The localized surface plasmon resonance of metal nanoparticles is the collective oscillation of electrons on particle surface, induced by incident light, and is a particle composition-, morphology-, and coupling-dependent property. Plasmonic engineering deals with highly precise formation of the targeted nanostructures with targeted plasmonic properties (e.g., electromagnetic field distribution and enhancement) via controlled synthetic, assembling, and atomic/molecular tuning strategies. These plasmonically engineered nanoprobes (PENs) have a variety of unique and beneficial physical, chemical, and biological properties, including optical signal enhancement, catalytic, and local temperature-tuning photothermal properties. In particular, for biomedical applications, there are many useful properties from PENs including LSPR-based sensing, surface-enhanced Raman scattering, metal-enhanced fluorescence, dark-field light-scattering, metal-mediated fluorescence resonance energy transfer, photothermal effect, photodynamic effect, photoacoustic effect, and plasmon-induced circular dichroism. These properties can be utilized for the development of new biotechnologies and biosensing, bioimaging, therapeutic, and theranostic applications in medicine. This Perspective introduces the concept of plasmonic engineering in designing and synthesizing PENs for biomedical applications, gives recent examples of biomedically functional PENs, and discusses the issues and future prospects of PENs for practical applications in bioscience, biotechnology, and medicine.

The precise control of plasmonic nanostructures and their use for less invasive apoptotic pathway-based therapeutics are important but challenging. Here, we introduce a highly controlled synthetic strategy for plasmonic core-petal nanoparticles (CPNs) with massively branched and plasmonically coupled nanostructures. The formation of CPNs was facilitated by the gold chloride-induced oxidative disassembly and rupture of the polydopamine corona around Au nanoparticles and subsequent growth of Au nanopetals. We show that CPNs can act as multifunctional nanoprobes that induce dual photodynamic and photothermal therapeutic effects without a need for organic photosensitizers, coupled with the generation of reactive oxygen species (ROS), and allow for imaging and analyzing cells. Near-infrared laser-activated CPNs can optically monitor and efficiently kill cancer cells via apoptotic pathway by dual phototherapeutic effects and ROS-mediated oxidative intracellular damage with a relatively mild increase in temperature, low laser power, and short laser exposure time.

Rational engineering and assimilation of diverse chemo‐ and biocatalytic functionalities in a single nanostructure is highly desired for efficient multistep chemical reactions but has so far remained elusive. Here, we design and synthesize multimodal catalytic nanoreactors (MCNRs) based on a mesoporous metal‐organic framework (MOF). The MCNRs consist of customizable metal nanocrystals and stably anchored enzymes in the mesopores, as well as coordinatively unsaturated cationic metal MOF nodes, all within a single nanoreactor space. The highly intimate and diverse catalytic mesoporous microenvironments and facile accessibility to the active site in the MCNR enables the cooperative and synergistic participation from different chemo‐ and biocatalytic components. This was shown by one‐pot multistep cascade reactions involving a heterogeneous catalytic nitroaldol reaction followed by a [Pd/lipase]‐catalyzed chemoenzymatic dynamic kinetic resolution to yield optically pure (>99 % ee) nitroalcohol derivatives in quantitative yields.

Next-generation electrocatalysts with smart integrated designs, maximizing the chemical cascade synergy for sustainable hydrogen production, are needed to address the urgent environmental threats, but scalable synthesis of precisely architectured nanohybrids rendering a few-nanometer interfacial controllability to augment the catalytic reactivity and operational stability is a major bottleneck. Herein, by inventing a surface-confined lateral growth of nanometer-thin and nanoporous two-dimensional (2D)-Pt on NiFe-LDH nanosheets, a highly reactive 2D−2D interfacially integrated nanoplatform is synthesized for an alkaline hydrogen evolution reaction (HER) which not only extracts high Pt-atomic utilization efficiency but also synergistically accelerates the water dissociation and hydrogen generation cascade on the colocalized Pt/M(OH) x active sites, endowing a 6.1-fold higher Pt mass activity than 20% Pt/C and also empowers a record-high HER operational stability for 50 h, due to the chemically enforced lamellar architecture. This work offers a gateway to produce active metal nanosheets tailored with a suitable active-template surface in order to invent and enforce futuristic catalysis technologies.

