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21.
Pierre Thuéry Nelly Keller Monique Lance Julien-Daniel Vigner Martine Nierlich 《Journal of inclusion phenomena and macrocyclic chemistry》1994,20(1):89-96
The doubly deprotonated form of calix[6]arene, with two protonated triethylamines as counter-ions, crystallizes in the monoclinic system: space groupP21/n,a=8.465(4),b=17.822(8),c=15.182(6) Å,=90.18(4)°,V=2291(2) Å3,Z=2. Refinement led to a final conventionalR value of 0.063 for 1046 reflections. The macrocycle conformation is not apinched cone, usual for freeR-calix[6]arene, but a distorted 1,2,3-alternate cone, since the molecule lies on a symmetry center. Furthermore, one of the torsion angles defined by the methylene bridges is near to zero, which is unusual in calixarene structures.
Supplementary Data relating to this article (atomic coordinates for hydrogen atoms, anisotropic displacement parameters for oxygen and nitrogen atoms, and observed and calculated structure factors) are deposited with the British Library as Supplementary Publication No. SUP 82182 (7 pages). 相似文献
22.
PHOTOSENSITIZING PROPERTIES OF BACTERIOCHLOROPHYLLIN a and BACTERIOCHLORIN a, TWO DERIVATIVES OF BACTERIOCHLOROPHYLL a 总被引:2,自引:0,他引:2
Eva M. Beems Tom M. A. R. Dubbelman Johan Lugtenburg Jaap A. van Best Monique F. M. A. Smeets J. Pierre J. Boegheim 《Photochemistry and photobiology》1987,46(5):639-643
Abstract The photosensitizing properties of two water soluble derivatives of bacteriochlorophyll a , bacteriochlorophyllin a and bacteriochlorin a (lacking the central Mg-ion) were investigated and compared to those of hematoporphyrin derivatives. At physiological pH the oxygen consumption rate of histidine, tryptophan, dithiothreitol and guanosine upon illumination was 3 to 4 times higher when bacteriochlorin a was used as photosensitizer than when hematoporphyrin derivatives were used. Especially bacteriochlorin a proved to be an effective sensitizer for the killing of L929 cells. Because bacteriochlorin a has an absorption maximum at 765 nm in phosphate buffered saline (allowing a light penetration in tissue about ten times larger than at 630 nm) and a high molar absorption coefficient (32 000 M cm−1 ) it has promising possibilities for the application in photodynamic therapy. 相似文献
23.
Hughes RP Meyer MA Tawa MD Ward AJ Williamson A Rheingold AL Zakharov LN 《Inorganic chemistry》2004,43(2):747-756
Reaction of Pd(TMEDA)(CH(3))(2) [TMEDA = tetramethylethylenediamine] with fluoroalkyl iodides R(F)I affords a series of square planar Pd(II) complexes Pd(TMEDA)(CH(3))(R(F)) [R(F) = CF(2)CF(3) (9), CFHCF(3) (10), CH(2)CF(3) (11)], presumably by oxidative addition followed by reductive elimination of CH(3)I. The solid-state structures of each compound have been determined by single crystal X-ray diffraction studies, allowing the effect of increasing alpha-fluorination on the structural trans-influence of alkyl ligands to be examined. In these compounds there is no significant difference observed in the trans-influence of the three fluorinated alkyl ligands toward the trans-N atom, although a significant cis-influence on the neighboring methyl ligand is apparent. Oxidative addition of the same series of fluoroalkyl ligands to the corresponding Pt(TMEDA)(CH(3))(2) affords octahedral Pt(IV) complexes trans-Pt(TMEDA)(CH(3))(2)(R(F))I [R(F) = CF(2)CF(3) (12), CFHCF(3) (13), CH(2)CF(3) (14)] as the kinetic products. In each case, subsequent isomerization to the corresponding all cis-isomers is observed; in the case of 13, the stereocenter at the alpha-carbon results in two diastereomeric cis-isomers, which are formed at different rates. The molecular structures of 13 and its more stable all cis-isomer 16b have been crystallographically determined. Kinetic studies of the trans-cis isomerization reactions show the mechanism to involve a polar transition state, presumably involving iodide dissociation, followed by rearrangement of the cation, and iodide recombination. High dielectric solvents increase the rate, but solvent coordinating ability has no effect. Dissolved salts (LiI, LiOTf) show normal accelerative salt effects, with no inhibition in the case of added iodide, consistent with the formation of an intimate ion pair intermediate. The kinetic parameters show that the trans-effects of fluoroalkyl ligands in these compounds follow the order expected from the relative sigma-donor properties of the ligands, with CF(2)CF(3) < CFHCF(3) < CH(2)CF(3). 相似文献
24.
Monique Nanot Francine Queyroux Jean-Claude Gilles 《Journal of solid state chemistry》1979,28(2):137-147
The homologous phases corresponding to the formula AnBnO3n+2 observed in the systems: La2Ti2O7CaTiO3, Nd2Ti2O7CaTiO3 and Ca2Nb2O7CaTiO3, have a structure derived from the structure of perovskite by periodic crystallographic shears, which delimitate n octahedra thick sheets. In the [0 1 0]1 direction, the sheets are following each other with two types of arrangement.Crystals of terms n = 4,5, 5 and 6 were investigated by X-ray diffraction. According to the type of arrangement of the sheets, the phases studied have either an orthorhombic symmetry or a monoclinic symmetry, this last one giving rise to merohedral twins. 相似文献
25.
