Green Fabrication of Sustainable Porous Chitosan/Kaolin Composite Membranes Using Polyethylene Glycol as a Porogen: Membrane Morphology and Properties.

One of the major challenges in membrane manufacturing today is to reduce the environmental footprint by promoting biobased raw materials and limiting the use of toxic solvents. In this context, environmentally friendly chitosan/kaolin composite membranes, prepared using phase separation in water induced by a pH gradient, have been developed. Polyethylene glycol (PEG) with a molar mass ranging from 400 to 10,000 g·mol-1 was used as a pore forming agent. The addition of PEG to the dope solution strongly modified the morphology and properties of the formed membranes. These results indicated that PEG migration induced the formation of a network of channels promoting the penetration of the non-solvent during the phase separation process, resulting in an increase in porosity and the formation of a finger-like structure surmounted by a denser structure of interconnected pores of 50-70 nm in diameter. The hydrophilicity of the membrane surface increased likely related to PEG trapping in the composite matrix. Both phenomena were more marked as the PEG polymer chain was longer, resulting in a threefold improvement in filtration properties.

Immobilization of poly(vinyl pyrrolidone) in Polysulfone Membranes by Radically-Initiated Crosslinking Using Potassium Persulfate.

Polysulfone (PSU) membranes with poly(vinyl pyrrolidone) (PVP) as a pore-forming and hydrophilic additive were prepared using the non-solvent-induced phase separation (NIPS) technique. PVP immobilization by radical-initiated crosslinking using potassium persulfate (KPS) was studied in view of obtaining membranes with high and long-lasting surface hydrophilicity. A method based on the ATR-FTIR technique was developed to discriminate crosslinked PVP from unreacted PVP in the membrane. The crosslinking progress was investigated as a function of temperature, KPS concentration, and reaction time. The results showed that temperature was the main factor influencing the crosslinking reaction since radical formation is temperature-dependent. Increasing the concentration of KPS and the reaction time led to an increase in the crosslinking rate. The effect of the degree of PVP crosslinking on the structure and properties of the prepared membranes was examined by studying mechanical properties, morphology by SEM, surface hydrophilicity by contact angle measurements, and water permeability.

Partial depolymerization of hydroxypropylmethyl cellulose for production of low molar mass polymer chains.

Low molar mass (LMM) biopolymers are highly required to design functional nanomaterials, which mainly find application in biomedical fields. However, the synthesis of LMM polymer is a challenging task. In this work, we report a partial enzymatic depolymerization process which allows to produce a series of LMM hydroxypropylmethyl cellulose (HPMC) polymer, with a weight average molar mass (Mw) under and over 10,000 g mol-1 and low dispersity (Ɖ < 1.5). Variation of the starting HPMC grade, reaction time, and enzyme concentration were the key parameters to control the Mw and yield of the target molecules. This approach provides a versatile way of producing LMM HPMCs with varying degrees of substitution, and having a single reactive aldehyde function at one chain extremity. LMM HPMC can find for instance application as building blocks for the development of new functional molecular architectures.

Concentration of 1,3-dimethyl-2-imidazolidinone in Aqueous Solutions by Sweeping Gas Membrane Distillation: From Bench to Industrial Scale.

Sweeping gas membrane distillation (SGMD) is a useful option for dehydration of aqueous solvent solutions. This study investigated the technical viability and competitiveness of the use of SGMD to concentrate aqueous solutions of 1,3-dimethyl-2-imidazolidinone (DMI), a dipolar aprotic solvent. The concentration from 30% to 50% of aqueous DMI solutions was attained in a bench installation with Liqui-Cel SuperPhobic® hollow-fiber membranes. The selected membranes resulted in low vapor flux (below 0.15 kg/h·m2) but were also effective for minimization of DMI losses through the membranes, since these losses were maintained below 1% of the evaporated water flux. This fact implied that more than 99.2% of the DMI fed to the system was recovered in the produced concentrated solution. The influence of temperature and flowrate of the feed and sweep gas streams was analyzed to develop simple empirical models that represented the vapor permeation and DMI losses through the hollow-fiber membranes. The proposed models were successfully applied to the scaling-up of the process with a preliminary multi-objective optimization of the process based on the simultaneous minimization of the total membrane area, the heat requirement and the air consumption. Maximal feed temperature and air flowrate (and the corresponding high operation costs) were optimal conditions, but the excessive membrane area required implied an uncompetitive alternative for direct industrial application.

Synthesis and self-assembly of AB2-type amphiphilic copolymers from biobased hydroxypropyl methyl cellulose and poly(L-lactide).

