Correction: Diamond nanowires modified with poly[3-(pyrrolyl)carboxylic acid] for the immobilization of histidine-tagged peptides.

Correction for 'Diamond nanowires modified with poly[3-(pyrrolyl)carboxylic acid] for the immobilization of histidine-tagged peptides' by Palaniappan Subramanian et al., Analyst, 2014, 139, 4343-4349, https://doi.org/10.1039/C4AN00146J.

Critical Role of Phosphorus in Hollow Structures Cobalt-Based Phosphides as Bifunctional Catalysts for Water Splitting.

Cobalt phosphides electrocatalysts have great potential for water splitting, but the unclear active sides hinder the further development of cobalt phosphides. Wherein, three different cobalt phosphides with the same hollow structure morphology (CoP-HS, CoP2 -HS, CoP3 -HS) based on the same sacrificial template of ZIF-67 are prepared. Surprisingly, these cobalt phosphides exhibit similar OER performances but quite different HER performances. The identical OER performance of these CoPx -HS in alkaline solution is attributed to the similar surface reconstruction to CoOOH. CoP-HS exhibits the best catalytic activity for HER among these CoPx -HS in both acidic and alkaline media, originating from the adjusted electronic density of phosphorus to affect absorption-desorption process on H. Moreover, the calculated ΔGH* based on P-sites of CoP-HS follows a quite similar trend with the normalized overpotential and Tafel slope, indicating the important role of P-sites for the HER process. Moreover, CoP-HS displays good performance (cell voltage of 1.67 V at a current density of 50 mA cm-2 ) and high stability in 1 M KOH. For the first time, this work detailly presents the critical role of phosphorus in cobalt-based phosphides for water splitting, which provides the guidance for future investigations on transition metal phosphides from material design to mechanism understanding.

Reduced graphene oxide-based field effect transistors for the detection of E7 protein of human papillomavirus in saliva.

Several challenging biological sensing concepts have been realized using electrolyte-gated reduced graphene oxide field effect transistors (rGO-FETs). In this work, we demonstrate the interest of rGO-FET for the sensing of human papillomavirus (HPV), one of the most common sexually transmitted viruses and a necessary factor for cervical carcinogenesis. The highly sensitive and selective detection of the HPV-16 E7 protein relies on the attractive semiconducting characteristics of pyrene-modified rGO functionalized with RNA aptamer Sc5-c3. The aptamer-functionalized rGO-FET allows for monitoring the aptamer-HPV-16 E7 protein binding in real time with a detection limit of about 100 pg mL-1 (1.75 nM) for HPV-16 E7 from five blank noise signals (95% confidence level). The feasibility of this method for clinical application in point-of-care technology is evaluated using HPV-16 E7 protein suspended in saliva and demonstrates the successful fabrication of a promising field effect transistor biosensor for HPV diagnosis.Graphical abstract.

Cobalt Oxide Porous Nanocubes-Based Electrochemical Immunobiosensing of Hepatitis B Virus DNA in Blood Serum and Urine Samples.

In this work, we report a new biosensing platform for hepatitis B virus (HBV) DNA genosensing using cobalt oxide (Co3O4) nanostructures. The tunable morphologies of Co3O4 nanostructures such as porous nanocubes (PNCs), nanooctahedra (NOHs), and nanosticks (NSKs) are synthesized, and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) patterns, nitrogen adsorption/desorption isotherms (BET), and electrochemical impedance spectral (EIS) methods. The HBV probe DNA (ssDNA) is immobilized on the Co3O4 nanostructures through coordinate bond formation between nucleic acid of ssDNA and Co metal, which results in highly stable nanostructured biosensing platform. To the best of our knowledge, first time the target cDNA of HBV is detected using ssDNA/Co3O4PNCs/GCE electrode by EIS method with a limit of detection (LOD) of 0.38 pM (signal-to-noise ratio (S/N) = 3). Moreover, the ssDNA/Co3O4PNCs/GCE has shown excellent specificity to HBV target cDNA, compared with noncomplementary DNA, and 1- and 3-mismatch DNAs. Finally, we explore ssDNA/Co3O4PNCs/GCE as potential electrode to test HBV DNA in blood serum and urine samples for practical applications.

