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Silage of high moisture sorghum grains is a highly relevant source of energy in cattle production systems in South America. There is little information related to the chemical characteristics, the kinetics of fermentation and the toxic fungal populations of these feedstuffs. The aim of this study was to evaluate the effect of storage time and condensed tannins content of the grain on chemical composition, in vitro fermentation parameters, and toxicogenic fungal populations of moist sorghum grain stored in silo-bags. Samples of 2 varieties of sorghum grains (high-tannin [HT] and low-tannin [LT]), were obtained during the grain harvest before silage making and after 30, 90, and 180 d of storage (n = 16). High-tannin grains had higher acid detergent fiber, tannins, gas production (P

Species of the genus Senecio have been traditionally employed with medical purposes and it has been demonstrated that some of them have anti-proliferative activity on cancer-derived cell lines. In South America S. madagascariensis is one of the most important representatives of the genus. Almost all species contain pyrrolizidine alkaloids (PA), substances that can lead to hepatic damage. Thus, the aim of this work was to determine the cytotoxic activity of a low PAs extract of S. madagascariensis on a cancer-derived cell line. A chloroform extract from plant material was produced and it was demonstrated to have a PAs concentration lower than 200 µg/g (w/w). Two stock solutions were made with DMSO and acetone as solvents and were diluted in culture medium (DMEM). Cells from urinary bladder transitional cell carcinoma T24 were cultured in 96 well plates (10⁴ cells/well) and incubated for 24 hours with dilutions of the extracts at the following concentrations, 0.5 mg/mL, 0.25 mg/mL, 0.125 mg/mL and 0.06 mg/mL. Cell viability was evaluated by the MTT colorimetric technique. Both solutions of S. madagascariensis extracts (acetone and DMSO) showed cytotoxic activity. In both cases, the degree of cytotoxicity was dependent on the concentration of the solution.

Background Direct Acting Antivirals (DAAs) represent a large improvement in the treatment of chronic hepatitis C, resulting in Methods A descriptive, ambispective, longitudinal study was conducted. A cohort of 261 adult patients received PegIFNα2a+RBV therapy before 2014; 167 (64%) did not respond, 83 of these were subsequently treated with SOF/LDV ± RBV or OBV/PTV/r/DSV ± RBV. Child-Pugh-Score (CPS), Fibrosis-4 (FIB-4), and AST to Platelet Ratio Index (APRI) were evaluated before and after treatment. Results SVR with PegIFNα2a+RBV was 36%, and 97.5% with DAAs. CPS, FIB-4 and APRI improved significantly after DAA treatment, mainly because of liver transaminase reduction. Conclusions DAA treatment showed excellent SVR rates in Mexican patients who had not responded to PegIFNα2a+RBV therapy. Improvement in CPS, FIB-4 and APRI without improvement in fibrosis was observed in cirrhotic and non-cirrhotic patients, as well as considerable reduction in liver transaminases, which suggests a reduction in hepatic necroinflammation.

the effect of partially replacing wheat flour by 10%, 20% or 30% of native breadfruit starch (Artocarpus altilis) on the cooking parameters in short Fusilli type pastes, obtained by extrusion, was evaluated. Optimum cooking time, percentage of swelling and weight loss by cooking were evaluated. The results indicate that the cooking time of the pastes of 0% substitution (10.66 ± 0.31 minutes), 10% (8.08 ± 0.05 minutes), 20% (8.10 ± 0.10) minutes), 30% (7.87 ± 0.27 minutes) decreases with the percentage of substitution, as well as the weight losses by cooking that were 2.39; 2.46; 3.16 and 4.05% for 0, 10, 20 and 30% substitution, respectively. In relation to the percentage of swelling, the values were 69.09 ± 0.21; 62.93 ± 0.26; 84.19 ± 0.53 and 82.06 ± 0.63% for 0, 10, 20 and 30% substitution, respectively.

Resumen: Las micotoxinas, metabolitos secundarios producidos por hongos toxicogénicos que contaminan alimentos destinados al hombre y/o animales que una vez ingeridos pueden ocasionar problemas en la salud. Existen más de 250 micotoxinas, siendo las aflatoxinas una de las más estudiadas ya que son potenciales carcinogénicos. Las aflatoxinas consumidas por los animales son metabolizadas y excretadas en parte por leche como aflatoxina M1, representando un riesgo potencial para humanos. La fuente de aflatoxinas para los animales son los alimentos, por ello los niveles máximos permitidos están regulados, así como la presencia de aflatoxina M1 en leche y derivados. El objetivo del presente estudio fue evaluar 18 establecimientos lecheros comerciales de Uruguay, la presencia natural de aflatoxinas en alimentos destinados a vacas lecheras en producción y su correlación con la presencia de aflatoxina M1 en la leche de los animales que estaban consumiendo esos alimentos. Se seleccionaron establecimientos comerciales remitentes de las zonas centro-sur y este del Uruguay, se tomaron muestras de los alimentos que consumían los animales y de la leche del tanque de frío al momento de la visita. Las aflatoxinas fueron cuantificadas mediante la técnica de Elisa, obteniéndose el 100% de muestras de alimento contaminadas y el 91,8% de muestras de leche con niveles de aflatoxinas. Los niveles de aflatoxinas no se correlacionaron con los de aflatoxina M1. La aflatoxina M1 determinada en este estudio no representó riesgo para la salud ya que no superó los niveles máximos permitidos para el consumo en Uruguay. Summary: Mycotoxins are secondary metabolites produced by toxicogenic fungi species. They can contaminate humans and animals’ food and once ingested can cause health harms. There are more than 250 mycotoxins, being aflatoxins one of the most studied due to their potential carcinogenic effect. It is known that the aflatoxins consumed by animals are metabolized and excreted in part by milk as aflatoxin M1, representing a potential risk for human health. Aflatoxins source for animals is feed, therefore, the maximum permitted levels are regulated, as well as the presence of aflatoxin M1 in milk and derivatives. The aim of the present study was to evaluate the natural presence of aflatoxins in the feeds destined to dairy cows in production in 18 commercial dairy farms of Uruguay. It also aimed to determine the correlation between the consumption of those feeds and the presence of aflatoxin M1 in the milk of the animals. In order to achieve this objective, feed and milk samples were taken randomly from 18 dairy farms located in the south central area and the east region of Uruguay. Milk was taken from the cold tank. Aflatoxins were quantified by Elisa technique. The totally of the feed samples and 91.8% of the milk samples were contaminated with some aflatoxin levels. The levels of aflatoxins did not correlate with those of aflatoxin M1. The levels of aflatoxin M1 in milk did not exceed the maximum consumption levels allowed in Uruguay, thus did not represent a risk for human health.

