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Plasmonic nanovesicles show broad applications in areas such as cancer theranostics and drug delivery, but the preparation of nanovesicles from shaped nanoparticles remains challenging. This article describes the vesicular self-assembly of shaped nanoparticles, such as gold nanocubes grafted with amphiphilic block copolymers, in selective solvents. The nanocubes assembled within the vesicular membranes exhibit two distinctive packing modes, namely square-like and hexagonal packing, depending on the relative dimensions of the copolymer ligands and nanocubes. The corresponding optical properties of the plasmonic nanovesicles can be tuned by varying the length of the grafted copolymers and the size of the nanocubes. This work provides guidance for the fabrication of functional plasmonic vesicles for applications in catalysis, nanomedicines and optical devices.

Plasmonic surface lattice resonances (SLRs) supported by metallic nanoparticle (NP) arrays show diverse applications including nanolasers, sensors, photocatalysis, and nonlinear optics. However, to rationally fabricate high-quality plasmonic NP arrays with ultranarrow SLR line widths over large areas remains challenging. This article describes a general approach for the efficient fabrication of centimeter-scale inorganic NP arrays with precisely controlled NP size, composition, position, and lattice geometry. This method combines the processes of solvent-assisted soft lithography and in situ site-specific NP growth to reproducibly create many replicates of NP arrays without utilizing cleanroom and specialized equipment. For demonstration, we show that Au NP arrays exhibit ultranarrow SLRs with a line width of 4 nm and a quality factor of 218 toward the theoretical limit.

The strain characteristic and load transmission of mixed granular matter are different from those of homogeneous granular matter. Cyclic loading renders the mechanical behaviours of mixed granular matter more complex. To investigate the dynamic responses of gravel–sand mixtures, the discrete element method (DEM) was used to simulate the cyclic loading of gravel–sand mixtures with low fines contents. Macroscopically, the evolution of the axial strain and volumetric strain was investigated. Mesoscopically, the coordination number and contact force anisotropy were studied, and the evolution of strong and weak contacts was explored from two dimensions of loading time and local space. The simulation results show that increasing fines content can accelerate the development of the axial strain and volumetric strain but has little effect on the evolution of contact forces. Strong contacts tend to develop along the loading boundary, presenting the spatial difference. Weak contacts are firstly controlled by confining pressure and then controlled by axial stress, while strong contacts are mainly controlled by axial stress throughout the whole cyclic loading. Once compression failure occurs, the release of axial stress causes the reduction of strong contact proportion in all local regions. These findings are helpful to understand the dynamic responses of gravel–sand mixtures, especially in deformation behaviours and the Spatio-temporal evolution of contact forces.

Colloidal molecules (CMs) assembled from plasmonic nanoparticles are an emerging class of building blocks for creating plasmonic materials and devices, but precise yet reversible assembly of plasmonic CMs remains a challenge. This communication describes the reversible self-assembly of binary plasmonic nanoparticles capped with complementary copolymer ligands into different CMs via halogen bonding interactions at high yield. The coordination number of the CMs is governed by the number ratio of complementary halogen donor and acceptor groups on the interacting nanoparticles. The reversibility of the halogen bonds allows for controlling the repeated formation and disassociation of the plasmonic CMs and hence their optical properties. Furthermore, the CMs can be designed to further self-assemble into complex structures in selective solvents. The precisely engineered reversible nanostructures may find applications in sensing, catalysis, and smart optoelectronic devices.

The precise organization and orientation of anisotropic nanoparticles (NPs) on substrates over a large area is key to the application of NP assemblies in functional optical, electronic, and magnetic devices, but achieving such high-precision NP assembly still remains challenging. Here, we demonstrate the site-selective assembly of magnetic nanoellipsoids into large-area precisely positioned, orientationally controlled arrays via a combination of chemical patterning and magnetic manipulation. Magnetic ellipsoidal NPs are selectively positioned on predetermined chemical patterns with high fidelity through electrostatic interactions and aligned uniformly in line with an applied magnetic field. The position, orientation, and interparticle spacing of the ellipsoids can be precisely tuned by controlling the chemical patterns and magnetic field. This approach is simple to implement and can generate centimeter-scale arrays in high yield (up to 99%). The arrays exhibit collective magnetic responses that are dependent on the orientation of the ellipsoids. This work offers a tool for the fabrication of precisely engineered arrays of anisotropic NPs for applications such as metasurface and artificial spin ice.

The precise organization and orientation of plasmonic molecules on substrates is crucial to their application in functional devices but still remains a grand challenge. This article describes a bottom-up strategy to efficiently fabricate centimeter-scale superlattices of three-dimensionally oriented plasmonic dimers with highly tunable collective optical properties on substrates. The in-plane (i.e.

Volcanic cinder is a low-cost subgrade fill material in East Africa. A reluctance to use volcanic cinders for subgrades in the past has stemmed from the compactness is substandard and variable. Con...

Particle shape is an important factor that affects particle breakage and the mechanical behaviour of granular materials. This report explored the effect of angularity on the mechanical behaviour of breakable granular materials under triaxial tests. Various angular particles are generated using the quasi-spherical polyhedron method. The angularity α is defined as the mean exterior angle of touching faces in a particle model. A breakable particle is constructed as an aggregate composed of coplanar and glued Voronoi polyhedra. After being prepared under the densest conditions, all assemblies were subjected to triaxial compression until a critical state was reached. The macroscopic characteristics, including the shear strength and dilatancy response, were investigated. Then, particle breakage characteristics, including the extent of particle breakage, breakage pattern and correlation between the particle breakage and energy input, were evaluated. Furthermore, the microscopic characteristics, including the contact force and fabric anisotropy, were examined to probe the microscopic origins of the shear strength. As α increases, the peak shear strength increases first and then remains constant, while the critical shear strength generally increases. Assemblies with larger angularity tend to cause more serious particle breakage. The relative breakage is linearly correlated with α under shear loading. Compared with unbreakable particles, the peak shear strength and the critical volumetric strain decline, and the degree of decline linearly increases with increasing α.

In discrete element method (DEM) simulations, multi-sphere (MS) clumped and convex particles are two main particle models that are used to study the mechanical behaviours of granular materials. Of interest is the evaluation of the effect of multiple contacts between clumped particles or single contacts between convex particles on the mechanical behaviours of granular materials. In this context, a series of drained triaxial compression tests were conducted on convex true (CT) ellipsoids and MS ellipsoids with aspect ratios (ARs) ranging from 1.0–2.0. The microscale results indicate that at a given AR, the critical friction angle φc changes with the particle type, whereas the peak friction angle φp is nearly independent of the particle type. The anisotropic analysis provides underlying mechanisms of the shear strength evolution from two perspectives. First, the anisotropies of granular materials are essential to shear strength as the deviatoric (q)-to-effective mean (p′) stress ratio can be expressed as the sum of the anisotropies, i.e., q / p ′ ≈ 0 .4 a c + 0 .4 a n + 0 .6 a t , where ac, an and at are the normal contact anisotropy, normal contact force anisotropy and tangential contact force anisotropy, respectively. For all samples, ac and an underpin the shear strength and are influenced by the particle type. The similar φp displayed by the CT and MS ellipsoids does not translate to similar an and ac but similar ac+an for the two particle types. In addition, owing to their larger ac+an, the CT ellipsoids have a higher φc than the MS ellipsoids. Second, there is a satisfactory linear relationship between q / p ′ and ac within strong and non-sliding (sn) contacts a c sn (i.e., q/p′ = k a c sn ), where k is the fitting parameter. Accordingly, in the peak state, the subtle difference in shear strength is attributed to the greater a c sn in the CT ellipsoids than in the MS ellipsoids that is counteracted by the smaller k. However, in the critical state, the greater difference in a c sn between the CT and MS ellipsoids is partially offset by the smaller difference in k, causing a higher φc in the CT ellipsoids than in the MS ellipsoids.

The coarse particles in mixed soils can be cobbles or gravels, with the main difference being their roundness (an indicator describing particle shape characteristics at an intermediate scale). The influence of coarse particle shape (i.e., roundness) on the macroscopic and microscopic shear behaviours of cohesionless mixed soils with various fines contents (FCs) was investigated via the discrete element method in this study. The shapes of coarse particles were formed using the rotation-invariant spherical harmonic method proposed by previous investigators. An equation was proposed to predict the initial void ratios of samples in this study. A decrease in the roundness of coarse particles can increase the peak friction angle (FC ≤ 40%) and critical friction angle (FC ≤ 30%). As the roundness of coarse particles decreases, the peak dilatancy angle initially increases and then decreases (FC ≤ 20%). Furthermore, it was found that the roundness of coarse particles hardly affects the classification of cohesionless mixed soils, as determined by probing the percentage contributions of coarse–coarse, coarse–fine, and fine–fine contacts. When cohesionless mixed soils change from an underfilled structure to an interactive-underfilled structure at the critical state, the main forms of coarse–coarse contacts were discovered. Additionally, the force-fabric anisotropy mechanisms of the influences of the roundness and rolling resistance coefficient of coarse particles on the shear strengths of cohesionless mixed soils were found to be different.

Current interest in nanoparticle ensembles is motivated by their collective synergetic properties that are distinct from or better than those of individual nanoparticles and their bulk counterparts. These new advanced optical, electronic, magnetic, and catalytic properties can find applications in advanced nanomaterials and functional devices, if control is achieved over nanoparticle organization. Self-assembly offers a cost-efficient approach to produce ensembles of nanoparticles with well-defined and predictable structures. Nanoparticles functionalized with polymer molecules are promising building blocks for self-assembled nanostructures, due to the comparable dimensions of macromolecules and nanoparticles, the ability to synthesize polymers with various compositions, degrees of polymerization, and structures, and the ability of polymers to self-assemble in their own right. Moreover, polymer ligands can endow additional functionalities to nanoparticle assemblies, thus broadening the range of their applications.In this Account, we describe recent progress of our research groups in the development of new strategies for the self-assembly of nanoparticles tethered to macromolecules. At the beginning of our journey, we developed a new approach to patchy nanoparticles and their self-assembly. In a thermodynamically driven strategy, we used poor solvency conditions to induce homopolymer surface segregation in pinned micelles (patches). Patchy nanoparticles underwent self-assembly in a well-defined and controlled manner. Following this work, we overcame the limitation of low yield of the generation of patchy nanoparticles, by using block copolymer ligands. For block copolymer-capped nanoparticles, patch formation and self-assembly were "staged" by using distinct stimuli for each process. We expanded this work to the generation of patchy nanoparticles via dynamic exchange of block copolymer molecules between the nanoparticle surface and micelles in the solution. The scope of our work was further extended to a series of strategies that utilized the change in the configuration of block copolymer ligands during nanoparticle interactions. To this end, we explored the amphiphilicity of block copolymer-tethered nanoparticles and complementary interactions between reactive block copolymer ligands. Both approaches enabled exquisite control over directional and self-limiting self-assembly of complex hierarchical nanostructures. Next, we focused on the self-assembly of chiral nanostructures. To enable this goal, we attached chiral molecules to the surface of nanoparticles and organized these hybrid building blocks in ensembles with excellent chiroptical properties. In summary, our work enables surface engineering of polymer-capped nanoparticles and their controllable and predictable self-assembly. Future research in the field of nanoparticle self-assembly will include the development of effective characterization techniques, the synthesis of new functional polymers, and the development of environmentally responsive self-assembly of polymer-capped nanoparticles for the fabrication of nanomaterials with tailored functionalities.

Fabricating alginate fibers of high strength and toughness remains a great challenge because of the difficulty in improving both strength and toughness simultaneously. Herein, this work reported the hierarchical assembly of sodium alginate nano-helix and its potential application as a new reinforcing unit for alginate fibers. Contributed from the hierarchical structures of α-helix, β-sheet and tertiary helical alignment of nanofibrils, nano-helix improved the tensile strength of fibers with enhanced modulus, and prolonged elongation through unravelling the tertiary structures. Thus, the strength, elongation and toughness of alginate fibers were all enhanced by200 %, solving the tradeoff of strength and toughness. The mechanical performance of nano-helix engineered alginate fibers is superior to present alginate fibers and even some other biomass-based fibers. The assembly of nano-helix provides a feasible reinforcing strategy for polysaccharide based materials, achieving simultaneous improvement of strength and toughness.

