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1.
BMC Geriatr ; 24(1): 361, 2024 Apr 23.
Artículo en Inglés | MEDLINE | ID: mdl-38654160

RESUMEN

BACKGROUND: The association between socioeconomic status and depression is weaker in older adults than in younger populations. Loneliness may play a significant role in this relationship, explaining (at least partially) the attenuation of the social gradient in depression. The current study examined the relationship between socioeconomic status and depression and whether the association was affected by loneliness. METHODS: A cross-sectional design involving dwelling and nursing homes residents was used. A total of 887 Spanish residents aged over 64 years took part in the study. Measures of Depression (GDS-5 Scale), Loneliness (De Jong-Gierveld Loneliness Scale), Socioeconomic Status (Education and Economic Hardship), and sociodemographic parameters were used. The study employed bivariate association tests (chi-square and Pearson's r) and logistic regression analyses. RESULTS: The percentage of participants at risk of suffering depression was significantly higher among those who had not completed primary education (45.5%) and significantly lower among those with university qualifications (16.4%) (X2 = 40.25;p <.001), and respondents who could not make ends meet in financial terms faced a higher risk of depression (X2 = 23.62;p <.001). In terms of the respondents who experienced loneliness, 57.5% were at risk of depression, compared to 19% of those who did not report loneliness (X2 = 120.04;p <.001). The logistic regression analyses showed that having university qualifications meant a 47% reduction in the risk of depression. This risk was 86% higher among respondents experiencing financial difficulties. However, when scores for the loneliness measure were incorporated, the coefficients relating to education and economic hardships ceased to be significant or were significantly reduced. CONCLUSION: Loneliness can contribute to explaining the role played by socioeconomic inequalities in depression among older adults.


Asunto(s)
Depresión , Soledad , Clase Social , Humanos , Soledad/psicología , Estudios Transversales , Masculino , Anciano , Femenino , España/epidemiología , Depresión/epidemiología , Depresión/psicología , Anciano de 80 o más Años , Persona de Mediana Edad
2.
Molecules ; 29(7)2024 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-38611702

RESUMEN

This mini-review offers a comprehensive overview of the advancements made over the last three years in utilizing highly polar s-block organometallic reagents (specifically, RLi, RNa and RMgX compounds) in organic synthesis run under bench-type reaction conditions. These conditions involve exposure to air/moisture and are carried out at room temperature, with the use of sustainable solvents as reaction media. In the examples provided, the adoption of Deep Eutectic Solvents (DESs) or even water as non-conventional and protic reaction media has not only replicated the traditional chemistry of these organometallic reagents in conventional and toxic volatile organic compounds under Schlenk-type reaction conditions (typically involving low temperatures of -78 °C to 0 °C and a protective atmosphere of N2 or Ar), but has also resulted in higher conversions and selectivities within remarkably short reaction times (measured in s/min). Furthermore, the application of the aforementioned polar organometallics under bench-type reaction conditions (at room temperature/under air) has been extended to other environmentally responsible reaction media, such as more sustainable ethereal solvents (e.g., CPME or 2-MeTHF). Notably, this innovative approach contributes to enhancing the overall sustainability of s-block-metal-mediated organic processes, thereby aligning with several key principles of Green Chemistry.

3.
Chem Sci ; 15(16): 5929-5937, 2024 Apr 24.
Artículo en Inglés | MEDLINE | ID: mdl-38665519

RESUMEN

A straightforward and selective conversion of nitriles into highly substituted tetrahydropyridines, aminoketones or enamines by using allylmagnesium bromide as an addition partner (under neat conditions) and subsequent treatment with different aqueous-based hydrolysis protocols is reported. Refuting the conventional wisdom of the incompatibility of Grignard reagents with air and moisture, we herein report that the presence of water allows us to promote the chemoselective formation of the target tetrahydropyridines over other competing products (even in the case of highly challenging aliphatic nitriles). Moreover, the careful tuning of both the reaction media employed (acid or basic aqueous solutions for the hydrolysis protocol) and the electronic properties of the starting nitriles allowed us to design a multi-task system capable of producing either ß-aminoketones or enamines in a totally selective manner. Importantly, and for the first time in the chemistry of main-group polar organometallic reagents in non-conventional protic solvents (e.g., water), both experimental and computational studies showed that the excellent efficiency and selectivity observed in aqueous media cannot be replicated by using standard dry volatile organic solvents (VOCs) under inert atmosphere conditions.

