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31.
Dr. Jean-François Ayme Dr. Sébastien Dhers Prof. Dr. Jean-Marie Lehn 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(30):12584-12592
Three imine-based metal complexes, having no overlap in terms of their compositions, have been simultaneously generated from the self-sorting of a constitutional dynamic library (CDL) containing three amines, three aldehydes, and three metal salts. The hierarchical ordering of the stability of the three metal complexes assembled and the leveraging of the antagonistic and agonistic relationships existing between the constituents within the constitutional dynamic network corresponding to the CDL were pivotal in achieving the sorting. Examination of the process by NMR spectroscopy showed that the self-sorting of the FeII and ZnII complexes depended on an interplay between the thermodynamic driving forces and a kinetic trap involved in their assembly. These results also exemplify the concept of “simplexity”—the fact that the output of a self-assembling system may be simplified by increasing its initial compositional complexity—as the two complexes could self-sort only in the presence of the third pair of organic components, those of the CuI complex. 相似文献
32.
J.-M. Colet C. Piérart F. Seghi I. Gabric R.N. Muller 《Journal of magnetic resonance (San Diego, Calif. : 1997)》1998,134(2):199-205
The relative contributions of intravascular and intracellular compartments to the proton transverse relaxation of the isolated and excised rat liver were determined during the phagocytosis of superparamagnetic particles. The evolution of the proton transverse magnetization of the organ perfused with increasing doses of starch-coated magnetic microspheres was followed up using a Carr–Purcell–Meiboom–Gill sequence with various echo times. From the multiexponential fit of the echo train, the amplitudes and the relaxation ratesR2of the liver tissue were obtained. The results clearly indicate that shortly after contrast medium administration, an internalization takes place which can be followed by the rapid and biphasic evolution of the transverse relaxation rate of the water protons. A very fast decaying component looking like an initial loss of the magnetization is observed together with an increase of the relaxation rate of the remaining water tissue. This regime is strongly dependent on both the echo time and the iron concentration, a behavior characteristic of the agglomeration of magnetic particles. The examination of the liver tissues by electron microscopy shows that this clustering arises in cytoplasmic vacuoles. 相似文献
33.
Jean-Marie Mirebeau 《Numerische Mathematik》2012,120(2):271-305
Given a function f defined on a bounded polygonal domain
W ì \mathbbR2{\Omega \subset \mathbb{R}^2} and a number N > 0, we study the properties of the triangulation TN{\mathcal{T}_N} that minimizes the distance between f and its interpolation on the associated finite element space, over all triangulations of at most N elements. The error is studied in the W
1, p
semi-norm for 1 ≤ p < ∞, and we consider Lagrange finite elements of arbitrary polynomial order m − 1. We establish sharp asymptotic error estimates as N → +∞ when the optimal anisotropic triangulation is used. A similar problem has been studied in Babenko et al. (East J Approx.
12(1):71–101, 2006), Cao (J Numer Anal. 45(6):2368–2391, 2007), Chen et al. (Math Comput. 76:179–204, 2007), Cohen (Multiscale, Nonlinear and Adaptive Approximation. Springer, Berlin, 2009), Mirebeau (Constr Approx. 32(2):339–383, 2010), but with the error measured in the L
p
norm. The extension of this analysis to the W
1, p
norm is required in order to match more closely the needs of numerical PDE analysis, and it is not straightforward. In particular,
the meshes which satisfy the optimal error estimate are characterized by a metric describing the local aspect ratio of each
triangle and by a geometric constraint on their maximal angle, a second feature that does not appear for the L
p
error norm. Our analysis also provides with practical strategies for designing meshes such that the interpolation error satisfies
the optimal estimate up to a fixed multiplicative constant. 相似文献
34.
