Vertically Oriented and Interpenetrating CuSe Nanosheet Films with Open Channels for Flexible All-Solid-State Supercapacitors

As a p-type multifunctional semiconductor, CuSe nanostructures show great promise in optoelectronic, sensing, and photocatalytic fields. Although great progress has been achieved, controllable synthesis of CuSe nanosheets (NSs) with a desirable spacial orientation and open frameworks remains a challenge, and their use in supercapacitors (SCs) has not been explored. Herein, a highly vertically oriented and interpenetrating CuSe NS film with open channels is deposited on an Au-coated polyethylene terephthalate substrate. Such CuSe NS films exhibit high specific capacitance (209 F g–1) and can be used as a carbon black- and binder-free electrode to construct flexible, symmetric all-solid-state SCs, using polyvinyl alcohol–LiCl gel as the solid electrolyte. A device fabricated with such CuSe NS films exhibits high volumetric specific capacitance (30.17 mF cm–3), good cycling stability, excellent flexibility, and desirable mechanical stability. The excellent performance of such devices results from the vertically oriented and interpenetrating configuration of CuSe NS building blocks, which can increase the available surface and facilitate the diffusion of electrolyte ions. Moreover, as a prototype for application, three such solid devices in series can be used to light up a red light-emitting diode

Applications of Nanomaterials in Electrochemical Enzyme Biosensors

A biosensor is defined as a kind of analytical device incorporating a biological material, a biologically derived material or a biomimic intimately associated with or integrated within a physicochemical transducer or transducing microsystem. Electrochemical biosensors incorporating enzymes with nanomaterials, which combine the recognition and catalytic properties of enzymes with the electronic properties of various nanomaterials, are new materials with synergistic properties originating from the components of the hybrid composites. Therefore, these systems have excellent prospects for interfacing biological recognition events through electronic signal transduction so as to design a new generation of bioelectronic devices with high sensitivity and stability. In this review, we describe approaches that involve nanomaterials in direct electrochemistry of redox proteins, especially our work on biosensor design immobilizing glucose oxidase (GOD), horseradish peroxidase (HRP), cytochrome P450 (CYP2B6), hemoglobin (Hb), glutamate dehydrogenase (GDH) and lactate dehydrogenase (LDH). The topics of the present review are the different functions of nanomaterials based on modification of electrode materials, as well as applications of electrochemical enzyme biosensors

Versatile Biosensing Platform for DNA Detection Based on a DNAzyme and Restriction-Endonuclease-Assisted Recycling

On the basis of a DNAzyme and a restriction-endonuclease-assisted target recycling strategy using Pd–Au alloy nanocrystals to immobilize probe DNA on an electrode and catalyze the reduction of H₂O₂ which amplified signal and promoted the detection sensitivity, a versatile biosensing platform for DNA detection was proposed. Using p53 and oral cancer genes as models, hemin/G-quadruplex simultaneously acted as a reduced nicotinamide adenine dinucleotide (NADH) oxidase and a horseradish peroxidase (HRP)-mimicking DNAzyme, and a versatile DNA biosensor was designed for the first time based on the good electrocatalytic activity of Pd–Au alloy nanocrystals. Hemin/G-quadruplex catalyzed the reduction of H₂O₂, which was generated from NADH in the presence of O₂, to produce an electrochemical signal when thionine functioned as the electron mediator. Moreover, the nicking endonuclease N.BstNB I caused the target DNA to cycle for multiple rounds and further amplified the electrochemical response. This versatile DNA biosensor exhibited linear ranges for the detection of p53 and oral cancer genes from 0.1 fmol L^–1 to 0.1 nmol L^–1 and 0.1 fmol L^–1 to 1 nmol L^–1, respectively. The detection limits, established as 3σ, were estimated to be 0.03 and 0.06 fmol L^–1 for the p53 and oral cancer genes, respectively. The as-prepared biosensor could discriminate mismatched sequences, indicating a satisfactory selectivity and validating the feasibility of the proposed strategy. More importantly, simply by changing the helper DNA, this versatile DNA biosensor could detect different target DNA species, which could create a new avenue for the potential diagnosis of cancer

Tin Nanoparticles Impregnated in Nitrogen-Doped Graphene for Lithium-Ion Battery Anodes

Tin possesses a high theoretical specific capacity as anode materials for Li-ion batteries, and considerable efforts have been contributed to mitigating the capacity fading along with its huge volume expansion during lithium insertion and extraction processes, mainly through nanostructured material design. Herein, we present Sn nanoparticles encapsulated in nitrogen-doped graphene sheets through heat-treatment of the SnO₂ nanocrystals/nitrogen-doped graphene hybrid. The specific architecture of the as-prepared Sn@N-RGO involves three advantages, including a continuous graphene conducting network, coating Sn surface through Sn–N and Sn–O bonding generated between Sn nanoparticles and graphene, and porous and flexible structure for accommodating the large volume changes of Sn nanoparticles. As an anode material for lithium-ion batteries, the hybrid exhibits a reversible capacity of 481 mA h g^–1 after 100 cycles under 0.1 A g^–1 and a charge capacity as high as 307 mA h g^–1 under 2 A g^–1

Sequence and Structure Dual-Dependent Interaction between Small Molecules and DNA for the Detection of Residual Silver Ions in As-Prepared Silver Nanomaterials

