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141.
Substitution pattern elucidation of hydroxypropyl Pinus pinaster (Ait.) bark polyflavonoid derivatives by ESI(−)‐MS/MS 下载免费PDF全文
Danny E. García Marrero Wolfgang G. Glasser Antonio Pizzi Sebastian Paczkowski Marie‐Pierre G. Laborie 《Journal of mass spectrometry : JMS》2014,49(10):1050-1058
The structure of condensed tannins (CTs) from Pinus pinaster bark extract and their hydroxypropylated derivatives with four degrees of substitution (DS 1, 2, 3 and 4) has been characterized for the first time using negative‐ion mode electrospray ionization tandem mass spectrometry (ESI(?)‐MS/MS). The results showed that P. pinaster bark CTs possess structural homogeneity in terms of monomeric units (C15, catechin). The oligomer sizes were detected to be dimers to heptamers. The derivatives showed typical phenyl‐propyl ether mass fragmentation by substituent elimination (58 amu) and inherent C15 flavonoid fissions. The relative abundance of the product ions revealed a preferential triple, tetra‐/penta‐ and octa‐ hydroxypropylation substitution pattern in the monomer, dimer and trimer derivatives, respectively. A defined order of –OH reactivity towards propylene oxide was established by means of multistage experiments (A‐ring ≥ B‐ring > C‐ring). A high structural heterogeneity of the modified oligomers was detected. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
142.
Nikola Peřinka Markéta Držková Milena Hajná Bohumil Jašúrek Petra Šulcová Tomáš Syrový Marie Kaplanová Jaroslav Stejskal 《Journal of Thermal Analysis and Calorimetry》2014,116(2):589-595
The polyaniline dispersions stabilized with poly(N-vinylpyrrolidone) (PANI/PVP) were synthesized by oxidative polymerization with different mass ratios of PANI and PVP and different molar concentrations of the components in the polymerization mixture. The composite powders prepared from colloidal PANI/PVP dispersions were characterized by thermogravimetry and differential thermal analysis. The change in the ratio of PANI and PVP as well as the starting molar concentrations of aniline hydrochloride and oxidant has influence on the resulting properties of the dispersions. Concerning the doping, the results show that PANI/PVP powders are stable up to approximately 160 °C. Degradation of polymer chains starts at temperatures above 250 °C. The PANI/PVP composite powders with lower content of PANI exhibit slightly higher thermal stability. Further, colloidal PANI/PVP dispersions were screen-printed on aluminum foil for infrared spectroscopic characterization and on poly(ethylene terephthalate) foil for electrical measurements. The sheet resistance of printed layers measured by two-point probe was of the order of tens to thousands of kΩ sq?1. The influence of both the change in the composition and the drying temperature is discussed. 相似文献
143.
144.
High‐Yield Formation of Substituted Tetracyanobutadienes from Reaction of Ynamides with Tetracyanoethylene 下载免费PDF全文
Dr. Marie Betou Nicolas Kerisit Esme Meledje Dr. Yann R. Leroux Dr. Claudine Katan Dr. Jean‐François Halet Dr. Jean‐Claude Guillemin Dr. Yann Trolez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9553-9557
A high‐yielding sequence of [2+2] cycloaddition–retroelectrocyclization of ynamides with tetracyanoethylene (TCNE) is described. The reaction provided tetracyanobutadiene (TCBD) species, which were characterized by various techniques. DFT and TD‐DFT calculations were also performed to complement experimental findings. 相似文献
145.
Self‐Assembly of a Highly Organized,Hexameric Supramolecular Architecture: Formation,Structure and Properties 下载免费PDF全文
Dr. Gaël Schaeffer Dr. Olaf Fuhr Prof. Dieter Fenske Prof. Jean‐Marie Lehn 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):179-186
Two derivatives, 3 L and 9 L , of a ditopic, multiply hydrogen‐bonding molecule, known for more than a decade, have been found, in the solid state as well as in solvents of low polarity at room temperature, to exist not as monomers, but to undergo a remarkable self‐assembly into a complex supramolecular species. The solid‐state molecular structure of 3 L , determined by single‐crystal X‐ray crystallography, revealed that it forms a highly organized hexameric entity 3 L 6 with a capsular shape, resulting from the interlocking of two sets of three monomolecular components, linked through hydrogen‐bonding interactions. The complicated 1H NMR spectra observed in o‐dichlorobenzene (o‐DCB) for 3 L and 9 L are consistent with the presence of a hexamer of D3 symmetry in both cases. DOSY measurements confirm the hexameric constitution in solution. In contrast, in a hydrogen‐bond‐disrupting solvent, such as DMSO, the 1H NMR spectra are very simple and consistent with the presence of isolated monomers only. Extensive temperature‐dependent 1H NMR studies in o‐DCB showed that the L 6 species dissociated progressively into the monomeric unit on increasing th temperature, up to complete dissociation at about 90 °C. The coexistence of the hexamer and the monomer indicated that exchange was slow on the NMR timescale. Remarkably, no species other than hexamer and monomer were detected in the equilibrating mixtures. The relative amounts of each entity showed a reversible sigmoidal variation with temperature, indicating that the assembly proceeded with positive cooperativity. A full thermodynamic analysis has been applied to the data. 相似文献
146.
