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Nanozymes mimic enzymes and that includes their selectivity. To achieve selectivity, significant inspiration for nanoparticle design can come from the geometric and molecular features that make enzymes selective catalysts. The two central features enzymes use are control over the arrangement of atoms in the active site and the placing of the active site down a nanoconfined substrate channel. The implementation of enzyme-inspired features has already been shown to both improve activity and selectivity of nanoparticles for a variety of catalytic and sensing applications. The tuning and control of active sites on metal nanoparticle surfaces ranges from simply changing the composition of the surface metal to sophisticated approaches such as the immobilization of single atoms on a metal substrate. Molecular frameworks provide a powerful platform for the implementation of isolated and discrete active sites while unique diffusional environments further improve selectivity. The implementation of nanoconfined substrate channels around these highly controlled active sites offers further ability to control selectivity through altering the solution environment and transport of reactants and products. Implementing these strategies together offers a unique opportunity to improve nanozyme selectivity in both sensing and catalysis., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Creating high surface area nanocatalysts that contain stacking faults is a promising strategy to improve catalytic activity. Stacking faults can tune the reactivity of the active sites, leading to improved catalytic performance. The formation of branched metal nanoparticles with control of the stacking fault density is synthetically challenging. In this work, we demonstrate that varying the branch width by altering the size of the seed that the branch grows off is an effective method to precisely tune the stacking fault density in branched Ni nanoparticles. A high density of stacking faults across the Ni branches was found to lower the energy barrier for Ni 2+ /Ni 3+ oxidation and result in enhanced activity for electrocatalytic oxidation of 5-hydroxylmethylfurfural. These results show the ability to synthetically control the stacking fault density in branched nanoparticles as a basis for enhanced catalytic activity.

Branched metal nanoparticles have unique catalytic properties because of their high surface area with multiple branches arranged in an open 3D structure that can interact with reacting species and tailorable branch surfaces that can maximize the exposure of desired catalytically active crystal facets. These exceptional properties have led to the exploration of the roles of branch structural features ranging from the number and dimensions of branches at the larger scales to the atomic-scale arrangement of atoms on precise crystal facets. The fundamental significance of how larger-scale branch structural features and atomic-scale surface faceting influence and control the catalytic properties has been at the forefront of the design of branched nanoparticles for catalysis. Current synthetic advances have enabled the formation of branched nanoparticles with an unprecedented degree of control over structural features down to the atomic scale, which have unlocked opportunities to make improved nanoparticle catalysts. These catalysts have high surface areas with controlled size and surface facets for achieving exceedingly high activity and stability. The synthetic advancement has recently led to the use of branched nanoparticles as ideal substrates that can be decorated with a second active metal in the form of islands and single atoms. These decorated branched nanoparticles have new and highly effective catalytic active sites where both branch metal and decorating metal play essential roles during catalysis.In the opening half of this Account, we critically assess the important structural features of branched nanoparticles that control catalytic properties. We first discuss the role of branch dimensions and the number of branches that can improve the surface area but can also trap gas bubbles. We then investigate the atomic-scale structural features of exposed surface facets, which are critical for enhancing catalytic activity and stability. Well-defined branched nanoparticles have led to a fundamental understanding of how the branch structural features influence the catalytic activity and stability, which we highlight for the oxygen evolution reaction (OER) and biomass oxidation. In discussing recent breakthroughs for branched nanoparticles, we explore the opportunities created by decorated branched nanoparticles and the unique bifunctional active sites that are exposed on the branched nanoparticle surfaces. This class of catalysts is of rapidly growing importance for reactions including the hydrogen evolution reaction (HER) and methanol oxidation reaction (MOR), where two exposed metals are required for efficient catalysis. In the second half of this Account, we explore recent advances in the synthesis of branched nanoparticles and highlight the cubic-core hexagonal-branch growth mechanism that has achieved excellent control of all of the important structural features, including branch dimensions, number of branches, and surface facets. We discuss the slow precursor reduction as an effective strategy for decorating metal islands with controlled loadings on the branched nanoparticle surfaces and the spread of these metal islands to form single-atom active sites. We envisage that the key synthetic and structural advances identified in this Account will guide the development of the next-generation electrocatalysts.

