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1.
Control over Nanostructures and Associated Mesomorphic Properties of Doped Self‐Assembled Triarylamine Liquid Crystals
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Dr. Yuya Domoto Dr. Eric Busseron Prof. Dr. Mounir Maaloum Dr. Emilie Moulin Prof. Dr. Nicolas Giuseppone 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(5):1938-1948
We have synthesized a series of triarylamine‐cored molecules equipped with an adjacent amide moiety and dendritic peripheral tails in a variety of modes. We show by 1H NMR and UV/Vis spectroscopy that their supramolecular self‐assembly can be promoted in solution upon light stimulation and radical initiation. In addition, we have probed their molecular arrangements and mesomorphic properties in the bulk by integrated studies on their film state by using differential scanning calorimetry (DSC), variable‐temperature polarizing optical microscopy (VT‐POM), variable‐temperature X‐ray diffraction (VT‐XRD), and atomic force microscopy (AFM). Differences in the number and the disposition of the peripheral tails significantly affect their mesomorphic properties associated with their lamellar‐ or columnar‐packed nanostructures, which are based on segregated stacks of the triphenylamine cores and the lipophilic/lipophobic periphery. Such structural tuning is of interest for implementation of these soft self‐assemblies as electroactive materials from solution to mesophases. 相似文献
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Brian R. Holder Colleen A. McNaney David Luchetti Eric Schaeffer Dieter M. Drexler 《Biomedical chromatography : BMC》2015,29(9):1375-1379
Acetyl‐l ‐carnitine (ALCAR) is a potential biomarker for the modulation of brain neurotransmitter activity, but is also present in cerebrospinal fluid (CSF). Recent studies have utilized hydrophilic interaction liquid chromatography–tandem mass spectrometry (HILIC‐MS/MS) based assays to detect and quantify ALCAR within biofluids such as urine, plasma and serum, using various sample pretreatment procedures. In order to address the need to quantify ALCAR in CSF on a high‐throughput scale, a new and simple HILIC‐MS/MS assay has been successfully developed and validated. For rapid analysis, CSF sample pretreatment was performed via ‘dilute and shoot’ directly onto an advanced HILIC column prior to MS/MS detection. This newly developed HILIC‐MS/MS assay shows good recoveries of ALCAR without the need for chemical derivatization and multistep sample extraction procedures. The employment of this assay is suitable for the high‐throughput bioanalysis and quantification of ALCAR within the CSF of various animal models and human clinical studies. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
4.
Modification of the visual appearance when a rough surface is covered by a varnish is mostly attributed to the levelling of the substrate surface, which depends on the molecular weight of the varnish. The topography of varnished surfaces, however, has never been measured directly. Surfaces of varnishes applied over glass substrates of varying roughness were studied, therefore, using mechanical profilometry. Two different varnishes made with a low and a high molecular weight resin were studied. Both varnishes lower the r.m.s. roughness of the substrates and filter the high spatial frequencies. These results are amplified for the varnish containing the low molecular weight resin. The light reflected by the varnished samples is modelled from these topographical data. Its angular distribution, calculated from the probability density of slopes is presented, taking into account separately the air/varnish and the varnish/substrate interfaces. These analyses are presented in a back-scattering configuration. They show that varnishing significantly reduces the angular width of the reflected light and that this effect is magnified for the low molecular weight resin. Modelling furthermore shows that the influence of the roughness of the varnish/substrate interface is negligible in the total reflected light. 相似文献
5.
Compared with linear polymers, more factors may affect the glass‐transition temperature (Tg) of a hyperbranched structure, for instance, the contents of end groups, the chemical properties of end groups, branching junctions, and the compactness of a hyperbranched structure. Tg's decrease with increasing content of end‐group free volumes, whereas they increase with increasing polarity of end groups, junction density, or compactness of a hyperbranched structure. However, end‐group free volumes are often a prevailing factor according to the literature. In this work, chain‐end, free‐volume theory was extended for predicting the relations of Tg to conversion (X) and molecular weight (M) in hyperbranched polymers obtained through one‐pot approaches of either polycondensation or self‐condensing vinyl polymerization. The theoretical relations of polymerization degrees to monomer conversions in developing processes of hyperbranched structures reported in the literature were applied in the extended model, and some interesting results were obtained. Tg's of hyperbranched polymers showed a nonlinear relation to reciprocal molecular weight, which differed from the linear relation observed in linear polymers. Tg values decreased with increasing molecular weight in the low‐molecular‐weight range; however, they increased with increasing molecular weight in the high‐molecular‐weight range. Tg values decreased with increasing log M and then turned to a constant value in the high‐molecular‐weight range. The plot of Tg versus 1/M or log M for hyperbranched polymers may exhibit intersecting straight‐line behaviors. The intersection or transition does not result from entanglements that account for such intersections in linear polymers but from a nonlinear feature in hyperbranched polymers according to chain‐end, free‐volume theory. However, the conclusions obtained in this work cannot be extended to dendrimers because after the third generation, the end‐group extents of a dendrimer decrease with molecular weight. Thus, it is very possible for a dendrimer that Tg increases with 1/M before the third generation; however, it decreases with 1/M after the third generation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1235–1242, 2004 相似文献
6.
