1 a 26.2 %. Ninguna cruza tuvo heterosis media importante para caracteres de calidad de forraje

Metabolic syndrome, adiposity, diet, and emotional eating are associated with oxidative stress in adolescents

Background: Metabolic syndrome (MS), a condition related to adiposity and oxidative stress, can develop in adolescence, a critical stage in life that impacts health in adulthood. However, there is scarce scientific research about the relationship between lifestyle factors, emotion management, and oxidative stress in this phase of life.Aim: To analyze whether nutritional parameters, lifestyle factors, emotion management, and MS in adolescents are associated with oxidative stress measured by the biomarker 8-isoprostane.Methods: A cross-sectional study was carried out in 132 adolescents (48.5% girls, aged 12 ± 0.48 years) and data were collected on nutritional parameters (anthropometric measurements, biochemical analyzes, and blood pressure), lifestyle factors (physical activity, sleep, and diet), and emotion management (self-esteem, emotional eating, and mood). 8-isoprostane was analyzed in spot urine samples. The study population was categorized in three groups (healthy, at-risk, and with MS) using the International Diabetes Federation definition of MS in adolescents. To capture more complex interactions, a multiple linear regression was used to analyze the association between 8-isoprostane and the aforementioned variables.Results: Urinary 8-isoprostane levels were significantly higher in the MS group compared to the healthy group (1,280 ± 543 pg./mg vs. 950 ± 416 pg./mg respectively). In addition, univariable analysis revealed positive significant associations between 8-isoprostane and body mass index, waist circumference, waist-to-height ratio, body fat percentage, blood lipid profile and glucose, emotional eating, and refined cereal intake. Conversely, a negative significant association was found between 8-isoprostane and sleep duration and fish intake. The multiple linear regression analysis revealed associations between 8-isoprostane and LDL-c (β = 0.173 value of p = 0.049), emotional eating (low β = 0.443, value of p = 0.036; high β = 0.152, value of p = 0.470), refined cereal intake (β =0.191, value of p = 0.024), and fish intake (β = -0.187, value of p = 0.050).Conclusion: The MS group, LDL-c, emotional eating, and high refined cereals and low fish intakes were associated with higher levels of oxidative stress in an adolescent population.</p

Identifying non-destructive growth and maturity indexes of Prickly pear (Opuntia albicarpa S. Var. Burrona) and evaluation of freeze-drying conditions

Around the world, prickly pear fruits are valued as a source of dietary functional compounds and ingredients for innovative foods. Growth and physicochemical changes of Opuntia albicarpa S. fruits were recorded from 0 to 132 days-after-flowering (DAF) to identify non-destructive maturity-indices. Optimum-ripened fruits were freeze-dried to study physicochemical and functional characteristics of dried and rehydrated pulp. Principal component analysis confirmed growth turned into fruit ripening in DAF 99, and it lasted until DAF 132. Changes in color parameters of the peel correlated with fruit texture and pulp sugar content and taste index (P < 0.01). During freeze-drying, plate temperature had more significant effects than the thickness (P < 0.05). At 30°C, color ΔE between dried and fresh slices augmented, but, texture Δ´s (medium force) between rehydrated and fresh pulp was lower. Color tests could be used to harvest commercially-ripened fruits. Freeze-drying at 30°C improves the rehydrated slices texture regarding thickness maintaining rehydration coefficients.Las tunas son apreciadas en todo el mundo como fuente de compuestos funcionales dietarios e ingredientes para alimentos innovadores. Para identificar índices de maduración no destructivos, se registraron cambios en el crecimiento y en los parámetros fisicoquímicos de frutos de Opuntia albicarpa S. entre los días después de la floración (DAF) 0 al 132. Frutos con maduración óptima fueron liofilizados para evaluar características fisicoquímicas y funcionales de pulpa seca y rehidratada. El análisis de componentes principales confirmo que el crecimiento dio lugar a la maduración en el DAF 99 y ésta prosiguió hasta el DAF 132. Los cambios en parámetros de color en cáscara correlacionaron con la textura del fruto, y en pulpa, con el contenido de azúcares y el índice de sabor (P< 0.01). Durante la liofilización, la temperatura de placa tiene más efectos significativos que el espesor (P≤ 0.05). A 30°C, el ΔE de color entre la pulpa seca y fresca aumentó, pero, el Δ de textura (fuerza media) fue menor entre la rehidratada y la fresca. Se pueden emplear evaluaciones de color para cosechar frutos en su madurez comercial, y liofilizar estos frutos a 30°C mejora la textura sin importar el espesor, manteniendo los coeficientes de rehidratación.This work was supported by the SIMORELOS program of CONACyT