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Gold coated magnetic nanoparticles (Au@MNPs), modified with DNA sequences give dispersible electrodes that can detect ultralow amounts of microRNAs and other nucleic acids but, as with most other sensors, they require calibration. Herein we show how to adapt a calibration free approach for electrochemical aptamer-based sensors on bulk electrodes to microRNA (miR-21) detection with methylene blue terminated DNA modified Au@MNPs. The electrochemical square wave voltammetry signal from the DNA-Au@MNPs when collected at a bulk electrode under magnetic control, decreases upon capture of miR-21. We show that the square wave voltammogram has concentration dependent and independent frequencies that can be used to give a calibration free signal.

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Selective isolation of individual target cells from a heterogeneous population is technically challenging; however, the ability to retrieve single cells can have high significance in various aspects of biological research. Here, we present a new photoelectrochemical surface based on a transparent electrode that is compatible with high-resolution fluorescence microscopy for isolating individual rare cells from complex biological samples. This is underpinned by two important factors: (i) careful design of the electrode by patterning discrete Au disks of micron dimension on amorphous silicon-indium tin oxide films and (ii) orthogonal surface chemistry, which modifies the patterned electrode with self-assembly layers of different functionalities, to selectively capture target cells on the Au disks and resist cell binding to the amorphous silicon surface. The co-stimulation of the surface using light from a microscope and an electric potential triggers the reductive desorption of the alkanethiol monolayer from the Au disks to release the single cells of interest from the illuminated regions only. Using circulating tumor cells as a model, we demonstrate the capture of cancer cells on an antibody-coated surface and selective release of single cancer cells with low expression of epithelial cell adhesion molecules.

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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.

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The direct quantification of programmed death-ligand 1 (PD-L1) as a biomarker for cancer diagnosis, prognosis and treatment efficacy is an unmet clinical need. Herein, we demonstrate the first report of rapid, ultrasensitive and selective electrochemical detection of PD-L1 directly in undiluted whole blood using modified gold-coated magnetic nanoparticles as "dispersible electrodes" with an ultralow detection limit of 15 attomolar and a response time of only 15 minutes.

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Pt islands with different sizes were grown on amorphous Ni nanoparticles, allowing the tuning of the Pt-Ni interface without changing the hydrogen binding energy of the Pt sites. As a result, the HER activity of the electrocatalysts increases by decreasing the size of the Pt islands due to the greater surface area of the Pt-Ni interfaces.

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Thiols and disulfide contacts have been, for decades, key for connecting organic molecules to surfaces and nanoclusters as they form self-assembled monolayers (SAMs) on metals such as gold (Au) under mild conditions. In contrast, they have not been similarly deployed on Si owing to the harsh conditions required for monolayer formation. Here, we show that SAMs can be simply formed by dipping Si-H surfaces into dilute solutions of organic molecules or proteins comprising disulfide bonds. We demonstrate that S-S bonds can be spontaneously reduced on Si-H, forming covalent Si-S bonds in the presence of traces of water, and that this grafting can be catalyzed by electrochemical potential. Cyclic disulfide can be spontaneously reduced to form complete monolayers in 1 h, and the reduction can be catalyzed electrochemically to form full surface coverages within 15 min. In contrast, the kinetics of SAM formation of the cyclic disulfide molecule on Au was found to be three-fold slower than that on Si. It is also demonstrated that dilute thiol solutions can form monolayers on Si-H following oxidation to disulfides under ambient conditions; the supply of too much oxygen, however, inhibits SAM formation. The electron transfer kinetics of the Si-S-enabled SAMs on Si-H is comparable to that on Au, suggesting that Si-S contacts are electrically transmissive. We further demonstrate the prospect of this spontaneous disulfide reduction by forming a monolayer of protein azurin on a Si-H surface within 1 h. The direct reduction of disulfides on Si electrodes presents new capabilities for a range of fields, including molecular electronics, for which highly conducting SAM-electrode contacts are necessary and for emerging fields such as biomolecular electronics as disulfide linkages could be exploited to wire proteins between Si electrodes, within the context of the current Si-based technologies.