[EN] Natural radioactivity represents one of the main backgrounds in the search for neutrinoless double beta decay. Within the NEXT physics program, the radioactivity- induced backgrounds are measured with the NEXT-White detector. Data from 37.9 days of low-background operations at the Laboratorio Subterraneo de Canfranc with xenon depleted in Xe-136 are analyzed to derive a total background rate of (0.84 +/- 0.02) mHz above 1000 keV. The comparison of data samples with and without the use of the radon abatement system demonstrates that the contribution of airborne-Rn is negligible. A radiogenic background model is built upon the extensive radiopurity screening campaign conducted by the NEXT collaboration. A spectral fit to this model yields the specific contributions of Co-60, K-40, Bi-214 and Tl-208 to the total background rate, as well as their location in the detector volumes. The results are used to evaluate the impact of the radiogenic backgrounds in the double beta decay analyses, after the application of topological cuts that reduce the total rate to (0.25 +/- 0.01) mHz. Based on the best-fit background model, the NEXT-White median sensitivity to the two-neutrino double beta decay is found to be 3.5 sigma after 1 year of data taking. The background measurement in a Q(beta beta)+/- 100 keV energy window validates the best-fit background model also for the neutrinoless double beta decay search with NEXT-100. Only one event is found, while the model expectation is (0.75 +/- 0.12) events., The NEXT collaboration acknowledges support from the following agencies and institutions: the European Research Council (ERC) under the Advanced Grant 339787-NEXT; the European Union's Framework Programme for Research and Innovation Horizon 2020 (2014-2020) under the Marie Sklodowska-Curie Grant Agreements No. 674896, 690575 and 740055; the Ministerio de Economia y Competitividad and the Ministerio de Ciencia, Innovacion y Universidades of Spain under grants FIS2014-53371-C04, RTI2018-095979, the Severo Ochoa Program SEV-2014-0398 and the Maria de Maetzu Program MDM-2016-0692; the GVA of Spain under grants PROMETEO/2016/120 and SEJI/2017/011; the Portuguese FCT under project PTDC/FIS-NUC/2525/2014, under project UID/FIS/04559/2013 to fund the activities of LIBPhys, and under grants PD/BD/105921/2014, SFRH/BPD/109180/2015 and SFRH/BPD/76842/2011; the U.S. Department of Energy under contracts number DE-AC02-06CH11357 (Argonne National Laboratory), DE-AC02-07CH11359 (Fermi National Accelerator Laboratory), DE-FG02-13ER42020 (Texas A&M) and DE-SC0019223/DE-SC0019054 (University of Texas at Arlington); and the University of Texas at Arlington. DGD acknowledges Ramon y Cajal program (Spain) under contract number RYC-2015-18820. We also warmly acknowledge the Laboratori Nazionali del Gran Sasso (LNGS) and the Dark Side collaboration for their help with TPB coating of various parts of the NEXT-White TPC. Finally, we are grateful to the Laboratorio Subterraneo de Canfranc for hosting and supporting the NEXT experiment.

A study on the dynamic of transport and occurrence of ozone in the air basin of the Puebla-Tlaxcala Valley (PTV) was performed between March and April 2012. The ozone (O 3 ), nitrogen oxides (NOx) and several meteorological variables were measured at the surface level in the rural sites of Huaquechula (HUAQ), Chipilo (CHIP), and Amozoc (AMOZ). The vertical O 3 profile and the associated meteorological conditions, were measured intermittently in CHIP. The 1 hour Mexican air quality standard of 0.095 ppm for O 3 , was exceeded in five and one days in CHIP and AMOZ, respectively. A rapid increase in the morning for O 3 levels was observed in the three sites and was associated with the mixing of O 3 above the inversion layer once started the growing of the turbulent mixing layer. Unusual O 3 evening events of around 0.080 ppm were recorded for several hours in the three sites that could be associated with the recirculation of air masses with ozone formed within the VPT and O 3 advectively transported from the Cuernavaca-Cuautla Valley. The vertical O 3 profile showed an increase with height at concentrations even higher than those observed at the surface, and the 2-D analysis of backward trajectories suggested favorable conditions for O 3 transported from the free troposphere to the surface. It is concluded that the implementation of control strategies in the VPT should consider the influence of the inter-basin exchange, the meteorological local and synoptic seasonality, and the possible contributions of O 3 from the free troposphere and not be limited to local conditions.

