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.

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.

Layer-by-layer self-assembly and clinical application in orthopedics

Orthopedic implants for the treatment of bone defects from various causes have been challenged by insufficient osseointegration,bacterial infection,oxidative stress,immune rejection,and insufficient individualized treatment.These challenges not only impact treatment outcomes but also severely impact patients’daily lives.Layer-by-Layer(LbL)serves as a simple surface coating technique,in simple terms,to functionalize implants by sequentially adsorbing oppositely charged materials onto a substrate.In orthopaedics,LbL self-assembly technology solves some of the challenges by loading various drugs or biological agents on the implant surface and controlling their release precisely to the site of bone defects in a personalized way.This review will introduce the basic principle and the development of LbL in orthopaedics,review and analyze the chemical strategy of LbL in the preparation of bone implants to ensure the stability of the implant,and introduce the use of LbL bone implants in orthopaedics in recent years.The application of LbL includes the realization of programmed drug delivery and sustained release,thereby promoting osseointegration and the formation of new blood vessels,antibacterial,antioxidant,etc.This review focuses on the LbL technology,involving the technology selection for the preparation of bone implants,the chemical strategies of the stability guarantee of LbL implants,the pharmacological properties,loading and release mechanisms of loaded drugs,and the molecular mechanisms of osteogenesis and angiogenesis.The aim of this review is to provide an overview of current research advances,and a prospect in this field was also described.

Supramolecular flow chemistry: Construction of multiscale supramolecular assemblies by micro/nanofluidic techniques

The rapid and precise fabrication of multiscale supramolecular assemblies using micro/nanofluidic techniques has emerged as a dynamic area of research in supramolecular chemistry, materials chemistry, and organic chemistry. This review summarizes the application of micro/nanofluidic techniques in constructing supramolecular assemblies, including nanoscale supramolecular assemblies such as macrocycles and cages, microscale supramolecular assemblies such as metal organic frameworks (MOFs) and covalent organic frameworks (COFs), and macroscale supramolecular assemblies such as supramolecular hydrogels. Compared to conventional synthesis methods, micro/nanofluidic techniques for the production of supramolecular assemblies have significant advantages, including enhanced safety, high reaction rates, improved selectivity/yield, and scalability. Additionally, micro/nanofluidic systems facilitate the creation of precisely controllable micro/nanoconfined environments, allowing for a unique flow behavior that improves our understanding of the supramolecular self-assembly process. Such systems may also lead to the development of novel supramolecular assemblies that differ from those generated via traditional methods.

Mg-Zn-Y-Nd coated with citric acid and dopamine by layer-by-layer self-assembly to improve surface biocompatibility

Magnesium alloy has been generally accepted as an important biodegradable material on cardiovascular stent development for a long time. However, its limited biocompatibility, especially delayed endothelialization process restricts its further application. In this contribution, we modified the Mg-Zn-Y-Nd alloy surface with citric acid and dopamine via a layer-by-layer self-assembly assay, aiming at improving the biocompatibility of the magnesium alloy. The citric acid/dopamine(CA/PDA) layer exhibited a remarkable suppression of platelet activation/aggregation and thrombosis under 15 dyn/cm2 blood flowing. Inhibition on vascular smooth muscle cells growth and macrophages attachment/activation were also observed on this layer. In particular, the CA/PDA layer presented a promoted property for the vascular endothelial cells growth and spreading compared with the bare magnesium alloy, suggesting the pro-endotelialized function. In conclusion, this research may support potential application on surface modification of magnesium alloy based cardiovascular stents for better biocompatibility.

Preparation of Au/Ag Multilayers via Layer-by-Layer Self-assembly in Spherical Polyelectrolyte Brushes and Their Catalytic Activity

Spherical polyelectrolyte brushes （SPBs） consisting of polystyrene （PS） core and poly（2-aminoethyl methacrylate hydrochloride） （PAEMH） shell were prepared by photo-emulsion polymerization. Au nanoparticles （Au-NPs） with controlled size and size distribution were synthesized in situ using SPBs as nanoreactors. Via layer-by-layer deposition technique on the surface of SPBs, nano-composite particles with Au/Ag-NPs bilayer and Au/Ag/Au-NPs trilayer were prepared. The structures of the as-prepared Au/Ag multilayer SPBs were characterized by UV-Vis spectroscopy, TEM, ICP-AES and DLS. The charge reversal of the nano-composite particles observed by zeta potential confirmed the success of layer-by-layer assembly. The Au/Ag-NPs bilayer nano-composite particles showed high catalytic efficiency with an apparent activation energy of about 41.2 kJ/mol in the reduction reaction of 4-nitrophenol to 4-aminophenol in the existence of sodium borohydride monitored. The catalytic activity ofAu/Ag-NPs multilayer SPBs close to that of Au-NPs SPBs and much higher than that of Ag-NPs SPBs reveals its potential applications in cost-effective catalysts with high-performance.

