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Abstract In biological systems, molecular assembly primarily relies on the assistance of molecular chaperones. Inspired by nature, strategies like ‘chaperone‐assisted assembly’ and ‘catalyzed assembly’ have been proposed for the sophisticated control of molecular assembly. Nonetheless, significant challenges remain in the rational design of such systems, calling for a deep understanding of underlying principles. Herein, we demonstrate an artificial chaperone serves a dual role, that is catalyst in low dosages and inhibitor in high dosages, in regulating the supramolecular polymerization of peptides. Low dosages of carboxymethyl cellulose, as the chaperones, catalyze the assembly of Aβ16‐22 peptides into fibrils through multi‐step phase separation, while high dosages trap the peptides into coacervate intermediates and therefore inhibit the fibrillation. Consequently, the quantity of chaperones does not follow the intuition that ‘more is better’ for catalyzing assembly but instead has an optimal molar ratio. Investigation reveals that the interplay and evolution of electrostatic and hydrophobic interactions are the keys to achieving these processes. This study provides insights into the multifaceted roles artificial chaperones may play in a dosage‐dependent manner and enriches the toolkit for efficient and controllable construction of complex assembly systems.

Abstract The solid-electrolyte interphase (SEI) plays crucial roles for the reversible operation of lithium metal batteries. However, fundamental understanding of the mechanisms of SEI formation and evolution is still limited. Herein, we develop a depth-sensitive plasmon-enhanced Raman spectroscopy (DS-PERS) method to enable in-situ and nondestructive characterization of the nanostructure and chemistry of SEI, based on synergistic enhancements of localized surface plasmons from nanostructured Cu, shell-isolated Au nanoparticles and Li deposits at different depths. We monitor the sequential formation of SEI in both ether-based and carbonate-based dual-salt electrolytes on a Cu current collector and then on freshly deposited Li, with dramatic chemical reconstruction. The molecular-level insights from the DS-PERS study unravel the profound influences of Li in modifying SEI formation and in turn the roles of SEI in regulating the Li-ion desolvation and the subsequent Li deposition at SEI-coupled interfaces. Last, we develop a cycling protocol that promotes a favorable direct SEI formation route, which significantly enhances the performance of anode-free Li metal batteries.

Abstract Carbon-supported nanoparticles are indispensable to enabling new energy technologies such as metal-air batteries and catalytic water splitting. However, achieving ultrasmall and high-density nanoparticles (optimal catalysts) faces fundamental challenges of their strong tendency toward coarsening and agglomeration. Herein, we report a general and efficient synthesis of high-density and ultrasmall nanoparticles uniformly dispersed on two-dimensional porous carbon. This is achieved through direct carbothermal shock pyrolysis of metal-ligand precursors in just ~100 ms, the fastest among reported syntheses. Our results show that the in situ metal-ligand coordination (e.g., N → Co2+) and local ordering during millisecond-scale pyrolysis play a crucial role in kinetically dominated fabrication and stabilization of high-density nanoparticles on two-dimensional porous carbon films. The as-obtained samples exhibit excellent activity and stability as bifunctional catalysts in oxygen redox reactions. Considering the huge flexibility in coordinated precursors design, diversified single and multielement nanoparticles (M = Fe, Co, Ni, Cu, Cr, Mn, Ag, etc) were generally fabricated, even in systems well beyond traditional crystalline coordination chemistry. Our method allows for the transient and general synthesis of well-dispersed nanoparticles with great simplicity and versatility for various application schemes.

The plasmon-exciton interaction between gap-mode nanocavities and A excitons of MoS2 is investigated, and the longitudinal distribution of the plasmon-exciton interactions is obtained at ~1 nm spatial resolution.

