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41.
In this paper we report the first chemoselective asymmetric hydrogenation of (1-bromo-1-alkenyl)boronic esters, which constitutes a new route to (α-bromoalkyl)boronic esters. The study demonstrates that excellent chemoselectivities along with full conversions can be obtained for hydrogenation of alkyl substituted derivatives with iridium–PˆN complexes. Moreover, acyclic alkyl derivatives afford (α-bromoalkyl)boronic esters in good enantioselectivities ranging from 64 to 73% ee. A cyclic alkyl derivative was obtained only in a nearly racemic form. The (1-bromo-1-alkenyl)boronic esters appear to be less reactive towards homogenous hydrogenation conditions than their chloro analogues as demonstrated by the higher catalyst loadings required to achieve full conversions for alkyl derivatives and lower conversions observed for the aryl substituted derivatives. 相似文献
42.
Filip Botha Jan Budka Václav Eigner Oldřich Hudeček Lukáš Vrzal Ivana Císařová Pavel Lhoták 《Tetrahedron》2014
A new type of calixarene-based receptor designed for the recognition of chiral anions was prepared by the introduction of (S)-2-methylbutan-1-ol moieties into the lower rim of calixarene. The immobilization of calixarene skeleton in the 1,3-alternate conformation enabled the construction of a cavity consisting of preorganised ureido functions and chiral substituents in close proximity. This cavity is capable of chiral discrimination of selected anions as demonstrated on d- and l-phenylalaninates. 相似文献
43.
采用基于拉普拉斯算符聚焦形貌恢复方法,提出了模拟目标深度测量的数值模型。数值模拟的核心是基于通过几何光学预测的理想图像的卷积与透镜广义孔径函数的多色点扩散函数,即用聚焦误差替代抛物线圆柱形貌或高斯函数。该模型可以使用基于聚焦形貌恢复方法的传感器真实组件参数、光源光谱、光学系统离差、相机的光谱灵敏度。提出了光学系统离差(消球差、消色差、色差)对确定目标表面形貌的精确度和可靠性的影响。结果表明,该模型可以有效提高实验效率,缩短时滞,降低成本。 相似文献
44.
David E. Salazar Marcano Mhamad Aly Moussawi Alexander V. Anyushin Sarah Lentink Luc Van Meervelt Ivana Ivanovi-Burmazovi Tatjana N. Parac-Vogt 《Chemical science》2022,13(10):2891
Hybrid structures incorporating different organic and inorganic constituents are emerging as a very promising class of materials since they synergistically combine the complementary and diverse properties of the individual components. Hybrid materials based on polyoxometalate clusters (POMs) are particularly interesting due to their versatile catalytic, redox, electronic, and magnetic properties, yet the controlled incorporation of different clusters into a hybrid structure is challenging and has been scarcely reported. Herein we propose a novel and general strategy for combining multiple types of metal-oxo clusters in a single hybrid molecule. Two novel hybrid POM structures (HPOMs) bis-functionalised with dipentaerythritol (R–POM1–R; R = (OCH2)3CCH2OCH2C(CH2OH)) were synthesised as building-blocks for the formation of heterometallic hybrid triads (POM2–R–POM1–R–POM2). Such a modular approach resulted in the formation of four novel heterometallic hybrids combing the Lindqvist {V6}, Anderson–Evans {XMo6} (X = Cr or Al) and trisubstituted Wells–Dawson {P2V3W15} POM structures. Their formation was confirmed by multinuclear Nuclear Magnetic Resonance (NMR), infrared (IR) and UV-Vis spectroscopy, as well as Mass Spectrometry, Diffusion Ordered Spectroscopy (DOSY) and elemental analysis. The thermal stability of the hybrids was also examined by Thermogravimetric Analysis (TGA), which showed that the HPOM triads exhibit higher thermal stability than comparable hybrid structures containing only one type of POM. The one-pot synthesis of these novel compounds was achieved in high yields in aqueous and organic media under simple reflux conditions, without the need of any additives, and could be translated to create other hybrid materials based on a variety of metal-oxo cluster building-blocks.A versatile modular approach has been developed for incorporating different metal-oxo nanoclusters with characteristic structures into a single hybrid molecule by covalently linking them with polyol ligands. 相似文献
45.
Ivana Brekalo David E. Deliz Leonard J. Barbour Michael D. Ward Tomislav Fri
i K. Travis Holman 《Angewandte Chemie (International ed. in English)》2020,59(5):1997-2002
Guanidinium organosulfonates (GSs) are a large and well‐explored archetypal family of hydrogen‐bonded organic host frameworks that have, over the past 25 years, been regarded as nonporous. Reported here is the only example to date of a conventionally microporous GS host phase, namely guanidinium 1,4‐benzenedisulfonate ( p ‐G2BDS ). p ‐G2BDS is obtained from its acetone solvate, AcMe@ G2BDS , by single‐crystal‐to‐single‐crystal (SC‐SC) desolvation, and exhibits a Type I low‐temperature/pressure N2 sorption isotherm (SABET=408.7(2) m2 g?1, 77 K). SC‐SC sorption of N2, CO2, Xe, and AcMe by p ‐G2BDS is explored under various conditions and X‐ray diffraction provides a measurement of the high‐pressure, room temperature Xe and CO2 sorption isotherms. Though p ‐G2BDS is formally metastable relative to the “collapsed”, nonporous polymorph, np ‐G2BDS , a sample of p ‐G2BDS survived for almost two decades under ambient conditions. np ‐G2BDS reverts to zCO2@ p ‐G2BDS or yXe@ p ‐G2BDS (y,z=variable) when pressure of CO2 or Xe, respectively, is applied. 相似文献
46.