Monique Perrin Sylvain Lecocq 《Journal of inclusion phenomena and macrocyclic chemistry》1991,11(2):171-183
A cyclic pentamer was obtained fromp-(1,1,3,3-tetramethylbutyl) phenol. It crystallizes from a mixture of acetone and toluene at room temperature giving a 1 : 1 complex with toluene (compound A), whereas at 50°C the empty form (compound B) is obtained. Crystals of A are orthorhombic, space groupPna21,a = 20.083(2),b = 12.936(6),c = 28,423(1) Å,Z = 4, finalR value = 0.067. The empty form, B, is monoclinicP21/c,a = 18.695(2),b = 11.673(5),c = 35.100(4) Å, = 114.33(1),Z = 4, finalR value = 0.135. The macrocycle is in the cone conformation for both compounds; the toluene molecule lies in the cone as often found for calix[4]arenes. 相似文献
26.
We study facets of the cut coneC
n
, i.e., the cone of dimension 1/2n(n – 1) generated by the cuts of the complete graph onn vertices. Actually, the study of the facets of the cut cone is equivalent in some sense to the study of the facets of the cut polytope. We present several operations on facets and, in particular, a lifting procedure for constructing facets ofC
n+1 from given facets of the lower dimensional coneC
n
. After reviewing hypermetric valid inequalities, we describe the new class of cycle inequalities and prove the facet property for several subclasses. The new class of parachute facets is developed and other known facets and valid inequalities are presented. 相似文献
27.
Aresta M Tommasi I Quaranta E Fragale C Mascetti J Tranquille M Galan F Fouassier M 《Inorganic chemistry》1996,35(14):4254-4260
Extended labeling experiments have shown that formation of rhodium peroxocarbonate from CO(2) and [RhCl(eta(2)-O(2))(P)(3)] (P is PEt(2)Ph or PEtPh(2)) proceeds through O-O bond cleavage and CO(2) insertion. O-transfer to ancillary phosphine ligand to give R(3)P=O selectively (>85%) involves the Rh-linked O atom of the peroxo group of RhCl(CO(4))(P)(3). 相似文献
28.
Noëlle Ehlinger Monique Perrin 《Journal of inclusion phenomena and macrocyclic chemistry》1995,22(1):33-40
The structure of thep-tetrakis-(4-nitrophenylazo)calix[4]arene-4-picoline (14) complex has been determined by X-ray crystallography. Crystals are monoclinic, space groupC2/c,a=24.9097) Å,b=8.425(6) Å,c=33.81(1) Å, =101.13(2)°,D
c
=1.330 g/cm3,Z=4, finalR value =0.067. The cone conformation adopted by this azocalixarene is disturbed by the positions of the picoline molecules. Two of them are inside the macorocycle cavity and the two others are outside.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. Sup. 82190 (32 pages). 相似文献
29.
Monique G.A. da Silva Ábner M. Nunes Simoni M.P. Meneghetti Mario R. Meneghetti 《Comptes Rendus Chimie》2013,16(7):640-650
Gold nanorods (AuNRs) were obtained via a wet chemistry technique, in aqueous medium, employing crystallisation seeds. The kinetics of formation, the aspect ratio, and the selectivity of the particles were evaluated according to the parameters of synthesis: the growth-driving agent, seed, and gold precursor concentrations. In 2–4 h, the rod particles attained the expected size and shape under kinetic control, and were stable for at least 2 days. In order to obtain good quality AuNRs in good yields, without enrichment, we suggest keeping the growth-driving agent/gold molar ratio, the AuI/seed ratio, and the concentration of the reagents in the final solution within specific ranges. For example, even if good molar ratios between the reagents are maintained, relatively highly concentrated reaction solutions lead to AuNRs with lower aspect ratios. The main properties of the prepared colloidal systems and the nanoparticles were evaluated by UV–vis spectroscopy and transmission electron microscopy, respectively. 相似文献
30.
Anne-Catherine Huet Monique Bienenmann-Ploum Ursula Vincent Philippe Delahaut 《Analytical and bioanalytical chemistry》2013,405(24):7733-7751
This article presents a review of the current trends in the analysis of coccidiostats in various matrices, focusing principally on screening and rapid methods. Coccidiosis is an infectious disease having a high negative impact on the animal industry. Drugs are therefore necessary to prevent and/or to combat this disease. However, it is also of crucial importance that these veterinary drugs do not enter the human food chain. European legislation has therefore established the boundaries for the use of coccidiosats and has also addressed the unavoidable problem of cross-contamination of the feed, mainly caused by the use of the same production lines. Consequently there is a need for analytical methods and/or analytical strategies for the monitoring and control of the residues of anticoccidials, both in feed and in the resulting matrices for human consumption. In the frame of the European collaborative project CONffIDENCE, such attempts to establish the required analytical tools were made, which required beforehand a review of the state of the art in this domain. Aiming at this objective, in this review we consider the most interesting publications since 2000. In essence, both a rapid approach with mainly immunoassays and chromatographic methods were developed. To date, the obstacle to routine use of the first approach has been its inability to detect more than two compounds simultaneously, but recent developments in flow cytometry have made it possible to detect six coccidiostats at once. On the other hand, an increasingly popular approach for detecting multiple coccidiostats simultaneously is liquid chromatography coupled with tandem mass spectrometry. There remains a need to adapt these analytical methods to legislative requirements. 相似文献