Jean-Marie De Koninck 《Monatshefte für Mathematik》1993,116(1):13-37
Let
and, for each integern such that (n)k, denote byP
k
(n) itsk
th largest prime factor. Further, given a set of primesQ of positive density <1 satisfying a certain regularity condition, defineP(n, Q), as the largest prime divisor ofn belonging toQ, assuming thatP(n,Q)=+ if no such prime factor exists. We provide estimates of
, fork2, and of
. We also study the median value of the functionP(n,Q) and that of the functionP
k
(n) for eachk1. 相似文献
35.
Ana-Maria Udrea Andra Dinache Jean-Marie Pags Ruxandra Angela Pirvulescu 《Molecules (Basel, Switzerland)》2021,26(8)
Multidrug resistance of bacteria is a worrying concern in the therapeutic field and an alternative method to combat it is designing new efflux pump inhibitors (EPIs). This article presents a molecular study of two quinazoline derivatives, labelled BG1189 and BG1190, proposed as EPIs. In silico approach investigates the pharmacodynamic and pharmacokinetic profile of BG1189 and BG1190 quinazolines. Molecular docking and predicted ADMET features suggest that BG1189 and BG1190 may represent attractive candidates as antimicrobial drugs. UV-Vis absorption spectroscopy was employed to study the time stability of quinazoline solutions in water or in dimethyl sulfoxide (DMSO), in constant environmental conditions, and to determine the influence of usual storage temperature, normal room lighting and laser radiation (photostability) on samples stability. The effects of irradiation on BG1189 and BG1190 molecules were also assessed through Fourier-transform infrared (FTIR) spectroscopy. FTIR spectra showed that laser radiation breaks some chemical bonds affecting the substituents and the quinazoline radical of the compounds. 相似文献
36.
John J. Daly Peter Schnholzer Jean-Paul Behr Jean-Marie Lehn 《Helvetica chimica acta》1981,64(5):1444-1451
The crystal and molecular structure of the complex formed by the ionized bistartro-[18]-crown-6 receptor molecule 1 with the ethylenediammonium cation, is described. The macrocycle is roughly planar, the carboxy groups of each tartaric acid residue being in a diaxial relationship and extending above and below this plane. This conformation allows ‘lateral’ interactions with bound species to occur. The substrate is sandwiched between two macrocycles, with one of its NH heads anchored to the polyether core, and the other one in contact with the two carboxy groups of the neighboring molecule. 相似文献
37.
Podsiadlo P Paternel S Rouillard JM Zhang Z Lee J Lee JW Gulari E Kotov NA 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11915-11921
In a recent report, we have presented the layer-by-layer (LBL) assembly of a biomimetic nanostructured composite from Na(+)-montmorillonite clay nanosheets and poly(diallylmethylammonium chloride) (Tang, Z.; Kotov, N.; Magonov, S.; Ozturk, B. Nat. Mater. 2003, 2, 413). The structure, deformation mechanism, and mechanical properties of the material are very similar to those of natural nacre and lamellar bones. This fact prompts further investigation of these composites as potential bone implants. LBL assembly affords preparation of multifunctional composites, and here we demonstrate that not only mechanical strength, but also antibacterial activity, can be introduced in these implantable materials by alternating clay layers with starch-stabilized silver nanoparticles. The resulting composite showed excellent structural stability with no detectable levels of silver lost over a 1 month period. Evaluation of the antibacterial properties showed almost complete growth inhibition of E. coli over an 18 h period. The amount of silver eluted from the LBL composite over a 1 month period was determined to be only 0.5-3.0 microg/L. This concentration of silver did not prevent the growth of the mammalian tissue cultures. The LBL composite has shown biocompatibility with the human osteoblast cell line. 相似文献
38.