EnglishIn Eastern Uruguay there has been a significant increase of seneciosis in grazing livestock with most affected localities related to counties neighboring the Brazilian border. A survey in 28 farms associated with poisoning outbreaks in grazing cattle in Eastern Uruguay was carried out. Fifty populations of Senecio plants were collected for alkaloid analysis and species identification. Four species were identified: S. oxyphyllus DC, S. madagascariensis Poir, S. brasiliensis (Spreng.) Less., and S. selloi DC. Alkaloids were identified by a combination of GC-MS and HPLC-MS analysis and included: retrorsine in S. oxyphyllus; retrorsine, usaramine, and senecivernine/senecionine in S. selloi; retrorsine, senecivernine/senecionine, integerrimine, and usaramine in S. madagascariensis; and integerrimine, retrorsine and senecionine in S. brasiliensis. Total mean alkaloid concentration was reported to be highest in S. brasiliensis (17.6mg/g) followed by S. oxyphyllus (6.2mg/g), S. selloi (1.8mg/g) and S. madagascariensis (0.6mg/g). Alkaloid concentrations were also reported to be higher in 2015 vs. 2016 probably due to a common environmental factor. The species S. oxyphyllus and S. madagascariensis were not previously recognized as toxic plants in Eastern Uruguay. Particularly, S. oxyphyllus was present in 82% of the farms surveyed and occurred in high density with relative high concentrations of pyrrolizidine alkaloids suggesting S. oxyphyllus may be the main species involved in the reported outbreaks of seneciosis. Key words: seneciosis; plant secondary metabolites; ruminants; poisonous plants; Asteraceae portuguesNo leste do Uruguai houve um aumento significativo da seneciosis no gado de pastagem com a maioria das localidades afetadas em municipios vizinhos a fronteira brasileira. Aplicou-se um questionario em 28 fazendas associadas a surtos de intoxicacao em bovinos de pastagem na fronteira leste do Uruguai. Coletaram-se cinquenta populacoes de Senecio para analise de alcaloides e identificacao de especies. Identificaram-se quatro especies: S. oxyphyllus DC, S. madagascariensis Poir, S. brasiliensis (Spreng.) Less. e S. selloi DC. Identificaram-se os seguintes alcaloides mediante analise combinado de GC-MS e HPLC-MS: retrorsina em S. oxyphyllus; retrorsina, usaramina e senecivernina/senecionina em S. selloi; retrorsina, senecivernina/senecionina, integerimina e usaramina em S. madagascariensis; e integerrimina, retrorsina e senecionina em S. brasiliensis. A concentracao media total de alcaloides foi mais elevada em S. brasiliensis (17,6mg/g) seguido de S. oxyphyllus (6,2mg/g), S. selloi (1,8mg/g) e S. madagascariensis (0,6mg/g). As concentracoes de alcaloides foram maiores em 2015 em vista a 2016, provavelmente, devido a um fator ambiental comum. As especies S. oxyphyllus e S. madagascariensis nao foram previamente reconhecidas como plantas toxicas no leste do Uruguai. Particularmente, S. oxyphyllus esteve presente em 82% das fazendas pesquisadas e ocorreu em alta densidade com concentracoes relativamente elevadas de alcaloides de pirrolizidina sugerindo que S. oxyphyllus pode ser a principal especie envolvida nos surtos relatados de seneciosis. Palavras-chave: seneciosis; metabolitos secundarios de plantas; ruminantes; intoxicacao por plantas; Asteraceae

Six new diorganotin (IV) complexes, [Ph2Sn(Pr-ACDA)2] 1, [Bu2Sn(Pr-ACDA)2] 2, [Ph2Sn(Bz-ACDA)2] 3, [Bu2Sn(Bz-ACDA)2] 4, [Me2Sn(Bz-ACDA)2] 5, [t-Bu2Sn(Bz-ACDA)2] 6 are reported (where ACDA is the 2-amino-1-cyclopentene-1-carbodithioic anion). The diorganotin complexes were prepared from reactions between sodium N-propyl and N-benzyl-2-amino-1-cyclopentene-1-carbodithioate with R2SnCl2 (R=Ph, Bu, Me, tBu) in a 2:1 ratio. All complexes were characterized by elemental analysis, IR, multinuclear NMR (1H, 13C, and 119Sn), FAB+ mass spectrometry and in the case of 2, 3 and 5 by single-crystal X-ray diffraction. Both solution and solid state studies show that dithioacid ligands are coordinated to tin in an aniso-bidentate manner. In all complexes coordination takes place only through the carbodithioate moieties. 119Sn NMR data indicate pentacoordination of tin in solution. The tin coordination geometry, in all three structures is a highly distorted octahedral geometry, where tin is bonded to the four sulfur atoms of the two aniso-bidentate carbodithioate ligands in the equatorial plane and the organic substituents on tin atom in trans-positions. In addition, the crystal structures show the presence of N-H…S hydrogen bonding contacts.

Sodium tetraphenylimidodiphosphinochalcogenide salts Na[(Ph2P(X)NP(X)Ph2)] (X = S, Se), react with 15-crown-5 ether to give two complexes [Na(15C5)][(Ph2P(X)NP(X)Ph2)] (X = S, Se), 1 and 2 respectively. The crystal and molecular structures of the resulting compounds were determined by X-ray diffractometry. The compounds are isostructural showing sodium–sulfur and sodium–selenium interactions, respectively, forming discrete inorganic (carbon free) chelate rings. These are different from the complex from the oxygen homolog which is an aggregated poly-ion, containing sodium ions with different coordination environments.

Four new stibocanes substituted with cyclic dithiophosphate ligands O(CH2CH2S)2SbS2P(OCH2)2CEt2 (1), O(CH2CH2S)2SbS2P(OCH2)2C(Me)Pr (2), S(CH2CH2S)2SbS2P(OCH2)2CEt2 (3) and S(CH2CH2S)2SbS2P(OCH2)2C(Me)Pr (4) were prepared from the corresponding chloro oxa- and thia-stibocanes and the sodium salt of the dithiophosphoric acids 5,5-diethyl-(2-mercapto-2-thiono-1,3,2-dioxaphosphinane) and 5-methyl-5-propyl-(2-mercapto-2-thiono-1,3,2-dioxaphosphinane) in ethanol. The compounds obtained were characterized by IR, EI-MS and multinuclear NMR (1H, 13C, 31P) spectroscopies. The single-crystal structures of 1 and 2 were determined which show the presence of three types of secondary bonding: i.e. strong Sb- - -O transannular interactions of 2.607(4) and 2.600(4) A, respectively, anisobidentate coordination of the ligand (exocyclic chelation) average Sb- - -S distance 3.355 A and intermolecular interactions that lead to supramolecular associations. The coordination geometry around antimony atom in both 1 and 2 can be described as Ψ tricapped trigonal bipyramidal AB4CD2E. The eight membered ring presents a boat-chair conformation in both compounds and the 1,3,2-dioxaphosphinane ring has the chair conformation, with the stibocane in the axial position.

