Controlled Synthesis of Metal-Nanoparticles Decorated Block Copolymer Hybrid Particles via Emulsion Confined Self-assembly and Their Catalytic Applications

Comprehensive Summary Metal nanoparticles(NPs)decorated block copolymer(BCP)hybrid nanoparticles have attracted enormous attention for their actual value in catalysis,medical therapy,and bioengineering.The confined assembly of BCPs within evaporative emulsion droplet is verified as an effective method to provide polymeric scaffolds to load metal NPs.However,to date,it remains challenging to generate different types of metal NPs decorated BCP hybrid nanoparticles.Herein,we employed the emulsion confined self-assembly of poly(styrene-b-2-vinylpyridine)(PS-b-P2VP)and the followed seed-mediated growth of Au and palladium(Pd)NPs onto well-defined BCP particles to design a series of Au/Pd decorated BCP hybrid nanoparticles,which exhibited excellent catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol with the reductant of NaBH4.This work may inspire more researchers to investigate the selective decoration of different metal NPs onto the polymeric scaffolds,broadening the potential applications of the inorganic/organic hybrid nanoparticles.

Confined cobalt single-atom catalysts with strong electronic metal-support interactions based on a biomimetic self-assembly strategy

Designing high-performance and low-cost electrocatalysts for oxygen evolu-tion reaction(OER)is critical for the conversion and storage of sustainable energy technologies.Inspired by the biomineralization process,we utilized the phosphorylation sites of collagen molecules to combine with cobalt-based mononuclear precursors at the molecular level and built a three-dimensional(3D)porous hierarchical material through a bottom-up biomimetic self-assembly strategy to obtain single-atom catalysts confined on carbonized biomimetic self-assembled carriers(Co SACs/cBSC)after subsequent high-temperature annealing.In this strategy,the biomolecule improved the anchoring efficiency of the metal precursor through precise functional groups;meanwhile,the binding-then-assembling strategy also effectively suppressed the nonspecific adsorption of metal ions,ultimately preventing atomic agglomeration and achieving strong electronic metal-support interactions(EMSIs).Experimental characterizations confirm that binding forms between cobalt metal and carbonized self-assembled substrate(Co–O_(4)–P).Theoretical calculations disclose that the local environment changes significantly tailored the Co d-band center,and optimized the binding energy of oxygenated intermediates and the energy barrier of oxygen release.As a result,the obtained Co SACs/cBSC catalyst can achieve remarkable OER activity and 24 h durability in 1 M KOH(η10 at 288 mV;Tafel slope of 44 mV dec-1),better than other transition metal-based catalysts and commercial IrO_(2).Overall,we presented a self-assembly strategy to prepare transition metal SACs with strong EMSIs,providing a new avenue for the preparation of efficient catalysts with fine atomic structures.

Asymmetric Mesoporous Carbon Microparticles by 3D-Confined Self-Assembly of Block Copolymer/Homopolymer Blends and Selective Carbonization

Shape control of mesoporous carbon microparticles(MCMPs)is of critical importance;in particular,asymmetric shapes that can yield unique properties have attracted significant attention.However,the tailored synthesis of asymmetric MCMPs with ordered structures remains challenging.Herein,we report a facile route to prepare asymmetric MCMPs by dynamic neutral interface-guided 3D-confined self-assembly(3D-CSA)of block copolymer/homopolymer(BCP/hP)blends,followed by a self-templated selective direct carbonization strategy.BCP/h P Janus microparticles with ordered hierarchical mesostructures were prepared with emulsion solvent evaporation-induced 3D-CSA.The continuous phase of BCP domains was then crosslinked.Composite asymmetric MCMPs are successfully generated after selective carbonization of the crosslinked continuous phase.This method allows tuning the shape of MCMPs easily by varying the blending ratio of BCP/h P.The composite asymmetric MCMPs combine the advantages of asymmetric shape,ordered structure,high specific surface area,chemical inertness and thermal stability and could provide great possibilities for applications in catalysis,drug delivery,energy conversion and storage.