Uppadine LH Gisselbrecht JP Kyritsakas N Nättinen K Rissanen K Lehn JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(8):2549-2565
An extended family of heterometallic [(M1)2(M2)2(L-)4](n+) [2x2] grid-type arrays 1-9 has been prepared. The three-tiered synthetic route encompasses regioselective, redox and enantioselective features and is based on the stepwise construction of heteroditopic hydrazone ligands A-C. These ligands contain ionisable NH and nonionisable NMe hydrazone units, which allows the metal redox properties to be controlled according to the charge on the ligand binding pocket. The 2-pyrimidine (R) and 6-pyridine (R') substituents have a significant effect on complex geometry and influence both the electrochemical and magnetic behaviour of the system. 1H NMR spectroscopic studies show that the Fe(II) ions in the grid can be low spin, high spin or spin crossover depending on the steric effect of substituents R and R'. This steric effect has been manipulated to construct an unusual array possessing two low-spin and two spin-crossover Fe(II) centres (grid 8). Electrochemical studies were performed for the grid-type arrays 1-9 and their respective mononuclear precursor complexes 10-13. The grids function as electron reservoirs and display up to eight monoelectronic, reversible reduction steps. These processes generally occur in pairs and are assigned to ligand-based reductions and to the Co(III)/Co(II) redox couple. Individual metal ions in the heterometallic grid motif can be selectively addressed electrochemically (e.g., either the Co(III) or Fe(II) ions can be targeted in grids 2 and 5). The Fe(II) oxidation potential is governed by the charge on the ligand binding unit, rather than the spin state, thus permitting facile electrochemical discrimination between the two types of Fe(II) centre in 7 or in 8. Such multistable heterometallic [2x2] gridlike arrays are of great interest for future supramolecular devices incorporating multilevel redox activity. 相似文献
39.
A major hurdle in the development of complex constitutional dynamic networks (CDNs) is the lack of strategies to simultaneously control the output of two (or more) interconnected dynamic processes over several species, namely reversible covalent imine bond formation and dynamic metal–ligand coordination. We have studied in detail the self-sorting process of 11 constitutional dynamic libraries containing two different amines, aldehydes and metal salts into two imine-based metal complexes, having no overlap in terms of their compositions. This study allowed us to determine the factors influencing the fidelity of this process (concentration, electronic and steric parameters of the organic components, and nature of the metal cations). In all 11 systems, the outcome of the process was primarily determined by the ability of the octahedral metal ion to select its pair of components from the initial pool of components, with the composition of the weaker tetrahedral complex being imposed by the components rejected by the octahedral metal ions. Different octahedral metal ions required different levels of precision in the “assembling instructions” provided by the organic components of the CDN to guide it towards a sorted output. The concentration of the reaction mixture, and the electronic and steric properties of the initial components of the library were all found to influence the lifetime of unwanted metastable intermediates formed during the assembling of the two complexes.Constitutional dynamic networks have been developed to simultaneously control the output of two interconnected dynamic processes over several species of the same reaction mixture. 相似文献
40.
Mohamed Fatnassi Corine Tourné-Péteilh Pradial Peralta Thomas Cacciaguerra Philippe Dieudonné Jean-Marie Devoisselle Bruno Alonso 《Journal of Sol-Gel Science and Technology》2013,68(2):307-316
Two model drugs of different physico-chemical and pharmaceutical properties (ibuprofen, acetaminophen) have been incorporated together or separately in silica-based microspheres using sol–gel and spray-drying processes. A variable amount of a neutral surfactant Brij-56© has also been added. The properties of the microspheres vary significantly depending on their composition. Three kinds of texture are identified: (1) silica containing spheroid nano-domains (formed by ibuprofen; diameters between 20 and 100 nm), (2) silica containing worm-like mesophases (formed by Brij-56© and both model drugs, typical correlation distances ~6 nm), (3) silica intimately mixed with the drug (acetaminophen) without visible phase-separation. The kinetics of drug release in simulated intestinal fluid strongly depend on these textures. The association of ibuprofen and acetaminophen in a single type of microsphere and without surfactant favours a concomitant release. Possible mechanisms of materials’ formation are discussed. 相似文献