Thirteen new stannacyclododecane dithiocarbamate complexes have been prepared by reacting 12-chloro-12-n-butyl-1,11-dioxa-4,8-dithia-12-stannacyclododecane (1) and 12-chloro-12-n-butyl-1,4,8,11-tetrathia-12-stannacyclododecane (2) with pyrrolidine-, morpholine-, thiomorpholine-, piperidine-, piperazinebis-, and 3-pyrroline-carbodithioates, respectively, as well as with diethyl-dithiocarbamate. All complexes were characterized by elemental analyses, IR, EI-MS, and NMR (1H, 13C, and 119Sn) studies. The spectroscopic data suggest the replacement of the chlorides by the corresponding dithiocarbamates with monodentate coordination, leading to six-coordinate tin atoms in all the cases.

Eleven mixed-ligand organotellurium(IV) compounds of composition R2Te(dtc)(dtp) have been prepared employing two different dithiocarbamate (dtc) and dithiophosphate (dtp) ligands: 1, R2 = C4H8, dtc = S2CNEt2, dtp = S2P(OCH2)2CEt2; 2, R2 = C8H8, dtc = S2CNEt2, dtp = S2P(OCH2)2CEt2; 3, R2 = C4H8O, dtc = S2CNEt2, dtp = S2P(OCH2)2CEt2; 4, R2 = C5H10, dtc = S2CNEt2, dtp = S2P(OCH2)2CEt2; 5, R2 = C4H8, dtc = S2CN(CH2)4, dtp = S2P(OCH2)2CEt2; 6, R2 = C8H8, dtc = S2CN(CH2)4, dtp = S2P(OCH2)2CEt2; 7, R2 = C4H8O, dtc = S2CN(CH2)4, dtp = S2P(OCH2)2CEt2; 8, R2 = C5H10, dtc = S2CN(CH2)4, dtp = S2P(OCH2)2CEt2; 9, R2 = C4H8, dtc = S2CN(CH2)4, dtp = S2P(OCH2)2CMenPr; 10, R2 = C8H8, dtc = S2CN(CH2)4, dtp = S2P(OCH2)2CMenPr; 11, R2 = C4H8O, dtc = S2CN(CH2)4, dtp = S2P(OCH2)2CMenPr. 1–11 were characterized by mass spectrometry, IR spectroscopy and multinuclear NMR (1H, 13C, 31P, 125Te) spectroscopy. The molecular structures of 2, 4 and 6, of which 2 crystallized in form of two different polymorphs (2a and 2b), were analyzed by single-crystal X-ray diffraction analysis. This analysis showed that the coordination mode of both ligand types is anisobidentate. When considering only covalent Te–C and Te–S bonds, the coordination geometry of the tellurium atoms is distorted Ψ-trigonal-bipyramidal, since the lone pair is stereochemically active and occupies an equatorial position together with the carbon atoms of the tellurocycles. If secondary Te⋯S interactions are considered also, the coordination sphere around tellurium is best described as bicapped Ψ-trigonal-bipyramidal for the complexes with two intramolecular Te⋯S secondary bonds and monomeric molecular structures, and pentagonal-bipyramidal for the complexes in which neighboring molecules in the crystal lattice are linked through additional weak intermolecular Te⋯S secondary bonds to form dimeric supramolecular aggregates.

Six novel monosubstituted dithiocarbamate compounds containing organotellurium(IV) heterocycles, C4H8OTeI[S2CN(CH2CH3)2] (1), C5H10TeI[S2CN(CH2CH3)2] (2), C4H8TeI[S2CN(CH2CH2)2] (3), C8H8TeI[S2CN(CH2CH2)2] (4), C4H8OTeI[S2CN(CH2CH2)2] (5) and C5H10TeI[S2CN(CH2CH2)2] (6) were synthesized. The compounds were characterized by common spectroscopic methods; IR, EI-MS and multinuclear NMR (1H, 13C and 125Te). The structure of compounds 2, 3, 5 and 6 was uniequivocally established by single-crystal X-ray diffraction studies. Compounds 3, 4 and 5 exhibit dimeric arrangements achieved through secondary bonding (Te···S) and in the case of 2, an additional Te···S interaction resulted in the formation of a self-assembled chain. Furthermore, the geometrical arrangement displayed in the tellurium atoms of all the compounds corresponds to a distorted octahedron while the coordination mode for the dithiocarbamate ligands is considered anisobidentate in all cases.

One dinuclear chlorodiphenyltin (IV) dithiocarbamate complex (1) and four mononuclear complexes of general formula Ph2Sn(S2CNR)Cl (2, 3, 5, and 6) have been synthesized and characterized both in solidstate and solution. X-ray structures for complexes 1, 3 and 6 demonstrated a five-coordination geometry around of tin atoms, in which dithiocarbamate ligand chelates asymmetrically the metal center. As shown by 119 Sn NMR spectroscopy, five-coordination geometry observed in the solid-state remains in solution. The stability of these chlorodiphenyltin(IV) dithiocarbamate complexes in the presence of biologically relevant anions such as acetate, dicarboxylates of general formula � OOC-(CH2)n-COO � (n = 2–8), dihydrogenphosphate, hydrogensulfate, and halides has been examined in acetonitrile solutions. For all of these organotin(IV) complexes the displacement of the coordinated ligands (i.e., chloride and dithiocarbamate) from the organotin(IV) moiety occurred in the presence of monoanions like acetate, dihydrogenphosphate, hydrogensulfate and fluoride. A stepwise mechanism for ligand exchange is proposed based on UV–Vis, 1

The present study examines the feasibility of producing hydrogen by dark fermentation using unsterilised cheese whey in a UASB reactor. A lab-scale UASB reactor was operated for more than 250 days and unsterilised whey was used as the feed. The evolution of the microbial community was studied during reactor operation using molecular biology tools (T-RFLP, 16S rRNA cloning library and FISH) and conventional microbiological techniques. The results showed that hydrogen can be produced but in low amounts. For the highest loading rate tested (20 gCOD/L.d), hydrogen production was 122 mL H 2 /L.d. Maintenance of low pH (mean = 5) was insufficient to control methanogenesis; methane was produced concomitantly with hydrogen, suggesting that the methanogenic biomass adapted to the low pH conditions. Increasing the loading rate to values of 2.5 gCOD/gVSS.d favoured hydrogen production in the reactor. Microbiological studies showed the prevalence of fermentative organisms from the genera Megasphaera , Anaerotruncus , Pectinatus and Lactobacillus , which may be responsible for hydrogen production. However, the persistence of methanogenesis and the presence of other fermenters, not clearly recognised as hydrogen producers indicates that competition for the substrate may explain the low hydrogen production.

