Cross-linking Step Research Articles

4-Amino-1-(3-mercapto-propyl)-pyridine hexafluorophosphate ionic liquid functionalized gold nanoparticles for IgG immunosensing enhancement.

A novel ionic liquid, 4-amino-1-(3-mercapto-propyl)-pyridine hexafluorophosphate (AMPPH), was successfully synthesized and characterized. Subsequently, AMPPH was used as a functional monomer to fabricate AMPPH-modified gold nanoparticles (AMPPH-AuNPs) via a one-pot synthesis method. The as-prepared AMPPH-AuNPs were confirmed with transmission electron microscopy and X-ray photoelectron spectroscopy. AMPPH-AuNPs were used to construct a biocompatible interface to immobilize rabbit anti-human IgG (anti-HIgG) onto a glassy carbon electrode (GCE) surface, followed by a cross-linking step with glutaraldehyde to fabricate an anti-HIgG-AMPPH-AuNPs/GCE. The nonspecific binding sites were enclosed with bovine serum albumin (BSA) to develop an immunosensor for human IgG. Electrochemical impedance spectroscopy, cyclic voltammetry and differential pulse voltammetry were used to investigate the electrochemical properties of the developed immunosensor. The results indicate that AMPPH-AuNPs can improve the immunosensing performance. The current response of the immunosensor was found linearly related to human IgG concentration in the range of 0.1-5.0 ng mL(-1) and 5.0-100.0 ng mL(-1). The detection limit is estimated to be 0.08 ng mL(-1) (S/N = 3). The obtained immunosensor was successfully applied to the analysis human IgG immunoglobulin in human serum, and the results were well consistent with ELISA method.

The leaving group strongly affects H₂O₂-induced DNA cross-linking by arylboronates.

We evaluated the effects of the benzylic leaving group and core structure of arylboronates on H2O2-induced formation of bisquinone methides for DNA interstrand cross-linking. The mechanism of DNA cross-linking induced by these arylboronates involves generation of phenol intermediates followed by departure of benzylic leaving groups leading to QMs which directly cross-link DNA via alkylation. The QM formation is the rate-determining step for DNA cross-linking. A better leaving group (Br) and stepwise bisquinone methide formation increased interstrand cross-linking efficiency. These findings provide essential guidelines for designing novel anticancer prodrugs.

An innovative synthesis approach toward the preparation of structurally defined multiresponsive polymer (co)networks

A new and facile synthesis approach employed for the fabrication of multiresponsive polymer conetworks characterized by predefined architecture and composition is described for the first time. The presented methodology involves the crosslinking of well-defined 2-(dimethylamino)ethyl methacrylate (DMAEMA) homopolymers and polyDMAEMA-containing diblock and triblock copolymers prepared by Reversible Addition Fragmentation chain Transfer (RAFT) polymerization, using 1,2-bis-(2-iodoethoxy)ethane (BIEE) as a crosslinker. Unlike other controlled polymerization methods used for the synthesis of well-defined polymer structures, herein the crosslinking step is undemanding since no special synthesis requirements are necessary such as heat and inert conditions. Most importantly it enables the encapsulation of inorganic nanoparticulate systems within the 3-dimensional polymer structures, resulting in the generation of polymer-based nanocomposite (co)networks with structurally defined characteristics. More precisely, the BIEE-crosslinking step is carried out in the presence of pre-formed oleic acid coated magnetite (Fe3O4) nanoparticles. The swelling behavior of the resulting (co)networks is investigated in organic and aqueous media at different pHs. Moreover, the magnetic response of the Fe3O4-containing (co)networks is studied by means of vibrational sample magnetometry, demonstrating their superparamagnetic behavior at room temperature. This new approach may be easily expanded to generate structurally defined multiblock (and hence multifunctional) copolymer conetworks and organic–inorganic nanocomposites.

