Gradient nanoporous phenolics as substrates for high-flux nanofiltration membranes by layer-by-layer assembly of polyelectrolytes

Thin film composite(TFC) membranes represent a highly promising platform for efficient nanofiltration(NF)processes. However, the improvement in permeance is impeded by the substrates with low permeances. Herein,highly permeable gradient phenolic membranes with tight selectivity are used as substrates to prepare TFC membranes with high permeances by the layer-by-layer assembly method. The negatively charged phenolic substrates are alternately assembled with polycation polyethylenimine(PEI) and polyanion poly(acrylic acid)(PAA)as a result of electrostatic interactions, forming thin and compact PEI/PAA layers tightly attached to the substrate surface. Benefiting from the high permeances and tight surface pores of the gradient nanoporous structures of the substrates, the produced PEI/PAA membranes exhibit a permeance up to 506 L? m-2?h-1?MPa-1, which is ~2–10 times higher than that of other membranes with similar rejections. The PEI/PAA membranes are capable of retaining N 96.1% of negatively charged dyes following the mechanism of electrostatic repulsion. We demonstrate that the membranes can also separate positively and neutrally charged dyes from water via other mechanisms.This work opens a new avenue for the design and preparation of high-flux NF membranes, which is also applicable to enhance the permeance of other TFC membranes.

Novel layer-by-layer assembly of rGO-hybridised ZnO sandwich thin films for the improvement of photo-catalysed hydrogen production

Metal oxide semiconductor materials such as ZnO have tremendous potential as light absorbers for photocatalysed electrodes in the electrochemical reduction of water. Promoters such as rGO have been added to reduce the recombination losses of charge carriers and improve its photoelectrochemical activity. In this study, the effect of layer ordering on the charge transfer properties of rGO-hybridised ZnO sandwich thin films for the photo-catalysed electrochemical reduction of water was investigated. rGO-hybridised ZnO sandwich thin films were prepared via a facile electrode position technique using a layer-by-layer approach. The thin films were analysed using FESEM, XRD, Raman, PL, UV–vis, EIS and CV techniques to investigate its morphological, optical and electrochemical properties. The FESEM images show the formation of distinct layers of rGO and ZnO nanorods/flakes via the layer-by-layer method. XRD confirmed the wurtzite structure of ZnO. PL spectroscopy revealed a reduction of photoemission intensity in the visible region（580 nm） when rGO was incorporated into the ZnO thin film. Among the six thin films prepared, ZnO/rGO showed superior performance compared to the other thin films（0.964 m A/cm） due to the presence of graphene edges which participate as heterogenous electrocatalysts in the photocatalysed electrolysis of water. rGO also acts as electron acceptor, forming an n-p heterojunction which improves the activity of ZnO to oxidise water molecules to O2. EIS revealed that the application of rGO as back contact（rGO/ZnO, rGO/ZnO/rGO） reduces the charge transfer resistance of a semiconductor thin film. Alternatively, rGO as front contact（ZnO/rGO, rGO/ZnO/rGO） improves the photo-catalysed electrolysis of water through the participation of the rGO edges in the chemical activation of water. The findings from this study indicate that the layer ordering significantly affects the thin film＇s electrostatic properties and this understanding can be further advantageous for tunable applications.

In vitro corrosion and antibacterial properties of layer-by-layer assembled GS/PSS coating on AZ31 magnesium alloys

To enhance the corrosion resistance of magnesium（Mg） alloy and to impart its surface with antibacterial functionality for inhibiting biofilm formation and biocorrosion, Mg（OH）2 films were fabricated on AZ31 magnesium alloy substrates by an in-situ hydrothermal method and well-defined multilayer coatings, consisting of gentamicin sulfate（GS） and poly（sodium 4-styrene sulfonate）（PSS）, were prepared via layer-by-layer（Lb L） assembly. The morphologies, chemical compositions and corrosion resistance of the obtained（PSS/GS）n/Mg sample were investigated using scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, electrochemical methods and immersion tests. Finally, the bactericidal activity of（PSS/GS）n/Mg samples against Staphylococcus aureus was assessed by the zone of inhibition methods and plate-counting method. The so-synthesized composite coating on the Mg alloy substrates exhibits good corrosion resistance and antibacterial performance, which make them attractive as coatings for medical implanted devices.