4.
Chemistry ; 29(57): e202302892, 2023 Oct 13.
Artículo en Inglés | MEDLINE | ID: mdl-37713100

RESUMEN

Invited for the cover of this issue is the group of Vicente del Amo, Alejandro Presa Soto and Joaquín García-Álvarez (QuimSinSos Group) at the University of Oviedo. The image depicts the use of the FeIII -based deep eutectic mixture [FeCl3 ⋅6 H2 O/Gly (3:1)] (Gly = glycerol) as both promoter and solvent for the straightforward and selective hydration of alkynes, working under mild (45 °C), bench-type reaction conditions (air) and in the absence of ligands, co-catalysts or co-solvents. Read the full text of the article at 10.1002/chem.202301736.

5.
Chemistry ; 29(57): e202301736, 2023 Oct 13.
Artículo en Inglés | MEDLINE | ID: mdl-37439586

RESUMEN

An efficient, simple and general protocol for the selective hydration of terminal alkynes into the corresponding methyl ketones has been developed by using a cheap, easy-to-synthesise and sustainable FeIII -based eutectic mixture [FeCl3 ⋅ 6H2 O/Gly (3 : 1)] as both promoter and solvent for the hydration reaction, working: i) under mild (45 °C) and bench-type reaction conditions (air); and ii) in the absence of ligands, co-catalysts, co-solvents or toxic, non-abundant and expensive noble transition metals (Au, Ru, Pd). When the final methyl ketones are solid/insoluble in the eutectic mixture, the hydration reaction takes place in 30 min, and the obtained methyl ketones can be isolated by simply decanting the liquid FeIII -DES, allowing the direct isolation of the desired ketones without VOC solvents. By using this straightforward and simple isolation protocol, we have been able to recycle the FeIII -based eutectic mixture system up to eight consecutive times. Furthermore, the FeIII -eutectic mixture is able to promote the selective and efficient formal oxidation of internal alkynes into 1,2-diketones, with the possibility of recycling this system up to three consecutive times. Preliminary investigations into a possible mechanism for the oxidation of the internal alkynes seem to indicate that it proceeds through the formation of the corresponding methyl ketones and α-chloroketones.

6.
Med. intensiva (Madr., Ed. impr.) ; 47(4): 193-202, abr. 2023.
Artículo en Español | IBECS | ID: ibc-218039

RESUMEN

Objective To assess the impact of a multimodal interventional project (“Zero Resistance”) on the acquisition of multidrug-resistant bacteria (MDR-B) during the patient’s ICU stay. Design Prospective, open-label, interventional, multicenter study. Setting 103 ICUs. Patients Critically ill patients admitted to the ICUs over a 27-month period. Interventions Implementation of a bundle of 10 recommendations to prevent emergence and spread of MDR-B in the ICU. Main variable of interest Rate of patients acquiring MDR-B during their ICU stay, with differentiation between colonization and infection. Results A total of 139,505 patients were included. In 5409 (3.9%) patients, 6020 MDR-B on ICU admission were identified, and in 3648 (2.6%) patients, 4269 new MDR-B during ICU stay were isolated. The rate of patients with MDR-B detected on admission increased significantly (IRR 1.43, 95% CI 1.31–1.56) (p<0.001) during the study period, with an increase of 32.2% between the initial and final monthly rates. On the contrary, the rate of patients with MDR-B during ICU stay decreased non-significantly (IRR 0.93, 95% CI 0.83–1.03) (p=0.174), with a 24.9% decrease between initial and final monthly rates. According to the classification into colonization or infection, there was a highly significant increase of MDR-B colonizations detected on admission (IRR 1.69, 95% CI 1.52–1.83; p<0.0001) and a very significant decrease of MDR-B-infections during ICU stay (IRR 0.67, 95% CI 0.57–0.80, p<0.0001). Conclusions The implementation of ZR project-recommendations was associated with a significantly reduction an infection produced by MDR-B acquired during the patient’s ICU stay (AU)


