Kinetically controlled, seed-mediated co-reduction provides a robust and versatile synthetic approach to multimetallic nanoparticles with precisely controlled geometries and compositions. Here, we demonstrate that single-crystalline cylindrical Au nanorods selectively transform into a series of structurally distinct Au@Au–Pd alloy core–shell bimetallic nanorods with exotic multifaceted geometries enclosed by specific types of facets upon seed-mediated Au–Pd co-reduction under diffusion-controlled conditions. By adjusting several key synthetic parameters, such as the Pd/Au precursor ratio, the reducing agent concentration, the capping surfactant concentration, and foreign metal ion additives, we have been able to simultaneously fine-tailor the atomic-level surface structures and fine-tune the compositional stoichiometries of the multifaceted Au–Pd bimetallic nanorods. Using the catalytic hydrogenation of 4-nitrophenol by ammonia borane as a model reaction obeying the Langmuir–Hinshelwood kinetics, we further show that the relative surface binding affinities of the reactants and the rates of interfacial charge transfers, both of which play key roles in determining the overall reaction kinetics, strongly depend upon the surface atomic coordinations and the compositional stoichiometries of the colloidal Au–Pd alloy nanocatalysts. The insights gained from this work not only shed light on the underlying mechanisms dictating the intriguing geometric evolution of multimetallic nanocrystals during seed-mediated co-reduction but also provide an important knowledge framework that guides the rational design of architecturally sophisticated multimetallic nanostructures toward optimization of catalytic molecular transformations.Keywords: alloy nanoparticles; hetero-nanostructures; high-index facets; low-index facets; nanocatalysis; nanocrystal growth; seed-mediated co-reduction;

The interfacial adsorption, desorption, and exchange behaviors of thiolated ligands on nanotextured Au nanoparticle surfaces exhibit phenomenal site-to-site variations essentially dictated by the local surface curvatures, resulting in heterogeneous thermodynamic and kinetic profiles remarkably more sophisticated than those associated with the self-assembly of organothiol ligand monolayers on atomically flat Au surfaces. Here we use plasmon-enhanced Raman scattering as a spectroscopic tool combining time-resolving and molecular fingerprinting capabilities to quantitatively correlate the ligand dynamics with detailed molecular structures in real time under a diverse set of ligand adsorption, desorption, and exchange conditions at both equilibrium and nonequilibrium states, which enables us to delineate the effects of nanoscale surface curvature on the binding affinity, cooperativity, structural ordering, and the adsorption/desorption/exchange kinetics of organothiol ligands on colloidal Au nanoparticles. This work provides mechanistic insights on the key thermodynamic, kinetic, and geometric factors underpinning the surface curvature-dependent interfacial ligand behaviors, which serve as a central knowledge framework guiding the site-selective incorporation of desired surface functionalities into individual metallic nanoparticles for specific applications.Keywords: ligand dynamics; ligand exchange; metallic nanoparticles; nanoscale surface curvature; plasmon-enhanced spectroscopy; Surface capping ligands;

Percolation dealloying of multimetallic alloys entangles the selective dissolution of the less-noble elements with nanoscale restructuring of the more-noble components, resulting in the formation of spongelike, nanoporous architectures with a unique set of structural characteristics highly desirable for heterogeneous catalysis. Although the dealloyed nanoporous materials are compositionally dominated by the more-noble elements, they inevitably contain residual less-noble elements that cannot be completely removed through the percolation dealloying process. How to employ the less-noble elements to rationally guide the structural evolution and optimize the catalytic performances of the dealloyed noble metal nanocatalysts still remains largely unexplored. Here, we have discovered that incorporation of Ag into Au–Cu binary alloy nanoparticles substantially enhances the Cu leaching kinetics while effectively suppressing the ligament coarsening during the nanoporosity-evolving percolation dealloying of the alloy nanoparticles. The controlled coleaching of Ag and Cu from Au–Ag–Cu ternary alloy nanoparticles provides a unique way to optimize both the surface area-to-mass ratios and specific activities of the dealloyed nanosponge particles for the electrocatalytic oxidation of alcohols. The residual Ag in the fully dealloyed nanosponge particles plays crucial roles in stabilizing the surface active sites and maintaining the nanoporous architectures during the electrocatalytic reactions, thereby greatly enhancing the durability of the electrocatalysts. The insights gained from this work shed light on the underlying roles of residual less-noble elements that are crucial to the rational optimization of electrocatalysis on noble-metal nanostructures.Keywords: electrocatalysis; nanoporosity; noble-metal nanoparticles; percolation dealloying; Residual less-noble elements;

