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121.
Diferrocenophosphaborin: A Planar‐Chiral,Redox‐Active and Anion‐Responsive Ambiphilic Ligand
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Dr. Jiawei Chen Didier A. Murillo Parra Prof. Dr. Roger A. Lalancette Prof. Dr. Frieder Jäkle 《Angewandte Chemie (International ed. in English)》2015,54(35):10202-10205
A new class of Janus‐like ambiphilic ligands is introduced. The rigid diferrocene backbone in heterocycles 4‐SnP and 4‐BP creates an unprecedented chiral environment as demonstrated by multinuclear NMR and single‐crystal X‐ray studies. In addition, the ligands are redox‐responsive and the Lewis acidic borane moiety in 4‐BP can be exploited to further tune the properties: a clear decrease in the CO stretching frequency of a Vaska‐type RhI complex 5‐BP is observed upon addition of fluoride ions. Thus, the Lewis acid and Lewis base sites influence each other and their strength can be modulated by redox chemistry and anion binding. 相似文献
122.
Highly Diastereoselective Synthesis of Methylenecyclobutanes by Merging Boron‐Homologation and Boron‐Allylation Strategies
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Michael Eisold Dr. Dorian Didier 《Angewandte Chemie (International ed. in English)》2015,54(52):15884-15887
A highly diastereoselective synthesis of methylenecyclobutanes possessing a quaternary stereocenter is reported, in which boron homologation of an easily‐generated cyclobutenylmetal species is performed, followed by an allylation reaction. Combining three steps in a one‐pot process further optimized the method, which afforded the expected adducts in excellent yields and stereoselectivity, starting from commercially available 4‐bromobutyne. 相似文献
123.
Gas‐Phase Infrared Spectra of Three Compounds of Astrochemical Interest: Vinyl,Allenyl, and Propargyl Isocyanides
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Dr. Abdessamad Benidar Prof. Dr. Didier Bégué Dr. Falk Richter Prof. Dr. Claude Pouchan Prof. Dr. Mohammed Lahcini Dr. Jean‐Claude Guillemin 《Chemphyschem》2015,16(4):848-854
Isocyanides, isomers of the cyanides detected in the interstellar medium, are also possible components of this medium. The infrared spectra (5000–500 cm?1) of gaseous vinyl isocyanide, allenyl isocyanide, and propargyl isocyanide have been recorded at 0.1 cm?1 resolution. When prepared on a gram scale to produce a partial pressure of 10 mbar after evaporation in the cell, these three isocyanides, which have previously been reported to be kinetically unstable, do not display any sign of decomposition when recording the spectra. Geometry optimizations and harmonic and anharmonic vibrational frequencies were calculated using the LCCSD(T) method with the cc‐pVTZ basis set. Anharmonic frequencies of fundamental, overtone, and combination transitions were calculated using a variational approach implemented in the P Anhar.v2.0 code, to assign the experimental data for each compound. These results improve our knowledge of these under‐investigated compounds and pave the way for other physicochemical studies on functionalized isocyanides. 相似文献
124.
Determination of four acidic nonsteroidal anti‐inflammatory drugs in wastewater samples by dispersive liquid–liquid microextraction based on solidification of floating organic droplet and high‐performance liquid chromatography
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Mihail Simion Beldean‐Galea Virginia Coman Didier Thiébaut Jérome Vial 《Journal of separation science》2015,38(4):641-648
A simple, environmentally friendly, and sensitive dispersive liquid–liquid microextraction based on solidification of floating organic droplet for the extraction of four acidic nonsteroidal anti‐inflammatory drugs (ketoprofen, naproxen, ibuprofen, and diclofenac) from wastewater samples subsequent by high‐performance liquid chromatography analysis was developed. The influence of extraction parameters such as pH, the effect of solution ionic strength, type of extraction solvent, disperser solvent, and extraction solvent volume were studied. High enrichment factors (283–302) were obtained through the developed method. The method provides good linearity (r > 0.999) in a concentration range of 1–100 μg/L, good intra‐ and inter‐day precision (relative standard deviation < 7%) and low limits of quantification. The relative recoveries of the selected compounds were situated over 80% both in synthetic and real water samples. The developed method has been successfully applied for the analysis of the selected compounds in wastewater samples. 相似文献
125.
Amos J. Rosenthal Marc Devillard Karinne Miqueu Ghenwa Bouhadir Didier Bourissou 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(32):9330-9334
The P‐coordinated boryl radical [Ph2P(naphthyl)BMes]. (Mes=mesityl) was prepared by (electro)chemical reduction of the corresponding borenium salt or bromoborane. Electron paramagnetic resonance (EPR) analysis in solution and DFT calculations indicate large spin density on boron (60–70 %) and strong P–B interactions (P→B σ donation and B→P negative hyperconjugation). The radical is persistent in solution and participates in a Gomberg‐type dimerization process. The associated quinoid‐type dimer has been characterized by single‐crystal X‐ray diffraction. 相似文献
126.