Self-assembly of lamella-forming diblock copolymers confined in nanochannels: Effect of confinement geometry

The self-assembly of symmetric diblock copolymers confined in the channels of variously shaped cross sections （regu- lar triangles, squares, and ellipses） is investigated using a simulated annealing technique. In the bulk, the studied symmetric diblock copolymers form a lamellar structure with period LL. The geometry and surface property of the confining channels have a large effect on the self-assembled structures and the orientation of the lamellar structures. Stacked perpendicular lamellae with period LL are observed for neutral surfaces regardless of the channel shape and size, but each lamella is in the shape of the corresponding channel＇s cross section. In the case of triangle-shaped cross sections, stacked parallel lamel- lae are the majority morphologies for weakly selective surfaces, while morphologies including a triangular-prism-shaped B-cylinder and multiple tridentate lamellae are obtained for strongly selective surfaces. In the cases of square-shaped and ellipse-shaped cross sections, concentric lamellae are the signature morphology for strongly selective surfaces, whereas for weakly selective surfaces, stacked parallel lamellae, and several types of folding lamellae are obtained in the case of square-shaped cross sections, and stacked parallel lamellae are the majority morphologies in the case of ellipse-shaped cross sections when the length of the minor axis is commensurate with the bulk lamellar period. The mean-square end- to-end distance, the average contact number between different species and the surface concentration of the A-monomers are computed to elucidate the mechanisms of the formation of the different morphologies. It is found that the resulting morphology is a consequence of competition among the chain stretching, interfacial energy, and surface energy. Our results suggest that the self-assembled morphology and the orientation of lamellae can be manipulated by the shape, the size, and the surface property of the confining channels.

Engineering the Morphologies of Block Copolymer Particles from the Confined Self-assembly within Emulsion Droplets

Block copolymers(BCPs)can automatically assemble into various regulated nanoparticles when they are confined within the emulsion droplet be-cause of the structural frustration of polymer chains and the soft template effect of the oil/water interface.In the past few years,great efforts have been made to regulate the morphologies of the resulting BCP particles.In this review article,various strategies for tuning oil/water interfacial prop-erties to engineer the as-formed BCP particles were summarized.Then,the comprehensive scenarios of the applications of the resulting BCP parti-cles were discussed.Finally,the future tendency and challenge of the self-assembly of BCPs confined in emulsion droplet were suggested.

70 Gbps PAM-4850-nm oxide-confined VCSEL without equalization and pre-emphasis

Directly modulated 850-nm vertical-cavity surface-emitting lasers(VCSELs)with the advantages of low cost,high modulation speed,good reliability,and low power consumption,are the key sources in the optical interconnects with multimode fibers for the supercomputers,data centers,and machine learning applications[1−3].Typically,non-return-tozero(NRZ)modulation format is used.

Strong shock propagation for the finite-source circular blast in a confined domain

The circular explosion wave produced by the abrupt discharge of gas from a high-temperature heat source serves as a crucial model for addressing explosion phenomena in compressible flow.The reflection of the primary shock and its propagation within a confined domain are studied both theoretically and numerically in this research.Under the assumption of strong shock,the scaling law governing propagation of the main shock is proposed.The dimensionless frequency of reflected shock propagation is associated with the confined distance.The numerical simulation for the circular explosion problem in a confined domain is performed for validation.Under the influence of confinement,the principal shock wave systematically undergoes reflection within the domain until it weakens,leading to the non-monotonic attenuation of kinetic energy in the explosion fireball and periodic oscillations of the fireball volume with a certain frequency.The simulation results indicate that the frequency of kinetic energy attenuation and the volume oscillation of the explosive fireball align consistently with the scaling law.

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.