Enhanced Cell Affinity of Chitosan Membranes Mediated by Superficial Cross-Linking: A Straightforward Method Attainable by Standard Laboratory Procedures

It is well accepted that the surface modification of biomaterials can improve their biocompatibility. In this context, techniques like ion etching, plasma-mediated chemical functionalization, electrospinning, and contact microprinting have successfully been employed to promote the cell adhesion and proliferation of chitosan (CH) substrates. However, they prove to be time-consuming, highly dependent on environmental conditions, and/or limited to the use of expensive materials and sophisticated instruments not accessible to standard laboratories, hindering to a high extent their straightforward application. Filling this gap, this paper proposes the superficial cross-linking of CH as a much simpler and accessible means to modify its superficial properties in order to enhance its cellular affinity. CH membranes were prepared by solvent casting followed by a cross-linking step mediated by the chemical vapor deposition (CVD) of glutaraldehyde (GA). The membranes were characterized against non- and solution cross-linked membranes in terms of their mechanical/surface properties and biological performance. Among others, the CVD membranes proved (i) to be more mechanically stable against cell culture and sterilization than membranes cross-linked in solution and (ii) to prompt the adherence and sustained proliferation of healthy cells to levels even superior to commercial tissue culture plates (TCPs). Accordingly, the CVD cross-linking approach was demonstrated to be a simple and cost-effective alternative to the aforementioned conventional methods. Interestingly, this concept can also be applied to other biomaterials as long as GA (or other volatile components alike) can be employed as a cross-linker, making possible the cross-linking reaction at mild experimental conditions, neither requiring sophisticated lab implements nor using any potentially harmful procedure.

Anisotropic Colloidal Micromuscles from Liquid Crystal Elastomers

Monodomain liquid crystal elastomers (LCEs) are new materials uniquely suitable for artificial muscles, as they undergo large reversible uniaxial shape changes, with strains of 20-500% and stresses of 10-100 kPa, falling exactly into the dynamic range of a muscle. LCEs exhibit little to no fatigue over thousands of actuation cycles. Their practical use has been limited, however, owing to the difficulty of synthesizing components, achieving consistent alignment during cross-linking across the whole material and often a high nematic-isotropic phase transition temperature. The most widely studied method for LC alignment involves mechanical stretching of the material during one of two cross-linking steps, which makes fabrication difficult to control and lends itself mainly to samples that can be easily grasped (with sizes of the order of mm). In this article, we describe a method of adapting the LCE synthesis to microscale objects, achieving monodomain alignment with a single cross-linking step, and lowering the cycling temperature. LCE precursor droplets are embedded in and then stretched in a polymer matrix at high temperature. Confinement of the uniaxially stretched droplets maintains the alignment achieved during stretching and allows us to eliminate one of the cross-linking steps and the variability associated with it. Adding a comonomer during the polymerization leads to lowering of the nematic-to-isotropic transition temperature (58 °C), significantly expanding the range of potential applications for these micromuscles. We demonstrate reversible thermal switching of the micromuscles in line with the largest strain changes observed for side-chain LCEs and a differential scanning calorimetry characterization of the material phase transitions. The method demonstrates the parallel fabrication of many microscale actuators and is amenable to further scale-up and manufacturing.

Optimization of PAMAM-gold nanoparticle conjugation for gene therapy

The development of efficient and biocompatible non-viral vectors for gene therapy remains a great challenge, and exploiting the properties of both nanoparticle carriers and cationic polymers is an attractive approach. In this work, we have developed gold nanoparticle (AuNP) polyamidoamine (PAMAM) conjugates for use as non-viral transfection agents. AuPAMAM conjugates were prepared by crosslinking PAMAM dendrimers to carboxylic-terminated AuNPs via EDC and sulfo-NHS chemistry. EDC and sulfo-NHS have been utilized widely and in numerous applications such as amino acid coupling; however, their use in the coupling of PAMAM dendrimers to AuNPs presents new challenges to form effective and stable constructs for delivery that have not yet been examined. Enhanced colloidal stability and DNA condensation ability was established by probing two critical synthetic parameters: the reaction rate of the PAMAM crosslinking step, and the amine to carboxyl ratio. Based on this work, increasing the amine to carboxyl ratio during conjugation of PAMAM onto AuNPs yielded the optimal vector with respect to colloidal stability and transfection efficiency in vitro. AuPAMAM conjugates present attractive candidates for non-viral gene delivery due to their commercial availability, ease of fabrication and scale-up, high yield, high transfection efficiency and low cytotoxicity.