Hierarchical core-shell structured Ni3S2/NiMoO4 nanowires: a high-performance and reusable electrochemical sensor for glucose detection.

Designing highly active electrode is important for the fabrication of electrochemical sensing platforms, and core-shell nanostructures with large specific surface areas and ease of accessibility are effective probes for the detection of biomolecules. In this work, we report the development of hierarchical core-shell Ni3S2/NiMoO4 nanowires on a nickel foam substrate (Ni-Ni3S2/NiMoO4) as a non-noble metal catalyst electrode for the electrochemical oxidation of glucose in alkaline electrolyte. As an electrochemical sensor for glucose detection, the fabricated hierarchical Ni-Ni3S2/NiMoO4 core-shell nanowires display an enhanced catalytic response, a fast response time of 1 s with a limit of detection (LOD) of 0.055 µM (S/N = 3), and a higher sensitivity of 10.49 µA µM-1 cm-2. Unlike Ni3S2 or NiMoO4 electrodes, the observed superior catalytic activity towards glucose is mainly due to the promotional effect of NiMoO4 nanosheets on the Ni3S2 nanowires, which can increase the large active surface area and generate numerous active sites within and on the surface walls of the nanowire structures. The developed Ni-Ni3S2/NiMoO4 nanowire electrode can selectively detect glucose in the presence of other carbohydrates, such as fructose, sucrose, lactose, maltose, galactose, mannose, and xylose, indicating potential anti-interference properties. The Ni-Ni3S2/NiMoO4 nanowire electrode is highly stable for reuse and its practical application is demonstrated using real blood serum samples. These results demonstrate that hierarchical core-shell Ni3S2/NiMoO4 nanowires show potential for application in the development of low-cost applied glucose sensors.

Diamond nanowires modified with poly[3-(pyrrolyl)carboxylic acid] for the immobilization of histidine-tagged peptides.

Coating boron-doped diamond nanowires (BDD NWs) with a conducting polymer, poly[3-(pyrrolyl)carboxylic acid], has been reported. Polymer coating was achieved through electropolymerization of 3-(pyrrolyl)carboxylic acid at the electrode interface by amperometrically biasing the BDD NWs interface until a predefined charge has passed. The poly[3-(pyrrolyl)carboxylic acid] modified BDD NWs (PPA-BDD NWs) were characterized by scanning electron microscopy (SEM) and cyclic voltammetry (CV). Using a deposition charge of 11 mC cm(-2) resulted in a thin polymer film deposition. The availability of the carboxylic groups of the polymer coated BDD NWs electrode was demonstrated through copper ion (Cu(2+)) chelation. The resulting complex was successfully used for the site-specific immobilization of histidine-tagged peptides. The binding process was followed by electrochemical impedance spectroscopy (EIS). The Cu(2+)-chelated PPA-BDD NWs interface showed peptide loading capability comparable to those of commercially available interfaces and can be easily regenerated several times using ethylenediaminetetraacetic acid (EDTA).

An impedimetric immunosensor based on diamond nanowires decorated with nickel nanoparticles.

Nanostructured boron-doped diamond has been investigated as a sensitive impedimetric electrode for the detection of immunoglobulin G (IgG). The immunosensor was constructed in a three-step process: (i) reactive ion etching of flat boron-doped diamond (BDD) interfaces to synthesize BDD nanowires (BDD NWs), (ii) electrochemical deposition of nickel nanoparticles (Ni NPs) on the BDD NWs, and (iii) immobilization of biotin-tagged anti-IgG onto the Ni NPs. Electrochemical impedance spectroscopy (EIS) was used to follow the binding of IgG at different concentrations without the use of any additional label. A detection limit of 0.3 ng mL(-1) (2 nM) with a dynamic range up to 300 ng mL(-1) (2 µM) was obtained with the interface. Moreover, the study demonstrated that this immunosensor exhibits good stability over time and allows regeneration by incubation in ethylenediaminetetraacetic acid (EDTA) aqueous solution.

