Search

Plasmonic nanoparticles show highly sensitive optical properties upon local dielectric environment changes. Hybridisation of plasmonic nanoparticles with active polymeric materials can allow stimuli-responsive and multiplex sensing over conventional monotonic sensing capacity. Such heterogeneous adlayers around the plasmonic core component, however, are likely to perturb the local refractive index in the nanometre regime and lead to uncertainty in its intrinsic sensitivity. Herein we prepare a series of polystyrene-grafted polyhedral gold nanoparticles, cubic and concave cubic cores, with different edge lengths and polymer thicknesses with precise synthesis control. Their localised surface plasmon resonance (LSPR) spectral changes are monitored to understand the effect of core morphological details in the interplay of nanoscale polymeric shells. Quantitative image analysis of changes in the core and shell shape contours and finite-difference time-domain simulations of the corresponding LSPR spectra and electric field distributions reveal that the magnitude of the LSPR spectral shift is closely dependent on the core morphology, polymer shell thickness and electric field intensity. We also demonstrate that the polystyrene-grafted gold concave cube displays higher sensitivity for nanoscale refractive index change in the polymer shell than the polystyrene-grafted gold cube at different temperatures. Our systematic investigation will help design polymer-composited plasmonic nanosensors for desirable applications.

Magnetic activated carbons were prepared from waste macroporous resin. The carbon materials were characterized by nitrogen adsorption–desorption isotherms, scanning and transmission electron microscopy, X-ray diffraction, and vibrating sample magnetometer. The results showed that Fenton’s reagent has a significant impact on the pore size and porosity distributions, crystal structures, and magnetic properties of the magnetic activated carbons. Fenton’s reagent as impregnation agent not only provides strong oxidant for degradation organic contaminants and cleaning bolcked pore of waste macroporous resin simultaneously, but also makes it easier for the iron ion (Fe2+/Fe3+) to penetrate into the pore of waste macroporous resin. The carbon/iron composite MAC-2 exhibited better pore structure, magnetic properties, and adsorption performance than that of controlled carbon materials AC-1 and MAC-1. A superparamagnetic property revealed that MAC-2 can be manipulated by an external magnetic field. Recycling of waste macroporous resin and preparation of magnetic activated carbons are economically feasible and high-efficiency.

Fungi play key roles in various fields, including fermentation-based industries, medicine, and public health. The rapid and precise evaluation of fungal viability is critical for fungi-related fields. However, the methods currently applied have a series of limitations, such as time-consuming, laborious, and cumbersome. In this study, we designed and synthesized a water-dispersible fluorescent probe DPASI with typical aggregation-induced emission (AIE) characteristics for selectively lighting up dead Candida cells within 5 minutes. The rapid staining of the dead Candida cells could be ascribed to the efficient binding of DPASI with mitochondria, which was revealed by high-resolution fluorescence images taken by a structured illumination microscope (SIM) and colocalization images taken by a confocal laser scanning microscope (CLSM). Compared with traditional probes for the identification of dead Candida cells, the DPASI probe does not require tedious centrifugation and washing steps and has significant advantages in time-and-labor-saving. It thus provides a facile and promising tool for the rapid evaluation of antifungal susceptibility and screening of new antifungal drugs, which would greatly contribute to the fungal research.

Polyamide membranes serve as the active layer in thin-film composites used for nanofiltration and reverse osmosis, and their surface morphology strongly impacts separation performance. However, because these surface morphologies are highly irregular and heterogeneous, linking morphology parameters to membrane synthesis conditions quantitatively is challenging. Here we utilize a quantitative morphometry approach, together with the surface feature classification scheme reported in our earlier work, to image and analyse the surface morphologies of polyamide membranes synthesized with a range of monomer concentrations. From transmission electron micrographs of polyamide membranes, we measure projected morphology parameters of “dome” and “dimple” crumples in the membrane, including surface curvature, Feret dimensions, thickness, circularity, perimeter, and area. All features except circularity, which remains constant, exhibit opposite trends when charted against the concentrations of m-phenylene diamine or trimesoyl chloride monomers used in synthesis suggesting competing roles of these two monomers in shaping crumples. Surprisingly, mathematical fittings (linear, logarithmic, or exponential) relate these morphology parameters quantitatively to the monomer concentration ratio, despite the apparent irregularity of crumples. Our highly quantitative approach sheds insight into predictive design of membrane materials with desirable properties.

