Phosphorus-containing gradient (block)copolymers via RAFT polymerization and post-polymerization modification

Reversible addition‐fragmentation chain transfer (RAFT) copolymerization of styrene (St) and 4‐(diphenylphosphino)styrene (DPPS) is explored to establish the statistical distribution of the phosphine‐functional monomer within the copolymer. RAFT copolymerization of St and DPPS at a variety of feed ratios provides phosphine‐functional copolymers of low dispersity at moderate monomer conversion (Ð 60%). In all cases, the fraction of DPPS in the resulting polymers is greater than that in the monomer feed. Estimation of copolymerization reactivity ratios indicates DPPS has a strong tendency to homopolymerize while St preferentially copolymerizes with DPPS (rDPPS = 4.4; rSt = 0.31). The utility of the copolymers as macro‐RAFT agents in block copolymer synthesis is demonstrated via chain extension with hydrophilic acrylamide (N,N‐dimethylacrylamide (DMAm)) and acrylate (poly(ethylene glycol) methyl ether acrylate (mPEGA), and di(ethylene glycol) ethyl ether acrylate (EDEGA)) monomers. Finally, access to polymers containing phosphine oxide and phosphonium salt functionalities is shown through postpolymerization modification of the phosphine‐containing copolymers

Potential biological role of poly (ADP-ribose) polymerase (PARP) in male gametes

Maintaining the integrity of sperm DNA is vital to reproduction and male fertility. Sperm contain a number of molecules and pathways for the repair of base excision, base mismatches and DNA strand breaks. The presence of Poly (ADP-ribose) polymerase (PARP), a DNA repair enzyme, and its homologues has recently been shown in male germ cells, specifically during stage VII of spermatogenesis. High PARP expression has been reported in mature spermatozoa and in proven fertile men. Whenever there are strand breaks in sperm DNA due to oxidative stress, chromatin remodeling or cell death, PARP is activated. However, the cleavage of PARP by caspase-3 inactivates it and inhibits PARP's DNA-repairing abilities. Therefore, cleaved PARP (cPARP) may be considered a marker of apoptosis. The presence of higher levels of cPARP in sperm of infertile men adds a new proof for the correlation between apoptosis and male infertility. This review describes the possible biological significance of PARP in mammalian cells with the focus on male reproduction. The review elaborates on the role played by PARP during spermatogenesis, sperm maturation in ejaculated spermatozoa and the potential role of PARP as new marker of sperm damage. PARP could provide new strategies to preserve fertility in cancer patients subjected to genotoxic stresses and may be a key to better male reproductive health

Elaboration of stable hybrid colloidal particles of LDH/DHBC from hybrid polyion complex micelle : Study of the formation mechanisms

