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91.
Dr. Sébastien Lemouzy Florian Cuminet Dimitri Berne Dr. Sylvain Caillol Dr. Vincent Ladmiral Prof. Rinaldo Poli Dr. Eric Leclerc 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(48):e202201135
Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α- or β-position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate. 相似文献
92.
Amir Omidvarnia Raphaël Ligeois Enrico Amico Maria Giulia Preti Andrew Zalesky Dimitri Van De Ville 《Entropy (Basel, Switzerland)》2022,24(8)
Measuring the temporal complexity of functional MRI (fMRI) time series is one approach to assess how brain activity changes over time. In fact, hemodynamic response of the brain is known to exhibit critical behaviour at the edge between order and disorder. In this study, we aimed to revisit the spatial distribution of temporal complexity in resting state and task fMRI of 100 unrelated subjects from the Human Connectome Project (HCP). First, we compared two common choices of complexity measures, i.e., Hurst exponent and multiscale entropy, and observed a high spatial similarity between them. Second, we considered four tasks in the HCP dataset (Language, Motor, Social, and Working Memory) and found high task-specific complexity, even when the task design was regressed out. For the significance thresholding of brain complexity maps, we used a statistical framework based on graph signal processing that incorporates the structural connectome to develop the null distributions of fMRI complexity. The results suggest that the frontoparietal, dorsal attention, visual, and default mode networks represent stronger complex behaviour than the rest of the brain, irrespective of the task engagement. In sum, the findings support the hypothesis of fMRI temporal complexity as a marker of cognition. 相似文献
93.
Bytchenkoff D Pelupessy P Bodenhausen G 《Journal of the American Chemical Society》2005,127(14):5180-5185
A new method has been developed to obtain dynamic and structural information about peptide planes in proteins by a combination of measurements of weak short-range cross-correlation rates R(H(N)N/NC') that are due to concerted fluctuations of the H(N)-N and N-C' dipole-dipole interactions and stronger long-range cross-correlation rates R(C'H(N)/H(N)N) and R(NH(N)/H(N)C(alpha)). The rates were interpreted using the axially symmetric Gaussian axial fluctuation model (GAF). The oscillation amplitudes as well as the positions of H(N) atoms with respect to peptide planes in ubiquitin were determined. Most N-H(N) bonds were found not to lie exactly along the bisector of the N-C' and N-C(alpha) bonds but to be slightly tilted toward the carbon-terminal side of the peptide. 相似文献
94.
Zhu X Beginn U Möller M Gearba RI Anokhin DV Ivanov DA 《Journal of the American Chemical Society》2006,128(51):16928-16937
Complexes consisting of poly(4-vinylpyridine) and mesogenic wedge-shaped ligands 4'-[3",4",5"-tris(dodecyloxy)benzoyloxy]azobenzene-4-sulfonic acid and 4'-[3",4",5"-tris(octyloxy)benzoyloxy]azobenzene-4-sulfonic acid have been prepared with different monomer/ligand ratios. Upon protonation of the poly(4-vinylpyridine) chains by the wedge-shaped sulfonic acid molecules a hypsochromic and hyperchromic effect was observed with the pi-pi* transition of the azo-chromophor, allowing us to monitor the neutralization process by means of UV-vis spectroscopy in solution. The changes of the absorption characteristics implied a conformational change of the polymer backbone. In the bulk the interaction between pyridine and sulfonic acid moieties was proved by FT-IR spectroscopy. Polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction measurements were used to study the bulk structure of the complexes. The complexes formed a liquid crystalline lamellar phase at low degrees of substitution, while a hexagonal columnar mesophase was observed at degrees of neutralization of 80% and higher. 相似文献
95.
