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3D interconnected structures can be made with molecular precision or with micrometer size. However, there is no strategy to synthesize 3D structures with dimensions on the scale of tens of nanometers, where many unique properties exist. Here, we bridge this gap by building up nanosized gold cores and nickel branches that are directly connected to create hierarchical nanostructures. The key to this approach is combining cubic crystal-structured cores with hexagonal crystal-structured branches in multiple steps. The dimensions and 3D morphology can be controlled by tuning at each synthetic step. These materials have high surface area, high conductivity, and surfaces that can be chemically modified, which are properties that make them ideal electrocatalyst supports. We illustrate the effectiveness of the 3D nanostructures as electrocatalyst supports by coating with nickel-iron oxyhydroxide to achieve high activity and stability for oxygen evolution reaction. This work introduces a synthetic concept to produce a new type of high-performing electrocatalyst support.

Growing Pt on Ag nanoparticles is a promising approach to forming catalysts that present active sites with both Pt and Ag available to improve the activity for the hydrogen evolution reaction (HER). By carefully controlling the concentration of a Pt precursor, the amount of Pt-decorated particles onto the Ag nanoparticles could be controlled to grow Pt islands between 0.6 and 1.5 nm. As a result, the relative amounts of the Ag-Pt active sites could be tuned. The smallest, 0.6 nm Pt islands on the Ag nanoparticle, with the highest ratio of Ag-Pt to Pt-Pt sites was found to have the highest activity and an accelerated Volmer step. DFT modeling showed that the improved performance was due to increased electron density on Pt from electron donation from neighboring Ag that leads to weaker Pt-H binding and the presence of more oxophilic Ag that can bind −OH on the active site that accelerates the water splitting.

Magnetic Particle Imaging (MPI) is a novel and emerging non-invasive technique that promises to deliver high quality images, no radiation, high depth penetration and nearly no background from tissues. Signal intensity and spatial resolution in MPI are heavily dependent on the properties of tracers. Hence the selection of these nanoparticles for various applications in MPI must be carefully considered to achieve optimum results. In this review, we will provide an overview of the principle of MPI and the key criteria that are required for tracers in order to generate the best signals. Nanoparticle materials such as magnetite, metal ferrites, maghemite, zero valent iron@iron oxide core@shell, iron carbide and iron-cobalt alloy nanoparticles will be discussed as well as their synthetic pathways. Since surface modifications play an important role in enabling the use of these tracers for biomedical applications, coating options including the transfer from organic to inorganic media will also be discussed. Finally, we will discuss different biomedical applications and provide our insights into the most suitable tracer for each of these applications.

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 Ni2+/Ni3+ 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.

Single Pt atom catalysts are key targets because a high exposure of Pt substantially enhances electrocatalytic activity. In addition, PtRu alloy nanoparticles are the most active catalysts for the methanol oxidation reaction. To combine the exceptional activity of single Pt atom catalysts with an active Ru support we must overcome the synthetic challenge of forming single Pt atoms on noble metal nanoparticles. Here we demonstrate a process that grows and spreads Pt islands on Ru branched nanoparticles to create single-Pt-atom-on-Ru catalysts. By following the spreading process by in situ TEM, we found that the formation of a stable single atom structure is thermodynamically driven by the formation of strong Pt–Ru bonds and the lowering of the surface energy of the Pt islands. The stability of the single-Pt-atom-on-Ru structure and its resilience to CO poisoning result in a high current density and mass activity for the methanol oxidation reaction over time. [Figure not available: see fulltext.]

Gold-coated magnetic nanoparticles are key materials for the fast separation and ultrasensitive detection of analytes in magnetoplasmonic sensors. However, the synthesis of gold-coated magnetic nanoparticles typically requires small-scale, colloidal methods over hours or days and often results in incomplete shells with variable optical properties. A robust, rapid, and scalable synthesis method is still needed to reliably form a complete gold nanoshell around magnetic nanoparticles. Herein, a new methodology for the synthesis of gold-coated magnetic nanoparticles via a flow-based manufacturing system that can easily be scaled up is presented. The developed method first produces gold-seeded silica coated magnetic nanoparticles and then a complete, tunable gold shell with relatively uniform size and shape. The flow-based method can be performed in a total time of less than 2 min, enabling rapid and complete gold coating. The particles show both excellent magnetic and plasmonic properties, which facilitates application as biosensing agents in dark-field microscopy and surface-enhanced Raman scattering.

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 nanopart

The integration of hierarchical structure, chemistry, and functional activity within tissue-engineered scaffolds is of great importance in mimicking native bone tissue. Bone is a highly mineralized tissue which forms at ambient conditions by continuous crystallization of the mineral phase within an organic matrix in the presence of bone residing cells. Despite recent advances in the biofabrication of complex engineered tissues, replication of the heterogeneity of bone microenvironments has been a major challenge in constructing biomimetic bone scaffolds. Herein, inspired by the bone biomineralization process, the first example of bone mimicking constructs by 3D writing of a novel apatite-transforming ink in a supportive microgel matrix with living cells is demonstrated. Using this technique, complex bone-mimicked constructs are made at room temperature without requiring invasive chemicals, radiation, or postprocessing steps. This study demonstrates that mineralized constructs can be deposited within a high density of stem cells, directing the cellular organization, and promoting osteogenesis in vitro. These findings offer a new strategy for fabrication of bone mimicking constructs for bone tissue regeneration with scope to generate custom bone microenvironments for disease modeling, multicellular delivery, and in vivo bone repair.

