Bio-adipic acid prepared by base-free aerobic oxidation of bio-based 1,6-hexanediol over Pt-Au/ZrO2 and Pd-Au/ZrO2 catalysts.

SSCI-VIDE+CDFA+MMG:NPR:CPI:MBEInternational audience1. Introduction There is an interest in the production of bio-based adipic acid derived from lignocellulosic biomass as an alternative or a supplement to the petrochemical process.1 Adipic acid is an important monomer in the manufacture of nylon 6,6 and polyurethanes, and a chemical used as food and cosmetic additives.1 It is commonly produced by nitric acid oxidation of a cyclohexanol/cyclohexanone mix.1 Recently, synthesis of 1,6-hexanediol (HDO) from renewables has been described via 5-hydroxymethylfurfural2 or tetrahydropyran-2-methanol3. Thereafter, catalytic oxidation of HDO to adipic acid can be carried out in water using oxygen and Pt/C under acidic conditions or Au/C under basic conditions.4 However, Au-Pt and Au-Pd bimetallic supported catalysts have already shown good performance in oxidation of alcohols or polyols in neutral water.5 Herein we report for the first time the oxidation of 1,6-hexanediol to adipic acid in base-free aqueous medium over Pt-Au/ZrO2 and Pd-Au/ZrO2 catalysts.2. Experimental Monometallic (Pd, Pt, Au) and Pt-Au/ZrO2 and Pd-Au/ZrO2 bimetallic catalysts with different compositions were prepared by wet impregnation of a ZrO2 support (MEL Chemicals, SBET=139 m2 g−1) with aqueous solutions of H2PtCl6, HAuCl4 and PdCl2 and NaBH4 reduction.5,6 The solids were characterized by ICP-OES, XRD, XPS, and TEM. Catalytic oxidation of HDO (0.1 mol. L-1) was carried out in water in a 300 mL batch reactor at 70°C under 40 bar of air, with a HDO/metal molar ratio of 100. Liquid samples were periodically taken during reaction and analyzed by HPLC and Total Organic Carbon (TOC). 3. Results and discussion XRD patterns of the bimetallic catalysts demonstrated the formation of Au-Pd and Au-Pt alloys whose composition, according to Vegard’s law, matched with the metal loadings. Fig.1 shows the evolution of HDO conversion and yields to the different products vs. time over 3.7%Pt/ZrO2. HDO was rapidly and totally converted within 3 h. DA was formed by sequential oxidation of HDO via 6-hydroxyhexanal (ALD), 6-hydroxyhexanoic acid (HA), and 6-oxohexanoic acid (AA) (Scheme 1). A final yield of 80% was observed after 48 h. Comparison of TOC and carbon balance from HPLC analysis were in very good agreement. Scheme 1. Reaction pathway for oxidation of HDO. Figure 1. HDO (0.1M) conversion () and yields to ALD (), HA (), AA (▲) and DA () over Pt/ZrO2 at 70°C under 40 bar of air. C balance (-), TOC (□).Table 1. HDO oxidation over ZrO2 supported Pt, Au, Pd, Pt-Au and Pd-Au. Reaction conditions: 0.1 M HDO, HDO/metal = 100, 70°C, 40 bar air, 48 h.Au/PtConv.Yield (%)Cata (Au/Pd) (%)ALDHAAADAPt-10020080AuPt0.1610000087AuPt0.4210000084AuPt0.7710000097AuPt0.910000096AuPt1.6610000096AuPt6.478532324Au-170603AuPd0.15100020162AuPd0.5895020065AuPd0.9610009081AuPd1.1210005082AuPd3.7855025013Pd-44121615HDO conversion and yields of the different products over the mono- and bimetallic catalysts containing different Au/Pt and Au/Pd ratios after 48 h are gathered in Table 1. Monometallic 3.1%Pd/ZrO2 and 3.6%Au/ZrO2 in the absence of a base were poorly active for oxidation (44% and 17% conversion after 48 h, respectively). Upon addition of Au to Pt and with increasing the Au content of the Au-Pt catalysts, the final yield of diacid increased progressively from 80% to a large maximum of 96-97% with a Au/Pt molar ratio in the range 0.8-1.7. The activity then dropped drastically and HDO conversion was even not total for Au/Pt = 6.4. The addition of Au to Pd and formation of the alloy also significantly improved the performances of the Pd catalyst. The maximum yield of DA was also observed for a Au/Pd ratio of ca. 1. However, the Au-Pd catalysts were less active than the Au-Pt catalysts; after 48 h of reaction, conversion of all intermediates was not complete. However, a higher temperature of 90°C used for Au-Pd/ZrO2 (Au/Pd ca. 1) yielded 96% DA. Comparison of the evolution of the selectivity to the different intermediates as a function of conversion shows different relative reaction rates for the different consecutive steps to DA (Scheme 1).4. Conclusions Pd-Au/ZrO2 and Pt-Au/ZrO2 prepared by a simple preparation procedure were performant catalysts for 1,6-hexanediol oxidation in non-alkaline aqueous medium. The optimization of the catalyst composition showed that adipic acid yield was the highest (96%) at Au/Pd and Au/Pt molar ratio of ca. 1 at 90°C over Pd-Au/ZrO2 and at 70°C over Pt-Au/ZrO2.References 1.S. Van de Vyver, Y. Romàn-Leshkov, Catal. Sci. Technol. 3 (2013) 1467-1479.2.J.G. de Vries, T. Buntara, P. Huat Phua, I.V. Melian Cabrera, H.J. Heeres, WO2011/149339 (2011). 3.S. P. Burt, K. J. Barnett, D. J. McClelland, P. Wolf, J. A. Dumesic, G. W. Huber, I. Hermans, Green Chem. 19 (2017) 1390.4.M. S. Ide, R. J. Davis, J. Catal. 308 (2013) 50-59.5.E. Derrien, M. Mounguengui-Diallo, N. Perret, ́ P. Marion, C. Pinel, Michele Besson, Ind. Eng. Chem. Res. (2017) DOI: 10.1021/acs.iecr.7b01576.K. Heidkamp, M. Aytemir, K.-D. Vorlop, U. Prüsse, Catal. Sci. Technol. 3 (2013) 2984-2992