Summary of the 11th Conference on Magnetic Confined Fusion Theory and Simulation

This conference report summarizes recent progress in plasma theory and simulation that was presented in contributed papers and discussions at the 11th Conference on Magnetic Confined Fusion Theory and Simulation(CMCFTS)held in Chengdu,China,27–30 October,2023.Progress in various fields has been achieved.For example,results on zonal flow generation by mode coupling,simulations of the key physics of divertor detachment,energetic particle effects on magnetohydrodynamic(MHD)modes in addition to ion-and electron-scale turbulence,physics of edge coherent modes and edge-localized modes,and the optimization of ion heating schemes as well as confinement scenarios using advanced integrated modeling are presented at the conference.In this conference,the scientific research groups were organized into six categories:(a)edge and divertor physics;(b)impurity,heating,and current drive;(c)energetic particle physics;(d)turbulent transport;(e)MHD instability;and(f)integrated modeling and code development.A summary of the highlighted progress in these working groups is presented.

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.

Influence of confined water on the limit support pressure of tunnel face in weakly water-rich strata

In the process of shield tunneling through soft soil layers,the presence of confined water ahead poses a significant threat to the stability of the tunnel face.Therefore,it is crucial to consider the impact of confined water on the limit support pressure of the tunnel face.This study employed the finite element method(FEM)to analyze the limit support pressure of shield tunnel face instability within a pressurized water-containing layer.Subsequently,a multiple linear regression approach was applied to derive a concise solution formula for the limit support pressure,incorporating various influencing factors.The analysis yields the following conclusions:1)The influence of confined water on the instability mode of the tunnel face in soft soil layers makes the displacement response of the strata not significant when the face is unstable;2)The limit support pressure increases approximately linearly with the pressure head,shield tunnel diameter,and tunnel burial depth.And inversely proportional to the thickness of the impermeable layer,soil cohesion and internal friction angle;3)Through an engineering case study analysis,the results align well with those obtained from traditional theoretical methods,thereby validating the rationality of the equations proposed in this paper.Furthermore,the proposed equations overcome the limitation of traditional theoretical approaches considering the influence of changes in impermeable layer thickness.It can accurately depict the dynamic variation in the required limit support pressure to maintain the stability of the tunnel face during shield tunneling,thus better reflecting engineering reality.

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.

Influence of Confined Concrete Models on the Seismic Response of RC Frames

In this study, the influence of confined concrete models on the response of reinforced concrete structures is investigatedat member and global system levels. The commonly encountered concrete models such as Modified Kent-Park, Saatçioğlu-Razvi, and Mander are considered. Two moment-resisting frames designed according to thepre-modern code are taken into consideration to reflect the example of an RC moment-resisting frame in thecurrent building stock. The building is in an earthquake-prone zone located on Z3 Soil Type. The inelasticresponse of the building frame is modelled by considering the plastic hinges formed on each beam and columnelement for different concrete classes and stirrups spacings. The models are subjected to non-linear static analyses.The differences between confined concrete models are comparatively investigated at both reinforced concretemember and system levels. Based on the results of the comparative analysis, it is revealed that the column behaviouris mostly influenced by the choice of model, due to axial loads and confinement effects, while the beams areless affected, and also it is observed that the differences exhibited in the moment-curvature response of columncross-sections do not significantly affect the overall behaviour of the global system. This highlights the critical roleof model selection relative to the concrete strength and stirrup spacing of the member.

Hydrophobic nanochannel self-assembled by amphipathic Janus particles confined in aqueous nano-space

Hydrophobic nanochannel plays a significant role in many physical, biological, and geological phenomena and ex- hibits impressive applications due to both its ubiquitous distribution and great ability to transport hydrophobic molecules, including various oils and gases. Based on theoretical modeling, we herein reveal that the amphipathic Janus nanoparticles have a large probability to self-assemble into uninterrupted hydrophobic nanochannels inside the aqueous nano-space, al- though there are large portions of the Janus nanoparticles to be hydrophilic. The key to this observation is the attractions between the hydrophobic regimes on neighboring amphipathic Janus particles through hydrophobic interaction in aqueous nano-space. More surprisingly, the permeation efficiency of hydrophobic molecules through the uninterrupted hydrophobic channel in Janus particles aggregate is even higher than that in the aggregate of hydrophobic particles. We note that the proposed amphipathic Janus particles can be transported to the appropriate positions by the water since the hydrophilic regimes still remain a strong particle-water interaction. We also note that most natural subsurface rocks are not completely hydrophobic or hydrophilic but have complex surfaces with inhomogeneous wetting property. Our work therefore provides a detailed molecular level understanding of the formation of underground strata as well as the new insight for constructing the artificial hydrophobic channels for various applications, such as the design of proppants to enhance the recovery of the unconventional oil/gas.

Ultimate flexural strength of normal section of FRP-confined RC circular columns

Numerical analysis is carried out to study the sectional properties of the fiber-reinforced polymer（FRP）-confined reinforced concrete（RC）circular columns. The axial load ratio, the FRP confinement ratio and the longitudinal reinforcement characteristic value are the three main parameters that can influence the neutral axis depth when concrete compression strain reaches an ultimate value. The formula for computing the central angle θ, corresponding to the compression zone, is established according to the data regression of the numerical analysis results. The numerical analysis results demonstrate that the concrete stress enhancement from transverse confinement and strain hardening of the longitudinal reinforcement can cause a much greater flexural strength than that defined by the design code. Based on the analytical studies and the test results of 36 large scale columns, the formula to calculate the flexural strength when columns fail under seismic loading is proposed, and the calculated results agree well with the test results. Finally, parametric studies are conducted on a typical column with different axial load ratios, longitudinal reinforcement characteristic value and FRP confinement ratios. Analysis of the results shows that the calculated flexural strength can be increased by 50% compared to that of unconfined columns defined by the code.

Characterization of carbon encapsulated Fe-nanoparticles prepared by confined arc plasma

Carbon encapsulated Fe nanoparticles were successfully prepared via confined arc plasma method. The composition, morphology, microstructure, specific surface area and particle size of the product were characterized via X-ray diffraction, transmission electron microscopy, high resolution transmission electron microscopy, energy dispersive X-ray spectrometry and Brunauer-Emmett-Teller N2 adsorption. The experiment results show that the carbon encapsulated Fe nanoparticles have clear core-shell structure. The core of the particles is body centered cubic Fe, and the shell is disorder carbons. The particles are in spherical or ellipsoidal shapes. The particle size of the nanocapsules ranges from 15 to 40 nm, with the average value of about 30 nm. The particle diameter of the core is 18 nm, the thickness of the shells is 6-8 nm, and the specific surface area is 24 m2/g.

New Hexagonal-rhombic Trilayer Ice Structure Confined between Hydrophobic Plates

We perform molecular dynamics simulations for water confined between two smooth hydrophobic walls and observe two crystalline structures with one being first reported. Both of these structures obey the ice rule. The novel ice phase is a flat hexagonal-rhombic trilayer ice, obtained under 1 GPa load at wall separation of 1.0 nm. In this structure, the water molecules in the two layers next to one of the walls （outer layers） and in the middle layer form hexagonal rings and rhombic rings, respectively. For a molecule in the outer layers, three of its four hydrogen bonds are in the same layer, and the other one hydrogen bond connects to the middle layer. For a molecule in the middle layer, only two of its four hydrogen-bonds are located in the same layer, and the other two connect to two different outer layers. Despite their different motifs, the area densities of the three layers are almost equal. The other structure is a flat hexagonal bilayer ice produced at wall separation of 0.8 nm under lateral pressure of 100 MPa, analogous to a system demonstrated by Koga et al [Phys. Rev. Lett. 79, 5262 （1997）]. Both first-order and continuous phase transitions take place in these simulations.