Julien Huser Sophie Bistac Christelle Delaite Didier Dentel Mickaël Derivaz Mohamed Zanouni 《Surface and interface analysis : SIA》2015,47(4):523-528
The grafting of trialkoxysilane molecules should also give rise to the formation of a siloxane network at the substrate's surface when trialkoxysilanes are used. Other candidates that might be able to act as adhesion promoters at metallic surfaces are dimethylalkoxysilanes. The advantage of dimethylalkoxysilanes is that only one silanol group is produced during the hydrolysis step, leading to the formation of a grafted monolayer onto the steel. Moreover, the chemical grafting of stainless steel, which exhibits a low surface reactivity, is of great interest for industrial applications such as adhesive bonding or coatings. The objective of this work was to chemically graft dimethylalkoxysilanes onto AISI 316L stainless steel and to analyze the grafted layer by X‐ray photoelectron spectroscopy (XPS). Investigation of the hydrolysis of these molecules in aqueous solutions was also performed by proton nuclear magnetic resonance spectroscopy (1H NMR). The grafting of 3‐(ethoxydimethylsilyl)propylamine (APDES) and 3‐glycidoxypropyldimethylethoxysilane (GPDES) was achieved onto stainless steel after a controlled hydrolysis reaction. A pH inferior or equal to 5 was necessary to obtain a sufficient hydrolysis of silanes. XPS results have evidenced the grafting of the silanes onto stainless steel. The signal of the Si 2p peak clearly showed the formation of a covalent bond between APDES and the stainless steel surface through the O atoms giving rise to a uniform layer of adsorbed molecules. Moreover, this grafted layer is strongly stable as no removal of the alkoxysilane was observed after immersion in hot water which is very critical for these molecules. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
127.
128.
Cristina Díez Davy Guillarme Aline Staub Spörri Emmanuelle Cognard Didier Ortelli Patrick Edder Serge Rudaz 《Analytica chimica acta》2015
In this study, fourteen highly polar aminoglycoside (AGs) antibiotics were selected. Various stationary phases were tested, including Obelisc R, ZIC-HILIC, BEH amide and aminopropyl. The nature of the stationary phase, mobile phase (water or buffer solutions and acetonitrile), pH (percentage of formic acid), gradient conditions and injection solvents were systematically studied as relevant parameters for tuning retention selectivity and detectability of AGs in liquid chromatography electrospray tandem mass spectrometry (LC–(ESI)–MS/MS). Only the two zwitterionic phases (Obelisc R and ZIC-HILIC) achieved a proper chromatographic separation considering interferences due to the crosstalk effect in low resolution mass spectrometers. The water/acetonitrile mobile phase containing 1% formic acid used with Obelisc R provided more sensitivity than the highly concentrated buffered mobile phases required for ZIC-HILIC. A solid phase extraction (SPE) clean-up procedure with polymeric weak cation exchange (WCX) cartridges was optimized for honey, milk and liver samples. Different brands of cartridges and elution solvents were tested, and the Taurus WCX offered the best recovery rate with a buffer elution at pH 3. The final optimized method was validated in these matrices according to Decision 2002/657/EC. A monitoring campaign for sixty honey, milk and liver samples was carried out at the Food Authority Control in Geneva. The concentration of dihydrostreptomycin (DSTP) found in one ovine liver exceeded the established maximum residue levels (MRLs) within the European and Swiss legislations but it was compliant taking into account the validation data. 相似文献
129.
Computational Studies on Intramolecular Cycloadditions of Azidoenynes and Azidobutenenitriles to Give 6H‐Pyrrolo[1,2‐c][1,2,3]triazoles and 5H‐Pyrrolo[1,2‐d]tetrazoles
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Gérard Audran Paul Brémond Douniazad El Abed Sylvain R. A. Marque Didier Siri Maurice Santelli 《Helvetica chimica acta》2015,98(7):1018-1027
Energetics of intramolecular cycloadditions of azidoenynes and azidobutenenitriles to give 6H‐pyrrolo[1,2‐c][1,2,3]triazoles and 5H‐pyrrolo[1,2‐d]tetrazoles have been calculated at the B3LYP/6.311++G(3df,3pd) level of theory in ideal gas and in H2O as solvent. Stabilities of the corresponding anions, tautomers, and isomers are discussed. Transition states of the cyclization of parent compounds are determined at the same level of theory. 相似文献
130.
Dr. Graeme J. Stasiuk Dr. Florencia Minuzzi Dr. Myra Sae‐Heng Charlotte Rivas Dr. Hans‐Paul Juretschke Dr. Lorenzo Piemonti Dr. Peter R. Allegrini Dr. Didier Laurent Andrew R. Duckworth Prof. Andrew Beeby Prof. Guy A. Rutter Prof. Nicholas J. Long 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(13):5023-5033
Despite the contribution of changes in pancreatic β‐cell mass to the development of all forms of diabetes mellitus, few robust approaches currently exist to monitor these changes prospectively in vivo. Although magnetic‐resonance imaging (MRI) provides a potentially useful technique, targeting MRI‐active probes to the β cell has proved challenging. Zinc ions are highly concentrated in the secretory granule, but they are relatively less abundant in the exocrine pancreas and in other tissues. We have therefore developed functional dual‐modal probes based on transition‐metal chelates capable of binding zinc. The first of these, Gd ?1 , binds ZnII directly by means of an amidoquinoline moiety (AQA), thus causing a large ratiometric Stokes shift in the fluorescence from λem=410 to 500 nm with an increase in relaxivity from r1=4.2 up to 4.9 mM ?1 s?1. The probe is efficiently accumulated into secretory granules in β‐cell‐derived lines and isolated islets, but more poorly by non‐endocrine cells, and leads to a reduction in T1 in human islets. In vivo murine studies of Gd ?1 have shown accumulation of the probe in the pancreas with increased signal intensity over 140 minutes. 相似文献