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91.
92.
93.
Wolfgang Zarges Jonathan Hall Jean-Marie Lehn Carsten Bolm 《Helvetica chimica acta》1991,74(8):1843-1852
The chiral tris, and pentakis(bipyridine) ligand strands 3a and 4 were synthesised, each in optically pure form with (S,S)-configuration. Ligand 3a yielded substituted double-helical metal complexes, derived from the parent trihelicate structure 2 , with CuI and AgI ions. The spectral data, in particular the 1H-NMR spectra and the large positive Cotton effect, indicate that helicate formation occurs with very high induction of helicity. Together with consideration of the steric effects in the two possible helical diastereoisomers (P)- 1 and (M)- 1 that may be formed, the data favour the preferential generation of the right-handed double helicate (P)- 1 from the tris(bipyridine) strand 3a of(S,S)-configuration. 相似文献
94.
95.
The long spacing l of lamellar crystals of linear polyethylene increases with the crystallization temperature Tc. For low degrees of supercooling, the ratio Δl/ΔT is around 0.5 nm K?1 for PE single crystals obtained from solution in xylene. In the restricted situation where only conduction in the crystallization vessel is involved, a heat transfer analysis shows that about 20 s is needed to change by 5 K the crystallization temperature Tc in a cylindrical vessel of 1.5 mm radius. Such rapid change of the crystallization temperature induces a sharp increase or decrease of the thickness of the single crystals. After conventional shadowing with palladium–gold alloy, the steps on the crystals are observed by conventional bright-field electron microscopy. A pioneering work was performed in this way by Bassett and Keller in 1962. Our technique allows one to determine both the shape and the dimensions of single crystals or twinned crystals of polyethylene as a function of the time of crystallization, and therefore give the quasi-instantaneous growth rates at various times. 相似文献
96.
Claude Valle Jean-Marie Souriau Gry de Saxc Danielle Fortun 《Comptes Rendus Mecanique》2004,332(12):1013-1018
We show that the affine structure of the 3-dimensional space is deeply enmeshed with the static laws expression. The relevance of tensorial rules for calculus in mechanics is thus enhanced. The virtual work principle is stated precisely but a little twist is given to the usual statements: the tensorial nature of the so-called virtual displacement vector is asserted to be covariant. To cite this article: C. Vallée et al., C. R. Mecanique 332 (2004).
Résumé
Nous montrons que la structure affine de l'espace tridimensionnel est fortement imbriquée avec l'expression des lois de la statique. La pertinence de l'application des règles du calcul tensoriel à la mécanique est ainsi renforcée. Le principe des travaux virtuels est établi précisément avec une seule entorse aux exposés classiques : la nature tensorielle de l'habituel vecteur déplacement virtuel est affirmée covariante. Pour citer cet article : C. Vallée et al., C. R. Mecanique 332 (2004). 相似文献97.
1-(ω-Phenylalkyl)-2-(nitromethylene)pyrrolidines in triflic acid undergo a C,O-diprotonation, followed by loss of water, to form conjugated iminium–hydroxynitrilium dications, which react with the tethered phenyl ring by electrophilic aromatic substitution to afford tricyclic iminium compounds as triflate salts. The scope and mechanism of this reaction are discussed. 相似文献
98.
Bulard E Guo Z Zheng W Dubost H Fontaine-Aupart MP Bellon-Fontaine MN Herry JM Briandet R Bourguignon B 《Langmuir : the ACS journal of surfaces and colloids》2011,27(8):4928-4935
Understanding bacterial adhesion on a surface is a crucial step to design new materials with improved properties or to control biofilm formation and eradication. Sum Frequency Generation (SFG) vibrational spectroscopy has been employed to study in situ the conformational response of a self-assembled monolayer (SAM) of octadecanethiol (ODT) on a gold film to the adhesion of hydrophilic and hydrophobic ovococcoid model bacteria. The present work highlights vibrational SFG spectroscopy as a powerful and unique non-invasive biophysical technique to probe and control bacteria interaction with ordered surfaces. Indeed, the SFG vibrational spectral changes reveal different ODT SAM conformations in air and upon exposure to aqueous solution or bacterial adhesion. Furthermore, this effect depends on the bacterial cell surface properties. The SFG spectral modeling demonstrates that hydrophobic bacteria flatten the ODT SAM alkyl chain terminal part, whereas the hydrophilic ones raise this ODT SAM terminal part. Microorganism-induced alteration of grafted chains can thus affect the desired interfacial functionality, a result that should be considered for the design of new reactive materials. 相似文献
99.
Giovanelli E Leroux S Moisan L Carreyre H Thuéry P Buisson DA Meddour A Coustard JM Thibaudeau S Rousseau B Nicolas M Hellier P Doris E 《Organic letters》2011,13(15):4116-4119
Detailed investigations on one of the key steps of the superacidic fluorination of Vinca alkaloids that is the origin of C20' activation are reported. While two different pathways can be envisioned for the emergence of the transient secondary carbocationic intermediate, isotopic labeling experiments unambiguously revealed the involvement of a 1,2-hydride shift mechanism. 相似文献
100.
Adaptive approximation (or interpolation) takes into account local variations in the behavior of the given function, adjusts
the approximant depending on it, and hence yields the smaller error of approximation. The question of constructing optimal
approximating spline for each function proved to be very hard. In fact, no polynomial time algorithm of adaptive spline approximation can be designed and no exact
formula for the optimal error of approximation can be given. Therefore, the next natural question would be to study the asymptotic
behavior of the error and construct asymptotically optimal sequences of partitions. In this paper we provide sharp asymptotic
estimates for the error of interpolation by splines on block partitions in
\mathbbRd{\mathbb{R}^d} . We consider various projection operators to define the interpolant and provide the analysis of the exact constant in the
asymptotics as well as its explicit form in certain cases. 相似文献