Jamming of Miscible Liquids via Electrostatic Repulsion Between Polystyrene-Modified Gold Nanorods and Toluene.

Structured liquids in miscible fluids, due to ineffective resistance to withstand particle self-diffusion, differ from that in immiscible liquids because of interfacial interactions. Here, a kind of structured liquid, jammed by thiol-terminated polystyrene-modified gold nanorods (GNRs) within tetrahydrofuran and toluene (TOL), is developed by introducing electrostatic repulsion to counterbalance the self-diffusion of GNRs. First-principle calculations reveal charge transfer between the GNRs and TOL, resulting in the electrostatic repulsion. The structured liquids can be regarded as mimic "loading vehicles" to controllably carry and transport matter under electric or magnetic fields, where release rate can be adjusted by changing the concentration of the soluble matter for slow release and using the photothermal effect of the assembled GNRs for fast release. This work has developed a new assembly mechanism to form structured liquids, allowing the construction of a flexible and robust droplet platform with possible applications in microreactors, biomimetic permeable membranes, and functional liquid robots.

Random fractal-enabled physical unclonable functions with dynamic AI authentication.

A physical unclonable function (PUF) is a foundation of anti-counterfeiting processes due to its inherent uniqueness. However, the self-limitation of conventional graphical/spectral PUFs in materials often makes it difficult to have both high code flexibility and high environmental stability in practice. In this study, we propose a universal, fractal-guided film annealing strategy to realize the random Au network-based PUFs that can be designed on demand in complexity, enabling the tags' intrinsic uniqueness and stability. A dynamic deep learning-based authentication system with an expandable database is built to identify and trace the PUFs, achieving an efficient and reliable authentication with 0% "false positives". Based on the roughening-enabled plasmonic network platform, Raman-based chemical encoding is conceptionally demonstrated, showing the potential for improvements in security. The configurable tags in mass production can serve as competitive PUF carriers for high-level anti-counterfeiting and data encryption.

Effect of rhodamine 6G dye molecular interactions on counterintuitive self-assembly of noble metal nanorods.

HYPOTHESIS: Self-assembled nanostructures with highly ordered and diversified patterns can be obtained by adding additives that directionally control the interparticle interactions. However, due to the complex non-covalent weak interactions in the self-assembly process, the active mechanism of additives is not fully understood, resulting in the limitation of obtaining the nano-superstructures. The introduction of rhodamine 6G (R6G) enables gold nanorods (GNRs) self-assembled into a counterintuitive tetragonal superlattice, during which the exploration of the influence of R6G molecular interactions on the GNRs self-assembly is of importance. EXPERIMENTS: We present the detailed investigations of spacial configuration, binding modes, and aggregated degree of R6G molecule on formation of the tetragonal GNRs superlattices by combining the experimental and simulated results. FINDINGS: By analyzing the peak position and peak intensity in the fluorescent spectra of assembled samples and pure R6G samples, H-dimer is verified as the main cause for inducing the tetragonal superstructures. Molecular dynamics simulations reveal that 2-3 H-dimers adsorbed obliquely in a zigzag chain manner on the surface of GNRs is the most stable state of the self-assembly. This work would contribute to a deeper understanding of the complex colloidal nanoparticle self-assemblies and push forward the development of the bottom-up nanoscale superstructures.

Morphological and Orientational Controls of Self-Assembly of Gold Nanorods Directed by Evaporative Microflows.

Evaporative self-assembly of noble metal nanoparticles into ordered structures holds great promise for fabricating optical and plasmonic devices by virtue of its low cost, high efficiency, and ease of operation. However, poor control of Marangoni flows is one of the challenges accounting for realizing a well-defined assembly. Herein, based on the theoretical analysis of the influence of evaporative intensity on the assembly, two simple but reliable flow-field-confinement platforms are designed to control the evaporative microflows and to work concurrently with depletion forces to enable the regulated self-assembly of gold nanorods. Orientationally ordered assemblies are realized by the designed strong unidirectional microflow in a capillary, and a device-scale assembly of monolayer membrane is obtained by the created weak convection in homemade glass cells. Morphologically diversified superstructure assemblies, such as spherulite-like, boundary-twisted, chiral spiral assemblies, and merging membranes with a π-twisted domain wall, are obtained due to the spontaneous symmetry breaking or in the presence of defects, such as surface steps and screw dislocations. Optical anisotropy and polarization-dependent behaviors of these assemblies are further revealed, implying the potential applications in plasmonic coupling devices and optoelectronic components. An understanding of the entropy-driven assembly behaviors and control of evaporative microflows to guide the self-assembly of gold nanorods provides insights into the general bottom-up approach that is helpful for constructing complex yet robust nanosuperstructures.

Depletion-Mediated Uniform Deposition of Nanorods with Patterned, Multiplexed Assembly.

Device-scale, uniform, and controllable deposition of nanoparticles on various substrates is fundamentally important not only for the fabrication of thin-film devices but also for the large sample statistics of single-particle performances. However, it is challenging to obtain such predefined depositions using a simple and efficient method. Here, we present a novel strategy for obtaining the uniform and particle density/spacing-tunable deposition of nanorods on a linker-free substrate. The deposition is driven by the tailored particle-substrate depletion attraction owing to the size-matched design of the substrate roughness and the nanorod diameter. Both gold nanorods and upconversion nanorods were applied to demonstrate the generality of the method. The high particle density of more than 21 per µm2 and correspondingly the small particle spacing of fewer than 0.3 µm were achieved on a scalable substrate template. On this basis, orientational ordering and pattern-selective deposition of nanorods were realized by controlling the liquid flow rate and employing the substrate with patterned roughness areas, respectively. With the roughness-directed density-tunable depositions of nanorods integrated onto a single platform, multiplexed gold nanorod assembly and programmable surface-enhanced Raman mapping were achieved, with a promising prospect in information encoding by using the Raman signals as the translation units. The thermal stability and related transition temperature of about 160 °C of gold nanorods were also revealed as an application of single-particle statistics. This practical method could be extended to wide ranges of potential applications in plasmonic coupling devices, cryptography, or single-particle performance statistics with the feature of the high-throughput, low-cost, and scalable fabrication.

Enhanced dyes adsorption from wastewater via Fe3O4 nanoparticles functionalized activated carbon.

Fe3O4 nanoparticles functionalized activated carbon (Fe3O4/AC) as an adsorbent was prepared and used for fast and effectively removing rhodamine B (RhB) and methyl orange (MO) from aqueous solution. Its physical and chemical properties characterized indicate that the adsorbent possesses abundant surface functional groups, sensitive magnetic response and enhanced specific surface area. Batch experiments were carried out to investigate the adsorption capacity and mechanisms. The obtained experimental data fitted well with the general-order kinetic equation and Liu's isotherm model with a maximum adsorption capacity of 182.48 mg g-1 for RhB and 150.35 mg g-1 for MO, respectively. The thermodynamic parameter was analyzed further and it showed an exothermic and spontaneous adsorption process. This composite with high adsorption efficiency and rapid magnetic separation can be a promising and recyclable adsorbent for practical wastewater treatment and purification processes.