A joint theoretical and experimental investigation on the 13C and 1H NMR chemical shifts of coumarin derivatives

¹H and ¹³C NMR chemical shifts of coumarin derivatives have been determined using first principles approaches with and without accounting for the effects of the solvent and compared to experiment in order to assess their reliability. Good linear relationships are obtained between theory and experiment, which allows correcting the calculated values for systematic errors. This is particularly the case when using the PCM scheme to model the solvent effects because the δ values larger than 150 ppm are more difficult to reproduce. The final accuracy of the method amounts to about 1 ppm for ¹³C and 0.05 ppm for ¹H.     

Theoretical and experimental investigation of the structural and spectroscopic properties of coumarin 343 fluoroionophores

A joint theoretical-experimental investigation has been carried out to unravel the details of the complexation of cations by fluoroionophores based on coumarin 343 and to interpret the modifications in the ligand and also in the coumarin structural, electronic, magnetic, and vibrational properties. It is confirmed that C343-dea (1) complexes the cations by both the lactone and the amide oxygen atoms whereas for C343-crown (2) and C343-dibenzocrown (3), the cations are complexed by the oxygen atoms of the lactone as well as those of the crown ligand. These complexations induce geometric modifications, which are delocalized over the coumarin backbone and are related to electronic reorganizations that modify the spectroscopic signatures. This paper analyzes these signatures and shows how they are related as well as how they can be used to monitor the complexation process. Upon complexation, the UV-visible absorption spectra display a bathochromic shift of the most intense electronic transition; this shift is generally larger for the most flexible compound 1 as well as when complexing divalent cations. NMR spectra bear many signatures of the complexation, of which the most remarkable ones are the large shielding of C(1) and the large deshieldings of C(9) and C(16). Additional makers of complexation are highlighted in the IR vibrational spectra, in particular the bands associated with the lactone and amide CO vibrations, which are downshifted when the corresponding CO is involved in the complexation mode and, otherwise, upshifted. A high degree of consistency characterizes the different geometrical, electronic, magnetic, and vibrational signatures, which substantiates the assignment of the modes of complexation in 1-3. In addition, the agreement between the experimental data and the theoretical values is rather satisfactory, in that it at least enables us to interpret the spectral signatures.     

Can a traveling wave connect two unstable states? The case of the nonlocal Fisher equation

This Note investigates the properties of the traveling waves solutions of the nonlocal Fisher equation. The existence of such solutions has been proved recently in Berestycki et al. (2009) [3] but their asymptotic behavior was still unclear. We use here a new numerical approximation of these traveling waves which shows that some traveling waves connect the two homogeneous steady states 0 and 1, which is a striking fact since 0 is dynamically unstable and 1 is unstable in the sense of Turing.     

Symplectic microgeometry II: generating functions

We adapt the notion of generating functions for lagrangian submanifolds to symplectic microgeometry. We show that a symplectic micromorphism always admits a global generating function. As an application, we describe hamiltonian flows as special symplectic micromorphisms whose local generating functions are the solutions of Hamilton-Jacobi equations. We obtain a purely categorical formulation of the temporal evolution in classical mechanics.     

Wrapping an adhesive sphere with an elastic sheet

We study the adhesion of an elastic sheet on a rigid spherical substrate. Gauss's Theorema Egregium shows that this operation necessarily generates metric distortions (i.e., stretching) as well as bending. As a result, a large variety of contact patterns ranging from simple disks to complex branched shapes are observed as a function of both geometrical and material properties. We describe these different morphologies as a function of two nondimensional parameters comparing, respectively, bending and stretching energies to adhesion. A complete configuration diagram is finally proposed.     

Efficient One-Step Passivation of Polyurethane Using Transurethanization

The uncontrolled accumulation of biological materials on the surface of medical devices through protein adsorption or cell adhesion causes adverse biological reactions in the living host system, leading to complications. In this study, poly(ethylene glycol) (PEG) is successfully grafted onto polyurethane (PU) surfaces by using a new strategy through a simple and efficient transurethanization reaction. The PEG hydroxyl group is deprotonated and then reacted with the PU surface to provide antiadhesive hydrophilic surfaces in a single step. Surface analysis techniques proved the grafting to be efficient and the formation of a hydrophilic polymeric layer at the surface of PU. Biological assays showed that the surface modification induced lower protein adsorption, cell, platelet, and bacterial adhesion than untreated surfaces, showing a potential for biomedical applications.     

Yet another short proof of Bourgain’s distortion estimate for embedding of trees into uniformly convex Banach spaces

We use a self-improvement argument to give a very short and elementary proof of the result of Bourgain saying that infinite regular trees do not admit bi-Lipschitz embeddings into uniformly convex Banach spaces.     

New practical tools for the implementation and use of ultrafast 2D NMR experiments

Ultrafast (UF) 2D NMR is a very promising methodology enabling the acquisition of 2D spectra in a single scan. In the last few years, the analytical performance of UF 2D NMR has been highly increased, consequently maximizing its range of applications. However, its implementation and use by non‐specialists are far from being straightforward, because of the specific acquisition and processing procedures and parameters characterizing UF NMR. To make this methodology implementable and applicable by non‐specialists, we developed a simple routine capable of translating conventional parameters (spectral widths and transmitter frequencies) into specific UF parameters (gradient and chirp pulse parameters). This macro was subsequently implemented in a Web page, which is available for external users. Although the algorithm was designed for two widely used 2D experiments, COSY and HSQC, it can easily be extended to any other pulse sequence. The robustness of this routine was verified successfully on a variety of small molecules. We believe that this tool will eliminate much of the technical difficulties related to UF 2D NMR and will make the technique accessible to a wider audience of organic and analytical chemists. Copyright © 2013 John Wiley & Sons, Ltd.