Eric P. Bescher Atif Noori John D. Mackenzie 《Journal of Sol-Gel Science and Technology》2004,32(1-3):69-72
A fluorinated copolymer/metal oxide hybrid is fabricated by refluxing a high hydroxyl content fluorinated copolymer with tetraethoxysilane. The resulting organic-inorganic hybrids are transparent throughout the entire compositional range if processed with HCl as a catalyst. They exhibit a continuous variation in hardness, hydrophobicity, and abrasion resistance, intermediary between the properties of the pure polymer and that of a silica gel. The catalyst has a strong influence over the microstructure of the hybrid. 29Si MAS-NMR indicates the presence of highly condensed silica clusters within the structure of the hybrid. If a Nd(III) alkoxide is used instead of TEOS, a Nd 3+-doped fluoropolymer is obtained. These results indicate that when a fluorinated copolymer contains groups amenable to hydrolysis and condensation, cross-linking with a metal alkoxide is possible, leading to an interesting families of hybrids. 相似文献
7.
Alain Bachelot Eric Darrigrand Katherine Mer-Nkonga 《Comptes Rendus Mathematique》2003,336(6):505-510
The aim of this work is to propose an accurate and efficient numerical approximation for high frequency diffraction of electromagnetic waves. In the context of the boundary integral equations presented in F. Collino and B. Després, to be published in J. Comput. Appl. Math., the strategy we propose combines the microlocal discretization (T. Abboud et al., in: Third International Conference on Mathematical Aspects of Wave Propagation Phenomena, SIAM, 1995, pp. 178–187) and the multilevel fast multipole method (J.M. Song, W.C. Chew, Microw. Opt. Tech. Lett. 10 (1) (1995) 14–19). This leads to a numerical method with a reduced complexity, of order O(N4/3ln(N)+NiterN2/3), instead of the complexity O(NiterN2) for a classical numerical iterative solution of integral equations. Computations on an academic geometry show that the new method improves the efficiency, for a solution with a good level of accuracy. To cite this article: A. Bachelot et al., C. R. Acad. Sci. Paris, Ser. I 336 (2003). 相似文献
8.
R. Eric Berson John S. Young Thomas R. Hanley 《Applied biochemistry and biotechnology》2006,130(1-3):612-620
Following detoxification of the liquid hydrolysate produced in a corn stover pretreatment process, inhibitor levels are seen
to increase with the re-addition of solids for the ensuing hydrolysis and fermentation processes. The solids that were separated
from the slurry before detoxification of the liquor contain approx 60% (w/w) moisture, and contamination occurs owing to the
diffusion of inhibitors from the moisture entrained in the porous structure of the corn stover solids into the bulk fluid.
This evidence suggests the need for additional separation and detoxification steps to purge residual inhibitors entrained
in the moisture in the solids. An overliming process to remove furans from the hydrolysate failed to reduce total organic
acids concentration, so acids were removed by treatment with an activated carbon powder. Smaller carbon doses proved more
efficient in removing organic acids in terms of grams of acid removed per gram of carbon powder. Sugar adsorption by the activated
carbon powder was minimal. 相似文献
9.
We study the number of determining modes necessary for continuous data assimilation in the two-dimensional incompressible Navier–Stokes equations. Our focus is on how the spatial structure of the body forcing affects the rate of continuous data assimilation and the number of determining modes. We treat this problem analytically by proving a convergence result depending on the H
–1 norm of f and computationally by considering a family of forcing functions with identical Grashof numbers that are supported on different annuli in Fourier space. The rate of continuous data assimilation and the number of determining modes is shown to depend strongly on the length scales present in the forcing. 相似文献
10.
Numerical schemes for systems with multiple spatio-temporal scales are investigated. The multiscale schemes use asymptotic results for this type of systems which guarantee the existence of an effective dynamics for some suitably defined modes varying slowly on the largest scales. The multiscale schemes are analyzed in general, then illustrated on a specific example of a moderately large deterministic system displaying chaotic behavior due to Lorenz. Issues like consistency, accuracy, and efficiency are discussed in detail. The role of possible hidden slow variables as well as additional effects arising on the diffusive time-scale are also investigated. As a byproduct we obtain a rather complete characterization of the effective dynamics in Lorenz model. 相似文献