Práxis psicoterapêutica de estagiários de psicologia: análise do relato e da trama narrativa

Este artigo apresenta uma proposta de análise narrativa das intervenções realizadas pelos estagiários de Psicologia em sua práxis psicoterapêutica. As fontes dos dados foram as transcrições das sessões de psicoterapia, conduzidas pelos estagiários com seus pacientes, associadas ao material discutido em supervisão acadêmica. A análise do texto transcrito, entendido nesse estudo como uma narrativa da prática, se deu em dois níveis: o do relato e o da trama narrativa. Os resultados explicitam os diferentes movimentos realizados pelos estagiários na tentativa de intervir em consonância com os pressupostos da psicoterapia de orientação analítica. Essas intervenções mostraram ser algumas vezes contraditórias, explicitando assim os equívocos e as vicissitudes constituintes do processo de formação do pensamento clínico

Enteral versus parenteral early nutrition in ventilated adults with shock : a randomised, controlled, multicentre, open-label, parallel-group study (NUTRIREA-2)

International audienceBackgroundWhether the route of early feeding affects outcomes of patients with severe critical illnesses is controversial. We hypothesised that outcomes were better with early first-line enteral nutrition than with early first-line parenteral nutrition.MethodsIn this randomised, controlled, multicentre, open-label, parallel-group study (NUTRIREA-2 trial) done at 44 French intensive-care units (ICUs), adults (18 years or older) receiving invasive mechanical ventilation and vasopressor support for shock were randomly assigned (1:1) to either parenteral nutrition or enteral nutrition, both targeting normocaloric goals (20–25 kcal/kg per day), within 24 h after intubation. Randomisation was stratified by centre using permutation blocks of variable sizes. Given that route of nutrition cannot be masked, blinding of the physicians and nurses was not feasible. Patients receiving parenteral nutrition could be switched to enteral nutrition after at least 72 h in the event of shock resolution (no vasopressor support for 24 consecutive hours and arterial lactate <2 mmol/L). The primary endpoint was mortality on day 28 after randomisation in the intention-to-treat-population. This study is registered with ClinicalTrials.gov, number NCT01802099.FindingsAfter the second interim analysis, the independent Data Safety and Monitoring Board deemed that completing patient enrolment was unlikely to significantly change the results of the trial and recommended stopping patient recruitment. Between March 22, 2013, and June 30, 2015, 2410 patients were enrolled and randomly assigned; 1202 to the enteral group and 1208 to the parenteral group. By day 28, 443 (37%) of 1202 patients in the enteral group and 422 (35%) of 1208 patients in the parenteral group had died (absolute difference estimate 2·0%; [95% CI −1·9 to 5·8]; p=0·33). Cumulative incidence of patients with ICU-acquired infections did not differ between the enteral group (173 [14%]) and the parenteral group (194 [16%]; hazard ratio [HR] 0·89 [95% CI 0·72–1·09]; p=0·25). Compared with the parenteral group, the enteral group had higher cumulative incidences of patients with vomiting (406 [34%] vs 246 [20%]; HR 1·89 [1·62–2·20]; p<0·0001), diarrhoea (432 [36%] vs 393 [33%]; 1·20 [1·05–1·37]; p=0·009), bowel ischaemia (19 [2%] vs five [<1%]; 3·84 [1·43–10·3]; p=0·007), and acute colonic pseudo-obstruction (11 [1%] vs three [<1%]; 3·7 [1·03–13·2; p=0·04).InterpretationIn critically ill adults with shock, early isocaloric enteral nutrition did not reduce mortality or the risk of secondary infections but was associated with a greater risk of digestive complications compared with early isocaloric parenteral nutrition.FundingLa Roche-sur-Yon Departmental Hospital and French Ministry of Health.Copyright © 2017 Elsevier Ltd. All rights reserved

Limited Resection Versus Pancreaticoduodenectomy for Duodenal Gastrointestinal Stromal Tumors? Enucleation Interferes in the Debate: A European Multicenter Retrospective Cohort Study

International audienc

Women and health professionals’ perspectives on a conditional cash transfer programme to improve pregnancy follow-up: a qualitative analysis of the NAITRE randomised controlled study

Objectives Women of low socioeconomic status have been described as having suboptimal prenatal care, which in turn has been associated with poor pregnancy outcomes. Many types of conditional cash transfer (CCT) programmes have been developed, including programmes to improve prenatal care or smoking cessation during pregnancy, and their effects demonstrated. However, ethical critiques have included paternalism and lack of informed choice. Our objective was to determine if women and healthcare professionals (HPs) shared these concerns.Design Prospective qualitative research.Setting We included economically disadvantaged women, as defined by health insurance data, who participated in the French NAITRE randomised trial assessing a CCT programme during prenatal follow-up to improve pregnancy outcomes. The HP worked in some maternities participating in this trial.Participants 26 women, 14 who received CCT and 12 who did not, mostly unemployed (20/26), and - 7 HPs.Interventions We conducted a multicentre cross-sectional qualitative study among women and HPs who participated in the NAITRE Study to assess their views on CCT. The women were interviewed after childbirth.Results Women did not perceive CCT negatively. They did not mention feeling stigmatised. They described CCT as a significant source of aid for women with limited financial resources. HP described the CCT in less positive terms, for example, expressing concern about discussing cash transfer at their first medical consultation with women. Though they emphasised ethical concerns about the basis of the trial, they recognised the importance of evaluating CCT.Conclusions In France, a high-income country where prenatal follow-up is free, HPs were concerned that the CCT programme would change their relationship with patients and wondered if it was the best use of funding. However, women who received a cash incentive said they did not feel stigmatised and indicated that these payments helped them prepare for their baby’s birth.Trial registration number NCT0240285