We report the development of metal-organic framework (MOF)-based probes for the direct and rapid detection and quantification of perfluorooctanoic acid (PFOA) by mass spectrometry. Four water-resistant MOFs - ZIF-8, UiO-66, MIL88-A, and Tb2(BDC)3 - were coated on poly(dopamine) precoated stainless steel needles and used to rapidly preconcentrate PFOA from water for direct analysis by nanoelectrospray ionization mass spectrometry. The analytical performance of each MOF for detecting PFOA was correlated with both the calculated binding energy of the MOF for PFOA and the relative change in the surface area of the MOF upon exposure to PFOA. MOF-functionalized probes can be used for the rapid (<5 min) and sensitive quantification of PFOA molecules at low ng L-1 levels in environmental water samples (i.e., tap water, rainwater, and seawater) with no sample preparation. The limit of detection of PFOA in ultrapure water was 11.0 ng L-1. Comparable accuracy to an accredited analytical method was achieved, despite the MOF-functionalized probe approach being 40 times quicker and requiring 10 times less sample. These features indicate that MOF-coated probes are promising for the direct and rapid monitoring of polyfluorinated substances and other pollutants in the field.

Disease diagnosis at earlier stages requires the development of ultrasensitive biosensors for detecting low-abundance biomarkers in complex biological fluids within a reasonable time frame. Here, we demonstrate the development of an ultrasensitive nanopore blockade biosensor that can rapidly diagnose a model protein biomarker, prostate-specific antigen (PSA) with high selectivity. The solid-state nanopores have gold located only along the length of the nanopore whilst the rest of the membrane is silicon nitride. The orthogonal use of materials allows nanopore arrays with a different surface chemistry inside the nanopore relative to the rest of the membrane to be fabricated. The importance of this differential surface chemistry is it can improve the detection limit of nanopore blockade sensors in quantitative analysis. Based on such functionalized nanopore devices, nanopore blockade sensors lower the limit of detection by an order of magnitude and enable ultrasensitive detection of PSA as low as 80 aM. The findings from this study open new opportunities for nanopore sensors in further developments including optical detection and ultralow detection limit biosensing at complex biological fluids.

Single molecule measurements are revolutionizing the understanding of the stochastics of behavior of single molecules. There is a common theme referred to as a near-field approach, in how many single molecule measurements are being performed in assays. The term near field is used because the measurement volume is typically very small such that a single molecule, or a single molecule binding pair, within that volume is of an appreciable concentration. The next development in detection will be performing many single molecule measurements at one time such that single molecule measurements can be used as the basis for quantitative analysis. There have already been some notable developments in this direction. Again, all have a common theme in that nanoparticles are used to create many near-field volumes that can be measured simultaneously. Herein, the coupled developments in nanoparticles and measurement strategies that allow nanoparticles to be the backbone of the next generation of sensing technologies are discussed.

Controlling which facets are exposed in nanocrystals is crucial to understanding different activity between ordered and disordered alloy electrocatalysts. We modify the degree of ordering of Pt3Sn nanocubes, while maintaining the shape and size, to enable a direct evaluation of the effect of the order on ORR catalytic activity. We demonstrate a 2.3-fold enhancement in specific activity by 60- A nd 30%-ordered Pt3Sn nanocubes compared to 95%-ordered. This was shown to be likely due to surface vacancies in the less-ordered particles. The greater order, however, results in higher stability of the electrocatalyst, with the more disordered nanoparticles showing the dissolution of tin and platinum species during electrocatalysis.

Heterojunctions are typically used to generate large photovoltages and to influence the direction of flow of charge carriers on photovoltaic and photocatalytic devices. Herein, we propose how heterojunctions can be used as a pathway for tuning the peak position of redox active monolayers. This was possible by exploring the principle of contact between materials in heterojunctions leading to a common equilibrium Fermi level for both sides of the heterojunction. The phenomenon was demonstrated with thin layers of intrinsic amorphous silicon deposited on platinum, indium tin oxide, and either n-type or p-type crystalline silicon electrodes. At fixed light-intensity conditions, the potential required for electron transfer of a model redox probe was modulated according to the substrate on which the amorphous silicon was deposited. This allowed us to alter the peak position of a redox process occurring on the electrolyte side of the junction despite it being isolated from the underlying conducting material. We show how such an effect can be explored in a potential range that encompasses any of the redox monolayers electroactive in aqueous electrolytes.

