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111.
On the Synthesis,Characterization and Reactivity of N‐Heteroaryl–Boryl Radicals,a New Radical Class Based on Five‐Membered Ring Ligands 下载免费PDF全文
Dr. Mohamad‐Ali Tehfe Dr. Stéphane Schweizer Dr. Anne‐Caroline Chany Dr. Cédric Ysacco Dr. Jean‐Louis Clément Dr. Didier Gigmes Dr. Fabrice Morlet‐Savary Prof. Jean‐Pierre Fouassier Dr. Markus Neuburger Dr. Théophile Tschamber Dr. Nicolas Blanchard Prof. Jacques Lalevée 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(17):5054-5063
The synthesis and physical characterization of a new class of N‐heterocycle–boryl radicals is presented, based on five membered ring ligands with a N(sp2) complexation site. These pyrazole–boranes and pyrazaboles exhibit a low bond dissociation energy (BDE; B?H) and accordingly excellent hydrogen transfer properties. Most importantly, a high modulation of the BDE(B?H) by the fine tuning of the N‐heterocyclic ligand was obtained in this series and could be correlated with the spin density on the boron atom of the corresponding radical. The reactivity of the latter for small molecule chemistry has been studied through the determination of several reaction rate constants corresponding to addition to alkenes and alkynes, addition to O2, oxidation by iodonium salts and halogen abstraction from alkyl halides. Two selected applications of N‐heterocycle–boryl radicals are also proposed herein, for radical polymerization and for radical dehalogenation reactions. 相似文献
112.
Clément B Decherchi P Féron F Bertin D Gigmes D Trimaille T Marqueste T 《Macromolecular bioscience》2011,11(9):1175-1184
The properties of poly(D ,L ‐lactide)‐block‐poly(2‐hydroxyethyl acrylate) (PLA‐b‐PHEA) block copolymers by means of in vitro / in vivo (rat) degradation are investigated and compared to those of PLA homopolymer. Over 12 weeks, we observe mass loss and molecular weight decrease. In vitro and in vivo findings are very similar for each polymer tested. When a short PHEA block is used (PLA‐b‐PHEA 15 000–3 000 g · mol?1, 85/15 wt%), the degradation process is found to be very similar to that of homo‐PLA, and to be typical of a bulk erosion mechanism, with no mass loss observed until week 7 and continuous decrease of molar mass within this timeframe. For a longer PHEA block length within the block copolymer (PLA‐b‐PHEA 15 000–7 500 g · mol?1, 65/35 wt%), the degradation mechanism is modified, with a significant mass loss observed at early times and only a slight decrease in molar mass. The latter finding is related to the pronounced hydrophilicity and softness of the material induced by the PHEA block, which allow easy diffusion and rapid leakage of the degradation residues from the material towards the aqueous medium. Schwann cells are found to better adhere on spin‐coated films of PLA‐b‐PHEA (85/15 wt%) than on PLA ones. These results show the potential of such hydrophilized PLA‐based copolymers for use in peripheral nerve repair.
113.
Miyasaka H Nezu T Sugimoto K Sugiura K Yamashita M Clérac R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(5):1592-1602
Mn(III)-Ni(II)-Mn(III) linear-type trinuclear complexes bridged by oximate groups were selectively synthesized by the assembly reaction of [Mn2(5-Rsaltmen)2(H2O)2](ClO4)2 (5-Rsaltmen2-=N,N'-(1,1,2,2-tetramethylethylene) bis(5-R-salicylideneiminate); R=Cl, Br) with [Ni(pao)2(phen)] (pao-=pyridine-2-aldoximate; phen=1,10-phenanthroline) in methanol/water: [Mn2(5-Rsaltmen)2Ni(pao)2(phen)](ClO4)2 (R=Cl, 1; R=Br, 2). Structural analysis revealed that the [Mn(III)-ON-Ni(II)-NO-Mn(III)] skeleton of these trimers is in every respect similar to the repeating unit found in the previously reported series of 1D materials [Mn2(saltmen)2Ni(pao)2(L1)2](A)(2) (L(1)=pyridine, 4-picoline, 4-tert-butylpyridine, N-methylimidazole; A=ClO4-, BF4-, PF6-, ReO4-). Recently, these 1D compounds have attracted a great deal of attention for their magnetic properties, since they exhibit slow relaxation of the magnetization (also called single-chain magnet (SCM) behavior). This unique magnetic behavior was explained in the framework of Glauber's theory, generalized for chains of ferromagnetically coupled anisotropic spins. Thus, in these 1D compounds, the [Mn(III)-ON-Ni(II)-NO-Mn(III)] unit was considered as an S(T)=3 anisotropic spin. Direct-current magnetic measurements on 1 and 2 confirm their S(T)=3 ground state and strong uniaxial anisotropy (D/k(B) approximately -2.4 K), in excellent agreement with the magnetic characteristic deduced in the study on the SCM series. The ac magnetic susceptibility of these trimers is strongly frequency-dependent and characteristic of single-molecule magnet (SMM) behavior. The relaxation time tau shows a thermally activated (Arrhenius) behavior with tau0 approximately 1x10(-7) s and Delta(eff)/k(B) approximately 18 K. The effective energy barrier for reversal of the magnetization Delta(eff) is consistent with the theoretical value (21 K) estimated from |D| S2T. The present results reinforce consistently the interpretation of the SCM behavior observed in the [Mn2(saltmen)2Ni(pao)2(L1)2](A)2 series and opens new perspectives to design single-chain magnets. 相似文献
114.