The past two decades have witnessed great success achieved in the geometry-controlled synthesis of metallic nanoparticles using the seed-mediated nanocrystal growth method. Detailed mechanistic understanding of the synergy among multiple key structure-directing agents in the nanocrystal growth solutions, however, has long been lagging behind the development and optimization of the synthetic protocols. Here we investigate the foreign ion- and surfactant-coguided overgrowth of single-crystalline Au nanorods as a model system to elucidate the intertwining roles of Ag+ foreign ions, surface-capping surfactants, and reducing agents that underpin the intriguing structural evolution of Au nanocrystals. The geometry-controlled nanorod overgrowth involves two distinct underlying pathways, Ag underpotential deposition and Au–Ag electroless codeposition, which are interswitchable upon maneuvering the interplay of the Ag+ ions, surfactants, and reducing agents. The pathway switch governs the geometric and compositional evolution of nanorods during their overgrowth, allowing the cylindrical Au nanorods to selectively transform into a series of anisotropic nanostructures with interesting geometric, compositional, and plasmonic characteristics. The insights gained from this work shed light on the mechanistic complexity of geometry-controlled nanocrystal growth and may guide the development of new synthetic approaches to metallic nanostructures with increasing architectural complexity, further enhancing our capabilities of fine-tuning the optical, electronic, and catalytic properties of the nanoparticles.

Atomic-level understanding of the structural transformations of multimetallic nanoparticles triggered by external stimuli is of vital importance to the enhancement of our capabilities to fine-tailor the key structural parameters and thereby to precisely tune the properties of the nanoparticles. Here, we show that, upon thermal annealing in a reducing atmosphere, Au@Cu2O core–shell nanoparticles transform into Au–Cu alloy nanoparticles with tunable compositional stoichiometries that are predetermined by the relative core and shell dimensions of their parental core–shell nanoparticle precursors. The Au–Cu alloy nanoparticles exhibit distinct dealloying behaviors that are dependent upon their Cu/Au stoichiometric ratios. For Au–Cu alloy nanoparticles with Cu atomic fractions above the parting limit, nanoporosity-evolving percolation dealloying occurs upon exposure of the alloy nanoparticles to appropriate chemical etchants, resulting in the formation of particulate spongy nanoframes with solid/void bicontinuous morphology composed of hierarchically interconnected nanoligaments. The nanoporosity evolution during percolation dealloying is synergistically guided by two intertwining structural rearrangement processes, ligament domain coarsening driven by thermodynamics and framework expansion driven by Kirkendall effects, both of which can be maneuvered by controlling the Cu leaching rates during the percolation dealloying. The dealloyed nanoframes possess large open surface areas accessible by the reactant molecules and high abundance of catalytically active undercoordinated atoms on the ligament surfaces, two unique structural features highly desirable for high-performance electrocatalysis. Using the room temperature electro-oxidation of methanol as a model reaction, we further demonstrate that, through controlled percolation dealloying of Au–Cu alloy nanoparticles, both the electrochemically active surface areas and the specific activity of the dealloyed metallic nanoframes can be systematically tuned to achieve the optimal electrocatalytic activities.Keywords: alloy nanoparticles; electrocatalysis; nanoframes; nanoporosity; percolation dealloying; undercoordinated surface atoms

While great success has been achieved in fine-tuning the aspect ratios and thereby the plasmon resonances of cylindrical Au nanorods, facet control with atomic level precision on the highly curved nanorod surfaces has long been a significantly more challenging task. The intrinsic structural complexity and lack of precise facet control of the nanorod surfaces remain the major obstacles for the atomic-level elucidation of the structure–property relationships that underpin the intriguing catalytic performance of Au nanorods. Here we demonstrate that the facets of single-crystalline Au nanorods can be precisely tailored using cuprous ions and cetyltrimethylammonium bromide as a unique pair of surface capping competitors to guide the particle geometry evolution during nanorod overgrowth. By deliberately maneuvering the competition between cuprous ions and cetyltrimethylammonium bromide, we have been able to create, in a highly controllable and selective manner, an entire family of nanorod-derived anisotropic multifaceted geometries whose surfaces are enclosed by specific types of well-defined high-index and low-index facets. This facet-controlled nanorod overgrowth approach also allows us to fine-tune the particle aspect ratios while well-preserving all the characteristic facets and geometric features of the faceted Au nanorods. Taking full advantage of the combined structural and plasmonic tunability, we have further studied the facet-dependent heterogeneous catalysis on well-faceted Au nanorods using surface-enhanced Raman spectroscopy as an ultrasensitive spectroscopic tool with unique time-resolving and molecular finger-printing capabilities.Keywords: gold nanorods; high-index facets; low-index facets; nanocatalysis; overgrowth; plasmon resonances; surface-enhanced Raman spectroscopy;