Ce travail concerne la préparation directe dans l’eau de nanoparticules colloïdales de HDL stables et peu agrégées utilisant des DHBC PAm-b-PAA ou PAm-b-PVPA constitués d’un bloc ionisable complexant poly(acide-acrylique) (PAA) ou poly(acide vinylphosphonique (PVPA) et d’un bloc neutre stabilisant poly(acrylamide) (PAm). La synthèse est en 2 étapes: i) complexation par le bloc anionique du DHBC des Mg2+ ou Cu 2+ et Al3+ donnant des micelles hybrides complexes de polyions (HPIC) ; ii) co-hydroxylation des cations à pH constant. Les DHBC sont préparés par polymérisation RAFT/MADIX à partir des monomères et d’un agent de transfert. Les mélanges copolymère PAA3000-b-PAm10000 et cations Mg2+ et Al3+ forment des micelles HPIC DHBC/Al3+ coexistant avec des complexes solubles de Mg2+. La co-hydroxylation progressive (jusqu’à pH 10) des mélanges transforme les micelles DHBC/Al3+ en colloïdes DHBC/Al(OH)3 ; puis la dissolution partielle de l’hydroxyde d’aluminium et l’incorporation progressive des Mg2+ conduisent à la précipitation du HDL dans le cœur du colloïde. Les diamètres hydrodynamiques des colloïdes (200 à 50 nm) et les tailles des particules individuelles de HDL (40 à 20 nm ; 3-4 feuillets) intercalées par le PAA décroissent avec le taux de complexation (R = AA/(Mg+Al)). Le taux critique de fonction complexante par cation, au-delà duquel il y a stabilité colloïdale, varie avec le degré d’asymétrie des DHBC (Am/AA(VPA)), contrairement au nombre critique de fonctions stabilisantes par cation. Le volume de chaînes neutres PAm gouverne donc la stabilisation stérique et la taille des particules. Le seuil de stabilité dépend aussi de l’architecture du DHBC et, à même degré d’asymétrie, la stabilité est meilleure en présence de copolymères diblocs que triblocs. Les propriétés des micelles HPIC et du HDL dépendent du bloc complexant car les rendements en Mg et Al dans les micelles HPIC PAm-b-PVPA/Mg-Al sont plus élevés que dans les PAm-b-PAA/Mg-Al. Après hydroxylation, le rendement en HDL colloïdal est de 100% et les particules sont plus petites avec les polyphosphonates. Le mécanisme de formation des colloïdes dépend aussi de la spéciation du M2+ puisque, contrairement à Mg2+ et Al3+, l’hydroxylation de Cu2+ et Al3+ est concomitante à bas pH.Mots-clés : Hydroxydes doubles lamellaires (HDL), Copolymères à blocs double hydrophiles (DHBC), Polymérisation RAFT/MADIX, Micelles hybrides complexes de polyions, colloïdes, chimie douceIn this work a direct preparation route in water of stable and poorly aggregated colloidal LDH nanoparticles was developed using PAm-b-PAA or PAm-b-PVPA DHBC. These latter contain a ionizable complexing block poly(acrylic acid) (PAA) or poly(vinylphosphonic acid) (PVPA) and a stabilizing neutral block poly(acrylamide) (PAm). The preparation is achieved in 2 steps: i) complexing Mg2+ or Cu2+ and Al3+ cations by the DHBC anionic block leading to HPIC micelles; ii) co-hydroxylation of the cations at constant pH. The synthesis of DHBC was performed by RAFT/MADIX polymerization route using monomers and a transfer agent. The mixture of PAA3000-b-PAm10000 copolymer and Mg2+ and Al3+ cations lead to HPIC DHBC/Al3+ micelles that coexist with soluble Mg2+complexes. DHBC/Al(OH)3 colloids are obtained from the DHBC/Al3+ micelles by progressive co-hydroxylation (up to pH 10) of the mixtures. Then partial dissolution of the Al hydroxide and incorporation of Mg2+ induce LDH precipitation in the colloid core. The hydrodynamic size of the colloids (200 to 50 nm) and the size of the individual LDH particles (40 to 20 nm; 3-4 sheets) intercalated by PAA blocks decrease when the complexing degree (R = AA/(Mg+Al)) increases. The critical ratio of complexing function per cation, above which colloidal stability is reached, varies with the polymer asymmetry degree (Am/AA(VPA)), in contrast to the critical number of stabilizing function by cation. This shows that the volume of the neutral chains governs the steric stabilization and the size of the particles. The stability threshold also depends on the DHBC architecture because, at same asymmetry degree, the stability is improved with diblock copolymers compared to triblock copolymers. The properties of the HPIC micelles and of the LDH depend on the nature of the complexing block because the yields of Mg and Al in the HPIC micelles are higher with PAm-b-PVPA than with PAm-b-PAA. After hydroxylation, a 100% yield of LDH in colloidal form is obtained and the particles are of smaller size with the polyphosphonates. The formation mechanism of the colloids depends on the M2+ speciation, because contrary to Mg2+ and Al3+, Cu2+ and Al3+ are simultaneously hydroxylated at low pH.Keywords : Layered double hydroxides (LDH), Double-Hydrophilic-block Copolymers (DHBC), Polymérization RAFT/MADIX, Polyions complex micelles (HPIC), Colloids, Soft chemistr

Étude de la mort cellulaire programmée ou apoptose dans les spermatozoïdes humains et les cellules de la granulosa en phase lutéale au cours de la fécondation in vitro

PARIS-BIUSJ-Thèses (751052125) / SudocPARIS-BIUP (751062107) / SudocPARIS-BIUSJ-Physique recherche (751052113) / SudocSudocFranceF

Synthesis of layered double hydroxides through continuous flow processes: A review

