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41.
Werner Marty Pramesh N. Kapoor Hans-Beat Bürgi Erwin Fischer 《Helvetica chimica acta》1987,70(1):158-170
The bidentate diphosphine ligand, 3,3′-oxybis[(dipenylphosphino)methylbenzene] ( 1 ) forms monomeric, trans-square-planar complexes MX2( 1 ) (M = Ni, Pd, Pt; X = Cl?, Br? I?, and, in part, N, NCS?, CN?, NO) as well as Pt(H)Cl( 1 ), Pt(H)Br( 1 ), and RhCl(CO)( 1 ). Polymeric species have been observed with substitutionally inert metal centres: trans-[PtCl2( 1 )]2 and cis-[PtCl2( 1 )]n (mean value of n ≈ 4–5) 31P-NMR, and selected IR and UV/VIS parameters are reported. Ligand 1 shows a marked preference for trans-spanning and monomeric chelate formation, despite its various degrees of freedom of internal rotation in the lignad backbone. The readily available ligand 1 as well as analogues with other donor atoms, therefore, appear useful in most potential applications of trans-spanning chelate ligands. The crystal structure of AgCl( 1 )·0.5 (CH3)2C?O·0.39 C6H12 (space group C2/c,a = 21.02 Å, b = 14.57 Å, c = 24.79 Å, β = 99.77°, V = 7531.4 Å3, Z = 8) confirms the presence of three-coordinate Ag( I ), with a coordination intermediate between a trigonal-planar and a T-shaped geometry (P-Ag-P = 145.61(8)°). 相似文献
42.
Cyclofusene is a corona-condensed benzenoid whose graph-theoretic representation consists of hexacycles each having exactly two non-adjacent shared edges. Multilayered cyclofusene is a fused hexacylic system which can be partitioned into successive layers of cyclofusene. In such systems, an edge shared by two consecutive hexacycles in the same layer is termed radial. We present upper bounds for the number of radial π-bonds in a convex k-layered cyclofusene. 相似文献
43.
Thomas Merakis Annette Murphy Leone Spiccia Alan Beguin Werner Marty 《Helvetica chimica acta》1989,72(5):993-995
Crystalline salts of the hydrolytic dimer of Cr(III), [Cr2(μ-OH)2(H2O)8]X4·n H2O (X = p-toluenesulfonate (tos) or mesitylene-2-sulfonate (dmtos)) have been prepared in good yields via a simple two-step procedure: H+ oxidation of Cr metal to give Cr2+ (T ≈? 70°) followed by O2 oxidation, of Cr2+ to give the dimer (T ≈? 25°). The mechanism of conversion of Cr2+ into the dimer is discussed. 相似文献
44.
Jeanty G Wojciechowska A Marty JL Trojanowicz M 《Analytical and bioanalytical chemistry》2002,373(8):691-695
Determination of the organophosphorus pesticides paraoxon, chlorpyrifos oxon, and malaoxon has been performed by a method based on inhibition of acetylcholinesterase (AChE) and amperometric detection in a flow-injection system with enzymes obtained from the electric eel (eeAChE) and Drosophila melanogaster (dmAChE) and immobilized on the surface of platinum electrode within a layer of poly(vinyl alcohol) bearing styrylpyridinium groups. dmAChE is more sensitive than eeAChE to inhibition by chlorpyrifos oxon and paraoxon. The sensitivity difference was largest for chlorpyrifos oxon (detection limit approx. 17 times lower), and practically none for malaoxon. Determination of the analytes in spiked river water samples by use of the dmAChE biosensor resulted in recoveries from 50 to 90 % for chlorpyrifos oxon at levels of 20 to 40 nmol L(-1), 50 to 100 % for paraoxon at 0.6 to 0.8 micro mol L(-1), and 140 to 190 % for malaoxon at 0.6 to 1.2 micro mol L(-1). 相似文献
45.
Waêl Moukarzel Jean‐Daniel Marty Dietmar Appelhans Monique Mauzac Juliette Fitremann 《Journal of polymer science. Part A, Polymer chemistry》2013,51(17):3607-3618
A straightforward method for the preparation of polysiloxanes grafted with carbohydrate side groups is described. Two kinds of backbones have been functionalized, namely one‐dimensional, linear polysiloxanes, and hyperbranched poly(siloxysilane)s based on cyclotetrasiloxanes. The method enables us to keep a good integrity of the polysiloxane backbone. The introduction of intermediate activated esters as side groups on the polysiloxane backbone ensures a complete homogeneity of the reaction medium during sugar grafting in dimethyl sulfoxide, and consequently an easy grafting with the unprotected amino sugar. Solubility of the resulting polysiloxanes has been tested in various solvents. The sugar‐grafted polysiloxanes are good candidates for applications such as silicone formulations, hydrophilic silicone elastomers, interactions with metallic nanoparticles, and suspension stabilization, or as starting point for the design of more complex polysiloxanes for molecular recognition. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3607–3618 相似文献
46.
