Examining the adsorption of gases into solid crystalline molecular copper(II) 3,5-bis(trifluoromethyl)benzoate derivatives

Altres ajuts: acords transformatius de la UABTwo copper(II) complexes, both involving the anionic 3,5-bis(trifluoromethyl)benzoate ligand (TFMBz), have been prepared and their structure elucidated by single crystal-X ray diffraction. [Cu(TFMBz)2(ISNA)2] (1) is a mononuclear complex, in which the sphere of coordination of Cu(II) is completed by two neutral isonicotinamide (ISNA) auxiliary ligands. Hydrogen bonding formed between auxiliary ISNA ligands determines the formation of a 2D supramolecular network. [Cu2(TFMBz)4(DMSO)2] (2) is a binuclear complex, in which the four carboxylate ligands define the typical paddle wheel structure often found in copper complexes, containing also the ancillary dimethyl sulfoxide (DMSO) ligand in axial positions. The elucidated crystallographic data provide the static view of the crystal structures, which reveals only non-interconnected voids for both materials. Even that, compound 1shows an appreciable adsorption of CO2 at 273 K (ca. 1 CO2 molecule/Cu atom at 100 kPa), concomitant with a reduced adsorption of Ar or N2 under similar conditions, which implies a considerable degree of selectivity for CO2. Moreover, 1 does not adsorb N2 or Ar at 77 K and 100 kPa. This behavior suggests that the stablished intermolecular hydrogen bonds rest flexibility and dynamism to 1 at low temperature. Contrarily, increasing the temperature transient porosity is originated, which allows guest molecules to diffuse through the cavities. Compound 2 shows adsorption of N2 and Ar at 77 K, indicating that vibrations in the network and rotation of some CF3 groups, necessary to favor adsorbate diffusion, are still feasible at this low temperature

One-dimensional metal-organic frameworks built by coordinating 2,4,6-tris(4-pyridyl)-1,3,5-triazine linker with copper nodes : CO2 adsorption properties

Altres ajuts: acord transformatiu CRUE-CSICThe reaction between 2,4,6-tris(4-pyridyl)-1,3,5-triazine (4-tpt) and copper(II) hexafluoroacetylacetone (Cu(hfa)2) yields two different 1D metal-organic frameworks (MOFs), [(Cu(hfa)2)2(4-tpt)]n (1) and [Cu(hfa)2(4-tpt)]n (2). The Cu:4-tpt ratio in the new MOFs is determined by the reaction medium, particularly, the solvent used. The two compounds have been fully characterized, including crystal structure elucidation. [(Cu(hfa)2)2(4-tpt)]n (1), with a 2:1 Cu:4-tpt ratio, could be precipitated in either 1,1,2-trichloroethane or supercritical CO2. In (1), 4-tpt shows a tritopic coordination mode, but only half of the Cu(hfa)2 subunits act as a node, thus connecting two 4-tpt and giving a 1D network. The other half of Cu(hfa)2 subunits are connected only to one pyridine and thus protrude along the chains. The later Cu(hfa)2 fragments show a labile character and can be dissolved in diethyl ether to give the second MOF [Cu(hfa)2(4-tpt)]n (2), with a 1:1 Cu:4-tpt ratio. The compound (2) has also a 1D structure, with all the incorporated copper atoms acting as nodes. In this case, the packing of the chains defines accessible channels, which are perpendicular to the chain axis. After activation, N2 adsorption/desorption measurements at 77 K confirm the microporous character of (2) with an apparent surface area of 190 m2 g−1. Besides, at 273 K this material clearly shows a significant adsorption of CO2 prompted by noncoordinated nitrogen in the triazine linker

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 < 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

Utilización de técnicas de adsorción de gases para la caracterización textural de materiales micro y mesoporosos