Tumor fibrotic stroma forms complex barriers for therapeutic nanomedicine. Although nanoparticle vehicles are promising in overcoming biological barriers for drug delivery, fibrosis causes hypoxia, immunosuppression and limited immunocytes infiltration, and thus reduces antitumor efficacy of nanosystems. Herein, we report the development of cancer-associated fibroblasts (CAFs) responsive honeycomb-like nanoassemblies of carbon dots (CDs) to spatially program the delivery of multiple therapeutics for enhanced antitumor chemoimmunotherapy. Doxorubicin (DOX) and immunotherapeutic enhancer (Fe ions) are immobilized on the surface of CDs, whereas tumor microenvironment modifier (losartan, LOS) is encapsulated within the mesopores. The drugs-loaded nanoassemblies disassociate into individual CDs to release LOS to mitigate stroma and hypoxia in response to CAFs. The individual CDs carrying DOX and Fe ion efficiently penetrate deep into tumor to trigger intensified immune responses. Our in vitro and in vivo studies show that the nanoassemblies exhibit effective T cells infiltration, tumor growth inhibition and lung metastasis prevention, thereby providing a therapeutic platform for desmoplasia solid tumor.

Core/shell nanocrystals (NCs) integrate collaborative functionalization that would trigger advanced properties, such as high energy conversion efficiency, nonblinking emission, and spin-orbit coupling. Such prospects are highly correlated with the crystal structure of individual constituents. However, it is challenging to achieve novel phases in core/shell NCs, generally non-existing in bulk counterparts. Here, we present a fast and clean high-pressure approach to fabricate heterostructured core/shell MnSe/MnS NCs with a new phase that does not occur in their bulk counterparts. We determine the new phase as an orthorhombic MnP structure (B31 phase), with close-packed zigzagged arrangements within unit cells. Encapsulation of the solid MnSe nanorod with an MnS shell allows us to identify two separate phase transitions with recognizable diffraction patterns under high pressure, where the heterointerface effect regulates the wurtzite → rocksalt → B31 phase transitions of the core. First-principles calculations indicate that the B31 phase is thermodynamically stable under high pressure and can survive under ambient conditions owing to the synergistic effect of subtle enthalpy differences and large surface energy in nanomaterials. The ability to retain the new phase may open up the opportunity for future manipulation of electronic and magnetic properties in heterostructured nanostructures.

The fragments from crushed rock are initially very angular. The erosion process causes the fragment shape to evolve from angular to well rounded and affects the mechanical behaviour of granular materials. This report explores the effect of particle shape caused by erosion (Er) on macroscopic and microscopic behaviour under triaxial compression tests of granular materials via the discrete element method. A convex rigid block was employed to model particles with different erosion degrees. After being prepared in the densest condition, all particle assemblies were subjected to axial compression until a critical state was reached. The macroscopic characteristics, including the shear strength and dilatancy response, were investigated. As Er increased, the shear strength generally decreased, and the volumetric strain monotonically decreased. Then, the microscopic characteristics, including the coordination number, particle rotation, percentage of sliding contacts and contact force, were examined. Finally, analysis-related anisotropy coefficients of the entire contact network were evaluated to probe the microscopic origins of the peak and residual shear strength related to Er.

Multi-sphere clumps are commonly used to simulate non-spherical particles in discrete element method simulations. It is of interest whether the degree of local non-convexity λ affects the mechanical behaviour of granular materials with the same non-convexity η. A series of discrete-element-method biaxial shear tests are conducted on rough particle packings with η = 0.075 and different λ values (ranging from 0.134 to 0.770). The microscale results show that the contact type changes with an increase in λ. However, the critical strength is independent of λ. The evaluation of the contributions of different contact types to the critical shear strength and a detailed analysis of the anisotropies help clarify the microscopic mechanisms that result in the independence of the critical shear strength from λ.

Nanoparticle (NP) clusters are attractive for many applications, but controllable and regioselective assembly of clusters remains challenging. This communication reports a strategy to precisely assemble Ag nanoplates (NP-As) and Au nanospheres (NP-Bs) grafted with copolymer ligands into defined ABx clusters with controlled coordination number (x) and orientation of the NPs. The directional bonding of shaped NPs relies on the stoichiometric reaction of complementary reactive groups on copolymer ligands. The x value of NP clusters can be tuned from 1 to 4 by varying the number ratio of reactive groups on single NP-Bs to NP-As. The regioselective bonding of nanospheres to the edge or face of a central nanoplate is governed by the steric hindrance of copolymeric ligands on the nanoplate. The clusters exhibit distinctive plasmonic properties that are dependent on the bonding modes of NPs. This study paves a route to fabricating nanostructures with high precision and complexity for applications in plasmonics, catalysis, and sensing.