Surface-Functionalized Nanoparticles as Catalysts for Artificial Photosynthesis

Altres ajuts: acords transformatius de la UABAnalogously to enzymatic catalysis, where the active metal sites and their environment are controlled by protein residues, the catalytic properties of metal nanoparticles (NPs) can be tuned by carefully selecting their surface-coordinated species. In artificial photosynthesis, surface-functionalization emerged in the last decade, grounded on the development of reliable methods for tailored synthesis, advanced characterization and theoretical modeling of metal NPs, altogether with the aim of transferring to the nanoscale the mechanistic knowledge acquired from molecular complexes. Metal NPs surface-functionalization modulates the energetics of key catalytic intermediates, introduces second coordination sphere effects, influences the catalyst-electrolyte interface, and determines the metal NPs surface coverage and, accordingly, the number of accessible active sites. In photoactivated systems, metal NPs surface-functionalization may play a key role in modulating the charge transfers and recombination processes between the light absorber and the active sites and in the light absorber itself. Thus, after a presentation of the most relevant synthetic methods to produce well-defined surface-functionalized metal NPs, a critical analysis of why the above effects are the cornerstone in enhancing their catalytic performance in the key processes of artificial photosynthesis, namely the oxygen evolution reaction, the hydrogen evolution reaction, and the CO2 reduction reaction, is given

Spontaneous reperfusion enhances succinate concentration in peripheral blood from stemi patients but its levels does not correlate with myocardial infarct size or area at risk

Cardiovascular biology; Diagnostic markers; Prognostic markersBiología cardiovascular; Marcadores de diagnóstico; Marcadores pronósticosBiologia cardiovascular; Marcadors diagnòstics; Marcadors pronòsticsSuccinate is enhanced during initial reperfusion in blood from the coronary sinus in ST-segment elevation myocardial infarction (STEMI) patients and in pigs submitted to transient coronary occlusion. Succinate levels might have a prognostic value, as they may correlate with edema volume or myocardial infarct size. However, blood from the coronary sinus is not routinely obtained in the CathLab. As succinate might be also increased in peripheral blood, we aimed to investigate whether peripheral plasma concentrations of succinate and other metabolites obtained during coronary revascularization correlate with edema volume or infarct size in STEMI patients. Plasma samples were obtained from peripheral blood within the first 10 min of revascularization in 102 STEMI patients included in the COMBAT-MI trial (initial TIMI 1) and from 9 additional patients with restituted coronary blood flow (TIMI 2). Metabolite concentrations were analyzed by 1H-NMR. Succinate concentration averaged 0.069 ± 0.0073 mmol/L in patients with TIMI flow ≤ 1 and was significantly increased in those with TIMI 2 at admission (0.141 ± 0.058 mmol/L, p < 0.05). However, regression analysis did not detect any significant correlation between most metabolite concentrations and infarct size, extent of edema or other cardiac magnetic resonance (CMR) variables. In conclusion, spontaneous reperfusion in TIMI 2 patients associates with enhanced succinate levels in peripheral blood, suggesting that succinate release increases overtime following reperfusion. However, early plasma levels of succinate and other metabolites obtained from peripheral blood does not correlate with the degree of irreversible injury or area at risk in STEMI patients, and cannot be considered as predictors of CMR variables. Trial registration: Registered at www.clinicaltrials.gov (NCT02404376) on 31/03/2015. EudraCT number: 2015-001000-58.This work was supported by the Spanish Ministry of Economy and Competitiveness, Instituto de Salud Carlos III (Grants PI17/01397 and CIBERCV) and the Spanish Society of Cardiology (Proyectos de la FEC para Investigación Básica en Cardiología 2018, Sociedad Española de Cardiología), and was cofinanced by the European Regional Development Fund (ERDF-FEDER, a way to build Europe). Antonio Rodríguez-Sinovas has a consolidated Miguel Servet contract

The impact of stapling technique and surgeon specialism on anastomotic failure after right?sided colorectal resection: an international multicentre, prospective audit

