Simultaneous electrochemical detection of guanine and adenine using reduced graphene oxide decorated with AuPt nanoclusters.

A rapid and sensitive electrochemical sensing platform is reported based on bimetallic gold-platinum nanoclusters (AuPtNCs) dispersed on reduced graphene oxide (rGO) for the simultaneous detection of guanine and adenine using square wave voltammetry (SWV). The synthesis of AuPtNCs-rGO nanocomposite was achieved by a simultaneous reduction of graphene oxide (GO) and metal ions (Au3+ and Pt4+) in an aqueous solution. The developed AuPtNCs-rGO electrochemical sensor with the optimized 50:50 bimetallic (Au:Pt) nanoclusters exhibited an outstanding electrocatalytic performance towards the simultaneous oxidation of guanine and adenine without the aid of any enzymes or mediators in physiological pH. The electrochemical sensor platform showed low detection limits of 60 nM and 100 nM (S/N = 3) for guanine and adenine, respectively, with high sensitivity and an extensive linear range from 1.0 µM to 0.2 mM for both guanine and adenine. The interference from the most common electrochemically active interferents, including ascorbic acid, uric acid, and dopamine, was almost negligible. The simultaneous sensing of guanine and adenine in denatured Salmon Sperm DNA sample was successfully achieved using the proposed platform, showing that the AuPtNCs-rGO nanocomposite could provide auspicious clinical diagnosis and biomedical applications.

Ultrahigh and Durable Volumetric Lithium/Sodium Storage Enabled by a Highly Dense Graphene-Encapsulated Nitrogen-Doped Carbon@Sn Compact Monolith.

Tin-based composites hold promise as anodes for high-capacity lithium/sodium-ion batteries (LIBs/SIBs); however, it is necessary to use carbon coated nanosized tin to solve the issues related to large volume changes during electrochemical cycling, thus leading to the low volumetric capacity for tin-based composites due to their low packing density. Herein, we design a highly dense graphene-encapsulated nitrogen-doped carbon@Sn (HD N-C@Sn/G) compact monolith with Sn nanoparticles double-encapsulated by N-C and graphene, which exhibits a high density of 2.6 g cm-3 and a high conductivity of 212 S m-1. The as-obtained HD N-C@Sn/G monolith anode exhibits ultrahigh and durable volumetric lithium/sodium storage. Specifically, it delivers a high volumetric capacity of 2692 mAh cm-3 after 100 cycles at 0.1 A g-1 and an ultralong cycling stability exceeding 1500 cycles at 1.0 A g-1 with only 0.019% capacity decay per cycle in lithium-ion batteries. Besides, in situ TEM and ex situ SEM have revealed that the unique double-encapsulated structure effectively mitigates drastic volume variation of the tin nanoparticles during electrode cycling. Furthermore, the full cell using HD N-C@Sn/G as an anode and LiCoO2 as a cathode displays a superior cycling stability. This work provides a new avenue and deep insight into the design of high-volumetric-capacity alloy-based anodes with ultralong cycle life.

Sensitive Electrochemical Detection of Nitric Oxide Release from Cardiac and Cancer Cells via a Hierarchical Nanoporous Gold Microelectrode.

The importance of nitric oxide (NO) in many biological processes has garnered increasing research interest in the design and development of efficient technologies for the sensitive detection of NO. Here we report on a novel gold microelectrode with a unique three-dimensional (3D) hierarchical nanoporous structure for the electrochemical sensing of NO, which was fabricated via a facile electrochemical alloying/dealloying method. Following the treatment, the electrochemically active surface area (ECSA) of the gold microelectrode was significantly increased by 22.9 times. The hierarchical nanoporous gold (HNG) microelectrode exhibited excellent performance for the detection of NO with high stability. On the basis of differential pulse voltammetry (DPV) and amperometric techniques, the obtained sensitivities were 21.8 and 14.4 µA µM-1 cm-2, with detection limits of 18.1 ± 1.22 and 1.38 ± 0.139 nM, respectively. The optimized HNG microelectrode was further utilized to monitor the release of NO from different cells, realizing a significant differential amount of NO generated from the normal and stressed rat cardiac cells as well as from the untreated and treated breast cancer cells. The HNG microelectrode developed in the present study may provide an effective platform in monitoring NO in biological processes and would have a great potential in the medical diagnostics.

