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.

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.

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.

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.

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.

Layer-by-layer assembly of nanocomposite films with thickness up to hundreds of nanometers

Polyelectrolyte/polyelectrolyte, organic molecule/colloidal CdS and polyelectrolyte/MWCNT films were fabricated via the layer-by-layer assembling technique. The assembled films were characterized by UV-vis spectrophotometer, X-ray diffractometry, nano profilometer and scanning electron microscopy. The results demonstrate that the layer-by-layer assembling technique can be used to make the nanoscaled films from polyelectrolytes and thicker composite films from suitable precursor materials. Both organic molecule/colloidal CdS films and PEI/MWCNT films with thickness of hundreds of nanometers were obtained. For the organic molecule/colloidal CdS films, a reasonable explanation for the result is that both the organic molecules and the CdS particles aggregate in the films. For the PEI/MWCNT films, obviously, it is the MWCNT that makes the great contribution to the film thickness.

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.

Novel self-assembled films of La-based phosphonate 3-aminopropyltriethoxysilane

Silane coupling reagent (3-aminopropyltriethoxysilane (APTES)) was prepared on single-crystal silicon substrates to form two-dimensional self-assembled monolayer (SAM). The terminal-NH2 groups in the film were in situ phosphorylated to -PO(OH)2 group to endow the film with good chemisorption ability. Then La-based thin films were deposited on phosphorylated APTES-SAM in order to make good use of the chemisorption ability of -PO(OH)2 groups. The thickness of the film was determined with ellipsometer, while phase transformation and surface morphology, surface energy, phase composition were analyzed by means of atomic force microscope (AFM), contact angle measurements and X-ray photoelectron spectroscopy (XPS). The results indicated that the terminal-NH2 groups could be completely transformed into desirable-PO(OH)2 groups after phosphorylation of APTES-SAM. Detailed XPS analysis of the La3+ peaks revealed that lanthanum element existed in the films in different states. As a result, conclusion could be made that lanthanum reacted with -PO(OH)2 groups on the surface of the substrate by chemical bond which would improve the bonding strength between the film and silicon substrate. Since the La-based thin films were well adhered to the silicon substrate, it might find promising application in the surface-modification of single-crystal Si and SiC in microelectromechanical systems (MEMS).

Characterization and tribological investigation of self-assembled MPTS-MPTES/RE composite films

γ-mercapto-propyl trimethoxysilane （MPTS） and γ-methacryloxy propyltrimethoxysilane （MPTES） were self-assembled on a hy- droxylated glass substrate to form a two-dimensional organic monolayer （MPTS-MPTES SAM）. The terminal thiol groups （-SH） in the MPTS-MPTES SAM were in-situ oxidized into sulfonic acid groups （-SO3H） to endow the film with good chemisorption ability. Then rare earth （RE） （lanthanum-based） composite thin films were prepared by self-assembly technique based on the as-prepared SAM, taking advantage of the chemisorption ability of the sulfonic acid groups. Automatic force microscope （AFM）, X-ray photoelectron spectrometry （XPS）, contact angle measurement and ellipsometer were used to characterize MPTS-MPTES/RE composite films. The macrofriction and wear behaviors of the films sliding against an AISI-52100 steel ball were examined on a unidirectional friction and wear tester, and the worn surface morphologies were observed on an AFM. The results showed that MPTS-MPTES/RE films had a low friction coefficient （0.09） and a long wear life （5980 sliding pass） at a light load （50 mN）. It indicated that the superior tribological properties of the MPTS-MPTES/RE composite films were attributed to the special characteristic of RE elements, the mobility of the films and good bonding strength.

Characterization and tribological investigation of self-assembled trimethoxysilyl-functionalized poly(phthalazinone ether ketone)thin films on glass substrates

Trimethoxysilyl-functionalized PPEK（PKGS） films had been designed to serve as wear resistant coatings for silicon surfaces. These surface films were formed by a dip-coating technique applied to self-assembled monolayers（SAMs）.The formation and wetting behavior of PKGS films were characterized by means of contact angle measurement.The friction coefficient of the film prepared is very low（about 0.1）,and the anti-wear behavior is good,with a lack of failure after sliding over 1800 s.

Hybrid Self-Assembled Multilayer Films Formed by Alternating Layers of Keggin Polyoxometalates and 1,10DAD

Hybrid self-assembled multilayer films were prepared by alternate adsorption of 1,10-diaminodecane (1,10-DAD) and Keggin polyoxometalates of SiW12O404-, SiW11VO405-, and PMo12O403-, respectively. The films were reproducibly grown at each adsorption cycle as monitored by UV spectroscopy.

