Luminescent Thermochromism of 2D Coordination Polymers Based on Copper(I) Halides with 4-Hydroxythiophenol

This is the peer-reviewed version of the following article: Troyano, J., Perles, J., Amo‐Ochoa, P., Martínez, J. I., Concepción Gimeno, M., Fernández‐Moreira, V., ... & Delgado, S. (2016). Luminescent Thermochromism of 2D Coordination Polymers Based on Copper (I) Halides with 4‐Hydroxythiophenol. Chemistry–A European Journal, 22(50), 18027-18035., which has been published in final form at https://doi.org/10.1002/chem.201603675. This article may be used for non-commercial purposes in accordance with Wiley-VCH Terms and Conditions for Self-ArchivingSolvothermal reactions between copper(I) halides and 4-mercaptophenol give rise to the formation of three coordination polymers with general formula [Cu3X(HT)2]n(X=Cl, 1; Br, 2; and I, 3). The structures of these coordination polymers have been determined by X-ray diffraction at both room- and low temperature (110 K), showing a general shortening in Cu−S, Cu−X and Cu−Cu bond lengths at low temperatures. 1 and 2 are isostructural, consisting of layers in which the halogen ligands act as μ3-bridges joining two Cu1 and one Cu2 atoms whereas in 3 the iodine ligands is as μ4-mode but the layers are quasi-isostructural with 1 or 2. These compounds show a reversible thermochromic luminescence, with strong orange emission for 1 and 2, but weaker for 3 at room temperature, whereas upon cooling at 77 K 1 and 2 show stronger yellow emission, and 3 displays stronger green emission. DFT calculations have been used to rationalize these observations. These results suggest a high potential for this novel and promising stimuli-responsive materialsThis work was supported by MICINN (MAT2013-46753-C2-1-P). JIM acknowledges funding from the ERC-Synergy Program (Grant ERC-2013-SYG-610256 NANOCOSMOS) and computing resources from CTI-CSIC

Effectiveness of an intervention for improving drug prescription in primary care patients with multimorbidity and polypharmacy:Study protocol of a cluster randomized clinical trial (Multi-PAP project)

This study was funded by the Fondo de Investigaciones Sanitarias ISCIII (Grant Numbers PI15/00276, PI15/00572, PI15/00996), REDISSEC (Project Numbers RD12/0001/0012, RD16/0001/0005), and the European Regional Development Fund ("A way to build Europe").Background: Multimorbidity is associated with negative effects both on people's health and on healthcare systems. A key problem linked to multimorbidity is polypharmacy, which in turn is associated with increased risk of partly preventable adverse effects, including mortality. The Ariadne principles describe a model of care based on a thorough assessment of diseases, treatments (and potential interactions), clinical status, context and preferences of patients with multimorbidity, with the aim of prioritizing and sharing realistic treatment goals that guide an individualized management. The aim of this study is to evaluate the effectiveness of a complex intervention that implements the Ariadne principles in a population of young-old patients with multimorbidity and polypharmacy. The intervention seeks to improve the appropriateness of prescribing in primary care (PC), as measured by the medication appropriateness index (MAI) score at 6 and 12months, as compared with usual care. Methods/Design: Design:pragmatic cluster randomized clinical trial. Unit of randomization: family physician (FP). Unit of analysis: patient. Scope: PC health centres in three autonomous communities: Aragon, Madrid, and Andalusia (Spain). Population: patients aged 65-74years with multimorbidity (≥3 chronic diseases) and polypharmacy (≥5 drugs prescribed in ≥3months). Sample size: n=400 (200 per study arm). Intervention: complex intervention based on the implementation of the Ariadne principles with two components: (1) FP training and (2) FP-patient interview. Outcomes: MAI score, health services use, quality of life (Euroqol 5D-5L), pharmacotherapy and adherence to treatment (Morisky-Green, Haynes-Sackett), and clinical and socio-demographic variables. Statistical analysis: primary outcome is the difference in MAI score between T0 and T1 and corresponding 95% confidence interval. Adjustment for confounding factors will be performed by multilevel analysis. All analyses will be carried out in accordance with the intention-to-treat principle. Discussion: It is essential to provide evidence concerning interventions on PC patients with polypharmacy and multimorbidity, conducted in the context of routine clinical practice, and involving young-old patients with significant potential for preventing negative health outcomes. Trial registration: Clinicaltrials.gov, NCT02866799Publisher PDFPeer reviewe