Objetivo Evaluar el impacto de un proyecto de intervención multimodal (“Resistencia Zero”, RZ) en la adquisición de bacterias multirresistentes (BMR) durante la estancia en UCI. Diseño Estudio prospectivo, abierto, intervencionista, multicéntrico. Ámbito 103 UCI. Pacientes Pacientes críticos ingresados en UCI, durante un período de 27 meses. Intervenciones Implementación de un paquete de 10 recomendaciones para prevenir la aparición y propagación de BMR en UCI. Principal variable de interés Tasa de pacientes que adquieren BMR durante su estancia en UCI, diferenciando entre colonización e infección. Resultados Se incluyeron 139.505 pacientes. En 5.409(3,9%), se identificaron 6.020 BMR al ingreso y en 3.648(2,6%), se aislaron 4.269 nuevas BMR durante la estancia en UCI. La tasa de pacientes con BMR detectadas al ingreso aumentó significativamente (IRR 1,43, IC 95% 1,31–1,56) (p<0,001) durante el periodo de estudio, con un incremento del 32,2% entre las tasas mensuales inicial y final. Por el contrario, la tasa de pacientes con BMR detectadas durante la estancia en UCI disminuyó, no significativamente (IRR 0,93, IC 95% 0,83–1,03) (p=0,174), con una disminución del 24,9% entre las tasas mensuales iniciales y finales. Según la clasificación en colonización o infección, hubo un aumento significativo de colonizaciones por BMR detectadas al ingreso (IR 1,69, IC 95% 1,52–1,83; p<0,0001) y una disminución significativa de infecciones producidas por BMR adquiridas durante la estancia en UCI (IR 0,67, IC 95% 0,57–0,80, p<0,0001). Conclusiones La implementación de las recomendaciones del proyecto RZ se asoció con una reducción significativa de pacientes con infecciones por BMR adquiridas en UCI (AU)


Asunto(s)
Humanos , Unidades de Cuidados Intensivos , Farmacorresistencia Bacteriana Múltiple , Control de Infecciones/métodos , Infección Hospitalaria/prevención & control , Estudios Prospectivos , España
7.
Org Biomol Chem ; 21(21): 4414-4421, 2023 May 31.
Artículo en Inglés | MEDLINE | ID: mdl-37000523

RESUMEN

The highly efficient biodeoximation of aromatic ketoximes, promoted by the enzymatic oxidative system laccase/TEMPO/O2, has been successfully assembled with the fast and chemoselective addition of highly-polar s-block organometallic reagents (RLi/RMgX) en route to highly-substituted tertiary alcohols. By using this hybrid one-pot tandem protocol, tertiary alcohols have been selectively synthesized in good yields and under mild and bench-type reaction conditions (room temperature, the absence of a protecting atmosphere and aqueous media, which are non-typical conditions for polar organometallic reagents). The overall hybrid one-pot tandem transformation amalgamates two distant organic synthetic tools (RLi/RMgX reagents and enzymes) without the need for any tedious and energy/time-consuming intermediate isolation/purification steps.