Iron Oxide with Different Crystal Phases (α- and γ-Fe2O3) in Electroanalysis and Ultrasensitive and Selective Detection of Lead(II): An Advancing Approach Using XPS and EXAFS.

Iron oxide with different crystal phases (α- and γ-Fe2O3) has been applied to electrode coatings and been demonstrated to ultrasensitive and selective electrochemical sensing toward heavy metal ions (e.g., Pb(II)). A range of Pb(II) contents in micromoles (0.1 to 1.0 µM) at α-Fe2O3 nanoflowers with a sensitivity of 137.23 µA µM(-1) cm(-2) and nanomoles (from 0.1 to 1.0 nM) at γ-Fe2O3 nanoflowers with a sensitivity of 197.82 µA nM(-1) cm(-2) have been investigated. Furthermore, an extended X-ray absorption fine structure (EXAFS) technique was applied to characterize the difference of local structural environment of the adsorbed Pb(II) on the surface of α- and γ-Fe2O3. The results first showed that α- and γ-Fe2O3 had diverse interaction between Pb(II) and iron (hydro)oxides, which were consistent with the difference of electrochemical performance. Determining the responses of Cu(II) and Hg(II) as the most appropriate choice for comparison, the stripping voltammetric quantification of Pb(II) with high sensitivity and selectivity at γ-Fe2O3 nanoflower has been demonstrated. This work reveals that the stripping performances of a nanomodifier have to be directly connected with its intrinsic surface atom arrangement.

Sensitive electrochemical detection of nitric oxide based on AuPt and reduced graphene oxide nanocomposites.

Since nitric oxide (NO) plays a critical role in many biological processes, its precise detection is essential toward an understanding of its specific functions. Here we report on a facile and environmentally compatible strategy for the construction of an electrochemical sensor based on reduced graphene oxide (rGO) and AuPt bimetallic nanoparticles. The prepared nanocomposites were further employed for the electroanalysis of NO using differential pulse voltammetry (DPV) and amperometric methods. The dependence of AuPt molar ratios on the electrochemical performance was investigated. Through the combination of the advantages of the high conductivity from rGO and highly electrocatalytic activity from AuPt bimetallic nanoparticles, the AuPt-rGO based NO sensor exhibited a high sensitivity of 7.35 µA µM(-1) and a low detection limit of 2.88 nM. Additionally, negligible interference from common ions or organic molecules was observed, and the AuPt-rGO modified electrode demonstrated excellent stability. Moreover, this optimized electrochemical sensor was practicable for efficiently monitoring the NO released from rat cardiac cells, which were stimulated by l-arginine (l-arg), showing that stressed cells generated over 10 times more NO than normal cells. The novel sensor developed in this study may have significant medical diagnostic applications for the prevention and monitoring of disease.

Facet-dependent stripping behavior of Cu2O microcrystals toward lead ions: a rational design for the determination of lead ions.

Facet-dependent stripping behavior in the determination of Pb(II): Well-defined Cu2O microcrystals with different structures show facet-dependent electrochemical behaviors toward heavy metal ions. This provides an important insight into the understanding the efficiency of facet-dependent properties of microcrystals on electroanalytical performance for the rational design of electrochemical analytical techniques for efficient detection of heavy metal ions.

SnO2 tube-in-tube nanostructures: Cu@C nanocable templated synthesis and their mutual interferences between heavy metal ions revealed by stripping voltammetry.

SnO2 tube-in-tube nanostructures are synthesized using Cu@C nanocables as effective sacrificial templates. It is revealed by stripping voltammetry that SnO2 tube-in-tube nanostructures show excellent performances in the determination of heavy metal ions, which might be related to the extraordinary adsorbing capacities of the hollow structure to metal ions, i.e., metal ions could diffuse into the interior of tubular structure.

Nanoporous gold microelectrode for electrochemical sensing of As(III) in cellular environment.

