Iron-catalysed, general and operationally simple formal hydrogenation using Fe(OTf)3 and NaBH4.
ABSTRACT: An operationally simple and environmentally benign formal hydrogenation protocol has been developed using highly abundant iron(iii) salts and an inexpensive, bench stable, stoichiometric reductant, NaBH4, in ethanol, under ambient conditions. This reaction has been applied to the reduction of terminal alkenes (22 examples, up to 95% yield) and nitro-groups (26 examples, up to 95% yield). Deuterium labelling studies indicate that this reaction proceeds via an ionic rather than radical mechanism.
Project description:Gold nanoparticles (Au NPs) were prepared by reducing HAuCl4 with NaBH4. Their average particle sizes could be tuned in the range of 1.7 and 8.2 nm, by adjusting the amount of NaBH4 used during synthesis. The obtained Au NPs (colloids) were then loaded onto a commercial Al2O3 support to prepare Au/Al2O3 catalysts with tunable Au particle sizes. An optimal pH value (5.9) of the Au colloid solution was found to be essential for loading Au NPs onto Al2O3 while avoiding the growth of Au NPs. Au NPs and Au/Al2O3 catalysts were tested in the reduction of p-nitrophenol with NaBH4. Interestingly, the catalytic activity depended on the size of Au NPs, being the highest when the average size was 3.4 nm. Relevant characterization by UV-Vis, TEM, and XRD was conducted.
Project description:The role of natural killer (NK) cells in organ transplantation is controversial. This study aims to decipher their role in kidney transplant tolerance in humans. Previous studies highlighted several modulated genes involved in NK cell biology in blood from spontaneously operationally tolerant patients (TOLs; drug-free kidney-transplanted recipients with stable graft function). We performed a phenotypic, functional, and genetic characterization of NK cells from these patients compared to kidney-transplanted patients with stable graft function under immunosuppression and healthy volunteers (HVs). Both operationally TOLs and stable patients harbored defective expression of the NKp46 activator receptor and lytic molecules perforin and granzyme compared to HVs. Surprisingly, NK cells from operationally TOLs also displayed decreased expression of the CD16 activating marker (in the CD56Dim NK cell subset). This decrease was associated with impairment of their functional capacities upon stimulation, as shown by lower interferon gamma (IFN?) production and CD107a membranous expression in a reverse antibody-dependent cellular cytotoxicity (ADCC) assay, spontaneous lysis assays, and lower target cell lysis in the 51Cr release assay compared to HVs. Conversely, despite impaired K562 cell lysis in the 51Cr release assay, patients with stable graft function harbored a normal reverse ADCC and even increased amounts of IFN?+ NK cells in the spontaneous lysis assay. Altogether, the strong impairment of the phenotype and functional cytotoxic capacities of NK cells in operationally TOLs may accord with the establishment of a pro-tolerogenic environment, despite remaining highly activated after transplantation in patients with stable graft function.
Project description:This SuperSeries is composed of the following subset Series: GSE26622: MOLECULAR CHARACTERIZATION OF LIVER ALLOGRAFTS FROM OPERATIONALLY TOLERANT TRANSPLANT RECIPIENTS (Affymetrix) GSE26625: MOLECULAR CHARACTERIZATION OF LIVER ALLOGRAFTS FROM OPERATIONALLY TOLERANT TRANSPLANT RECIPIENTS (Illumina) Refer to individual Series
Project description:A highly enantioselective Lewis base-catalysed formal [3+2] cycloaddition of ammonium enolates and oxaziridines to give stereodefined oxazolidin-4-ones in high yield is described. Employing an enantioenriched oxaziridine in this process leads to a matched/mis-matched effect with the isothiourea catalyst and allowed the synthesis of either syn- or anti-stereodefined oxazolidin-4-ones in high d.r., yield and ee. Additionally, the oxazolidin-4-one products have been derivatised to afford functionalised enantioenriched building blocks.
Project description:The large number of reagents that have been developed for the synthesis of trifluoromethylated compounds is a testament to the importance of the CF3 group as well as the associated synthetic challenge. Current state-of-the-art reagents for appending the CF3 functionality directly are highly effective; however, their use on preparative scale has minimal precedent because they require multistep synthesis for their preparation, and/or are prohibitively expensive for large-scale application. For a scalable trifluoromethylation methodology, trifluoroacetic acid and its anhydride represent an attractive solution in terms of cost and availability; however, because of the exceedingly high oxidation potential of trifluoroacetate, previous endeavours to use this material as a CF3 source have required the use of highly forcing conditions. Here we report a strategy for the use of trifluoroacetic anhydride for a scalable and operationally simple trifluoromethylation reaction using pyridine N-oxide and photoredox catalysis to affect a facile decarboxylation to the CF3 radical.