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The evolution of gaseous products is a feature common to several electrochemical processes, often resulting in bubbles adhering to the electrode's surface. Adherent bubbles reduce the electrode active area, and are therefore generally treated as electrochemically inert entities. Here, we show that this general assumption does not hold for gas bubbles masking anodes operating in water. By means of imaging electrochemiluminescent systems, and by studying the anisotropy of polymer growth around bubbles, we demonstrate that gas cavities adhering to an electrode surface initiate the oxidation of water-soluble species more effectively than electrode areas free of bubbles. The corona of a bubble accumulates hydroxide anions, unbalanced by cations, a phenomenon which causes the oxidation of hydroxide ions to hydroxyl radicals to occur at potentials at least 0.7 V below redox tabled values. The downhill shift of the hydroxide oxidation at the corona of the bubble is likely to be a general mechanism involved in the initiation of heterogeneous electrochemical reactions in water, and could be harnessed in chemical synthesis.

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Porous materials can be modified with physical barriers to control the transport of ions and molecules through channels via an external stimulus. Such capability has brought attention toward drug delivery, separation methods, nanofluidics, and point-of-care devices. In this context, gated platforms on which access to an electrode surface of species in solution can be reversibly hindered/unhindered on demand are appearing as promising materials for sensing and microfluidic switches. The preparation of a reversible gated device usually requires mesoporous materials, nanopores, or molecularly imprinted polymers. Here, we show how the breath-figure method assembly of graphene oxide can be used as a simple strategy to produce gated electrochemical materials. This was achieved by forming an organized porous thin film of graphene oxide onto an ITO surface. Localized brushes of thermoresponsive poly(N-isopropylacrylamide) were then grown to specific sites of the porous film by in situ reversible addition-fragmentation chain-transfer polymerization. The gating mechanism relies on the polymeric chains to expand and contract depending on the thermal stimulus, thus modulating the accessibility of redox species inside the pores. The resulting platform was shown to reversibly hinder or facilitate the electron transfer of solution redox species by modulating temperature from the room value to 45 °C or vice versa.

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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.

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Avoiding the growth of SiOx has been an enduring task for the use of silicon as an electrode material in dynamic electrochemistry. This is because electrochemical assays become unstable when the SiOx levels change during measurements. Moreover, the silicon electrode can be completely passivated for electron transfer if a thick layer of insulating SiOx grows on the surface. As such, the field of silicon electrochemistry was mainly developed by electron-transfer studies in nonaqueous electrolytes and by applications employing SiOx-passivated silicon-electrodes where no DC currents are required to cross the electrode/electrolyte interface. A solution to this challenge began by functionalizing Si-H electrodes with monolayers based on Si-O-Si linkages. These monolayers have proven very efficient to avoid SiOx formation but are not stable for a long-term operation in aqueous electrolytes due to hydrolysis. It was only with the development of self-assembled monolayers based on Si-C linkages that a reliable protection against SiOx formation was achieved, particularly with monolayers based on α,ω-dialkynes. This review discusses in detail how this surface chemistry achieves such protection, the electron-transfer behavior of these monolayer-modified silicon surfaces, and the new opportunities for electrochemical applications in aqueous solution.

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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.

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Light can be used to address electrochemical reactions on a monolithic semiconducting electrode with spatial and temporal resolution. Herein, such principle was used for the electrodeposition of Au, Ag and Cu nanoparticles on a unique silicon-based electrode. The parallel nature of the process granted manufacturing speed and platforms were applied to discriminate molecules via multi-wavelength and multivariate Raman analysis.

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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- and 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.

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Alexa Fluor 647 is a widely used fluorescent probe for cell bioimaging and super-resolution microscopy. Herein, the reversible fluorescence switching of Alexa Fluor 647 conjugated to bovine serum albumin (BSA) and adsorbed onto indium tin oxide (ITO) electrodes under electrochemical potential control at the level of single protein molecules is reported. The modulation of the fluorescence as a function of potential was observed using total internal reflectance fluorescence (TIRF) microscopy. The fluorescence intensity of the Alexa Fluor 647 decreased, or reached background levels, at reducing potentials but returned to normal levels at oxidizing potentials. These electrochemically induced changes in fluorescence were sensitive to pH despite that BSA-Alexa Fluor 647 fluorescence without applied potential is insensitive to pH between values of 4-10. The observed pH dependence indicated the involvement of electron and proton transfer in the fluorescence switching mechanism.

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An effective strategy for regioselective modification and directional assembly of anisotropic nanoparticles is demonstrated to explore the electric field enhancement in assembled gold nanobipyramids compared with gold nanorods. The well-defined secondary plasmonic hot spots between the coupled gold nanobipyramids exhibit the capability for single molecule detection.

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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.

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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.