Aim There is little evidence to support choice of technique and configuration for stapled anastomoses after right hemicolectomy and ileocaecal resection. This study aimed to determine the relationship between stapling technique and anastomotic failure. Method Any unit performing gastrointestinal surgery was invited to contribute data on consecutive adult patients undergoing right hemicolectomy or ileocolic resection to this prospective, observational, international, multicentre study. Patients undergoing stapled, side?to?side ileocolic anastomoses were identified and multilevel, multivariable logistic regression analyses were performed to explore factors associated with anastomotic leak. Results One thousand three hundred and forty?seven patients were included from 200 centres in 32 countries. The overall anastomotic leak rate was 8.3%. Upon multivariate analysis there was no difference in leak rate with use of a cutting stapler for apical closure compared with a noncutting stapler (8.4% vs 8.0%, OR 0.91, 95% CI 0.54–1.53, P = 0.72). Oversewing of the apical staple line, whether in the cutting group (7.9% vs 9.7%, OR 0.87, 95% CI 0.52–1.46, P = 0.60) or noncutting group (8.9% vs 5.7%, OR 1.40, 95% CI 0.46–4.23, P = 0.55) also conferred no benefit in terms of reducing leak rates. Surgeons reporting to be general surgeons had a significantly higher leak rate than those reporting to be colorectal surgeons (12.1% vs 7.3%, OR 1.65, 95% CI 1.04–2.64, P = 0.04). Conclusion This study did not identify any difference in anastomotic leak rates according to the type of stapling device used to close the apical aspect. In addition, oversewing of the anastomotic staple lines appears to confer no benefit in terms of reducing leak rates. Although general surgeons operated on patients with more high?risk characteristics than colorectal surgeons, a higher leak rate for general surgeons which remained after risk adjustment needs further exploration

Relationship between method of anastomosis and anastomotic failure after right hemicolectomy and ileo-caecal resection: an international snapshot audit

Aim: The anastomosis technique used following right-sided colonic resection is widely variable and may affect patient outcome. This study aimed to assess the association between leak and anastomosis technique (stapled vs handsewn). Method: This was a prospective, multicentre, international audit including patients undergoing elective or emergency right hemicolectomy or ileo-caecal resection operations over a 2-month period in early 2015. The primary outcome measure was the presence of anastomotic leak within 30\ua0days of surgery, determined using a prespecified definition. Mixed effects logistic regression models were used to assess the association between leak and anastomosis method, adjusting for patient, disease and operative cofactors, with centre included as a random-effect variable. Results: This study included 3208 patients, of whom 78.4% (n\ua0=\ua02515) underwent surgery for malignancy and 11.7% (n\ua0=\ua0375) underwent surgery for Crohn's disease. An anastomosis was performed in 94.8% (n\ua0=\ua03041) of patients, which was handsewn in 38.9% (n\ua0=\ua01183) and stapled in 61.1% (n\ua0=\ua01858). Patients undergoing handsewn anastomosis were more likely to be emergency admissions (20.5% handsewn vs 12.9% stapled) and to undergo open surgery (54.7% handsewn vs 36.6% stapled). The overall anastomotic leak rate was 8.1% (245/3041), which was similar following handsewn (7.4%) and stapled (8.5%) techniques (P\ua0=\ua00.3). After adjustment for cofactors, the odds of a leak were higher for stapled anastomosis (adjusted OR\ua0=\ua01.43; 95% CI: 1.04\u20131.95; P\ua0=\ua00.03). Conclusion: Despite being used in lower-risk patients, stapled anastomosis was associated with an increased anastomotic leak rate in this observational study. Further research is needed to define patient groups in whom a stapled anastomosis is safe

The relationship between method of anastomosis and anastomotic failure after right hemicolectomy and ileo-caecal resection: an international snapshot audit.

BACKGROUND: Anastomosis technique following right sided colonic resection is widely variable and may affect patient outcomes. This study aimed to assess the association between leak and anastomosis technique (stapled versus handsewn) METHODS: This was a prospective, multicentre, international audit including patients undergoing elective or emergency right hemicolectomy or ileo-caecal resection operations over a two-month period in early 2015. The primary outcome measure was the presence of anastomotic leak within 30 days of surgery, using a pre-specified definition. Mixed effects logistic regression models were used to assess the association between leak and anastomosis method, adjusting for patient, disease and operative cofactors, with centre included as a random effect variable. RESULTS: This study included 3208 patients, of whom 78.4% (n=2515) underwent surgery for malignancy and 11.7% (n=375) for Crohn's disease. An anastomosis was performed in 94.8% (n=3041) of patients, which was handsewn in 38.9% (n=1183) and stapled in 61.1% (n=1858) cases. Patients undergoing handsewn anastomosis were more likely to be emergency admissions (20.5% handsewn versus 12.9% stapled) and to undergo open surgery (54.7% versus 36.6%). The overall anastomotic leak rate was 8.1% (245/3041), which was similar following handsewn (7.4%) and stapled (8.5%) techniques (p=0.3). After adjustment for cofactors, the odds of a leak were higher for stapled anastomosis (adjusted odds ratio 1.43, 95% confidence interval 1.04-1.95, p=0.03). DISCUSSION: Despite being used in lower risk patients, stapled anastomosis was associated with an increased anastomotic leak rate in this observational study. Further research is needed to define patient groups in whom a stapled anastomosis is safe. This article is protected by copyright. All rights reserve