Peroxynitrite activity of hemin-functionalized reduced graphene oxide.

Conducting interfaces modified with reduced graphene oxide (rGO) have shown improved electrochemical response for different analytes. The efficient formation of functionalized rGO based materials is thus of current interest for the development of sensitive and selective biosensors. Herein, we report a simple and environmentally friendly method for the formation of a hemin-functionalized rGO hybrid nanomaterial that exhibits remarkable sensitivity to peroxynitrite (ONOO(-)) in solution. The hemin-functionalized rGO hybrid nanomaterial was formed by mixing an aqueous solution of graphene oxide (GO) with hemin and sonicating the suspension for 5 h at room temperature. In addition to playing a key role in biochemical and electrocatalytic reactions, hemin has been proven to be a good reducing agent for GO. The sensitivity of the peroxynitrite sensor is ≈7.5 ± 1.5 nA mM(-1) with a detection limit of 5 ± 1.5 nM.

Chemical-Dealloying-Derived PtPdPb-Based Multimetallic Nanoparticles: Dimethyl Ether Electrocatalysis and Fuel Cell Application.

In this work, we report a novel multimetallic nanoparticle catalyst composed of Pt, Pd, and Pb and its electrochemical activity toward dimethyl ether (DME) oxidation in liquid electrolyte and polymer electrolyte fuel cells. Chemical dealloying of the catalyst with the lowest platinum-group metal (PGM) content, Pt2PdPb2/C, was conducted using HNO3 to tune the catalyst activity. Comprehensive characterization of the chemical-dealloying-derived catalyst nanoparticles unambiguously showed that the acid treatment removed 50% Pb from the nanoparticles with an insignificant effect on the PGM metals and led to the formation of smaller-sized nanoparticles. Electrochemical studies showed that Pb dissolution led to structural changes in the original catalysts. Chemical-dealloying-derived catalyst nanoparticles made of multiple phases (Pt, Pt3Pb, PtPb) provided one of the highest PGM-normalized power densities of 118 mW mgPGM-1 in a single direct DME fuel cell operated at low anode catalyst loading (1 mgPGM cm-2) at 70 °C. A possible DME oxidation pathway for these multimetallic catalysts was proposed based on an online mass spectrometry study and the analysis of the reaction products.

Ni2P Nanoparticle-Inserted Porous Layered NiO Hetero-Structured Nanosheets as a Durable Catalyst for the Electro-Oxidation of Urea.

The electro-oxidation of urea (EOU) is a remarkable but challenging sustainable technology, which largely needs a reduced electro-chemical potential, that demonstrates the ability to remove a notable harmful material from wastewater and/or transform the excretory product of humans into treasure. In this work, an Ni2P-nanoparticle-integrated porous nickel oxide (NiO) hetero-structured nanosheet (Ni2P@NiO/NiF) catalyst was synthesized through in situ acid etching and a gas-phase phosphating process. The as-synthesized Ni2P@NiO/NiF catalyst sample was then used to enhance the electro-oxidation reaction of urea with a higher urea oxidation response (50 mA cm-2 at 1.31 V vs. RHE) and low onset oxidation potential (1.31 V). The enhanced activity of the Ni2P@NiO/NiF catalyst was mainly attributed to effective electron transport after Ni2P nanoparticle insertion through a substantial improvement in active sites due to a larger electrochemical surface area, and a faster diffusion of ions occurred via the interactive sites at the interface of Ni2P and NiO; thus, the structural reliability was retained, which was further evidenced by the low charge transfer resistance. Further, the Ni2P nanoparticle insertion process into the NiO hetero-structured nanosheets effectively enabled a synergetic effect when compared to the counter of the Ni2P/NiF and NiO/NiF catalysts. Finally, we demonstrate that the as-synthesized Ni2P@NiO/NiF catalyst could be a promising electrode for the EOU in urea-rich wastewater and human urine samples for environmental safety management. Overall, the Ni2P@NiO/NiF catalyst electrode combines the advantages of the Ni2P catalyst, NiO nanosheet network, and NiF current collector for enhanced EOU performance, which is highly valuable in catalyst development for environmental safety applications.