Sensing Escherichia coli O157:H7 via frequency shift through a self-assembled monolayer based QCM immunosensor

By means of the specific immuno-recognition and ultra-sensitive mass detection, a quartz crystal microbalance (QCM) biosensor for Escherichia coli O157:H7 detection was developed in this work. As a suitable surfactant, 16-mercaptohexadecanoic acid (MHDA) was introduced onto the Au surface of QCM, and then self-assembled with N-hydroxysuccinimide (NHS) raster as a reactive intermediate to provide an active interface for the specific antibody immobilization. The binding of target bacteria with the immobilized antibodies decreased the sensor’s resonant frequency, and the frequency shift was correlated to the bacterial concentration. The stepwise assembly of the immunosensor was characterized by means of the electrochemical techniques. Using the immersion-dry-immersion procedure, this QCM biosensor could detect 2.0×102 colony forming units (CFU)/ml E. coli O157:H7. In order to reduce the fabrication time, a polyelectrolyte layer-by-layer self-assembly (LBL-SA) method was adopted for fast construction. Finally, the reproducibility of this biosensor was discussed.

Layer-by-layer stacked graphene nanocoatings by Marangoni self-assembly for corrosion protection of stainless steel

Graphene nanosheets are widely used in anti-corrosion polymeric coating as filler,owing to the excellent electrochemical inertness and barrier property.However,as the arrangement of graphene nanosheets is difficult to form a perfect layered structure,polymeric coating with graphene nanosheets usually needs micron-scale thickness to ensure the enhancement of corrosion protection.In this work,layer-by-layer stacked graphene nanocoatings were fabricated on stainless steel by self-assembly based on Marangoni effect.The anti-corrosion property of graphene coatings were studied through Tafel polarization curves,electrochemical impedance spectroscopy and accelerated corrosion test with extra applied voltage.The self corrosion current density of optimized three-layered graphene coated sample was one quarter of that of bare stainless steel.And the self corrosion potential of optimized sample is increased to-0.045 V.According to the results,graphene nanocoatings composed of layered nanosheets exhibits good anticorrosion property.Besides,the self-assembly method provide a promising approach to make layeredstructure coating for other researches about 2 D material nanosheets.

Layer-by-layer Multilayer Films Self-assembled from a Rare-earth-containing Poly-oxometalate Na_9[Eu(W_5O_(18))_2] and Poly(allylamine hydrochloride) and Their Photoluminescent Properties

Ultrathin multilayer films of a rare-earth-containing polyoxo-metalateNa_9[Eu(W_5O_(18))_] (EW) and poly ( allylamine hydrochloride) (PAH) have been prepared bylayer-by-layer self-assembly from dilute aqueous solutions. The fabrication process of the EW/PAHmultilayer films was followed by UV-vis spec-troscopy and ellipsometry, which show that thedeposition process is linear and highly reproducible from layer to layer. An average EW/PAH bilayerthickness of ca. 2.1 nm was determined by ellipsometry. In addition, the scanning electronmicroscopy (SEM) image of the EW/PAH film indicates that the film surface is relatively uniform andsmooth. The photolumi-nescent properties of these films were also investigated by fluorescencespectroscopy.

有机超薄膜及其在摩擦学中的应用

本文介绍了分子排列高度有序的有机超薄膜的基本概念，简要地描述了ＬＢ膜，自组装（ＳＡＭ）膜和蒸发沉积膜的制备方法及性能特点，并综述了有机薄膜在摩擦学中的应用研究现状，建议对摩擦过程中有机薄膜的稳定性，界面结合强度，摩擦重构和表面迁移性等问题开展深人的研究。

PREPARATION OF POLYELECTROLYTE MULTILAYER COATED MICROBUBBLES FOR USE AS ULTRASOUND CONTRAST AGENT

Objeelive To prepare and characterize polyelectrolyte multilayer film coated microbubbles for use as ultrasound contrast agent （UCA） and evaluate its effects in ultrasonic imaging on normal rabbit＇s fiver parenchyma. Methods Perfluorocarbon （PFC）-containing microbubbles （ST68-PFC） were prepared by sonication based on suffactant （ Span 60 and Tween 80）. Subsequently, the resulting ST68-PFC microbubbles were coated using oppositely charged polyelectrolytes by microbubble-templated layer-by-layer self-assembly technique via electrostatic interaction. The enhancement effects in ultrasonic imaging on normal rabbit＇s liver parenchyma were assessed. Results The obtained microbubbles exhibited a narrow size distribution. The polyelectrolytes were successfully assembled onto the surface of ST68-PFC microbubbles. In vivo experiment showed that polyelectrolyte multilayer film coated UCA effectively enhanced the imaging of rabbit＇s liver parenchyma. Conclusions The novel microbubbles UCA coated with polyelectrolyte multilayer, when enabled more function, has no obvious difference in enhancement effects compared with the pre-modified microbubbles. The polymers with chemically active groups （ such as amino group and carboxyl group） can be used as the outermost layer for attachment of targeting ligands onto microbubbles, allowing selective targeting of the microbubbles to combine with desired sites.