A strategy of direct growth of Pt on Ni was used to create and control Pt crystal defects on the surface of Ni-Pt core-shell nanoparticles. The control over the types of defects was easily achieved by changing the surfactant system. In this work, two types of crystal defects have been introduced into Ni-Pt core-shell nanoparticles: polycrystalline shells with multiple grain boundaries and step-edge shells with undercoordinated atoms at corners and steps. We show that the step-edge shell has a higher specific activity for the oxygen reduction reaction (ORR), while the thinner polycrystalline shell results in a higher activity per mass and stability. Our results suggest that Ni-Pt core-shell nanoparticles with a thin Pt shell that have high density of crystal defect should be targeted for high performance ORR catalysts.

Zero valent iron core–iron oxide shell nanoparticles coated with a multi-phosphonate brush co-polymer are shown to be small and effective magnetic nanoparticle imaging tracers.

Spatial control of surface functionalization and interactions is essential for microarray-based analysis. This study reports the fabrication of two-dimensional molecular films with site-specific functionalities, forming microarrays at discrete locations. Arrays of microsized gold disks were produced on a silicate membrane using microfabrication. On these arrays, orthogonal self-assembly of molecules was performed that can specifically bind to gold or silicate. The gold array elements were functionalized with a range of alkanethiols and the silicate with polymeric poly-l-lysine-grafted-poly(ethylene glycol) (PLL-PEG). The surface functionalization on the gold disk array and the surrounding substrate was characterized at each step using X-ray photoelectron spectroscopy (XPS) to show that alkanethiols are specifically attached to the gold. PLL-PEG was used to provide resistance against nonspecific protein and cell adsorption and attached exclusively to the silicate. The effectiveness of the surface chemistry was validated by the selective self-assembly of a gold nanoparticle monolayer array on the gold regions. In a more sophisticated example, selective adhesion of MCF-7 cells to anti-EpCAM antibody modified gold areas of the gold-silicate surface was demonstrated to give a cell microarray. This study provides a general approach to fabricate chemical patterns on silicon-based devices with the convergence of microfabrication and material-specific surface modification, which may be useful to expand the functionalities and potential applications for patterned biomolecular films. Importantly, the ability to pattern surfaces with different surface chemistries is not limited to planar surfaces using this orthogonal surface-coupling approach.

We report on the characterisation of the optical properties and dynamic behaviour of optically trapped single stimuli-responsive plasmonic nanoscale assemblies. Nano-assemblies consist of a core-satellite arrangement where the constituent nanoparticles are connected by the thermoresponsive polymer, poly(DEGA-co-OEGA). The optical tweezers allow the particles to be held isolated in solution and interrogated using dark-field spectroscopy. Additionally, controlling the optical trapping power provides localised heating for probing the thermal response of the nanostructures. Our results identify a number of distinct core-satellite configurations that can be stably trapped, which are verified using finite element modelling. Laser heating of the nanostructures through the trapping laser yields irreversible modification of the arrangement, as observed through the scattering spectrum. We consider which factors may be responsible for the observed behaviour in the context of the core-satellite geometry, polymer-solvent interaction, and the bonding of the nanoparticles.

The detection principle of nanopore sensors relies on measuring changes in electrical signal as analyte molecules translocate through a nanoscale pore. There are two challenges with this experimental construct when using nanopores for quantitative sensing with low detection limits in complex samples. The first is getting the analyte to the nanopore in a reasonable time frame and the second is other species in the sample also translocating through the nanopore and generating erroneous signals. We have developed a nanopore blockade sensor that alleviates the limitations of diffusion-limited mass transport and non-specific signals. Antibody-modified magnetic nanoparticles are utilized to deliver analytes of interest extracted from sample to an array of antibody-modified nanopores under a controlled electromagnet, resulting in long-term nanopore blocking events due to the formation of sandwiched immunocomplexes. Herein, this study reports on understanding some of important parameters in determining the performance of nanopore blockade sensing system, where prostate-specific antigen (PSA) is used as a model analyte. We describe the characterization of nanopore blockade sensing of PSA by (1) tuning on/off the electromagnet, (2) varying nanopore number in a nanopore chip, and (3) deploying the sensor in human plasma. Results show that magnetophoresis effectively facilitates active delivery and selective sensing of PSA to the nanopore. Nanopore chips with a larger number of nanopores are shown to receive more nanopore blockades for a given concentration of analyte. Furthermore, identifiable blockade events accounted for successful detection of PSA in plasma, indicate the high specificity of the sensing system.

Light-activated electrochemistry (LAE) consists of employing a focused light beam to illuminate a semiconducting area and make it electrochemically active. Here, we show how to reduce the electrochemical spatial resolution to submicron by exploiting the short lateral diffusion of charge carriers in amorphous silicon to improve the resolution of LAE by 60 times. This journal is

The electrocatalysis of the oxygen evolution reaction (OER) at the surface of oxidized metal electrocatalysts is highly dependent on the structure and composition of the surface oxide. Here, Au core- Co branched nanoparticles were synthesized using a cubic-core hexagonal-branch growth approach in a slow reductive solution synthesis, resulting in highly crystalline metallic hcp Co branches. Electrochemical surface oxidation of the Co branched nanoparticles resulted in formation of Co(OH)2 that enable the formation of a higher number of active sites under OER conditions compared to Co3O4. Differently from polycrystalline spherical Au−Co core-shell nanoparticles, the oxidized structure on the Co branched nanoparticle surface is retained with electrochemical cycling, resulting in improved OER activity and stability.

