Frédéric Violleau

Polymeric Micelles Encapsulating Photosensitizer: Structure/Photodynamic Therapy Efficiency Relation

Various polymeric micelles were formed from amphiphilic block copolymers, namely, poly(ethyleneoxide-b-ε-caprolactone), poly(ethyleneoxide-b-d,l-lactide), and poly(ethyleneoxide-b-styrene). The micelles were characterized by static and dynamic light scattering, electron microscopy, and asymmetrical flow field-flow fractionation. They all displayed a similar size close to 20 nm. The influence of the chemical structure of the block copolymers on the stability upon dilution of the polymeric micelles was investigated to assess their relevance as carriers for nanomedicine. In the same manner, the stability upon aging was assessed by FRET experiments under various experimental conditions (alone or in the presence of blood proteins). In all cases, a good stability over 48 h for all systems was encountered, with PDLLA copolymer-based systems being the first to release their load slowly. The cytotoxicity and photocytotoxicity of the carriers were examined with or without their load. Lastly, the photodynamic activity was assessed in the presence of pheophorbide a as photosensitizer on 2D and 3D tumor cell culture models, which revealed activity differences between the 2D and 3D systems.

Low temperature RAFT/MADIX gel polymerisation: access to controlled ultra-high molar mass polyacrylamides

We pushed back the limits of molar mass control in aqueous RAFT/MADIX polymerisation through a fast and quantitative gel polymerisation of a series of acrylamido monomers. Unprecedentedly high Mn up to 106 g mol−1 with low dispersities (Đ < 1.2) was achieved in homopolymerisation, statistical and block copolymerisation of a selection of acrylamido monomers such as AM, DMA, AMPS and NIPAM. The reasons for access to an abnormally high kinetic chain length in the presence of a RAFT/MADIX agent are discussed.

Aqueous RAFT/MADIX polymerisation of vinylphosphonic acid

RAFT/MADIX polymerisation of vinylphosphonic acid (VPA) was controlled in water with an O-ethyl xanthate transfer agent. This represents the first example of reversible deactivation radical polymerisation of a monomer bearing an unprotected phosphonic acid function. Hence, macromolecular engineering of polyphosphonates can now be envisioned by directly polymerising VPA in water.

Ozonation of imidacloprid in aqueous solutions: Reaction monitoring and identification of degradation products

This paper presents the degradation of imidacloprid by ozonation. Solutions of 39.0 μg/mL imidacloprid were prepared either by dissolution of standard or by dilution of Gaucho Blé(®) seed loading solution and then ozonated under different conditions. The concentration of imidacloprid and oxidation products in both solutions was monitored by HPLC-UV as a function of the treatment time for a concentration of 100g/m(3) of ozone in the inlet gas. No significant difference was observed: in both cases, imidacloprid degradation was a pseudo-first order reaction with similar reaction rates (0.129-0.147 min(-1)), degradation by-products with the same HPLC retention times were observed and their concentrations as a function of the treatment time followed a very similar trend. The study of ozone concentration in the inlet gas (from 25 to 100g/m(3)) showed that imidacloprid degradation is also a first-order reaction with respect to ozone. The ozonation by-products were then collected and identified by ESI(+)-MS. A degradation pathway of imidacloprid was finally proposed.

Asymmetrical flow field-flow fractionation with multi-angle light scattering and quasi elastic light scattering for characterization of poly(ethyleneglycol-b-ɛ-caprolactone) block copolymer self-assemblies used as drug carriers for photodynamic therapy

Poly(ethyleneoxide-b-ɛ-caprolactone) (PEO-b-PCL) self-assemblies in water were characterized by asymmetrical flow field-flow fractionation (AsFlFFF), with on-line coupling with quasi-elastic light scattering (QELS), multi-angle light scattering (MALS), refractive index and UV/Vis detection. We report here the AsFlFFF analysis of three different nanoparticular self-assembled systems of PEO-PCL polymers in aqueous media, each polymer differing by the mass of the PEO and PCL fragments. Thus, self-assembled water samples of {PEO(2000)-b-PCL(2600)}, {PEO(5000)-b-PCL(1400)} and {PEO(5000)-b-PCL(4000)} were analyzed by AsFlFFF. In most cases, the size obtained by AsFlFFF was similar to the one characterized by DLS. However, in some instances, only AsFlFFF revealed the presence of several self-assemblies with very different sizes. These nanoparticles being used for the targeted delivery of photosensitizers in photodynamic therapy, it was important to fully characterize the samples in terms of size and size distribution, molecular weight, Ip, aggregation number and also to assess whether the photosensitizer was inside the nanoparticles. AsFlFFF proved to be a very efficient technique which enabled this study without any destruction of the nanoparticles.

