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.

Electrostatic Interaction-directed Construction of Hierarchical Nanostructured Carbon Composite with Dual Electrical Conductive Networks for Zinc-ion Hybrid Capacitors with Ultrastability

Metal-organic framework(MOF)-derived carbon composites have been considered as the promising materials for energy storage.However,the construction of MOF-based composites with highly controllable mode via the liquid-liquid synthesis method has a great challenge because of the simultaneous heterogeneous nucleation on substrates and the self-nucleation of individual MOF nanocrystals in the liquid phase.Herein,we report a bidirectional electrostatic generated self-assembly strategy to achieve the precisely controlled coatings of single-layer nanoscale MOFs on a range of substrates,including carbon nanotubes(CNTs),graphene oxide(GO),MXene,layered double hydroxides(LDHs),MOFs,and SiO_(2).The obtained MOF-based nanostructured carbon composite exhibits the hierarchical porosity(V_(meso)/V_(micro)∶2.4),ultrahigh N content of 12.4 at.%and"dual electrical conductive networks."The assembled aqueous zinc-ion hybrid capacitor(ZIC)with the prepared nanocarbon composite as a cathode shows a high specific capacitance of 236 F g^(-1)at 0.5 A g^(-1),great rate performance of 98 F g^(-1)at 100 A g^(-1),and especially,an ultralong cycling stability up to 230000 cycles with the capacitance retention of 90.1%.This work develops a repeatable and general method for the controlled construction of MOF coatings on various functional substrates and further fabricates carbon composites for ZICs with ultrastability.

Preparation of Bentonite Supported Nano Titanium Dioxide Photocatalysts by Electrostatic Self-assembly Method

Electrostatic self-assembly method （ESAM） was used to prepare bentonite supported-nano titanium dioxide photocatalysts. The materials were characterized by X-ray diffraction （XRD）, fourier transform infrared spectroscopy （FT-IR） and scanning electron microscopy （SEM）. Methyl orange was used to estimate the photocatalytic activity of the materials. The effects of the calcination temperature and silane dosage on the photocatalytic activity of the samples were investigated. The experimental results show that the bentonite facilitates the formation of anatase and restrains the transformation of anatase to rutile. Part of nano-size TiO2 particles insert into the galleries of bentonite. The photocatalysts exhibit a synergistic effect of adsorption and photocatalysis on methyl orange. Photocatalysts prepared by ESAM method exhibit higher photocatalytic activity and better recycle ability than those of the traditional method.

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.

Fabrication of TiO_2 Thin Film by Electrostatic Self-Assembly Method on Optical Fiber

Anionic surfactant sodium lauryl sulfate(SDS), cationic surfactant palmityl trimethyl ammonium chloride(CTAC) and TiO_2 were used to prepare multilayer films on quartz optic fibers by the electrostatic self-assembly (ESA) method. The whole self-assemble process, the function of surfactant and the effect of TiO_2 slurry′s concentration to the self-assemble were discussed. The isoelectric point of TiO_2 slurry measured by experiment is 6.8. The results show that whatever the concentration of the TiO_2 dispersion, a flat and compact adsorbed monolayer on the optic fiber can be built in a stable dispersion at lower pH. There is a adsorbed equilibrium on the substrate (fiber)/solution interface when enough time of incubation is given. A rough and loosen adsorbed layer is formed on the fiber surface by immersed the substrate in a high pH dispersion (pH>10) because the presence of hydroxyl on particle surface. Film thickness can be controlled by controlling the number of layers in the film.

Gold Nanoparticulate Thin Films Fabricated by the Electrostatic Self-Assembly Process

Gold colloids were prepared by citrate-induced reduction of hydrogen tetrachloroaurale, and gold nanoparticles were electrostatically self-assembled with poly( diallyldimethylammonium chloride) into multi-layer thin films on si/icon and quartz substrates. The paniculate thin films were characterized by UV-vis spea-troscopy, surface, enhanced Raman scattering, atomic force microscopy and resistivity measurements. Due to the interparticle coupling between individual gold particles, an obvious collective particle plasmon resonance was ob-served on UV-vis spectra , and the particulate thin films exhibited a strong SERS effect. For multilayer thin films with a high particle coverage on substrates , resistivity of the order of 10-4 Ω·cm was yielded.