Localized surface plasmon resonance interfaces coated with poly[3-(pyrrolyl)carboxylic acid] for histidine-tagged peptide sensing.

The paper reports on a novel localized surface plasmon resonance (LSPR) substrate architecture for the immobilization and detection of histidine-tagged peptides. The LSPR interface consists of an ITO (indium tin oxide) substrate coated with gold nanostructures. The latter are obtained by thermal deposition of a thin (2 nm thick) gold film followed by post-annealing at 500 °C. The LSPR interface was coated with poly[3-(pyrrolyl)carboxylic acid] thin films using electrochemical means. The ability of the LSPR interfaces coated with poly[3-(pyrrolyl)carboxylic acid] to chelate copper ions was investigated. Once loaded with metal ions, the modified LSPR interface was able to bind specifically to histidine-tagged peptides. The binding process was followed using LSPR.

Co Nanoparticle-Encapsulated Nitrogen-Doped Carbon Nanotubes as an Efficient and Robust Catalyst for Electro-Oxidation of Hydrazine.

Structural engineering is an effective methodology for the tailoring of the quantities of active sites in nanostructured materials for fuel cell applications. In the present study, Co nanoparticles were incorporated into the network of 3D nitrogen-doped carbon tubes (Co@NCNTs) that were obtained via the molten-salt synthetic approach at 800 °C. Morphological representation reveals that the Co@NCNTs are encompassed with Co nanoparticles on the surface of the mesoporous walls of the carbon nanotubes, which offers a significant active surface area for electrochemical reactions. The CoNPs/NCNTs-1 (treated with CaCl2) nanomaterial was used as a potential candidate for the electro-oxidation of hydrazine, which improved the response of hydrazine (~8.5 mA) in 1.0 M NaOH, as compared with CoNPs/NCNTs-2 (treated without CaCl2), NCNTs, and the unmodified GCE. Furthermore, the integration of Co helps to improve the conductivity and promote the lower onset electro-oxidation potential (-0.58 V) toward the hydrazine electro-oxidation reaction. In particular, the CoNPs/NCNTs-1 catalysts showed significant catalytic activity and stability performances i.e., the i-t curves showed notable stability when compared with their initial current responses, even after 10 days, which indicates the significant durability of the catalyst materials. This work could present a new approach for the design of efficient electrode materials, which can be used as a favorable candidate for the electro-oxidation of liquid fuels in fuel cell applications.

Nickel-phosphate pompon flowers nanostructured network enables the sensitive detection of microRNA.

An electrochemical immuno-nanogenosensor is developed based on noble-metal-free nickel phosphate nanostructure (NiPNs) as an excellent biocompatible material for miRNA detection in blood serum and urine samples without using indicators for the first time. The pompon flower-like morphology of NiPNs is synthesized, and characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction pattern (XRD), fourier transform-infrared spectroscopy (FT-IR), and electrochemical impedance methods. The novel NiPNs nanostructured interface was constructed by coordinate covalent bonding between Ni and phosphate group of probe DNA. The constructed NiPNs-p-DNA surface served as the amplified hybridization platform enabling efficient access to numerous target microRNA sequences. As a result, the developed NiPFNs biosensing platform displayed excellent sensitivity, selectivity, and ultralow experimental limit-of-detection (LOD) of 0.034 pM (S/N = 3) as compared with other Ni phosphide nanostructures. This simple and efficient approach is highly suitable for the development of point-of-care detection systems. To the extent of our knowledge, this is the first report on trace level detection of miRNAs employing non-noble Ni metal nanostructures based biosensing platform.

Simultaneous Mapping of Oxygen Reduction Activity and Hydrogen Peroxide Generation on Electrocatalytic Surfaces.