L'adsorció física de gasos és la tècnica de primera elecció per estudiar les característiques dels porus originats en materials sòlids. La tècnica determina amb precisió la quantitat de gas adsorbit en un material sòlid, i és considerada com una mesura directa de les propietats texturals en estructures poroses. Com avantatge d'aquesta tècnica, destaca l'existència d'equips de mesura d'adsorció de gasos automàtics amb, en principi, una fàcil operativitat. Tot i això, les isotermes obtingudes han de ser acuradament interpretades perquè proporcionin informació sobre l'àrea superficial, el volum de porus i la seva distribució per mida. En aquest treball es remarca que aquestes mesures d'adsorció no són tan directes i infal·libles com es descriu usualment a la literatura. La influència de l'equip utilitzat i les seves condicions de manteniment, la perícia i la precisió de l'operari en quant al maneig de l'equip, així com el correcte ús del model de tractament de dades utilitzat influeixen significativament en el resultat, especialment en materials d'estructura de porus complexa. S'ha observat que, interpretacions incorrectes de les isotermes d'adsorció/desorció, i la consegüent assignació fallida dels valors de les propietats texturals deduïdes, són presentades concurrentment en publicacions recents, sovint deduint-se d'aquestes mesures conclusions importants en la descripció del material. La introducció i l'experimental d'aquesta Tesi pretén contribuir a l'anàlisi correcta de l'adsorció de gasos amb els equips de fisisorció automàtics de Micromeritics, així com evitar una mala interpretació de les dades derivades de l'adsorció. El capítol 1 es focalitza en l'anàlisi de materials mesoporosos. El principal objectiu d'aquest capítol és definir una sèrie de pautes que permetin treballar amb petites quantitats de mostra en equips d'adsorció automàtics, sense perdre precisió en les mesures de les propietats texturals. Especialment, el desenvolupament experimental de la tècnica se centrarà en el tractament i la caracterització d'aerogels mesoporosos de grafè. Per això, s'ha realitzat un estudi previ amb un altre material mesoporós estandarditzat, nanopartícules de sílica-alúmina, que posseeix més densitat que els aerogels. Finalment, el capítol 2 es dedica a l'anàlisi textural de materials microporosos. L'evolució dels materials microporosos ha estat espectacular en els darrers anys, apareixent els polímers de coordinació tipus MOFs. Molts d'aquests materials són sistemes cristal·lins microporosos rígids, amb paràmetres d'adsorció similars als de les zeolites, però d'altres tenen una estructura flexible, per la qual cosa varien el volum intern en funció de la pressió aplicada durant la mesura d'adsorció. Aquest tipus de materials s'analitza extensament en aquest capítol, que té com a objectiu definir els mètodes que cal utilitzar per estudiar l'adsorció en MOFs de manera adequada. En resum, en aquesta Tesi, els errors i les limitacions més comunes en l'anàlisi d'àrees superficials i distribucions de mida de porus derivades d'isotermes d'adsorció/desorció de N2 a 77K en materials mesoporosos i microporosos s'identifiquen i es discuteixen en profunditat, amb especial èmfasi en materials mesoporosos de baixa densitat, p. ex. aerogels, i en materials microporosos flexibles, p. ex. MOFs i ZIFs.La adsorción física de gases es la técnica de primera elección para estudiar las características de los poros originados en materiales sólidos. La técnica determina con precisión la cantidad de gas adsorbido en un material sólido, y es considerada como una medida directa de las propiedades texturales en estructuras porosas. Como ventaja de esta técnica destaca la existencia de equipos de medida de adsorción de gases automáticos con, en principio, fácil operatividad. Sin embargo, las isotermas obtenidas han de ser cuidadosamente interpretadas para que proporcionen información sobre el área superficial, el volumen de poro y su distribución por tamaño. En este trabajo se remarca que estas medidas de adsorción no son tan directas e infalibles como se describe usualmente en la literatura. La influencia del equipo utilizado y sus condiciones de mantenimiento, la pericia y precisión del operario en cuanto al manejo del equipo, así como el correcto uso del modelo de tratamiento de datos utilizado influyen significativamente en el resultado, especialmente en materiales de estructura de poro compleja. Se ha observado que, interpretaciones incorrectas de las isotermas de adsorción/desorción, y la consiguiente asignación fallida de los valores de las propiedades texturales deducidas, son concurrentemente presentadas en publicaciones recientes, a menudo deduciéndose de estas medidas conclusiones importantes en la descripción del material. La introducción y el experimental de esta Tesis pretende contribuir al análisis correcto de la adsorción de gases con los equipos de fisisorción automáticos de Micromeritics, así como a