Silver(I) and copper(I) complexes with ferrocenyl ligands bearing imidazole or pyridyl substituents

The reactions between five ferrocenyl derivatives containing both a CO and at least an imidazole or pyridine nitrogen atom and AgPF6, AgOTf, or [Cu(NCCH3)4]PF6 precursors were studied. The ligand {[bis(2-pyridyl)amino]carbonyl}ferrocene (L3), derived from (2-pyridyl)amine, favored tetrahedral coordination of Ag+ (with two ligands) and of Cu+ (with two acetonitrile ligands left from the precursor). In all the other ligands, both metal centers coordinated linearly to two ligands, preferring the imidazole or pyridinic nitrogen to other nitrogen atoms (amine) or oxygen donors. When the counter anions were triflate, the crystal structure showed a dimerization of the complex, with the ferrocenyl moieties occupying cis positions, by means of a weak Ag⋯Ag interaction. This was shown experimentally in the crystal structure of complex [Ag(L1)2]OTf (L1 = ferrocenylimidazole) and in the presence of peaks corresponding to {Ag2(L2)3(OTf)}+ and {Ag2(L2)4(OTf)}+ in the mass spectra of [Ag(L2)2]OTf (L2 = ferrocenyl benzimidazole). In all complexes containing PF6, there was no evidence for dimerization. Indeed, in the crystal structure of [Ag(L2)2]PF6, the ferrocenyl moieties occupy trans positions and the metal centers are far from each other. DFT calculations showed that the energy of the cis and trans conformers is practically the same and the balance of crystal packing forces leads to dimerization when triflate is present.S.Q. thanks FCT for a postdoctoral fellowship (SFRH/BPD/11463/ 2002) and M.J.C. thanks FCT, POCI, and FEDER (project PPCDT/QUI/ 58925/2004). M.C.G. and A.L. thank the Dirección General de Investigación Científica y Técnica (CTQ2007-67273-C02-01) for financial support.Peer Reviewe

Assessment of Analysis of Urinary Pneumococcal Antigen by Immunochromatography for Etiologic Diagnosis of Community-Acquired Pneumonia in Adults

The limitations of conventional microbiologic methods (CMM) for etiologic diagnosis of community pneumococcal pneumonia have made faster diagnostic techniques necessary. Our aim was to evaluate the usefulness of the immunochromatography (ICT) technique for detecting urinary Streptococcus pneumoniae antigen in the etiologic diagnosis of community-acquired pneumonias (CAP). This was a prospective study on in-patients with CAP in a tertiary hospital conducted from October 2000 to March 2004. Apart from using CMM to reach an etiologic diagnosis, we determined pneumococcal antigen in concentrated urine by ICT. We also determined the urinary pneumococcal antigen (UPA) content in patients from two control groups to calculate the specificity of the technique. One group was comprised of in-patients diagnosed with chronic obstructive pulmonary disease (COPD) or asthma, with respiratory infection, and without pneumonia; the other group included fractures. We studied 959 pneumonia patients and determined UPA content in 911 (95%) of them. We diagnosed the etiology of 253 cases (28%) using CMM; S. pneumoniae was the most common etiologic agent (57 cases). ICT analysis was positive for 279 patients (31%). Using this technique, the percentage of diagnoses of pneumococcal pneumonias increased by 26%, while the overall etiologic diagnosis increased from 28 to 49%. The technique sensitivity was 81%; the specificity oscillated between 80% in CAP with nonpneumococcal etiology and 99% for patients with fractures without infections. Determination of UPA is a rapid, simple analysis with good sensitivity and specificity, which increased the percentage of etiologic diagnoses. Positive UPA may persist in COPD patients with probable pneumococcal colonization or recent pneumococcal infections

Synthesis and ligand properties towards gold and silver of the ferrocenylamidobenzimidazole ligand