Alterations in DNA methylation, a stable epigenetic marker, are important components in the development of cancer. It is vital to develop diagnostic systems with the ability to rapidly quantify DNA methylation with high sensitivity and selectivity. However, the analysis of DNA methylation must address two main challenges: (i) ultralow abundance and (ii) differentiating methylated cytosine from normal cytosine on target DNA sequence in the presence of an overwhelming background of circulating cell-free DNA. Here we report the development of an ultrasensitive and highly-selective electrochemical biosensor for the rapid detection of DNA methylation in blood. The sensing of DNA methylation involves the hybridization on a network of probe DNA modified gold-coated magnetic nanoparticles (DNA-Au@MNPs) complementary to target DNA, and subsequently enzymatic cleavage to differentiate methylated DNA strands from corresponding unmethylated DNA strands. The biosensor presents a dynamic range from 2 aM to 20 nM for 110 nucleotide DNA sequences containing a single-site methylation with the lowest detected concentration of 2 aM. This DNA-Au@MNPs based sensor provides a promising method to achieve 35 min response time and minimally invasive diagnosis of ovarian cancer., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Tumorigenic environments, especially aberrantly overexpressed oncogenic microRNAs, play a critical role in various activities of tumor progression. However, developing strategies to effectively utilize and manipulate these oncogenic microRNAs for tumor therapy is still a challenge. To address this challenge, spherical nucleic acids (SNAs) consisting of gold nanoparticles in the core and antisense oligonucleotides as the shell are fabricated. Hybridized to the oligonucleotide shell is a DNA sequence to which doxorubicin is conjugated (DNA-DOX). The oligonucleotides shell is designed to capture overexpressed miR-21/miR-155 and inhibit the expression of these oncogenic miRNAs in tumor cells after tumor accumulation to manipulate genetic environment for accurate gene therapy. This process further induces the aggregation of these SNAs, which not only generates photothermal agents to achieve on-demand photothermal therapy in situ, but also enlarges the size of SNAs to enhance the retention time in the tumor for sustained therapy. The capture of the relevant miRNAs simultaneously triggers the intracellular release of the DNA-DOX from the SNAs to deliver tumor-specific chemotherapy. Both in vivo and in vitro results indicate that this combination strategy has excellent tumor inhibition properties with high survival rate of tumor-bearing mice, and can thus be a promising candidate for effective tumor treatment., (© 2022 Wiley-VCH GmbH.)

Surface-enhanced Raman scattering (SERS) probes offer considerable opportunities in label-based biosensing and analysis. However, achieving specific and reproducible performance, where low detection limits are needed in complex media, remains a challenge. Herein, we present a general strategy employing gold nanorod SERS probes and rationally designed surface chemistry involving protein resistant layers and antibodies to allow for the selective detection of species in complex media. By utilizing the ability of gold nanorods for selective surface modification, Raman reporters (4-mercaptobenzoic acid) were attached to the tips. Importantly, the sides of the nanorods were modified using a mixed layer of two different length stabilizing ligands (carboxyl-terminated oligo ethylene glycols) to ensure colloidal stability, while antibodies were attached to the stabilizing ligands. The nanoparticle interfacial design improves the colloidal stability, unlocks the capability of the probes for targeting biomolecules in complex matrices, and gives the probes the high SERS efficiency. The utility of this probe is demonstrated herein via the detection of Salmonella bacteria at the single bacterium level in complex food matrices using an anti- Salmonella IgG antibody-conjugated probe. The modular nature of the surface chemistry enables the SERS probes to be employed with a molecularly diverse range of biorecognition species ( e.g. , antibodies and peptides) for many different analytes, thus opening up new opportunities for efficient biosensing applications.