8.
J Cardiothorac Surg ; 18(1): 32, 2023 Jan 17.
Artículo en Inglés | MEDLINE | ID: mdl-36650554

RESUMEN

BACKGROUND: Less invasive monitoring, such as radial arterial pulse contour analysis (ProAQT® sensor), represents an alternative when hemodynamic monitoring is necessary to guide postoperative management and invasive monitoring is not technically feasible. The aim of the study is to evaluate the accuracy of the ProAQT® sensor cardiac output measurements in comparison with Pulmonary Artery Catheter (PAC) during the postoperative course of patients who underwent cardiac surgery with cardiopulmonary bypass. CASE PRESENTATION: Prospective observational study in a Surgical Intensive Care Unit of a tertiary university hospital. Ten patients with a mean age of 73.5 years were included. The main comorbidities were hypertension, diabetes, dyslipidemia and the preoperative left ejection fraction was 43.8 ± 14.5%. Regarding the type of surgery, six patients underwent valve surgery, two underwent coronary artery bypass grafting and two underwent aortic surgery. The cardiac index measured simultaneously by the ProAQT® sensor was compared with the PAC. The parameters were evaluated at predefined time points during the early postoperative courses (6 h, 12 h, 24 h, 48 h and 72 h). The degree of agreement with the cardiac index between the PAC and the ProAQT® sensor along the time points was measured using the concordance correlation coefficient, Bland-Altman analysis, and four-quadrant plot. Sixty-three pairs of measurements were analyzed. We showed that measurements of cardiac index were slightly higher with PAC (ß Ì‚ = - 0.146, p-value = 0.094). The concordance correlation coefficient for the additive model of cardiac index was 0.64 (95% Confidence Interval: 0.36, 0.82), indicating a high concordance between both sensors. Bland-Altmann analysis showed a mean bias of 0.45 L·min-1·m-2, limits of agreement from - 1.65 to 2.3 L·min-1·m-2, and percentage of error was 82.5%. Four-quadrant plot of changes in cardiac index showed a good concordance rate (75%), which increases after applying the exclusion zone (87%). CONCLUSIONS: In patients undergoing cardiac surgery, the ProAQT® sensor may be useful to monitor cardiac index during the postoperative period, especially when more invasive monitoring is not possible.


Asunto(s)
Presión Arterial , Procedimientos Quirúrgicos Cardíacos , Humanos , Anciano , Gasto Cardíaco , Monitoreo Intraoperatorio , Puente de Arteria Coronaria , Reproducibilidad de los Resultados
9.
Med Intensiva (Engl Ed) ; 47(4): 193-202, 2023 04.
Artículo en Inglés | MEDLINE | ID: mdl-36670011

RESUMEN

OBJECTIVE: To assess the impact of a multimodal interventional project ("Zero Resistance") on the acquisition of multidrug-resistant bacteria (MDR-B) during the patient's ICU stay. DESIGN: Prospective, open-label, interventional, multicenter study. SETTING: 103 ICUs. PATIENTS: Critically ill patients admitted to the ICUs over a 27-month period. INTERVENTIONS: Implementation of a bundle of 10 recommendations to prevent emergence and spread of MDR-B in the ICU. MAIN VARIABLE OF INTEREST: Rate of patients acquiring MDR-B during their ICU stay, with differentiation between colonization and infection. RESULTS: A total of 139,505 patients were included. In 5409 (3.9%) patients, 6020 MDR-B on ICU admission were identified, and in 3648 (2.6%) patients, 4269 new MDR-B during ICU stay were isolated. The rate of patients with MDR-B detected on admission increased significantly (IRR 1.43, 95% CI 1.31-1.56) (p<0.001) during the study period, with an increase of 32.2% between the initial and final monthly rates. On the contrary, the rate of patients with MDR-B during ICU stay decreased non-significantly (IRR 0.93, 95% CI 0.83-1.03) (p=0.174), with a 24.9% decrease between initial and final monthly rates. According to the classification into colonization or infection, there was a highly significant increase of MDR-B colonizations detected on admission (IRR 1.69, 95% CI 1.52-1.83; p<0.0001) and a very significant decrease of MDR-B-infections during ICU stay (IRR 0.67, 95% CI 0.57-0.80, p<0.0001). CONCLUSIONS: The implementation of ZR project-recommendations was associated with a significantly reduction an infection produced by MDR-B acquired during the patient's ICU stay.


