Structural and Proton Conductivity Studies of Fibrous π-Ti2O(PO4)2·2H2O: Application in Chitosan- Based Composite Membranes

Although the fibrous polymorphic modification of titanium phosphate, π-Ti2O(PO4)2·2H2O (π-TiP) is known for decades, its crystal structure has remained unsolved. Herewith we report the crystal structure of π-TiP at a room temperature, determined from the synchrotron radiation powder X-ray diffraction, and corroborated by 31P solid state NMR and the accurate density functional theory calculations. In contrast to the previously reported ρ-TiP polymorph, the as-synthesized hydrated phase crystallizes in the monoclinic system (P21/c, a = 5.1121(2) Å, b = 14.4921(9) Å, c = 12.0450(11), β = 115.31(1)°, Z=4) and is composed of corner-sharing titanium octahedra and phosphate units arranged in a pattern distinct of ρ-TiP polymorph. The unit cell was confirmed by SAED, while the formation of planar packing imperfections and stacking faults along the [101] was revealed by HRTEM analysis. In situ dehydration study of π-TiP, monitored by high-temperature powder X-ray diffraction, led to a new anhydrous monoclinic [P21/c, a = 5.1187(13) Å, b = 11.0600(21) Å, c = 14.4556(26), β = 107.65(2)°, Z=4) phase that crystallizes at 500°C. The latter resembles the packing fashion of the parental π-TiP, albeit titanium atoms are present both in distorted tetrahedral and octahedral coordination environments. Anhydrous π-TiP was found to partially rehydrate at room temperature adopting reversibly the structure of the initial phase. The studies carried out under different conditions of leaching and impregnation with H3PO4 showed that π-TiP exhibits an extrinsic proton conductivity (1.3·10−3 S·cm−1 at 90 °C and 95% RH) due to the presence of protonated phosphate species bounded on the particles surface, as revealed by 31P MAS-NMR spectroscopy data. The composite membranes of Chitosan (CS) matrices filled with H3PO4-impregnated π-TiP solid show an increment of proton conductivity up to 4.5·10–3 S·cm–1, at 80 °C and 95% RH, 1.8-fold higher than those of bare CS membranesMAT2016-77648-R and PID2019-110249RB-I00), Junta deAndalucía (FQM-113) M. Bazaga-García thanks Junta de Andalucía for her Postdoc PAIDI grant and R. M. P. Colodrero thanks UMA Research Plan for her financial support

CARB-ES-19 Multicenter Study of Carbapenemase-Producing Klebsiella pneumoniae and Escherichia coli From All Spanish Provinces Reveals Interregional Spread of High-Risk Clones Such as ST307/OXA-48 and ST512/KPC-3

ObjectivesCARB-ES-19 is a comprehensive, multicenter, nationwide study integrating whole-genome sequencing (WGS) in the surveillance of carbapenemase-producing K. pneumoniae (CP-Kpn) and E. coli (CP-Eco) to determine their incidence, geographical distribution, phylogeny, and resistance mechanisms in Spain.MethodsIn total, 71 hospitals, representing all 50 Spanish provinces, collected the first 10 isolates per hospital (February to May 2019); CPE isolates were first identified according to EUCAST (meropenem MIC > 0.12 mg/L with immunochromatography, colorimetric tests, carbapenem inactivation, or carbapenem hydrolysis with MALDI-TOF). Prevalence and incidence were calculated according to population denominators. Antibiotic susceptibility testing was performed using the microdilution method (EUCAST). All 403 isolates collected were sequenced for high-resolution single-nucleotide polymorphism (SNP) typing, core genome multilocus sequence typing (cgMLST), and resistome analysis.ResultsIn total, 377 (93.5%) CP-Kpn and 26 (6.5%) CP-Eco isolates were collected from 62 (87.3%) hospitals in 46 (92%) provinces. CP-Kpn was more prevalent in the blood (5.8%, 50/853) than in the urine (1.4%, 201/14,464). The cumulative incidence for both CP-Kpn and CP-Eco was 0.05 per 100 admitted patients. The main carbapenemase genes identified in CP-Kpn were blaOXA–48 (263/377), blaKPC–3 (62/377), blaVIM–1 (28/377), and blaNDM–1 (12/377). All isolates were susceptible to at least two antibiotics. Interregional dissemination of eight high-risk CP-Kpn clones was detected, mainly ST307/OXA-48 (16.4%), ST11/OXA-48 (16.4%), and ST512-ST258/KPC (13.8%). ST512/KPC and ST15/OXA-48 were the most frequent bacteremia-causative clones. The average number of acquired resistance genes was higher in CP-Kpn (7.9) than in CP-Eco (5.5).ConclusionThis study serves as a first step toward WGS integration in the surveillance of carbapenemase-producing Enterobacterales in Spain. We detected important epidemiological changes, including increased CP-Kpn and CP-Eco prevalence and incidence compared to previous studies, wide interregional dissemination, and increased dissemination of high-risk clones, such as ST307/OXA-48 and ST512/KPC-3