Au nanorods are optically tunable anisotropic nanoparticles with built-in catalytic activities. The state-of-the-art seed-mediated nanorod synthesis offers excellent control over the aspect ratios of cylindrical Au nanorods, which enables fine-tuning of plasmon resonances over a broad spectral range. However, facet control of Au nanorods with atomic-level precision remains significantly more challenging. The coexistence of various types of low-index and high-index facets on the highly curved nanorod surfaces makes it extremely challenging to quantitatively elucidate the atomic-level structure–property relationships that underpin the catalytic competence of Au nanorods. Here we demonstrate that cylindrical Au nanorods undergo controlled facet evolution during their overgrowth in the presence of Cu2+ and cationic surfactants, resulting in the formation of anisotropic nanostructures enclosed by well-defined facets, such as low-index faceting nanocuboids and high-index faceting convex nanocuboids and concave nanocuboids. These faceted Au nanorods exhibit enriched optical extinction spectral features, broader plasmonic tuning range, and enhanced catalytic tunability in comparison to the conventional cylindrical Au nanorods. The capabilities to both fine-tailor the facets and fine-tune the plasmon resonances of anisotropic Au nanoparticles open up unique opportunities for us to study, in great detail, the facet-dependent interfacial molecular transformations on Au nanocatalysts using surface-enhanced Raman scattering as a time-resolved spectroscopic tool.

Galvanic replacement provides a simple but versatile way of converting less noble metallic solid nanoparticles into structurally more complex multimetallic hollow nanostructures composed of more noble metals. In contrast to the well-studied Ag–Au bimetallic hollow nanostructures, limited success has been achieved on the geometry control over Ag–Pd bimetallic nanoparticles through galvanic replacement reactions. Here we demonstrate that the capability of geometry control over Ag–Pd bimetallic hollow nanostructures through nanoscale galvanic replacement can be greatly enhanced by the use of appropriate mild reducing agents, such as ascorbic acid and formaldehyde. With the aid of mild reducing agents, we have been able to fine-tailor the compositions, interior architectures, and surface morphologies of Ag–Pd bimetallic hollow nanoparticles with increased structural complexity through surface ligand-free galvanic replacement processes at room temperature. This reducing agent-mediated galvanic replacement provides a unique way of achieving both enhanced optical tunability and optimized catalytic activities through deliberate control over the geometries of complex Ag–Pd bimetallic nanoparticles.

Noble metal nanoparticles have been of tremendous interest due to their intriguing size- and shape-dependent plasmonic and catalytic properties. Combining tunable plasmon resonances with superior catalytic activities on the same metallic nanoparticle, however, has long been challenging because nanoplasmonics and nanocatalysis typically require nanoparticles in two drastically different size regimes. Here, we demonstrate that creation of high-index facets on subwavelength metallic nanoparticles provides a unique approach to the integration of desired plasmonic and catalytic properties on the same nanoparticle. Through site-selective surface etching of metallic nanocuboids whose surfaces are dominated by low-index facets, we have controllably fabricated nanorice and nanodumbbell particles, which exhibit drastically enhanced catalytic activities arising from the catalytically active high-index facets abundant on the particle surfaces. The nanorice and nanodumbbell particles also possess appealing tunable plasmonic properties that allow us to gain quantitative insights into nanoparticle-catalyzed reactions with unprecedented sensitivity and detail through time-resolved plasmon-enhanced spectroscopic measurements.

We have discovered that magnetic Fe3O4 nanoparticles exhibit an intrinsic catalytic activity toward the electrochemical reduction of small dye molecules. Metallic nanocages, which act as efficient signal amplifiers, can be attached to the surface of Fe3O4 beads to further enhance the catalytic electrochemical signals. The Fe3O4@nanocage core–satellite hybrid nanoparticles show significantly more robust electrocatalytic activities than the enzymatic peroxidase/H2O2 system. We have further demonstrated that these nonenzymatic nanoelectrocatalysts can be used as signal-amplifying nanoprobes for ultrasensitive electrochemical cytosensing.