Method of Spectrophotometric Microanalysis Based on HRP/PET Self-assembly Film

Horseradish peroxidase monolayer was assembled on the surface of PET-CO2 substrate. The reaction kinetics of HRP/PET film and H2O2 in micro reactor was studied using improved spectrophotometer. The relative activity of self-assembly HRP/PET film still remains above 80% after storing for 150 days at 4℃. When applied to determination of H2O2 in sample, the recoveries of H2O2 are 96.5%~101.1%.

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.

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.

Recent progress in polymerization-induced self-assembly:From the perspective of driving forces

Polymerization-induced self-assembly(PISA)enables the simultaneous growth and self-assembly of block copolymers in one pot and therefore has developed into a high-efficiency platform for the preparation of polymer assemblies with high concentration and excellent reproducibility.During the past decade,the driving force of PISA has extended from hydrophobic interactions to other supramolecular interactions,which has greatly innovated the design of PISA,enlarged the monomer/solvent toolkit,and endowed the polymer assemblies with intrinsic dynamicity and responsiveness.To unravel the important role of driving forces in the formation of polymeric assemblies,this review summarized the recent development of PISA from the perspective of driving forces.Motivated by this goal,here we give a brief overview of the basic principles of PISA and systematically discuss the various driving forces in the PISA system,including hydrophobic interactions,hydrogen bonding,electrostatic interactions,andπ-πinteractions.Furthermore,PISA systems that are driven and regulated by crystallization or liquid crystalline ordering were also highlighted.

Hybrid HMX multi-level assembled under the constraint of 2D materials with efficiently reduced sensitivity and optimized thermal stability

The interfacial interaction between HMX molecules and coating materials is the key to the safety performance of explosives and has received extensive attention.However,screening suitable coating agents to enhance the interfacial effect to obtain high-energy and low-sensitivity explosives has long been a major challenge.In this work,HMX-PEI/rGO/g-C_(3)N_(4)(HPrGC)composites were innovatively prepared by a multi-level coating strategy of two-dimensional graphite rGO and g-C_(3)N_(4).The g-C_(3)N_(4) used for desensitization has a richπ-conjugated system and shows outstanding ability in reducing friction sensitivity.The hierarchical structure of HPrGC formed by electrostatic self-assembly andπ-πstacking can effectively dissipate energy accumulation under heat and mechanical stimulation through structural evolution,thus exhibiting a prominent synergistic desensitization effect on HMX.The results show that rGO/gC_(3)N_(4) coating has no effect on the crystal structure and chemical structure of HMX.More importantly,the perfect combination of g-C_(3)N_(4) and rGO endows HPrGC with enhanced thermal stability and ideal mechanical sensitivity(IS:21 J,FS:216 N).Obviously,the new fabrication of HPrGC enriches the variety of desensitizer materials and helps to deepen the understanding of the interaction between explosives and coatings.

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.

Scalable construction of SiO/wrinkled MXene composite by a simple electrostatic self-assembly strategy as anode for high-energy lithium-ion batteries

Available onlineSilicon monoxide(SiO)is a promising anode material fo r lithium-ion batteries(LIBs)due to its high theoretical specific capacity(~2400 mAh/g),low working potential(<0.5 V vs.Li^+/Li),low cost,easy synthesis,nontoxicity,abundant natural source and smaller volume expansion than Si.However,low intrinsic electrical conductivity,low initial Coulombic efficiency(ICE)and inevitable volume expansion(~200%)impede its practical application.Here we fabricate SiO/wrinkled MXene composite(SiO-WM)by an electrostatic self-assembly method.Importantly,this method is simple,scalable and taking into account all the issues of SiO.As a result,the SiO-WM exhibits imp roved rate capability,cycling performance and ICE than bare SiO.

Enhanced thermal conductivity and dielectric properties in electrostatic self-assembly 3D pBN@nCNTs fillers loaded in epoxy resin composites

High-performance epoxy(EP)composites with excellent thermal conductivity and dielectric properties have attracted increasing attention for effective thermal management.In this work,three-dimensional(3D)structural functional fillers were prepared by an electrostatic self-assembly approach.The negatively charged carbon nanotubes(nCNTs)prepared by carboxylation on the surface of CNTs were attached to the positively charged boron nitride(pBN)to form the 3D pBN@nCNTs functional fillers.The morphological characterizations of the formed 3D pBN@nCNTs fillers and epoxy composites were established,illustrating that nCNTs were linearly overlapped between the BN sheets,thus forming a 3D heat conduction network in the epoxy matrix.The synergistic effect of pBN with nCNTs on the enhancement of thermal conductivity and dielectric properties of composites was systematically studied.The experimental results demonstrated that the thermal conductivity of pBN@nCNTs/EP composites could reach 1.986 W m1K1 with the loading of 50 wt%fillers at 10:1 mass ratio of pBN:nCNTs,which is 464%and 124%higher than that of pure EP and BN/EP,respectively.Simultaneously,the dielectric permittivity was successfully increased to 15.14.Moreover,the thermal stability of the composites was synchronously enhanced.This study provides a facile path to fabricate thermosetting polymer composites with high thermal conductivity and dielectric properties.

