Antibacterial Activity of Two Zn-MOFs Containing a Tricarboxylate Linker

Metal–organic frameworks (MOFs) can be used as reservoirs of metal ions with relevant antibacterial effects. Here, two novel Zn-based MOFs with the formulas [Zn4( 4-O)( -FA)L2] (GR-MOF-8) and [Zn4( 4-O)L2(H2O)] (GR-MOF-9) (H3L: 5-((4-carboxyphenyl)ethynyl) in isophthalic acid and FA (formate anion) were solvothermally synthetized and fully characterized. The antibacterial activity of GR-MOF-8 and 9 was investigated against Staphylococcus aureus (SA) and Escherichia Coli (EC) by the agar diffusion method. Both bacteria are among the most relevant human and animal pathogens, causing a wide variety of infections, and are often related with the development of antimicrobial resistances. While both Zn-based materials exhibited antibacterial activity against both strains, GR-MOF-8 showed the highest inhibitory action, likely due to a more progressive Zn release under the tested experimental conditions. This is particularly evidenced in the inhibition of SA, with an increasing effect of GR-MOF-8 with time, which is of great significance to ensure the disappearance of the microorganism.MCIN/AEI by the European Union NextGenerationEU/PRTR) PCI2020-111998 MCIN/AEI PID2019-104228RB-100 PGC2018-102052-B-C21 JC2019-038894-IJunta de Andalucia B-FQM-734-UGR20 B-FQM-478-UGR20 FQM-394Comunidad de Madrid RED2018-102471-TEuropean Regional Development Fund-FEDER 2014-2020-OE REACT-UE 1SKA South Africa 897678Madrid Community 2018-T2/IND-11407 2017-T2/IND-5149European Union NextGenerationEU/PRT

1,8-Diamidocarbazoles: an easily tuneable family of fluorescent anion sensors and transporters

The synthesis, structure and anion recognition properties of an extensive, rationally designed series of bisamide derivatives of 1,8-diaminocarbazole and 1,8-diamino-3,6-dichlorocarbazole are described. Despite simple structures and the presence of only three hydrogen bond donors, such compounds are remarkably strong and selective receptors for oxyanions in DMSO + 0.5%H2O. Owing to their carbazole fluorophore, they are also sensitive turn-on fluorescent sensors for H2PO4− and AcO−, with a more than 15-fold increase in fluorescence intensity upon binding. Despite relatively weak chloride affinity, some of the diamidocarbazoles have also been shown, for the first time, to be very active chloride transporters through lipid bilayers. The binding, sensing and transport properties of these receptors can be easily modulated by the usually overlooked variations in the length and degree of branching of their alkyl side arms. Overall, this study demonstrates that the 1,8-diamidocarbazole binding unit is a very promising and synthetically versatile platform for the development of fluorescent sensors and transporters for anions.Polish National Science Centre for grant OPUS (2011/01/B/ST5/03900). The study was carried out at the Biological and Chemical Research Centre, University of Warsaw, established within a project co-financed by the European Union through the European Regional Development Fund under the Operational Programme Innovative Economy 2007–2013. R. Q. thanks financial support provided by Consejería de Educación – Junta de Castilla y León (Project BU092U16