Conspectus The extensive research performed in the past two decades has enabled the production of a range of colloidal nanocrystals, mostly through solution-based procedures that generate and transform nanostructures in bulk-phase solutions containing precursors and surfactants. However, the understanding and control of each nanocrystal (trans)­formation step during the synthesis are still complicated because of the high complexity of this process, in which multiple diverse events such as nucleation, subsequent growth, attachment, and ripening occur simultaneously in bulk suspensions. Unlike well-established solution-based methods, solid-state reactions, which had been at the forefront of traditional inorganic materials chemistry, are quite rarely utilized in the realm of nanomaterials because of the high temperatures required for most solid-state reactions, as a result of which the clusters and NCs are prone to migrate through the bulk reaction medium and sinter together uncontrollably into large particles. We have been pursuing the “nanospace-confined approach” to explore the use of a variety of solid and hollow silica nanoparticles as either solid-state or solution-phase reaction media to carry out the syntheses and transformations of nanocrystals in a unique microenvironment, partitioning the reactants, intermediates, and transition states from the rest of the bulk reaction medium. Such nanoconfined systems have the potential not only to enable efficient and selective nanocrystal conversion chemistries but also to provide fundamental understanding pertaining to the synthetic evolution of nanostructures and transient mechanistic steps. The unique spaces with sizes of a few tens of nanometers inside nanoconfined systems offer the opportunity to observe and elucidate novel deconvoluted chemical phenomena that are impossible to investigate in bulk systems, and comprehensive understanding of nanoconfined chemistry can be implicated in explaining and controlling the macroscopic chemical behaviors. This Account describes our focused research on developing spatially confined platforms for nanocrystal syntheses and transformations, highlighting our diversity-oriented strategy, namely, the “postdecoration approach”, which results in the evolution of new nanocatalytic sites in a preformed cavity for diversifying and controlling their morphologies, number, density and combinations. We discuss key examples of the “nanoconfined solid-state conversion approach” that involve novel reactions of nanocrystals within thermally stable solid silica nanospheres to synthesize and transform complex hybrid nanocrystals with increased complexity and functionality. In addition, an enlightening discussion of the examples of nanocrystal syntheses and conversions in nanoconfined solutions inside enclosed and exposed cavities of silica nanospheres is included. Finally, the important applications of nanospace-confined systems in various fields are also briefly discussed.

Artificial nanoreactors that can facilitate catalysis in living systems on-demand with the aid of a remotely operable and biocompatible energy source are needed to leverage the chemical diversity and expediency of advanced chemical synthesis in biology and medicine. Here, we designed and synthesized plasmonically integrated nanoreactors (PINERs) with highly tunable structure and NIR-light-induced synergistic function for efficiently promoting unnatural catalytic reactions inside living cells. We devised a synthetic approach toward PINERs by investigating the crucial role of metal-tannin coordination polymer nanofilmthe pH-induced decomplexation-mediated phase-transition processfor growing arrays of Au-nanospheroid-units, constructing a plasmonic corona around the proximal and reactant-accessible silica-compartmentalized catalytic nanospace. Owing to the extensive plasmonic coupling effect, PINERs show strong and tunable optical absorption in the visible to NIR range, ultrabright plasmonic light scattering, controllable thermoplasmonic effect, and remarkable catalysis; and, upon internalization by living cells, PINERs are highly biocompatible and demonstrate dark-field microscpy-based bioimaging features. Empowered with the synergy between plasmonic and catalytic effects and reactant/product transport, facilitated by the NIR-irradiation, PINERs can perform intracellular catalytic reactions with dramatically accelerated rates and efficiently synthesize chemically activated fluorescence-probes inside living cells.

Nanostructures converting chemical energy to mechanical work by using benign metabolic fuels,h ave huge implications in biomedical science.Here,weintroduce Au/Ptbased Janus nanostructures,r esembling to "egg-in-nest" morphology (Au/Pt-ENs), showing enhanced motion as aresult of dual enzyme-relay-like catalytic cascade in physiological biomedia, and in turn showing molecular-laden transport to living cells.W ed eveloped dynamic-casting approach using silica yolk-shell nanoreactors:f irst, to install al arge Au-seed fixing the silica-yolk aside while providing the anisotropically confined concave hollown anospace to grow curved Ptdendritic networks.O wing to the intimately interfaced Au and Pt catalytic sites integrated in au nique anisotropic nestlike morphology, Au/Pt-ENse xhibited high diffusion rates and displacements as the result of glucose-converted oxygen concentration gradient. High diffusiophoresis in cell culture media increased the nanomotor-membrane interaction events, in turn facilitated the cell internalization. In addition, the porous network of Au/Pt-ENsf acilitated the drug-molecule cargo loading and delivery to the living cells.

Highly reliable detection, imaging, and monitoring of reactive oxygen species (ROS) are critical for understanding and studying the biological roles and pathogenesis of ROS. This study describes the design and synthesis of myoglobin and polydopamine-engineered surface-enhanced Raman scattering (MP-SERS) nanoprobes with strong, tunable SERS signals that allow for specifically detecting and imaging ROS sensitively and quantitatively. The study shows that a polydopamine nanolayer can facilitate the modification of Raman-active myoglobins and satellite Au nanoparticles (s-AuNPs) to a plasmonic core AuNP (c-AuNP) in a controllable manner and the generation of plasmonically coupled hot spots between a c-AuNP and s-AuNPs that can induce strong SERS signals. The six-coordinated Fe(III)-OH of myoglobins in plasmonic hotspots is reacted with ROS (H O , •OH, and O ) to form Fe(IV)O. The characteristic Raman peaks of Fe(IV)O from the Fe-porphyrin is used to analyze and quantify ROS. This chemistry allows for these probes to detect ROS in solution and image ROS in cells in a highly designable, specific, and sensitive manner. This work shows that these MP-SERS probes allow for detecting and imaging ROS to differentiate cancerous cells from noncancerous cells. Importantly, for the first time, SERS-based monitoring of the autophagy process in living cells under starvation conditions is validated.