An emergent theme in mono- and multivalent ion batteries is to utilize nanoparticles (NPs) as electrode materials based on the phenomenological observations that their short ion diffusion length and large electrode–electrolyte interface can lead to improved ion insertion kinetics compared to their bulk counterparts. However, the understanding of how the NP size fundamentally relates to their electrochemical behaviors (e.g., charge storage mechanism, phase transition associated with ion insertion) is still primitive. Here, we employ spinel λ-MnO2 particles as a model cathode material, which have effective Mg2+ ion intercalation but with their size effect poorly understood to investigate their operating mechanism via a suite of electrochemical and structural characterizations. We prepare two differently sized samples, the small nanoscopic λ-MnO2 particles (81 ± 25 nm) and big micron-sized ones (814 ± 207 nm) via postsynthesis size-selection. Analysis of the charge storage mechanisms shows that the stored ch...

Recent studies on the effect of particle shapes have led to extensive applications of anisotropic colloids as complex materials building blocks. Although much research has been devoted to colloids of convex polyhedral shapes, branched colloids remain largely underexplored because of limited synthesis strategies. Here we achieved the preparation of metal-organic framework (MOF) colloids in a hexapod shape, not directly from growth but from postsynthesis etching of truncated rhombic dodecahedron (TRD) parent particles. To understand the branch development, we used in situ optical microscopy to track the local surface curvature evolution of the colloids as well as facet-dependent etching rate. The hexapods show unique properties, such as improved catalytic activity in a model Knoevenagel reaction likely due to enhanced access to active sites, and the assembly into open structures which can be easily integrated with a self-rolled-up nanomembrane structure. Both the postsynthesis etching and the hexapod colloids demonstrated here show a new route of engineering micrometer-sized building blocks with exotic shapes and intrinsic functionalities originated from the molecular structure of materials.

The increasing popularity of wearable electronic devices has led to the rapid development of flexible energy conversion systems. Flexible rechargeable zinc-air batteries (ZABs) with high theoretical energy densities demonstrate significant potential as next-generation flexible energy devices that can be applied in wearable electronic products. The design of highly efficient and air-stable cathodes that can electrochemically catalyze both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly desirable but challenging. Flexible carbon-based catalysts for ORR/OER catalysis can be broadly categorized into two types: (i) self-supporting catalysts based on the in situ modification of flexible substrates; (ii) non-self-supporting catalysts based on surface coatings of flexible substrates. Methods used to optimize the catalytic performance include doping with atoms and regulation of the electronic structure and coordination environment. This review summarizes the most recently proposed strategies for the synthesis of designer carbon-based electrocatalysts and the optimization of their electrocatalytic performances in air electrodes. And we significantly focus on the analysis of the inherent active sites and their electrocatalytic mechanisms when applied as flexible ZABs catalysts. The findings of this review can assist in the design of more valuable carbon-based air electrodes and their corresponding flexible ZABs for application in wearable electronic devices.

Numerous mechanisms have been studied for chemical reactions to provide quantitative predictions on how atoms spatially arrange into molecules. In nanoscale colloidal systems, however, less is known about the physical rules governing their spatial organization, i.e., self-assembly, into functional materials. Here, we monitor real-time self-assembly dynamics at the single nanoparticle level, which reveal marked similarities to foundational principles of polymerization. Specifically, using the prototypical system of gold triangular nanoprisms, we show that colloidal self-assembly is analogous to polymerization in three aspects: ensemble growth statistics following models for step-growth polymerization, with nanoparticles as linkable “monomers”; bond angles determined by directional internanoparticle interactions; and product topology determined by the valency of monomeric units. Liquid-phase transmission electron microscopy imaging and theoretical modeling elucidate the nanometer-scale mechanisms for these polymer-like phenomena in nanoparticle systems. The results establish a quantitative conceptual framework for self-assembly dynamics that can aid in designing future nanoparticle-based materials., Few models exist that describe the spontaneous organization of colloids into materials. Here, the authors combine liquid-phase TEM and single particle tracking to observe the dynamics of gold nanoprisms, finding that nanoscale self-assembly can be understood within the framework of atomic polymerization.