8 pages, 4 figures, 5 tables.The treatment of FcCOCl (Fc = (C5H5)Fe(C5H4)) with aminobenzimidazole in 1:1 or 2:1 ratio gives the ferrocenyl-amido derivatives FcCO(benzimNH2) or (FcCO)2(NHbenzim), respectively. The reactivity of FcCO(benzimNH2) with silver or gold complexes has been studied. The reaction with the basic gold compounds [Au(acac)(PPh3)] or [O(AuPPh3)3]ClO4 occurs with deprotonation of the NH2 group and coordination of one or three gold(phosphine) fragments. The treatment of this ligand with silver compounds, such as Ag(OTf) or [Ag(OTf)(PPh3)], gives the complexes of stoichiometry [Ag(OTf)L] or [Ag(OTf)(PPh3)L]. The ligand FcCO(benzimNH2) and the complex [Ag(OTf){FcCO(benzimNH2)}(PPh3)] have been characterized by X-ray diffraction studies. DFT calculations were performed on models of this dimeric silver complex and showed that dimerization is energetically favourable, because Ag(I) achieves a four coordination environment, despite some bonds being relatively weak.This work was supported by the Ministerio de Educación y Ciencia-FEDER (No. CTQ2004-05495-C02-01). We thank the Acción Integrada HP20030147 and Acção Integrada E-31/04. PJC acknowledges FCT for Grant (SFRH/BD/10535/2002) and S. Quintal for Grant (SFRH/BPD/11463/2002).Peer reviewe

Heteropolynuclear gold complexes with metallophilic interactions: Modulation of the luminescent properties

Metalloligands of stoichiometry [AuCl(P−N)] have been obtained by the reaction of the heterofunctional phosphines P−N = PPh2py, PPh2CH2CH2py, or PPhpy2 with [AuCl(tht)] (tht = tetrahydrothiophene). Reactions of these metalloligands with several metal compounds have afforded heteropolynuclear species which exhibit luminescent properties. The stoichiometries depend on the molar ratio and the heterometal. Thus, the reaction with [Cu(NCMe)4]+ in a molar ratio 2:1 gives the trinuclear compounds [Au2CuCl2(P−N)2]+, in which the structure and Au···Cu interactions depend on the phosphine ligand. With rhodium and iridium derivatives the reactivity is different leading to complexes of the type [AuMCl2(cod)(P−N)] for P−N = PPh2py, PPhpy2, and [Au2M2Cl(cod)2(P−N)2]Cl with PPh2CH2CH2py. Using [MCl2(NCPh)2] (M = Pd, Pt) in a 2:1 molar ratio yields [Au2MCl4(P−N)2] and in a 1:1 molar ratio [AuPdCl3(μ3-PPhpy2)]. Several compounds have been characterized by X-ray diffraction showing in many cases short Au···M distances. The luminescence of these derivatives has been studied. The metalloligands display bands assigned to intraligand (IL) transitions. For the bimetallic (Au/M) systems the luminescence depends on the heterometal present and on the metallophilic interactions. The most important excitations in the relevant energy range were assigned essentially a MMLCT character (from Rh/Ir and Au to ligands) based on density functional theory (DFT) calculations in selected complexes. The luminescence behavior in Rh/Ir [AuMCl2(cod)(PPh2py)] complexes was interpreted on the basis of the different nature of the half occupied orbitals in the triplet state.We thank the Dirección General de Investigación Científica y Técnica (CTQ2007-67273-C02-01) for financial support. M.J.C. and P.D.V. acknowledge FCT, POCI, and FEDER (project PTDC/QUI/58925/2004) for financial support.Peer Reviewe

Structural and electronic properties in asymmetric binuclear Zn(II) amphiphilic compounds