Tolerabilidad de la desvenlafaxina en una muestra psiquiátrica ambulatoria española

Introduction. Desvenlafaxine is a serotonin and norepinephrine reuptake inhibitor recently approved in Spain, with a potentially promising tolerability and interaction profile. Most available data on side-effects are based on phase III clinical trials (RCT-III) carried out by laboratories, and there are still no tolerability studies on Spanish population. Therefore, the aim of this study is to evaluate the side effects incidence and discontinuation rate in a Spanish psychiatric setting and compare them with data from RCT-III. Methods: Demographic variables are collected and the “UKU side effects rating scale” is administered after drug titration period in a psychiatric outpatient sample with depressive symptomatology (n=39). The incidence of side effects and discontinuation rate are then compared with the results obtained from RCT-III. Results: The most frequently reported side effects in our sample are “sleepiness/sedation” (10,25%) and “increased tendency to sweating” (10,25%). In comparison with results from RCT-III, there is a significantly greater incidence of “concentration difficulties” (7,69% vs 1,24%, p=0,0091) and “paraesthesias” (7,69% vs 1,62%, p=0,03) and a lower incidence of “nausea/vomiting” (5,12% vs 32%, p=0,0007) and “headache” (7,69% vs 23,37%, p=0,036) in the Spanish sample. There are no statistically significant differences among the rest of SE or discontinuation rate. Conclusions: Despite these differences, results obtained from RCT-III seem to be comparable to Spanish population. Regarding potential advantages of desvenlafaxine with respect to other pharmacologic alternatives, and based on available literature, the former has apparently a better sexual side-effect profile and weight gain is less common than with other antidepressants.Introducción: La desvenlafaxina es un inhibidor de la recaptación de serotonina y noradrenalina introducido recientemente en España, con un perfil de tolerabilidad e interacciones potencialmente prometedor. Los datos disponibles sobre su perfil de efectos secundarios (ES) provienen principalmente de ensayos clínicos de fase III (ECA-III) realizados por el laboratorio, y no existen aún estudios en población española. El objetivo de este estudio es evaluar la incidencia de ES y discontinuación en población psiquiátrica española y compararlo con los datos disponibles.Metodología: Se recogen variables demográficas y se administra la “Escala de Efectos Secundarios (UKU)” tras el período de titulación del fármaco en una muestra de pacientes psiquiátricos ambulatorios con clínica depresiva (n=39). Se compara la incidencia de ES y discontinuación con los resultados obtenidos en ECA-III.Resultados: Los ES más frecuentes en nuestra muestra son “somnolencia/sedación” (10,25%) y “aumento de la sudoración” (10,25%). Comparándolo con los datos de ECA-III, se observa una incidencia significativamente más elevada de “dificultad de concentración” (7,69% vs 1,24%, p=0,0091) y “parestesias” (7,69% vs 1,62%, p=0,03) y más baja de “nauseas/vómitos” (5,12% vs 32%, p=0,0007) y “cefaleas” (7,69% vs 23,37%, p=0,036). No hay diferencias significativas para el resto de ES ni la discontinuación.Conclusiones: A pesar de estas diferencias, los datos provenientes de ECA-III parecen en general extrapolables a población española. En relación a beneficios que aporta respecto a otros fármacos disponibles, y en base a la literatura existente, podemos extraer que desvenlafaxina posee un perfil de secundarismos sexuales más benigno y menor aumento de peso

