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21.
Jean-Franjois Nierengarten Andreas Herrmann Rik R. Tykwinski Markus Riittimann Francois Diederich Corinne Boudon Jean-Paul Gisselbrecht Maurice Gross 《Helvetica chimica acta》1997,80(1):293-316
The synthesis of (E)-hex-3-ene-l, 5-diynes and 3-methylidenepenta-1, 4-diynes with pendant methano[60]-fullerene moieties as precursors to C60-substituted poly(triacetylenes) (PTAs, Fig. 1) and expanded radialenes (Fig. 2) is described. The Bingel reaction of diethyl (E)-2, 3-dialkynylbut-2-ene-1, 4-diyl bis(2-bromopropane-dioates) 5 and 6 with two C60 molecules (Scheme 2) afforded the monomeric, silyl-protected PTA precursors 9 and 10 which, however, could not be effectively desilylated (Scheme 4). Also formed during the synthesis of 9 and 10 , as well as during the reaction of C60 with thedesilylated analogue 16 (Scheme 5 ), were the macrocyclic products 11, 12 , and 17 , respectively, resulting from double Bingel addition to one C-sphere. Rigorous analysis revealed that this novel macrocyclization reaction proceeds with complete regio- and diastereoselectivity. The second approach to a suitable PTA monomer attempted N, N′-dicyclohexylcarbodiimide(DCC)-mediated esterification of (E)-2, 3-diethynylbut-2-ene-l, 4-diol ( 18 , Scheme 6) with mono-esterified methanofullerene-dicarboxylic acid 23 ; however, this synthesis yielded only the corresponding decarboxylated methanofullerene-carboxylic ester 27 (Scheme 7). To prevent decarboxylation, a spacer was inserted between the reacting carboxylic-acid moiety and the methane C-atom in carboxymethyl ethyl 1, 2-methano[60]fullerene-61, 61-dicarboxylate ( 28 , Scheme 8), and DCC-mediated esterification with diol 18 afforded PTA monomer 32 in good yield. The formation of a suitable monomeric precursor 38 to C60-substituted expanded radialenes was achieved in 5 steps starting from dihydroxyacetone (Schemes 9 and 10), with the final step consisting of the DCC-mediated esterification of 28 with 2-[1-ethynyl(prop-2-ynylidene)]propane-1, 3-diol ( 33 ). The first mixed C60-C70 fullerene derivative 49 , consisting of two methano[60]fullerenes attached to a methano[70]fullerene, was also prepared and fully characterized (Scheme 13). The Cs-symmetrical hybrid compound was obtained by DCC-mediated esterification of bis[2-(2-hydroxy-ethoxy)ethyl] 1, 2-methano[70]fullerene-71, 71-dicarboxylate ( 46 ) with an excess of the C60-carboxylic acid 28 . The presence of two different fullerenes in the same molecule was reflected by its UV/VIS spectrum, which displayed the characteristic absorption bands of both the C70 and C60 mono-adducts, but at the same time indicated no electronic interaction between the different fullerene moieties. Cyclic voltammetry showed two reversible reduction steps for 49 , and comparison with the corresponding C70 and C60 mono-adducts 46 and 30 indicated that the three fullerenes in the composite fullerene compound behave as independent redox centers. 相似文献
22.
Serge Raynal Gilberte Ndebeka Paul Caubere Satira Suparno Joseph Sledz Francois Schue 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(4):667-674
The stereoregularity of polystyrenes obtained with complex bases and salt complex bases in various solvents was determined by 13C-NMR spectroscopy. Polystyrenes produced by complex bases are mostly syndiotactic and obey Bernoullian statistics. 相似文献
23.
Franck J. Vernerey Kamtornkiat Musiket Francois Barthelat 《International Journal of Solids and Structures》2014
Natural materials and structures are increasingly becoming a source of inspiration for the design novel of engineering systems. In this context, the structure of fish skin, made of an intricate arrangement of flexible plates growing out of the dermis of a majority of fish, can be of particular interest for materials such as protective layers or flexible electronics. To better understand the mechanics of these composite shells, we introduce here a general computational framework that aims at establishing a relationship between their structure and their overall mechanical response. Taking advantage of the periodicity of the scale arrangement, it is shown that a representative periodic cell can be introduced as the basic element to carry out a homogenization procedure based on the Hill-Mendel condition. The proposed procedure is applied to the specific case of the fish skin structure of the Morone saxatilis, using a computational finite element approach. Our numerical study shows that fish skin possesses a highly anisotropic response, with a softer bending stiffness in the longitudinal direction of the fish. This softer response arises from significant scale rotations during bending, which induce a stiffening of the response under large bending curvature. Interestingly, this mechanism can be suppressed or magnified by tuning the rotational stiffness of the scale-dermis attachment but is not activated in the lateral direction. These results are not only valuable to the engineering design of flexible and protective shells, but also have implications on the mechanics of fish swimming. 相似文献
24.
F. Mathey N. Maigrot C. Charrier 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4)
Abstract The reaction of compounds (1) with lithium or sodium can lead to different results depending on the length of the exocyclic chain : when n=1,2 or 4, we observe cleavage of both exocyclic P-C bonds, giving pure phospholyllithium or sodium. 相似文献
25.
Ngoc Hoa Tran Huy Francois Mathey 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):477-481
Abstract The reaction of electron-rich alkynes such as ethoxyacetylene or propynyldiethylamine with a transient terminal phosphinidene complex such as [PhP?W(CO)5] directly yields the corresponding phosphole complexes via a formal [2 + 2 + I] cycloaddition involving two molecules of alkyne and one phosphorus center. 相似文献
26.
