Hybrid organic–inorganic materials from (3-glycidoxypropyl)methyldiethoxysilane (GPMD) and [3-(2-aminoethyl)aminopropyl]trimethoxysilane (AEAPTMS) have been synthesized. The structure of the hybrid material has been studied as a function of AEAPTMS content by a combination of vibrational and nuclear magnetic resonance spectroscopies. The amine groups in AEAPTMS have shown to be very effective epoxy curing agents and the degree of condensation inside the hybrid material can be finely tuned with the amount of AEAPTMS. Fourier transform near infrared spectroscopy coupled with 2D infrared analysis has been used to elucidate the role of amines in epoxy curing. Several reactions of the amines with the epoxies have been observed, via tertiary, secondary and primary amines. At low AEAPTMS contents the hybrid material exhibits a residual mobility of the organic species, as revealed by solid state NMR spectroscopy. This property has been evaluated comparing qualitatively the residual mobility in hybrid materials synthesized with different types of organically modified alkoxides containing epoxy functional groups. 相似文献
Pepped up polymers : The synthesis and properties of novel chiral cyclic peptides designed to complex with suitable polymers through hydrogen bonding are described. A substituted cyclic peptide self‐assembles into supramolecular nanotubes and develops noncovalent interactions with poly(vinyl alcohol) (PVA) by means of its carboxyl side chains.
The first diphosphines based on a double calixarene, namely 1,4 (or 1,3)‐bis‐(5‐diphenylphosphino‐25,26,27,28‐tetrapropoxycalix[4]aren‐17‐yl)benzene ( L2 , L3 ) were each prepared in four steps starting from 5,17‐dibromo‐25,26,27,28‐tetrapropoxycalix[4]arene. Upon reaction of L2 with [Au(tht)(thf)]BF4, (tht=C4H8S) a rigid metallo‐capsule was quantitatively formed, which adopts an oblique form owing to the distinct nature of the spacers linking the two calixarene half‐spheres. In the solid state, the 1,4‐substituted phenylene linker is turned towards the gold ion, suggesting the existence of weak bonding interactions between two aromatic CH protons of this ring and the metal centre (Au???H=2.67 Å). In contrast to this gold complex, the related silver complex shows dynamic behaviour in solution, the exchange between two enantiomeric oblique forms being facilitated by the greater stereochemical flexibility of AgI vs. AuI. A heteronuclear 109Ag{1H} HMQC experiment established strong correlations between the CH protons of the phenylene linker and the 109Ag ion. Dynamic behaviour similar to that observed for the silver complex was further observed in trans‐[PtCl2? L2 ], a chelate complex that could be obtained quantitatively from L2 and [PtCl2(PhCN)2]. The intended formation of a chelate complex leading to a capsule with an endo‐oriented metal centre was achieved by reacting L3 with [Pd(allyl)(thf)2]BF4. The complex thus formed constitutes the first organometallic transition metal complex embedded in a cavity with large portals. Binding of [RuCl2(p‐cymene)] to L2 and L3 resulted in self‐compacting bimetallic complexes in which each calixarene basket entraps a Ru(p‐cymene) unit, thereby forming molecules occupying a minimal volume. 相似文献
A multitasking C‐silylation strategy using the readily available compound 26 as a surrogate for cinnamic acid represents the key design element of a total synthesis of all known members of the ipomoeassin family of resin glyosides. This protecting group maneuver allows the unsaturated acids decorating the glucose subunit of the targets to be attached at an early phase of the synthesis, prevents their participation in the ruthenium‐catalyzed ring‐closing metathesis (RCM) used to form the macrocyclic ring, and protects them against reduction during the hydrogenation of the resulting cycloalkene over Wilkinson’s catalyst. As the C‐silyl group can be concomitantly removed with the O‐TBS substituent using tris(dimethylamino)sulfonium difluorotrimethylsilicate (TASF) in acetonitrile, no separate protecting group manipulations were necessary in the final stages, thus contributing to a favorable overall “economy of steps”. In addition to the naturally occurring ipomoeassins, a small set of synthetic analogues has also been prepared by “diverted total synthesis”. The cytotoxicity of these compounds was assayed with two different cancer cell lines. The recorded data confirm previous findings that the acylation‐ and oxygenation pattern of these amphiphilic glycoconjugates is highly correlated with their biological activity profile. Ipomoeassin F turned out to be the most promising member of the series, showing IC50 values in the low nanomolar range. 相似文献
Three‐ring circus : An expedient route to tricyclic fused 2‐trimethylsilyl‐3‐aminopyridines exhibiting unprecedented skeletons is described. The key step is a very efficient cobalt‐catalyzed [2+2+2] cycloaddition of a polyunsaturated compound displaying an ynamide, an alkyne, and a nitrile functionality (see picture).
