Abdelhafid Aqil

Temperature responsive complex coacervate core micelles with a PEO and PNIPAAm corona.

In aqueous solutions at room temperature, poly( N-methyl-2-vinyl pyridinium iodide)- block-poly(ethylene oxide), P2MVP 38- b-PEO 211 and poly(acrylic acid)- block-poly(isopropyl acrylamide), PAA 55- b-PNIPAAm 88 spontaneously coassemble into micelles, consisting of a mixed P2MVP/PAA polyelectrolyte core and a PEO/PNIPAAm corona. These so-called complex coacervate core micelles (C3Ms), also known as polyion complex (PIC) micelles, block ionomer complexes (BIC), and interpolyelectrolyte complexes (IPEC), respond to changes in solution pH and ionic strength as their micellization is electrostatically driven. Furthermore, the PNIPAAm segments ensure temperature responsiveness as they exhibit lower critical solution temperature (LCST) behavior. Light scattering, two-dimensional 1H NMR nuclear Overhauser effect spectrometry, and cryogenic transmission electron microscopy experiments were carried out to investigate micellar structure and solution behavior at 1 mM NaNO 3, T = 25, and 60 degrees C, that is, below and above the LCST of approximately 32 degrees C. At T = 25 degrees C, C3Ms were observed for 7 < pH < 12 and NaNO 3 concentrations below approximately 105 mM. The PEO and PNIPAAm chains appear to be (randomly) mixed within the micellar corona. At T = 60 degrees C, onion-like complexes are formed, consisting of a PNIPAAm inner core, a mixed P2MVP/PAA complex coacervate shell, and a PEO corona.

Preparation of stable suspensions of gold nanoparticles in water by sonoelectrochemistry

Stable suspensions of gold nanoparticles in water were prepared with high yield by a novel one-step ultrasound assisted electrochemical process. Various strategies based on the addition of either tailor-made polymers or mixtures of commercially available polymers, in the electrochemical bath have been found successful to avoid nanoparticles aggregation commonly observed by sonoelectrochemistry. alpha-Methoxy-omega-mercapto-poly(ethylene oxide) or poly(vinyl pyrrolidone)/polyethylene oxide mixtures were able to build up a coalescence barrier around the gold nanoparticles. The results showed that the size of the gold nanoparticles could be easily tuned between 5 nm and 35 nm by simple control of the electrochemical parameters, i.e. the deposition time (T(ON)) from 10 ms to 20 ms. The properties of as-prepared gold nanoparticles were compared to the ones of gold colloids prepared by the more conventional wet nanoprecipitation method using chemical reductive agents.

Physicochemical properties of pH-controlled polyion complex (PIC) micelles of poly(acrylic acid)-based double hydrophilic block copolymers and various polyamines

AbstractThe physicochemical properties of polyion complex (PIC) micelles were investigated in order to characterize the cores constituted of electrostatic complexes of two oppositely charged polyelectrolytes. The pH-sensitive micelles were obtained with double hydrophilic block copolymers containing a poly(acrylic acid) block linked to a modified poly(ethylene oxide) block and various polyamines (polylysine, linear and branched polyethyleneimine, polyvinylpyridine, and polyallylamine). The pH range of micellization in which both components are ionized was determined for each polyamine. The resulting PIC micelles were characterized using dynamic light scattering and small-angle X-ray scattering experiments (SAXS). The PIC micelles presented a core–corona nanostructure with variable polymer density contrasts between the core and the corona, as revealed by the analysis of the SAXS curves. It was shown that PIC micelle cores constituted by polyacrylate chains and polyamines were more or less dense depending on the nature of the polyamine. It was also determined that the density of the cores of the PIC micelles depended strongly on the nature of the polyamine. These homogeneous cores were surrounded by a large hairy corona of hydrated polyethylene oxide block chains. Auramine O (AO) was successfully entrapped in the PIC micelles, and its fluorescence properties were used to get more insight on the core properties. Fluorescence data confirmed that the cores of such micelles are quite compact and that their microviscosity depended on the nature of the polyamine. The results obtained on these core–shell micelles allow contemplating a wide range of applications in which the AO probe would be replaced by various cationic drugs or other similarly charged species to form drug nanocarriers or new functional nanodevices. FigurePoly ion complex micelles of PAA-b-PAMPEO double hydrophilic block copolymer and polyamines containing AO in the micelle core

Transparent superhydrophobic coatings from amphiphilic-fluorinated block copolymers synthesized by aqueous polymerization-induced self-assembly

Preparation of transparent and superhydrophobic coatings by co-deposition of an aqueous solution of an amphiphilic fluorinated block copolymer (FBC) with silica particles was developped. Spin-coating of this aqueous solution onto glass followed by an appropriate thermal treatment promotes the self-assembly of the hybrid material with the formation of superhydrophobic, robust and transparent coatings.

