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81.
Andrea Guerrini Greta Varchi Rizzo Daniele Cristian Samorì Arturo Battaglia 《Tetrahedron》2007,63(33):7949-7969
Reactions of chiral (2S)-enolates of dioxolan-4-ones, derived from lactic, mandelic, and phenyllactic acids, with aliphatic (SS)- and (SR)-tert-butylsulfinyl aldimines afforded conformationally restrained C2-disubstituted N,O-orthogonally protected 3-amino-2-hydroxyalkanoates in the form of N-sulfinyl protected 1′-aminodioxolan-4-ones. The product distribution showed that there is significant kinetic selectivity, due to the presence of ‘matched’ and ‘mismatched’ components, between the (S)- or (R)-tert-butylsulfinyl aldimines and the (2S)-enolates of the 1,3-dioxolan-4-ones. Selective methoxide-induced removal of the acetal group of the N-sulfinyl-1′-aminodioxolanones yielded the corresponding N-sulfinyl protected methyl alkanoates. In addition, the selective acid-induced removal of the sulfinyl group of the N-sulfinyl-1′-aminodioxolanones provided the corresponding N-unprotected 1′-aminodioxolanones, whose base-induced cyclization afforded the corresponding β-lactams. 相似文献
82.
Curcio A Marotta R Riedinger A Palumberi D Falqui A Pellegrino T 《Chemical communications (Cambridge, England)》2012,48(18):2400-2402
We here exploit pH-responsive nanogels as carriers to deliver functional anti-GFP siRNA and superparamagnetic IONPs to HeLa-GFP cells. The siRNA release via pH-mediated endosomal escape is shown. The IONPs act first as magnetofection agents to boost cellular uptake and then as probes to track the release mechanism by electron microscopy. 相似文献
83.
Time-resolved fluorescence spectra from the RuN719 dye exhibit very short lifetimes (<30 fs) in solutions, on non-injecting substrates and on injecting ones. This reveals <10 fs intramolecular energy redistribution competing with the injection. We conclude that injection proceeds on a sub-10 fs time scale from non-thermalized levels of the dye. 相似文献
84.
Golub IE Filippov OA Gutsul EI Belkova NV Epstein LM Rossin A Peruzzini M Shubina ES 《Inorganic chemistry》2012,51(12):6486-6497
The mechanism of transition-metal tetrahydroborate dimerization was established for the first time on the example of (Ph(3)P)(2)Cu(η(2)-BH(4)) interaction with different proton donors [MeOH, CH(2)FCH(2)OH, CF(3)CH(2)OH, (CF(3))(2)CHOH, (CF(3))(3)CHOH, p-NO(2)C(6)H(4)OH, p-NO(2)C(6)H(4)N═NC(6)H(4)OH, p-NO(2)C(6)H(4)NH(2)] using the combination of experimental (IR, 190-300 K) and quantum-chemical (DFT/M06) methods. The formation of dihydrogen-bonded complexes as the first reaction step was established experimentally. Their structural, electronic, energetic, and spectroscopic features were thoroughly analyzed by means of quantum-chemical calculations. Bifurcate complexes involving both bridging and terminal hydride hydrogen atoms become thermodynamically preferred for strong proton donors. Their formation was found to be a prerequisite for the subsequent proton transfer and dimerization to occur. Reaction kinetics was studied at variable temperature, showing that proton transfer is the rate-determining step. This result is in agreement with the computed potential energy profile of (Ph(3)P)(2)Cu(η(2)-BH(4)) dimerization, yielding [{(Ph(3)P)(2)Cu}(2)(μ,η(4)-BH(4))](+). 相似文献
85.
Andrea Olmos Aurélien Alix Jean Sommer Prof. Dr. Patrick Pale Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(42):11229-11234
ScIII‐doped solids based on zeolite materials have been investigated for the first time as catalysts in organic synthesis. ScIII–USY zeolite proved to be a novel and very efficient heterogeneous catalyst for the Mukaiyama aldol reaction. This easy‐to‐prepare catalyst exhibited wide scope and compatibility with functional groups and is very simple to use, easy to remove (by simple filtration), and is recyclable (up to three times without loss of activity). 相似文献
86.
87.
Andrei Hutanu Steffen Kiessig Andrea Bathke Rolf Ketterer Sonja Riner Jan Olaf Stracke Markus Wild Bernd Moritz 《Electrophoresis》2019,40(22):3014-3022
Charge heterogeneity profiling is important for the quality control (QC) of biopharmaceuticals. Because of the increasing complexity of these therapeutic entities [1], the development of alternative analytical techniques is needed. In this work, flow‐through partial‐filling affinity capillary electrophoresis (FTPFACE) has been established as a method for the analysis of a mixture of two similar monoclonal antibodies (mAbs). The addition of a specific ligand results in the complexation of one mAb in the co‐formulation, thus changing its migration time in the electric field. This allows the characterization of the charged variants of the non‐shifted mAb without interferences. Adsorption of proteins to the inner capillary wall has been circumvented by rinsing with guanidine hydrochloride before each injection. The presented FTPFACE approach requires only very small amounts of ligands and provides complete comparability with a standard CZE of a single mAb. 相似文献
88.
Influence of external electric field as well as base substitution effects on the reduction/oxidation free energies of single stranded DNA suggest that base sequencing via measuring redox properties might be feasible under the conditions that (i) a difference of ~ 230 kJ mol(-1) in the oxidation potentials is enough to discriminate between nucleobases conductance signals and (ii) the strand is long enough to reduce end effects. 相似文献
89.
A dirhodium(II) complex with N-perfluorooctylsulfonylprolinate ligands is found to catalyze the cyclopropanation of olefins with simple aryl diazomethanes. In contrast to previously reported dirhodium(II) catalysts, the present complex works well not only with very electron-rich olefins such as enol ethers, but also with styrenes. Consequently, the present catalyst allows to prepare functionalized diarylcyclopropanes in moderate yields with good diastereoselectivity for the cis product, whereas the enantioselectivity of the reaction appears negligible. 相似文献
90.
Attila Takács Andrea Czompa Gábor Krajsovszky Péter Mátyus László Kollár 《Tetrahedron》2012,68(38):7855-7860
5-Iodo- and 4,5-dibromo-2-methylpyridazin-3(2H)-ones were aminocarbonylated in the presence of various amines including amino acid methyl esters in a palladium-catalysed reaction. The iodo derivative afforded the corresponding amides with complete conversion and high isolated yields. The dibromo derivative has shown unexpectedly high reactivity in this reaction, resulting in 4,5-dicarboxamides using primary amines as N-nucleophiles. Monoaminocarbonylation has not been observed, i.e., neither 4-bromo-5-carboxamide nor 4-carboxamido-5-bromo derivatives have been formed. However, the use of secondary amines such as piperidine and morpholine resulted in the formations of mixtures of amino-substituted bromopyridazinones. That is, no carbon monoxide insertion took place in these cases. Some mechanistic details of the formation of aminocarbonylation and amination products are also discussed. 相似文献