A water soluble Cu(I)-NHC for CuAAC ligation of unprotected peptides under open air conditions

A reducing agent-free version of CuAAC able to operate under open air conditions is reported. A readily-synthesizable, hydrophilic and highly stable Cu(I)-NHC allows the clean ligations of unprotected peptides comprising sensitive side chains, at millimolar concentrations.     

Ligand designed with pending phenol group

The synthesis of a salicylaldehyde derivative facing an encumbered phenol group on a naphthalene block as a molecular shaft is reported. This molecular unit has been designed to elaborate coordinating ligands holding non-coordinating phenol group for the generation of phenoxyl radical in the close proximity of a metal complex.     

Ring‐opening polymerization of ε‐caprolactone and L‐lactide from silica nanoparticles surface

Coating of silica nanoparticles by biocompatible and biodegradable polymers of ε‐caprolactone and L ‐lactide was performed in situ by ring‐opening polymerization of the cyclic monomers with aluminum, yttrium, and tin alkoxides as catalysts. Hydroxyl groups were introduced on the silica surface by grafting of a prehydrolyzed 3‐glycidoxypropyl trimethoxysilane to initiate a catalytic polymerization in the presence of metal alkoxides. In this manner, free polymer chains were formed to grafted ones, and the graft density was controlled by the nature of the metal and the alcohol‐to‐metal ratio. The grafting reaction was extensively characterized by spectroscopic techniques and quantified. Nanocomposites containing up to 96% of polymer were obtained by this technique. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1976–1984, 2004     

Practical route to relative diffusion coefficients and electronic relaxation rates of paramagnetic metal complexes in solution by model-independent outer-sphere NMRD. Potentiality for MRI contrast agents

The relaxation of electronic spins S of paramagnetic species is studied by the field-dependence of the longitudinal, transverse, and longitudinal in the rotating frame relaxation rates R1, R2, and R1rho of nuclear spins I carried by dissolved probe solutes. The method rests on the model-independent low-frequency dispersions of the outer-sphere (OS) paramagnetic relaxation enhancement (PRE) of these rates due to the three-dimensional relative diffusion of the complex with respect to the probe solute. We propose simple analytical formulas to calculate these enhancements in terms of the relative diffusion coefficient D, the longitudinal electronic relaxation time T1e, and the time integral of the time correlation function of the I-S dipolar magnetic interaction. In the domain of vanishing magnetic field, these parameters can be derived from the low-frequency dispersion of R1 thanks to sensitivity improvements of fast field-cycling nuclear relaxometers. At medium field, we present various approaches to obtain these parameters by combining the rates R1, R2, and R1rho. The method is illustrated by a careful study of the proton PREs of deuterated water HOD, methanol CH3OD, and tert-butyl alcohol (CH3)3COD in heavy water in the presence of a recently reported nonacoordinate Gd(III) complex. The exceptionally slow electronic relaxation of the Gd(III) spin in this complex is confirmed and used to test the accuracy of the method through the self-consistency of the low- and medium-field results. The study of molecular diffusion at a few nanometer scale and of the electronic spin relaxation of other complexed metal ions is discussed.     

Multiscale NMR investigations of two anatomically contrasted genotypes of sorghum under watered conditions and during drought stress

Today, in the presence of global warming, understanding how plants respond to drought stress is essential to meet the challenge of developing new cultivars and new irrigation strategies, consistent with the maintenance of crop productivity. In this context, the study of the relation between plants and water is of central interest for modeling their responses to biotic and abiotic constraints. Paradoxically, there are very few direct and noninvasive methods to quantify and measure the level and the flow of water in plants. The present work aims to develop a noninvasive methodology for living plant based on nuclear magnetic resonance (NMR) at low magnetic field and imaging (MRI) to tackle the issue of water quantity in plants. For this purpose, a portable NMR device measuring the signal level at 8 mT was built. This instrument addresses specific challenges such as miniaturization, accessibility, and overheating in order to maintain the plant intact of time over long period. Time dependence of the water content in sorghum plants is reported under abiotic stress as well as the fraction of transpirable soil water and the photosynthesis activity through the leaves. At high magnetic field (9.4 T), T2 maps were acquired on the same sorghum plants at two time points. The combination of these approaches allows us to identify ecophysiological biomarkers of drought stress. One particular interesting result concerns the spatial distribution of water in two anatomically contrasted sorghum genotypes.     