Five new hetero-organotellurium (IV) dithiocarbamates O[Si(CH 3 ) 2 CH 2 ] 2 TeIS 2 CN(CH 2 CH 2 ) 2 ( 1 ), O[Si(CH 3 ) 2 CH 2 ] 2 TeIS 2 CN(CH 2 CH) 2 ( 2 ), O[Si(CH 3 ) 2 CH 2 ] 2 TeIS 2 CN(CH 2 CH 2 ) 2 O ( 3 ), O[Si(CH 3 ) 2 CH 2 ] 2 -TeIS 2 CN(CH 2 CH 2 ) 2 S ( 4 ) and O[Si(CH 3 ) 2 CH 2 ] 2 TeIS 2 CN(CH 2 CH 2 ) 2 CH 2 ( 5 ) were prepared from the 2,2,6,6-tetramethyl-1-oxa-4,4-diiodo-4-tellura-2,6-disilacyclohexane and the corresponding dithiocarbamate (dtc) sodium salts in ethanol. The compounds were characterized by means of Elemental Analyses, FAB MS, IR, 1 H, 13 C, 125 Te NMR spectroscopy. The crystal structures of 1 , 3 and 4 were determined. Dithiocarbamate ligands display an anisobidentate chelating coordination mode on interacting with the tellurium center in all compounds. The Te(IV) immediate environment can be described as that of a sawhorse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position in a distorted trigonal bipyramid. The two methylene groups occupy the other equatorial positions with a sulfur atom of the dithiocarbamate group and the iodine atom occupying the axial positions. The solid state structures of 3 and 4 exhibit important intermolecular interaction Te⋯S(2B). This interaction results in the formation of a dimer, which is better described as a distorted octahedron with an apparently inactive lone pair.

The synthesis of the four disubstituted organotellurium (IV) compounds, C4H8Te[S2P(OCH2)2CEt2]2 (1), C4H8Te[S2P(OCH2)2CMe-nPr]2 (2), C4H8OTe[S2P(OCH2)2CEt2]2 (3), C4H8OTe[S2P(OCH2)2CMe- nPr]2 (4), and one monosubstituted compound C4H8OTe(I)[S2P(OCH2)2CMe-nPr] (5), was achieved. All compounds were characterized by IR, EI, MS, and multinuclear NMR (1H, 13C, 31P, 125Te). In addition, the molecular structures of 2 and 3 were determined by X-ray analyses. Both structures are monomeric and the tellurium atom is bonded to two carbon atoms and to one sulfur atom of each one of the two anisobidentate dithiophosphate ligands. In 2, the geometry around Te(IV) is as that of a sawhorse structure in which the lone pair is apparently stereochemically active and occupying an equatorial position in a ψ-trigonal bipyramid. However, when the second sulfur atom of the dithiophosphate ligand is included in the coordination sphere, the environment about tellurium in the compound 2 can be described as bicapped ψ-trigonal bipyramid. Whereas in 3 it is a distorted octahedral structure in which the lone pair is stereochemically inactive.

Organotin(IV) compounds of the potentially ambidentate O-cholesteryl-O-phenyl phosphorothioate ligand formulated as Me3SnOSPR′R′′ (1), Ph3SnOSPR′R′′ (2), O(CH2CH2S)2Sn(n-Bu)OSPR′R′′ (3), S(CH2CH2S)2Sn(n-Bu)OSPR′R′′ (4), (R′=O-Ph; R′′=O-cholesteryl) were obtained and characterized by elemental analyses, IR, MS and multinuclear NMR (1H, 13C, 31P and 119Sn) spectroscopy. The spectroscopic data are consistent with bonding of the phosphorothioate ligand through both sulfur and oxygen atoms to the Sn(IV) center.

The preparation and conformational study of two stannocanes, 5-n-butyl-5-(5′,5′-diethyl-2′-thioxo-1′,3′,2′-dioxaphosphorinane-2′-thiolate)-1-oxa-4,6-dithia-5-stannocane, O(CH2CH2S)2SnnBu[S2P(OCH2CEt2CH2O)] (1) and 2-n-butyl-5-(5′5′-diethyl-2′-thioxo-1′,3′,2′-dioxaphosphorinane-2-thiolate)-1,3,6-trithia-2-stannocane S(CH2CH2S)2SnnBu[S2P(OCH2CEt2CH2O)] (2) is reported. These compounds were prepared from the corresponding chloro-oxa and -thia-stannocanes and the sodium salt of dithiophosphoric acid (2-mercapto-2-thiono-1,3,2-dioxaphosphorinane) in ethanol. Compounds 1 and 2 were characterized by IR, EI-MS and multinuclear NMR (1H, 13C, 31P). The molecular structures were determined by X-ray analyses. The eight-membered ring in both compounds has a boat–chair conformation with a 1,5 transannular Sn⋯O (2.468 A), Sn⋯S (2.94 A) interaction. The 1,3,2-dioxaphosphorinane ring in 1 and 2 present a chair conformation with the stannocane in the axial position, in accordance with the anomeric effect. The coordination of the Sn-atoms is trigonal-bipyramidal in 1 and intermediate between trigonal-bipyramidal and a bicapped tetrahedral arrangement in 2.