Damien Hueber Marie Hoffmann Dr. Benoît Louis Prof. Dr. Patrick Pale Dr. Aurélien Blanc 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):3903-3907
Gold(I)‐polyoxometalate hybrid complexes 1 – 4 ([PPh3AuMeCN]xH4?xSiW12O40, x=1–4) were synthesized and characterized. The structure of the primary gold(I)–polyoxometalate 1 (x=1) was fully ascertained by XRD, FTIR, 31P and 29Si magic‐angle spinning (MAS) NMR, mass spectroscopy, and SEM–energy dispersive X‐ray spectroscopy (EDX) techniques. Moreover, this complex exhibited better catalytic activity and selectivity compared with standard, homogeneous, gold catalysts in the new rearrangement of propargylic gem‐diesters. 相似文献
147.
Exploring the Molecular Structure of Imidazolium–Silica‐Based Nanoparticle Networks by Combining Solid‐State NMR Spectroscopy and First‐Principles Calculations 下载免费PDF全文
Dr. Marie‐Alexandra Neouze Martin Kronstein Dr. Marco Litschauer Dr. Michael Puchberger Dr. Cristina Coelho Prof. Christian Bonhomme Prof. Christel Gervais Dr. Frederik Tielens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15188-15196
A DFT‐based molecular model for imidazolium–silica‐based nanoparticle networks (INNs) is presented. The INNs were synthesized and characterized by using small‐angle X‐ray scattering (SAXS), NMR spectroscopy, and theoretical ab initio calculations. 11B and 31P HETCOR CP MAS experiments were recorded. Calculated 19F NMR spectroscopy results, combined with the calculated anion–imidazolium (IM) distances, predicted the IM chain density in the INN, which was also confirmed from thermogravimetric analysis/mass spectrometry results. The presence of water molecules trapped between the nanoparticles is also suggested. First considerations on possible π–π stacking between the IM rings are presented. The predicted electronic properties confirm the photoluminescence emissions in the correct spectral domain. 相似文献
148.
1,10‐Phenanthroline and Non‐Symmetrical 1,3,5‐Triazine Dipicolinamide‐Based Ligands For Group Actinide Extraction 下载免费PDF全文
Dr. Julia Bisson Dr. Jérémy Dehaudt Dr. Marie‐Christine Charbonnel Dr. Denis Guillaneux Dr. Manuel Miguirditchian Dr. Cécile Marie Nathalie Boubals Guy Dutech Dr. Muriel Pipelier Dr. Virginie Blot Prof. Didier Dubreuil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(25):7819-7829
The synthesis and evaluation of new extractants for spent nuclear fuel reprocessing are described. New bitopic ligands constituted of phenanthroline and 1,3,5‐triazine cores functionalized by picolinamide groups were designed. Synthetic routes were investigated and optimized to obtain twelve new polyaza‐heterocyclic ligands. In particular, an efficient and versatile methodology was developed to access non‐symmetric 2‐substituted‐4,6‐di(6‐picolin‐2‐yl)‐1,3,5‐triazines from the 1,3,5‐triazapentadiene precursor in the presence of anhydride reagents. Extraction studies showed the ability of both ligand series to extract and separate actinides selectively at different oxidation states (UVI, NpV,VI, AmIII, CmIII, and PuIV) from an acidic solution (3 M HNO3). Phenanthroline‐based ligands show the most promising efficiency for use in the group actinide extraction (GANEX) process due to a higher number of donor nitrogen atoms and a suitable pre‐organization of the dipicolinamide‐1,10‐phenanthroline architecture. 相似文献
149.
Lead Structures for New Antibacterials: Stereocontrolled Synthesis of a Bioactive Muraymycin Analogue 下载免费PDF全文
Daniel Wiegmann Dr. Stefan Boettcher Agnes Mihalyi Prof. Timothy D. H. Bugg Prof. Christian Ducho 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(47):15292-15297
Naturally occurring muraymycin nucleoside antibiotics represent a promising class of novel antibacterial agents. The structural complexity suggests the investigation of simplified analogues as potential lead structures, which can then be further optimized towards highly potent antimicrobials. Herein we report studies on muraymycin‐derived potential lead structures lacking an aminoribose motif found in most naturally occurring muraymycins. We have identified a 5′‐defunctionalized motif to be ideal in terms of stability and chemical accessibility and have synthesized a full‐length muraymycin analogue based on this structure using a novel fully stereocontrolled route. The obtained 5′‐deoxy analogue of the natural product muraymycin C4 showed good inhibitory properties towards the bacterial target protein MraY, sufficient pharmacokinetic stability and no cytotoxicity against human cells, thus making it a promising lead for antibacterial drug development. 相似文献
150.
Dr. Marina Büchert Torben Steenbock Christian Lukaschek Marie C. Wolff Prof. Dr. Carmen Herrmann Prof. Dr. Jürgen Heck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(44):14351-14361
Parallel alignment of dipolar electron‐donor–π‐bridge‐electron‐acceptor entities can strongly enhance their nonlinear optical properties. This favorable arrangement can be in principle achieved by linking these units covalently or through metal coordination. Four dipolar single‐strand chromophores decorated with a 5‐electron‐donor–5′‐electron‐acceptor‐modified 2,2′‐bipyridine functionality were synthesized. For two of these chromophores triple‐stranded dendritic structures were successfully formed. All of the compounds were characterized with respect to their linear and nonlinear optical properties. For the aldehyde derivatives an enhancement of the first hyperpolarizability of 4.5 rather than 3 was obtained when going from single to triple strands. Theoretical calculations with density functional theory suggest that interstrand transitions contribute to the optical properties of the dendritic structures. 相似文献