Amplitude and phase of light scattered by micro-scale aggregates of dielectric spheres: Comparison between theory and microwave analogy experiments

Light scattering is a useful diagnostic tool for characterization of particles. Direct scattering measurements for arbitrarily shaped micro-scale particles is difficult due to small-scale limitations. Microwave analogy is a convenient approach to realize such measurements as it enables realization of analogous experiments with larger model particles in a spectral domain where wavelengths are on centimeter scale. In the present study a test model analogous to light scattering by a micro-scale aggregate of dielectric spheres was constructed and experimentally characterized in the microwave regime. Measured amplitude and phase of the scattered field were compared with theoretical predictions obtained from quasi-exact multiple-scattering T-matrix method and discrete dipole approximation (DDA). Excellent agreement demonstrates the validities of both the experiment and the models.     

Complexation Studies of Phosphorus Containing Bis and Tris (Benzocrown Ether) Moieties

The complexation behaviour between salts of Li⁺-Rb⁺ in CD₃CN and tris(benzocrown ether)s 2a,bX=P(NMeN=CH-B15C5)₃ (X = O, S) and tri[bis(benzocrown ether)][N=P(NMeN=CH-B15C5)₂]₃ 3 was investigated by ¹³ C NMR spectroscopy. Using the program RMNSTAB, the complexation constants for the different possible complexes (M₂L, ML andML₂ were L represents one benzo-15-crown-5) were obtained and were compared with those of the corresponding monomer material. A remarkable ``biscrown effect' for compounds 2a,b and 3 was found, especially for potassium and rubidium by the predominant formation of stable ML₂ complexes. The strong chelate effect make these ligands highly efficient extracting agents for alkali metal picrate salts of K⁺, Rb⁺ and Cs⁺,as shown by UV-Vis spectroscopy.     

Fully validated assay for the quantification of endogenous nucleoside mono- and triphosphates using online extraction coupled with liquid chromatography–tandem mass spectrometry

An analytical method coupling online solid-phase extraction (SPE) and liquid chromatography–tandem mass spectrometry (LC-MS/MS) was developed to quantify 16 endogenous nucleoside mono- and triphosphates in cellular samples. Separation was achieved on a porous graphitic carbon (PGC) column without ion-pairing agent in the mobile phase. Low levels of the ion-pairing agent diethylamine (DEA) added to the reconstitution solution were necessary to prevent peak tailing of nucleoside triphosphates. The mass spectrometer, a triple quadrupole with an electrospray ionisation source, was operated in positive mode. Two multiple reaction monitoring (MRM) segments were programmed, each an internal standard. Extraction and separation of nucleoside mono- and triphosphates were obtained within 20 min. The total duration of a single run was 37 min. Calibration curves, performed with labelled nucleotides added to the sample matrix, ranged from 0.29 to 18.8 pmol injected for deoxyribonucleotides and from 3.9 to 3,156 pmol for ribonucleotides. Accuracy did not deviate more than ?14.6 and 10.2 % from nominal values for all compounds at all levels. CV results were all lower than 17.0 % for the LLOQ level and 14.6 % for the other levels. Quality control (QC) samples were also in agreement with acceptance criteria, except for the lower QC of GMP. Ion suppression, matrix effect, extraction recoveries and stability were assessed. After validation, the method was applied to the evaluation of the effects of gemcitabine and hydroxyurea on nucleotide pools in Messa cells.