Asunto(s)
Hospitalización , Unidades de Cuidados Intensivos , Humanos , España/epidemiología , Estudios Prospectivos , Bacterias
10.
Molecules ; 27(21)2022 Nov 05.
Artículo en Inglés | MEDLINE | ID: mdl-36364422

RESUMEN

Dimethindene is a selective histamine H1 antagonist and is commercially available as a racemate. Upon analyzing the synthetic pathways currently available for the industrial preparation of dimethindene, we set up a sustainable approach for the synthesis of this drug, switching from petroleum-based volatile organic compounds (VOCs) to eco-friendly solvents, such as 2-methyltetrahydrofuran (2-MeTHF) and cyclopentyl methyl ether (CPME) belonging to classes 3 and 2, respectively. Beyond decreasing the environmental impact of the synthesis (E-factor: 24.1-54.9 with VOCs; 12.2-22.1 with 2-MeTHF or CPME), this switch also improved the overall yield of the process (from 10% with VOCs to 21-22% with 2-MeTHF or CPME) and remarkably simplified the manual operations, working under milder conditions. Typical metrics applied at the first and second pass, according to the CHEM21 metrics toolkit, were also calculated for the whole synthetic procedure of dimethindene, and the results were compared with those of the classical procedure.


Asunto(s)
Dimetindeno , Éteres Metílicos , Solventes , Histamina
11.
Enferm. infecc. microbiol. clín. (Ed. impr.) ; 40(9): 479-482, Nov. 2022. tab
Artículo en Español | IBECS | ID: ibc-211205

RESUMEN

Introducción: El tratamiento de los abscesos mamarios se basa en el drenaje y la antibioticoterapia dirigida a las bacterias causantes de la infección. El objetivo de este estudio fue conocer los agentes etiológicos de los abscesos mamarios. Métodos: Se incluyó en el estudio a los pacientes que, entre septiembre de 2015 y enero de 2020, tuvieron un absceso mamario con cultivo positivo. Se consultaron los resultados de los cultivos en la base de datos del laboratorio. Se recogió de las historias clínicas si los pacientes presentaban los siguientes factores de riesgo: lactancia, diabetes o hábito fumador. Se excluyeron los abscesos secundarios a una infección de herida quirúrgica. Resultados: Se incluyeron 60 pacientes: 58 mujeres y 2 varones. Staphylococcus aureus fue el agente más frecuente en mujeres lactantes. Se aislaron bacterias anaerobias en 28 (61%) de los 46 abscesos en pacientes no lactantes. En los no lactantes, la frecuencia de anaerobios en los abscesos fue menor en diabéticos que en el resto (0/5 frente a 26/38; p=0,013). En los no lactantes y no diabéticos, la proporción de abscesos con anaerobios fue mayor en fumadores que en no fumadores (21/24 frente a 5/14; p=0,003). Los cocos grampositivos aerobios fueron los agentes más frecuentes en los diabéticos. Conclusión: Los anaerobios fueron los agentes más frecuentes, seguidos por S.aureus. La etiología de los abscesos mamarios varió con los factores de riesgo estudiados.(AU)


Introduction: Treatment of breast abscesses is based on drainage and antibiotic therapy directed at the bacteria causing the infection. The aim of this study was to know the etiological agents of breast abscesses. Methods: Patients who had a culture-positive breast abscess between September 2015 and January 2020 were included in the study. Culture results were consulted in the laboratory database. It was collected from medical records if the patients presented the following risk factors: breastfeeding, diabetes or smoking. Abscesses secondary to surgical wound infection were excluded. Results: Sixty patients were included: 58 women and 2 men. Staphylococcus aureus was the most frequent agent in lactating women. Anaerobic bacteria were isolated in 28 (61%) of 46 abscesses in non-lactating patients. In non-lactating patients, the frequency of anaerobes in abscesses was lower in diabetics than in the rest (0/5 vs 26/38; P=.013). In non-lactating and non-diabetic patients, the proportion of abscesses with anaerobes was higher in smokers than in non-smokers (21/24 vs 5/14; P=.003). Aerobic gram-positive cocci were the most frequent agents in diabetics. Conclusion: Anaerobes were the most frequent agents, followed by S.aureus. The etiology of breast abscesses varied with the risk factors studied.(AU)