Study of enzyme biosensor based on carbon nanotubes modified electrode for detection of pesticides residue

The paper describes a controllable layer-by-layer （LBL） self-assembly modification technique of multi-walled carbon nanotubes （MWNTs） and poly（diallyldimethylammonium chloride） （PDDA） towards glassy carbon electrode （GCE）, Acetylcholinesterase （ACHE） was immobilized directly to the modified GCE by LBL self-assembly method, the activity value of AChE was detected by using i-t technique based on the modified Ellman method. Then the composition of carbaryl were detected by the enzyme electrode with 0.01U activity value and the detection limit of carbaryl is 10^- 12 g L ^-1 so the enzyme biosensor showed good properties for pesticides residue detection.

Delivery of surface-mediated non-viral gene nanoparticles from ultrathin layer-by-layer multilayers

An efficient and safe gene delivery system remains a challenge in the development of gene therapy.Polycation-based gene nanoparticles are a typical non-viral gene delivery system,which are able to transfect cells in vitro and in vivo.This paper reported a facile method for constructing biodegradable multilayers via layer-by-layer self-assembly,in which the polycation-based gene nanoparticles were loaded.Through this surface-mediated delivery system,adherent cells on the multilayer could be transfected in situ.Gene nanoparticles-loaded multilayers transfect cells with higher efficiency than naked DNA-loaded multilayers because of the complex configuration of the DNA.DNA nanoparticles/PGA multilayers constructed on the scaffold surface could also realize in situ transfection on the adherent cells.The well-structured,easy-processed multilayers may provide a novel approach to precisely controlled delivery of gene nanoparticles,which may have potential applications for gene therapy in tissue engineering and medical implants.

Density-controllable nonvolatile memory devices having metal nanocrystals through chemical synthesis and assembled by spin-coating technique

A novel two-step method is employed, for the first time, to fabricatc nonvolatile memory devices that have metal nanoerystals. First, size-averaged Au nanocrystals are synthesized chemically; second, they are assembled into memory devices by a spin-coating technique at room temperature. This attractive approach makes it possible to tailor the diameter and control the density of nanocrystals individually. In addition, processes at room temperature prevent Au diffusion, which is a main concem for the application of metal nanocrystal-based memory. The experimental results, both the morphology characterization and the electrical measurements, reveal that there is an optimum density of nanocrystal monolayer to balance between long data retention and a large hysteresis memory window. At the same time, density-controllable devices could also feed the preferential emphasis on either memory window or retention time. All these facts confirm the advantages and novelty of our two-step method.

Assembly of layer-by-layer films of superoxide dismutase and gold nanorods:A third generation biosensor for superoxide anion

Based on the layer-by-layer self-assembly of positively charged cetyltrimethylammonium bromide （CTAB） wrapped gold na- norods （AuNRs） and negatively charged superoxide dismutase （SOD） from their aqueous solutions on cysteine modified gold electrode （Cys/Au）, a third generation electrochemical biosensor （（SOD/AuNRs）2/Cys/Au） for superoxide anion （02＂-） was developed. The two layers assembly of SOD/AuNRs can significantly enhance the direct electron transfer between SOD and the electrode. The functional enzymatic activities of the SOD offer an electrochemical approach to the determination of 02＂-. In the reductive regions, the proposed sensor exhibits excellent analytical performances, such as wide linear range （200 nM to 0.2 mM O2-）, low detection limit （100 nM O2-）, high sensitivity （22.11 nA cm-2 μM-1）, short response time （less than 5 s）, good stability and reproducibility, while no obvious interferences are caused by commonly met interfering species including hydrogen peroxide （H202）, uric acid （UA） and ascorbic acid （AA）.

Smoothing of Fast Assembled Layer-by-layer Films by Adjusting Assembly Conditions

To prepare layer-by-layer（LbL） multilayers in time-efficient manners by the dipping method is highly ap- pealing. However, the fast LbL assembly produces multilayers with high surface roughness. In our attempt to smooth the surface morphologies of LbL multilayers obtained by fast assembly（5 s dipping）, we studied the influence of the assembly conditions on the surface morphologies. The study shows that by properly adjusting the assembly condi- tions, such as washing duration, water annealing period, and drying with nitrogen flow, LbL multilayers with en- hanced surface smoothness could be obtained through fast LbL assembly.

