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.

Biomimetic“Nacre-like”Films Prepared via Layer-by-Layer Self-assembly of Mica,Polyvinyl Alcohol and Polymethyl Methacrylate

A film with“brick-and-mortar”structure was prepared by layer-by-layer(LBL)technique using polyvinyl alcohol(PVA)and polymethyl methacrylate(PMMA)as the flexible material or“mortar”and mica as the rigid material or“brick”.The film deposited on a glass slide after self-assembly cycles had a thickness of 3μm thick and an uneven,wavy surface.The film exhibits enhanced mechanical properties,i e,the hardness and indentation modulus values could reach 6.14 and 68.41 GPa,respectively.The hardness and elastic toughness were found to be depended on three factors,i e,the ratio of PVA to mica,the number of self-assembly cycles,and the pretreatment method of the mica suspension.The self-assembly process was driven by formation of the hydrogen bonds between the silanol groups of mica and the hydroxyl groups of PVA and carbonyl groups of PMMA.

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.

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.

Self-assembly of perovskite nanocrystals:From driving forces to applications

Self-assembly of metal halide perovskite nanocrystals(NCs)into superlattices can exhibit unique collective properties,which have significant application values in the display,detector,and solar cell field.This review discusses the driving forces behind the self-assembly process of perovskite NCs,and the commonly used self-assembly methods and different self-assembly structures are detailed.Subsequently,we summarize the collective optoelectronic properties and application areas of perovskite superlattice structures.Finally,we conclude with an outlook on the potential issues and future challenges in developing perovskite NCs.

Alcohol solvent effect on the self-assembly behaviors of lignin oligomers

The interactions between lignin oligomers and solvents determine the behaviors of lignin oligomers self-assembling into uniform lignin nanoparticles(LNPs).Herein,several alcohol solvents,which readily interact with the lignin oligomers,were adopted to study their effects during solvent shifting process for LNPs’production.The lignin oligomers with widely distributed molecular weight and abundant guaiacyl units were extracted from wood waste(mainly consists of pine wood),exerting outstanding self-assembly capability.Uniform and spherical LNPs were generated in H_(2)O-n-propanol cosolvent,whereas irregular LNPs were obtained in H_(2)O-methanol cosolvent.The unsatisfactory self-assembly performance of the lignin oligomers in H_(2)O-methanol cosolvent could be attributed to two aspects.On one hand,for the initial dissolution state,the distinguishing Hansen solubility parameter and polarity between methanol solvent and lignin oligomers resulted in the poor dispersion of the lignin oligomers.On the other hand,strong hydrogen bonds between methanol solvent and lignin oligomers during solvent shifting process,hindered the interactions among the lignin oligomers for self-assembly.

Hollow tubes constructed by carbon nanotubes self-assembly for CO_(2) capture

Carbon nanotubes(CNTs)have garnered significant attention in the fields of science,engineering,and medicine due to their numerous advantages.The initial step towards harnessing the potential of CNTs involves their macroscopic assembly.The present study employed a gentle and direct self-assembly technique,wherein controlled growth of CNT sheaths occurred on the metal wire’s surface,followed by etching of the remaining metal to obtain the hollow tubes composed of CNTs.By controlling the growth time and temperature,it is possible to alter the thickness of the CNTs sheath.After immersing in a solution containing 1 g/L of CNTs at 60℃for 24 h,the resulting CNTs layer achieved a thickness of up to 60μm.These hollow CNTs tubes with varying inner diameters were prepared through surface reinforcement using polymers and sacrificing metal wires,thereby exhibiting exceptional attributes such as robustness,flexibility,air tightness,and high adsorption capacity that effectively capture CO_(2) from the gas mixture.

A Non-parametric Gradient-Based Shape Optimization Approach for Solving Inverse Problems in Directed Self-Assemblyof Block Copolymers

We consider the inverse problem of finding guiding pattern shapes that result in desired self-assembly morphologies of block copolymer melts.Specifically,we model polymer selfassembly using the self-consistent field theory and derive,in a non-parametric setting,the sensitivity of the dissimilarity between the desired and the actual morphologies to arbitrary perturbations in the guiding pattern shape.The sensitivity is then used for the optimization of the confining pattern shapes such that the dissimilarity between the desired and the actual morphologies is minimized.The efficiency and robustness of the proposed gradient-based algorithm are demonstrated in a number of examples related to templating vertical interconnect accesses(VIA).

Layer by Layer Self-assembly Fiber-based Flexible Electrochemical Transistor

Poly(3,4-ethylenedioxyethiophene)-polystyrene sulfonic acid(PEDOT:PSS)/polyallyl dimethyl ammonium chloride modified reduced graphene oxide(PDDA-rGO)was layer by layer self-assembled on the cotton fiber.The surface morphology and electric property was investigated.The results confirmed the dense membrane of PEDOT:PSS and the lamellar structure of PDDA-rGO on the fibers.It has excellent electrical conductivity and mechanical properties.The fiber based electrochemical transistor(FECTs)prepared by the composite conductive fiber has a maximum output current of 8.7 mA,a transconductance peak of 10 mS,an on time of 1.37 s,an off time of 1.6 s and excellent switching stability.Most importantly,the devices by layer by layer self-assembly technology opens a path for the true integration of organic electronics with traditional textile technologies and materials,laying the foundation for their later widespread application.