Transglutaminase activity arising from Factor XIIIA is required for stabilization and conversion of plasma fibronectin into matrix in osteoblast cultures

Circulating plasma fibronectin (pFN), produced by hepatocytes, is a major component of the noncollagenous bone matrix where it was recently shown in vivo in mice to control the biomechanical quality as well as the mineral-to-matrix ratio in bone. FN fibrillogenesis is a process generally requiring FN binding to cellular integrins, and cellular tension to elongate and assemble the molecule. Whether soluble pFN undergoes cell-mediated assembly in bone is not fully established. FN is a well-known substrate for transglutaminases (TGs), which are protein-crosslinking enzymes capable of stabilizing macromolecular structures. The role of this modification regarding the function of FN in bone matrix has remained unknown. Osteoblasts express two TGs—transglutaminase 2 and Factor XIIIA—and we have shown that Factor XIIIA is the main TG active during osteoblast differentiation. In the present study, conducted using MC3T3-E1 osteoblast cultures and bone marrow stromal cells, we demonstrate that pFN requires a TG-mediated crosslinking step to form osteoblast matrix in vitro. This modification step is specific for pFN; cellular FN (EDA-FN) does not serve as a TG substrate. Inhibition of pFN assembly using a TG inhibitor, or depletion of pFN from cell culture serum, dramatically decreased total FN matrix assembly in the osteoblast cultures and affected both the quantity and quality of the type I collagen matrix, and decreased lysyl oxidase and alkaline phosphatase levels, resulting in decreased mineralization. Experiments with isozyme-specific substrate peptides showed that FXIIIA is responsible for the crosslinking of pFN. Addition of exogenous preactivated FXIIIA to osteoblast cultures promoted pFN assembly from the media into matrix. Exogenous TG2 had no effect. Analysis of pFN and EDA-FN fibrils by immunofluorescence microscopy demonstrated that they form distinct matrix network, albeit with minor overlap, suggesting different functions for the two FN forms. Further analysis using EDA-FN blocking antibody showed that it regulated preosteoblast proliferation whereas pFN depletion from the serum had no effect on this process. In conclusion, our study shows that pFN assembly into bone matrix in vitro requires FXIIIA transglutaminase activity making pFN assembly an active, osteoblast-mediated process.

A chromatin immunoprecipitation (ChIP) protocol for use in whole human adipose tissue

Chromatin immunoprecipitation (ChIP) has become a central method when studying in vivo protein-DNA interactions, with the major challenge being the hope to capture "authentic" interactions. While ChIP protocols have been optimized for use with specific cell types and tissues including adipose tissue-derived cells, a working ChIP protocol addressing the challenges imposed by fresh whole human adipose tissue has not been described. Utilizing human paired omental and subcutaneous adipose tissue obtained during elective abdominal surgeries, we have carefully identified and optimized individual steps in the ChIP protocol employed directly on fresh tissue fragments. We describe a complete working protocol for using ChIP on whole adipose tissue fragments. Specific steps required adaptation of the ChIP protocol to human whole adipose tissue. In particular, a cross-linking step was performed directly on fresh small tissue fragments. Nuclei were isolated before releasing chromatin, allowing better management of fat content; a sonication protocol to obtain fragmented chromatin was optimized. We also demonstrate the high sensitivity of immunoprecipitated chromatin from adipose tissue to freezing. In conclusion, we describe the development of a ChIP protocol optimized for use in studying whole human adipose tissue, providing solutions for the unique challenges imposed by this tissue. Unraveling protein-DNA interaction in whole human adipose tissue will likely contribute to elucidating molecular pathways contributing to common human diseases such as obesity and type 2 diabetes.