LIGHT-SCATTERING STUDY OF POLYELECTROLYTE HOLLOW CAPSULES

Silver halide (AgX) microcrystal was used as template to synthesize hollow polyelectrolyte capsules. These hollow capsules were characterized by laser light scattering (LLS) used to measure the size of the capsules in solution. The ratio of hydrodynamic radius (R h ) from dynamic LLS to the radius of gyration (Rg) from static LLS is almost unity, revealing that the entities are hollow in solution. The results suggest that the LLS method can be regarded as a good complement to the confocal laser scanning microscopy (CLSM) method for the characterization of small hollow capsules, and it possesses the advantage of not needing fluorescence labeling.

Self-assembled supramolecular immunomagnetic nanoparticles throughπ-πstacking strategy for the enrichment of circulating tumor cells

Owing to their high-specific binding toward targets as well as fast and convenient separation operations,immunomagnetic beads(IMBs)are widely used in the capture and detection of circulating tumor cells(CTCs).To construct the IMBs,surface modifications are generally performed to functionalize the magnetic cores(e.g.Fe_(3)O_(4)nanoparticles),and the employed surface modification strategies normally influence the structure and functions of the prepared IMBs in return.Different from the existing work,we proposed the use of supramolecular layer-by-layer(LBL)self-assembly strategy to construct the IMBs.In general,owing to theπ-πstacking interactions,the polydopamine,graphene oxide and‘molecular glue’γ-oxo-1-pyrenebutyric acid were self-assembled on Fe_(3)O_(4)nanoparticles sequentially,thereby accomplishing the integration of different functional components onto magnetic cores to prepare the self-assembled supramolecular immunomagnetic beads(ASIMBs).The ASIMBs showed high sensitivity,specificity and good biocompatibility to the model CTCs and low nonspecific adsorption to the negative cells(∼93%for MCF-7 cells and 17%for Jurkat cells).Meanwhile,ASIMBs possessed a remarkable potential to screen the rare MCF-7 cells out of large amounts of interfering Jurkat cells with the capture efficiency of 75-100%or out of mouse whole blood with the capture efficiency of 20-90%.The captured cells can be further recultured directly without any more treatment,which showed huge applicability of the ASIMBs for in vitro detection in clinical practices.

Ionic strength directed self-assembled polyelectrolyte single-bilayer membrane for low-pressure nanofiltration

Layer-by-layer assembly is a versatile technique for fabricating nanofiltration membranes,where multiple layers of polyelectrolytes are usually required to achieve reasonable separation performance.In this work,an ionic strength directed self-assembly procedure is described for the preparation of nanofiltration membranes consisting of only a single bilayer of poly(diallyldimethylammoniumchloride)and poly(sodium-4-styrenesulfoate).The influence of background ionic strength as well as membrane substrate properties on the formation of singlebilayer membranes are systematically evaluated.Such a simplified polyelectrolyte deposition procedure results in membranes having outstanding separation performance with permeating flux of 14.21.5 L∙m^(–2)∙h^(-1)∙bar^(–1) and Na2SO4 rejection of 97.1%0.8%under a low applied pressure of 1 bar.These results surpass the ones for conventional multilayered polyelectrolyte membranes.This work encompasses an investigation of ionic strength induced coiling of the polyelectrolyte chains and emphasizes the interplay between-polyelectrolyte chain configuration and substrate pore profile.It thus introduces a new concept on the control of membrane fabrication process toward high performance nanofiltration.

Hierarchical construction of CNT networks in aramid papers for high-efficiency microwave absorption

Carbon nanotubes(CNTs)incorporated polymeric composites have been extensively investigated for microwave absorption at target frequencies to meet the requirement of radar cross-section reduction.In this work,a strategy of efficient utilization of CNT in producing CNT incorporated aramid papers is demonstrated.The layer-by-layer self-assembly technique is used to coat the surfaces of meta-aramid fibers and fibrils with CNT,providing novel raw materials available for the large-scale papermaking.The hierarchical construction of CNT networks resolves the dilemma of increasing CNT content and avoiding the agglomeration of CNT,which is a frequent challenge for CNT incorporated polymeric composites.The composite paper,which contains abundant heterogeneous interfaces and long-range conductive networks,is capable of reaching a high permittivity and dielectric loss tangent at a low CNT loading,its complex permittivity is,so far,adjustable in the range of(1.20−j0.05)to(25.17−j18.89)at 10 GHz.Some papers with optimal matching thicknesses achieve a high-efficiency microwave absorption with a reflection loss lower than−10 dB in the entire X-band.