Antibacterial Activity of Two Zn-MOFs Containing a Tricarboxylate Linker

Metal–organic frameworks (MOFs) can be used as reservoirs of metal ions with relevant antibacterial effects. Here, two novel Zn-based MOFs with the formulas [Zn(μ-O)(μ-FA)L] (GR-MOF-8) and [Zn(μ-O)L(HO)] (GR-MOF-9) (HL: 5-((4-carboxyphenyl)ethynyl) in isophthalic acid and FA (formate anion) were solvothermally synthetized and fully characterized. The antibacterial activity of GR-MOF-8 and 9 was investigated against Staphylococcus aureus (SA) and Escherichia Coli (EC) by the agar diffusion method. Both bacteria are among the most relevant human and animal pathogens, causing a wide variety of infections, and are often related with the development of antimicrobial resistances. While both Zn-based materials exhibited antibacterial activity against both strains, GR-MOF-8 showed the highest inhibitory action, likely due to a more progressive Zn release under the tested experimental conditions. This is particularly evidenced in the inhibition of SA, with an increasing effect of GR-MOF-8 with time, which is of great significance to ensure the disappearance of the microorganism.GR-MOF preparation was co-funded by the M-ERA-NET C-MOF.cell project (PCI2020-111998 funded by MCIN/AEI/10.13039/501100011033 by the European Union NextGenerationEU/PRTR); MOFSEIDON project (PID2019-104228RB-100, MCI/AEI/FEDER, UE); MagChirop project PGC2018-102052-B-C21 funded by MCIN/AEI/10.13039/501100011033; B-FQM-734-UGR20, B-FQM-478-UGR20 and FQM-394 funded from Junta de Andalucía; the Multifunctional Metallodrugs in Diagnosis and Therapy Network (MICIU, RED2018-102471-T); VIRMOF-CM project associated with R&D projects in response to COVID-19 from “Comunidad de Madrid” and European Regional Development Fund-FEDER 2014-2020-OE REACT-UE 1; and Margarita Salas contract 401 funded by Ministerio de Universidades and Next Generation. TH and PH acknowledge the European Union’s Horizon 2020 Research and Innovation Programme under the Marie Sklodowska-Curie grant agreement and the Talento Mod. 2 fellowship from Madrid Community (2018-T2/IND-11407). SR and PH thank the Regional Madrid fellowship funding Talento 2017 Modality 2, 2017-T2/IND-5149. SR and ARD acknowledge the Juan de la Cierva Incorporation grant JC2019-038894-I funded by MCIN/AEI/10.13039/501100011033 and the European Union NextGenerationEU/PRTR

Catalytic Performance and Electrophoretic Behavior of an Yttrium-Organic Framework Based on a Tricarboxylic Asymmetric Alkyne

A new Y-based metal-organic framework (MOF) GR-MOF-6 with a chemical formula of {[YL(DMF)2]·(DMF)}n {H3L = 5-[(4-carboxyphenyl)ethynyl] isophthalic acid; DMF = N,N-dimethylformamide} has been prepared by a solvothermal route. Structural characterization reveals that this novel material is a three-dimensional MOF in which the coordination of the tritopic ligand to Y(III) metal ions leads to an intercrossing channel system extending over three dimensions. This material has proven to be a very efficient catalyst in the cyanosilylation of carbonyls, ranking second in catalytic activity among the reported rare earth metal-based MOFs described so far but with the lowest required catalyst loading. In addition, its electrophoretic behavior has been studied in depth, providing a zero-charge point between pH 4 and 5, a peak electrophoretic mobility of -1.553 μm cm V-1 s-1, and a ζ potential of -19.8 mV at pH 10.This research has been funded by the State Research Agency (Grants RTC-2016-5239-2, CTQ2017-84334-R, PGC2018-102052-A-C22, and PGC2018-102052-B-C21) of the Spanish Ministry of Science, Innovation and Universities, the European Union [European Regional Development Fund (ERDF)], and Junta de Andalucía (FQM-376 and FQM-394). S.R. acknowledges the Juan de la Cierva Incorporación Fellowship (Grant Agreement IJC2019-038894-I)

Treatment with tocilizumab or corticosteroids for COVID-19 patients with hyperinflammatory state: a multicentre cohort study (SAM-COVID-19)

Objectives: The objective of this study was to estimate the association between tocilizumab or corticosteroids and the risk of intubation or death in patients with coronavirus disease 19 (COVID-19) with a hyperinflammatory state according to clinical and laboratory parameters. Methods: A cohort study was performed in 60 Spanish hospitals including 778 patients with COVID-19 and clinical and laboratory data indicative of a hyperinflammatory state. Treatment was mainly with tocilizumab, an intermediate-high dose of corticosteroids (IHDC), a pulse dose of corticosteroids (PDC), combination therapy, or no treatment. Primary outcome was intubation or death; follow-up was 21 days. Propensity score-adjusted estimations using Cox regression (logistic regression if needed) were calculated. Propensity scores were used as confounders, matching variables and for the inverse probability of treatment weights (IPTWs). Results: In all, 88, 117, 78 and 151 patients treated with tocilizumab, IHDC, PDC, and combination therapy, respectively, were compared with 344 untreated patients. The primary endpoint occurred in 10 (11.4%), 27 (23.1%), 12 (15.4%), 40 (25.6%) and 69 (21.1%), respectively. The IPTW-based hazard ratios (odds ratio for combination therapy) for the primary endpoint were 0.32 (95%CI 0.22-0.47; p < 0.001) for tocilizumab, 0.82 (0.71-1.30; p 0.82) for IHDC, 0.61 (0.43-0.86; p 0.006) for PDC, and 1.17 (0.86-1.58; p 0.30) for combination therapy. Other applications of the propensity score provided similar results, but were not significant for PDC. Tocilizumab was also associated with lower hazard of death alone in IPTW analysis (0.07; 0.02-0.17; p < 0.001). Conclusions: Tocilizumab might be useful in COVID-19 patients with a hyperinflammatory state and should be prioritized for randomized trials in this situatio

