7 research outputs found
How intramolecular hydrogen bonding (IHB) controls the C-ON bond homolysis in alkoxyamines
International audienceRecent amazing results (Nkolo et al., Org. Biomol. Chem., 2017, 6167) on the effect of solvents and polarity on the C-ON bond homolysis rate constants kd of alkoxyamine R1R2NOR3 led us to re-investigate the antagonistic effect of intramolecular hydrogen-bonding (IHB) on kd. Here, IHB is investigated both in the nitroxyl fragment R1R2NO and in the alkyl fragment R-3, as well as between fragments, that is, the donating group on the alkyl fragment and the accepting group on the nitroxyl fragment, and conversely. It appears that IHB between fragments (inter IHB) strikingly decreases the homolysis rate constant kd, whereas IHB within the fragment (intra IHB) moderately increases kd. For one alkoxyamine, the simultaneous occurrence of IHB within the nitroxyl fragment and between fragments is reported. The protonation effect is weaker in the presence than in the absence of IHB. A moderate solvent effect is also observed
Chemical composition and antimicrobial activity of the essential oils of leaves, roots and bark of Glossocalyx staudtii
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The beta-phosphorus hyperfine coupling constant in nitroxides: 6. Solvent effects in non-cyclic nitroxides
International audienceIn two recent articles (Org. Biomol. Chem., 2015 and 2016), we showed that changes in the phosphorus hyperfine coupling constant a(P) at position beta in beta-phosphorylated nitroxides can be dramatic. Such changes were applied to the titration of water in organic solvents and conversely of organic solvents in water. One of the molecules tested was a non-cyclic nitroxide meaning that a thorough investigation of the solvent effect on the EPR hyperfine coupling constant is timely due. In this article, we show that the aP of persistent non-cyclic beta-phosphorylated nitroxides decrease with the normalized polarity Reichardt's constant ENT. The Koppel-Palm and Kalmet-Abboud-Taft relationships were applied to gain deeper insight into the effects influencing a(N) and a(P): polarity/polarizability, hydrogen bond donor properties, and the structuredness of the cybotactic region
Hyperfine coupling constants of beta-phosphorylated nitroxides: Subtle interplay between steric strain, hyperconjugation, and dipole-dipole interactions
International audienceSolvent effects in beta-phosphorylated nitroxides show that nitrogen and phosphorus hyperfine coupling constants a(N) and a(p), increase and decrease with increasing polarity, polarizity, and Hydrogen Bond Donor effects of solvents, respectively. In a series of articles, it was shown that the driving interaction controlling the change in a(p) is the maximization of the N+center dot O-center dot center dot center dot center dot center dot center dot P+-O- dipole - dipole interaction. In this work, we show that the steric strain in Spiro beta-phosphotylated nitroxides affords the opposite trend for a(p) that is, a(p) increases with increasing solvent properties features. (C) 2017 Elsevier Ltd. All rights reserved
Detection of Bisphenol A in aqueous medium by screen printed carbon electrodes incorporating electrochemical molecularly imprinted polymers
International audienceElectrochemical molecularly imprinted polymers (e-MIPs) were for the first time introduced in screen-printed carbon electrodes (SPCE) as the sensing element for the detection of an organic pollutant. To play this sensing role, a redox tracer was incorporated inside the binding cavities of a cross-linked MIP, as a functional monomer during the synthesis step. Ferrocenylmethyl methacrylate was used for this purpose. It was associated with 4-vinylpyridine as a co-functional monomer and ethylene glycol dimethacrylate as cross-linker for the recognition of the endocrine disruptor, Bisphenol A (BPA), as a target. Microbeads of e-MIP and e-NIP (corresponding non-imprinted polymer) were obtained via precipitation polymerization in acetonitrile. The presence of ferrocene inside the polymers was assessed via FTIR and elemental analysis and the polymers microstructure was characterized by SEM and nitrogen adsorption/desorption experiments. Binding isotherms and batch selectivity experiments evidenced the presence of binding cavities inside the e-MIP and its high affinity for BPA compared to carbamazepine and ketoprofen. e-MIP (and e-NIP) microbeads were then incorporated in a graphite-hydroxyethylcellulose composite paste to prepare SPCE. Electrochemical properties of e-MIP-SPCE revealed a high sensitivity in the presence of BPA in aqueous medium compared to e-NIP-SPCE with a limit of detection (LOD) of 0.06âŻnM. Selectivity towards carbamazepine and ketoprofen was also observed with the e-MIP-SPCE
Normal, Leveled, and Enhanced Steric Effects in Alkoxyamines Carrying a ÎČâPhosphorylated Nitroxyl Fragment
The design of new
R<sub>1</sub>R<sub>2</sub>NOR<sub>3</sub> alkoxyamines
for various applications relies on the accurate prediction of two
kinetic parameters, the CâON bond homolysis rate constant (<i>k</i><sub>d</sub>) and its re-formation rate constant (<i>k</i><sub>c</sub>). Relationships to describe the steric and
polar effects of the R<sub>1</sub>R<sub>2</sub>NO fragment ruling <i>k</i><sub>d</sub> have been developed. For all cyclic nitroxyl
fragments, the steric effect is described as the sum of the bulkiness
of the R<sub>1</sub> and R<sub>2</sub> groups (i.e., normal steric
effect), while for the noncyclic nitroxyl fragment (except for one
case), a leveled steric effect is assumed. In this work, we show that
the normal steric effect also applies to noncyclic nitroxyl fragments
and that for one case an enhanced steric effect is also observed,
i.e., experimental <i>k</i><sub>d</sub> >5-fold larger
than
the predicted value
Design of a targeting and oxygen-independent platform to improve photodynamic therapy: A proof of concept
International audiencePhotodynamic therapy (PDT) is a promising technique to treat different kinds of disease especially cancer. PDT requires three elements: molecular oxygen, a photoactivatable molecule called the photosensitizer (PS), and appropriate light. Under illumination, the PSs generate, in the presence of oxygen, the formation of reactive oxygen species including singlet oxygen, toxic, which then destroys the surrounding tissues. Even if PDT is used with success to treat actinic keratosis or prostate cancer for example, PDT suffers from two major drawbacks: the lack of selectivity of most of the PSs currently used clinically as well as the need for oxygen to be effective. To remedy the lack of selectivity, targeting the tumor neovessels is a promising approach to destroy the vascularization and cause asphyxia of the tumor. KDKPPR peptide affinity for the neuropilin-1 (NRP-1) receptor overexpressed on endothelial cells has already been proven. To compensate for the lack of oxygen, we focused on photoactivatable alkoxyamines (Alks), molecules capable of generating toxic radicals by light activation. In this article, we describe the synthesis of a multifunctional platform combining three units: a PS for an oxygen-dependent PDT, a peptide to target tumor neovessels, and an Alk for an oxygen-independent activity. The synthesis of the compound was successfully carried out, and the study of its photophysical properties showed that the PS retained its capacity to form singlet oxygen and the affinity tests confirmed the affinity of the compound for NRP-1. Thanks to the electron paramagnetic resonance spectroscopy, a technique of choice for radical investigation, the radicals generated by the illumination of the Alk could be detected. The proof of concept was thus successfully established