AB2-type amphiphilic (HPMC)2-PLA copolymers with various hydrophilic block lengths were synthesized using a three step procedure: ring-opening polymerization of L-lactide initiated by propynol, amination reduction of the aldehyde endgroup of HPMC, and thiol-click reaction. The resulted copolymers were characterized by NMR, DOSY-NMR, SEC and FT-IR. The cloud point (CP) was determined by UV-vis spectrometer. Data show that the HPMC block length has little effect on the Cp of the copolymers which is lower than that of HPMC. The self-assembly behavior of the copolymers was investigated from DLS, TEM, and critical micelle concentration (CMC) measurements. Spherical micelles are obtained by self-assembly of copolymers in aqueous solution. The micelle size and the CMC of copolymers increase with increasing HPMC block length. It is concluded that biobased and biodegradable (HPMC)2-PLA copolymers could be promising as nano-carrier of hydrophobic drugs.

Desalination and removal of pesticides from surface water in Mekong Delta by coupling electrodialysis and nanofiltration.

The shortage of drinking water is a major problem in the rural areas of the Mekong Delta, especially, when surface water, a main local direct drinking water source is being threatened by pesticide pollution and salinity intrusion. A hybrid process coupling electrodialysis (ED) and nanofiltration (NF) is proposed as an effective process easy to setup in a small plant to treat complex matrix with high salinity and pesticide concentration as is the Mekong Delta surface water. Performance of the ED-NF integration was evaluated with synthetic solutions based on the comparison with a single NF step generally used for pesticide removal. Both energy consumption and water product quality were considered to assess process efficiency. The ED stage was designed to ensure a 50% removal of salinity before applying NF. As expected, the NF rejection is better in the hybrid process than in a case of a single NF step, especially for pesticide rejection. The integration of a NF stage operated with NF270 membrane consumes less energy than that with NF90 membrane but its efficiency was observed not high enough to respect the Vietnamese guidelines. Using NF90, the optimal recovery rate of the NF stage varies from 30 to 50% depending on the salt content in the feed.

Negatively Charged Porous Thin Film from ABA Triblock Copolymer Assembly.

The preparation of well-arranged nano-porous thin films from an ABA triblock copolymer of polystyrene-block-poly(sodium 4-styrenesulfonate)-block-polystyrene (PS-PNaSS-PS) is reported. This copolymer was self-assembled in a N,N-dimethylformamide (DMF)/water mixture and the resulting micellar solution was used to prepare thin films via the compact packing of the flower-like micelles using spin coating method. The films were characterized by several microscopy techniques such as TEM, AFM, and SEM. Permeation test was performed to highlight the interconnected porous nature of the polymeric network obtained. Under applied water pressure, the micellar morphology was altered and a partial fusion of the micelles was observed that resulted in a change in the water permeability. Such hydrophilic nanoporous thin films with negatively charged interface could find applications in membrane filtration.

Translocation across a self-healing block copolymer membrane.

Herein, a membrane prepared from the self-assembly of poly(styrene-co-acrylonitrile)-b-poly(ethylene oxide)-b-poly(styrene-co-acrylonitrile) micelles is found to exhibit translocation of nano-objects dispersed in aqueous solution. With the water flow as a driving force, temporary pores are created in between the micelles to facilitate the passage of nano-objects. These temporary pores close afterwards through a self-healing mechanism. As main results, polystyrene and silica nanoparticles exhibited a selective translocation directly influenced by their size and applied pressure.

A Zwitterionic-Shielded Carrier with pH-Modulated Reversible Self-Assembly for Gene Transfection.

Cationic vectors are ideal candidates for gene delivery thanks to their capability to carry large gene inserts and their scalable production. However, their cationic density gives rise to high cytotoxicity. We present the proper designed core-shell polyplexes made of either poly(ethylene imine) (PEI) or poly(2-dimethylamino ethyl methacrylate) (PDMAEMA) as the core and zwitterionic poly(acrylic acid)-block-poly(sulfobetaine methacrylate) (PAA-b-PSBMA) diblock copolymer as the shell. Gel retardation and ethidium bromide displacement assays were used to determine the PEI/DNA or PDMAEMA/DNA complexation. At neutral pH, the copolymer serves as a protective shell of the complex. As PSBMA is a nonfouling block, the shell reduced the cytotoxicity and enhanced the hemocompatibility (lower hemolysis activity, longer plasma clotting time) of the gene carriers. PAA segments in the copolymer impart pH sensitivity by allowing deshielding of the core in acidic solution. Therefore, the transfection efficiency of polyplexes at pH 6.5 was better than at pH 7.0, from ß-galactosidase assay, and for all PAA-b-PSBMA tested. These results were supported by more favorable physicochemical properties in acidic solution (zeta potential, particle size, and interactions between the polymer and DNA). Thus, the results of this study offer a potential route to the development of efficient and nontoxic pH-sensitive gene carriers.

