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.

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.

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.

Chitosan/Sodium Alginate Multilayer pH-Sensitive Films Based on Layer-by-Layer Self-Assembly for Intelligent Packaging

The abuse of plastic food packaging has brought about severe white pollution issues around the world.Developing green and sustainable biomass packaging is an effective way to solve this problem.Hence,a chitosan/sodium alginate-based multilayer film is fabricated via a layer-by-layer(LBL)self-assembly method.With the help of superior interaction between the layers,the multilayer film possesses excellent mechanical properties(with a tensile strength of 50 MPa).Besides,the film displays outstanding water retention property(blocking moisture of 97.56%)and ultraviolet blocking property.Anthocyanin is introduced into the film to detect the food quality since it is one natural plant polyphenol that is sensitive to the pH changes ranging from 1 to 13 in food when spoilage occurs.It is noted that the film is also bacteriostatic which is desired for food packaging.This study describes a simple technique for the development of advanced multifunctional and fully biodegradable food packaging film and it is a sustainable alternative to plastic packaging.

Layer by Layer 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.

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.

Mechanical properties and influence mechanism of confined concrete arches in high-stress tunnels

Deep underground projects(e.g., coal mines), are often faced with complex conditions such as high stress and extremely soft rock. The strength and rigidity of the traditional support system are often insufficient,which makes it difficult to meet the requirements of ground control under complex conditions. As a new support form with high strength and rigidity, the confined concrete arch plays an important role in controlling the rock deformation under complex conditions. The section shape of the tunnel has an important impact on the mechanical properties and design of the support system. However, studies on the mechanical properties and influence mechanism of the new confined concrete arch are rarely reported. To this end, the mechanical properties of traditional U-shaped steel and new confined concrete arches are compared and comparative tests on arches of circular and straight-leg semicircular shapes in deep tunnels are conducted. A large mechanical testing system for underground engineering support structure is developed. The mechanical properties and influence mechanism of confined concrete arches with different section shapes under different loading modes and cross-section parameters are systematically studied. Test results show that the bearing capacity of the confined concrete arch is 2.10 times that of the U-shaped steel arch, and the bearing capacity of the circular confined concrete arch is 2.27 times that of the straight-leg semicircular arch. Among the various influencing factors and their engineering parameters,the lateral stress coefficient has the greatest impact on the bearing capacity of the confined concrete arch,followed by the steel pipe wall thickness, steel strength, and core concrete strength. Subsequently, the economic index of bearing capacity and cost is established, and the optimization design method for the confined concrete arch is proposed. Finally, this design method is applied to a high-stress tunnel under complex conditions, and the deformation of the surrounding rock is effectively controlled.

Summary of the 10th Conference on Magnetically Confined Fusion Theory and Simulation(CMCFTS)

This paper gives a summary of the organization and the presentations delivered at the 10th Conference on Magnetically Confined Fusion Theory and Simulation(CMCFTS)held in Zhuhai,China,from 28th to 31st October 2022.The conference focused on the latest progress in the research of the magnetic confined fusion plasma theory and simulations,as well as the largescale numerical simulation techniques developed in recent years.This conference is held both online and offline,with about 110 domestic participants from 18 institutes participating in the live conference,and the statistical data from the live broadcast platform indicated that the online conference attracted over 20000 views per day.A summary of the conference is given,and the history of the CMCFTS is presented.A brief introduction to the poster section is also included in this paper.

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.

Liquid–liquid phase transition in confined liquid titanium

We report the layering and liquid–liquid phase transition of liquid titanium confined between two parallel panel walls.Abnormal changes in the volume and the potential energy confirm the existence of the liquid–liquid phase transition of the liquid titanium. The typical feature of the liquid–liquid phase transition is layering, which is induced by the slit size,pressure and temperature. We highlight the fact that the slit size and pressure will determine the number of layers. In addition, with the change in the slit size, the density of the confined liquid expresses a fluctuating law. The phase diagram of the layering transition is drawn to clearly understand the layering. This study provides insights into the liquid–liquid phase transition of liquid metal in a confined space.

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.

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.

Effects of confining pressure and pore pressure on multipole borehole acoustic field in fluid-saturated porous media

In-situ stress is a common stress in the exploration and development of oil reservoirs. Therefore, it is of great significance to study the propagation characteristics of borehole acoustic waves in fluid-saturated porous media under stress.Based on the acoustoelastic theory of fluid-saturated porous media, the field equation of fluid-saturated porous media under the conditions of confining pressure and pore pressure and the acoustic field formula of multipole source excitation in open hole are given. The influences of pore pressure and confining pressure on guided waves of multipole borehole acoustic field in fluid-saturated porous media are investigated. The numerical results show that the phase velocity and excitation intensity of guided wave increase significantly under the confining pressure. For a given confining pressure, the phase velocity of the guided wave decreases with pore pressure increasing. The excitation intensity of guided wave increases at low frequency and then decreases at high frequency with pore pressure increasing, except for that of Stoneley wave which decreases in the whole frequency range. These results will help us get an insight into the influences of confining pressure and pore pressure on the acoustic field of multipole source in borehole around fluid-saturated porous media.

Multiscale confinement nitridation in molybdenum carbide for efficient hydrogen production

The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inherent limitation of high density of empty valence band significantly reduces its catalytic reactivity by reason of strong hydrogen desorption resistance.Herein,we propose a multiscale confinement synthesis method to design the nitrogen-rich Mo_(2)C for modulating the band structure via decomposing the pre-coordination bonded polymer in a pressure-tight tube sealing system.Pre-bonded c/N-Mo in the coordination precursor constructs a micro-confinement space,enabling the homogeneous nitrogenization in-situ happened during the formation of Mo_(2)C.Simultaneously,the evolved gases from the precursor decomposition in tube sealing system establish a macro-confinement environment,preventing the lattice N escape and further endowing a continuous nitridation.Combining the multiscale confinement effects,the nitrogen-rich Mo2C displays as high as 25%N-Mo concentration in carbide lattice,leading to a satisfactory band structure.Accordingly,the constructed nitrogen-rich Mo_(2)C reveals an adorable catalytic activity for HER in both alkaline and acid solution.It is anticipated that the multiscale confinement synthesis strategy presents guideline for the rational design of electrocatalysts and beyond.

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.