Project description:Achieving drug-free tolerance or successfully using only small doses of immunosuppression is a major goal in organ transplantation. To investigate the potential mechanisms by which some kidney transplant recipients can achieve operational tolerance, we compared the expression profiles of microRNA in peripheral blood mononuclear cells of operationally tolerant patients with those of stable patients treated with conventional immunosuppression. B cells from operationally tolerant patients overexpressed miR-142-3p. The expression of miR-142-3p was stable over time and was not modulated by immunosuppression. In Raji B cells, overexpression of miR-142-3p modulated nearly 1000 genes related to the immune response of B cells, including potential miR-142-3p targets and molecules previously identified in the blood of operationally tolerant patients. Furthermore, our results suggested that a negative feedback loop involving TGF-? signaling and miR-142-3p expression in B cells may contribute to the maintenance of tolerance. In summary, miR-142-3p expression in peripheral blood mononuclear cells correlates with operational tolerance. Whether upregulation of miR-142-3p modulates inflammatory responses to promote tolerance or is a result of this tolerance state requires further study.
Project description:A two-step approach of improving the thermoelectric properties of Poly(3,4-ethylenedioxythiophene)poly(4-styrenesulfonate) (PEDOT:PSS) via the addition of the ionic liquid, 1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM:TFSI) and subsequent reduction with NaBH4 is presented. The addition of 2.5 v/v% of EMIM:TFSI to PEDOT:PSS increases the electrical conductivity from 3 S·cm-1 to 1439 S·cm-1 at 40 °C. An additional post treatment using the reducing agent, NaBH4, increases the Seebeck coefficient of the film from 11 µV·K-1 to 30 µV·K-1 at 40 °C. The combined treatment gives an overall improvement in power factor increase from 0.04 µW·m-1·K-2 to 33 µW·m-1·K-2 below 140 °C. Raman and XPS measurements show that the increase in PEDOT:PSS conductivity is due to PSS separation from PEDOT and a conformational change of the PEDOT chains from the benzoid to quinoid molecular orientation. The improved Seebeck coefficient is due to a reduction of charge carriers which is evidenced from the UV-VIS depicting the emergence of polarons.
Project description:Cellulose, the most abundant renewable biopolymer, exists in many forms, such as microgranular cellulose (MGCell), sigmacell cellulose (SCell), cellulose fibers (FCell), and ?-cellulose (AlfaCell). Several of these cellulose forms were protonated with an amine-containing agent polyethyleneimine (PEI), and the modified celluloses (XCell-PEI+) were studied as catalysts in methanolysis of NaBH4 for hydrogen (H2) generation. It was found that the SCell-PEI+-catalyzed reaction is the fastest one among the modified celluloses with a hydrogen generation rate of 5520 ± 119 mL H2/(g of catalyst × min). The activation energies of MGCell-PEI+, SCell-PEI+, FCell-PEI+, and AlfaCell-PEI+ were determined as +21.7, +23.4, +24.8, and + 21.8 kJ/mol, respectively. Reusability of catalysts was investigated, and regeneration of cellulose based catalysts after the fifth cycle could be readily achieved by HCl treatment to completely recover its activity. Therefore, PEI-modified-protonated cellulose forms constitute sustainable, re-generable, and renewable catalysts for production of H2, an environmentally benign green energy carrier.
Project description:Herein we report the first catalytic transfer hydrogenation of silyl enol ethers. This metal free approach employs tris(pentafluorophenyl)borane and 2,2,6,6-tetramethylpiperidine (TMP) as a commercially available FLP catalyst system and naturally occurring ?-terpinene as a dihydrogen surrogate. A variety of silyl enol ethers undergo efficient hydrogenation, with the reduced products isolated in excellent yields (29 examples, 82?% average yield).
Project description:An operationally simple and efficient workup method for tetrabutylammonium fluoride (TBAF)-mediated t-butyldimethylsilyl (TBS) deprotection has been developed. The procedure includes addition of a sulfonic acid resin and calcium carbonate, followed by filtration and evaporation. This method eliminates the tedious aqueous-phase extraction process to remove excess TBAF and materials derived from TBAF, thereby making the protocol highly amenable to multiple TBS deprotections. Its efficiency and usefulness were demonstrated by using the transformation of 1a to 3a in the halichondrin synthesis. [reaction: see text].