Asunto(s)
Humanos , Masculino , Femenino , Absceso/terapia , Antiinfecciosos/farmacología , Antiinfecciosos/uso terapéutico , Drenaje , Enfermedades de la Mama , Registros Médicos , Staphylococcus aureus/virología , Enfermedades Transmisibles , Microbiología , España/epidemiología
12.
ChemistryOpen ; 11(10): e202200160, 2022 10.
Artículo en Inglés | MEDLINE | ID: mdl-36229408

RESUMEN

An efficient, selective and sustainable protocol was developed for the CuCl2 /TEMPO/TMEDA-catalyzed aerobic oxidation of activated alcohols to the corresponding carbonyl compounds using water or the environmentally friendly low melting mixture (LMM) d-fructose-urea as the reaction medium. Such oxidation reactions proceed under mild (room temperature or 40 °C) and aerobic conditions, with the carbonyl derivatives isolated in up to 98 % yield and within 4 h reaction time when using the above-mentioned LMM. The potential application of this methodology is demonstrated by setting up useful telescoped, one-pot two-step hybrid transformations for the direct conversion of primary alcohols either into secondary alcohols or into valuable nitroalkenes, by combining oxidation processes with nucleophilic additions promoted by highly polarized organometallic compounds (Grignard and organolithium reagents) or with nitroaldol (Henry) reactions, respectively.


Asunto(s)
Alcoholes , Compuestos Organometálicos , Catálisis , Fructosa , Urea , Agua
13.
Behav Sci (Basel) ; 12(8)2022 Jul 29.
Artículo en Inglés | MEDLINE | ID: mdl-36004832

RESUMEN

Teaching is one of the most stressful work contexts, psychologically affecting professionals. The objective of this study is to analyse the effect of the frustration of NPB basic psychological needs, resilience, emotional intelligence and inclusion from the perspective of teachers in the time of the COVID-19 pandemic. The study is carried out with 542 teachers of therapeutic pedagogy and special educational needs using the Psychological Need Thwarting Scale PNTS questionnaires as a research method, the Resilience Scale (RS-14), the Trait Meta Mood Scale 24 (TMMS-24), the Maslach Burnout Inventory, and the Index for Inclusion. The results revealed positive correlations, on the one hand, between the factors of frustration among themselves and with burnout and, on the other hand, the positive correlation between emotional intelligence, resilience and the inclusion index. In conclusion, the resilience of teachers plays a protective role in the inclusion of students with SEN in the face of emotional exhaustion and the frustration of psychological needs.

14.
ChemSusChem ; 15(19): e202201348, 2022 Oct 10.
Artículo en Inglés | MEDLINE | ID: mdl-35904929

RESUMEN

Highly-efficient and selective one-pot/two-step modular double addition of different highly polar organometallic reagents (RLi/RMgX) to nitriles en route to asymmetric tertiary alcohols (without the need for isolation/purification of any halfway reaction intermediate) has been studied, for the first time, in the absence of external/additional organic solvents (neat conditions), at room temperature and under air/moisture (no protecting atmosphere is required), which are generally forbidden reaction conditions in the field of highly-reactive organolithium/organomagnesium reagents. The one-pot modular tandem protocol demonstrated high chemoselectivity with a broad range of nitriles, as no side reactions (Li/halogen exchange, ortho-lithiations or benzylic metalations) were detected. Finally, this protocol could be scaled up, thus proving that this environmentally friendly methodology is amenable for a possible applied synthesis of asymmetric tertiary alcohols under bench type reaction conditions and in the absence of external organic solvents.