Knowledge of the interaction between aptamer and protein is integral to the design and development of aptamer-based biosensors. Nanoparticles functionalized with aptamers are commonly used in these kinds of sensors. As such, studies into how the number of aptamers on the nanoparticle surface influence both kinetics and thermodynamics of the binding interaction are required. In this study, aptamers specific for interferon gamma (IFN-γ) were immobilized on the surface of gold nanoparticles (AuNPs), and the effect of surface coverage of aptamer on the binding interaction with its target was investigated using fluorescence spectroscopy. The number of aptamers were adjusted from an average of 9.6 to 258 per particle. The binding isotherm between AuNPs-aptamer conjugate and protein was modeled with the Hill-Langmuir equation, and the determined equilibrium dissociation constant ( K ' D ) decreased 10-fold when increasing the coverage of aptamer. The kinetics of the reaction as a function of coverage of aptamer were also investigated, including the association rate constant ( k on ) and the dissociation rate constant ( k off ). The AuNPs-aptamer conjugate with 258 aptamers per particle had the highest k on , while the k off was similar for AuNPs-aptamer conjugates with different surface coverages. Therefore, the surface coverage of aptamers on AuNPs affects both the thermodynamics and the kinetics of the binding. The AuNPs-aptamer conjugate with the highest surface coverage is the most favorable in biosensors considering the limit of detection, sensitivity, and response time of the assay. These findings deepen our understanding of the interaction between aptamer and target protein on the particle surface, which is important to both improve the scientific design and increase the application of aptamer-nanoparticle based biosensor.

A massively parallel single particle sensing method based on core-satellite formation of Au nanoparticles was introduced for the detection of interleukin 6 (IL-6). This method exploits the fact that the localized plasmon resonance (LSPR) of the plasmonic nanoparticles will change as a result of core-satellite formation, resulting in a change in the observed color. In this method, the hue (color) value of thousands of 67 nm Au nanoparticles immobilized on a glass coverslip surface is analyzed by a Matlab code before and after the addition of reporter nanoparticles containing IL-6 as target protein. The average hue shift as the result of core-satellite formation is used as the basis to detect small amount of proteins. This method enjoys two major advantages. First it is able to analyze the hue values of thousands of nanoparticles in parallel in less than a minute. Secondly the method is able to circumvent the effect of non-specific adsorption, a major issue in the field of biosensing., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Controlling the formation of nanosized branched nanoparticles with high uniformity is one of the major challenges in synthesizing nanocatalysts with improved activity and stability. Using a cubic-core hexagonal-branch mechanism to form highly monodisperse branched nanoparticles, we vary the length of the nickel branches. Lengthening the nickel branches, with their high coverage of active facets, is shown to improve activity for electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF), as an example for biomass conversion., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Enzymes are characterized by an active site that is typically embedded deeply within the protein shell thus creating a nanoconfined reaction volume in which high turnover rates occur. We propose nanoparticles with etched substrate channels as a simplified enzyme mimic, denominated nanozymes, for electrocatalysis. We demonstrate increased electrocatalytic activity for the oxygen reduction reaction using PtNi nanoparticles with isolated substrate channels. The PtNi nanoparticles comprise an oleylamine capping layer that blocks the external surface of the nanoparticles participating in the catalytic reaction. Oxygen reduction mainly occurs within the etched channels providing a nanoconfined reaction volume different from the bulk electrolyte conditions. The oxygen reduction reaction activity normalized by the electrochemically active surface area is enhanced by a factor of 3.3 for the nanozymes compared to the unetched nanoparticles and a factor of 2.1 compared to mesoporous PtNi nanoparticles that possess interconnecting pores.

The integration of plasmonic nanoparticles into biosensors has the potential to increase the sensitivity and dynamic range of detection, through the use of single nanoparticle assays. The analysis of the localized surface plasmon resonance (LSPR) of plasmonic nanoparticles has allowed the limit of detection of biosensors to move towards single molecules. However, due to complex equipment or slow analysis times, these technologies have not been implemented for point-of-care detection. Herein, we demonstrate an advancement in LSPR analysis by presenting a technique, which utilizes an inexpensive CMOS-equipped digital camera and a dark-field microscope, that can analyse the λ max of over several thousand gold nanospheres in less than a second, without the use of a spectrometer. This improves the throughput of single particle spectral analysis by enabling more nanoparticles to be probed and in a much shorter time. This technique has been demonstrated through the detection of interleukin-6 through a core-satellite binding assay. We anticipate that this technique will aid in the development of high-throughput, multiplexed and point-of-care single nanoparticle biosensors., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Herein, we report a facile fabrication of a polymer (azobenzene and α-cyclodextrin-functionalized hyaluronic acid) and gold nanobipyramids (AuNBs) conjugated mesoporous silica nanoparticles (MSNs) to be used as an injectable drug delivery system for sustained cancer treatment. Because of the specific affinity between the hyaluronic acid (HA) on MSNs and the CD44 antigen overexpressed on tumor cells, the MSNs can selectively attach to tumor cells. The nanocomposite material then exploits thermoresponsive interactions between α-cyclodextrin and azobenzene, and the photothermal properties of gold nanobipyramids, to in situ self-assemble into a hydrogel under near-infrared (NIR) radiation. Upon gelation, the drug (doxorubicin)-loaded MSNs carriers were enclosed in the HA network of the hydrogel, whereas further degradation of the HA in the hydrogel due to the upregulation of hyaluronidase (HAase) around the tumor tissue will result in the release of MSNs from the hydrogel, which can then be taken by tumor cells and deliver their drug to the cell nuclei. This design is able to provide a microenvironment with rich anticancer drugs in, and around, the tumor tissue for time periods long enough to prevent the recrudescence of the disease. The extra efficacy that this strategy affords builds upon the capabilities of conventional therapies.

An unclonable plasmonic anti-counterfeiting strategy is demonstrated, which involves the use of molecule-embedded metal@silica core-shell nanoparticles as information carriers. A shadow-mask-lithography-assisted self-assembly is developed for the fabrication of the plasmonic security labels. The produced security labels show multiple sets of coding information that are highly unique, technically unreplicable, and can be robustly decoded by portable microscopes within seconds., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The phenomenon of nanoparticles attached to an electrode passivated by an organic layer allowing efficient electron transfer between redox species in solution and the underlying electrode to be restored has resulted in Chazalviel and Allongue proposing a theory [Chazalviel, J.-N.; Allongue, P. J. Am. Chem. Soc.2011, 133, 762-764] to explain this phenomenon. The theory suggests that with electrode-organic layer-nanoparticle constructs, high exchange current densities, compared with when the nanoparticles are absent, results in the rate of electron transfer being independent of the thickness of the organic layer until a threshold thickness is exceeded. Thereafter, the thicker the organic layer, the slower the rate of electron transfer. Herein we provide the first experimental data to support this theory using a single experimental system that can show the transition from thickness independent electron transfer kinetics to distant dependent kinetics. This was achieved using ethylenediamine electrodeposited on a glassy carbon electrode. Different numbers of deposition cycles were applied in order to fabricate different thicknesses of the organic film. The deposited films showed progressively greater blocking abilities toward ruthenium hexamine, as a redox active probe in solution, as the films got thicker. Electron transfer kinetics of nanoparticle-decorated surfaces showed a change from thickness independent to thickness dependent as the organic layer exceeded an average thickness of 20 Å. Electrochemical impedance spectroscopy, cyclic voltammetry, scanning electron microscopy, ellipsometry, and atomic force microscopy were used to characterize the fabricated surfaces.

New sensation: A resistance-based biosensor uses gold-coated magnetic nanoparticles (Au@MNPs) functionalized with the antibiotic enrofloxin (see picture; purple), which bind to anti-enrofloxin as analyte (blue). The Au@MNPs can be magnetically assembled between electrodes, and the measured resistance R is a function of analyte concentration., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Silver nanoparticles capped with mercaptoacetic acid and 2-aminoethanethiol short-chain alkanethiols were prepared by a one-step method in aqueous solution for monitoring pH and a range of heavy metal ions. The mode of transduction is optical, based on the change in aggregation of the nanoparticles in solution. Because of the different ionic interactions between the modified nanoparticles, these nanoparticle sensors can rapidly detect Pb(2+), Cu(2+) and Fe(2+), with detection limits as low as 1 × 10(-5) M, 5 × 10(-7) M and 5 × 10(-5) M respectively, as well as having the ability to detect Cu(2+) ions from Pb(2+) and Fe(2+). Furthermore, the same functionalised nanoparticles are also sensitive to pH; exhibiting a good linear dynamic response between pH 1 and 10.

