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81.
Ponnuswamy N Pantoş GD Smulders MM Sanders JK 《Journal of the American Chemical Society》2012,134(1):566-573
Amino-acid functionalized naphthalenediimides self-assemble into hydrogen-bonded supramolecular helical nanotubes via a noncooperative, isodesmic process; the self-assembly of ordered helical systems is usually realized through a cooperative process. This unexpected behavior was rationalized as a manifestation of entropy-enthalpy compensation. Fundamental insights into the thermodynamics governing this self-assembly were obtained through the fitting of the isodesmic model to (1)H NMR spectrometry and circular dichroism spectroscopy measurements. Furthermore, we have extended the application of this mathematical model, for the first time, to quantitatively estimate the effect of guests, solvents, and side chains on the stability of the supramolecular nanotube; most significantly, we demonstrate that C(60) acts as a template to stabilize the nanotube assembly and thereby substantially increase the degree of polymerization. 相似文献
82.
Dr. Martin Wolffs Juliën L. J. van Velthoven Dr. Xianwen Lou Ralf A. A. Bovee Maarten Pouderoijen Joost L. J. van Dongen Dr. Albertus P. H. J. Schenning Prof. Dr. E. W. Meijer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(47):15057-15064
The self‐assembly of two enantiomerically pure hexa(oligo (p‐phenylene vinylene))‐substituted benzenes having 24 stereocenters was studied in pure methylcyclohexane (MCH) and in a mixture of MCH/toluene (4:1). Irrespective of the solvent a cooperative supramolecular polymerization mechanism was determined for these star‐shaped molecules by using temperature‐dependent CD and UV/Vis spectroscopy. Quite remarkably, a transition from one helical supramolecular state (A) to a second more thermodynamically stable supramolecular helical assembly (B) was observed. The rate of the A→B transition was strongly dependent on the nature of the solvent; being faster in the solvent mixture than in pure MCH. By using size exclusion chromatography we could relate the increased rate to a decreased stability of the supramolecular A state in the solvent mixture. Next, we mixed the two enantiomerically pure hexa‐substituted benzene derivatives in a so‐called majority‐rules experiment, which lead to the anitcipated chiral amplification in the A state. More importantly it appeared that the A→B transition was significantly hampered in these mixed systems. Furthermore, the absence of chiral amplification in the B state revealed the formation of separated enantiomerically pure assemblies. Therefore, by using a wide variety of spectroscopic and chromatographic techniques we determined the influence of solvent and enantiomeric purity on the transition between different supramolecular states. 相似文献
83.
Wim Fremout Maarten Dhaenens Steven Saverwyns Jana Sanyova Peter Vandenabeele Dieter Deforce Luc Moens 《Analytica chimica acta》2012
In recent years, the use of liquid chromatography tandem mass spectrometry (LC–MS/MS) on tryptic digests of cultural heritage objects has attracted much attention. It allows for unambiguous identification of peptides and proteins, and even in complex mixtures species-specific identification becomes feasible with minimal sample consumption. Determination of the peptides is commonly based on theoretical cleavage of known protein sequences and on comparison of the expected peptide fragments with those found in the MS/MS spectra. In this approach, complex computer programs, such as Mascot, perform well identifying known proteins, but fail when protein sequences are unknown or incomplete. Often, when trying to distinguish evolutionarily well preserved collagens of different species, Mascot lacks the required specificity. Complementary and often more accurate information on the proteins can be obtained using a reference library of MS/MS spectra of species-specific peptides. Therefore, a library dedicated to various sources of proteins in works of art was set up, with an initial focus on collagen rich materials. This paper discusses the construction and the advantages of this spectral library for conservation science, and its application on a number of samples from historical works of art. 相似文献
84.
Cucu T Devreese B Trashin S Kerkaert B Rogge M De Meulenaer B 《Journal of AOAC International》2012,95(1):149-156
Hazelnuts are widely used nowadays, and can pose a serious threat to allergic consumers due to cross-contamination that may occur during processing. This might lead to the presence of hidden hazelnut in foods. Therefore, reliable tests are needed to detect hazelnut, especially in processed foods. A hazelnut-specific indirect competitive ELISA based on polyclonal chicken antibodies was developed. The polyclonal antibodies were raised against modified hazelnut proteins in order to improve the detectability of hazelnut proteins in processed foods. The assay showed a detection limit of 1.36 microg hazelnut protein/mL of 5 mM urea in phosphate-buffered saline buffer (pH 7.4). Limited cross-reactivity with walnut and pecan nut was observed; no cross-reactivity was observed with other food ingredients. Blank cookies spiked before analysis showed recoveries of 73-107%. However, cookies spiked before baking showed that the detectability was severely decreased. Addition of lactose to the cookies, which led to more severe modification through the Maillard reaction, led to an increase in the detectability. These results indicate that using antibodies developed toward allergens modified through food processing-simulating reactions is a better approach for detection. 相似文献
85.
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87.
Maarten H. van der Vlerk 《Mathematical Methods of Operations Research》2005,62(2):225-242
We consider multiple simple recourse (MSR) models, both continuous and integer versions, which generalize the corresponding
simple recourse (SR) models by allowing for a refined penalty cost structure for individual shortages and surpluses. It will
be shown that (convex approximations of) such MSR models can be represented as explicitly specified continuous SR models,
and thus can be solved efficiently by existing algorithms.
This research has been made possible by a fellowship of the Royal Netherlands Academy of Arts and Sciences. 相似文献
88.
89.
Seismic data is modeled in the high‐frequency approximation, using the techniques of microlocal analysis. We consider general, anisotropic elastic media. Our methods are designed to allow for the formation of caustics. The data is modeled in two ways. First, we give a microlocal treatment of the Kirchhoff approximation, where the medium is assumed to be piecewise smooth, and reflection and transmission occur at interfaces. Second, we give a refined view on the Born approximation based upon a linearization of the scattering process in the medium parameters around a smooth background medium. The joint formulation of Born and Kirchhoff scattering allows us to take into account general scatterers as well as the nonlinear dependence of reflection coefficients on the medium parameters. The latter allows the treatment of scattering up to grazing angles. The outcome of the analysis is a characterization of the singular part of seismic data. We obtain a set of pseudodifferential operators that annihilate the data. In the process we construct a Fourier integral operator and a reflectivity function such that the data can be represented by this operator acting on the reflectivity function. In our construction this Fourier integral operator becomes invertible. We give the conditions for invertibility for general acquisition geometry. The result is also of interest for inverse scattering in acoustic media. © 2002 John Wiley & Sons, Inc. 相似文献
90.
Maarten de Hoop Gunther Uhlmann Yiran Wang 《Annales de l'Institut Henri Poincaré (C) Analyse Non Linéaire》2019,36(2):347-363
For scalar semilinear wave equations, we analyze the interaction of two (distorted) plane waves at an interface between media of different nonlinear properties. We show that new waves are generated from the nonlinear interactions, which might be responsible for the observed nonlinear effects in applications. Also, we show that the incident waves and the nonlinear responses determine the location of the interface and some information of the nonlinear properties of the media. In particular, for the case of a jump discontinuity at the interface, we can determine the magnitude of the jump. 相似文献