Spatiotemporal Characteristics of the Largest HIV-1 CRF02_AG Outbreak in Spain: Evidence for Onward Transmissions

Background and Aim: The circulating recombinant form 02_AG (CRF02_AG) is the predominant clade among the human immunodeficiency virus type-1 (HIV-1) non-Bs with a prevalence of 5.97% (95% Confidence Interval-CI: 5.41–6.57%) across Spain. Our aim was to estimate the levels of regional clustering for CRF02_AG and the spatiotemporal characteristics of the largest CRF02_AG subepidemic in Spain.Methods: We studied 396 CRF02_AG sequences obtained from HIV-1 diagnosed patients during 2000–2014 from 10 autonomous communities of Spain. Phylogenetic analysis was performed on the 391 CRF02_AG sequences along with all globally sampled CRF02_AG sequences (N = 3,302) as references. Phylodynamic and phylogeographic analysis was performed to the largest CRF02_AG monophyletic cluster by a Bayesian method in BEAST v1.8.0 and by reconstructing ancestral states using the criterion of parsimony in Mesquite v3.4, respectively.Results: The HIV-1 CRF02_AG prevalence differed across Spanish autonomous communities we sampled from (p &lt; 0.001). Phylogenetic analysis revealed that 52.7% of the CRF02_AG sequences formed 56 monophyletic clusters, with a range of 2–79 sequences. The CRF02_AG regional dispersal differed across Spain (p = 0.003), as suggested by monophyletic clustering. For the largest monophyletic cluster (subepidemic) (N = 79), 49.4% of the clustered sequences originated from Madrid, while most sequences (51.9%) had been obtained from men having sex with men (MSM). Molecular clock analysis suggested that the origin (tMRCA) of the CRF02_AG subepidemic was in 2002 (median estimate; 95% Highest Posterior Density-HPD interval: 1999–2004). Additionally, we found significant clustering within the CRF02_AG subepidemic according to the ethnic origin.Conclusion: CRF02_AG has been introduced as a result of multiple introductions in Spain, following regional dispersal in several cases. We showed that CRF02_AG transmissions were mostly due to regional dispersal in Spain. The hot-spot for the largest CRF02_AG regional subepidemic in Spain was in Madrid associated with MSM transmission risk group. The existence of subepidemics suggest that several spillovers occurred from Madrid to other areas. CRF02_AG sequences from Hispanics were clustered in a separate subclade suggesting no linkage between the local and Hispanic subepidemics

The Helicobacter pylori Genome Project : insights into H. pylori population structure from analysis of a worldwide collection of complete genomes

Helicobacter pylori, a dominant member of the gastric microbiota, shares co-evolutionary history with humans. This has led to the development of genetically distinct H. pylori subpopulations associated with the geographic origin of the host and with differential gastric disease risk. Here, we provide insights into H. pylori population structure as a part of the Helicobacter pylori Genome Project (HpGP), a multi-disciplinary initiative aimed at elucidating H. pylori pathogenesis and identifying new therapeutic targets. We collected 1011 well-characterized clinical strains from 50 countries and generated high-quality genome sequences. We analysed core genome diversity and population structure of the HpGP dataset and 255 worldwide reference genomes to outline the ancestral contribution to Eurasian, African, and American populations. We found evidence of substantial contribution of population hpNorthAsia and subpopulation hspUral in Northern European H. pylori. The genomes of H. pylori isolated from northern and southern Indigenous Americans differed in that bacteria isolated in northern Indigenous communities were more similar to North Asian H. pylori while the southern had higher relatedness to hpEastAsia. Notably, we also found a highly clonal yet geographically dispersed North American subpopulation, which is negative for the cag pathogenicity island, and present in 7% of sequenced US genomes. We expect the HpGP dataset and the corresponding strains to become a major asset for H. pylori genomics