A new anionic phosphorothioate ligand that incorporates the bioactive cholesteryl group was obtained (2), Na(RR′P(S)O; R, O-phenyl; R′, O-cholesteryl) from the phenylphosphoramidate (1) and NaH in dioxane. In order to test the coordination ability of 2, two organoarsenic derivatives were prepared, O(C6H4)2AsS(O)PRR′ (3) and S(C6H4)2AsS(O)PRR′ (4) by reacting 2 with 10-chlorophenoxarsine or 10-chlorophenothiarsine. Compounds 2, 3, and 4 were characterized by elemental microanalysis, IR, multi-element NMR (1H, 13C, and 31P), and mass spectrometry. The spectroscopic data suggest that the ligand is bonded to the arsenic only through the sulfur donor atom in both organoarsenic derivatives. © 2000 John Wiley & Sons, Inc. Heteroatom Chem 11:6–10, 2000

5-Chloro-5- n -butyl-1-oxa-4,6-dithia-5-stannocane ( 1 ) and 2-chloro-2- n -butyl-1,3,6-trithia-2-stannocane ( 2 ) have been prepared by reacting n -butyltin trichloride with 2-mercaptoethyl ether and 2-mercaptoethyl sulphide, respectively. Complexes 1 and 2 were characterised by elemental analyses, IR, EI MS, and multinuclear NMR ( 1 H, 13 C, 119 Sn). The molecular structures of 1 and 2 were determined by X-ray analyses. The eight-membered rings in both compounds are in the boat–chair conformation with a 1,5 transannular Sn⋯O (2.409(7) A) or Sn⋯S (2.7855(16) A) interaction. The coordination around the Sn atoms can be described as trigonal bipyramidal with Cl and X in the apical positions.

The physical and spectroscopic data of (R)-2-[N-(1-phenylethyl)amino]-1-cyclopentenedithiocarboxylic acid are reviewed and the synthesis of (R)-di-[2-(N-(1-phenylethyl)amino]-1-cyclopentenedithiocarboxylic acid disulfide is described. The product resulting from the conjugate addition of the dithioacid to 2(5H)-furanone is also characterised.

The anion [N(SePPh2)(2)](-) forms stable complexes with cations M(II, III); [M(II) = Sn, Se, Cd, Hg; M(III) = In, Sb, Bi], they exhibit a large diversity of structural arrangements around the metal centre. Tin(II) complex crystallizes dimorphically, as square planar and distorted tetragonal pyramidal, Pb(II) is also distorted tetragonal pyramidal, Cd(II) and Hg(II) are tetrahedral, but the Se(II) is square planar. The coordination geometry in the M(III) complexes can be described as a distorted octahedron. The structural situation around the Sb(III) and Bi(III) suggests a stereochemically non-active electron lone pair.

12-Chloro-12-n-butyl-1,11-dioxa-4,8- dithia-12-stannacyclododecane (3a) and 12-chloro- 12-n-butyl-1,4,8,11-tetrathia-12-stannacyclododecane (3b) have been prepared by reacting n-butyltin trichloride with 1,11-dioxa-4,8-dithiaundecane and 1,4,8,11-tetrathiaundecane, respectively. Complexes 3a,b were characterized by elemental analyses, IR, electron impact mass spectrometry, and multinuclear NMR (1H, 13C, and 119Sn). The spectroscopic data are consistent with bonding of the ligands through both sulfur and oxygen atoms in 3a and through all sulfur atoms in 3b to the Sn(IV) center. We suggest hexacoordination around the Sn atoms. © 2004 Wiley Periodicals, Inc. Heteroatom Chem 15:451–453, 2004; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20040

1-oxa-4,6-dithia-5-arsocane morpholinyldithiocarbamate (1) and 1,3,6-trithia-2-arsocane 2-diethyldithiocarbamate (2) have been prepared by reacting the corresponding sodium dithiocarbamates with 1-oxa-4,6-dithia-5-arsocane or 1,3,6-trithia-2-arsocane. (1) and (2) were characterized by elemental analyses, IR, MS, 1H and 13CNMR. The X-ray single-crystal molecular structures of (1) [monoclinic, a = 9.931(5), b = 18.253(5), c = 8.076(3) A; β = 92.56(2)°; V = 1462.5(7) A3; space group P21/c; Z = 4; R = 4.33%] and (2) [monoclinic, a = 7.830(2), b = 10.465(2), c = 19.025(6) A; β = 95.82(2)°; V = 1550.8(10) A3; space group P21/c; Z = 4; R = 3.41%], show that the compounds are monomeric and contain an asymetric monometallic biconnective dithiocarbamate ligand with a large distortion in the geometry around the As and a weak heterocyclic arsocane transannular secondary interaction.

Phenoxarsin-10-yl derivatives of 2-amino-cyclopent-1-ene-1-carbodithioic acid, (ACDA), and its N-alkyl derivatives O(C 6 H 4 ) 2 AsS 2 C-C 5 H 6 -NHR-2 (R=H, CH 2 CH 3 , CH 2 C 6 H 11 ), have been prepared by reacting O(C 6 H 4 ) 2 AsCl with the corresponding ACDA 1,1-dithioic acid. The compounds were obtained by stirring stoichiometric amounts of the reagents in ethanol, over 24 h, at room temperature. The scale of the preparations were in the order of 2 mmol and the yields of the compounds ca 75%. The reactions were carried out in absolute ethanol. The compounds were characterized by IR, mass and NMR ( 1 H, 13 C) spectroscopy. The molecular structure of O(C 6 H 4 ) 2 AsS 2 C-C 5 H 6 -NH 2 -2 was determined using X-ray diffractometry, achieving and R-value of 6.3%; this compound is monomeric and contains an asymmetric monometallic biconnective 1,1-dithiolato ligand [As-S(1) 2.272(2)A, As...S(2) 3.125(2)A]. An intramolecular hydrogen bond is established between one hydrogen atom of the NH 2 group and the sulfur [S(2)] atom involved in the secondary interaction to arsenic. The dihedral angle (150.3(3) o ) of the phenoxarsine moiety is practically unaffected by substitution of chlorine on arsenic by the carbodithioato ligand

O-Cholesteryl-O-phenyl-N-phenylphosphoramidate (1) and four organotin (lV) derivatives of the ambidentate O-cholesteryl-O -phenyl phosphorothioate ligand formulated as Me3 SnOSPR’R”(2), Ph3 SnOSPR’R”(3), O(CH2CH2S)2 Sn(n-Bu)OSPR’R”(4), S(CH2CH2S)2 Sn(n-Bu)OSPR’R”(5), (R’ = O-phenyl; R”= O-cholesteryl) were subjected to cytotoxicity screening against KB (nasopharingel carcinoma), OVCAR-5 (ovarium carcinoma) and SQC-1 UlSO (squamous cell cervix carcinoma) cell cultures. The results of the bioassay showed that these compounds possess potent antitumor activities against the studied human carcinoma cell lines.