Anti-Bioadhesive Coating Based on Easy to Make Pseudozwitterionic RAFT Block Copolymers for Blood-Contacting Applications.

Amphiphilic diblock copolymer containing randomly distributed positive and negative charged monomers are synthesized using RAFT polymerization technique to be used as anti-bioadhesion coatings for hydrophobic surfaces. Quaternized 2-(dimethylamino) ethyl methacrylate and potassium 3-sulfopropyl methacrylate (P[qDMAEMA-co-KSPMA]) are randomly polymerized to yield an anti-bioadhesion block which is, in one pot, copolymerized with styrene as an anchoring block. This copolymer has demonstrated high anti-bioadhesion properties to avoid the blood clotting in medical devices through a simple and facile approach to preparation of pseudozwitterionic copolymers.

Reverse micelles prepared from amphiphilic polylactide-b-poly(ethylene glycol) block copolymers for controlled release of hydrophilic drugs.

This work aims to evaluate the potential of reverse micelles prepared from amphiphilic polylactide-b-poly(ethylene glycol) (PLA-b-PEG) block copolymers for controlled release of hydrophilic drugs. Different PLA-b-PEG diblock and triblock copolymers were synthesized by ring-opening polymerization of D- or L-lactide in the presence of a PEG macroinitiator. Reverse micelles were prepared by self-assembly of copolymers in a solvent/co-solvent/water system. Toluene was used as solvent, and ethanol as co-solvent to solubilize appropriate amount of water. The resulting nano-sized reverse micelles were able to encapsulate heparin in the hydrophilic core. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to determine the size and morphology of reverse micelles. The results show that reverse micelles are spherical in shape with sizes below 100 nm. Drug loaded reverse micelles were embedded in biocompatible membranes by mixing with 10% PLA solution in toluene with 1:3 volume ratio. In vitro release studies were realized in phosphate buffer saline (PBS) at 37°C. Heparin was almost totally released within 24h. Triblock copolymer reverse micelles exhibited faster drug release than diblock ones probably due to the more compact micelle structure of the latter. Therefore, PLA-b-PEG reverse micelles could be promising for applications as carrier of hydrophilic drugs when embedded in biocompatible membranes.

Reversible 2D/3D coatings from zipper-assembly of block copolymer micelles.

A zipper-assembly of micelles into 2D/3D coatings is reported. Block copolymer micelles that incorporate a poly(n-octadecyl methacrylate) block are zipped and unzipped on demand onto a PMMA surface. The mechanism implies an interdigitation of molecular brushes enabling 15 nm micelles to be assembled into monolayers or multilayers.

"Schizophrenic" hemocompatible copolymers via switchable thermoresponsive transition of nonionic/zwitterionic block self-assembly in human blood.

"Schizophrenic" diblock copolymers containing nonionic and zwitterionic blocks were prepared with well-controlled molecular weights via atom-transfer radical polymerization (ATRP). In this work, we report a systematic study of how morphological changes of poly(N-isopropylacrylamide)-block-poly(sulfobetaine methacrylate) (PNIPAAm-b-PSBMA) copolymers affect hemocompatibility in human blood solution. The "schizophrenic" behavior of PNIPAAm-b-PSBMA was observed by (1)H NMR, dynamic light scattering (DLS), and turbidity measurement with double morphological transition, exhibiting both lower critical solution temperature (LCST) and upper critical solution temperature (UCST) in aqueous solution. Below the UCST of PSBMA block, micelles were obtained with a core of insoluble PSBMA association and a shell of soluble PNIPAAm, whereas the opposite micelle structure was observed above the LCST of PNIPAAm block. In between the UCST and LCST, unimers with both soluble blocks were detected. Hydrodynamic size of prepared polymers and copolymers is determined to illustrate the correlations between intermolecular nonionic/zwitterionic associations and blood compatibility of PNIPAAm, PNIPAAm-b-PSBMA, and PSBMA suspension in human blood. Human fibrinogen adsorption onto the PNIPAAm-b-PSBMA copolymers from single-protein solutions was measured by DLS to determine the nonfouling stability of copolymer suspension. The new nonfouling nature of PNIPAAm-b-PSBMA copolymers was demonstrated to show extremely high anticoagulant activity and antihemolytic activity in human blood over a wide range of explored temperatures from 4 to 40 °C. The temperature-independent blood compatibility of nonionic/zwitterionic block copolymer along with their schizophrenic phase behavior in aqueous solution suggests their potential in blood-contacting applications.

