Selectivity enhancement in the aqueous acid-catalyzed conversion of glucose to 5-hydroxymethylfurfural induced by choline chloride.

International audienceIn this work we wish to show that choline chloride (ChCl), a cheap and safe quaternary ammonium salt industrially produced at a few thousand tons per year through a 100% atom economy process, is capable of enhancing the selectivity of metal chlorides such as AlCl3, FeCl3 and CuCl2 in the aqueous tandem isomerization/dehydration of glucose to HMF. Under optimized conditions, 70% yield of HMF was obtained in a water/methylisobutylketone (MIBK) biphasic system which is a competitive yield to those traditionally obtained in imidazolium-based ionic liquids in the presence of hazardous chromium salts. By means of counter experiments, we show that the selectivity enhancement is optimal for a ChCl content of 50 wt% in water. At higher loading of ChCl, strong molecular interaction occurs between ChCl and HMF making the extraction of HMF from the aqueous phase difficult with MIBK, thus enhancing side reactions of HMF with water and hexoses to unwanted products. Interestingly, this process can be transposed to the direct conversion of cellulose to HMF which is an even more challenging reaction. In this case, we show that combination of FeCl3 with AlCl3 allowed cellulose to be converted to HMF with 49% yield in a one pot reaction. From the viewpoint of sustainable chemistry, this work shows noticeable advantages such as the use of (1) water as a solvent, (2) ChCl as a cheap and safe additive, (3) cheap and naturally abundant metals (Al, Fe, and Cu) and (4) renewable raw materials

Overweight is associated to a better prognosis in metastatic colorectal cancer: A pooled analysis of FFCD trials

IF 7.191 (2017)International audienceBACKGROUND:Previous studies showed that high and low body mass index (BMI) was associated with worse prognosis in early-stage colorectal cancer (CRC), and low BMI was associated with worse prognosis in metastatic CRC (mCRC). We aimed to assess efficacy outcomes according to BMI.PATIENTS AND METHODS:A pooled analysis of individual data from 2085 patients enrolled in eight FFCD first-line mCRC trials from 1991 to 2013 was performed. Comparisons were made according to the BMI cut-off: Obese (BMI ≥30), overweight patients (BMI ≥ 25), normal BMI patients (BMI: 18.5-24) and thin patients (BMI <18.5). Interaction tests were performed between BMI effect and sex, age and the addition of antiangiogenics to chemotherapy.RESULTS:The rate of BMI ≥25 patients was 41.5%, ranging from 37.6% (1991-1999 period) to 41.5% (2000-2006 period) and 44.8% (2007-2013 period). Comparison of overweight patients versus normal BMI range patients revealed a significant improvement of median overall survival (OS) (18.5 versus 16.3 months, HR = 0.88 [0.80-0.98] p = 0.02) and objective response rate (ORR) (42% versus 36% OR = 1.23 [1.01-1.50] p = 0.04) but a comparable median progression-free survival (PFS) (7.8 versus 7.2 months, HR = 0.96 [0.87-1.05] p = 0.35). Subgroup analyses revealed that overweight was significantly associated with better OS in men. OS and PFS were significantly shorter in thin patients.CONCLUSION:Overweight patients had a prolonged OS compared with normal weight patients with mCRC. The association of overweight with better OS was only observed in men. The pejorative prognosis of BMI <18.5 was confirmed.Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserve