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.

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.

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.

Self-assembly and UV-curing Property of Polymerized Lyotropic Liquid Crystal Monomer of Sodium 3,4,5-tris（ll-acryloxyundecyloxy）benzoate

A polymerized lyotropic liquid crystal monomer of sodium 3,4,5-tris（11-acryloxyundecyloxy）- benzoate was synthesized by a convenient route starting from 3,4,5-trihydroxybenzoic acid via esterification followed by etherification, acylation and finally neutralization. The chemi- cal structure was confirmed by Fourier transform infrared （FT-IR） and 1H nuclear magnetic resonance spectral analysis. The self-organization behavior of the monomer with deionized water in methanol at room temperature was also demonstrated. The assemblies were char- acterized by polarized optical microscope and X-ray diffraction. The results show that a solution containing 80：20 of the monomer to water was found to be able to self-organize into Lamellar （La） phase and 92：8 with inverted hexagonal （H]I） phase, which was in ac- cordance with the theoretical calculation of critical packing parameter. It suggests that the concentration of the monomer was the key factor to influence assembly structure. Addi- tionally, the acrylate conversion with different photoinitiators and nanostructure retention after polymerization were investigated. The research shows that the acrylate conversion of the monomer with Darocur2959 could reach up to 78% when irradiated by 30 mW/cm2 UV light of 365 nm for 30 min characterized by Real-time FT-IR as well as the sol-gel method. Meanwhile, the La and HII phase nanostructures were both retained after polymerization.

Tailoring the Self-assembly of Melamine on Au（111） via Doping with Cu Atoms

The doping effect of Cu on the self-assembly film of melamine on an Au（111） surface has been investigated with scanning tunneling microscopy （STM）. The evaporated Cu adatoms occupy the positions underneath the amino groups and change the hydrogen bonding pat- tern between the melamine molecules. Accordingly, the self-assembly structure has changed stepwise from a well-defined honeycomb into a track-like and then a triangular structure depending on the amount of Cu adatoms. The interaction between Cu adatom and melamine is moderate thus the Cu adatoms can be released upon mild heating to around 100 ℃. These findings are different from previous observations of either the coordination assembly or the physically trapped metal adatoms.

Self-assembly of Binary Particles with Electrostatic and van der Waals Interactions

Nanoparticles with competitive interactions in solution can aggregate into complex structures. In this work, the synergistic self-assembles of binary particles with electrostatic and van der Waals interactions are studied with the particle Langevin dynamics simulation using a simple coarse-grained particle model. Various aggregations such as spherical, stacking-disk and tube structures are observed by varying the particles size and the interaction strength. The aggregation structures are explained with the packing theories of amphiphilic molecules in solution and dibolck copolymers in bulk. When the opposite ions are introduced into solution, the distribution of structures in the phase diagram appears an obvious offset. The simulation result is helpful to deeply understand the formation mechanism of complex nanostructures of multicomponent particles in solution.

Intermolecular Interactions in Self-Assembly Process of Sodium Dodecyl Sulfate by Vertically Polarized Raman Spectra

Molecular self-assembly is extremely important in many fields, but the characterization of their corresponding intermolecular interactions is still lacking. The C-H stretching Raman band can reflect the hydrophobic interactions during the self-assembly process of sodium dodecyl sulfate （SDS） in aqueous solutions. However, the Raman spectra in this region are seriously overlapped by the OH stretching band of water. In this work, vertically polarized Raman spectra were used to improve the detection sensitivity of spectra of C-H region for the first time. The spectral results showed that the first critical micelle concentration and the second critical micelle concentration of SDS in water were 8.5 and 69 mmol/L, respectively, which were consistent with the results given by surface tension measurements. Because of the high sensitivity of vertically polarized Raman spectra, the critical micelle concentration of SDS in a relatively high concentration of salt solution could be obtained in our experiment. The two critical concentrations of SDS in 100 mmol/L NaCl solution were recorded to be 1.8 and 16.5 mmol/L, respectively. Through comparing the spectra and surface tension of SDS in water and in NaCl solution, the self-assembly process in bulk phase and at interface were discussed. The interactions among salt ions, SDS and water molecules were also analyzed. These results demonstrated the vertically polarized Raman spectra could be employed to study the self-assembly process of SDS in water.