Dynamic interactive membranes with pressure-driven tunable porosity and self-healing ability.

When pressure is applied to dynamic interactive membranes consisting of micelles composed of a triblock copolymer, their morphologies can be fine-tuned. Membranes with a range of porosities are accessible which can regulate and thereby control filtration performance and also display effective autonomous healing.

Interplay between the transport of solutes across nanofiltration membranes and the thermal properties of the thin active layer.

The thin active layer (TAL) of seven nanofiltration (NF) membranes was studied using differential scanning calorimetry, and the membranes were classified into two groups according to the polymer physical state (amorphous or semicrystalline). NF membrane performance in terms of permeate volume flux density and rejection of neutral solutes was investigated in temperature cycles. The modeling of rejection using a hindered transport theory showed irreversible and opposite pore size changes for the two groups of NF membranes when the maximum operating temperature of the cycle exceeded the glass-transition temperature of the TAL. A mechanism of pore deformation is proposed to explain the variation of the solute transport properties as a function of the temperature and the polymer physical state in the TAL.

An expeditious multigram-scale synthesis of lysine dendrigraft (DGL) polymers by aqueous N-carboxyanhydride polycondensation.

The synthesis and characterisation of new arborescent architectures of poly(L-lysine), called lysine dendrigraft (DGL) polymers, are described. DGL polymers were prepared through a multiple-generation scheme (up to generation 5) in a weakly acidic aqueous medium by polycondensing N(epsilon)-trifluoroacetyl-L-lysine-N-carboxyanhydride (Lys(Tfa)-NCA) onto the previous generation G(n-1) of DGL, which was used as a macroinitiator. The first generation employed spontaneous NCA polycondensation in water without a macroinitiator; this afforded low-molecular-weight, linear poly(L-lysine) G1 with a polymerisation degree of 8 and a polydispersity index of 1.2. The spontaneous precipitation of the growing N(epsilon)-Tfa-protected polymer (GnP) ensures moderate control of the molecular weight (with unimodal distribution) and easy work-up. The subsequent alkaline removal of Tfa protecting groups afforded generation Gn of DGL as a free form (with 35-60% overall yield from NCA precursor, depending on the DGL generation) that was either used directly in the synthesis of the next generation (G(n+1)) or collected for other uses. Unprotected forms of DGL G1-G5 were characterised by size-exclusion chromatography, capillary electrophoresis and (1)H NMR spectroscopy. The latter technique allowed us to assess the branching density of DGL, the degree of which (ca. 25%) turned out to be intermediate between previously described dendritic graft poly(L-lysines) and lysine dendrimers. An optimised monomer (NCA) versus macroinitiator (DGL G(n-1)) ratio allowed us to obtain unimodal molecular weight distributions with polydispersity indexes ranging from 1.3 to 1.5. Together with the possibility of reaching high molecular weights (with a polymerisation degree of ca. 1000 for G5) within a few synthetic steps, this synthetic route to DGL provides an easy, cost-efficient, multigram-scale access to dendritic polylysines with various potential applications in biology and in other domains.

Comparison of tertiary treatment by nanofiltration and reverse osmosis for water reuse in denim textile industry.

The wastewaters resulting from different baths of a dyeing factory specialized in denim fabric are collected and treated by an activated sludge plant. This study investigated the coupling of activated sludge treatment with either nanofiltration (NF) or reverse osmosis (RO) to recycle water and reuse it in the process. We first conducted NF experiments with a HL membrane in different configurations: dead end and cross-flow for flat sheets and also in spiral wound form. Results on water permeation and salt rejection show that performances are configuration dependent. Then, for the study of the NF/RO textile wastewater treatment, experiments were conducted with spiral wound membranes in order to be closest to the industrial configuration. After analyzing the removal efficiencies of suspended solids and chemical oxygen demand (COD) of the treatment plant, we conducted NF experiments using an HL2514TF spiral wound membrane preceded by ultrafiltration (UF) treatment. We used as well an RO membrane (AG2514TF) to compare performances in water yield and quality for the same pumping costs. The results show that NF allows higher yield, while respecting the Tunisian standard of water reuse (COD<90 mg L(-1)). Above 9bar, the TDS rejection reaches 60% and the hardness is lower than the factory constraint (100 mg L(-1) CaCO(3)), allowing the reuse of the water in the process.