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Stereodivergent Carbamate Synthesis by Selective in Situ Trapping of Organic Carbonate Intermediates 下载免费PDF全文
Dr. Eddy Martin Eduardo C. Escudero‐Adán Prof. Dr. Arjan W. Kleij 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(5):1722-1727
Trans carbamates have been prepared in a diastereoselective approach by a judicious one‐pot combination of organic carbonates, prepared in situ, and suitable amine reagents under appropriate reaction conditions. This unprecedented approach allows for stereodivergence from a single oxirane substrate with easy access to both cis and trans carbamate isomers with high stereoselectivity (>19:1 d.r.). Key to the control of the diastereoselective nature of the conversions that lead to the trans carbamates is the in situ formation of trans‐configured oligo/polycarbonates through Al catalysis, which provides the targeted products after aminolysis. The present results demonstrate the valorization of a renewable carbon‐based reagent (CO2) into new valuable scaffolds and an unusual stereocontrol exerted through carbonate intermediates. A series of control experiments support the proposed mechanistic rationale towards the trans carbamate products, which is based on the trapping of an in situ formed trans‐configured oligo/polycarbonate. 相似文献
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Angela Somavilla Higioka Renata Cristina Messores Rudolf-Oliveira Flavia Martinello Maria Luiza Bazzo 《Accreditation and quality assurance》2016,21(2):143-149
Point-of-care (POC) testing of glucose (glucometers) represents a convenient alternative to monitor glycemia since the measurement procedure is performed without delay after sampling of the capillary blood, thereby avoiding the metabolism by the blood cells of glucose present in plasma. Likely because of sample instability, there is no proficiency test provider in Brazil for this type of POC sample. In this context, this study aimed to evaluate the analytical performance of glucometers used in a tertiary care hospital. The glucometers used were the Accu-Chek Performa® model from Roche Diagnostics, which use the principle of amperometry. The reference method was the reaction with modified hexokinase/glucose-6-phosphate in a Dimension® device. The stability evaluation of the control samples showed that it can be performed up to 90 min after the collection of whole blood samples. In the two rounds performed, only one result of the 17 glucometers evaluated was out of the threshold of two standard deviation. Thus, this method for control of glucometers met the expectations and enabled comparing the glucometers in a hospital. Given the current quality guidelines, daily internal quality control of glucometers is recommended, besides at least two annual comparisons between the results of the glucometers and the reference method and one EQA every 3 months. 相似文献
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Cristiana Cesari Iacopo Ciabatti Cristina Femoni Maria Carmela Iapalucci Stefano Zacchini 《Journal of Cluster Science》2017,28(4):1963-1979
The reactions of [Ni16(C2)2(CO)23]4? and [Ni38C6(CO)42]6? with CuCl afforded mixtures of the previously reported [HNi42C8(CO)44(CuCl)]7? bimetallic octa-carbide cluster and the new [HNi43C8(CO)45]7? and [HNi44C8(CO)46]7? homo-metallic octa-carbides. The three species have very similar properties resulting always in co-crystals such as [NMe4]7[HNi42+2xC8(CO)44+2x(CuCl)1?x]·6.5MeCN (x = 0.14) (86% [HNi42C8(CO)44(CuCl)]7?, 14%[HNi43C8(CO)45]7?/[HNi44C8(CO)46]7?) and [NMe4]7[HNi42+2xC8(CO)44+2x(CuCl)1?x]·5.5MeCN (x = 0.30) (70% [HNi42C8(CO)44(CuCl)]7?, 30% [HNi43C8(CO)45]7?/[HNi44C8(CO)46]7?). The new homo-metallic octa-carbides can be obtained free from the Ni–Cu octa-carbido cluster by reacting [Ni10(C2)(CO)16]2? in thf with a stoichiometric amount of CuCl, and crystals of [NMe4]6[H2Ni43+xC8(CO)45+x]·6MeCN (x = 0.72), which contain [H2Ni44C8(CO)46]6? (72%) and [H2Ni43C8(CO)45]6? (28%), have been obtained. Despite the different charges and compositions, these anions display almost identical structures, which are also closely related to those previously reported for the bimetallic Ni–Cd octa-carbido clusters [Ni42+xC8(CO)44+x(CdCl)]7? and [HNi42+xC8(CO)44+x(CdBr)]6?. Indeed, all these clusters are based on the same Ni42C8 cage decorated by miscellaneous [CdX]+ (X = Cl, Br), [CuCl] and [Ni(CO)] fragments. 相似文献
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Malva sylvestris L. extract suppresses desferrioxamine‐induced PGE2 and PGD2 release in differentiated U937 cells: the development and validation of an LC‐MS/MS method for prostaglandin quantification 下载免费PDF全文
Cleverson Antonio Ferreira Martins Almeriane Maria Weffort‐Santos João Cleverson Gasparetto Angela Cristina Leal Badaró Trindade Michel Fleith Otuki Roberto Pontarolo 《Biomedical chromatography : BMC》2014,28(7):986-993
Malva sylvestris is a species used worldwide as an alternative to anti‐inflammatory therapies; however, its mechanism of action remains unknown. In this paper, the anti‐inflammatory effects of M. sylvestris alcoholic extracts were evaluated by measuring the pro‐inflammatory mediators PGE2 and PGD2 in desferrioxamine‐stimulated phorbol 12‐myristate 13‐acetate‐differentiated U937 cells. An HPLC‐DAD fingerprint of the M. sylvestris extract was performed and caffeic acid, ferulic acid and scopoletin were identified and quantified. An HPLC‐MS/MS method was developed and validated to separate and measure the prostaglandins. The lower limits of detection (~0.5 ng/mL for PGE2 and PGD2) and quantification (1.0 ng/mL for PGE2 and PGD2) indicated that the method is highly sensitive. The calibration curves showed excellent coefficients of correlation (r > 0.99) over the range of 1.0–500.0 ng/mL, and at different levels, the accuracy ranged from 96.4 to 106.4% with an RSD < 10.0% for the precision study. This method was successfully applied using U937‐d cells. A significant dose‐dependent reduction of PGE2 and PGD2 levels occurred using 10 µg/mL (10.74 ± 2.86 and 9.60 ± 6.89%) and 50 µg/mL of extract (48.37 ± 3.24 and 53.06 ± 6.15%), suggesting that the anti‐inflammatory mechanisms evoked by M. sylvestris may be related to modulation of these mediators. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
110.
Anthony Linden Teresa de Haro Cristina Nevado 《Acta Crystallographica. Section C, Structural Chemistry》2012,68(1):m1-m3
The molecule of the title compound, [AuCl(C27H36N2)], which belongs to a class of potentially catalytically active N‐heterocyclic carbene complexes, has crystallographic C2 symmetry and approximate C2v symmetry. The structure is isostructural with the CuI and AgI analogues. A previous report of the structure of the title compound as its toluene solvate [Fructos et al. (2005). Angew. Chem. Int. Ed. 44 , 5284–5288] has inaccurate geometry for the complex molecule as a consequence of probable incorrect refinement in the space group Cc, instead of C2/c [Marsh (2009). Acta Cryst. B 65 , 782–783]. The Au—C bond length of 1.998 (4) Å in the title compound is more consistent with the mean distance of 1.979 (14) Å found in 52 other reported [AuCl(carbene)] complexes than with the shorter distance of 1.942 (3) Å given for the refinement in the space group Cc for the toluene solvate and the value of 1.939 Å obtained from the recalculation of that structure in C2/c. 相似文献