© 2020 Wiley-VCH GmbH Recent advances in CRISPR based biotechnologies have greatly expanded our capabilities to repurpose CRISPR for the development of biomolecular sensors for diagnosing diseases and understanding cellular pathways. The key attribute that allows CRISPR to be widely utilized is the programmable and highly selective mechanism. In this Minireview, we first illustrate the molecular principle of CRISPR functioning process from sensing to actuating. Next, the CRISPR based biosensing strategies for nucleic acids, proteins and small molecules are summarized. We highlight some of recent advances in applications for in vitro detection of biomolecules and in vivo imaging of cellular networks. Finally, the challenges with, and exciting prospects of, CRISPR based biosensing developments are discussed.

The reaction of hydrogen-terminated Si(100) with 1,8-nonadiyne was previously shown to afford robust surfaces where oxidation of the substrate is not evident. Here, the experimental conditions required for reacting hydrogen-terminated Si(100) with α,ω-diynes of different lengths is explored via thermal hydrosilylation of 1,6-heptadiyne, 1,8-nonadiyne, 1,10-undecadiyne and 1,15-hexadecadiyne. X-ray photoelectron spectroscopy indicated monolayers were successfully formed with oxide levels below the XPS detection limit for molecules with lengths varying from 7 to 11 carbons. It was observed that the apparent rate of electron transfer (ket) was affected not only by the SAM thickness, but also by hopping between ferrocene moieties where the presence of tiny oxidative defects act as electron transfer hotspots.

Branched nanoparticles are one of the most promising nanoparticle catalysts as their branch sizes and surfaces can be tuned to enable both high activity and stability. Understanding how the crystallinity and surface facets of branched nanoparticles affect their catalytic performance is vital for further catalyst development. In this work, a synthesis is developed to form highly branched ruthenium (Ru) nanoparticles with control of crystallinity. It is shown that faceted Ru branched nanoparticles have improved stability and activity in the oxygen evolution reaction (OER) compared with polycrystalline Ru nanoparticles. This work achieves a low 180 mV overpotential at 10 mA cm −2 for hours, demonstrating that record-high stability for Ru nanocrystals can be achieved while retaining high activity for OER. The superior electrocatalytic performance of faceted Ru branched nanoparticles is ascribed to the lower Ru dissolution rate under OER conditions due to low-index facets on the branch surfaces.

Driven by the quest for future energy solution, faceted metal nanoparticles are being pursued as the next generation electrocatalysts for renewable energy applications. Thanks to recent advancement in solution phase synthesis, different low- and high-index facets on metal nanocrystals become accessible and are tested for specific electrocatalytic reactions. This minireview summarises the key approaches to prepare nanocrystals containing the most catalytically active platinum group metals (Pt, Pd, Ru, Ir and Rh) exposed with low- and high-index facets using solution phase synthesis. Electrocatalytic studies related to the different facets are highlighted to emphasise the importance of exposing facets for catalysing these reactions, namely oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), alcohol oxidation including methanol (MOR) and ethanol oxidation reactions (EOR), formic acid oxidation reaction (FAOR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). The future outlook discusses the challenges and opportunities for making electrocatalysts that are even more active and stable.

The direct growth of Pt islands on lattice mismatched Ni nanoparticles is a major synthetic challenge and a promising strategy to create highly strained Pt atoms for electrocatalysis. By using very mild reaction conditions, Pt islands with tunable strain were formed directly on Ni branched particles. The highly strained 1.9 nm Pt-island on branched Ni nanoparticles exhibited high specific activity and the highest mass activity for hydrogen evolution (HER) in a pH 13 electrolyte. These results show the ability to synthetically tune the size of the Pt islands to control the strain to give higher HER activity.

The electrochemical formation of oxide on metallic surfaces often changes their electrocatalytic performance. In this work, we have studied this effect on the methanol oxidation reaction by systematically controlling the PdO formation/reduction potential using Au−Pd core-shell nanocrystals with different Pd shell thicknesses. AuPd0.4 core-shell nanocrystals have a 150 mV positive shift in the PdO reduction potential with respect to Pd nanocrystals and 2.9 and 8.8 times higher charge density in the anodic and cathodic scan of cyclic voltammetry respectively. The origin of the higher activity comes predominantly from electronic effects caused by the Au core that results in higher availability of Pd sites at more positive potentials.