In vitro corrosion resistance and antibacterial properties of layer-by-layer assembled chitosan/poly-L-glutamic acid coating on AZ31 magnesium alloys

Surface functionalization of magnesium(Mg)alloys is desired to obtain the surfaces with both improved corrosion resistance and antibacterial property.A corrosion-resistant and antimicrobial coating was prepared on Mg alloy surface by layer-by-layer(LbL)assembly of chitosan(CHI)and poly-L-glutamic acid(PGA)by electrostatic attraction.The functionalized surfaces of the Mg alloys were characterized by field-emission scanning electron microscopy(FE-SEM),Fourier transform infrared(FT-IR)spectroscopy and electrochemical tests.The bactericidal activity of the samples against Staphylococcus aureus was assessed by the zone of plate-counting method.The obtained coating on the Mg alloy substrates exhibits good corrosion resistance and antibacterial performance.

In vitro corrosion resistance,antibacterial activity and cytocompatibility of a layer-by-layer assembled DNA coating on magnesium alloy

A chitosan/deoxyribonucleic acid(CHI/DNA)_(5)coating was constructed by layer-by-layer(LbL)assembly dip coating method with Mg(OH)_(2)coating as an inner protective layer on AZ31 alloy.X-ray diffractometry,X-ray photoelectron spectrometry,Fourier transform infrared spectroscopy and field-emission scanning electron microscopy were utilized to represent the chemical compositions and surface morphologies of the coatings.Electrochemical tests and hydrogen evolution measurements were implemented to confirm the good corrosion resistance of the composite coating in artificial body fluid.Antimicrobial activity of the composite coatings was tested via the plate-counting method,and the cytotoxicity of the samples was appraised by MTT assay and Live/dead staining.A double action was put into effect for the composite coating,which the inner Mg(OH)2 coating plays the part of physical barrier,and the outer(CHI/DNA)5 coating is employed as an inducer to fabricate a biocompatible Ca-P corrosion product coating during immersion,making up for its thin thickness.Otherwise,the composite coating is also beneficial for the growth of bone,resulting from the biomineralization effect of the outer polyelectrolyte multilayer.The good antibacterial property of the(CHI/DNA)5/Mg(OH)2 coating is ascribed to the contact-killing strength of CHI.Thus,the obtained(CHI/DNA)5/Mg(OH)2 coating has a wide application prospect in the field of Mg-based bone implantation.

Power-Dependent Luminescence of CdSe/ZnS Nanocrystal Assembled Layer-by-Layer on a Silver Nanorod Array

We investigate the power-dependent luminescence of CdSe/ZnS semiconductor quantum dots closely packed layer- by-layer in the proximity of a silver nanorod array cavity. It is found that the emission peak shifts significantly to the longer wavelengths as the excitation power increases, especially when the longitudinal surface plasmon resonance of the Ag nanorod array cavity is adjusted to be close to the emission wavelength. The equivalent gain varies with the coating layer of CdSe/ZnS semiconductor quantum dots and the excitation power is also studied to explain this interesting spectrum-shifting effect. These findings could find applications in the dynamic information processing of active plasmonic and photonic nanodevices.

Assembly and Electrochemical Study of Transition Metal Substituted Polyoxometalates SiW_(11)NiO_(39)^(6-) and SiW_(11)MnO_(39)^(6-) on 4-Aminothio-phenol Modified Glassy Carbon Electrode

Via layer-by-layer assembly, the polyoxometalates of Keggin type, SiW_ 11O_ 39Ni(H_2O) 6-(SiNiW_ 11) and {SiW_ 11O_ 39Mn(H_2O) 6-}(SiMnW_ 11) were first immobilized on a 4-aminothiophenol(4-ATP) modified glassy carbon electrode surface. The electrochemical behavior of these polyoxometalates was investigated. They exhibited some special properties in the films, which are different from those in a homogeneous aqueous solution. Their reaction mechanism in a multilayer film is proposed. The electrocatalytic behavior of these multilayer film electrodes for the reduction of BrO-_3 and NO-_2 were comparatively studied.