The synthesis of a new ionic liquid-type monomer has been performed by association of a methacrylate polymerizable group, a polar tri(ethylene oxide) (TEO) spacer, a trifluoromethane sulfonic (TFSI−) anion and a free imidazolium (EMIm+) cation. The ionic liquid monomer (ILM) has demonstrated a good thermal stability and a high ionic conductivity around 2.1 × 10−3 S cm−1 at 20 °C. The corresponding homopolymer has shown an ionic conductivity closely related to the monomer (6.5 × 10−4 S cm−1 at 20 °C), which confirms the ILM as a valuable monomer for the formation of polymeric ionic liquid (PIL) materials. 相似文献
Pore structures have a major impact on the transport and electrical properties of electrochemical devices, such as batteries and electric double-layer capacitors (EDLCs). In this work we are concerned with the prediction of the electrical conductivity, ion diffusivity and volumetric capacitance of EDLC electrodes, manufactured from hierarchically porous carbons. To investigate the dependence of the effective properties on the pore structures, we use a structurally resolved parametric model of a random medium. Our approach starts from 3D FIB-SEM imaging, combined with automatic segmentation. Then, a random set model is fitted to the segmented structures and the effective transport properties are predicted using full field simulations by iterations of FFT on 3D pore space images and calculations based on the geometric properties of the structure model. A parameter study of the model is used to investigate the sensitivity of the effective conductivity and diffusivity to changes in the model parameters. Finally, we investigate the volumetric capacitance of the EDLC electrodes with a geometric model, make a comparison with experimental measurements and do a parameter study to suggest improved microstructures. 相似文献
The vector space spanned by rooted forests admits two graded bialgebra structures. The first is defined by Connes and Kreimer using admissible cuts, and the second is defined by Calaque, Ebrahimi-Fard and the second author using contraction of trees. In this article, we define the doubling of these two spaces. We construct two bialgebra structures on these spaces which are in interaction, as well as two related associative products obtained by dualization. We also show that these two bialgebras verify a commutative diagram similar to the diagram verified Calaque, Ebrahimi-Fard and the second author in the case of rooted trees Hopf algebra, and by the second author in the case of cycle-free oriented graphs. 相似文献
The purpose of this study is to identify a quantitative marker of the heat release rate (HRR) distribution using experimentally measurable species. Turbulent syngas (CO/H2/air) flames with different equivalence ratios, H2/CO ratios, and turbulence intensities are computed by Direct Numerical Simulations (DNS) in order to obtain an indirect but accurate estimation of heat release profiles. To check the robustness of the estimation, two different kinetic mechanisms have been considered. Based on a direct image analysis of the DNS results, normalized species concentrations combined with exponents are systematically tested in an attempt to reconstruct as accurately as possible the field of heat release rate. A systematic comparison is used to identify the best possible exponents associated with each species combination. Differing from previous studies, the present analysis takes into account the local thickness of the turbulent heat release zone. As a consequence, the obtained optimal species combinations represent not only the position of peak heat release but also local changes in the topology of the reaction zone (thickness, curvature). In the end, the heat release rate of atmospheric syngas flames can, in general, be best approximated using the concentrations of HCO and OH, using \(\overline {c}_{HCO}^{1.5}\times \overline {c}_{OH}^{0.75}\), when considering only species that are measurable by Laser-Induced Fluorescence. Another excellent reconstruction would be \(\overline {c}_{CH_{2}O}^{0.32}\times \overline {c}_{OH}^{0.8}\), for cases where CH2O is preferred to HCO. 相似文献
Sexual arousal and gaze behavior dynamics are used to characterize deviant sexual interests in male subjects. Pedophile patients and non-deviant subjects are immersed with virtual characters depicting relevant sexual features. Gaze behavior dynamics as indexed from correlation dimensions (D2) appears to be fractal in nature and significantly different from colored noise (surrogate data tests and recurrence plot analyses were performed). This perceptual-motor fractal dynamics parallels sexual arousal and differs from pedophiles to non-deviant subjects when critical sexual information is processed. Results are interpreted in terms of sexual affordance, perceptual invariance extraction and intentional nonlinear dynamics. 相似文献