A new type of asymmetric binuclear Zn(II) complex was synthesized from a suitable mononuclear precursor. One Zn(II) was coordinated to a salphen ligand (salphen = N,N′-disalicylidene-1,2-phenylenediamine) and the other to a modified salphen bearing OC12H25 chain in the 4,4’ positions, the two being joined by phenylene rings. The molecular structure, determined by DFT calculations (ADF/BP86(COSMO:THF)/TZ2P), showed the non-planarity of each of the two complexes, the dihedral angle at the junction being ∼36°. The absorption spectra of 2 and its precursor 1 in DMSO showed a strong band in the visible at 427 and 408 nm, respectively, assigned based on TDDFT calculations mainly to intra- and interligand π→π* transitions. Complex 2 displayed emission at 531 nm in DMSO and 534 nm in other solvents. The long alkyl chain of its substituents promoted self-assembly of these amphiphilic molecules. No gels were formed in DMSO, but several bands (420, 418 and 480 nm) and shoulders appeared in other solvents, and gels were detected when increasing concentration. The formation of aggregates was studied by scanning electron microscopy and atomic force microscopy, and the images found in the three solvents reflected different supramolecular arrangements. These studies revealed that the binuclear compound formed stable gels above 8.88 mM for tetrahydrofuran and 13.3 mM for toluene and chloroform.We thank the Fundação para a Ciência e a Tecnologia, Portugal, for financial support (UIDB/04046/2020 and UIDP/04046/2020) and project PTDC/QEQ­QIN/3414/2014. SQR thank FCT for fellowship (PD/BD/52368/2013) under the CATSUS doctoral programme. PNM thanks FTC for the programme CEECIND/00509/2017. We also thank Fundação Calouste Gulbenkian for financial support under the Estímulo à Investigação 2013 programme.Peer reviewe

Tracking the Emergence and Dissemination of a blaNDM-23 Gene in a Multidrug Resistance Plasmid of Klebsiella pneumoniae

ABSTRACT Since the discovery of blaNDM-1, NDM β-lactamases have become one of the most widespread carbapenemases worldwide. To date, 43 different NDM variants have been reported but some, such as blaNDM-23, have not been characterized in detail yet. Here, we describe the emergence of a novel blaNDM-23 allele from a blaNDM-1 ancestor and the multidrug resistance plasmid that has disseminated it through a Klebsiella pneumoniae ST437 clone in several Spanish hospitals. Between 2016 and 2019, 1,972 isolates were collected in an epidemiological survey for extended-spectrum-β-lactamase (ESBL)-producing Klebsiella pneumoniae in the Comunitat Valenciana (Spain). Three carbapenem-resistant strains failed to be detected by carbapenemase-producing Enterobacteriaceae (CPE) screening tests. These isolates carried a blaNDM-23 gene. To characterize this gene, its emergence, and its dissemination, we performed antimicrobial susceptibility tests, hybrid sequencing with Illumina and Nanopore technologies, and phylogenetic analyses. The MICs of the blaNDM-23 allele were identical to those of the blaNDM-1 allele. The blaNDM-23 allele was found in 14 isolates on a 97-kb nonmobilizable, multidrug-resistant plasmid carrying 19 resistance genes for 9 different antimicrobial families. In this plasmid, the blaNDM-23 gene is in the variable region of a complex class 1 integron with a singular genetic environment. The small genetic distance between blaNDM-23-producing isolates reflects a 5-year-long clonal dispersion involving several hospitals and interregional spread. We have characterized the genomic and epidemiological contexts in the emergence and community spread of a new blaNDM-23 allele in a multidrug resistance (MDR) plasmid of Klebsiella pneumoniae. IMPORTANCE At a time when antimicrobial resistance has become one of the biggest concerns worldwide, the emergence of novel alleles and extremely drug-resistant plasmids is a threat to public health worldwide, especially when they produce carbapenem resistance in one of the most problematic pathogens, such as Klebsiella pneumoniae. We used genomic epidemiology to describe the emergence of a novel NDM-23 allele and identify it in a MDR plasmid that has disseminated through a K. pneumoniae ST437 clone in several hospitals in Spain. Using bioinformatic and phylogenetic analyses, we have traced the evolutionary and epidemiological route of the new allele, the hosting plasmid, and the strain that carried both of them from Pakistan to Spain. A better understanding of the NDM-producing K. pneumoniae populations and plasmids has made evident the spread of this clone through the region, enhancing the importance of genomic surveillance in the control of antimicrobial resistance

New polynuclear Mo-Fe complexes with ferrocenylamidobenzimidazole ligands

8 pages, 2 tables, 7 figures, 1 scheme.The reaction between [Mo(3-C3H5)(CO)2(NCMe)2Br] (1) and the ferrocenylamidobenzimidazole ligands FcCO(NH2benzim) (L1) and (FcCO)2(NHbenzim) (L2) led to a binuclear (2) and a trinuclear (3) Mo-Fe complex, respectively. The single-crystal X-ray structure of [Mo(3-C3H5)(CO)2(L2)Br] [L2 = {[(5-C5H5)Fe(5-C5H4CO)]2(2-NH-benzimidazolyl)}] shows that L2 is coordinated to the endo Mo(3-C3H5)(CO)2 group in a 2-N,O-bidentate chelating fashion whereas the MoII centre displays a pseudooctahedral environment with Br occupying an equatorial position. Complex 2 was formulated as [Mo(3-C3H5)(CO)2(L1)Br] on the basis of a combination of spectroscopic data, elemental analysis, conductivity and DFT calculations. L1 acts as a 2-N,N-bidentate ligand. In both L1 and L2, the HOMOs are mainly localised on iron while the C=O bond(s) contribute to the LUMO(s) and the next highest energy orbitals are Fe-allyl antibonding orbitals. When the ligands bind to Mo(3-C3H5)(CO)2Br, the greatest difference is that Mo becomes the strongest contributor to the HOMO. Electrochemical studies show that, in complex 2, no electronic interaction exists between the two ferrocenyl ligands and that the first electron has been removed from the MoII-centred HOMO.We thank FCT for grant POCI/QUIM/58925/2004. PJC acknowledges FCT for grant (SFRH/BD/10535/2002) and SQ for grant (SFRH/BPD/11463/2002). MJC and MCG acknowledge the Acção Integrada Luso-Espanhola (CRUP). PZ gratefully acknowledges the financial support from the University of Siena (PAR 2005). MCG and AL thank the Ministerio de Educación y Ciencia (no. CTQ2004-05495-C02-01).Peer reviewe

Group 11 complexes with the bis(3,5-dimethylpyrazol-1-yl)methane ligand. How secondary bonds can influence the coordination environment of Ag(I): the role of coordinated water in [Ag2(µ-L)2(OH2)2](OTf)2

10 pages, 9 tables, 9 figures, 1 scheme.The complexation properties of the ligand bis(3,5-dimethylpyrazol-1-yl)methane ( L) towards group 11 metals have been studied. The reaction in a 1 : 1 molar ratio with [Cu(NCMe)4]PF6 or Ag(OTf) complexes gives the mononuclear [CuL(NCMe)]PF6 ( 1), with crystallographic mirror symmetry, or dinuclear [Ag2(µ-L)2](OTf)2 ( 2) (OTf = trifluoromethanesulfonate) in which the ligand bridges both silver centres, an unprecedented mode of coordination for this type of ligands. Compound 2 crystallizes with two water molecules and forms a supramolecular structure through classical hydrogen bonding. The reaction in a 2 : 1 ratio affords in both cases the four-coordinated derivatives [ML2]X (M = Cu, X = PF6 ( 3); Ag, X = OTf ( 4)). The treatment of [Ag(OTf)(PPh3)] with the ligand L gives [AgL(PPh3)]OTf ( 5). The gold(I) derivative [Au2(C6F5)2(µ-L)] ( 6) has also been obtained by reaction of L with two equivalents of [Au(C6F5)(tht)]. These complexes present a luminescent behaviour at low temperature; the emissions being mainly intraligand but enhanced after coordination of the metal. Compounds 1–4 have been characterized by X-ray crystallography. DFT studies showed that, in the silver complex 2, coordination of H2O to Ag in the binuclear complex is favoured by formation of a hydrogen-bonding network, involving the triflato anion, and releasing enough energy to allow distortion of the Ag2 framework.We thank the Ministerio de Educación y Ciencia (BQU2004- 05495-C02-01) for financial support. We thank the Acción Integrada HP20030147 and Acçâo Integrada E-31/04. P. J. C. acknowledges FCT for grant (SFRH/BD/10535/2002) and S. Quintal for grant (SFRH/BPD/11463/2002).Peer reviewe