evitar una mala interpretación de los datos derivados de la adsorción. El capítulo 1 se centra en el análisis de materiales mesoporos. El principal objetivo de este capítulo es definir una serie de pautas que permitan trabajar con cantidades de muestra pequeñas en equipos de adsorción automáticos, sin perder por ello precisión en las medidas de las propiedades texturales. Fundamentalmente, el desarrollo experimental de la técnica se centrará en el tratamiento y caracterización de aerogeles mesoporosos de grafeno. Para ello, se ha realizado un estudio previo con otro material mesoporoso estandarizado, nanopartículas de sílica-alúmina, que posee mayor densidad que los aerogeles. Finalmente, el capítulo 2 se dedica al análisis textural de materiales microporosos. La evolución de los materiales microporosos ha sido espectacular en los últimos años, apareciendo los polímeros de coordinación tipo MOFs. Muchos de estos materiales son sistemas cristalinos microporosos rígidos, con parámetros de adsorción similares a los de las zeolitas, pero otros poseen una estructura flexible por lo que varían su volumen interno en función de la presión aplicada durante la medida de adsorción. Este tipo de materiales se analiza extensamente en este capítulo, que tiene como objetivo definir los métodos a utilizar para estudiar la adsorción en MOFs de forma adecuada. En resumen, en esta Tesis, los errores y limitaciones más comunes en el análisis de áreas superficiales y distribuciones de tamaño de poro derivadas de isotermas de adsorción/desorción de N2 a 77 K en materiales mesoporosos y microporosos se identifican y discuten en profundidad, con especial énfasis en materiales mesoporosos de baja densidad, p.ej., aerogeles; y en materiales microporosos flexibles, p.ej. MOFs y ZIFs.The physical adsorption of gases is the technique of first choice to study the characteristics of the pores originated in solid materials. The technique accurately determines the amount of gas adsorbed on a solid material, and it is considered as a direct measurement of textural properties in porous structures. One advantage of this technique is the existence of automatic gas adsorption equipment that is, in principle, easy to operate. However, the obtained isotherms have to be carefully interpreted, so that they provide information on the surface area, the pore volume and pore size distribution. In this Thesis, it is emphasized that these adsorption measurements are not as direct and infallible as usually described in the literature. The influence of the equipment used and its maintenance conditions, the skill and precision of the technician in handling the equipment, as well as the correct use of the data processing model, significantly influence the result, especially in materials with a complex pore structure. It has been observed that, incorrect interpretation of the adsorption/desorption isotherms, and the consequent failed assignment of the values of the inferred textural properties, are concurrently presented in publications, often deducing from these measurements, important conclusions in the description of the material. The Introduction and Experimental sections of this Thesis aim to contribute to correctly measure gas adsorption with Micromeritics automatic physisorption equipment, as well as to avoid misinterpretation of data derived from adsorption. Chapter 1 focuses on the analysis of mesoporous materials. The main objective of this chapter is to define a series of guidelines that allow working with small amounts of sample in automatic adsorption equipment, without losing precision in the measurements of textural properties. Fundamentally, the experimental development of the technique focuses on the treatment and characterization of graphene mesoporous aerogels. For this, a previous study is carried out with another standardized mesoporous material, silica-alumina nanoparticles, which has a higher density than aerogels. Finally, chapter 2 is dedicated to the textural analysis of microporous materials. The evolution of microporous materials has been spectacular in recent years, with the appearance of MOF-type coordination polymers. Many of these materials are rigid microporous crystalline systems, with adsorption parameters similar to those of zeolites, but others have a flexible structure, so their internal volume varies depending on the pressure applied during the adsorption measurement. This type of materials is extensively analyzed in this chapter, which aims to define the methods to be used to study adsorption on MOFs adequately. In summary, in this Thesis, the most common errors and limitations in the analysis of surface area and pore size distribution derived from adsorption/desorption isotherms of N2 at 77 K in mesoporous and microporous materials are identified and discussed in depth, with special emphasis on low-density mesoporous materials, e.g. aerogels; and in flexible microporous materials, e.g. MOFs and ZIFs