Synthesis, Structural Features, and Hydrogen Adsorption Properties of Three New Flexible Sulfur-Containing Metal-Organic Frameworks

Three novel flexible sulfur-containing MOF materials named Co-URJC-5, Cu-URJC-6 and Zn-URJC-7, based on the 5,5′-thiodiisophthalic acid linker have been synthesized through solvothermal methods and characterized by different physicochemical techniques. Hydrogen adsorption analysis at room temperature reveals that these compounds display a gate-opening type adsorption mechanism at low pressures, attributed to the flexible nature of the H4TBTC ligand. This behavior is even more noticeable for Cu-URJC-6, since the layer arrangement by π-πstacking interactions between the aromatic layers could contribute to the flexibility of the structure. These results can be considered as a representative example to elucidate how MOF structures are built using flexible ligands and more significantly as a promising route for designing materials with selective gas sorption properties.This work has been supported by the Regional Government of Madrid (project ACES2030-CM, S2018/EMT-4319) and the Spanish Ministry of Science and Innovation and the Spanish State Research Agency (projects PGC2018-099296-B-I00, PGC2018-102052-B-C21, PGC2018-102047-B-I00) and Helena Montes’ grant (FPI BES-2016-076433

Synthesis, Structural Features, and Hydrogen Adsorption Properties of Three New Flexible Sulfur-Containing MetalOrganic Frameworks

Three novel flexible sulfur-containing MOF materials named Co-URJC-5, Cu-URJC-6 and Zn-URJC-7, based on the 5,5′-thiodiisophthalic acid linker have been synthesized through solvothermal methods and characterized by different physicochemical techniques. Hydrogen adsorption analysis at room temperature reveals that these compounds display a gate-opening type adsorption mechanism at low pressures, attributed to the flexible nature of the H4TBTC ligand. This behavior is even more noticeable for Cu-URJC-6, since the layer arrangement by π-πstacking interactions between the aromatic layers could contribute to the flexibility of the structure. These results can be considered as a representative example to elucidate how MOF structures are built using flexible ligands and more significantly as a promising route for designing materials with selective gas sorption properties.This work has been supported by the Regional Government of Madrid (project ACES2030-CM, S2018/EMT-4319) and the Spanish Ministry of Science and Innovation and the Spanish State Research Agency (projects PGC2018-099296-B-I00, PGC2018-102052-B-C21, PGC2018-102047-B-I00) and Helena Montes’ grant (FPI BES-2016-076433

Novel and Versatile Cobalt Azobenzene-Based Metal-Organic Framework as Hydrogen Adsorbent

A novel URJC-3 material based on cobalt and 5,5′-(diazene-1,2-diyl)diisophthalate ligand, containing Lewis acid and basic sites, has been synthesized under solvothermal conditions. Compound URJC-3, with polyhedral morphology, crystallizes in the tetragonal and P4 3 2 1 2 space group, exhibiting a three-dimensional structure with small channels along a and b axes. This material was fully characterized, and its hydrogen adsorption properties were estimated for a wide range of temperatures (77–298 K) and pressures (1–170 bar). The hydrogen storage capacity of URJC-3 is quite high in relation to its moderate surface area, which is probably due to the confinement effect of hydrogen molecules inside its reduced pores of 6 Å, which is close the ionic radii of hydrogen molecules. The storage capacity of this material is not only higher than that of active carbon and purified single-walled carbon nanotubes, but also surpasses the gravimetric hydrogen uptake of most MOF materials.This work has been support by “Comunidad de Madrid” (project: ALCCONES (S2013/MAE‐2985) and Spanish Ministry of Science and Innovation (project: MOF4Energy (CTQ2015‐64526) and grant (FPI BES‐2016‐076433)