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Light can be used to spatially resolve electrochemical measurements on a semiconductor electrode. This phenomenon has been explored to detect DNA hybridization with light-addressable potentiometric sensors and, more recently, with light-addressable amperometric sensors based on organic-monolayer-protected Si(100). Here, a contribution to the field is presented by comparing sensing performances when bovine serum albumin (BSA) and hexaethylene glycol (OEG6) are employed as antifouling layers that resist nonspecific adsorption to the DNA-modified interface on Si(100) devices. What is observed is that both sensors based on BSA or OEG6 initially allow electrochemical distinction among complementary, noncomplementary, and mismatched DNA targets. However, only surfaces based on OEG6 can sustain electroactivity over time. Our results suggest that this relates to accelerated SiO x formation occasioned by BSA proteins adsorbing on monolayer-protected Si(100) surfaces. Therefore, DNA biosensors were analytically explored on low-doped Si(100) electrodes modified on the molecular level with OEG6 as an antifouling layer. First, light-activated electrochemical responses were recorded over a range of complementary DNA target concentrations. A linear semilog relation was obtained from 1.0 × 10-11 to 1.0 × 10-6 mol L-1 with a correlation coefficient of 0.942. Then, measurements with three independent surfaces indicated a relative standard deviation of 4.5%. Finally, selectivity tests were successfully performed in complex samples consisting of a cocktail mixture of four different DNA sequences. Together, these results indicate that reliable and stable light-activated amperometric DNA sensors can be achieved on Si(100) by employing OEG6 as an antifouling layer.

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Electrochemical DNA biosensors composed of a redox marker modified nucleic acid probe tethered to a solid electrode is a common experimental construct for detecting DNA and RNA targets, proteins, inorganic ions, and even small molecules. This class of biosensors generally relies on the binding-induced conformational changes in the distance of the redox marker relative to the electrode surface such that the charge transfer is altered. The conventional design is to attach the redox species to the distal end of a surface-bound nucleic acid strand. Here we show the impact of the position of the redox marker, whether on the distal or proximal end of the DNA monolayer, on the DNA interface electrochemistry. Somewhat unexpectedly, greater currents were obtained when the redox molecules were located on the distal end of the surface-bound DNA monolayer, notionally furthest away from the electrode, compared with currents when the redox species were located on the proximal end, close to the electrode. Our results suggest that a limitation in ion accessibility is the reason why smaller currents were obtained for the redox markers located at the bottom of the DNA monolayer. This understanding shows that to allow the quantification of the amount of redox labeled target DNA strand that hybridizes to probe DNA immobilized on the electrode surface, the redox species must be on the distal end of the surface-bound duplex.

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The current work reports the simultaneous enhancement in efficiency and stability of low-temperature, solution-processed triple cation based MA0.57FA0.38Rb0.05PbI3 (MA: methyl ammonium, FA: formamidinium, Rb: rubidium) perovskite solar cells (PSCs) by means of adsorbed carbon nanomaterials at the perovskite/electron transporting layer interface. The quantity and quality of the adsorbents are precisely controlled to electronically modify the ETL surface and lower the energy barrier across the interface. Carbon derivatives namely fullerene (C60) and PC71BM ([6,6]-phenyl C71 butyric acid methyl ester) are employed as adsorbents in conjunction with ZnO and together serve as a bilayer electron transporting layer (ETL). The adsorbed fullerene (C60-ZnO, abbreviated as C-ZnO) passivates the interstitial trap-sites of ZnO with interstitial intercalation of oxygen atoms in the ZnO lattice structure. C-ZnO ETL based PSCs demonstrate about a 19% higher average PCE compared to conventional ZnO ETL based devices and a nearly 9% higher average PCE than PC71BM adsorbed-ZnO (P-ZnO) ETL based PSCs. In addition, the interstitial trap-state passivation with a C-ZnO film upshifts the Fermi-level position of the C-ZnO ETL by 130 meV, with reference to the ZnO ETL, which contributes to an enhanced n-type conductivity. The photocurrent hysteresis phenomenon in C-ZnO PSCs is also substantially reduced due to mitigated charge trapping phenomena and concomitant reduction in an electrode polarization process. Another major highlight of this work is that, C-ZnO PSCs demonstrate a superior device stability retaining about 94% of its initial PCE in the course of a month-long, systematic degradation study conducted in our work. The enhanced device stability with C-ZnO PSCs is attributed to their high resistance to aging-induced recombination phenomena and a water-induced perovskite degradation process, due to a lower content of oxygen-related chemisorbed species on the C-ZnO ETL. The intricate mechanisms behind the efficiency and stability enhancement are investigated in detail and explained in the context of enhanced surface and interfacial electronic properties.