Chitosan/Sodium Alginate Multilayer pH-Sensitive Films Based on Layer-by-Layer Self-Assembly for Intelligent Packaging

The abuse of plastic food packaging has brought about severe white pollution issues around the world.Developing green and sustainable biomass packaging is an effective way to solve this problem.Hence,a chitosan/sodium alginate-based multilayer film is fabricated via a layer-by-layer(LBL)self-assembly method.With the help of superior interaction between the layers,the multilayer film possesses excellent mechanical properties(with a tensile strength of 50 MPa).Besides,the film displays outstanding water retention property(blocking moisture of 97.56%)and ultraviolet blocking property.Anthocyanin is introduced into the film to detect the food quality since it is one natural plant polyphenol that is sensitive to the pH changes ranging from 1 to 13 in food when spoilage occurs.It is noted that the film is also bacteriostatic which is desired for food packaging.This study describes a simple technique for the development of advanced multifunctional and fully biodegradable food packaging film and it is a sustainable alternative to plastic packaging.

Solid Additive-Assisted Layer-by-Layer Processing for 19%Efficiency Binary Organic Solar Cells

Morphology is of great significance to the performance of organic solar cells(OSCs),since appropriate morphology could not only promote the exciton dissociation,but also reduce the charge recombination.In this work,we have developed a solid additive-assisted layer-by-layer(SAA-LBL)processing to fabricate high-efficiency OSCs.By adding the solid additive of fatty acid(FA)into polymer donor PM6 solution,controllable pre-phase separation forms between PM6 and FA.This intermixed morphology facilitates the diffusion of acceptor Y6 into the donor PM6 during the LBL processing,due to the good miscibility and fast-solvation of the FA with chloroform solution dripping.Interestingly,this results in the desired morphology with refined phase-separated domain and vertical phase-separation structure to better balance the charge transport/collection and exciton dissociation.Consequently,the binary single junction OSCs based on PM6:Y6 blend reach champion power conversion efficiency(PCE)of 18.16%with SAA-LBL processing,which can be generally applicable to diverse systems,e.g.,the PM6:L8-BO-based devices and thick-film devices.The efficacy of SAA-LBL is confirmed in binary OSCs based on PM6:L8-BO,where record PCEs of 19.02%and 16.44%are realized for devices with 100 and 250 nm active layers,respectively.The work provides a simple but effective way to control the morphology for high-efficiency OSCs and demonstrates the SAA-LBL processing a promising methodology for boosting the industrial manufacturing of OSCs.

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.

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.

Layer-by-layer electrostatic selfassembly of anionic and cationic carbon nanotubes

The layer-by-layer(LBL) self assembly of anionic and cationic multi-walled carbon nanotubes(MWNTs) through electrostatic interaction has been carried out to fabricate all-MWNT multilayer films.The alternate uniform assembly of anionic and cationic MWNTs was investigated by UV-vis spectroscopy.Scanning electron microscopy(SEM) images displayed the growth of the MWNT films.

Application of Layer-by-Layer Solidification Principle to Optimization of Large Chain Wheel Foundry Technology

In order to get a sound casting of the alloy with a solidification range, the principle of directional solidification (DS) and the layer-by-layer solidification(LBLS) should be followed, especially in designing foundry process of steel casting. Using the principles, the reasons for the forming of the defects on the surface of the chain wheels teeth and groove and the forming of MT (magnetic particle testing) thin lines were analyzed. The results of the metallographic observation and the numerical simulation show that the low temperature gradient results in a wider mushy zone at the S/L interface that causes the defects and MT thin lines on the surface of the chain wheel casting. Based on the analysis, a new casting technology of the chain wheel was designed and used in the casting production successfully.

Layer-by-layer growth of ZIF-8 on electrospun carbon nanofiber membranes for high-performance supercapacistor electrode

In the past few decades, supercapacitor(SC) has attracted great attention due to its significant advantages over traditional rechargeable battery systems, such as high power density, fast charge-discharge rate, long cycle life and environmental friendliness [1]. Up to now, supercapacitors have been widely used in backup power, electric vehicles, mobile power and so on [2,3].

Solvatochromic Probe Based on Nanocellulose Membrane Coated with Zn-terpyridine Complex in a Layer-by-Layer Manner

Solvatochromic materials have recently attracted increasing attention owing to their great significance in the security and sensor fields.In this study,ultrafast explicit and implicit information was collected regarding a fluorescent nanocellulose membrane produced from nanocellulose membranes coated with a Zn-terpyridine complex(Zn-tpy)in a layer-by-layer manner.The fluorescent emissions of the nanocellulose membrane changed from yellow(CIE:x=0.37,y=0.45)to green(CIE:x=0.32,y=0.47)under a dichloromethane environment and 365-nm irradiation.Due to the ease of dichloromethane volatilization,fluorescent emissions quickly returned to the original state.These solvatochromic nanocellulose membranes,with ultrafast explicit and implicit information,exhibited valuable application prospects in anti-counterfeiting techniques.

Deposition of Layer-by-layer Inorganic-organic Nano-hybrid Ultrathin Films onto SBA-15

Deposition of inorganic-organic nano-hybrid ultrathin films onto mesoporous silicate materials has been proven possible by using layer-by-layer assembly method. In combination with sol-gel method, titania, subsequently dye molecules (or polymer) were successfully fabricated onto the inner wall of SBA-15. Their structures were preliminarily characterized by FTIR and solid-state UV-Vis spectroscopy, thermal analysis, and BET surface area measurements, respectively.