Carbon-based surfaces were explored here for the synthesis of heterometallic surface-bound catalysts. This takes advantage of catalytic enhancements found using bimetallic catalysts relative to monometallic analogues, as well as the advantages of heterogeneous catalysts over homogeneous catalysts. To achieve this, two organometallic cations with different metal centers, oxidation states, and coligands, [Rh(N,N′)(CO) 2 ] + and [Ir(N,N′)Cp∗Cl] + (N,N′ = pyrazolyltriazolylmethane ligands), were simultaneously immobilized onto the surface of carbon materials (carbon black and reduced graphene oxide). The relative concentration of the rhodium and iridium cations in the synthetic media was varied allowing for different metal ratios on the carbon surfaces. The composition of the complexes bound to the surfaces was confirmed using XPS which revealed the relative ratios of the iridium and the rhodium species on the surface, agreeing well with the values obtained by MP-AES. The materials were further characterized by N 2 absorption. The qualitative distribution of rhodium and iridium ions on the carbon surfaces was determined by STEM-EDX, revealing a uniform distribution of both complexes on the carbon surfaces. The efficiency of the materials as catalysts for intramolecular hydroamination was investigated. The data acquired demonstrated that the optimized ratio of rhodium and iridium on the carbon black material led to more effective catalysts than their monometallic counterparts. Having both complexes on the same carbon black surface presented an improvement in the catalytic activity compared to the complexes immobilized on separate particles.

This Perspective focuses on the latest strategies and challenges for the development of bioanalytical sensors with sub-picomolar detection limits. Achieving sub-picomolar detection limits has three major challenges: (1) assay sensitivity, (2) response time, and (3) selectivity (including limiting background signals). Each of these challenges is discussed, along with how nanomaterials provide the solutions. One strategy to gain greater sensitivity involves confining the sensing volume to the nanoscale, as used in nanopore- or nanoparticle-based sensors, because nanoparticles are ubiquitous in amplification. Methods to improve response time typically focus on obtaining an intimate mixture between the sensor and the sample either by extending the length scale of nanoscale sensors using nanostructuring or by dispersing magnetic nanoparticles through the sample to capture the analyte. Loading nanoparticles with many biorecognition species is one solution to help address the challenge of selectivity. Many examples in this Perspective explore the detection of prostate-specific antigen which enables a comparison between strategies. Finally, exciting future opportunities in developing single-molecule sensors and the requirements to go even lower in concentration are explored.

© 2019 The Royal Society of Chemistry. This article focuses on how nanoparticle shape affects the cellular internalisation and transport of nanoparticles inside cells and what the different analytical methods for determining nanoparticle internalisation by cells tell us. Rod-shaped nanoparticles typically show greater cellular internalisation relative to spherical nanoparticles, although there are studies with contradictory conclusions. The contradiction may be a result of differences in the materials being used in the comparison and/or a result of the analytical method employed. Finally, future opportunities in studying cellular internalisation with 3D cell-culture models and light-sheet microscopy are discussed.

Rationale: The decolouration of brilliant blue FCF by the action of titanium dioxide (TiO2) under ultraviolet (UV) exposure has been recently reported as the basis of a paper-based sensor for monitoring UV sun exposure. The mechanism of brilliant blue FCF photodegradation in the presence of the photocatalyst and the resulting photoproducts are thus far unknown. Methods: The UV-initiated photodegradation of brilliant blue FCF in the presence of TiO2 for both the aqueous and the solid state was investigated. Degradation in the solid state was observed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-MS). Decomposition of the dye in the aqueous state was analyzed using liquid chromatography/mass spectrometry (LC/MS) and ultraviolet–visible (UV–Vis) spectroscopy. Results: After UV radiation exposure, the brilliant blue FCF base peak [M1 + NH4]+ (m/z calc. 766.194 found 766.194) decreased in the LC/MS chromatogram with a concomitant appearance of BB-FCF decomposition products involving the sequential loss of the N-ethyl and N-methylbenzene sulfonate (MBSA) groups, assigned as [M2 + H]+ (-MBSA, calc. 579.163 found 579.162), [M3 + H]+ (-MBSA, −Et, calc. 551.131 found 551.131), [M4 + H]+ (-2MBSA, calc. 409.158 found 409.158), [M5 + H]+ (-2MBSA, −Et, calc. 381.127 found 381.127). Ions [M2 + H]+ and [M3 + H]+ were also identified in the photodegradation products using MALDI-MS. Observation by UV–Vis indicated a decrease in the solution absorbance maxima and an associated blue-shift upon UV exposure in solution. Conclusions: The LC/MS analysis indicated two main oxidation processes. The most obvious was attack of the N-methylene, eliminating either ethyl or MBSA groups. The presence of the hydroxylated decomposition product M13 ([M13 + H]+, calc. 595.157 found 595.157) supported this assignment. In addition, the detection of photoproduct M8, proposed to be 3-((ethylamino)methyl)benzenesulfonic acid ([M8 + H]+, calc. 216.069 found 216.06

Electrically insulating objects gain a net electrical charge when brought in and out of contact. This phenomenon - triboelectricity - involves the flow of charged species, but conclusively establishing their nature has proven extremely difficult. Here, we demonstrate an almost linear relationship between a plastic sample's net negative charge and the amount of solution metal ions discharged to metallic particles with a coefficient of proportionality linked to its electron affinity (stability of anionic fragments). The maximum magnitude of reductive redox work is also material dependent: metallic particles grow to a larger extent over charged dielectrics that yield stable cationic fragments (smaller ionization energy). Importantly, the extent to which the sample can act as electron source greatly exceeds the net charging measured in a Faraday pail/electrometer set up, which brings direct evidence of triboeletricity being a mosaic of positive and negative charges rather than a homogeneous ensemble and defines for the first time their quantitative scope in electrochemistry.

Optical biosensors are defined as portable optical devices that use biorecognition molecules to interrogate a sample for the presence of a target. The capabilities of optical biosensors have expanded rapidly with advances in miniature optical components and molecular engineering. Biosensors to meet the needs in health and environmental monitoring and food safety have become commercially available, with many more in the pipeline. We review the innovative approaches to overcoming existing hurdles to practical biosensor designs and explore potential areas for future breakthroughs in optical biosensor technology.

Magnetic nanoparticles (MNPs) are of high significance in sensing as they provide viable solutions to the enduring challenges related to lower detection limits and nonspecific effects. The rapid expansion in the applications of MNPs creates a need to overview the current state of the field of MNPs for sensing applications. In this review, the trends and concepts in the literature are critically appraised in terms of the opportunities and limitations of MNPs used for the most advanced sensing applications. The latest progress in MNP sensor technologies is overviewed with a focus on MNP structures and properties, as well as the strategies of incorporating these MNPs into devices. By looking at recent synthetic advancements, and the key challenges that face nanoparticle-based sensors, this review aims to outline how to design, synthesize, and use MNPs to make the most effective and sensitive sensors.

Nanopore sensors detect individual species passing through a nanoscale pore. This experimental paradigm suffers from long analysis times at low analyte concentration and non-specific signals in complex media. These limit effectiveness of nanopore sensors for quantitative analysis. Here, we address these challenges using antibody-modified magnetic nanoparticles ((anti-PSA)-MNPs) that diffuse at zero magnetic field to capture the analyte, prostate-specific antigen (PSA). The (anti-PSA)-MNPs are magnetically driven to block an array of nanopores rather than translocate through the nanopore. Specificity is obtained by modifying nanopores with anti-PSA antibodies such that PSA molecules captured by (anti-PSA)-MNPs form an immunosandwich in the nanopore. Reversing the magnetic field removes (anti-PSA)-MNPs that have not captured PSA, limiting non-specific effects. The combined features allow detecting PSA in whole blood with a 0.8 fM detection limit. Our ‘magnetic nanoparticle, nanopore blockade’ concept points towards a strategy to improving nanopore biosensors for quantitative analysis of various protein and nucleic acid species.

Herein is reported a new type of transparent electrode, prepared by depositing a thin layer of amorphous silicon film on indium tin oxide, which enables photoswitchable electrochemistry and optical imaging to be performed simultaneously. This offers the opportunity to visualise a spatially controlled electrochemical event on an unstructured electrode surface.

Modern high-throughput biosensors with sensitivity down to a single analyte molecule may be possible with single-molecule localization microscopy (SMLM). Functionalized surfaces can be fabricated with self-assembly monolayer chemistry on indium tin oxide (ITO) substrates but not glass. However, characterizations of SMLM-compatible fluorophores are primarily performed on glass substrates. Here we collect single-molecule kinetics data of isolated Alexa Fluor 647 molecules on bare and functionalized glass and ITO surfaces. Extracting the photophysical dynamics of the fluorophores allows direct comparison of behavior of this dye on these substrates and fitting data to a model that accounts for multiple reversible dark states. All surfaces had sensitivity sufficient to image single fluorophore molecules. Photophysical kinetics observed are similar between the two substrates. The photon yield from individual fluorophores was greatest on bare glass, but functionalized ITO surfaces showed superior yield to functionalized glass surfaces and nearly matched the yield of bare glass. Together these results indicate functionalized ITO as a promising substrate for modern single-molecule biosensors.

Enzymes can perform complex multistep cascade reactions by linking multiple distinct catalytic sites via substrate channeling. We mimic this feature in a generalized approach with an electrocatalytic nanoparticle for the carbon dioxide reduction reaction comprising a Ag core surrounded by a porous Cu shell, providing different active sites in nanoconfined volumes. The architecture of the nanozyme provides the basis for a cascade reaction, which promotes C-C coupling reactions. The first step occurs on the Ag core, and the subsequent steps on the porous copper shell, where a sufficiently high CO concentration due to the nanoconfinement facilitates C-C bond formation. The architecture yields the formation of n-propanol and propionaldehyde at potentials as low as-0.6 V vs RHE.

