Syntheses and Crystal Structures of Mn(II), Ni(II) and Cu(II) Coordination Compounds Assembled by Maleato and Dimethyl-2,2′-bipyridines

We have reported the synthesis and crystalline molecular and supramolecular structures of three novel complexes of Mn(II), Ni(II) and Cu(II), 1–3, respectively, employing maleato and dimethyl-2,2′-bipyridines as ligands. 1 is a 1D polymer, where the Mn centers are six-coordinated in a distorted octahedral geometry. 2 is a dinuclear complex, generated by supramolecular interactions, where Ni ions are six-coordinated in a distorted octahedral geometry. 3 is a dinuclear complex with five-coordinated Cu ions having a slightly-distorted square pyramidal geometry. Furthermore, solid-state assemblies on the structures of 1–3 generate supramolecular frameworks, mainly through hydrogen bonding: 2D for complexes 1 and 2, and 3D for complex 3. Thus, the versatility in the different coordination modes of maleato ligand: chelate bidentate and bridging- monodentate for polymer 1, monodentate for complex 2 and chelate bidentate for complex 3; has been evidenced by generating divergent coordination compounds of three different transition metals using facile self-assembly reactionsThree complexes: {[Mn(H2O)(mal)(5dmb)·H2O}n] (1); [ Ni2(H2O)6(mal)2(4dmb)2]·3H2O (2); [ Cu2(mal)2(4dmb)2]·3H2O (3); where mal = maleato, 4dmb = 4,4′-dimethyl-2,2′-bipyridine, and 5dmb = 5,5′-dimethyl-2,2′-bipyridine; have been synthesized, using self-assembly solution reactions at ambient conditions. Crystallographic studies show that 1 crystallizes in an orthorhombic system, space group Pna21, with a = 17.4067(4) Å, b = 11.9672(2) Å, c = 8.2075(2) Å; V = 1709.70(6) Å3. Complex 2 has a monoclinic system, space group C2/c, with a = 21.206(8) Å, b = 7.523(3) Å, c = 25.399(10) Å; β = 109.755(8)°; V = 3813(2) Å3. Complex 3 crystallizes in a monoclinic system, space group C2/c, with a = 14.6976(12) Å, b = 11.3849(10) Å, c = 22.1638(18) Å; β = 101.2998(17)°; V = 3636.8(5) Å3. Complex 1 is a one-dimensional (1D) polymer, where the Mn centers are six-coordinated in a distorted octahedral geometry. 2 is a dinuclear complex, generated by supramolecular interactions, where Ni ions are six-coordinated in a distorted octahedral geometry. 3 is a dinuclear complex with five-coordinated Cu ions having a distorted square pyramidal geometry. All three complexes exhibit hydrogen bonding interactions, which generate 2D supramolecular structures in 1 and 2, whereas in complex 3 a 3D supramolecular array is formed. These novel complexes prove that the self-assembly of a dicarboxylate ligand (mal) with three different first-row transition metals, can afford coordination compounds with diverse structural characteristics and dimensionality, which can be attributed to the different ligand coordination modes and the coordination properties of the employed metals

Genome-wide distribution of histone trimethylation reveals a global impact of bisphenol A on telomeric binding proteins and histone acetyltransferase factors: a pilot study with human and in vitro data

International audienceObjective To assess the genetic and epigenetic effects promoted by Bisphenol A (BPA) exposure in adolescent males from the Spanish INMA-Granada birth cohort, and in human cells. Methods DNA methylation was analysed using MEDIP. Repeat number variation in genomic DNA was evaluated, along with the analysis of H3K4me3 by using chromatin immunoprecipitation followed by high-throughput sequencing (ChIP-seq). Analyses were performed with material extracted from whole blood of the adolescents, complemented by in vitro assessments of human (HeLa) cells exposed to 10 nM BPA, specifically, immunofluorescence evaluation of protein levels, gene expression analysis and ChIP‒qPCR analysis. Results Adolescents in the high urinary BPA levels group presented a higher level of Satellite A (SATA) repetitive region copy numbers compared to those in the low BPA group and a tendency towards increase in telomere length. We also observed decreased DNA methylation at the promoters of the imprinted genes H19, KCNQ1, and IGF2 ; at LINE1 retroelements; and at the ARID2, EGFR and ESRRA and TERT genes. Genome-wide sequencing revealed increased H3K4me3 occupancy at the promoters of genes encoding histone acetyltransferases, telomeric DNA binding factors and DNA repair genes. Results were supported in HeLa cells exposed to 10 nM BPA in vitro. In accordance with the data obtained in blood samples, we observed higher H3K4me3 occupancy and lower DNA methylation at some specific targets in HeLa cells. In exposed cells, changes in the expression of genes encoding DNA repair factors ( ATM, ARID2, TRP53 ) were observed, and increased expression of several genes encoding telomeric DNA binding factors ( SMG7, TERT, TEN1, UPF1, ZBTB48 ) were also found. Furthermore, an increase in ESR1/ERa was observed in the nuclei of HeLa cells along with increased binding of ESR1 to KAT5, KMT2E and TERF2IP promoters and decreased ESR1 binding at the RARA promoter. The DNA damage marker p53/TP53 was also increased. Conclusion In this pilot study, genome-wide analysis of histone trimethylation in adolescent males exposed to BPA revealed a global impact on the expression of genes encoding telomeric binding proteins and histone acetyltransferase factors with similar results in HeLa cells. Nevertheless, larger studies should confirm our findings

International Nosocomial Infection Control Consortiu (INICC) report, data summary of 43 countries for 2007-2012. Device-associated module

We report the results of an International Nosocomial Infection Control Consortium (INICC) surveillance study from January 2007-December 2012 in 503 intensive care units (ICUs) in Latin America, Asia, Africa, and Europe. During the 6-year study using the Centers for Disease Control and Prevention's (CDC) U.S. National Healthcare Safety Network (NHSN) definitions for device-associated health care–associated infection (DA-HAI), we collected prospective data from 605,310 patients hospitalized in the INICC's ICUs for an aggregate of 3,338,396 days. Although device utilization in the INICC's ICUs was similar to that reported from ICUs in the U.S. in the CDC's NHSN, rates of device-associated nosocomial infection were higher in the ICUs of the INICC hospitals: the pooled rate of central line–associated bloodstream infection in the INICC's ICUs, 4.9 per 1,000 central line days, is nearly 5-fold higher than the 0.9 per 1,000 central line days reported from comparable U.S. ICUs. The overall rate of ventilator-associated pneumonia was also higher (16.8 vs 1.1 per 1,000 ventilator days) as was the rate of catheter-associated urinary tract infection (5.5 vs 1.3 per 1,000 catheter days). Frequencies of resistance of Pseudomonas isolates to amikacin (42.8% vs 10%) and imipenem (42.4% vs 26.1%) and Klebsiella pneumoniae isolates to ceftazidime (71.2% vs 28.8%) and imipenem (19.6% vs 12.8%) were also higher in the INICC's ICUs compared with the ICUs of the CDC's NHSN