Three 1,1-dithioacids containing an additional functional group, 2-pyrrolidone-1-carbodithioic acid, 2-hydroxycyclopentene-1-carbodithioic acid, and 2-pyrrolidone-1,3-bis(carbodithioic) acid, were reacted with the Group 15 heterocycles 2-chloro-1,3-dithia-2-arsa- and stiba-cyclopentanes (CIMS2C2H4; M = As, Sb). The dithiocomplexes obtained were characterized by spectroscopic methods and elemental analyses. The X-ray structure determination of the 2-pyrrolidonedithiocarbamate of 1,3-dithia-arsacyclopentane shows a monodentate behavior of the dithiocarbamate entity and the absence of participation of the carbonyl oxygen in the coordination.

A series of diheterocyclic dithiocarbamate complexes of the typeRNCS2MS2C2H4, whereR=pyrrolidyl, 3-pyrrolyl, 4-morpholyl, 3-methlpiperidyl andM=As or Sb were obtained and characterized by IR,1H, and13C-NMR, mass spectroscopy and elemental analyses. The X-ray crystal structure determination of the 4-morpholinecarbodithioate of 1,3-dithia-2-arsa-cyclopentane shows a monodentate behaviour of theRNCS2 entity.

Folhas de Ateleia glazioviana Baill., dessecadas em estufa a 100ºC por 16 a 20 horas, foram administradas a sete vacas sem raça definida. Duas vacas receberam 9 g/kg da planta seca aos 4 meses de gestação em dose única. Três vacas no 8º mês de gestação, receberam doses diárias de 1 a 2 g/kg da planta seca, perfazendo totais de 10, 21 e 28 g/kg. Duas outras, também no 8º mês de gestação, receberam a planta seca em dose única 15,5 e 18 g/kg. Duas vacas, no 4º mês de gestação, receberam 35 g/kg da planta verde, em dose única. A vaca que recebeu 21 g/kg da planta seca foi a única a apresentar sinais clínicos de intoxicação e o bezerro nasceu morto. As demais vacas não apresentaram sinais clínicos. Os bezerros das vacas que receberam a planta seca nas doses de 9, 15,5 e 28 g/kg, apresentaram sinais clínicos de debilidade, dificuldade de manter-se em pé e mamar e foram sacrificados. Macroscopicamente, no bezerro que nasceu morto, foram observados áreas esbranquiçadas e espessamento da parede do ventrículo cardíaco direito. Os demais bezerros que nasceram fracos foram sacrificados e não apresentaram lesões macroscópicas, com exceção do bezerro da vaca que recebeu a planta seca, na dose total de 28g/kg, que apresentou, também, espessamento da parede do ventrículo direito. As alterações histológicas do bezerro que nasceu morto e dos que foram sacrificados por apresentarem sinais clínicos de debilidade caracterizaram-se por tumefação e vacuolização de feixes de fibras musculares e proliferação de tecido fibroso entre os cardiomiócitos. Essas lesões são semelhantes às observadas em casos espontâneos da intoxicação. Os cardiomiócitos mostraram reação PAS positiva no sarcoplasma, mais acentuada do que no animal controle. No bezerro que nasceu morto foi observado, também, espongiose discreta na substância branca do cerebelo, colículos rostrais e tálamo. O estudo ultra-estrutural do coração revelou fibras cardíacas com acúmulos de gliocogênio, situados entre feixes de miofibrilas, os quais mostravam perda de miofilamentos e desaparecimento de sarcômeros inteiros. No animal controle a presença de glicogênio foi substancialmente menor do que nos animais intoxicados. Leaves of Ateleia glaziovian Baill., dried in a 100º C oven for 16-20 hours, were given to seven crossbred cows, always as bolus. Two of them received 9 g/kg at 4 months of pregnancy. Three cows in the 8th month of pregnancy received daily doses of 1-2 g/kg of the leaves, until a total amount of 10, 21 and 28 g/kg/bw was reached. Two 8-month-pregnant cows were fed 15.5 and 18 g/kg of the dried leaves. Two 4-month-pregnant cows were fed 35 g/kg of green leaves of A. glazioviana. The cow treated with 21 g/kg of the dry plant material showed clinical signs of poisoning and delivered a stillborn calf. No clinical signs were observed in the other cows. The calves from cows that received 9, 15.5 and 28 g/kg of the dried leaves showed weakness and suckling difficulties, and were killed. Whitish areas and thickening of the right ventricle wall of the heart were observed in the stillborn calf. Thickening of the wall of the right ventricle was also observed in the calf delivered by the cow treated with 28g/kg of dry plant. The other calves had no gross lesions. The histological changes in all necropsied calves were characterized by tumefaction and vacuolization of muscle fibers and proliferation of fibrous tissue, similar as occurred in spontaneous cases of fibrosis of the heart muscle in cattle poisoned by A. glazioviana. PAS stained slides revealed positive granules in the cardiomyocytes more evident than those of the control calf. The stillborn calf had mild spongiosis of the white matter of the cerebellum, thalamus and rostral colliculi. The ultrastructural pathology revealed cardiac fibers with large glycogen storage within myofibril bundles, which showed loss of bundles and disappearance of whole sarcomers. Mild glycogen storage was observed in a control calf.

The molecular structures of two lipophilic polyion aggregates derived from tetraphenyl imidodiphosphinate are described: [Na(crown ether)][MNa(2)[Ph(2)P(O)NP(O)Ph(2)](4)] with crown ether = 15-crown-5 for 1and benzo-15-crown-5 for (M = Na(+) for 1 and Na(H(2)O)(+) for 2).