A simple colorimetric method for the detection of copper ions in water is described. This method is based on the 'click' copper(I)-catalyzed azide-alkyne cycloaddition reaction and its use in promoting the aggregation of azide-tagged gold nanoparticles by a dialkyne cross-linker is described. Nanoparticle cross-linking, evidenced as a colour change, is used for the detection of copper ions. The lowest detected concentration by the naked eye was 1.8 μM, with the response linear with log(concentration) between 1.8-200 μM. The selectivity relative to other potentially interfering ions was evaluated., (This journal is © The Royal Society of Chemistry 2012)

Electrodes modified with passivating organic layers have been shown to, here and previously, to exhibit good Faradaic electrochemistry upon attachment of gold nanoparticles (AuNP). Due to their low background capacitances these constructs have good potential in electrochemical sensing. Herein is reported the application of these electrode constructs for impedance based immunosensing. The immunosensor was constructed by modifying a gold electrode with 4-thiophenol (4-TP) passivating layers by diazonium salt chemistry. Subsequently, the attachment of AuNP and then a biotin derivative as a model epitope to detect anti-biotin IgG were carried out. The interfacial properties of the modified electrodes were evaluated in the presence of Fe(CN)(6)(4-/3-) redox couple as a probe by cyclic voltammetry and electrochemical impedance spectroscopy. The impedance change, due to the specific immuno-interaction at the immunosensor surface was utilized to detect anti-biotin IgG. The increase in charge-transfer resistance (R(ct)) was linearly proportional to the concentration of anti-biotin IgG in the range of 5-500 ng mL(-1), with a detection limit of 5 ng mL(-1)., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Herein, we introduce the concept of utilizing conductive gold-coated magnetic nanoparticles as 'dispersible electrodes', which serve as the active element in the selective capture and direct electro-analytical quantification of analytes. This concept reduces response times and decreases detection limits by bringing the sensor to the analyte rather than the conventional paradigm of the analyte finding the sensor.

Physical and electrochemical properties of gold nanoparticle-based electrodes are highlighted. Polycrystalline gold electrodes are passivated by a self-assembled monolayer, then the immobilization of gold nanoparticles "switch on" the electrochemical reactivity of ruthenium. Herein, gap-mode Raman studies show that the location of the nanoparticles is on the top of the monolayer, meaning that the "switching on" cannot be attributed to a direct electrical contact between nanoparticles and the gold support. This "switching on" feature is also not affected by the size of the gold nanoparticles with a range of diameters between 4 and 67 nm. Further, the charge of the nanoparticles is investigated by grafting chemical groups onto the nanoparticles which is observed to alter the electron-transfer kinetics. The variation in rate constant however is insufficient to attribute the "switching on" phenomenon to a possible adsorption of the redox species onto the nanoparticles.

Controlling the formation of nanosized branched nanoparticles with high uniformity is one of the major challenges in synthesizing nanocatalysts with improved activity and stability. Using a cubic‐core hexagonal‐branch mechanism to form highly monodisperse branched nanoparticles, we vary the length of the nickel branches. Lengthening the nickel branches, with their high coverage of active facets, is shown to improve activity for electrocatalytic oxidation of 5‐hydroxymethylfurfural (HMF), as an example for biomass conversion. [ABSTRACT FROM AUTHOR]

The adoption of plasmonic nanomaterials in optical sensors, coupled with the advances in detection techniques, has opened the way for biosensing with single plasmonic particles. Single nanoparticle sensors offer the potential to analyse biochemical interactions at a single-molecule level, thereby allowing us to capture even more information than ensemble measurements. We introduce the concepts behind single nanoparticle sensing and how the localised surface plasmon resonances of these nanoparticles are dependent upon their materials, shape and size. Then we outline the different synthetic approaches, like citrate reduction, seed-mediated and seedless growth, that enable the synthesis of gold and silver nanospheres, nanorods, nanostars, nanoprisms and other nanostructures with tunable sizes. Further, we go into the aspects related to purification and functionalisation of nanoparticles, prior to the fabrication of sensing surfaces. Finally, the recent developments in single nanoparticle detection, spectroscopy and sensing applications are discussed. [ABSTRACT FROM AUTHOR]

We demonstrate that silicon (Si) nanoparticles with scattering properties exhibiting strong dielectric resonances can be successfully manipulated using optical tweezers. The large dielectric constant of Si has a distinct advantage over conventional colloidal nanoparticles in that it leads to enhanced trapping forces without the heating associated with metallic nanoparticles. Further, the spectral features of the trapped nanoparticles provide a unique marker for probing size, shape, orientation and local dielectric environment. We exploit these properties to investigate the trapping dynamics of Si nanoparticles with different dimensions ranging from 50 to 200 nm and aspect ratios between 0.4 and 2. The unique combination of spectral and trapping properties make Si nanoparticles an ideal system for delivering directed nanoscale sensing in a range of potential applications. [ABSTRACT FROM AUTHOR]