BASE-INDUCED RELEASE OF MOLECULES FROM HYDROGEN BONDING DIRECTED LAYER-BY-LAYER FILM

On the basis of hydrogen bonding directed layer-by-layer (LbL) assembly we have fabricated two multilayersystems, poly(acrylic acid) bearng spironaphthoxazine (PAA-SO)/poly(4-vinylpyridine) and carboxyl-terminated polyetherdendrimer (dendrimer-COOH)/poly(4-vinylpyridine). UV-Vis spectroscopy indicates that either PAA-SO or dendrimer-COOH can be released from the corresponding multilayer assemblies upon immerssion in a basic aqueous solution.Furthermore, the rate of molecule release can be controlled either by changing the pH value or by adjusting the layerstructure.

Induction of Superhydrophobicity in a Cellulose Substrate by LbL Assembly of Covalently Linked Dual-Sized Silica Nanoparticles Layers

Micro/nano texturized oxidized cellulose membranes (MNOCM) were constructed by layer-by-layer (LbL) assembly in which a base cellulose film was modified by covalent linkages to amino-functionalized silica nanoparticles (amino-SiO2 NPs, 260 nm diameter) and epoxy-functionalized silica nanoparticles (epoxy-SiO2 NPs, 30 nm diameter). The amino-SiO2 NPs grafted onto the MNOCM surface through a standard amidation reaction between the amino groups of the SiO2 NPs and the carboxyl groups of the MNOCM surface in the presence of EDC and NHS consequently forming a first layer of large (260 nm) nanoparticles;subsequently, it was reacted with smaller (30 nm) epoxy-SiO2 NPs. Continuous repetitions of these alternating sized silica NPs through a standard LbL approach lead to a highly micro/nano-texturized MNOCM film as shown by SEM, which was ultimately sealed with a layer of hydrophobic PFOTES (1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane). Although the wettability of MNOCM was no longer hydrophilic, it was found that at five layers deep of NPs, it became superhydrophobic as evidenced by a water contact angle of 151° ± 2° and slide angle of 4°. The change in wettability was attributed to increases in final LbL layer surface roughness induced by the sufficient LbL layering of alternating sizes of NPs akin to what is observed in a lotus leaf surface. It was also noted that these superhydrophobic-MNOCM materials displayed good self-cleaning.

Positional assembly of multi-enzyme cascade reaction in polyelectrolyte doped microcapsule through electrospray and layer-by-layer assembly

Polyelectrolyte-doped microcapsules(PDM)was fabricated by coaxial electrospray of a mixture of glycerol and water containing 10 mg/mL cationic polyelectrolyte poly(allylamine hydrochloride)(PAH)fed as the core phase solution,and a N,N-dimethylacetylamide solution of 10 wt%polyurethane fed as the shell phase solution.Multienzyme system involving Candida Antarctica lipase B(CALB),glucose oxidase(GOD),and horseradish peroxidase(HRP)for cascade reaction was assembled in the PDM at three different places,namely,surface,shell,and lumen.Placing of enzyme inside aqueous lumen of the PDM was realized by in situ encapsulation through adding the enzyme in the core-phase solution for coaxial electrospray.By ion-pairing of enzyme with cationic surfactant CTAB,an organic soluble enzyme-CTAB complex was prepared,so that in situ embedding of enzyme in the shell of the PDM was realized by adding it into the shell phase solution.Surface attachment of enzymes was achieved by layer-by-layer(LbL)technology,which is based on the ion-exchange interactions between oppositely charged enzymes and PAH that was doped in PDM.The enzyme-decorated microcapsule was then studied as a microbioreactor,in which 1-Oxododecyla-α-glucopyranoside was converted by CALB to glucose,which was oxidised by GOD to gluconolactone in a second step.The hydrogen peroxide produced was then used by HRP to oxidize ABTS to form coloured radical cation ABTS•+for activity analysis.The successful fabrication of the PDM and precise localization of enzymes in the PDM by different strategies were fully characterized.By varying the immobilization strategy,totally six PDM bioreactors with three enzymes precisely positional assembled in different strategies were constructed and their activities for the cascade reaction were investigated and compared.The PDM micro-bioreactor prepared by novel electrospray technologies provide a smart platform for positional assembly of multi-enzyme cascade reaction in a precise and well-controlled manner.