How do women living with HIV experience menopause? Menopausal symptoms, anxiety and depression according to reproductive age in a multicenter cohort

CatedresBackground: To estimate the prevalence and severity of menopausal symptoms and anxiety/depression and to assess the differences according to menopausal status among women living with HIV aged 45-60 years from the cohort of Spanish HIV/AIDS Research Network (CoRIS). Methods: Women were interviewed by phone between September 2017 and December 2018 to determine whether they had experienced menopausal symptoms and anxiety/depression. The Menopause Rating Scale was used to evaluate the prevalence and severity of symptoms related to menopause in three subscales: somatic, psychologic and urogenital; and the 4-item Patient Health Questionnaire was used for anxiety/depression. Logistic regression models were used to estimate odds ratios (ORs) of association between menopausal status, and other potential risk factors, the presence and severity of somatic, psychological and urogenital symptoms and of anxiety/depression. Results: Of 251 women included, 137 (54.6%) were post-, 70 (27.9%) peri- and 44 (17.5%) pre-menopausal, respectively. Median age of onset menopause was 48 years (IQR 45-50). The proportions of pre-, peri- and post-menopausal women who had experienced any menopausal symptoms were 45.5%, 60.0% and 66.4%, respectively. Both peri- and post-menopause were associated with a higher likelihood of having somatic symptoms (aOR 3.01; 95% CI 1.38-6.55 and 2.63; 1.44-4.81, respectively), while post-menopause increased the likelihood of having psychological (2.16; 1.13-4.14) and urogenital symptoms (2.54; 1.42-4.85). By other hand, post-menopausal women had a statistically significant five-fold increase in the likelihood of presenting severe urogenital symptoms than pre-menopausal women (4.90; 1.74-13.84). No significant differences by menopausal status were found for anxiety/depression. Joint/muscle problems, exhaustion and sleeping disorders were the most commonly reported symptoms among all women. Differences in the prevalences of vaginal dryness (p = 0.002), joint/muscle complaints (p = 0.032), and sweating/flush (p = 0.032) were found among the three groups. Conclusions: Women living with HIV experienced a wide variety of menopausal symptoms, some of them initiated before women had any menstrual irregularity. We found a higher likelihood of somatic symptoms in peri- and post-menopausal women, while a higher likelihood of psychological and urogenital symptoms was found in post-menopausal women. Most somatic symptoms were of low or moderate severity, probably due to the good clinical and immunological situation of these women

COVID-19 in hospitalized HIV-positive and HIV-negative patients : A matched study

CatedresObjectives: We compared the characteristics and clinical outcomes of hospitalized individuals with COVID-19 with [people with HIV (PWH)] and without (non-PWH) HIV co-infection in Spain during the first wave of the pandemic. Methods: This was a retrospective matched cohort study. People with HIV were identified by reviewing clinical records and laboratory registries of 10 922 patients in active-follow-up within the Spanish HIV Research Network (CoRIS) up to 30 June 2020. Each hospitalized PWH was matched with five non-PWH of the same age and sex randomly selected from COVID-19@Spain, a multicentre cohort of 4035 patients hospitalized with confirmed COVID-19. The main outcome was all-cause in-hospital mortality. Results: Forty-five PWH with PCR-confirmed COVID-19 were identified in CoRIS, 21 of whom were hospitalized. A total of 105 age/sex-matched controls were selected from the COVID-19@Spain cohort. The median age in both groups was 53 (Q1-Q3, 46-56) years, and 90.5% were men. In PWH, 19.1% were injecting drug users, 95.2% were on antiretroviral therapy, 94.4% had HIV-RNA < 50 copies/mL, and the median (Q1-Q3) CD4 count was 595 (349-798) cells/μL. No statistically significant differences were found between PWH and non-PWH in number of comorbidities, presenting signs and symptoms, laboratory parameters, radiology findings and severity scores on admission. Corticosteroids were administered to 33.3% and 27.4% of PWH and non-PWH, respectively (P = 0.580). Deaths during admission were documented in two (9.5%) PWH and 12 (11.4%) non-PWH (P = 0.800). Conclusions: Our findings suggest that well-controlled HIV infection does not modify the clinical presentation or worsen clinical outcomes of COVID-19 hospitalization