The highly toxic arsenite (As(III)) could cause serious cytotoxicity on metabolism, resulting in several diseases. However, it is still a great challenge on the precise sensing of As(III) in complicated conditions, especially in cellular environment. In this work, a nanoporous gold microelectrode (NPG-µE) was fabricated by a simple electrochemical alloying/dealloying method and developed for the electroanalysis of As(III) in the lung cancer cellular (A549 cells) environment. The as-fabricated NPG-µE exhibited the excellent electrochemical performance towards As(III) detection at physiological pH (0.1 M PBS solution, pH 7.4) with a high sensitivity of 5.07 µA ppb-1 cm-2 and a low limit of detection of 0.25 ppb (S/N = 3). The large surface area derived from the nanoporous structure, and the well-dispersed active sites as well as the highly electro-catalytic activity of gold played a critical role on the improved electrochemical behaviors. Furthermore, the effect of the exposure time on electrochemical monitoring As(III) in A549 cellular environment was successfully investigated, revealing the fatal impact of As(III) on cell cycle. This work offered a great trial on investigating of the cytotoxicity of arsenite and their precise detection in complicated cellular environment.

Highly sensitive and selective serotonin (5-HT) electrochemical sensor based on ultrafine Fe3O4 nanoparticles anchored on carbon spheres.

Neurotransmitter serotonin (5-HT) is involved in various physiological and pathological processes. Therefore, its highly sensitive and selective detection in human serum is of great significance for early diagnosis of disease. In this work, employing iron phthalocyanine as Fe source, ultrafine Fe3O4 nanoparticles anchored on carbon spheres (Fe3O4/CSs) have been prepared, which exhibits an excellent electrochemical sensing performance toward 5-HT. With carbonecous spheres turned into conductive carbon spheres under the heat treatment in N2 atmosphere, iron phthalocyanine absorbed on their surfaces are simultaneously pyrolysised and oxidized, and finally transformed into ultrafine Fe3O4 nanoparticles. Electrochemical results demonstrate a high sensitivity (5.503 µA µM-1) and a low detection limit (4 nM) toward 5-HT for as-prepared Fe3O4/CSs. In combination with the morphology and physicochemical property of Fe3O4/CSs, the enhanced sensing mechanism toward 5-HT is disscussed. In addition, the developed electrochemical sensor also displays a good sensing stability and an anti-interferent ability. Further applied in real human serum samples, a satisfactory recovery rate is achieved. Promisingly, the developed electrochemical sensor can be employed for the determination of 5-HT in actual samples.

Sensitive sensing of Hg(II) based on lattice B and surface F co-doped CeO2: Synergies of catalysis and adsorption brought by doping site engineering.

Transition metal oxides are widely used in the detection of heavy metal ions (HMIs), and the co-doping strategy that introducing a variety of different dopant atoms to modify them can obtain a better detection performance. However, there is very little research on the co-doped transition metal oxides by non-metallic elements for electrochemical detection. Herein, boron (B) and fluorine (F) co-doped CeO2 nanomaterial (BFC) is constructed to serve as the electrochemically sensitive interface for the detection of Hg(II). B and F affect the sensitivity of CeO2 to HMIs when they were introduced at different doping sites. Through a variety of characterization, it is proved that B is successfully doped into the lattice and F is doped on the surface of the material. Through the improvement of the catalytic properties and adsorption capacity of CeO2 by different doping sites, this B and F co-doped CeO2 exhibits excellent square wave anodic stripping voltammetry (SWASV) current responses to Hg(II). Both the high sensitivity of 906.99 µA µM-1 cm-2 and the low limit of detection (LOD) of 0.006 µM are satisfactory. Besides, this BFC glassy carbon electrode (GCE) also has good anti-interference property, which has been successfully used in the detection of Hg(II) in actual water. This discovery provides a useful strategy for designing a variety of non-metallic co-doped transition metal oxides to construct trace heavy metal ion-sensitive interfaces.

Integrating Dually Encapsulated Si Architecture and Dense Structural Engineering for Ultrahigh Volumetric and Areal Capacity of Lithium Storage.