Direct Electrochemistry of Hemoglobin in Layer-by-layer {PDDA/Hb}_n Films Assembled on Pyrolytic Graphite Electrodes

Layer-by-layer {PDDA/Hb}(n) films were assembled by means of alternate adsorption of positively charged poly(diallyldimethyl ammonium) (PDDA) and negatively charged hemoglobin (Hb) at pH 9.2 from their aqueous solutions on pyrolytic graphite (PG) electrodes. Film growth during adsorption cycles was demonstrated by cyclic voltammetry and UV-Vis spectroscopy. Direct electrochemistry of Hb in {PDDA/Hb}(n) films on PG was studied.

Layer-by-layer nanostructured protein loaded nanoparticles: A feasibility study using lysozyme as model protein and chitosan as coating material

Stabilization of proteins in delivery devices and design of appropriate protein carriers are major research issues due to the extreme sensitivity of proteins.Previously,negatively charged nanoparticles,consisting of poly(lactic-co-glycolic acid)(PLGA)and poly(styrene-co-4–styrene-sulfonate)(PSS),showed considerably high loading capacity for positively charged model protein lysozyme depending on the surface charge density of nanoparticles.

Gold Nanoparticle-based Layer-by-Layer Enhancement of DNA Hybridization Electrochemical Signal at Carbon Nanotube Modified Carbon Paste Electrode

Colloid gold nanoparticle-based layer-by-layer amplification approach was applied to enhance the electrochemical detection sensitivity of DNA hybridization at carbon nanotube modified carbon paste electrodes （CNTPEs）. Streptavidin was immobilized onto the surface of CNTPEs, and the conjugation of biotin labeled target oligonucle,otides to the above immobilized streptavidin was performed, followed by the hybridization of target oligonucleotides with the gold nanoparticle-labeled DNA probe and then the layer-by-layer enhanced connection of gold nanoparticles, on which oligonucleotides complementary to the DNA probe were attached, to the hybridization system. The differential pulse voltammetry （DPV） signal of total gold nanoparticles was monitored. It was found that the layer-by-layer colloidal gold DPV detection enhanced the sensitivity by about one order of magnitude compared with that of one-layer detection. One-base mismatched DNA and complementary DNA could be distinguished clearly.

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.

Electron Communication Between Electrode and Dye-Linked L-Proline Dehydrogenase in Organized Layer-by-Layer Multilayer Film

Multilayer film was fabricated on an electrode surface by alternate layer-by-layer（LBL） adsorption of polycationic redox polymer（PEI-Fc） and dye-linked L-proline dehydrogenase（L-proDH）.The electrochemistry of the PEI-Fc/L-proDH multilayer modified electrode was investigated by cyclic voltammetry,and the enzyme catalysis mediated by the redox polymer was studied in a solution containing L-proline.It was observed that electron communication between L-proDH and the electrode was achieved with the help of PEI-Fc.A mathematical expression for the current response was evaluated based on the Michaelis-Menten kinetics mode,and the calculated currents fitted well with the experimental data.The kinetic analysis indicates that only a small fraction of the immobilized enzyme was efficiently electrically wired by the redox polymer.

Preparation of Microcapsules Containing Grape Polyphenol with the Spray Drying Method Followed by the Layer-by-Layer Method

It was tried to prepare the microcapsules containing grape polyphenol with the spray drying method followed by the layer-by-layer method. As grape polyphenol was water soluble, the spray drying method was adopted to obtain the higher content. As the shell material of the first microcapsules prepared by the spray drying method, palmitic acid with the melting point of 60&degC was adopted in order to prevent grape polyphenol from dissolution into water. As the shell material of the second microcapsules prepared by the layer-by-layer method, chitosan was used to coat the first microcapsules and to give the microcapsules alcohol resistance. In the experiment, the spray drying conditions such as the inlet temperature and the spraying pressure, the oil soluble surfactant species and the chitosan concentration were changed. The mean diameters of microcapsules could be controlled in the range from 5 μm to 35 μm by changing the spraying pressure and the inlet temperature. The yield of microcapsules and the microencapsulation efficiency over 50% could be obtained under the conditions of P = 1.0 kgf/cm2 and Tin = 100&degC. Furthermore, the microencapsulation efficiency could be increased by adding the oil soluble surfactant with the larger HLB value. Coating with chitosan could considerably increase alcohol resistance.

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.

Nucleation and Growth of Zinc Sulfide Nanoparticles in Ultrathin Polymer Films by Layer-by-Layer Polyionic Assemblies

In this work, zinc sulfide (ZnS) nanoparticles were formed by nucleation and growth in ultrathin films of polydiallyldi-methylammonium chloride (PDDA)–polystyrenesulfonate sodium salt (PSS) film produced by the Layer-by-Layer (LbL) deposition technique. Multilayer thin film assemblies, fabricated by sequential adsorption of polyelectrolytes on a quartz substrate, were used as a supramolecular reaction template to study the in-situ nucleation and growth of ZnS nanoparticles. ZnS nanoparticles were nucleated within the polymeric supramolecular structure through cyclic expo-sure to the solutions of Zn(NO3)2 and thiourea. The growth and nucleation of nanoparticles were accomplished by a cyclic repetition of reductive hydrolysis reactions. The growth of a thin film on a flat substrate via LbL was monitored by ultraviolet-visible (UV-Vis) spectroscopy. Analysis of the UV-visible absorption spectra of the films revealed that the nanoparticles grew with increasing number of cycles. The presence of ZnS nanoparticles were verified by transmission electron microscopy (TEM). Selected area electron diffraction (SAED) showed that the ZnS has a cubic spheralite structure.

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.