Coaxial-printed small-diameter polyelectrolyte-based tubes with an electrostatic self-assembly of heparin and YIGSR peptide for antithrombogenicity and endothelialization

Low patency ratio of small-diameter vascular grafts remains a major challenge due to the occurrence of thrombosis formation and intimal hyperplasia after transplantation.Although developing the functional coating with release of bioactive molecules on the surface of small-diameter vascular grafts are reported as an effective strategy to improve their patency ratios,it is still difficult for current functional coatings cooperating with spatiotemporal control of bioactive molecules release to mimic the sequential requirements for antithrombogenicity and endothelialization.Herein,on basis of 3D-printed polyelectrolyte-based vascular grafts,a biologically inspired release system with sequential release in spatiotemporal coordination of dual molecules through an electrostatic self-assembly was first described.A series of tubes with tunable diameters were initially fabricated by a coaxial extrusion printing method with customized nozzles,in which a polyelectrolyte ink containing of ε-polylysine and sodium alginate was used.Further,dual bioactive molecules,heparin with negative charges and Tyr-Ile-Gly-Ser-Arg(YIGSR)peptide with positive charges were layer-by-layer assembled onto the surface of these 3D-printed tubes.Due to the electrostatic interaction,the sequential release of heparin and YIGSR was demonstrated and could construct a dynamic microenvironment that was thus conducive to the antithrombogenicity and endothelialization.This study opens a new avenue to fabricate a small-diameter vascular graft with a biologically inspired release system based on electrostatic interaction,revealing a huge potential for development of small-diameter artificial vascular grafts with good patency.

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.

Self-assembly of supramolecular polymers in water from tetracationic and tetraanionic monomers in water through cooperative electrostatic attraction and aromatic stacking

The cooperative electrostatic attraction and π-π aromatic stacking interactions between tetrahedral tetrapyridinium TP and three tetraanionic tetraphenylethylene derivatives TPE-1～3 led to the formation of a new kind of supramolecular polymer networks in water, which have been confirmed by^1 H NMR,fluorescence, isothermal titration calorimetric(ITC) and dynamic light scattering(DLS) experiments. ITC studies show that the contributions of enthalpy and entropy were comparable, reflecting the importance of hydrophobicity in driving the intermolecular aromatic stacking. DLS experiments indicate that the linear supramolecular polymers formed by these tetratopic monomers further aggregated into networks of 10~2-nm size.

MXene-wrapped ZnCo_(2)S_(4)core-shell nanospheres via electrostatic self-assembly as positive electrode materials for asymmetric supercapacitors

Constructing electrode materials with large capacity and good conductivity is an effective approach to improve the capacitor performance of asymmetric supercapacitors(ASCs).In this paper,ZnCo_(2)S_(4)core-shell nanospheres are constructed by two-step hydrothermal method.In order to improve the chemical activity of ZnCo_(2)S_(4),ZnCo_(2)S_(4)is activated using cetyltrimethylammonium bromide(CTAB).Then,MXene nanosheets are fixed on the surface of ZnCo_(2)S_(4)by electrostatic selfassembly method to improve the specific surface area of ZnCo_(2)S_(4)and MXene-wrapped ZnCo_(2)S_(4)composite is prepared in this work.Owing to the synergy effect between MXene nanosheets and ZnCo_(2)S_(4)core-shell nanospheres,the as-prepared composite displays fast ion transfer rate and charge/discharge process.The capacity of the MXenewrapped ZnCo_(2)S_(4)composite can reach 1072 F·g^(-1),which is far larger than that of ZnCo_(2)S_(4)(407 F·g^(-1))at 1 A·g^(-1).An ASC device is assembled,which delivers 1.7 V potential window and superior cyclic stability(95.41%capacitance retention).Furthermore,energy density of this device is up to 30.46 Wh·kg^(-1)at a power density of850 W·kg^(-1).The above results demonstrate that MXenewrapped ZnCo_(2)S_(4)composite has great application prospects in electrochemical energy storage field.

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.