High-theoretical-capacity silicon anodes hold promise in lithium-ion batteries (LIBs). Nevertheless, their huge volume expansion (∼300%) and poor conductivity show the need for the simultaneous introduction of low-density conductive carbon and nanosized Si to conquer the above issues, yet they result in low volumetric performance. Herein, we develop an integration strategy of a dually encapsulated Si structure and dense structural engineering to fabricate a three-dimensional (3D) highly dense Ti3C2Tx MXene and graphene dual-encapsulated Si monolith architecture (HD-Si@Ti3C2Tx@G). Because of its high density (1.6 g cm-3), high conductivity (151 S m-1), and 3D dense dual-encapsulated Si architecture, the resultant HD-Si@Ti3C2Tx@G monolith anode displays an ultrahigh volumetric capacity of 5206 mAh cm-3 (gravimetric capacity: 2892 mAh g-1) at 0.1 A g-1 and a superior long lifespan of 800 cycles at 1.0 A g-1. Notably, the thick and dense monolithic anode presents a large areal capacity of 17.9 mAh cm-2. In-situ TEM and ex-situ SEM techniques, and systematic kinetics and structural stability analysis during cycling demonstrate that such superior volumetric and areal performances stem from its dual-encapsulated Si architecture by the 3D conductive and elastic networks of MXene and graphene, which can provide fast electron and ion transfer, effective volume buffer, and good electrolyte permeability even with a thick electrode, whereas the dense structure results in a large volumetric performance. This work offers a simple and feasible strategy to greatly improve the volumetric and areal capacity of alloy-based anodes for large-scale applications via integrating a dual-encapsulated strategy and dense-structure engineering.

Noble-metal-free Fe3O4/Co3S4 nanosheets with oxygen vacancies as an efficient electrocatalyst for highly sensitive electrochemical detection of As(III).

The electrochemical method for highly sensitive determination of arsenic(III) in real water samples with noble-metal-free nanomaterials is still a difficult but significant task. Here, an electrochemical sensor driven by noble-metal-free layered porous Fe3O4/Co3S4 nanosheets was successfully employed for As(III) analysis, which was prepared via a facile two-step method involves a hydrothermal treatment and a subsequent sulfurization process. As expected, the electrochemical detection of As(III) in 0.1 M HAc-NaAc (pH 6.0) by square wave anodic stripping voltammetry (SWASV) with a considerable sensitivity of 4.359 µA/µg·L-1 was obtained, which is better than the commonly used noble metals modified electrodes. Experimental and characterization results elucidate the enhancement of As(III) electrochemical performance could be attributed to its nano-porous structure, the presence of oxygen vacancies and strong synergetic coupling effects between Fe3O4 and Co3S4 species. Besides, the Fe3O4/Co3S4 modified screen printed carbon electrode (Fe3O4/Co3S4-SPCE) shows remarkable stability and repeatability, valuable anti-interference ability and could be used for detection in real water samples. Consequently, the results confirm that as-prepared porous Fe3O4/Co3S4 nanosheets is identified as a promising modifier to detect As(III) in real sample analysis.

Copper decorated with nanoporous gold by galvanic displacement acts as an efficient electrocatalyst for the electrochemical reduction of CO2.

The reduction of carbon dioxide (CO2) is recognized as a key component in the synthesis of renewable carbon-containing fuels. Herein, we report on nanoporous gold (NPAu) decorated with copper atoms for the efficient electrochemical reduction of CO2. A facile and green galvanic displacement technique was developed to incorporate Cu onto the surface of the nanoporous gold-zinc (NPAuZn) electrode. The effect of zinc on the morphology and electrochemical performance of the formed NPAuCu electrodes for CO2 reduction was systematically investigated. The NPAuCu electrode exhibited 16.9 and 2.86 times higher current density than those of polycrystalline gold and NPAuZn at -0.60 V (vs. RHE) in a 0.1 M CO2-saturated NaHCO3 solution, respectively. A far higher faradaic efficiency was achieved at the NPAuCu electrode for the electrochemical reduction of CO2 to CO, CH4 and HCOOH. The facile synthesis of the NPAuCu electrode demonstrated in the present study can be employed as a promising strategy in the development of high-performance electrocatalysts for energy and environmental applications.

Green, Template-Less Synthesis of Honeycomb-like Porous Micron-Sized Red Phosphorus for High-Performance Lithium Storage.