Dionisia Sanz Rosa M. Claramunt François Mathey Ibon Alkorta Goar Sánchez-Sanz José Elguero 《Comptes Rendus Chimie》2013,16(10):937-944
This paper reports the study by NMR spectroscopy and ab initio methods of the structure of 3,4-dimethyl-1-cyanophosphole and its dimer. The dimer presents a P···P interaction of the pnictogen type due to the presence of σ-holes. NMR of the monomer was recorded in CDCl3 solution while NMR of the dimer corresponds to the solid state (CPMAS) experiments. The 2pJPP spin–spin coupling constant has not been measured, but calculated at the B3LYP level. AIM, NBO and ELF methodologies have been used to describe the electronic structure of the dimer. 相似文献
27.
F. Bardot F. Villiéras L.J. Michot M. Francois G. Gérard J.M. Cases 《Journal of Dispersion Science and Technology》2013,34(6-7):739-759
ABSTRACT Ar and N2 high resolution adsorption volumetry coupled to the Derivative Isotherm Simulation method was applied on nine homoionic illite samples (Li ?, Na ? K ? Rb ? Cs ? Mg ? Ca ? Sr ? and Ba ? illites). By comparing the adsorption isotherms it appears that the nature of the surface cation strongly influences the adsorption mechanisms. The lateral and basal surface areas can only be derived from argon adsorption on monovalent samples. The argon adsorption energies varv with the nature of the surface compensating cation. Both cation size and electronegativity are involved. These interactions can, in first approach, be expressed in terms of surface tensionsγsv LW. Specific interactions appear when nitrogen is used revealing high energy adsorption sites located on basal faces. These sites could be related to some polar properties of the surface. 相似文献
28.
Enisa Omanovic-Miklicanin Sandro Valzacchi Catherine Simoneau Douglas Gilliland Francois Rossi 《Analytical and bioanalytical chemistry》2014,406(26):6629-6636
A complete characterization of the different physico-chemical properties of nanoparticles (NPs) is necessary for the evaluation of their impact on health and environment. Among these properties, the surface characterization of the nanomaterial is the least developed and in many cases limited to the measurement of surface composition and zetapotential. The biological surface adsorption index approach (BSAI) for characterization of surface adsorption properties of NPs has recently been introduced (Xia et al. Nat Nanotechnol 5:671–675, 2010; Xia et al. ACS Nano 5(11):9074–9081, 2011). The BSAI approach offers in principle the possibility to characterize the different interaction forces exerted between a NP's surface and an organic—and by extension biological—entity. The present work further develops the BSAI approach and optimizes a solid-phase microextraction gas chromatography–mass spectrometry (SPME/GC-MS) method which, as an outcome, gives a better-defined quantification of the adsorption properties on NPs. We investigated the various aspects of the SPME/GC-MS method, including kinetics of adsorption of probe compounds on SPME fiber, kinetic of adsorption of probe compounds on NP's surface, and optimization of NP's concentration. The optimized conditions were then tested on 33 probe compounds and on Au NPs (15 nm) and SiO2 NPs (50 nm). The procedure allowed the identification of three compounds adsorbed by silica NPs and nine compounds by Au NPs, with equilibrium times which varied between 30 min and 12 h. Adsorption coefficients of 4.66?±?0.23 and 4.44?±?0.26 were calculated for 1-methylnaphtalene and biphenyl, compared to literature values of 4.89 and 5.18, respectively. The results demonstrated that the detailed optimization of the SPME/GC-MS method under various conditions is a critical factor and a prerequisite to the application of the BSAI approach as a tool to characterize surface adsorption properties of NPs and therefore to draw any further conclusions on their potential impact on health. Graphical Abstract
29.
Zhibo Liu Maral Pourghiasian Mark Alex Radtke Joseph Lau Dr. Jinhe Pan Gemma M. Dias Dr. Donald Yapp Dr. Kuo‐Shyan Lin Prof. Dr. Francois Bénard Prof. Dr. David M. Perrin 《Angewandte Chemie (International ed. in English)》2014,53(44):11876-11880
A new zwitterionic organotrifluoroborate is appended to three radiosynthons that afford undergo facile bioconjugation to several clinically relevant peptides and one enzyme inhibitor. Molecularly complex bioconjugates are 18F‐labeled in a single aqueous step in rapid time (<15 min) without HPLC purification to afford tracers in good yields (>200 mCi, 20–40 %) at high specific activity (≥3 Ci/μmol) and at >98 % purity. PET imaging shows in vivo stability and tumor uptake. 相似文献
30.
Ania Alik Chafiaa Bouguechtouli Manon Julien Wolfgang Bermel Rania Ghouil Sophie Zinn‐Justin Francois‐Xavier Theillet 《Angewandte Chemie (International ed. in English)》2020,59(26):10411-10415
Abundant phosphorylation events control the activity of nuclear proteins involved in gene regulation and DNA repair. These occur mostly on disordered regions of proteins, which often contain multiple phosphosites. Comprehensive and quantitative monitoring of phosphorylation reactions is theoretically achievable at a residue‐specific level using 1H‐15N NMR spectroscopy, but is often limited by low signal‐to‐noise at pH>7 and T>293 K. We have developed an improved 13Cα‐13CO correlation NMR experiment that works equally at any pH or temperature, that is, also under conditions at which kinases are active. This allows us to obtain atomic‐resolution information in physiological conditions down to 25 μm . We demonstrate the potential of this approach by monitoring phosphorylation reactions, in the presence of purified kinases or in cell extracts, on a range of previously problematic targets, namely Mdm2, BRCA2, and Oct4. 相似文献