Using surface-enhanced Raman spectroscopy (SERS) to monitor catalytic reactions in real time on Au nanocatalysts has been a significant challenge because plasmon-enhanced spectroscopies require the utilization of subwavelength Au nanostructures as substrates while heterogeneous catalysis requires small Au nanoparticles in the sub-5 nm size regime. Here, we show that subwavelength Au nanoparticles with nanoscale surface porosity represent a unique bifunctional nanostructure that serves as both high-performance SERS substrates and efficient surface catalysts, allowing one to unravel the kinetics and pathways of surface-catalyzed reactions with unprecedented sensitivity and detail through time-resolved plasmon-enhanced spectroscopic measurements. The origin of the nanoporosity-enhanced catalytic activity can be interpreted as a consequence of high abundance of undercoordinated surface atoms at the steps and kinks on the highly curved surfaces of Au porous nanoparticles. By measuring SERS signals from the monolayer molecules preadsorbed on the surfaces of Au porous nanoparticles, we have been able to gain quantitative new insights into the intrinsic kinetics and mechanisms of Au-catalyzed hydrogenation of aromatic nitro compounds with minimal complication introduced by the molecular diffusion, adsorption, and desorption.

We employed surface-enhanced Raman scattering as a noninvasive in situ spectroscopic tool to quantitatively study the intrinsic facet-dependent catalytic activities of colloidal subwavelength Au nanoparticles enclosed by various types of well-defined high-index facets using the catalytic hydrogenation of 4-nitrothiophenol as a model reaction. Our results provide compelling experimental evidence on the crucial roles of undercoordinated surface atoms in Au-based heterogeneous catalysis and shed light on the underlying relationship between the atomic-level surface structures and the intrinsic catalytic activities of Au nanocatalysts.Keywords: Au nanoparticles; high-index facets; nanocatalysis; plasmon resonances; surface-enhanced Raman spectroscopy

We demonstrate that Au nanoparticles with tipped surface structures, such as concave nanocubes, nanotrisoctahedra, and nanostars, possess size-dependent tunable plasmon resonances and intense near-field enhancements exploitable for single-particle surface-enhanced Raman spectroscopy (spSERS) under near-infrared excitation. We report a robust seed-mediated growth method for the selective fabrication of Au concave nanocubes, nanotrisoctahedra, and nanostars with fine-controlled particle sizes and narrow size distributions. Through tight control over particle sizes, the plasmon resonances of the nanoparticles can be fine-tuned over a broad spectral range with respect to the excitation laser, allowing us to systematically quantify the SERS enhancements on individual nanoparticles as a function of particle size for each particle geometry. Understanding of the geometry-dependent plasmonic characteristics and SERS activities of the nanoparticles is further enhanced by finite-difference time-domain (FDTD) calculations. Our results clearly show that strong SERS enhancements can be obtained and further optimized on individual Au nanoparticles with nanoengineered “hot spots” on their tipped surfaces when the plasmon resonances of the nanoparticles are tuned to the optimal spectral regions with respect to the excitation laser wavelength. Using tunable plasmonic nanoparticles with tipped surface structures as substrates for spSERS represents a highly promising and feasible approach to the optimization of SERS-based sensing and imaging applications.Keywords: concave nanocubes; finite-difference time-domain; nanostars; nanotrisoctahedra; noble metal nanoparticles; plasmon resonances; surface-enhanced Raman spectroscopy

In this paper, we present a detailed, systematic study of the controlled overgrowth of Pd on Au nanorods. Pd nanoshells with fine-controlled dimensions and architectures were overgrown on single-crystalline Au nanorods through seed-mediated growth using H2PdCl4 as the Pd precursor and ascorbic acid as the reducing agent in the presence of cetyltrimethylammonium chloride (CTAC) or cetyltrimethylammonium bromide (CTAB) as the surface capping agent. The effects of surface capping agent, ascorbic acid to H2PdCl4 ratio, reaction temperature, and structure-directing foreign ions, such as Ag+, on the dimensions and architectures of the resulting Au@Pd core–shell heteronanostructures were systematically studied. At 30 °C, Au nanorods coated with polycrystalline Pd shells were obtained using CTAC as the surface capping agent, while single-crystalline Au@Pd core–shell nanocuboids formed in the presence of CTAB. The thicknesses of the polycrystalline and single-crystalline Pd shells were fine-controlled by adjusting the molar ratio of ascorbic acid to H2PdCl4. At an elevated reaction temperature of 60 °C, irregularly shaped and cylindrical co-axial core–shell nanorods were obtained in CTAC and CTAB, respectively. By introducing Ag+ ions into the Pd growth solution, Au nanorods coated with segregated Pd nanoislands and dumbbell-like core–shell heteronanostructures were obtained as a consequence of the underpotential deposition of Ag and sustainable galvanic replacements that concurred during the Pd overgrowth processes. The effects of the Pd shell dimensions and morphologies on the plasmonic properties of the Au@Pd core–shell nanostructures were also investigated.