Azide anation and racemization of optically pure mer-exo(H)- and mer-endo(H)-[Co(OH)(dien)(dapo)]2+ ( A and B (X = OH), resp.; dien = N-(2-aminoethyl)ethane-1,2-diamine; dapo = 1,3-diaminopropan-2-ol) involve the same symmetrical pentacoordinate intermediate as the base hydrolyses of the corresponding mer-exo(H)- and mer-endo(H)-[CoX(dien)(dapo)]2+ species A and B , respectively, where X = Cl, Br, or N3. The kinetic parameters of the anation process are fully compatible with the independently measured competition ratio. The rate data reveal that substitution of OH? is unexpectedly fast, viz. it is not consistent with the usual sequence Br? > Cl? > H2O > N > OH?. This behavior is interpreted on the basis of an internal conjugate base mechanism which involves an amino-hydroxo/aminato-aqua tautomerism, viz. the reaction is actually an OH? -catalyzed substitution of [CoH2O(dien)(dapo)]3+ where deprotonation occurs effectively at the secondary-amine site NH of dien. 相似文献
47.
48.
Montserrat Cortina‐Puig Anastasia C. H. Scangas Zachary S. Marchese Silvana Andreescu Jean‐Louis Marty Carole Calas‐Blanchard 《Electroanalysis》2010,22(20):2429-2433
This paper describes the development of a xanthine oxidase/poly‐m‐phenylenediamine (XOD‐PPD)‐modified electrode. The biosensor was constructed by encapsulating XOD in a sol‐gel matrix deposited onto a platinum based screen‐printed electrode functionalized with a permselective PPD membrane. The hydrogen peroxide generated as a final product of the enzymatic reaction between the hypoxanthine and the XOD or by the spontaneous dismutation of superoxide radicals was selectively monitored at +700 mV. The use of a highly selective PPD layer blocked the nonspecific oxidation of other oxidizable molecules. Finally the biosensor was applied to the determination of the antioxidant capacity of acetylsalicylic acid. 相似文献
49.
Prof. Clément Roux Dr. Céline Delmas Prof. Jean‐Daniel Marty Dr. Myrtil L. Kahn Dr. Christophe Mingotaud 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(35):12424-12429
Analysis of nanoparticle size through a simple 2D plot is proposed in order to extract the correlation between length and width in a collection or a mixture of anisotropic particles. Compared to the usual statistics on the length associated with a second and independent statistical analysis of the width, this simple plot easily points out the various types of nanoparticles and their (an)isotropy. For each class of nano‐objects, the relationship between width and length (i.e., the strong or weak correlations between these two parameters) may suggest information concerning the nucleation/growth processes. It allows one to follow the effect on the shape and size distribution of physical or chemical processes such as simple ripening. Various electron microscopy pictures from the literature or from the authors′ own syntheses are used as examples to demonstrate the efficiency and simplicity of the proposed 2D plot combined with a multivariate analysis. 相似文献
50.
Foley NA Lail M Lee JP Gunnoe TB Cundari TR Petersen JL 《Journal of the American Chemical Society》2007,129(21):6765-6781
Complexes of the type TpRu(L)(NCMe)R [L = CO or PMe3; R = Ph or Me; Tp = hydridotris(pyrazolyl)borate] initiate C-H activation of benzene. Kinetic studies, isotopic labeling, and other experimental evidence suggest that the mechanism of benzene C-H activation involves reversible dissociation of acetonitrile, reversible benzene coordination, and rate-determining C-H activation of coordinated benzene. TpRu(PMe3)(NCMe)Ph initiates C-D activation of C6D6 at rates that are approximately 2-3 times more rapid than that for TpRu(CO)(NCMe)Ph (depending on substrate concentration); however, the catalytic hydrophenylation of ethylene using TpRu(PMe3)(NCMe)Ph is substantially less efficient than catalysis with TpRu(CO)(NCMe)Ph. For TpRu(PMe3)(NCMe)Ph, C-H activation of ethylene, to ultimately produce TpRu(PMe3)(eta3-C4H7), is found to kinetically compete with catalytic ethylene hydrophenylation. In THF solutions containing ethylene, TpRu(PMe3)(NCMe)Ph and TpRu(CO)(NCMe)Ph separately convert to TpRu(L)(eta3-C4H7) (L = PMe3 or CO, respectively) via initial Ru-mediated ethylene C-H activation. Heating mesitylene solutions of TpRu(L)(eta3-C4H7) under ethylene pressure results in the catalytic production of butenes (i.e., ethylene hydrovinylation) and hexenes. 相似文献