Reagentless biosensor based on layer-by-layer assembly of functional multiwall carbon nanotubes and enzyme-mediator biocomposite

A simple and controllable layer-by-layer （LBL） assembly method was proposed for the construction of reagentless biosensors based on electrostatic interaction between functional multiwall carbon nanotubes （MWNTs） and enzyme-mediator biocomposites. The carboxylated MWNTs were wrapped with polycations poly（allylamine hydrochloride） （PAH） and the resulting PAH-MWNTs were well dispersed and positively charged. As a water-soluble dye methylene blue （MB） could mix well with horseradish peroxidase （HRP） to form a biocompatible and negativelycharged HRP-MB biocomposite. A （PAH-MWNTs/HRP-MB）, bionanomultilayer was then prepared by electrostatic LBL assembly of PAH-MWNTs and HRP-MB on a polyelectrolyte precursor film-modified Au electrode. Due to the excellent biocompatibility of HRP-MB biocomposite and the uniform LBL assembly, the immobilized HRP could retain its natural bioactivity and MB could efficiently shuttle electrons between HRP and the electrode. The incorporation of MWNTs in the bionanomultilayer enhanced the surface coverage concentration of the electroactive enzyme and increased the catalytic current response of the electrode. The proposed biosensor displayed a fast response （2 s） to hydrogen peroxide with a low detection limit of 2.0× 10^-7 mol/L （S/N=3）. This work provided a versatile platform in the further development of reagentless biosensors.

Surface modification of polypropylene non-woven fibers with TiO_2 nanoparticles via layer-by-layer self assembly method:Preparation and photocatalytic activity

Polypropylene（PP） meltblown fibers were coated with titanium dioxide（Ti O2） nanoparticles using layer-by-layer（Lb L） deposition technique. The fibers were first modified with 3layers of poly（4-styrenesulfonic acid）（PSS） and poly（diallyl-dimethylammonium chloride）（PDADMAC） to improve the anchoring of the Ti O2 nanoparticle clusters. PDADMAC, which is positively charged, was then used as counter polyelectrolyte in tandem with anionic Ti O2 nanoparticles to construct Ti O2/PDADMAC bilayer in the Lb L fashion. The number of deposited Ti O2/PDADMAC layers was varied from 1 to 7 bilayer, and could be used to adjust Ti O2 loading. The Lb L technique showed higher Ti O2 loading efficiency than the impregnation approach. The modified fibers were tested for their photocatalytic activity against a model dye, Methylene Blue（MB）. Results showed that the Ti O2 modified fibers exhibited excellent photocatalytic activity efficiency similar to that of Ti O2 powder dispersed in solution. The deposition of Ti O23 bilayer on the PP substrate was sufficient to produce nanocomposite fibers that could bleach the MB solution in less than 4 hr.Ti O2-Lb L constructions also preserved Ti O2 adhesion on substrate surface after 1 cycle of photocatalytic test. Successive photocatalytic test showed decline in MB reduction rate with loss of Ti O2 particles from the substrate outer surface. However, even in the third cycle, the Ti O2 modified fibers are still moderately effective as it could remove more than 95% of MB after 8 hr of treatment.