Fabrication of PTFE/Nomex fabric/phenolic composites using a layer-by-layer self-assembly method for tribology field application

Fabric composites are widely applied as self-lubricating liner for radial spherical plain bearings owing to their excellent mechanical and tribological properties.Nevertheless,the poor interfacial strength between fibers and the resin matrix limits the performance of composites utilized as tribomaterials.To overcome this drawback,a mild layer-by-layer(LbL)self-assembly method was successfully used to construct hybrid fabric composites in the present work.In addition,this investigation addressed the effect of self-assembly cycles on the friction and wear behaviors of hybrid fabric composites under dry sliding condition.The results demonstrate that fabric composites with three or more self-assembly cycles have significantly enhanced surface activities and anti-wear performances.The results obtained in this work can provide guidance in the preparation of self-lubricating liner composites and highlight how the LbL self-assembly techniques could influence the properties of hybrid fabric composites.

Photocatalytic Nanocomposite Films Fabricated by Layer-by-Layer Self-assembly of TiO2 Nanoparticles and Lignosulfonates

Photocatalytic multilayer nanocomposite films composed of anatase TiO2 nanoparticles and lignosulfonates （LS） were fabricated on quartz slides by the layer-by-layer （LBL） self-assembly technique. X-ray photoelectron spectroscopy （XPS）, UV-vis spectroscopy and atomic force microscopy （AFM） were used to characterize the TiO2/LS multilayer nanocomposite films. Moreover, the photocatalytic properties （decomposition of methyl orange and bacteria） of multilayer nanocomposite films were investigated. XPS results indicated that the intensities of titanium and sulfur peaks increased with the LBL deposition process. A linear increase in absorbance at 280 nm was found by UV-Vis spectroscopy, suggesting that stepwise multilayer growth occurs on the substrate and this deposition process is highly reproducible. AFM images showed that quartz slide was completely covered by TiO2 nanoparticles when a 10-bilayer multilayer film was formed. The decomposition efficiency of methyl orange by TiOz/LS multilayer films under the same UV irradiation time increased linearly with the number of TiO2 layers, and the results of decomposition of bacteria under UV irradiation showed that TiO2/LS multilayer nanocomposite films exhibited excellent decomposition activity of bacteria （Escherichia coil）.

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.

Combination therapy to overcome ferroptosis resistance by biomimetic self-assembly nano-prodrug

Ferroptosis has emerged as a potent form of no-apoptotic cell death that offers a promising alternative to avoid the chemoresistance of apoptotic pathways and serves as a vulnerability of cancer.Herein,we have constructed a biomimetic self-assembly nano-prodrug system that enables the co-delivery of gefitinib(Gefi),ferrocene(Fc)and dihydroartemisinin(DHA)for the combined therapy of both ferroptosis and apoptosis.In the tumor microenvironment,this nano-prodrug is able to disassemble and trigger drug release under high levels of GSH.Interestingly,the released DHA can downregulate GPX4 level for the enhancement of intracellular ferroptosis from Fc,further executing tumor cell death with concomitant chemotherapy by Gefi.More importantly,this nano-prodrug provides highly homologous targeting ability by coating related cell membranes and exhibits outstanding inhibition of tumor growth and metastasis,as well as no noticeable side-effects during treatments.This simple small molecular self-assembled nano-prodrug provides a new reasonably designed modality for ferroptosis-combined chemotherapy.

Efficient conversion of lignin waste and self-assembly synthesis of C@MnCo_(2)O_(4)for asymmetric supercapacitors with high energy density

Lignin waste from the papermaking and biorefineries industry is a significantly promising renewable resource to prepare advanced carbon materials for diverse applications,such as the electrodes of supercapacitors;however,the improvement of their energy density remains a challenge.Here,we design a green and universal approach to prepare the composite electrode material,which is composed of lignin-phenolformaldehyde resins derived hierarchical porous carbon(LR-HPC)as conductive skeletons and the self-assembly manganese cobaltite(MnCo_(2)O_(4))nanocrystals as active sites.The synthesized C@MnCo_(2)O_(4)composite has an abundant porous structure and superior electronic conductivity,allowing for more charge/electron mass transfer channels and active sites for the redox reactions.The composite shows excellent electrochemical performance,such as the maximum specific capacitance of~726 mF cm^(-2)at 0.5 mV s^(-1),due to the significantly enhanced interactive interface between LR-HPC and MnCo_(2)O_(4)crystals.The assembled all-solid-state asymmetric supercapacitor,with the LR-HPC and C@MnCo_(2)O_(4)as cathode and anode,respectively,exhibits the highest volumetric energy density of 0.68 mWh cm^(-3)at a power density of 8.2 mW cm^(-3).Moreover,this device shows a high capacity retention ratio of~87.6%at 5 mA cm^(-2)after 5000 cycles.