Denize C. Favaro Rubén H. Contreras Cláudio F. Tormena 《Magnetic resonance in chemistry : MRC》2013,51(6):334-338
SOPPA(CCSD) calculations show that the FC term is the most important contribution to the through‐space transmission of JFN coupling constants for the fluoroximes studied in this work. Because of the well‐known behavior of FC term, a new rationalization for the experimental TSJFN SSCC is presented. It is mainly based on the overlap matrix (Sij) between fluorine and nitrogen lone pairs obtained from NBO analyses. An expression is proposed to take into account the influence of the electronic density (Dij) between coupled nuclei as well as the s% character at the site of the coupling nuclei of bonds and non‐bonding electron pairs involved in Dij. In using this approach, a linear correlation between TSJFN versus Dij is obtained. The most important aspect of this rationalization is related to the facility for understanding the behavior of some unusual experimental coupling constants. It is shown that, at least in this case, the electronic origin of the so‐called through‐space coupling is transmitted through to the overlap of orbitals on the coupled atoms, suggesting that, at least for these compounds, instead of through‐space coupling, it should better be dubbed as ‘through overlapping orbital coupling’. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
115.
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117.
Cláudia Simões Vanda Simões Ana Reis Pedro Domingues M. Rosário M. Domingues 《Analytical and bioanalytical chemistry》2010,397(6):2417-2427
Phosphatidylethanolamine glycation occurs in diabetic patients and was found to be related with oxidative stress and with
diabetic complications. Glycated phosphatidylethanolamines seem to increase oxidation of other molecules; however, the reason
why is not understood. In this work, we have studied the oxidation of glycated phosphatidylethanolamines (1-palmitoyl-2-linoleoyl-sn-glycero-3-phosphatidylethanolamine (PLPE) and 1,2-dipalmitoyl-sn-glycero-3-phosphatidylethanolamine (dPPE)) using a Fenton system. Liquid chromatography–electrospray ionization (ESI)–mass
spectrometry and ESI–tandem mass spectrometry in both positive and negative modes were used for detecting and identifying
the oxidation products. We were able to identify several oxidation products with oxidation in unsaturated sn-2 acyl chain of PLPE, as long- and short-chain products with main oxidation sites on C-7, C-8, C-9, and C-12 carbons. Other
products were identified in both glycated PLPE and glycated dPPE, revealing that oxidation also occurs in the glycated polar
head. This fact has not been reported before. These products may be generated from oxidation of glycated phosphatidylethanolamines
(PE) as Schiff base, leading to short-chain product without the amine moiety, due to cleavage of glycated polar head and long-chain
product with two keto groups linked to the glycated polar head or from glycated PE as Amadori product, short-chain products
with –NHCHO and –NHCHOHCHO terminal in polar head. Oxidation of glycated phosphatidylethanolamines occurred more quickly than
the oxidation of non-glycated phosphatidylethanolamines probably because of the existence of more oxidation sites derived
from glycation of polar head group. Monitoring glycated polar head oxidation could be important to evaluate oxidative stress
modifications that occur in diabetic patients. 相似文献
118.
Sonia de Almeida Evaneide N. Lima Marisa S. Crespi Clóvis A. Ribeiro Valdir Schalch 《Journal of Thermal Analysis and Calorimetry》2009,97(2):529-533
Urban solid residues are constituted of food remaining, grass leaves, fruit peelings, paper, cardboard, rubber, plastic, etc.
The organic fraction formed represents about 50% during the decomposition yields biogas and leachate, which are sources of
pollution. Residue samples were collected from the landfill in different and cells from several ages and the corresponding
leachate, both after treatments, were submitted to thermal analysis. Kinetic parameters were determined using Flynn–Wall–Ozawa
method. The linear relation between the two kinetic parameters (ln A and E) was verified for organic residue urban’s samples, but not for leachate’s sample. The occurred difference can be attributed
to the constituents present in leachate. 相似文献
119.
120.
Gil V. J. da Silva Mauricio G. Constantino Cláudio F. Tormena R. Thomas Williamson Brian L. Marquez 《Magnetic resonance in chemistry : MRC》2007,45(3):282-282
The original article to which this Erratum refers was published in Magnetic Resonance in volume 45 issue 1. 相似文献