Asunto(s)
Alcoholes , Compuestos Organometálicos , Halógenos , Nitrilos , Solventes , Temperatura
15.
Enferm Infecc Microbiol Clin (Engl Ed) ; 40(9): 479-482, 2022 11.
Artículo en Inglés | MEDLINE | ID: mdl-35729052

RESUMEN

INTRODUCTION: Treatment of breast abscesses is based on drainage and antibiotic therapy directed at the bacteria causing the infection. The aim of this study was to know the etiological agents of breast abscesses. METHODS: Patients who had a culture-positive breast abscess between September 2015 and January 2020 were included in the study. Culture results were consulted in the laboratory database. It was collected from medical records if the patients presented the following risk factors: breastfeeding, diabetes or smoking. Abscesses secondary to surgical wound infection were excluded. RESULTS: Sixty patients were included, 58 women and 2 men. Staphylococcus aureus was the most frequent agent in lactating women. Anaerobic bacteria were isolated in 28 (61%) of 46 abscesses in non-lactating patients. In non-lactating patients, the frequency of anaerobes in abscesses was lower in diabetics than in the rest (0/5 vs 26/38; P = .013). In non-lactating and non-diabetic patients, the proportion of abscesses with anaerobes was higher in smokers than in non-smokers (21/24 vs 5/14; P = .003). Aerobic gram-positive cocci were the most frequent agents in diabetics. CONCLUSION: Anaerobes were the most frequent agents, followed by S. aureus. The etiology of breast abscesses varied with the risk factors studied.


Asunto(s)
Mastitis , Infecciones Estafilocócicas , Masculino , Humanos , Femenino , Absceso/microbiología , Staphylococcus aureus , Infecciones Estafilocócicas/tratamiento farmacológico , Mastitis/tratamiento farmacológico , Antibacterianos/uso terapéutico
16.
Chemistry ; 28(45): e202200847, 2022 Aug 10.
Artículo en Inglés | MEDLINE | ID: mdl-35612568

RESUMEN

A family of germyl rhodium complexes derived from the PGeP germylene 2,2'-bis(di-isopropylphosphanylmethyl)-5,5'-dimethyldipyrromethane-1,1'-diylgermanium(II), Ge(pyrmPi Pr2 )2 CMe2 (1), has been prepared. Germylene 1 reacted readily with [RhCl(PPh3 )3 ] and [RhCl(cod)(PPh3 )] (cod=1,5-cyclooctadiene) to give, in both cases, the PGeP-pincer chloridogermyl rhodium(I) derivative [Rh{κ3 P,Ge,P-GeCl(pyrmPi Pr2 )2 CMe2 }(PPh3 )] (2). Similarly, the reaction of 1 with [RhCl(cod)(MeCN)] afforded [Rh{κ3 P,Ge,P-GeCl(pyrmPi Pr2 )2 CMe2 }(MeCN)] (3). The methoxidogermyl and methylgermyl rhodium(I) complexes [Rh{κ3 P,Ge,P-GeR(pyrmPi Pr2 )2 CMe2 }(PPh3 )] (R=OMe, 4; Me, 5) were prepared by treating complex 2 with LiOMe and LiMe, respectively. Complex 5 readily reacted with CO to give the carbonyl rhodium(I) derivative [Rh{κ3 P,Ge,P-GeR(pyrmPi Pr2 )2 CMe2 }(CO)] (6), with HCl, HSnPh3 and Ph2 S2 rendering the pentacoordinate methylgermyl rhodium(III) complexes [RhHX{κ3 P,Ge,P-GeMe(pyrmPi Pr2 )2 CMe2 }] (X=Cl, 7; SnPh3 , 8) and [Rh(SPh)2 {κ3 P,Ge,P-GeMe(pyrmPi Pr2 )2 CMe2 }] (9), respectively, and with H2 to give the hexacoordinate derivative [RhH2 {κ3 P,Ge,P-GeMe(pyrmPi Pr2 )2 CMe2 }(PPh3 )] (10). Complexes 3 and 5 are catalyst precursors for the hydroboration of styrene, 4-vinyltoluene and 4-vinylfluorobenzene with catecholborane under mild conditions.

