Preparation of Silicon–Carbon-Based Dots@Dopamine and Its Application in Intracellular Ag⁺ Detection and Cell Imaging

A novel nanocomposite, silicon–carbon-based dots@dopamine (Si-CDs@DA) was prepared using (3-aminopropyl) triethoxysilane, glycerol, and dopamine as raw materials via a rapid microwave-assisted irradiation. This type of Si-CDs@DA exhibited ultrabright fluorescence emission (quantum yield of 12.4%) and could response to Ag⁺ selectively and sensitively. Moreover, the obtained Si-CDs@DA can be further applied in sensing intracellular Ag⁺ and cell imaging, because of its photostability, salt stability, and low cytotoxicity. This study provides a simple and efficient approach for preparing novel Ag⁺ fluorescent probes, which could expand the application of carbon nanomaterials in designing related biosensors

Stable and Reusable Electrochemical Biosensor for Poly(ADP-ribose) Polymerase and Its Inhibitor Based on Enzyme-Initiated Auto-PARylation

A stable and reusable electrochemical biosensor for the label-free detection of poly­(ADP-ribose) polymerase (PARP) is designed in this work. C-kit-1, a thiol-modified G-quadruplex oligonucleotide, is first self-assembled on a gold electrode surface. The G-quadruplex structure of c-kit-1 can specifically tether and activate PARP, resulting in the generation of negatively charged poly­(ADP-ribose) polymer (PAR). On the basis of electrostatic attraction, PAR facilitates the surface accumulation of positively charged electrochemical signal molecules. Through the characterization of electrochemical signal molecules, the label-free quantification of PARP is simply implemented. On the basis of the proposed method, selective quantification of PARP can be achieved over the linear range from 0.01 to 1 U with a calculated detection limit of 0.003U. Further studies also demonstrate the applicability of the proposed method to biosamples revealing the broad potential in practical applications. Furthermore, inhibitor of PARP has also been detected with this biosensor. Meanwhile, benefited from self-assembly on solid surface, this biosensor possesses two important features, i.e., reusability and stability, which are desirable in related biosensors

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

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 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

Aggregation of Individual Sensing Units for Signal Accumulation: Conversion of Liquid-Phase Colorimetric Assay into Enhanced Surface-Tethered Electrochemical Analysis

A novel concept is proposed for converting liquid-phase colorimetric assay into enhanced surface-tethered electrochemical analysis, which is based on the analyte-induced formation of a network architecture of metal nanoparticles (MNs). In a proof-of-concept trial, thymine-functionalized silver nanoparticle (Ag-T) is designed as the sensing unit for Hg²⁺ determination. Through a specific T-Hg²⁺-T coordination, the validation system based on functionalized sensing units not only can perform well in a colorimetric Hg²⁺ assay, but also can be developed into a more sensitive and stable electrochemical Hg²⁺ sensor. In electrochemical analysis, the simple principle of analyte-induced aggregation of MNs can be used as a dual signal amplification strategy for significantly improving the detection sensitivity. More importantly, those numerous and diverse colorimetric assays that rely on the target-induced aggregation of MNs can be augmented to satisfy the ambitious demands of sensitive analysis by converting them into electrochemical assays via this approach