Highly anisometric nanoparticles have distinctive mechanical, electrical, and thermal properties and are therefore appealing candidates for use as self-assembly building blocks. Here, we demonstrate that ultra-anisometric nanoplates, which have a nanoscale thickness but a micrometer-scale edge length, offer many material design capabilities. In particular, we show that these nanoplates "copolymerize" in a predictable way with patchy spheres (Janus and triblock particles) into one- and two-dimensional structures with tunable architectural properties. We find that, on the pathway to these structures, nanoplates assemble into chains following the kinetics of molecular step-growth polymerization. In the same mechanistic framework, patchy spheres control the size distribution and morphology of assembled structures, by behaving as monofunctional chain stoppers or multifunctional branch points during nanoplate polymerization. In addition, both the lattice constant and the stiffness of the nanoplate assemblies can be manipulated after assembly. We see highly anisometric nanoplates as one representative of a broader class of dual length-scale nanoparticles, with the potential to enrich the library of structures and properties available to the nanoparticle self-assembly toolbox.

For decades, one of the overarching objectives of self-assembly science has been to define the rules necessary to build functional, artificial materials with rich and adaptive phase behavior from the bottom-up. To this end, the computational and experimental efforts of chemists, physicists, materials scientists, and biologists alike have built a body of knowledge that spans both disciplines and length scales. Indeed, today control of self-assembly is extending even to supramolecular and molecular levels, where crystal engineering and design of porous materials are becoming exciting areas of exploration. Nevertheless, at least at the nanoscale, there are many stones yet to be turned. While recent breakthroughs in nanoparticle (NP) synthesis have amassed a vast library of nanoscale building blocks, NP-NP interactions in situ remain poorly quantified, in large part due to technical and theoretical impediments. While increasingly many applications for self-assembled architectures are being demonstrated, it remains difficult to predict-and therefore engineer-the pathways by which these structures form. Here, we describe how investigations using liquid-phase transmission electron microscopy (TEM) have begun to play a role in pursuing some of these long-standing questions of fundamental and far-reaching interest. Liquid-phase TEM is unique in its ability to resolve the motions and trajectories of single NPs in solution, making it a powerful tool for studying the dynamics of NP self-assembly. Since 2012, liquid-phase TEM has been used to investigate the self-assembly behavior of a variety of simple, metallic NPs. In this Account, however, we focus on our work with anisotropic NPs, which we show to have very different self-assembly behavior, and especially on how analysis methods we and others in the field are developing can be used to convert their motions and trajectories revealed by liquid-phase TEM into quantitative understanding of underlying interactions and dynamics. In general, liquid-phase TEM studies may help bridge enduring gaps in the understanding and control of self-assembly at the nanoscale. For one, quantification of NP-NP interactions and self-assembly dynamics will inform both computational and statistical mechanical models used to describe nanoscale phenomena. Such understanding will also lay the groundwork for establishing new and generalizable thermodynamic and kinetic design rules for NP self-assembly. Synergies with NP synthesis will enable investigations of building blocks with novel, perhaps even evolving or active behavior. Moreover, in the long run, we foresee the possibility of applying the guidelines and models of fundamental nanoscale interactions which are uncovered under liquid-phase TEM to biological and biomimetic systems at similar dimensions.