High-performance self-assembly MnCo2O4 nanosheets for asymmetric supercapacitors

In this study,MnCo2O4 nanosheets were proposed to be utilized as an electrode material for supercapacitors.A two-step hydrothermal method with post-annealing treatment was employed in preparation of the nanostructures.MnCo2O4 electrode delivered a high specific capacitance of 2000 F g^-1 at 0.5 A g^-1,remarkable high-rate capability of 1150 F g^-1 at 20 A g^-1,and an excellent cycling stability of 92.3%at 5 A g^-1 after 5000 cycles.It is found that a three-electrode supercapacitor based on MnCo2O4 exhibits a promising electrochemical performance,better than the other similar materials,benefited from the synergistic effects of MnCo2O4 nanosheets.In fact,the self-assembly of nanosheets structure with high specific surface area and mesoporous structure can potentially enhance the electrochemical performance of supercapacitors.

Self-assembly of α-6T Molecule on Ag（100） and Related STM Induced Luminescence

We have investigated the self-assembly and light emission properties of organic α- sexithiophene （α-6T） molecules on Ag（100） under different coverage by scanning tunneling microscopy （STM）. At very low coverage, the α-6T molecules form a unique enantiomer by grouping four molecules into a windmill supermolecular structure. As the coverage is increased,α-6T molecules tend to pack side by side into a denser stripe structure. Further increase of the coverage will lead to the layer-by-layer growth of molecules on Ag（100） with the lower-layer stripe pattern serving as a template. Molecular fluorescence for α-6T molecules on Ag（100） at a coverage of five monolayers has been detected by light excitations, which indicates a well decoupled electronic states for the top-layer α-6T molecules. However, the STM induced luminescent spectra for the same sample reveal only plasmonic-like emission. The absence of intramolecular fluorescence in this case suggests that the electronic decoupling is not a sufficient condition for generating photon emission from molecules. For intramolecular fluorescence to occur, the orientation of the dynamic dipole moment of molecules and the energy-level alignment at the molecule-metal interface are also important so that molecules can be effectively excited through efficient dipolar coupling with local plasmons and by injecting holes into the molecules.

The lipase monolayer film self-assembly on the negatively charged poly(ethylene terephthalate) substrate

The PET-CO2- film was prepared and the lipase was assembled on the surface of the PET-CO2- substrate The structure at the surface and activity of lipase/PET monolayer were studied by ATR-FTIR and AFM, and other methods.

Self-assembly to monolayer graphene film with high electrical conductivity

Monolayer chemically converted graphene （CCG） nanosheets can be homogeneously self-assembled onto silicon wafer modified by 3-aminopr- opyl triethoxysilane （APTES） to form very thin graphene film. The CCG film was characterized by FT-IR, XRD, SEM, TEM and AFM. Results show that CCG sheets formed monolayer film after assembled onto silicon wafer and there is a very tight chemical bond between sheets and wafer. Furthermore, the electrical measurements revealed that the monolayer graphene film has an excellent electrical conductivity.

Experimental Study on Self-assembly of KLD-12 Peptide Hydrogel and 3-D Culture of MSC Encapsulated within Hydrogel In Vitro

To synthesize KLD-12 peptide with sequence of AcN-KLDLKLDLKLDL-CNH2 and trigger its self-assembly in vitro, to encapsulate rabbit MSCs within peptide hydrogel for 3-D culture and to evaluate the feasibility of using it as injectable scaffold for tissue engineering of IVD. KLD-12 peptide was purified and tested with high performance liquid chromatography （HPLC） and mass spectroscopy （MS）. KLD-12 peptide solutions with concentrations of 5 g/L, 2.5 g/L and 1 g/L were triggered to self-assembly with 1 xPBS in vitro, and the self-assembled peptide hydrogel was morphologically observed. Atomic force microscope （AFM） was employed to examine the inner structure of self-assembled peptide hydrogel. Mesenchymal stem cells （MSCs） were encapsulated within peptide hydrogel for 3-D culture for 2 weeks. Calcein-AM/PI fluorescence staining was used to detect living and dead cells. Cell viability was observed to evaluate the bioactivity of MSCs in KLD-12 peptide hydrogel. The results of HPLC and MS showed that the relative molecular mass of KLD-12 peptide was 1467.83, with a purity quotient of 95.36%. KLD-12 peptide at 5 g/L could self-assemble to produce a hydrogel, which was structurally integral and homogeneous and was able to provide sufficient cohesion to retain the shape of hydrogel. AFM demonstrated that the self-assembly of KLD-12 peptide hydrogel was successful and the assembled material was composed of a kind of nano-fiber with a diameter of 3040 nm and a length of hundreds of nm. Calcein-AM/PI fluorescence staining revealed that MSCs in KLD-12 peptide hydrogel grew well. Cell activity detection exhibited that the A value increased over the culture time. It is concluded that KLD-12 peptide was synthesized successfully and was able to self-assemble to produce nano-fiber hydrogel in vitro. MSCs in KLD-12 peptide hydrogel grew well and proliferated with the culture time. KLD-12 peptide hydrogel can serve as an excellent injectable material of biological scaffolds in tissue engineering of IVD.