Supporting Information: Ruthenium carbene complexes analogous to grubbs-I catalysts featuring germylenes as ancillary ligands

-1H and 13C{1H} NMR spectra of L2, 3, and 7; 1H and 31P{1H} NMR spectra of the outcome of the reaction of 1 with 3; images and metric parameters of the DFT-optimized structures of 3, 4, 6, and 7; results of catalytic experiments; crystal, measurement, and refinement data for the compounds studied by XRD (PDF). -Atomic coordinates for the calculated structures (XYZ).Peer reviewe

Ruthenium carbene complexes analogous to grubbs-I catalysts featuring germylenes as ancillary ligands

Reactions of the first-generation Grubbs’ catalyst trans-[RuCl2(CHPh)(PCy3)2] (1) with the amidinatogermylenes Ge(tBu2bzam)R (R = tBu (L1), CH2SiMe3 (L2); tBu2bzam = N,N′-bis(tertbutyl)benzamidinate) have allowed the isolation and full characterization of the first specimens of Grubbs-type carbene complexes featuring heavier tetrylenes as ancillary ligands, namely, the disubstituted derivatives trans-[RuCl2(CHPh)(L1)2] (3) and cis-[RuCl2(CHPh)(L2)2] (7), which curiously differ in the arrangement of their germylene ligands. DFT calculations have revealed that the different volumes of L1 and L2 (the former is larger than the latter) are responsible for the different stereochemistry of 3 and 7. NMR-monitoring of the reaction solutions has allowed the observation of the monosubstituted intermediates trans-[RuCl2(CHPh)(L)(PCy3)] (L = L1 (2), L2 (5)) and their evolution to either the disubstituted final product (for L1) trans-[RuCl2(CHPh)(L1)2] (3) or the short-lived disubstituted intermediate (for L2) trans-[RuCl2(CHPh)(L2)2] (6). Complex 7 arises from a trans-to-cis isomerization of intermediate 6. As olefin metathesis catalysts, both 3 and 7 promoted the ring-closing metathesis of diethyl 2,2-diallylmalonate and the ring-opening metathesis polymerization of norbornene, but their catalytic activity decreased with the reaction time, indicating catalyst decomposition.This work has been supported by MINECO-FEDER (CTQ2016-75218-P, MAT2013-40950-R, RYC2012-10491 and CTQ2016-81797-REDC) and Gobierno del Principado de Asturias (GRUPIN14-009 and GRUPIN14-060) research grants. L.A.-R. thanks the University of Oviedo for a predoctoral fellowship.Peer reviewe

Diphosphanegermylene to nickel, palladium, and platinum complexes containing germyl PGeP pincer ligands

The PGeP pincer-type germylene Ge(NCH2 PtBu2 )C6 H4 (1) has been used to prepare a family of group 10 metal complexes, namely, [MCl{κ3 P,Ge,P-GeCl(NCH2 PtBu2 )2 C6 H4 }] (M=Ni (2Ni ), Pd (2Pd ), Pt (2Pt )), featuring a chloridogermyl PGeP pincer ligand and a Cl-Ge-M-Cl bond sequence. Their reactivity is not initially centered on the metal atom but on their Ge atom. Complexes 2Ni and 2Pd easily led to the hydrolyzed products [Ni2 Cl2 {μ-(κ3 P,Ge,P-Ge(NCH2 PtBu2 )2 C6 H4 )2 O}], which features a Cl-Ni-Ge-O-Ge-Ni-Cl bond sequence, and [PdCl{κ3 P,Ge,P-Ge(OH)(NCH2 PtBu2 )2 C6 H4 }], which contains a hydroxidogermyl PGeP pincer ligand (2Pt is reluctant to undergo hydrolysis). Simple chloride exchange reactions led to the methoxidogermyl, methylgermyl, and phenylgermyl derivatives [MCl{κ3 P,Ge,P-GeR(NCH2 PtBu2 )2 C6 H4 }] (M=Pd, Pt; R=OMe, Me, Ph). Whereas the palladium complexes [PdCl{κ3 P,Ge,P-GeR(NCH2 PtBu2 )2 C6 H4 }] (R=Me, Ph) reacted with more MeLi or PhLi to give palladium black and GeR2 (NCH2 PtBu2 )2 C6 H4 (R=Me, Ph), similar reactions with the analogous platinum complexes afforded the transmetalation derivatives [PtR{κ3 P,Ge,P-GeR(NCH2 PtBu2 )2 C6 H4 }] (R=Me, Ph). The short length of the CH2 PtBu2 arms of the PGeP pincer ligands forces the metal atoms of all these complexes to be in a very distorted square-planar ligand environment. The reactivity results have been rationalized with theoretical calculations.This work has been supported by research grants obtained from Ministerio de Economía y Competitividad (CTQ2016-75218-P, CTQ2016-81797-REDC, MAT2016-78155-C2-1-R, and RYC2012-10491) and Gobierno del Principado de Asturias (GRUPIN14-009 and GRUPIN14-060).Peer Reviewe

Synthesis and initial transition metal chemistry of the first PGeP pincer-type germylene

A PGeP pincer-type germylene, Ge(NCHPBu)CH, which contains two phosphane groups hanging from the N atoms of an N-heterocyclic germylene fragment, has been isolated for the first time. This compound has already furnished a rich transition metal derivative chemistry (Co, Rh, and Pd) that includes complexes containing bridging P,Ge,P-, chelating P,Ge- and pincer P,Ge,P-ligands.This work has been supported by grants from MINECO-FEDER (CTQ2016-75218-P, CTQ2013-40619-P, MAT2013-40950-R and RYC-2012-10491) and Gobierno del Principado de Asturias (GRUPIN14-009 and GRUPIN14-060). L. A.-R. thanks the University of Oviedo for a predoctoral fellowship.Peer Reviewe

Ansiedad en niños y cuidadores que acuden a un servicio de urgencias pediátricas hospitalarias

Introducción: La ansiedad, que en su origen tiene una función adaptativa, es una reacción emocional ante una situación que pone en peligro la integridad del individuo, sea esta amenaza real o no. Partiendo de la hipótesis de que acudir a un servicio de urgencia puede ser secundario a niveles elevados de ansiedad basal en los padres, proponemos un estudio en el que medimos la ansiedad estado y rasgo tanto de los niños como del progenitor y otros factores que pudieran influir en la frecuentación a este servicio.Objetivos: Determinar los niveles de ansiedad en los niños y acompañantes que demandan atención sanitaria en un servicio de urgencias hospitalarias, así como correlacionar otras variables que puedan influir o se asocien a los niveles de ansiedad de los mismos.Material y métodos: Se realiza entrevista individual a todos los niños entre 9 y 14 años y sus acompañantes, tras ser atendidos en el servicio de urgencias de pediatría y traumatología en horario de tarde. Se obtiene una muestra compuesta de un total de 105 casos. Además del cuestionario socio–demográfico, se aplican el Cuestionario de Autoevaluación ansiedad estado–rasgo en niños (STAIC) y el Inventario de ansiedad estado–rasgo (STAI) de adultos a los acompañantes.Resultados: No se han hallado niveles elevados de ansiedad estadísticamente significativos ni en los niños ni en sus cuidadores durante su paso por la urgencia ni en ansiedad–rasgo ni en ansiedad–estado. Un nivel de ansiedad elevado como rasgo de personalidad, no está relacionado con la visita a urgencias ni en los niños ni en sus cuidadores ante situaciones de no urgencia. Ni tampoco se encuentra un nivel de ansiedad–estado elevado que justifique la visita al servicio de urgencia debido a una situación percibida como urgente.Conclusión: Ninguna de las variables estudiadas ha demostrado una relación estadísticamente significativa con niveles elevados de ansiedad ni en los niños ni en sus cuidadores cuando acuden a un servicio de urgencias