Multi-Scale Modification of Metallic Implants With Pore Gradients, Polyelectrolytes and Their Indirect Monitoring <em>In vivo</em>

Metallic implants, especially titanium implants, are widely used in clinical applications. Tissue in-growth and integration to these implants in the tissues are important parameters for successful clinical outcomes. In order to improve tissue integration, porous metallic implants have being developed. Open porosity of metallic foams is very advantageous, since the pore areas can be functionalized without compromising the mechanical properties of the whole structure. Here we describe such modifications using porous titanium implants based on titanium microbeads. By using inherent physical properties such as hydrophobicity of titanium, it is possible to obtain hydrophobic pore gradients within microbead based metallic implants and at the same time to have a basement membrane mimic based on hydrophilic, natural polymers. 3D pore gradients are formed by synthetic polymers such as Poly-L-lactic acid (PLLA) by freeze-extraction method. 2D nanofibrillar surfaces are formed by using collagen/alginate followed by a crosslinking step with a natural crosslinker (genipin). This nanofibrillar film was built up by layer by layer (LbL) deposition method of the two oppositely charged molecules, collagen and alginate. Finally, an implant where different areas can accommodate different cell types, as this is necessary for many multicellular tissues, can be obtained. By, this way cellular movement in different directions by different cell types can be controlled. Such a system is described for the specific case of trachea regeneration, but it can be modified for other target organs. Analysis of cell migration and the possible methods for creating different pore gradients are elaborated. The next step in the analysis of such implants is their characterization after implantation. However, histological analysis of metallic implants is a long and cumbersome process, thus for monitoring host reaction to metallic implants in vivo an alternative method based on monitoring CGA and different blood proteins is also described. These methods can be used for developing in vitro custom-made migration and colonization tests and also be used for analysis of functionalized metallic implants in vivo without histology.

Multi-Scale Modification of Metallic Implants With Pore Gradients, Polyelectrolytes and Their Indirect Monitoring <em>In vivo</em>

Metallic implants, especially titanium implants, are widely used in clinical applications. Tissue in-growth and integration to these implants in the tissues are important parameters for successful clinical outcomes. In order to improve tissue integration, porous metallic implants have being developed. Open porosity of metallic foams is very advantageous, since the pore areas can be functionalized without compromising the mechanical properties of the whole structure. Here we describe such modifications using porous titanium implants based on titanium microbeads. By using inherent physical properties such as hydrophobicity of titanium, it is possible to obtain hydrophobic pore gradients within microbead based metallic implants and at the same time to have a basement membrane mimic based on hydrophilic, natural polymers. 3D pore gradients are formed by synthetic polymers such as Poly-L-lactic acid (PLLA) by freeze-extraction method. 2D nanofibrillar surfaces are formed by using collagen/alginate followed by a crosslinking step with a natural crosslinker (genipin). This nanofibrillar film was built up by layer by layer (LbL) deposition method of the two oppositely charged molecules, collagen and alginate. Finally, an implant where different areas can accommodate different cell types, as this is necessary for many multicellular tissues, can be obtained. By, this way cellular movement in different directions by different cell types can be controlled. Such a system is described for the specific case of trachea regeneration, but it can be modified for other target organs. Analysis of cell migration and the possible methods for creating different pore gradients are elaborated. The next step in the analysis of such implants is their characterization after implantation. However, histological analysis of metallic implants is a long and cumbersome process, thus for monitoring host reaction to metallic implants in vivo an alternative method based on monitoring CGA and different blood proteins is also described. These methods can be used for developing in vitro custom-made migration and colonization tests and also be used for analysis of functionalized metallic implants in vivo without histology.