Bioinspired Redox‐Active Catechol‐Bearing Polymers as Ultrarobust Organic Cathodes for Lithium Storage

Redox-active catechols are bioinspired precursors for ortho-quinones that are characterized by higher discharge potentials than para-quinones, the latter being extensively used as organic cathode materials for lithium ion batteries (LIBs). Here, this study demonstrates that the rational molecular design of copolymers bearing catechol- and Li+ ion-conducting anionic pendants endow redox-active polymers (RAPs) with ultrarobust electrochemical energy storage features when combined to carbon nanotubes as a flexible, binder-, and metal current collector-free buckypaper electrode. The importance of the structure and functionality of the RAPs on the battery performances in LIBs is discussed. The structure-optimized RAPs can store high-capacities of 360 mA h g-1 at 5C and 320 mA h g-1 at 30C in LIBs. The high ion and electron mobilities within the buckypaper also enable to register 96 mA h g-1 (24% capacity retention) at an extreme C-rate of 600C (6 s for total discharge). Moreover, excellent cyclability is noted with a capacity retention of 98% over 3400 cycles at 30C. The high capacity, superior active-material utilization, ultralong cyclability, and excellent rate performances of RAPs-based electrode clearly rival most of the state-of-the-art Li+ ion organic cathodes, and opens up new horizons for large-scalable fabrication of electrode materials for ultrarobust Li storage.

A facile and fast electrochemical route to produce functional few-layer graphene sheets for lithium battery anode application

A simple approach for the production of polymer functionalized graphene nanosheets is reported. The resulting polyacrylonitrile chemisorbed on graphene sheets is made of 1 to 2 layers, with a large majority of graphene single-layers. This novel functionalized graphene exhibits good cycling stability as an anode in Li-ion batteries without a conductive additive or binder.

Development of a procedure to simultaneously isolate RNA, DNA, and proteins from characterizing cells invading or cultured on chitosan scaffolds

For many years, chitosan and its derivatives have been considered to be promising biomaterials for tissue engineering and repair. However, information regarding their biological effect on cell phenotype is usually limited to evaluation of cell proliferation and survival, overlooking proteomic and transcriptomic analysis. This is largely related to the lack of efficient and quantitative procedures for protein and nucleic acid purification from cells cultured on, or inside, chitosan scaffold. Here we describe an ultracentrifugation procedure enabling the simultaneous and quantitative recovery of high quality RNA, DNA and proteins from cells growing in close contact of biomaterial matrices containing chitosan.

RAFT polymerization of an alkoxyamine bearing acrylate, towards a well-defined redox active polyacrylate

A new strategy for the synthesis of a well-defined redox active polymer, a polyacrylate bearing TEMPO, and its grafting onto a gold substrate is described. It consists of polymerizing an acrylate bearing an alkoxyamine by RAFT, followed by aminolysis of the trithiocarbonate chain-end into a thiol that is exploited for the polymer grafting onto the gold sensor. Thermal activation of the alkoxyamine under air provides the redox polymer with a high yield. Its electroactivity is evaluated by a electrochemical quartz crystal microbalance (EQCM).

Nanostructured 3D porous hybrid network of N-doped carbon, graphene and Si nanoparticles as an anode material for Li-ion batteries

We report a facile and scalable process to prepare nanostructured 3D porous networks combining graphene, N-doped carbon and silicon nanoparticles (G@Si@C) as a promising anode material for batteries. It consists of preparing polymethylmethacrylate particles decorated by Si/graphene oxide and polypyrrole (PPy) in a one-pot process, followed by an appropriate thermal treatment that decomposes PMMA and converts graphene oxide into graphene and polypyrrole into N-doped carbon. The so-formed electrically conducting 3D porous network containing Si nanoparticles inside the cell walls accommodates the large volume changes of Si during charging/discharging and provides a fast electrolyte penetration/diffusion. Therefore, the designed G@Si@C material presents an excellent reversible capacity of 740 mA h g−1 at a current density of 0.14 A g−1 based on the total mass loading of the composite, with more than 99% coulombic efficiency, high rate capability and good cyclability, suggesting great potential for application as an anode material for lithium-ion batteries.

Multiple Gas-Phase Conformations of a Synthetic Linear Poly(acrylamide) Polymer Observed Using Ion Mobility-Mass Spectrometry

AbstractIon mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures and topologies (linear, cyclic, star-shaped,…). Electrospray coupled to IM-MS already revealed the coexistence of several charge state-dependent conformations for a single charge state of biomolecules with strong intramolecular interactions, even when limited resolving power IM-MS instruments were used. For synthetic polymers, the sample’s polydispersity allows the observation of several chain lengths. A unique collision cross-section (CCS) trend is usually observed when increasing the degree of polymerization (DP) at constant charge state, allowing the deciphering of different polymer topologies. In this paper, we report multiple coexisting CCS trends when increasing the DP at constant charge state for linear poly(acrylamide) PAAm in the gas phase. This is similar to observations on peptides and proteins. Biomolecules show in addition population changes when collisionally heating the ions. In the case of synthetic PAAm, fragmentation occurred before reaching the energy for conformation conversion. These observations, which were made on two different IM-MS instruments (SYNAPT G2 HDMS and high resolution multi-pass cyclic T-Wave prototype from Waters), limit the use of ion mobility for synthetic polymer topology interpretations to polymers where unique CCS values are observed for each DP at constant charge state. Graphical Abstractᅟ