Electrochemical scanning probe microscopies have become valuable experimental tools, owing to their capability of capturing topographic features in addition to mapping the electrochemical activity of nanoscale oxygen reduction catalysts. However, most scanning probe techniques lack the ability to correlate topographic features with the electrochemical oxygen reduction and peroxide formation in real time. In this report, we show that it is indeed possible to construct high-resolution catalytic current maps at an electrified solid-liquid interface by placing a specially made Au-coated SiO2 Pt atomic force microscopy and scanning electrochemical microscopy (AFM-SECM) dual electrode tip approximately 4-8 nm above the reaction center. The catalytic current measured every 16 nm and high collection efficiency (≈90 %) of the reverse current of peroxide byproducts was also demonstrated with the help of the dual electrode tip. Simultaneous oxygen reduction and intermediate peroxide oxidation current mapping was demonstrated using this Au-coated SiO2 Pt probe on two model surfaces, namely highly oriented pyrolytic graphite and Pt nanoparticles (NPs) supported on a glassy carbon surface.

Nanoscale mapping of catalytic hotspots on Fe, N-modified HOPG by scanning electrochemical microscopy-atomic force microscopy.

The scanning electrochemical microscopy-atomic force microscopy (SECM-AFM) technique is used to map catalytic currents post Fe and N surface modification of graphitic carbon with an ultra-high resolution of 50 nm. The oxidation current of the partial reduction product, hydrogen peroxide, was also mapped in the same location in the graphitic carbon. The current mapping and ex situ spectroscopic evidence revealed that Fe-coordinated nitrogen sites formed both in the edge and basal planes of highly ordered pyrolytic graphite (HOPG) constitute the primary oxygen reduction catalytic sites in acid solutions of this important yet insufficiently understood class of catalysts.

Plasmon-Induced Electrocatalysis with Multi-Component Nanostructures.

Noble metal nanostructures are exceptional light absorbing systems, in which electron⁻hole pairs can be formed and used as "hot" charge carriers for catalytic applications. The main goal of the emerging field of plasmon-induced catalysis is to design a novel way of finely tuning the activity and selectivity of heterogeneous catalysts. The designed strategies for the preparation of plasmonic nanomaterials for catalytic systems are highly crucial to achieve improvement in the performance of targeted catalytic reactions and processes. While there is a growing number of composite materials for photochemical processes-mediated by hot charge carriers, the reports on plasmon-enhanced electrochemical catalysis and their investigated reactions are still scarce. This review provides a brief overview of the current understanding of the charge flow within plasmon-enhanced electrochemically active nanostructures and their synthetic methods. It is intended to shed light on the recent progress achieved in the synthesis of multi-component nanostructures, in particular for the plasmon-mediated electrocatalysis of major fuel-forming and fuel cell reactions.

Exceptionally Active and Stable Spinel Nickel Manganese Oxide Electrocatalysts for Urea Oxidation Reaction.

Spinel nickel manganese oxides, widely used materials in the lithium ion battery high voltage cathode, were studied in urea oxidation catalysis. NiMn2O4, Ni1.5Mn1.5O4, and MnNi2O4 were synthesized by a simple template-free hydrothermal route followed by a thermal treatment in air at 800 °C. Rietveld analysis performed on nonstoichiometric nickel manganese oxide-Ni1.5Mn1.5O4 revealed the presence of three mixed phases: two spinel phases with different lattice parameters and NiO unlike the other two spinels NiMn2O4 and MnNi2O4. The electroactivity of nickel manganese oxide materials toward the oxidation of urea in alkaline solution is evaluated using cyclic voltammetric measurements. Ni1.5Mn1.5O4 exhibits excellent redox characteristics and lower charge transfer resistances in comparison with other compositions of nickel manganese oxides and nickel oxide prepared under similar conditions.The Ni1.5Mn1.5O4modified electrode oxidizes urea at 0.29 V versus Ag/AgCl with a corresponding current density of 6.9 mA cm(-2). At a low catalyst loading of 50 µg cm(-2), the urea oxidation current density of Ni1.5Mn1.5O4 in alkaline solution is 7 times higher than that of nickel oxide and 4 times higher than that of NiMn2O4 and MnNi2O4, respectively.