Mid-infrared antennas (MIRAs) support highly-efficient optical resonance in the infrared, enabling multiple applications, such as surface-enhanced infrared absorption (SEIRA) spectroscopy and ultrasensitive mid-infrared detection. However, most MIRAs such as dipolar-antenna structures support only narrow-band dipolar-mode resonances while high-order modes are usually too weak to be observed, severely limiting other useful applications that broadband resonances make possible. In this study, we report a multiscale nanobridged rhombic antenna (NBRA) that supports two dominant resonances in the MIR, including a charge-transfer plasmon (CTP) band and a bridged dipolar plasmon (BDP) band which looks like a quadruple resonance. These assignments are evidenced by scattering-type scanning near-field optical microscopy (s-SNOM) imaging and electromagnetic simulations. The high-order mode only occurs with nanometer-sized bridge (nanobridge) linked to the one end of the rhombic arm which mainly acts as the inductance and the resistance by the circuit analysis. Moreover, the main hotspots associated with the two resonant bands are spatially superimposed, enabling boosting up the local field for both bands by multiscale coupling. With large field enhancements, multiband detection with high sensitivity to a monolayer of molecules is achieved when using SEIRA. Our work provides a new strategy possible to activate high-order modes for designing multiband MIRAs with both nanobridges and nanogaps for such MIR applications as multiband SEIRAs, IR detectors, and beam-shaping of quantum cascade lasers in the future.

This review focuses on the advance of optical design from nano/micro to macro in SERS and SEIRA, especially on the optical coupling between nano/micro and macro scales.

Abstract Interfacial host–guest complexation offers a versatile way to functionalize nanomaterials. However, the complicated interfacial environment and trace amounts of components present at the interface make the study of interfacial complexation very difficult. Herein, taking the advantages of near-single-molecule level sensitivity and molecular fingerprint of surface-enhanced Raman spectroscopy (SERS), we reveal that a cooperative effect between cucurbit[7]uril (CB[7]) and methyl viologen (MV2+2I−) in aggregating Au NPs originates from the cooperative adsorption of halide counter anions I−, MV2+, and CB[7] on Au NPs surface. Moreover, similar SERS peak shifts in the control experiments using CB[n]s but with smaller cavity sizes suggested the occurrence of the same guest complexations among CB[5], CB[6], and CB[7] with MV2+. Hence, an unconventional exclusive complexation model is proposed between CB[7] and MV2+ on the surface of Au NPs, distinct from the well-known 1:1 inclusion complexation model in aqueous solutions. In summary, new insights into the fundamental understanding of host–guest interactions at nanostructured interfaces were obtained by SERS, which might be useful for applications related to host–guest chemistry in engineered nanomaterials.

Abstract Organic–inorganic halide perovskites are emerging materials for photovoltaic applications with certified power conversion efficiencies (PCEs) over 25%. Generally, the microstructures of the perovskite materials are critical to the performances of PCEs. However, the role of the nanometer-sized grain boundaries (GBs) that universally existing in polycrystalline perovskite films could be benign or detrimental to solar cell performance, still remains controversial. Thus, nanometer-resolved quantification of charge carrier distribution to elucidate the role of GBs is highly desirable. Here, we employ correlative infrared-spectroscopic nanoimaging by the scattering-type scanning near-field optical microscopy with 20 nm spatial resolution and Kelvin probe force microscopy to quantify the density of electrons accumulated at the GBs in perovskite polycrystalline thin films. It is found that the electron accumulations are enhanced at the GBs and the electron density is increased from 6 × 1019 cm−3 in the dark to 8 × 1019 cm−3 under 10 min illumination with 532 nm light. Our results reveal that the electron accumulations are enhanced at the GBs especially under light illumination, featuring downward band bending toward the GBs, which would assist in electron-hole separation and thus be benign to the solar cell performance. Correlative infrared-spectroscopic nanoimaging by the scattering-type scanning near-field optical microscopy and Kelvin probe force microscopy quantitatively reveal the accumulated electrons at GBs in perovskite polycrystalline thin films.

Confidently separating the photothermal effect from the generation of energetic charge carriers and quantifying their relative contribution to chemical reactions remain a great challenge in plasmon-mediated chemical reactions. Here, authors describe a strategy based on the construction of a plasmonic electrode coupled with photoelectrochemistry to quantitatively disentangle these two effects.