Novel alginate/aloe vera hydrogel blends as wound dressings for the treatment of several types of wounds

Currently, there is a significant increase in the use of natural materials for biomedical applications, mainly due to their biocompatibility, biodegradability and similar properties to the constituents of natural tissues. In this work, hydrogel films composed of alginate and Aloe vera gel were prepared and characterized for application in the treatment of several types of wounds (e.g. exuding, painful and dry). The films were prepared through a two-step procedure encompassing the film formation by a solvent-casting method and an additional crosslinking step to improve their properties. The physical, morphological and water absorption properties were characterized by introducing several variations in the Aloe vera content. The in vitro degradation behaviour of the films was investigated in the presence of the enzyme alginate lyase for 2 weeks. Results showed that Aloe vera improves the water absorption and the in vitro degradation rate of the films. In conclusion, this study indicates that the alginate/Aloe vera hydrogel films can be potentially explored as wound dressing for the treatment of different wound types. Copyright ?? 2013, AIDIC Servizi S.r.l.

Synthesis of 1,3-di(4-amino-1-pyridinium)propane ionic liquid functionalized graphene nanosheets and its application in direct electrochemistry of hemoglobin

1,3-Di(4-amino-1-pyridinium)propane tetrafluoroborate (DAPPT) ionic liquid was successfully synthesized, and was used as a modifier to functionalize graphene nanosheets through covalent binding of amino groups and epoxy groups in an alkaline solution. The as-prepared graphene-DAPPT nanosheets (Gr-DAPPT) were confirmed with transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), UV/vis and FTIR spectroscopy. A biocompatible platform based on Gr-DAPPT was constructed for the immobilization of hemoglobin (Hb) through a cross-linking step with chitosan and glutaraldehyde. The direct electron transfer and bioelectrocatalytic reaction of Hb immobilized on Gr-DAPPT surface were achieved. A pair of reversible redox peaks of hemoglobin was observed, and bioelectrocatalytic activity toward the reduction of H2O2 was also demonstrated, displaying a potential application for the fabrication of novel biosensors to sense H2O2. Such results indicated that Gr-DAPPT based interface would be a promising platform for biomacromolecular immobilization and biosensor preparation.

Layered Gradient Nonwovens of In Situ Crosslinked Electrospun Collagenous Nanofibers Used as Modular Scaffold Systems for Soft Tissue Regeneration

AbstractIn a versatile modular scaffold system, gradient nonwovens of in situ crosslinked gelatin nanofibers (CGN), fabricated by reactive electrospinning, are laminated with perforated layers and nonwovens of thermoplastic non‐crosslinked biodegradable polyesters. The addition of glyoxal to a gelatin solution in a non‐toxic solvent mixture consisting of acetic acid, ethyl acetate, and water (5:3:2 w/w/w) enables the in situ crosslinking of gelatin nanofibers during electrospinning. The use of this fluorine‐free crosslinking system eliminates the need of post‐treatment crosslinking and purification steps typical for conventional CGN scaffolds. The slowly progressing crosslinking of the dissolved gelatin in the presence of glyoxal increases the viscosity of the gelatin solution during electrospinning so that the average diameter of the crosslinked gelatin nanofibers gradually increases from 90 to 680 nm. During the subsequent lamination process, alternating layers of CGN and polycaprolactone (PCL) nonwovens, produced by 3D microextrusion of micrometer‐sized PCL fibers, are bonded together upon heating above the PCL melting temperature. In contrast to the water‐soluble gelatin nanofibers and the comparatively weak CGN, the CGN/PCL/CGN layered biocomposites are water‐resistant and very robust. In such modular scaffold systems, strength, biodegradation rate, and biological functions can be controlled by varying the type, composition, fiber diameter, porosity, number, and sequence of the individual layers. The CGN/PCL multilayer biocomposites can be cut into any desired scaffold shape and attached to tissue by surgical sutures in order to suit the needs of individual patients.