Investigations on interaction between small molecules and DNA are the basis of designing advanced bioanalytical systems. We herein propose a novel interaction between heterocyclic aromatic compounds (HACs) and single-stranded DNA (ssDNA). Taking methylene blue (MB) as a typical HAC, it is found that MB can interact with cytosine (C)-rich ssDNA in an enthalpy-driven process. The interaction between MB and C-rich ssDNA is sequence and structure dual-dependent: at least three consecutive C and single-stranded structure are necessary, affecting the fluorescence response of metal nanoparticles. With the exception of the single-stranded structure, double-stranded, i-motif, and C–Ag–C mismatch structures will remarkably impede the interaction with MB. UV–vis absorption, fluorescent, and electrochemical curves demonstrate that the conjugated system, electron transition, and electron transfer of MB are remarkably affected by MB-C-rich ssDNA interaction. In particular, the absorption peak of MB at 664 nm decreases, and a new peak at 538 nm emerges. Therefore, the interaction can be characterized by a colorimetric and ratiometric signal. Relying on the inhibition of C–Ag–C mismatch and the enhanced analytical performances of the ratiometic signal, the MB-C-rich ssDNA interaction is further employed to quantify silver ions (Ag⁺) selectively and sensitively. In addition, since silver nanomaterials cannot introduce C–Ag–C mismatch, the fabricated biosensor is able to sense residual Ag⁺ in silver nanoparticles and silver nanowires, which is of great value in the precise and economical preparation of silver nanomaterials

Fluorescence Regulation of Poly(thymine)-Templated Copper Nanoparticles via an Enzyme-Triggered Reaction toward Sensitive and Selective Detection of Alkaline Phosphatase

The activity of alkaline phosphatase (ALP) is a crucial index of blood routine examinations, since the concentration of ALP is highly associated with various human diseases. To address the demands of clinical tests, efforts should be made to develop more approaches that can sense ALP in real samples. Recently, we find that fluorescence of poly­(30T)-templated copper nanoparticles (CuNPs) can be directly and effectively quenched by pyrophosphate ion (PPi), providing new perspective in designing sensitive biosensors based on DNA-templated CuNPs. In addition, it has been confirmed that phosphate ion (Pi), product of PPi hydrolysis, does not affect the intense fluorescence of CuNPs. Since ALP can specifically hydrolyze PPi into Pi, fluorescence of CuNPs is thus regulated by an ALP-triggered reaction, and a novel ALP biosensor is successfully developed. As a result, ALP is sensitively and selectively quantified with a wide linear range of 6.0 × 10^–2 U/L to 6.0 × 10² U/L and a low detection limit of 3.5 × 10^–2 U/L. Besides, two typical inhibitors of ALP are evaluated by this analytical method, and different inhibitory effects are indicated. More importantly, by challenging this biosensor with real human serums, the obtained results get a fine match with the data from clinical tests, and the serum sample from a patient with liver disease is clearly distinguished, suggesting promising applications of this biosensor in clinical diagnosis

Fluorescence Regulation of Copper Nanoclusters via DNA Template Manipulation toward Design of a High Signal-to-Noise Ratio Biosensor

Because of bioaccumulation of food chain and disability of biodegradation, concentration of toxic mercury ions (Hg²⁺) in the environment dramatically varies from picomolar to micromolar, indicating the importance of well-performed Hg²⁺ analytical methods. Herein, reticular DNA is constructed by introducing thymine (T)–Hg²⁺–T nodes in poly­(T) DNA, and copper nanoclusters (CuNCs) with aggregate morphology are prepared using this reticular DNA as a template. Intriguingly, the prepared CuNCs exhibit enhanced fluorescence. Meanwhile, the reticular DNA reveals evident resistance to enzyme digestion, further clarifying the fluorescence enhancement of CuNCs. Relying on the dual function of DNA manipulation, a high signal-to-noise ratio biosensor is designed. This analytical approach can quantify Hg²⁺ in a very wide range (50 pM to 500 μM) with an ultralow detection limit (16 pM). Besides, depending on the specific interaction between Hg²⁺ and reduced l-glutathione (GSH), this biosensor is able to evaluate the inhibition of GSH toward Hg²⁺. In addition, pollution of Hg²⁺ in three lakes is tested using this method, and the obtained results are in accord with those from inductively coupled plasma mass spectrometry. In general, this work provides an alternative way to regulate the properties of DNA-templated nanomaterials and indicates the applicability of this way by fabricating an advanced biosensor

Using Graphene-Based Plasmonic Nanocomposites to Quench Energy from Quantum Dots for Signal-On Photoelectrochemical Aptasensing

On the basis of the absorption and emission spectra overlap, an enhanced resonance energy transfer caused by excition-plasmon resonance between reduced graphene oxide (RGO)-Au nanoparticles (AuNPs) and CdTe quantum dots (QDs) was obtained. With the synergy of AuNPs and RGO as a planelike energy acceptor, it resulted in the enhancement of energy transfer between excited CdTe QDs and RGO-AuNPs nanocomposites. Upon the novel sandwichlike structure formed via DNA hybridization, the exciton produced in CdTe QDs was annihilated. A damped photocurrent was obtained, which was acted as the background signal for the development of a universal photoelectrochemical (PEC) platform. With the use of carcinoembryonic antigen (CEA) as a model which bonded to its specific aptamer and destroyed the sandwichlike structure, the energy transfer efficiency was lowered, leading to PEC response augment. Thus a signal-on PEC aptasensor was constructed. Under 470 nm irradiation at −0.05 V, the PEC aptasensor for CEA determination exhibited a linear range from 0.001 to 2.0 ng mL^–1 with a detection limit of 0.47 pg mL^–1 at a signal-to-noise ratio of 3 and was satisfactory for clinical sample detection. Since different aptamers can specifically bind to different target molecules, the designed strategy has an expansive application for the construction of versatile PEC platforms