Self-assembly constructed by perylene bisimide derivatives bearing complementary hydrogen-bonding moieties

An intermediate compound 2, 4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was prepared by stepwise nucleophilic substitution on triazine ring by lauryl amine and subsequently 1-（2-aminoethyl）-piperazine. Then imidization of perylene-3, 4, 9, 10-tetracarboxylic acid dianhydride with 2,4-bis（laurylamino）-6-（1-（2-aminoethyl）-piperazine）-1, 3, 5-triazine was carried out to afford a novel perylene derivative bearing two melamine blocks （S2） and 1, 6, 7, 12-tetra（4-tert-butyl phenoxy）-perylene-3, 4, 9, 10-tetracarboxylic acid bisimide （S1. The hydrogen-bonding interactions between S1 and S2 were investigated by IH NMR spectrum, UV/Vis spectrum and fluorescence spectrum. The influences on the morphologies of S1·S2 aggregates were investigated. The results show that well-defined nanofibers with a diameter of about 100 nm can be obtained by self-assembly between S1 and S2 only in CH2Cl2 solution. Based on these results, guidelines for the molecular design and self-assembly of supramolecular polymer materials are presented.

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.

Drying-Mediated Self-Assembly of Graphene for Inkjet Printing of High-Rate Micro-supercapacitors

Scalable fabrication of high-rate micro-supercapacitors(MSCs)is highly desired for on-chip integration of energy storage components.By virtue of the special self-assembly behavior of 2D materials during drying thin films of their liquid dispersion,a new inkjet printing technique of passivated graphene micro-flakes is developed to directly print MSCs with 3D networked porous microstructure.The presence of macroscale through-thickness pores provides fast ion transport pathways and improves the rate capability of the devices even with solid-state electrolytes.During multiple-pass printing,the porous microstructure effectively absorbs the successively printed inks,allowing full printing of 3D structured MSCs comprising multiple vertically stacked cycles of current collectors,electrodes,and sold-state electrolytes.The all-solid-state heterogeneous 3D MSCs exhibit excellent vertical scalability and high areal energy density and power density,evidently outperforming the MSCs fabricated through general printing techniques.

A Facile Self-assembly Synthesis of Hexagonal ZnO Nanosheet Films and Their Photoelectrochemical Properties

Here, large-scale and uniform hexagonal zinc oxide(ZnO) nanosheet films were deposited onto indium tin oxide(ITO)-coated transparent conducting glass substrates via a facile galvanic displacement deposition process. Compared with other commonly used solution methods, this process avoids high temperature and electric power as well as supporting agents to make it simple and cost-effective. The as-fabricated ZnO nanosheet films have uniform hexagonal wurtzite structure. The photoelectrochemical(PEC) cell based on ZnO nanosheet film/ITO photoelectrode was also fabricated and its performance was improved by optimizing the solution concentration. A higher photocurrent density of*500 l A cm^(-2)under AM 1.5 G simulated illumination of 100 m W cm^(-2)with zero bias potential(vs. Ag/AgCl electrode) was obtained, which may ascribe to the increased surface-to-volume ratio of disordered Zn O nanosheet arrays. Our developed method may be used to deposit other oxide semiconductors, and the Zn O nanosheet film/ITO PEC cell can be used to design low-cost optoelectronic and photoelectrochemical devices.

Perylene diimide self-assembly: From electronic structural modulation to photocatalytic applications

As an emerging organic semiconductor,perylene diimide(PDI)self-assembly has attracted tremendous attention in the aspects of solar cells,sensors,fluorescence probes and n-transistors,etc.In term of photocatalysis,various photocatalysts based on PDI self-assembly exhibit some unique properties,such as intrinsicΠ-Πstacking structure,fast internal charge transfer,band-like electronic structure,flexible structural modifiability,well-defined morphological adjustability and excellent light absorption.This paper mainly presents recent progress on PDI self-assembly regarding how to regulate the electronic structure of PDI self-assembly.In addition,the photocatalytic applications of PDI self-assembly and its complexes were reviewed,such as environmental remedy,energy productions,organic synthesis and photodynamic/photothermal therapy,further highlighting related photocatalytic mechanisms.Finally,the review contents and some perspectives on photocatalytic research of PDI selfassembly were summarized,and some key scientific problems were put forward to direct related photocatalytic research in future.