Vertically Aligned Nitrogen-Doped Carbon Nanotube Carpet Electrodes: Highly Sensitive Interfaces for the Analysis of Serum from Patients with Inflammatory Bowel Disease.

The number of patients suffering from inflammatory bowel disease (IBD) is increasing worldwide. The development of noninvasive tests that are rapid, sensitive, specific, and simple would allow preventing patient discomfort, delay in diagnosis, and the follow-up of the status of the disease. Herein, we show the interest of vertically aligned nitrogen-doped carbon nanotube (VA-NCNT) electrodes for the required sensitive electrochemical detection of lysozyme in serum, a protein that is up-regulated in IBD. To achieve selective lysozyme detection, biotinylated lysozyme aptamers were covalently immobilized onto the VA-NCNTs. Detection of lysozyme in serum was achieved by measuring the decrease in the peak current of the Fe(CN)6(3-/4-) redox couple by differential pulse voltammetry upon addition of the analyte. We achieved a detection limit as low as 100 fM with a linear range up to 7 pM, in line with the required demands for the determination of lysozyme level in patients suffering from IBD. We attained the sensitive detection of biomarkers in clinical samples of healthy patients and individuals suffering from IBD and compared the results to a classical turbidimetric assay. The results clearly indicate that the newly developed sensor allows for a reliable and efficient analysis of lysozyme in serum.

Graphene-coated surface plasmon resonance interfaces for studying the interactions between bacteria and surfaces.

A variety of physical and chemical parameters are of importance for adhesion of bacteria to surfaces. In the colonization of mammalian organisms for example, bacterial fimbriae and their adhesins not only seek particular glycan sequences exposed on diverse epithelial linings, they also enable the bacteria to overcome electrostatic repulsion exerted by their selected surfaces. In this work, we present a new technique based on simplified model systems for studying the adhesion strength of different Escherichia coli strains. For this purpose, gold-based surface plasmon resonance (SPR) interfaces were coated with thin films of reduced graphene oxide (rGO) through electrophoretic deposition. The rGO matrix was post-modified with polyethyleneimine (PEI), poly(sodium 4-styrenesulfonate) (PSS), mannose, and lactose through π-stacking and/or electrostatic interactions by simple immersion of the SPR interface into their respective aqueous solutions. The adhesion behaviors of one uropathogenic and two enterotoxigenic Escherichia coli clinical isolates, that each express structurally characterized fimbrial adhesins, were investigated. It was found that the UTI89 cystitis isolate that carries the mannose-binding FimH adhesin was most attracted to the PEI- and mannose-modified surfaces, whereas the att25 diarrhoeal strain with the N-acetylglucosamine-specific F17a-G adhesin disintegrated the lactose-modified rGO. The highly virulent 107/86 strain interacted strongly with the PSS-modified graphene oxide, in agreement with the polybasic surroundings of the ABH blood group-binding site of the FedF adhesin, and showed a linear SPR response in a concentration range between 1 × 10(2) and 1 × 10(9) cfu/mL.

Lysozyme detection on aptamer functionalized graphene-coated SPR interfaces.

The paper reports on a surface plasmon resonance (SPR)-based approach for the sensitive and selective detection of lysozyme. The SPR sensor consists of a 50 nm gold film coated with a thin film of reduced graphene oxide (rGO) functionalized with anti-lysozyme DNA aptamer. The SPR chip coating with rGO matrix was achieved through electrophoretic deposition of graphene oxide (GO) at 150 V. Electrophoretic deposition resulted in partial reduction of GO to rGO with a thickness depending on the deposition time. For very short time pulses of 20 s, the resulting rGO film had a thickness of several nanometers and was appropriate for SPR sensing. The utility of the graphene-based SPR sensor for the selective and sensitive detection of proteins was demonstrated using lysozyme as model protein. Functionalization of rGO matrix with anti-lysozyme DNA aptamer through π-stacking interactions allowed selective SPR detection of lysozyme. The graphene-based SPR biosensor provides a means for the label-free, concentration-dependent and selective detection of lysozymes with a detection limit of 0.5 nM.