Carbon and graphene quantum dots (CQDs and GQDs), known as zero-dimensional (0D) nanomaterials, have been attracting increasing attention in sensing and bioimaging. Their unique electronic, fluorescent, photoluminescent, chemiluminescent, and electrochemiluminescent properties are what gives them potential in sensing. In this Review, we summarize the basic knowledge on CQDs and GQDs before focusing on their application to sensing thus far followed by a discussion of future directions for research into CQDs-A nd GQD-based nanomaterials in sensing. With regard to the latter, the authors suggest that with the potential of these nanomaterials in sensing more research is needed on understanding their optical properties and why the synthetic methods influence their properties so much, into methods of surface functionalization that provide greater selectivity in sensing and into new sensing concepts that utilize the virtues of these nanomaterials to give us new or better sensors that could not be achieved in other ways.

© 2019 The Royal Society of Chemistry. Herein, a glucose meter-based immunosensing platform is developed that allows the quantification of procalcitonin (PCT) in whole blood samples. PCT is a biomarker for sepsis and its early detection would improve the safety of the patient, as the diagnostic process will be easier and faster. The method employs liposomes with encapsulated glucose as a signal generation tag, which are then used in a sandwich immunoassay by conjugating an antibody to the liposome. The optimal liposomes' size and concentration of encapsulated glucose is determined experimentally to be 200 nm and 27.8 mM, respectively. Upon the addition of a surfactant (Triton X-100), the glucose is released and a signal is detected with a personal glucose meter (PGM). This signal is directly proportional to the concentration of the PCT in the sample. The dynamic range of the assay developed was 0.153-15.38 nM, and could allow the detection of PCT as low as 0.15 nM. The assay showed a high selectivity toward PCT against other proteins such as C-reactive protein and human serum albumin and good reproducibility. This assay was able to quantitatively determine the amount of PCT in whole blood samples at clinically-relevant concentrations.

The work presented here describes the development of an optical label-free biosensor based on a porous silicon ( PSi) Bragg reflector to study heterogeneity in single cells. Photolithographic patterning of a poly(ethylene glycol) (PEG) hydrogel with a photoinitiator was employed on RGD peptide-modified PSi to create micropatterns with cell adhesive and cell repellent areas. Macrophage J774 cells were incubated to form cell microarrays and single cell arrays. Moreover, cells on the microarrays were lysed osmotically with Milli-Q™ water and the infiltration of cell lysate into the porous matrix was monitored by measuring the red shift in the reflectivity. On average, the magnitude of red shift increased with the increase in the number of cells on the micropatterns. The red shift from the spots with single cells varied from spot to spot emphasizing the heterogeneous nature of the individual cells.

Supercapacitors are attracting increasing research interest because they are expected to achieve battery-level energy density while having a long calendar life and a short charging time. However, the development of large-scale and cost-reasonable production methods for flexible, wearable and arbitrary-shaped supercapacitor devices still faces enormous challenges. Herein, a 3D-network, porous graphene/CoS 2 /Ni 3 S 4 (G/CoS 2 /Ni 3 S 4 ) composite electrode has been designed and synthesized through a combination of solvothermal and vulcanization methods. By combining the networked CoS 2 /Ni 3 S 4 nanoflakes with reduced graphene oxide (RGO) nanosheets, the as-prepared composite electrode exhibits good conductivity, a high density of electrochemically active sites and good cycling stability. The result is a high specific capacitance of 1739 F g −1 at a current density of 0.5 A g −1 . Significantly, the arbitrary-shaped G/CoS 2 /Ni 3 S 4 ||GF hybrid supercapacitor devices can be printed directly on different substrates, which favorably combine mechanical flexibility, good cycling performance and high energy density. This methodology may be feasible to prepare fully-printable and wearable supercapacitors, and other electronic devices in large scale, thereby holding enormous potential for wearable technologies.

The native architecture of tissue segregates populations of cells through nanostructured membranes of biopolymers (e.g., basement membranes) which serve the dual purpose of providing scaffolding for cells and filtration through size-exclusion. A multilayered approach to fabricate tissue scaffolds where populations of encapsulated cells are separated by porous silicon (PSi)-based photonic crystal membranes with nano- and microstructure that mimics the basement membranes is reported here. The PSi films are fabricated to display discreet photonic bandgaps such that remote optical interrogation provides a specific resonance for each film. Through careful control of surface chemistry, nanostructured PSi films are engineered to serve as optical biosensors and biomolecule release reservoirs, where the optical signature can report on these distinct functions remotely using a simple light source. The promise of this approach is demonstrated as a “smart” tissue scaffolding by monitoring matrix metalloprotease (MMP) activity from encapsulated multilayered co-cultures of mesenchymal stem cells and human microvascular endothelial cells, with concurrent attenuation of MMP activity through release of angiogenic-modulating compounds. The integration of optically registered biosensing and drug-release capabilities—within a multilayered hydrogel scaffold with multiple cell types—provides a new approach to tissue engineering where dynamic bioactivity can be monitored remotely in real-time.

