NMR investigations of the interaction between the azo-dye sunset yellow and Fluorophenol

The interaction of small molecules with larger noncovalent assemblies is important across a wide range of disciplines. Here, we apply two complementary NMR spectroscopic methods to investigate the interaction of various fluorophenol isomers with sunset yellow. This latter molecule is known to form noncovalent aggregates in isotropic solution, and form liquid crystals at high concentrations. We utilize the unique fluorine-19 nucleus of the fluorophenol as a reporter of the interactions via changes in both the observed chemical shift and diffusion coefficients. The data are interpreted in terms of the indefinite self-association model and simple modifications for the incorporation of a second species into an assembly. A change in association mode is tentatively assigned whereby the fluorophenol binds end-on with the sunset yellow aggregates at low concentration and inserts into the stacks at higher concentrations

Influence of structural isomerism and fluorine atom substitution on the self-association of naphthoic acid

The self-association of small aromatic systems driven by π-π stacking and hydrophobic interactions is well known. Understanding the nature of these interactions is important if they are to be used to control association. Here, we present results of an NMR study into the self-association of two isomers of naphthoic acid along with an investigation into the role of a fluorine substituent on that self- association. We interpret the results in terms of a simple isodesmic model of self- association and show that the addition of the fluorine atom appears to increase the stability of the aggregates by an order of magnitude (e.g. 1-naphothic acid vs 4- fluoro-1-naphthoic acid Keq = 0.05 increases to 0.35 M-1), a result which is supported by computational studies in the literature on the role of substituent effects on interaction energy. The use of fluorinated isomers to probe the assembly is also presented, with differing trends in fluorine-19 chemical shifts observed depending on the isomer substitution pattern

Catching the collision complex through a femtosecond coherently controlled pump/probe process

International audienceWe propose a very simple and efficient way to stabilize ions issued from a collision complex through a femtosecond coherently controlled pump/probe process. Starting from a van der Waals complex, one can initiate a collision at a well-defined time and with a restricted impact parameter. Formation of stable ionic complex can be achieved by ionizing the collision complex at the "right time." We present in this paper its application to the NaI–(CH3CN)1–2 system. Na+–CH3CN ion formation is coherently controlled by ionization of colliding Na atom on CH3CN molecules issued from the dissociation of NaI within NaI–(CH3CN)1–2. Classical mechanic calculations using simple ionization/dissociation conditions can reproduce the experimental data and give an insight into the control of such a reaction

Observation of the first vibrations of the newly born Cs–CH

The femtosecond photodissociation of CsI in the CsI–CH3CN complex has been studied. Recurrences are observed in the detection of the Cs+–CH3CN ion complex. They are assigned to the first vibrations of the Cs–NCCH3 bond formed after the CsI dissociation. This result is in good agreement with calculations on the similar NaI–CH3CN system which predict a linear structure for the ground state complex

Immune reconstitution inflammatory syndrome following allo-SCT in a patient with Dipodascus capitatus spondylodiscitis.

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