NEAR INFRARED ELECTROCHROMIC VARIABLE OPTICAL ATTENUATOR FABRICATED BY LAYER-BY-LAYER ASSEMBLY

An eleetrochromic variable optical attenuator （ECVOA） was fabricated by layer-by-layer （LBL） assembly of disodium N,N-bis（p-sulfonatophenyl）naphthalenedicarboximide （Naph-SO3Na） and common cationic polymer poly（diallyldimethylammonium） chloride （PDDA）. The UV-Vis absorption spectra of the multilayer films revealed that approximately an equal amount of Naph-SO3Na was assembled in each deposition cycle. Upon one-electron reduction, multilayer films exhibited intense absorption around 452 nm and also a broad absorption band from 1200 nm to 1900 nm. Owing to the improved ionic conductivity, the optical attenuation at 1550 nm of the films showed rapid response time and reached 1.3 dB/μm within 5 s. These results indicate that layer-by-layer assembly could be an effective method for the preparation of ECVOA operating in near infrared region.

Strengthened graphene oxide/diazoresin multilayer composites from layer-by-layer assembly and cross-linking

The layer-by-layer assembly of graphene oxide and diazoresin is carried out via the electrostatic and hydrogen bond interactions on planar substrates and colloidal templates.The successful planar and spherical growth of multilayer could be investigated by UV-vis spectrophotometry and scanning electron microscopy,respectively.Subsequent UV irradiation or heating would convert the ionic bonds and hydrogen bonds to covalent bands,which significantly improves the stability of the multilayer composite against solvent etching.For the cross-linked core-shell composites,the template cores could be removed by dissolution and hollow microspheres are obtained.

In vitro corrosion resistance of layer-by-layer assembled polyacrylic acid multilayers induced Ca–P coating on magnesium alloy AZ31

Biodegradable magnesium(Mg)-based alloys have aroused great concern owing to their promising characteristics as temporary implants for orthopedic application.But their undesirably rapid corrosion rate under physiological conditions has limited the actual clinical application.This study reports the use of a novel biomimetic polyelectrolyte multilayer template,based on polyvinylpyrrolidone(PVP)and polyacrylic acid(PAA)via layerby-layer(LbL)assembly,to improve the corrosion resistance of the alloy.Surface characterization techniques(field-emission scanning electron microscopy,Fourier transform infrared(FTIR)spectrophotometer and X-ray diffractometer)confirmed the formation of biomineralized Ca–P coating on AZ31 alloy.Both hydrogen evolution and electrochemical corrosion tests demonstrated that the corrosion protection of the polyelectrolyte-induced Ca–P coating on AZ31 alloy.The formation mechanism of biomineralized Ca–P coating was proposed.

Advances in layer-by-layer self-assembled coatings upon biodegradable magnesium alloys

Magnesium(Mg)and its alloys are considered as ideal biodegradable materials due to their excellent mechanical properties and biocompatibility.In order to improve the surface properties to allow better adaptation to the surrounding tissue of the body,surface modification has played a significant role in satisfying multiple clinical requirements such as corrosion resistance,biocompatibility,and antibacterial ability.Here,layer-by-layer(LbL)self-assembly,which can be applied for biodegradable Mg alloys due to its extensive choice of usable units,holds great promise among all the surface techniques.In this review,the mechanisms of the driving force(i.e.,electrostatic interaction,hydrogen bonding,charge transfer interaction and covalent bonding),cuttingedge advances in preparation methods(e.g.,dipping,spraying,and spinning)and the functional properties(corrosion resistance,antibacterial activity,and biocompatibility)that could be achieved by the LbL coatings are summarized.A reasonable trend of the potential development of LbL for bioMg alloys is also proposed at the end of this article.