Preparation and Characterization of SrTiO_3 Thin Film on Functional Organic Self-Assembled Monolayers

SrTiO3 thin film was successfully prepared on the functionalized organic self-assembled monolayers（SAMs） by the Liquid Phase Deposition（LPD） method.The as-prepared samples were characterized by X-ray diffraction（XRD）,atomic force microscope（AFM）,scanning electron microscopy（SEM） and metallographic microscope.Measurement of contact angle showed that the hydrophobe substrate was changed into hydrophile by UV irradiation.AFM photographs of octadecyl-trichloro-silane self-assembled monolayer（OTS-SAM） surface approved that UV irradiation did change the morphology of OTS monolayer and provided evidence for the conversion of hydrophilic characteristic.Photographs of Metallographic Microscope showed that OTS-SAM had an active effect on the deposition of SrTiO3 thin film.XRD and SEM indicated that the thin film was of pure cubic phase SrTiO3 and composed of nanosized grains with a size in the range of 100-500 nm.The formation mechanism of the SrTiO3 film was proposed.

FABRICATION AND AFM/FFM STUDIES OF C_(60)-CONTAINING POLYELECTROLYTE SELF-ASSEMBLED FILMS

An initial investigation on the roughness and frictional properties of the self-assembled thin films from polyelectrolytes is presented. Star-shaped C-60-Poly(styrene-maleic anhydride) was successful prepared. The multilayer thin films have been fabricated on mica with diazoresin as the cationic polyelectrolyte and hydrolyzed star-shaped C-60-poly(styrene-maleic anhydride) as the anionic polyelectrolyte via self-assembly technique. The crosslinking structure of the films is formed from the conversion of ionic bond to covalent bond after UV irradiation. AFM/FFM investigations provide insights into the roughness and frictional properties on a microscale. The roughness depends strongly on the number of film layers in the case of C-60-containing films. The frictional forces of the films exhibited a well behaved non-linear relationship in response to the change of applied load. It supports the prediction of enhanced load-bearing property Of C60-containing thin films.

Novel Covalently Linked Self-Assembled Films from a Functional Hyperbranched Conjugated Poly (Phenylene Vinylene)

A new self-assembled films of a functional dendritic molecule, hyperbranched conjugated poly (phenylene vinylene), is obtained through covalent bond linkage. The highly ordered and homogenous molecular films are obtained;and characterized by UV-vis spectra, fluorescent spectra and atomic force microscopy.

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.

Self Assembled Monolayer Films of C_（60） on O，O＇－Bis（2－aminoethyl）dithiophos Modified Copper

On the surface of O,O'-bis(2-aminoethyl) dithiophosphate modified copper C60forms self-assembled monolayer films (SAMs) through the chemical bond. The film was characterized by contact angle, X-ray photoelectron spectroscopy, electrochemisny, TOF Mass Spetropy.

STABILITY AND ELECTROCHEMICAL PROPERTIES OF FULL-CONJUGATED SELF-ASSEMBLED FILMS BASED ON POLYANILINE AND ITS ACID-SUBSTITUTED DERIVATES

The stability of full-conjugated self-assembled （SA） multilayer films based on partially doped polyaniline （PANI） as a polycation and poly（o-aminobenzoic acid） （PCAN）, poly（aniline-2-sulfonic acid） （PSAN） as polyanions is investigated in alkali aqueous solutions. The self-assembled PANI-PCAN films keep their stability within 24 h in 1 mol/L NaOH solution,-the PANI-PSAN films, however, maintain the stability for 20 min in the same condition because the solubility of PSAN in alkali solutions is much higher than that of PCAN. The electrochemical properties of the SA films are determined, and the film-CdS composites formed in situ are also reported.

Self-assembled Synthesis of Porous TiO_2 Film on the Electrophoretic-deposited Titanate Nanoribbon Film

The porous TiOz film was self-assembled on the surface of electrophoretic-deposited titanate nanoribbon film without the addition of templates by using TiF4 as the precursor. It was found that the hydrolysis of TiF4 was accompanied with the self-assembly processes of TiO2 nanoparticles on the surface of electrophoretic-deposited titanate nanoribbon film, resulting in the formation of porous TiO2 structures. Titanate nanoribbon film was demonstrated to provide the active sites for the effective self-assembly of porous TiO2 nanostructures owing to a large amount of hydroxyl groups. Compared with the nonporous TiO2 film, the prepared porous TiO2 films obviously showed an enhanced photocatalytic activity, which could be attributed to the rapider diffusion and more efficient transport of various reactants and products during photocatalytic reaction in the t^orous structures.