Summary: Light-excited energetic electrons, or so-called hot electrons (HEs), in plasmonic metal nanostructures have received much attention in the past few years. Plasmonic metal nanostructures, acting as light absorbers with higher efficiency and adjustability than dye molecules and inorganic semiconductors, can generate HEs under specific light conditions. However, the overall efficiency of the plasmonic systems remain unsatisfactory. Therefore, it is important to study the generation and transfer processes of plasmon-induced HEs, which are necessary for efficient plasmon-enhanced applications. In this review, we summarize the basic concepts and mechanisms of HE generation and transportation, then highlight the use of in situ surface-enhanced Raman spectroscopy (SERS) as a probe for HE-induced chemical reactions. We also discuss the opportunities and remaining challenges in promoting fundamental understanding of, and practical applications for, HEs.

Summary: Plasmon-assisted chemical transformation holds great potential for solar energy conversion. However, simultaneous enhancement of reactivity and selectivity is still challenging and the mechanism remains mysterious. Herein, we elucidate the localized surface plasmon resonance (LSPR)-induced principles underlying the enhanced activity (∼70%) and selectivity of photoelectrocatalytic redox of nitrobenzene (NB) on Au nanoparticles. Hot carriers selectively accelerate the conversion rate from NB to phenylhydroxylamine (PHA) by ∼14% but suppress the transformation rate from PHA to nitrosobenzene (NSB) by ∼13%. By adding an electron accepter, the as-observed suppression ratio is substantially enlarged up to 43%. Our experiments, supported by in situ surface-enhanced Raman spectroscopy and density functional theory simulations, reveal such particular hot-carrier-induced selectivity is conjointly contributed by the accelerated hot electron transfer and the corresponding residual hot holes. This work will help expand the applications of renewable sunlight in the directional production of value-added chemicals under mild conditions.

RNAs can mimic the information storage, replication and catalysis functions of DNAs and proteins, providing physical evidence for the widely accepted RNA world hypothesis that RNA alone constitutes earlier life forms. However, the currently found molecular chaperones for correcting RNA folding are proteins, which poses a question on whether RNA itself can avoid misfolding in the absence of proteins. Here, we report two examples that RNA/ssDNA strands can serve as molecular chaperones to assist the folding of RNA/ssDNA structures with complex intramolecular interactions. We found that these RNA chaperones can disrupt the misfolded double-hairpin structures, assisting them to refold into native single-hairpin structures, which is a typical catalytical assembly called catassembly. The refolding rate was increased by at least three orders of magnitude. The identification that RNA can function as molecular chaperone for RNA folding may expand our understanding on RNA molecular chaperone and provides clues to rational design of catassembler.

Rational design of heterogeneous catalysts requires molecular understanding of catalytic processes. Here, the authors attach PtFe and Pd nanocatalysts to Raman signal-enhancing Au-silica nanoparticles, allowing them to spectroscopically observe the active species and bonds involved in CO oxidation in real time.

Sixty years ago, Reddy, Devanatan, and Bockris performed the first in situ electrochemical ellipsometry experiment, which ushered in a new era in the study of electrochemistry, using optical spectroscopy. After six decades of development, electrochemical optical spectroscopy, particularly electrochemical vibrational spectroscopy, has advanced from a phase of immaturity with few methods and limited applications to a phase of maturity with excellent substrate generality and significantly improved resolutions. Here, we divide the development of electrochemical optical spectroscopy into four phases, focusing on the proof-of-concept of different electrochemical optical spectroscopy studies, the emergence of plasmonic enhancement-based electrochemical optical spectroscopic (in particular vibrational spectroscopic) methods, the realization of electrochemical vibrational spectroscopy on welldefined surfaces, and the efforts to achieve operando spectroelectrochemical applications. Finally, we discuss the future development trend of electrochemical optical spectroscopy, as well as examples of new methodology and research paradigms for operando spectroelectrochemistry. [ABSTRACT FROM AUTHOR]

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