Large-volume-expansion-induced material pulverization severely limits the electrochemical performance of high-capacity red phosphorus (RP) in alkali-ion batteries. Honeycomb-like porous materials can effectively solve the issues due to their abundant interconnected pore structures. Nevertheless, it is difficult and greatly challenging to fabricate a honeycomb-like porous RP that has not yet been fabricated via chemical synthesis. Herein, we successfully fabricate a honeycomb-like porous micron-sized red phosphorus (HPRP) with a controlled pore structure via a large-scale green and template-less hydrothermal strategy. It is demonstrated that dissolved oxygen in the solution can accelerate the destruction of P9 cages of RP, thus forming abundant active defects with a faster reaction rate, so the fast corrosion forms the honeycomb-like porous structure. Owing to the free volume, interconnected porous structure, and strong robustness, the optimized HPRP-36 can mitigate drastic volume variation and prevent pulverization during cycling resulting in tiny particle-level outward expansion, demonstrated by in situ TEM and ex situ SEM analysis. Thus, the HPRP-36 anode delivers a large reversible capacity (2587.4 mAh g-1 at 0.05 A g-1) and long-cycling stability with over 500 cycles (∼81.9% capacity retention at 0.5 A g-1) in lithium-ion batteries. This generally scalable, green strategy and deep insights provide a good entry point in designing honeycomb-like porous micron-sized materials for high-performance electrochemical energy storage and conversion.

Ultrahigh-Volumetric-Energy-Density Lithium-Sulfur Batteries with Lean Electrolyte Enabled by Cobalt-Doped MoSe2/Ti3C2Tx MXene Bifunctional Catalyst.

It is a significant challenge to design a dense high-sulfur-loaded cathode and meanwhile to acquire fast sulfur redox kinetics and suppress the heavy shuttling in the lean electrolyte, thus to acquire a high volumetric energy density without sacrificing gravimetric performance for realistic Li-S batteries (LSBs). Herein, we develop a cation-doping strategy to tailor the electronic structure and catalytic activity of MoSe2 that in situ hybridized with conductive Ti3C2Tx MXene, thus obtaining a Co-MoSe2/MXene bifunctional catalyst as a high-efficient sulfur host. Combining a smart design of the dense sulfur structure, the as-fabricated highly dense S/Co-MoSe2/MXene monolith cathode (density: 1.88 g cm-3, conductivity: 230 S m-1) achieves a high reversible specific capacity of 1454 mAh g-1 and an ultrahigh volumetric energy density of 3659 Wh L-1 at a routine electrolyte and a high areal capacity of ∼8.0 mAh cm-2 under an extremely lean electrolyte of 3.5 µL mgs-1 at 0.1 C. Experimental and DFT theoretical results uncover that introducing Co element into the MoSe2 plane can form a shorter Co-Se bond, impel the Mo 3d band to approach the Fermi level, and provide strong interactions between polysulfides and Co-MoSe2, thereby enhancing its intrinsic electronic conductivity and catalytic activity for fast redox kinetics and uniform Li2S nucleation in a dense high-sulfur-loaded cathode. This deep work provides a good strategy for constructing high-volumetric-energy-density, high-areal-capacity LSBs with lean electrolytes.

A Smartphone-Based Sensing System for On-Site Quantitation of Multiple Heavy Metal Ions Using Fluorescent Carbon Nanodots-Based Microarrays.

The development of cost-effective and versatile sensing system for simultaneous and rapid quantitation of multiple targets is highly demanded for environmental surveillance, food safety inspection, home healthcare, etc. This work reports on (1) paper-based microarrays relying on fluorescence turn-off of carbon nanodots (CDs) for analyte recognition and (2) a stand-alone smartphone-based portable reader (SBR) installed with a custom-designed APP (SBR-App), which can accurately and reproducibly acquire fluorescence change from the microarray chip, automatically report the results, generate and share the reports via wireless network. Simultaneous detection of Hg2+, Pb2+, and Cu2+ in the Pearl River water samples was achieved with the reported sensing system. End-user operation is limited to pipet samples to the microarray chip, insert the chip to the SBR, and open the SBR-App to acquire an image 5 min after sample introduction. There is no requirement for complicated sample pre-treatment and expensive equipment except for a smartphone. This versatile and cost-effective smartphone-based sensing system featured with reliability and simplicity is ideally suited for user- and eco-friendly point-of-need detection in resource-constrained environments.

A 3D printed smartphone optosensing platform for point-of-need food safety inspection.