17.
ChemSusChem ; 15(1): e202102211, 2022 Jan 10.
Artículo en Inglés | MEDLINE | ID: mdl-34762333

RESUMEN

An efficient and novel protocol was developed for a Cu-catalyzed Ullmann-type aryl alkyl ether synthesis by reacting various (hetero)aryl halides (Cl, Br, I) with alcohols as active components of environmentally benign choline chloride-based eutectic mixtures. Under optimized conditions, the reaction proceeded under mild conditions (80 °C) in air, in the absence of additional ligands, with a catalyst [CuI or CuII species] loading up to 5 mol% and K2 CO3 as the base, providing the desired aryloxy derivatives in up to 98 % yield. The potential application of the methodology was demonstrated in the valorization of cheap, easily available, and naturally occurring polyols (e. g., glycerol) for the synthesis of some pharmacologically active aryloxypropanediols (Guaiphenesin, Mephenesin, and Chlorphenesin) on a 2 g scale in 70-96 % yield. Catalyst, base, and deep eutectic solvent could easily and successfully be recycled up to seven times with an E-factor as low as 5.76.


Asunto(s)
Alcoholes , Cobre , Catálisis , Disolventes Eutécticos Profundos , Ligandos , Solventes
18.
Chem Commun (Camb) ; 57(99): 13534-13537, 2021 Dec 14.
Artículo en Inglés | MEDLINE | ID: mdl-34850798

RESUMEN

The one-pot/two-step combination of enzymes and polar organometallic chemistry in aqueous media is for the first time presented as a proof-of-concept study. The unprecedented combination of the catalytic oxidation of secondary alcohols by the system laccase/TEMPO with the ultrafast addition (3 s reaction time) of polar organometallic reagents (RLi/RMgX) to the in situ formed ketones, run under air at room temperature, allows the straightforward and chemoselective synthesis of tertiary alcohols with broad substrate scope and excellent conversions (up to 96%).

19.
ChemSusChem ; 14(9): 2084-2092, 2021 May 06.
Artículo en Inglés | MEDLINE | ID: mdl-33666346

RESUMEN

Fast addition of highly polar organometallic reagents (RMgX/RLi) to cyclic carbonates (derived from CO2 as a sustainable C1 synthon) has been studied in 2-methyltetrahydrofuran as a green reaction medium or in the absence of external volatile organic solvents, at room temperature, and in the presence of air/moisture. These reaction conditions are generally forbidden with these highly reactive main-group organometallic compounds. The correct stoichiometry and nature of the polar organometallic alkylating or arylating reagent allows straightforward synthesis of: highly substituted tertiary alcohols, ß-hydroxy esters, or symmetric ketones, working always under air and at room temperature. Finally, an unprecedented one-pot/two-step hybrid protocol is developed through combination of an Al-catalyzed cycloaddition of CO2 and propylene oxide with the concomitant fast addition of RLi reagents to the in situ and transiently formed cyclic carbonate, thus allowing indirect conversion of CO2 into the desired highly substituted tertiary alcohols without need for isolation or purification of any reaction intermediates.

20.
Artículo en Inglés, Español | MEDLINE | ID: mdl-33640150

RESUMEN

INTRODUCTION: Treatment of breast abscesses is based on drainage and antibiotic therapy directed at the bacteria causing the infection. The aim of this study was to know the etiological agents of breast abscesses. METHODS: Patients who had a culture-positive breast abscess between September 2015 and January 2020 were included in the study. Culture results were consulted in the laboratory database. It was collected from medical records if the patients presented the following risk factors: breastfeeding, diabetes or smoking. Abscesses secondary to surgical wound infection were excluded. RESULTS: Sixty patients were included: 58 women and 2 men. Staphylococcus aureus was the most frequent agent in lactating women. Anaerobic bacteria were isolated in 28 (61%) of 46 abscesses in non-lactating patients. In non-lactating patients, the frequency of anaerobes in abscesses was lower in diabetics than in the rest (0/5 vs 26/38; P=.013). In non-lactating and non-diabetic patients, the proportion of abscesses with anaerobes was higher in smokers than in non-smokers (21/24 vs 5/14; P=.003). Aerobic gram-positive cocci were the most frequent agents in diabetics. CONCLUSION: Anaerobes were the most frequent agents, followed by S.aureus. The etiology of breast abscesses varied with the risk factors studied.

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