We prove universality at the edge of the spectrum for unitary (β = 2), orthogonal (β = 1), and symplectic (β = 4) ensembles of random matrices in the scaling limit for a class of weights w(x) = e?V(x) where V is a polynomial, V(x) = κ2mx2m + · · ·, κ2m > 0. The precise statement of our results is given in Theorem 1.1 and Corollaries 1.2 and 1.4 below. For the same class of weights, a proof of universality in the bulk of the spectrum is given in [12] for the unitary ensembles and in [9] for the orthogonal and symplectic ensembles. Our starting point in the unitary case is [12], and for the orthogonal and symplectic cases we rely on our recent work [9], which in turn depends on the earlier work of Widom [46] and Tracy and Widom [42]. As in [9], the uniform Plancherel‐Rotach‐type asymptotics for the orthogonal polynomials found in [12] plays a central role. The formulae in [46] express the correlation kernels for β = 1, 4 as a sum of a Christoffel‐Darboux (CD) term, as in the case β = 2, together with a correction term. In the bulk scaling limit [9], the correction term is of lower order and does not contribute to the limiting form of the correlation kernel. By contrast, in the edge scaling limit considered here, the CD term and the correction term contribute to the same order: this leads to additional technical difficulties over and above [49]. © 2006 Wiley Periodicals, Inc. 相似文献
96.
Blundell Tom L. Bolanos-Garcia Victor Chirgadze Dimitri Y. Harmer Nicholas J. Lo Thomas Pellegrini Luca Sibanda B. Lynn 《Structural chemistry》2002,13(3-4):405-412
Signaling in living systems needs to achieve high specificity, to be reversible, and to achieve high signal to noise. Signaling mediated by multiprotein systems has evolved that avoids the requirement for high-affinity binary complexes that would be difficult to reverse and which, in the overcrowded cell, would lead to excessive noise in the system. Symmetrical structures are only occasionally formed. When they are, it is principally to colocate components, for example, the tyrosyl kinases of growth factors, where dimers form. Symmetry is, however, often broken, presumably to create more sensitivity and specificity in the signaling system by assembling other components, into higher-order multiprotein systems. The binding of a single heparin to two 1:1 FGF:FGFR complexes is an example, as is the binding of a single ligase to the Xrcc4 dimer, perhaps so creating a further DNA-binding site. 相似文献
97.
Cell culture chip using low-shear mass transport 总被引:1,自引:0,他引:1
Liu K Pitchimani R Dang D Bayer K Harrington T Pappas D 《Langmuir : the ACS journal of surfaces and colloids》2008,24(11):5955-5960
We have developed a flow cell that allows culturing adherent cells as well as suspended cells in a stable, homogeneous, and low-shear force environment. The device features continuous medium supply and waste exchange. In this paper, a simple and fast protocol for device design, fabrication, and assembly (sealing) based on a poly(dimethylsiloxane) (PMDS)/glass slide hybrid structure is described. The cell culture system performance was monitored, and the effective shear force inside the culture well was also determined. By manipulating the device dimensions and volumetric flow rate, shear stress was controlled during experiments. Cell adhesion, growth, proliferation, and death over long-term culture periods were observed by microscopy. The growth of both endothelial and suspension cells in this device exhibited comparable characteristics to those of traditional approaches. The low-shear culture device significantly reduced shear stress encountered in microfluidic systems, allowing both adherent and suspended cells to be grown in a simple device. 相似文献
98.
Vera P. Shmachkova Nina S. Kotsarenko Vladislav V. Kanazhevskiy Galina N. Kryukova Dimitri I. Kochubey Jacques Vedrine 《Reaction Kinetics and Catalysis Letters》2007,91(1):177-185
Methods of the preparation of catalysts for alkane skeletal isomerization based on uniform nanoparticles of sulfated zirconia
anchored to different supports were investigated. These catalysts were characterized by using the ICP, HRTEM and BET techniques.
The activities of the catalysts in the reaction of n-butane isomerization were measured and compared with those of bulk catalysts. 相似文献
99.
We prove that a class of discrete Schrödinger operators with a quasiperiodic potential taking only a finite number of values, exhibits purely continuous spectrum; in particular they cannot have localized eigenvectors.Groupe de Recherche 048 of C.N.R.S. 相似文献
100.
Dimitri Petritis 《Communications in Mathematical Physics》1989,125(4):579-595
The random set of instants where the Brownian bridge vanishes is constructed in terms of a random branching process. The Hausdorff measure supported by this set is shown to be equivalent to the partition function of a special class of disordered systems. This similarity is used to show rigorously the existence of a phase transition for this particular class of disordered systems. Moreover, it is shown that at high temperature the specific free energy has the strong self-averaging property and that at low temperature it has no self-averaging property. The unicity at high-temperature and the existence of many limits at low temperature are established almost surely in the disorder.Work supported by the Swiss National Science Foundation 相似文献