The deficiency in rapid and in-field detection methods and portable devices that are reliable, easy-to-use, and low cost, results in the difficulties to uphold the high safety standards in China. In this study, we introduce a rapid and cost-effective smartphone-based method for point-of-need food safety inspection, which employs aptamer-conjugated AuNPs as the colorimetric indicator, and a battery-powered optosensing accessory attached to the camera of a smartphone for transmission images capture. A user-friendly and easy-to-use Android application is developed for automatic digital image processing and result reporting. Streptomycin (STR) is selected as the proof-of-concept target, and its specific quantitation can be realized with a LOD of 12.3 nM (8.97 µg kg-1) using the reported smartphone-based method. The quantitation of STR in honey, milk and tap water confirm the reliability and applicability of the reported method. The extremely high acceptance of smartphone in remote and metropolitan areas of China and ease-of-use of the reported method facilitate active food contaminant and toxicant screening, thus making the implementation of the whole food supply chain monitoring and surveillance possible and hence significantly improving the current Chinese food safety control system.

Design and Electrochemical Study of Platinum-Based Nanomaterials for Sensitive Detection of Nitric Oxide in Biomedical Applications.

The extensive physiological and regulatory roles of nitric oxide (NO) have spurred the development of NO sensors, which are of critical importance in neuroscience and various medical applications. The development of electrochemical NO sensors is of significant importance, and has garnered a tremendous amount of attention due to their high sensitivity and selectivity, rapid response, low cost, miniaturization, and the possibility of real-time monitoring. Nanostructured platinum (Pt)-based materials have attracted considerable interest regarding their use in the design of electrochemical sensors for the detection of NO, due to their unique properties and the potential for new and innovative applications. This review focuses primarily on advances and insights into the utilization of nanostructured Pt-based electrode materials, such as nanoporous Pt, Pt and PtAu nanoparticles, PtAu nanoparticle/reduced graphene oxide (rGO), and PtW nanoparticle/rGO-ionic liquid (IL) nanocomposites, for the detection of NO. The design, fabrication, characterization, and integration of electrochemical NO sensing performance, selectivity, and durability are addressed. The attractive electrochemical properties of Pt-based nanomaterials have great potential for increasing the competitiveness of these new sensors and open up new opportunities in the creation of novel NO-sensing technologies for biological and medical applications.

Rapid determination of dopamine in human plasma using a gold nanoparticle-based dual-mode sensing system.

Dopamine plays a very important role in biological systems and has a direct relationship with the ability of learning and cognition, human desires, feelings and mental state, as well as motor functions. Traditional methods for the detection of dopamine are complicated and time-consuming, therefore it is necessary to explore rapid and accurate detection of dopamine with high sensitivity and specificity. Herein we report a dual-mode system of colorimetric and fluorometric analyses based on gold nanoparticles (AuNPs) and aptamers specifically targeting dopamine. Aptamers modified with the fluorophore were used as dopamine specific recognition probe and the sensing mechanism is based on the color change of AuNPs and the fluorescence recovery of fluorophore conjugated on the aptamers in the presence of dopamine. The addition of aptamers into AuNPs colloid solution would prevent the AuNPs from aggregation in the high-salt solution. The close distance between AuNPs and fluorophore conjugated on the aptamers would lead to the quenching of fluorescence signal. In the presence of dopamine, the conformation of the aptamers and the inter-particle distance would be changed, leading to the aggregation of AuNPs, which subsequently results in color change from red to blue and fluorescence signal recovery. The dual-mode sensing system demonstrated high specificity towards dopamine with the detection limit as low as 78.7 nM. The sensing system reflects on its simplicity as no surface functionalization is required for the nanoparticles, leading to less laborious and more cost-effective synthesis. The reaction time is only 6 min, demonstrating a simple approach for rapid analysis of dopamine. More importantly, the sensing system allows the detection of dopamine in both aqueous solution and complicated biological sample with sensitive response, illustrating the feasibility and reliability for the potential applications in clinical and biomedical analysis in the future.

A Versatile Environmental Impedimetric Sensor for Ultrasensitive Determination of Persistent Organic Pollutants (POPs) and Highly Toxic Inorganic Ions.

An impedimetric sensor for persistent toxic substances, including organic pollutants and toxic inorganic ions is presented. The persistent toxic substances are detected using an ultrasensitive technique that is based on electron-transfer blockage. This depends on the formation of guest-host complexes, hydrogen bonding, or a cyclodextrin (CD)-metal complex (Mm(OH)n-ß-CD) structure between the target pollutants and ß-CD.