We demonstrate that Ag–Cu2O core–shell nanoparticles exhibit geometry-dependent optical properties that are highly tunable across the visible and near-infrared spectral regions. We have developed a robust wet chemistry approach to the geometry control of Ag–Cu2O core–shell nanoparticles through epitaxial growth of Cu2O nanoshells on the surfaces of various Ag nanostructures, such as quasi-spherical nanoparticles, nanocubes, and nanocuboids. Precise control over the core and the shell geometries enables us to develop detailed, quantitative understanding of how the Cu2O nanoshells introduce interesting modifications to the resonance frequencies and the extinction spectral line shapes of multiple plasmon modes of the Ag cores. Finite-difference time-domain calculations provide further insights into the physical origin and the geometry-dependence of the various plasmon modes observed in the Ag–Cu2O core–shell nanoparticles.

Porous Au nanoparticles with fine-controlled overall particle sizes have been fabricated using a kinetically controlled seed-mediated growth method. In contrast to spherical Au nanoparticles with smooth surfaces, the porous Au nanoparticles exhibit far greater size-dependent plasmonic tunability and significantly intensified local electric field enhancements exploitable for single-particle plasmon-enhanced spectroscopies. The effects of the nanoscale porosity on the far- and near-field optical properties of the nanoparticles have been investigated both experimentally by optical extinction and single-nanoparticle Raman spectroscopic measurements and theoretically through finite-difference time-domain calculations.Keywords: finite-difference time-domain; nanoparticle; nanoporosity; plasmon resonance; seed-mediate growth; surface-enhanced Raman spectroscopy;

We have developed a robust, nanobiotechnology-based electrochemical cytosensing approach with high sensitivity, selectivity, and reproducibility toward the simultaneous multiplex detection and classification of both acute myeloid leukemia and acute lymphocytic leukemia cells. The construction of the electrochemical cytosensor involves the hierarchical assembly of dual aptamer-functionalized, multilayered graphene–Au nanoparticle electrode interface and the utilization of hybrid electrochemical nanoprobes co-functionalized with redox tags, horseradish peroxidase, and cell-targeting nucleic acid aptamers. The hybrid nanoprobes are multifunctional, capable of specifically targeting the cells of interest, amplifying the electrochemical signals, and generating distinguishable signals for multiplex cytosensing. The as-assembled electrode interface not only greatly facilitates the interfacial electron transfer process due to its high conductivity and surface area but also exhibits excellent biocompatibility and specificity for cell recognition and adhesion. A superstructured sandwich-type sensor geometry is adopted for electrochemical cytosensing, with the cells of interest sandwiched between the nanoprobes and the electrode interface. Such an electrochemical sensing strategy allows for ultrasensitive, multiplex acute leukemia cytosensing with a detection limit as low as ∼350 cells per mL and a wide linear response range from 5 × 102 to 1 × 107 cells per mL for HL-60 and CEM cells, with minimal cross-reactivity and interference from non-targeting cells. This electrochemical cytosensing approach holds great promise as a new point-of-care diagnostic tool for early detection and classification of human acute leukemia and may be readily expanded to multiplex cytosensing of other cancer cells.

We have developed a robust enzymatic peptide cleavage-based assay for the ultrasensitive dual-channel detection of matrix metalloproteinase-2 (MMP-2) in human serum using gold-quantum dot (Au-QD) core–satellite nanoprobes.

The variable susceptibility to the tumor necrosis factor-related apoptosis-inducing ligand (TRAIL) treatment observed in various types of leukemia cells is related to the difference in the expression levels of death receptors, DR4 and DR5, on the cell surfaces. Quantifying the DR4/DR5 expression status on leukemia cell surfaces is of vital importance to the development of diagnostic tools to guide death receptor-based leukemia treatment. Taking the full advantages of novel nanobiotechnology, we have developed a robust electrochemical cytosensing approach toward ultrasensitive detection of leukemia cells with detection limit as low as ∼40 cells and quantitative evaluation of DR4/DR5 expression on leukemia cell surfaces. The optimization of electron transfer and cell capture processes at specifically tailored nanobiointerfaces and the incorporation of multiple functions into rationally designed nanoprobes provide unique opportunities of integrating high specificity and signal amplification on one electrochemical cytosensor. The high sensitivity and selectivity of this electrochemical cytosensing approach also allows us to evaluate the dynamic alteration of DR4/DR5 expression on the surfaces of living cells in response to drug treatments. Using the TRAIL-resistant HL-60 cells and TRAIL-sensitive Jurkat cells as model cells, we have further verified that the TRAIL susceptibility of various types of leukemia cells is directly correlated to the surface expression levels of DR4/DR5. This versatile electrochemical cytosensing platform is believed to be of great clinical value for the early diagnosis of human leukemia and the evaluation of therapeutic effects on leukemia patients after radiation therapy or drug treatment.