The influence of interface engineering on the performance and photovoltaic properties of the PffBT4T-2OD poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3-di(2-octyldodecyl)-2,2′;5′,2″;5″,2-quaterthiophen-5,5-diy)] based polymer solar cells (PSCs) are investigated. Owing to the high crystallinity and processing parameter dependent morphology distribution of the PffBT4T-2OD polymer, the performance of the devices can vary significantly with power conversion efficiency (PCE) of around 10% has been reported via such morphology modification. In this work, we demonstrate the effect of trap state passivation at the electron transport layer (ETL)/Polymer interface on the performance of PffBT4T-2OD based PSCs. Aluminium doped ZnO (AZO) and pristine Zinc Oxide (ZnO) are employed as ETLs, which modified the polymer wettability and blend morphology. The interface engineered devices exhibited high PCE of over 11% with high Jsc of about 22.5 mA/cm2 which is about 19% higher than that of the conventional ZnO based devices. The reason behind such distinct enhancements is investigated using several material and device characterization methods including electrochemical impedance spectroscopy (EIS). The recombination resistance (Rrec) of the AZO based device is found to be 4.5 times higher than that of the ZnO devices. The enhanced photovoltaic parameters of the AZO based device are attributed to the superior charge transport characteristics in the ETL as well as at the ETL/polymer interface, enabling effective charge extraction at the respective electrodes with much lesser recombination. The mechanism and the processes behind such enhancements are also elaborated in detail.

Nanofabricated and nanopatterned surfaces have revealed the sensitivity of cell adhesion to nanoscale variations in the spacing of adhesive ligands such as the tripeptide arginine-glycine-aspartic acid (RGD). To date, surface characterisation and cell adhesion are often examined in two separate experiments so that the localisation of ligands and adhesion proteins cannot be combined in the same image. Here we developed self-assembled monolayer chemistry for indium tin oxide (ITO) surfaces for single molecule localisation microscopy (SMLM). Cell adhesion and spreading were sensitive to average RGD spacing. At low average RGD spacing, a threshold exists of 0.8 RGD peptides per µm2 that tether cells to the substratum but this does not enable formation of focal adhesions. These findings suggest that cells can sense and engage single adhesive ligands but ligand clustering is required for cell spreading. Thus, our data reveal subtle differences in adhesion biology that may be obscured in ensemble measurements.

Conjugating nanoparticles with polyethylene glycol (PEG) is a useful strategy to improve the colloidal and biological stability of nanoparticles. However, studies on PEGylation of two-dimensional layered double hydroxide (LDH) nanoparticles are very limited. The present work reported two functionalization approaches to synthesize PEG-conjugated LDH nanoparticles by introducing phosphonic acid terminated PEG before and after LDH aging. The successful PEGylation was confirmed and suggested to be via electrostatic interaction and a ligand exchange process. Different functionalization approaches resulted in different binding types of PEG on/in LDH nanoparticles. The PEG coating maintained the dispersity of LDH nanoparticles in water and saline with the feeding mass ratio of 1:1. Further colloidal stability tests of PEGylated LDHs revealed that the PEGylated LDH dispersity was affected by the feeding mass ratio of PEG/LDH, the molar weight of PEG and anions intercalated in the LDHs. In a test to determine the extent of non-specific protein adsorption, the PEGylation was effective at resisting non-specific bovine serum albumin adsorption on LDH nanoparticles with both functionalization methods investigated. Moreover, PEGylated LDH nanoparticles had no effect on cell viability up to 500 µg/mL, and demonstrated enhanced cellular uptake in a SK-MEL-28 cell culture. The results in this work indicate that conjugating phosphonic acid-terminated PEG on LDH nanoparticles is a promising strategy to improve the colloidal and biological stability of LDHs for biomedical applications.

Herein is described a facile method for the assembly of plasmonic gold nanoparticles into smart plasmonic core-satellite nanostructures that allow for the dynamic and reversible tuning of the localised surface plasmon resonance using temperature. This smart system takes advantage of the thermoresponsive polymer linker that modulates the gap distance between the core and satellites in response to the temperature, resulting in the tuning of the surface plasmon coupling and resultant optical shift. It permits optical shifts over a wide wavelength range and reversible control of the optical properties by altering the temperature, which may allow these systems to become candidates for temperature sensitive nanosensors.

We report here on a light addressable potassium (K+) sensor where light illumination of a semiconducting silicon electrode substrate results in a localized activation of the faradaic electrochemistry at the illuminated spot. This allows one, by electrochemical control, to oxidize surface bound ferrocene moieties that in turn trigger K+ transfer from the overlaid K+-selective film to the solution phase. The resulting voltammetric response is shown to be K+-selective, where peak position is a direct function of K+ activity at the surface of electrode. This concept was used to measure extracellular K+ concentration changes by stimulating living breast cancer cells. The associated decrease of intracellular K+ level was confirmed with a fluorescent K+ indicator. In contrast to light addressable potentiometry, the approach introduced here relies on dynamic electrochemistry and may be performed in tandem with other electrochemical analysis when studying biological events on the electrode.