Effect of carboxymethyl konjac glucomannan coating on curcumin-loaded multilayered emulsion:stability evaluation

The stability against various environmental stresses of the curcumin-loaded secondary and tertiary emulsions that was emulsified by whey protein isolate(WPI)and coated by chitosan(CHI),carboxymethyl konjac glucomannan(CMKGM),or their combination through layer-by-layer assembly was investigated.Generally,the multilayered emulsions were destabilized in high Na Cl concentrations or medium p H that could interrupt the electrostatic interaction between the three polyelectrolytes or deprotonate CHI,indicating that electrostatic interaction played an important role in the stability of emulsions.Compared with the primary emulsion that was solely stabilized by WPI,extra coating with CHI and CMKGM generally increased the stability of the emulsion against repeated freezing-thawing,improved the retention of curcumin against heating,UV irradiation,and long-term storage,and the effects were more remarkable in the tertiary emulsion with CMKGM locating in the outmost layer.Since CMKGM has shown the colon-targeted delivery potency,the multilayered emulsions assembled by layer-by-layer deposition,especially the tertiary emulsion,could be used as an effective carrier for the targeted delivery of curcumin.

Corrosion resistance of Ca-P coating induced by layer-by-layer assembled polyvinylpyrrolidone/DNA multilayer on magnesium AZ31 alloy

A hydrothermal deposition method was utilized to fabricate Ca-P composite coating induced by the layer-by-layer(LbL)assembled polyvinylpyrrolidone/deoxyribonucleic acid(PVP/DNA)_(20) multilayer on AZ31 alloy.The surface morphology and compositions were characterized by SEM,EDS,FTIR and XRD.Besides,the corrosion resistance and degradation behavior of the coating were tested via electrochemical polarization,impedance spectroscopy and immersion measurements.Results show that the main components of Ca-P coatings are hydroxyapatite,Ca_(3)(PO_(4))_(2) and Mg_(3)(PO_(4))_(2)·nH_(2)O.The LbL-assembled DNA and PVP promote the adsorption of Ca-P deposits on the sample surface,and structures and functional groups of the polyelectrolyte in the outermost layer are the primary influencing factor for the induction of the Ca-P coating.Carboxyl groups have the best biomineralization effect among all related functional groups.The enhanced corrosion resistance and adhesion highlight a promising use of(PVP/DNA)_(20)-induced Ca-P coatings in the field of biomedical magnesium alloys.

Fabrication and Properties of Graphene Oxide/Sulfonated Polyethersulfone Layer-by-layer Assembled Polyester Fiber Composite Proton Exchange Membranes

Using the hydrogen-bonding interaction between graphene oxide（GO） and sulfonated polyethersulfone （SPES）, we constructed the multilayer structure of GO and SPES on the polyester tiber mats via layer-by-layer self-assembly. In each self-assembled layer, sulfonic acid groups are arranged along the a^s of fiber, which provides the long-range proton transmission channels, promoting the rapidly proton conduction. The performances of the composite membranes based on SPES and multilayer assembled polyester fiber mats were studied. The results show that the proton conductivity of composite membranes increases with the increasing assembly layers. At the same time, the mechanical properties and methanol-resistance of the composite membranes were obviously improved.

Fabrication of Covalently Linked PAH/PVS Layer-by-layer Assembled Multilayers via a Post-photochemical Cross-linking Strategy

A post-photochemical cross-linking strategy was successfully demonstrated to enhance the stability of polyelectrolyte poly（allylamine hydrochloride）（PAH）/poly（vinylsulfonic acid sodium salt）（PVS） multilayers. Con- ventional polyelectrolyte multilayers of PAH/PVS are usually fabricated through electrostatic layer-by-layer（LbL） assembly, resulting in poor stability, especially in basic solutions, which leads to the urgent demand for converting weak electrostatic interactions into covalent bonds to enhance the stability of the multilayers. This stability problem has been ultimately addressed by post-infiltrating a photosensitive cross-linking agent, 4,4＇-diazostilbene-2,2＇- disulfonie acid disodium salt（DAS）, into the LbL assembled films to initiate the photochemical reaction to cross-link the multilayers. The obviously improved stability of the photo-cross-linked multilayers was demonstrated through experiments with basic solution treatments. Compared to the complete decomposition of uncross-linked multilayers in basic solution, over 74.4% of the covalently cross-linked multilayers were retained under the same conditions, even after a longer duration of basic solution treatment.