Sir, The development of melanocytic lesions following treatment with psoralen and ultraviolet A (PUVA therapy) is well documented. The first case of lentigines induced by cosmetic UVA tanning was reported in the 1980s (1), and another three cases have been published since then (2 – 5). We report the case of a woman with systemic lupus erythematosus (SLE) who developed generalized persistent melanocytic lesions while using UVA tanning beds.

Racemic trinuclear diphenyltin(IV) cavitands and capsules have been assembled from diphenyltin(IV) and tris-dithiocarbamate ligands.

The yellow complex [Sn{N(SePPh2)2-Se,Se′}2] is the first example of a true square-planar spiro tin(II) compound; the structure of the distorted tetragonal-pyramidal isomer is also described.

Reaction of [Ni(CH3CO)2]4H2O, H2PdCl4 or H2PtCl6 with HN[P(Se)Ph2]2 in water/acetone gave the title compounds in good yield. The compounds were characterised by IR/Raman, NMR and X-ray crystallography. The square planar metal centres form parts of spiro pseudo-boat rings. The X-ray structures allow comparison of the radii of Pt and Pd atoms.

12 Páginas.-- 6 Tablas.-- 1 Figura, Background-Epidemiological evidence suggests a cardioprotective role of α-linolenic acid (ALA), a plant-derived ω-3 fatty acid. It is unclear whether ALA is beneficial in a background of high marine ω-3 fatty acids (long-chain n-3 polyunsaturated fatty acids) intake. In persons at high cardiovascular risk from Spain, a country in which fish consumption is customarily high, we investigated whether meeting the International Society for the Study of Fatty Acids and Lipids recommendation for dietary ALA (0.7% of total energy) at baseline was related to all-cause and cardiovascular disease mortality. We also examined the effect of meeting the society's recommendation for long-chain n-3 polyunsaturated fatty acids (≥500 mg/day). Methods and Results-We longitudinally evaluated 7202 participants in the PREvención con DIeta MEDiterránea (PREDIMED) trial. Multivariable-adjusted Cox regressionmodels were fitted to estimate hazard ratios. ALA intake correlated towalnut consumption (r=0.94). During a 5.9-y follow-up, 431 deaths occurred (104 cardiovascular disease, 55 coronary heart disease, 32 sudden cardiac death, 25 stroke). The hazard ratios formeeting ALArecommendation (n=1615, 22.4%) were 0.72 (95% CI 0.56-0.92) for all-causemortality and 0.95 (95% CI 0.58-1.57) for fatal cardiovascular disease. The hazard ratios formeeting the recommendation for long-chain n-3 polyunsaturated fatty acids (n=5452, 75.7%) were 0.84 (95% CI 0.67-1.05) for all-causemortality, 0.61 (95% CI 0.39-0.96) for fatal cardiovascular disease, 0.54 (95% CI 0.29-0.99) for fatal coronary heart disease, and 0.49 (95% CI 0.22-1.01) for sudden cardiac death. The highest reduction in all-cause mortality occurred in participants meeting both recommendations (hazard ratio 0.63 [95% CI 0.45-0.87]). Conclusions-In participants without prior cardiovascular disease and high fish consumption, dietary ALA, supplied mainly by walnuts and olive oil, relates inversely to all-cause mortality, whereas protection from cardiac mortality is limited to fish-derived long-chain n-3 polyunsaturated fatty acids., This study was funded in part by Instituto de Salud Carlos III (ISCIII) (Spanish Ministry of Economy) through grants RTIC G03/140, RTIC RD 06/0045, Centro Nacional de Investigaciones Cardiovasculares CNIC 06/2007, ISCIII FIS PS09/01292, the Spanish Ministry of Science and Innovation (MICINN) AGL2010‐22319‐C03‐02 and AGL2009‐13906‐C02‐02, and an unrestricted grant from the California Walnut Commission. Sala‐Vila holds a Miguel Servet I fellowship from the Ministry of Economy and Competitiveness through the ISCIII.

Background There is limited evidence for the benefit of olaparib in platinum-resistant ovarian cancer (PROC) patients with BRCA wild-type tumors. This study investigated whether this combination of a DNA-damaging chemotherapy plus olaparib is effective in PROC regardless BRCA status. Patients and methods Patients with high-grade serous or endometrioid ovarian carcinoma and one previous PROC recurrence were enrolled regardless of BRCA status. Patients with ≤4 previous lines (up to 5 in BRCA-mut) with at least one previous platinum-sensitive relapse were included; primary PROC was allowed only in case of BRCA-mut. Patients initially received six cycles of olaparib 300 mg b.i.d. (biduum) + intravenous pegylated liposomal doxorubicin (PLD) 40 mg/m2 (PLD40) every 28 days, followed by maintenance with olaparib 300 mg b.i.d. until progression or toxicity. The PLD dose was reduced to 30 mg/m2 (PLD30) due to toxicity. The primary endpoint was progression-free survival (PFS) at 6 months (6m-PFS) by RECIST version 1.1. A proportion of 40% 6m-PFS or more was considered of clinical interest. Results From 2017 to 2020, 31 PROC patients were included. BRCA mutations were present in 16%. The median of previous lines was 2 (range 1-5). The overall disease control rate was 77% (partial response rate of 29% and stable disease rate of 48%). After a median follow-up of 10 months, the 6m-PFS and median PFS were 47% and 5.8 months, respectively. Grade ≥3 treatment-related adverse events occurred in 74% of patients, with neutropenia/anemia being the most frequent. With PLD30 serious AEs were less frequent than with PLD40 (21% versus 47%, respectively); moreover, PLD30 was associated with less PLD delays (32% versus 38%) and reductions (16% versus 22%). Conclusions The PLD–olaparib combination has shown significant activity in PROC regardless of BRCA status. PLD at 30 mg/m2 is better tolerated in the combination., Highlights • Olaparib with PLD is effective in PROC. • The combination achieved a 6m-PFS of 46.6%, above the pre-established futility threshold of 40%. • The olaparib–PLD combination reached efficacy independent of BRCA mutation status. • Olaparib 300 mg b.i.d. and PLD 30 mg/m2 were safely administered with a good toxicity profile.