Asymmetrical flow field-flow fractionation with multi-angle light scattering and quasi-elastic light scattering for characterization of polymersomes: comparison with classical techniques

AbstractPolymersomes formed from amphiphilic block copolymers, such as poly(ethyleneoxide-b-ε-caprolactone) (PEO-b-PCL) or poly(ethyleneoxide-b-methylmethacrylate), were characterized by asymmetrical flow field-flow fractionation coupled with quasi-elastic light scattering (QELS), multi-angle light scattering (MALS), and refractive index detection, leading to the determination of their size, shape, and molecular weight. The method was cross-examined with more classical ones, like batch dynamic and static light scattering, electron microscopy, and atomic force microscopy. The results show good complementarities between all the techniques; asymmetrical flow field-flow fractionation being the most pertinent one when the sample exhibits several different types of population. Figureᅟ

Characterization of Heat-Induced Changes in Skim Milk Using Asymmetrical Flow Field-Flow Fractionation Coupled with Multiangle Laser Light Scattering

Separation and size measurement of protein particles are a relevant approach to monitor heat-induced changes in skim milk. Unfortunately, no method is currently available at low cost and without excessive preparation of the samples. Therefore, the present study aimed at evaluating the interest of asymmetrical flow field-flow fractionation (AFlFFF) coupled with multiangle laser light scattering (MALLS) for this purpose. Unheated and heated skim milk samples at pH 6.5 and 7.2 were prepared and comparatively analyzed using AFlFFF-MALLS, size exclusion chromatography (SEC-MALLS) and dynamic light scattering. The results showed that AFlFFF could evidence the conversion of the native whey proteins of unheated milk into heat-induced whey protein/κ-casein complexes in the serum phase of milk and possibly on the surface of the casein micelles. The pH-induced changes in the partition of the complexes between the serum and the micellar phases could also be observed. The results therefore showed the interest of AFlFFF-MALLS to monitor the heat-induced changes in particle sizes in skim milk and to separate the different protein components of unheated and heated skim milk.

Effect of Oxidative Treatment on Corn Seed Germination Kinetics

Corn seeds were treated with high purity oxygen ([O3] = 0 g/m3) and oxygen mixed with ozone ([O3] = 20 g/m3) during 6.8 or 20.5 minutes. Germination tests started immediately or 48 h after treatment. Effects of oxidative treatments on germination were determined by measuring seedlings and roots (>3 and >20 mm) rate at 3, 4 and 5 days of germination test. Results obtained for treated seed samples were higher than for untreated ones. A faster start of germination was observed for treated samples. This early germination start led to a larger number of germinated seeds with longer roots at 4 and 5 days. Nevertheless, too long an ozone treatment seemed to be unfavorable for seed growth, whereas a short one seemed to be most beneficial.

Multimodal Dispersion of Nanoparticles: A Comprehensive Evaluation of Size Distribution with 9 Size Measurement Methods

ABSTRACTPurposeEvaluation of particle size distribution (PSD) of multimodal dispersion of nanoparticles is a difficult task due to inherent limitations of size measurement methods. The present work reports the evaluation of PSD of a dispersion of poly(isobutylcyanoacrylate) nanoparticles decorated with dextran known as multimodal and developed as nanomedecine.MethodsThe nine methods used were classified as batch particle i.e. Static Light Scattering (SLS) and Dynamic Light Scattering (DLS), single particle i.e. Electron Microscopy (EM), Atomic Force Microscopy (AFM), Tunable Resistive Pulse Sensing (TRPS) and Nanoparticle Tracking Analysis (NTA) and separative particle i.e. Asymmetrical Flow Field-Flow Fractionation coupled with DLS (AsFlFFF) size measurement methods.ResultsThe multimodal dispersion was identified using AFM, TRPS and NTA and results were consistent with those provided with the method based on a separation step prior to on-line size measurements. None of the light scattering batch methods could reveal the complexity of the PSD of the dispersion.ConclusionsDifference between PSD obtained from all size measurement methods tested suggested that study of the PSD of multimodal dispersion required to analyze samples by at least one of the single size particle measurement method or a method that uses a separation step prior PSD measurement.

Kinetic aspects and identification of by-products during the ozonation of bitertanol in agricultural wastewaters

The degradation of bitertanol by ozone treatment is investigated. Solutions of bitertanol (8.4 μg mL(-1)) were prepared either by dissolution of the standard or by dilution of Gaucho Blé seed loading solution and then ozonated under different conditions. Evolution of the concentrations of bitertanol and its ozonation by-products in both solutions was monitored by HPLC-UV as a function of the treatment time for a concentration of 100 gm(-3) of ozone in the inlet gas. Bitertanol degradation was found to follow a pseudo-first order reaction in both cases. However, the rate of the reaction in diluted seed loading solution was much lower (0.19 vs. 0.27 min(-1) in standard solution) and was close to the reaction rate observed in the presence of a radical scavenger, tert-butanol (0.11 min(-1)). Thus, it may be suggested that additives present in the seed loading solution may play the role of radical scavengers. Study of ozone concentration in the inlet gas (from 25 to 100 gm(-3)) showed that ozone degradation is also a first-order reaction with respect to ozone. Four ozonation by-products were highlighted, collected and identified by HPLC coupled with an ion trap mass spectrometer using positive electrospray ionization mode. A degradation pathway of bitertanol was finally proposed.