Patrícia Homobono Brito de Moura Wolfgang Brandt Andrea Porzel Roberto Carlos Campos Martins Ivana Correa Ramos Leal Ludger A. Wessjohann 《Molecules (Basel, Switzerland)》2022,27(8)
A rare dihydoxyflavan-epicatechin proanthocyanidin, entcassiflavan-(4β→8)-epicatechin, was isolated from Dalbergia monetaria, a plant widely used by traditional people from the Amazon to treat urinary tract infections. The constitution and relative configuration of the compound were elucidated by HR-MS and detailed 1D- and 2D-NMR measurements. By comparing the experimental electronic circular dichroism (ECD) spectrum with the calculated ECD spectra of all 16 possible isomers, the absolute configuration, the interflavan linkage, and the atropisomers could be determined. 相似文献
47.
48.
Fast simultaneous LC/MS/MS determination of 10 active compounds in human serum for therapeutic drug monitoring in psychiatric medication 下载免费PDF全文
Pavel Sistik Romana Urinovska Hana Brozmanova Ivana Kacirova Petr Silhan Karel Lemr 《Biomedical chromatography : BMC》2016,30(2):217-224
A UPLC/MS/MS method with simple protein precipitation has been validated for the fast simultaneous analysis of agomelatine, asenapine, amisulpride, iloperidone, zotepine, melperone, ziprasidone, vilazodone, aripiprazole and its metabolite dehydro‐aripiprazole in human serum. Alprenolol was applied as an internal standard. A BEH C18 (2.1 × 50 mm, 1.7 µm) column provided chromatographic separation of analytes using a binary mobile phase gradient (A, 2 mmol/L ammonium acetate, 0.1% formic acid in 5% acetonitrile, v/v/v; B, 2 mmol/L ammonium acetate, 0.1% formic acid in 95% acetonitrile, v/v/v). Mass spectrometric detection was performed in the positive electrospray ionization mode and ion suppression owing to matrix effects was evaluated. The validation criteria were determined: linearity, precision, accuracy, recovery, limit of detection, limit of quantification, reproducibility and matrix effect. The concentration range was as follows: 0.25–1000 ng/mL for agomelatine; 0.25–100 ng/mL for asenapine and iloperidone; 2.5–1000 ng/mL for amisulpride, aripiprazole, vilazodone and zotepine; 2.3–924.6 ng/mL for dehydroaripiprazole; 2.2–878.4 ng/mL for melperone; and 2.2–883.5 ng/mL for ziprasidone. Limits of quantitation below a therapeutic reference range were achieved for all analytes. Intra‐run precision of 0.4–5.5 %, inter‐run precision of 0.6–8.2% and overall recovery of 87.9–114.1% were obtained. The validated method was successfully implemented into routine practice for therapeutic drug monitoring in our hospital. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
49.
50.
Dmitrij Bondarev Jiří Zedník Ivana Šloufová Ahmed Sharf Marek Procházka Jiří Pfleger Jiří Vohlídal 《Journal of polymer science. Part A, Polymer chemistry》2010,48(14):3073-3081
High‐regioregular poly{3‐[6‐(1‐methylimidazolium‐3‐yl)hexyl]thiophene‐2,5‐diyl bromide}, PMHT‐Br, has been prepared by reaction of high‐regioregular (above 92%) poly[3‐(6‐bromohexyl)thiophene‐2,5‐diyl] with 1‐methylimidazole. PMHT‐Br is soluble in water and water miscible solvents such as methanol, DMSO and shows solvatochromism; λmax (nm): 423 (H2O); 435 (MeOH); 452 (DMSO). Increased absorption band broadening observed for aqueous solution as well as NMR spectra in D2O suggests a micelle‐like structure of PMHT‐Br molecules in these solutions: poly(3‐hexylthiophene) core and 1‐methylimidazolium bromide shell. Despite the disturbing effect of ionic groups, the solid‐state PMHT‐Br shows absorption maximum at 520 nm, the band edge at 660 nm (ca. 1.9 eV), and fluorescence emission with maximum at 635 nm, in a good agreement with the polymer regioregularity. Fluorescence emission maxima: λem (nm): 598 (H2O); 562 (MeOH); 574 (DMSO), occur in a vicinity of corresponding adsorption band edges. Plot of electrical conductivity of PMHT‐Br (measured under the dynamic vacuum conditions, 5 × 10?5 Pa) versus 1/T shows a break at about 70 °C same as the temperature dependence of λmax of the solid PMHT‐Br. These breaks indicate an increase in the mobility of polymer segments and ions within PMHT‐Br; however, a thermal analysis did not provide solid evidence for it. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3073–3081, 2010 相似文献