A simple method for fabrication of filler-free stretchable polydimethylsiloxane surfaces

We propose a simple method to elaborate a filler-free stretchable PDMS surface strong enough to resist to successive elongation/retraction cycles even at high degree of stretching. It consists in creating free radicals on a filler-containing PDMS surface by argon plasma exposure and reacting them with a filler-free PDMS resin during the crosslinking step. Changes of physical and chemical properties upon plasma modification are monitored by FTIR and XPS spectroscopies, contact angle measurements and atomic force microscopy. Electron spin resonance (ESR) is used to identify the nature of radicals involved in interfacial bonding. Although a brittle silica-like layer is created on the filler-containing PDMS surface after plasma treatment, an increase in the PDMS/PDMS interfacial strength is observed and a high interfacial resistance has been found under elongation/retraction (stretching/relaxation) cycles.

Alginate/Aloe Vera Hydrogel Films for Biomedical Applications

This paper describes a methodology to produce hydrogel films, composed of alginate and Aloe vera, for wound healing and drug delivery applications. The films were prepared through the solvent-casting method and subsequently submitted to an additional cross-linking step to improve their properties. Alginate films with different Aloe vera contents (5, 15 and 25%) were prepared and its properties evaluated in terms of thickness, transparency, swelling behavior and in vitro degradation. Results show a positive influence of Aloe vera on the transparency of the films, in both dry and wet state. Films were immersed in acetate buffer at pH 5.5 simulating the value of the skin, to evaluate its water absorption capacity. It was found that water absorption increases as the Aloe vera content increases, suggesting that Aloe vera enhances the hydrophilic properties of the films. The in vitro degradation tests were performed through the incubation of the films, for 10 weeks, in a simulated body fluid at 37°C. After this period, films kept its structure integrity exhibiting a weight loss in the range of 14.1-18.6%.

A method to resolve the composition of heterogeneous affinity-purified protein complexes assembled around a common protein by chemical cross-linking, gel electrophoresis and mass spectrometry

Protein complexes form, dissociate and re-form in order to perform specific cellular functions. In this two-pronged protocol, noncovalent protein complexes are initially isolated by affinity purification for subsequent identification of the components by liquid chromatography high-resolution mass spectrometry (LC-MS) on a hybrid LTQ Orbitrap Velos. In the second prong of the approach, the affinity-purification strategy includes a chemical cross-linking step to 'freeze' a series of concurrently formed, heterogeneous protein subcomplex species that are visualized by gel electrophoresis. This branch of the methodology amalgamates standard and well-practiced laboratory methods to reveal compositional changes that occur in protein complex architecture. By using mouse N-terminally tagged streptavidin-binding peptide-hemagglutinin-TANK-binding kinase 1 (SH-TBK1), we chemically cross-linked the affinity-purified complex of SH-TBK1 with the homobifunctional lysine-specific reagent bis(sulfosuccinimidyl) suberate (BS(3)), and we separated the resultant protein complexes by denaturation and by silver-stained one- and two-dimensional SDS-PAGE. We observed a range of cross-linked TBK1 complexes of variable pI and M(r) and confirmed them by immunoblotting. LC-MS analysis of in situ-digested cross-linked proteins shows differences in the composition of the TBK1 subcomplexes. The protocol is inherently simple and can be readily extended to the investigation of a range of protein complexes. From cell lysis to data generation by LC-MS, the protocol takes approximately 2.5 to 5.5 d to perform.