We have studied the conformational dynamics associated with the nanoscale DNA bending induced by human immunodeficiency virus type 1 (HIV-1) nucleocapsid (NC) protein using single-molecule Förster resonance energy transfer (SM-FRET). To gain molecular-level insights into how the HIV-1 NC locally distorts the structures of duplexed DNA segments, the dynamics, reversibility, and sequence specificity of the DNA bending behavior of NC have been systematically studied. We have performed SM-FRET measurements on a series of duplexed DNA segments with varying sequences, lengths, and local structures in the presence of the wide-type HIV-1 NC and NC mutants lacking either the basic N-terminal domain or the zinc fingers. On the basis of the SM-FRET results, we have proposed a possible mechanism for the NC-induced DNA bending in which both NC’s zinc fingers and N-terminal domain are found to play crucial roles. The SM-FRET results reported here add new mechanistic insights into the biological behaviors and functions of HIV-1 NC as a retroviral DNA-architectural protein which may play critical roles in the compaction, nuclear import, and integration of the proviral DNA during the retroviral life cycle.

Metal–semiconductor hybrid heteronanostructures may exhibit synergistically reinforced optical responses and significantly enhanced optical tunability that essentially arise from the unique nanoscale interactions between the metal and semiconductor components. Elaboration of multi-component hybrid nanoparticles allows us to achieve optimized or diversified material functionalities through precise control over the dimension and morphology of the constituent building units, on one hand, and through engineering their relative geometrical arrangement and interfacial structures, on the other hand. Here we study the geometry-dependent optical characteristics of metal–cuprous oxide (Cu2O) core–shell hybrid nanoparticles in great detail through combined experimental and theoretical efforts. We demonstrate that several important geometrical parameters, such as shell thickness, shell crystallinity, shell porosity, and core composition, of the hybrid nanoparticles can be tailored in a highly precise and controllable manner through robust wet chemistry approaches. The tight control over the particle geometries provides unique opportunities for us to develop quantitative understanding of how the dimensions, morphologies, and electronic properties of the semiconducting shells and the geometry and compositions of the metallic cores affect the plasmon resonance frequencies, the light scattering and absorption cross sections, and the overall extinction spectral line shapes of the hybrid nanoparticles. Mie scattering theory calculations provide further insights into the origin of the geometrically tunable optical responses and the interesting extinction spectral line shapes of the hybrid nanoparticles that we have experimentally observed.Keywords: core−shell; geometry control; heteronanostructures; hybrid nanoparticles; metal; optical tunability; plasmon resonance; semiconductor

Understanding the mechanism of surface-enhanced Raman scattering (SERS) of molecules on semiconductor nanostructures is directly related to our capabilities of designing and optimizing new SERS-active substrates for broad applications in the field of molecular detection and characterization. Here, we present an exploration of using cuprous oxide nanostructures with hierarchical porosity for enhancing Raman signals of adsorbed probe molecules. Distinct SERS signals were detected on both individual polycrystalline nanoshells and porous thin films composed of cuprous oxide nanocrystals. The observed enhancement of SERS signals can be interpreted as synergistic effects of strong chemical interactions between the probe molecules and cuprous oxide surfaces, localized electromagnetic field enhancement, and the unique hierarchical porosity of the nanostructures. Our work introduced a novel type of semiconductor substrates for high-performance SERS and extended the applications of cuprous oxide nanostructures to spectroscopy-based molecular sensing and characterizations.Keywords: chemical enhancement; electromagnetic enhancement; individual polycrystalline nanoshells; molecular sensing; optical scattering; semiconductor nanostructure;

We have developed a robust enzymatic peptide cleavage-based assay for the ultrasensitive dual-channel detection of matrix metalloproteinase-2 (MMP-2) in human serum using gold-quantum dot (Au-QD) core–satellite nanoprobes.