International audienceContinuous production processes allow scaling up of layered double hydroxides (LDHs) and avoid the drawbacks induced by conventional coprecipitation. These drawbacks result from variable supersaturation rate due to non constant pH and concentration of the solutions and from long residence times hindering a fine control of the size and morphology of the particles. Continuous flow processes allow reducing the residence time and maintaining almost constant supersaturation producing LDHs in large amounts with constant quality. We report here the different continuous flow methods for the production of LDHs particles with controlled size and morphology or individual nanosheets, and of LDH-based hybrids and nanocomposites. The paper will focus on the design of the reactors showing a decrease of their volume and an improvement of the mixing and heat and mass transfers. Cylindrical tank under steady-state conditions lead to particles with a narrower size distribution than in batch reactor. Then processes with vigorously stirred microreactors in the so-called in-line dispersion-precipitation method were developed. Counter-current flow reactors with particles formed at the interface of solutions flowing up and down were further used to obtain ultra-fine LDH nanoplates and efficient surface modification with surfactants. Hydrothermal continuous or co-flow reactors exhibit great versatility allowing the preparation of exfoliated or functional LDHs, LDH nanoplates on alumina-coated substrates, and reduced graphene oxide/LDH nanocomposite films. The microfluidic technology is very promising for preparing LDHs of different compositions and functionalities. The reaction conditions as well as the structural and morphological properties of the materials are discussed and applications are reported

Highly Stable Layered Double Hydroxide Colloids: A Direct Aqueous Synthesis Route from Hybrid Polyion Complex Micelles

International audienceAqueous suspensions of highly stable Mg/Al layered double hydroxide (LDH) nanoparticles were obtained via a direct and fully colloidal route using asymmetric poly(acrylic acid)-b-poly(acrylamide) (PAA-b-PAM) double hydrophilic block copolymers (DHBCs) as growth and stabilizing agents. We showed that hybrid polyion complex (HPIC) micelles constituted of almost only Al3+ were first formed when mixing solutions of Mg2+ and Al3+ cations and PAA(3000)-b-PAM(10000) due to the preferential complexation of the trivalent cations. Then mineralization performed by progressive hydroxylation with NaOH transformed the simple DHBC/Al3+ HPIC micelles into DHBC/aluminum hydroxide colloids, in which Mg2+ ions were progressively introduced upon further hydroxylation leading to the Mg-Al LDH phase. The whole process of LDH formation occurred then within the confined environment of the aqueous complex colloids. The hydrodynamic diameter of the DHBC/LDH colloids could be controlled: it decreased from 530 nm down to 60 nm when the metal complexing ratio R (R = AA/(Mg + Al)) increased from 0.27 to 1. This was accompanied by a decrease of the average size of individual LDH particles as R increased (for example from 35 nm at R = 0.27 down to 17 nm at R = 0.33), together with a progressive favored intercalation of polyacrylate rather than chloride ions in the interlayer space of the LDH phase. The DHBC/LDH colloids have interesting properties for biomedical applications, that is, high colloidal stability as a function of time, stability in phosphate buffered saline solution, as well as the required size distribution for sterilization by filtration. Therefore, they could be used as colloidal drug delivery systems, especially for hydrosoluble negatively charged drugs

Comparison of CuxZnAlO mixed oxide catalysts derived frommulticationic and hybrid LDH precursors for methane total oxidationMonica

International audienceCuxZnAlO mixed oxide catalysts for methane total oxidation have been obtained by thermal activa-tion of layered double hydroxides (LDHs) precursors. LDHs have been prepared following two differentroutes: (i) conventional coprecipitation (pH = 8 or 10) and (ii) hybridation achieved by intercalation ofCu-containing anionic complexes ([Cu-EDTA]2− and [Cu-citrate]−) into host ZnAl-LDH. The mixed oxidecatalysts showed only ZnO phase at Cu < 5 at.% and a mixture of ZnO and CuO phases at higher Cu con-tent. CuO particles differently interacting with the oxide supports were revealed by TPR analysis. Theywere reduced at lower temperature but with a lower H2 consumption in the mixed oxides derived fromthe hybrids suggesting lower accessibility. The activity of the catalysts in the total oxidation of methanestrongly depended on the method of preparation of the LDH precursors and on the Cu content. Cu10ZnAlO (10 at.% Cu) derived from a coprecipitated LDH showed the highest intrinsic activity and a good stabilitysuggesting an optimum dispersion of the copper-containing active species. Among the catalysts derivedfrom the hybrid precursors, the higher activity of the Cu(EDTA)-ZnAl ones may be due to their higher Cucontent. The lower intrinsic activities and higher activation energies of this series of catalysts comparedto the coprecipitated ones may be due to the lower accessibility to the CuO active sites

Hybrid polyion complex micelles from poly(vinylphosphonic acid)-based double hydrophilic block copolymers and divalent transition metal ions

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Controlled Growth of Cyano-Bridged Coordination Polymers into Layered Double Hydroxides

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Comprehensive study of the formation of stable colloids of Cu Al layered double hydroxide assisted by double hydrophilic block copolymers

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