Monitoring the effect of high pressure and transglutaminase treatment of milk on the evolution of flavour compounds during lactic acid fermentation using PTR-ToF-MS

In this study, the effects of thermal or high hydrostatic pressure (HHP) treatment of a milk base in the absence or presence of a transglutaminase (TGase) protein cross-linking step on the flavour development of yoghurt were investigated. The presence of several tentatively identified volatile flavour compounds (VOCs), both during the enzymatic treatment and the lactic acid fermentation of the milk base, were monitored using a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). The formation of the major flavour compounds (acetaldehyde, diacetyl, acetoin, and 2-butanone) followed a sigmoidal trend described by the modified Gompertz model. The HHP treatment of milk increased significantly the volatile compound formation rate whereas it did not affect the duration of the lag phase of formation, with the exception of acetaldehyde and diacetyl formation. On the contrary, the TGase cross-linking of milk did not significantly modify the formation rate of the volatile compounds but shortened the duration of the lag phase of their formation.

SiCN Nanofibers with a Diameter Below 100 nm Synthesized via Concerted Block Copolymer Formation, Microphase Separation, and Crosslinking

Ultrathin SiCN fibers are produced from inexpensive carbosilazane-polyethylene block copolymers. The two-step synthesis consists of a concerted block copolymer formation, microphase separation and crosslinking step, followed by pyrolysis. The fibers have a mean diameter of 45 nm and an aspect ratio of up to 100.

Synthesis and Characterization of Chemical Modified Carbon-Chitosan Composites Applied to Glucose Oxidase Fuel Cells

The immobilization of glucose oxidase (GOx) using cross-linked carbon-chitosan pastes demonstrated their functionality as conductive enzymatic membranes for electrode applications in biofuel cells. Carbon-chitosan pastes showed best results when gels of 1.0% chitosan were used combined with carbonaceous materials, obtaining high mechanical resistant membranes also with high flexibility, after cured with ammonium hydroxide and cross-linked with glutaraldehyde (GA). To improve conductivity chemical modification was performed on the carbon-chitosan membranes using ferrocene derivatives. The studied methodology showed to be efficient in terms of immobilization load (ILmax = 38.7%; 620 U cm−2) and immobilization yield (IYmax = 43,5%). Bioelectrodes stability was also improved by an additional cross-linking step with GA. Anodic mediators selected from previous studies according to their enzyme affinity and co-factor regeneration rate, were also evaluated. The power delivered as a function of cell voltage was studied for this device in a mediated system using soluble and immobilized electron shuttles. Using the developed materials a power out-put of up to 32.8 μW cm−2 can be reached depending on the redox mediator used.

Highly crosslinked layer-by-layer polyelectrolyte FO membranes: Understanding effects of salt concentration and deposition time on FO performance

Layer-by-layer (LbL) deposition of polyelectrolytes onto a negative charge membrane has been investigated under a highly crosslinking condition for forward osmosis (FO). The influence of salt concentration and deposition time on LbL FO membranes performance has been investigated in order to optimize the deposition process, followed by the investigation of polyelectrolyte layer's crosslinking. In the crosslinking steps, polycation layers of the three bilayer LbL membrane were firstly crosslinked using glutaraldehyde (GA) as the crosslinker. Compared to a non-crosslinked membrane, the reverse salt fluxes were reduced by 63% and 58% under the PRO (pressure retarded osmosis) testing mode using 0.5M MgCl2 and 0.5M NaCl as draw solutions, respectively. Subsequently, the polyanion layer of that membrane was photo-crosslinked under ultraviolent (UV) at the wavelength of 254nm. The reverse salt flux of the resulting membrane was further reduced by 55% and 53% under the PRO testing mode using 0.5M MgCl2 and 0.5M NaCl as draw solutions, respectively. Specially, the LbL membrane with only one bilayer after cross-linking by both GA and 4h-UV could achieve a water flux of about 11LMH and a reverse flux of 8gMH under the PRO test using 0.3M NaCl as a draw solution. This is the first time, a LbL polyelectrolyte membrane has been successfully demonstrated as a FO membrane with good rejection toward NaCl while none of previously reported LbL polyelectrolyte membranes have achieved based on the best of our knowledge.