3D coil structures through 2D processing, combined with ferrofluid core, achieve unprecedented high magnetic flux density., Monolithic strong magnetic induction at the mtesla to tesla level provides essential functionalities to physical, chemical, and medical systems. Current design options are constrained by existing capabilities in three-dimensional (3D) structure construction, current handling, and magnetic material integration. We report here geometric transformation of large-area and relatively thick (~100 to 250 nm) 2D nanomembranes into multiturn 3D air-core microtubes by a vapor-phase self-rolled-up membrane (S-RuM) nanotechnology, combined with postrolling integration of ferrofluid magnetic materials by capillary force. Hundreds of S-RuM power inductors on sapphire are designed and tested, with maximum operating frequency exceeding 500 MHz. An inductance of 1.24 μH at 10 kHz has been achieved for a single microtube inductor, with corresponding areal and volumetric inductance densities of 3 μH/mm2 and 23 μH/mm3, respectively. The simulated intensity of the magnetic induction reaches tens of mtesla in fabricated devices at 10 MHz.

Nucleation and growth are universally important in systems from the atomic to the micrometre scale as they dictate structural and functional attributes of crystals. However, at the nanoscale, the pathways towards crystallization have been largely unexplored owing to the challenge of resolving the motion of individual building blocks in a liquid medium. Here we address this gap by directly imaging the full transition of dispersed gold nanoprisms to a superlattice at the single-particle level. We utilize liquid-phase transmission electron microscopy at low dose rates to control nanoparticle interactions without affecting their motions. Combining particle tracking with Monte Carlo simulations, we reveal that positional ordering of the superlattice emerges from orientational disorder. This method allows us to measure parameters such as line tension and phase coordinates, charting the nonclassical nucleation pathway involving a dense, amorphous intermediate. We demonstrate the versatility of our approach via crystallization of different nanoparticles, pointing the way to more general applications.

Reconfigurable hybrid nanoparticles made by decorating flexible polymer shells on rigid inorganic nanoparticle cores can provide a unique means to build stimuli-responsive functional materials. The polymer shell reconfiguration has been expected to depend on the local core shape details, but limited systematic investigations have been undertaken. Here, two literature methods are adapted to coat either thiol-terminated polystyrene (PS) or polystyrene-poly(acrylic acid) (PS-b-PAA) shells onto a series of anisotropic gold nanoparticles of shapes not studied previously, including octahedron, concave cube, and bipyramid. These core shapes are complex, rendering shell contours with nanoscale details (e.g., local surface curvature, shell thickness) that are imaged and analyzed quantitatively using the authors' customized analysis codes. It is found that the hybrid nanoparticles based on the chosen core shapes, when coated with the above two polymer shells, exhibit distinct shell segregations upon a variation in solvent polarity or temperature. It is demonstrated for the PS-b-PAA-coated hybrid nanoparticles, the shell segregation is maintained even after a further decoration of the shell periphery with gold seeds; these seeds can potentially facilitate subsequent deposition of other nanostructures to enrich structural and functional diversity. These synthesis, imaging, and analysis methods for the hybrid nanoparticles of anisotropically shaped cores can potentially aid in their predictive design for materials reconfigurable from the bottom up.

We use liquid-phase transmission electron microscopy (LP-TEM) to characterize the structure and dynamics of a solution-phase superlattice assembled from gold nanoprisms at the single particle level. The lamellar structure of the superlattice, determined by a balance of interprism interactions, is maintained and resolved under low-dose imaging conditions typically reserved for biomolecular imaging. In this dose range, we capture dynamic structural changes in the superlattice in real time, where contraction and smaller steady-state lattice constants are observed at higher electron dose rates. Quantitative analysis of the contraction mechanism based on a combination of direct LP-TEM imaging, ensemble small-angle X-ray scattering, and theoretical modeling allows us to elucidate: (1) the superlattice contraction in LP-TEM results from the screening of electrostatic repulsion due to as much as a 6-fold increase in the effective ionic strength in the solution upon electron beam illumination; and (2) the lattice constant serves as a means to understand the mechanism of the in situ interaction modulation and precisely calibrate electron dose rates with the effective ionic strength of the system. These results demonstrate that low-dose LP-TEM is a powerful tool for obtaining structural and kinetic properties of nanoassemblies in liquid conditions that closely resemble real experiments. We anticipate that this technique will be especially advantageous for those structures with heterogeneity or disorder that cannot be easily probed by ensemble methods and will provide important insight that will aid in the rational design of sophisticated reconfigurable nanomaterials.