Enhanced performance of a solar cell based on a layer-by-layer self-assembled luminescence down-shifting layer of core–shell quantum dots

In this paper, core–shell quantum dots(QDs) with two polar surface functional groups(ZnSe/ZnS–COOH QDs and ZnSe/ZnS–NH_2 QDs) are synthesized in an aqueous phase. Photoluminescence(PL) and absorption spectra clearly indicate luminescence down-shifting(LDS) properties. On the basis of QDs, surface functional group multilayer LDS films(MLDSs) are fabricated through an electrostatic layer-by-layer(LBL) self-assembly method. The PL intensity increases linearly with the number of bilayers, showing a regular and uniform film growth. When the M-LDS is placed on the surface of a Si-based solar cell as an optical conversion layer for the first time, the external quantum efficiency(EQE) and shortcircuit current density(Jsc) notably increases for the LDS process. The EQE response improves in a wavelength region extending from the UV region to the blue region, and its maximum increase reaches more than 15% between 350 nm and 460 nm.

Analysis on the formation principle and present situation of nano phase state of multi-component self-assembly of traditional Chinese compound medicine decoction

Traditional Chinese medicine decoction is a complex polydispersed phase system containing real solution,colloid solution,emulsion and suspension.The compound decoction of traditional Chinese medicine has complex components,including saponins,alkaloids,polysaccharides,flavonoids,amino acids and so on,which can be self-assembled to form gels,fibers,micelles,vesicles and so on.The self-assembled nano-phase not only neutralizes the single drug and reduces the toxicity and side effects,but also has its own pharmacological effects,which complement each other to achieve synergistic effect,so as to achieve the role of drug supplement,which is of research significance.The formation principle,solubilization and synergism principle and characterization method of multi-component self-assembly of traditional Chinese medicine compound decoction are discussed in this paper.

Factors resisting protein adsorption on hydrophilic/hydrophobic self-assembled monolayers terminated with hydrophilic hydroxyl groups

The hydroxyl-terminated self-assembled monolayer(OH-SAM),as a surface resistant to protein adsorption,exhibits substantial potential in applications such as ship navigation and medical implants,and the appropriate strategies for designing anti-fouling surfaces are crucial.Here,we employ molecular dynamics simulations and alchemical free energy calculations to systematically analyze the factors influencing resistance to protein adsorption on the SAMs terminated with single or double OH groups at three packing densities(∑=2.0 nm^(-2),4.5 nm^(-2),and 6.5 nm^(-2)),respectively.For the first time,we observed that the compactness and order of interfacial water enhance its physical barrier effect,subsequently enhancing the resistance of SAM to protein adsorption.Notably,the spatial hindrance effect of SAM leads to the embedding of protein into SAM,resulting in a lack of resistance of SAM towards protein.Furthermore,the number of hydroxyl groups per unit area of double OH-terminated SAM at ∑=6.5 nm^(-2) is approximately 2 to 3 times that of single OH-terminated SAM at ∑=6.5 nm^(-2) and 4.5 nm^(-2),consequently yielding a weaker resistance of double OH-terminated SAM towards protein.Meanwhile,due to the structure of SAM itself,i.e.,the formation of a nearly perfect ice-like hydrogen bond structure,the SAM exhibits the weakest resistance towards protein.This study will complement and improve the mechanism of OH-SAM resistance to protein adsorption,especially the traditional barrier effect of interfacial water.

Morphological Evolution of Self-Assembled Sodium Dodecyl Sulfate/Dodecyltrimethylammonium Bromide@Epoxy-β-Cyclodextrin Supramolecular Aggregates Induced by Temperature

Bio-based cyclodextrins(CDs)are a common research object in supramolecular chemistry.The special cavity structure of CDs can form supramolecular self-assemblies such as vesicles and microcrystals through weak interaction with guest molecules.The different forms of supramolecular self-assemblies can be transformed into each other under certain conditions.The regulation of supramolecular self-assembly is not only helpful to understand the self-assembly principle,but also beneficial to its application.In the present study,the self-assembly behavior of epoxy-β-cyclodextrin(EP-β-CD)and mixed anionic and cationic surfactant system(sodium dodecyl sulfate/dodecyltrimethylammonium bromide,SDS/DTAB)in aqueous solution was studied.Morphological and particle size characterization found that the SDS/DTAB@EP-β-CD complex,as the basic building unit,self-assembled into worm-like micelles at lower temperatures and vesicles at higher temperatures.Nuclear magnetic resonance(NMR)and Fourier transform infrared spectroscopy(FT-IR)analysis revealed that the driving force for the formation of vesicles and worm-like micelles was the hydrogen bonds between EP-β-CD molecules,while water molecules played an important role in promoting vesicle formation between SDS/DTAB@EP-β-CD units.Herein,the mechanism of the morphologic transformation of SDS/DTAB@EP-β-CD supramolecular aggregates induced by temperature was elucidated by exploring the self-assembly process,which may provide an excellent basis for the development of delivery carriers.

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.