Detection of chemical and biological agents plays a fundamental role in biomedical, forensic and environmental sciences1–4 as well as in anti bioterrorism applications.5–7 The development of highly sensitive, cost effective, miniature sensors is therefore in high demand which requires advanced technology coupled with fundamental knowledge in chemistry, biology and material sciences.8–13

In general, sensors feature two functional components: a recognition element to provide selective/specific binding with the target analytes and a transducer component for signaling the binding event. An efficient sensor relies heavily on these two essential components for the recognition process in terms of response time, signal to noise (S/N) ratio, selectivity and limits of detection (LOD).14,15 Therefore, designing sensors with higher efficacy depends on the development of novel materials to improve both the recognition and transduction processes. Nanomaterials feature unique physicochemical properties that can be of great utility in creating new recognition and transduction processes for chemical and biological sensors15–27 as well as improving the S/N ratio by miniaturization of the sensor elements.28

Gold nanoparticles (AuNPs) possess distinct physical and chemical attributes that make them excellent scaffolds for the fabrication of novel chemical and biological sensors (Figure 1).29–36 First, AuNPs can be synthesized in a straightforward manner and can be made highly stable. Second, they possess unique optoelectronic properties. Third, they provide high surface-to-volume ratio with excellent biocompatibility using appropriate ligands.30 Fourth, these properties of AuNPs can be readily tuned varying their size, shape and the surrounding chemical environment. For example, the binding event between recognition element and the analyte can alter physicochemical properties of transducer AuNPs, such as plasmon resonance absorption, conductivity, redox behavior, etc. that in turn can generate a detectable response signal. Finally, AuNPs offer a suitable platform for multi-functionalization with a wide range of organic or biological ligands for the selective binding and detection of small molecules and biological targets.30–32,36 Each of these attributes of AuNPs has allowed researchers to develop novel sensing strategies with improved sensitivity, stability and selectivity. In the last decade of research, the advent of AuNP as a sensory element provided us a broad spectrum of innovative approaches for the detection of metal ions, small molecules, proteins, nucleic acids, malignant cells, etc. in a rapid and efficient manner.37



Figure 1

Physical properties of AuNPs and schematic illustration of an AuNP-based detection system.



In this current review, we have highlighted the several synthetic routes and properties of AuNPs that make them excellent probes for different sensing strategies. Furthermore, we will discuss various sensing strategies and major advances in the last two decades of research utilizing AuNPs in the detection of variety of target analytes including metal ions, organic molecules, proteins, nucleic acids, and microorganisms.

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Gold nanoparticles in chemical and biological sensing.

Over the past few decades, researchers have established artificial enzymes as highly stable and low-cost alternatives to natural enzymes in a wide range of applications. A variety of materials including cyclodextrins, metal complexes, porphyrins, polymers, dendrimers and biomolecules have been extensively explored to mimic the structures and functions of naturally occurring enzymes. Recently, some nanomaterials have been found to exhibit unexpected enzyme-like activities, and great advances have been made in this area due to the tremendous progress in nano-research and the unique characteristics of nanomaterials. To highlight the progress in the field of nanomaterial-based artificial enzymes (nanozymes), this review discusses various nanomaterials that have been explored to mimic different kinds of enzymes. We cover their kinetics, mechanisms and applications in numerous fields, from biosensing and immunoassays, to stem cell growth and pollutant removal. We also summarize several approaches to tune the activities of nanozymes. Finally, we make comparisons between nanozymes and other catalytic materials (other artificial enzymes, natural enzymes, organic catalysts and nanomaterial-based catalysts) and address the current challenges and future directions (302 references).

Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes

Because of the high catalytic activities and substrate specificity, natural enzymes have been widely used in industrial, medical, and biological fields, etc. Although promising, they often suffer from intrinsic shortcomings such as high cost, low operational stability, and difficulties of recycling. To overcome these shortcomings, researchers have been devoted to the exploration of artificial enzyme mimics for a long time. Since the discovery of ferromagnetic nanoparticles with intrinsic horseradish peroxidase-like activity in 2007, a large amount of studies on nanozymes have been constantly emerging in the next decade. Nanozymes are one kind of nanomaterials with enzymatic catalytic properties. Compared with natural enzymes, nanozymes have the advantages such as low cost, high stability and durability, which have been widely used in industrial, medical, and biological fields. A thorough understanding of the possible catalytic mechanisms will contribute to the development of novel and high-efficient nanozymes, and the rational regulations of the activities of nanozymes are of great significance. In this review, we systematically introduce the classification, catalytic mechanism, activity regulation as well as recent research progress of nanozymes in the field of biosensing, environmental protection, and disease treatments, etc. in the past years. We also propose the current challenges of nanozymes as well as their future research focus. We anticipate this review may be of significance for the field to understand the properties of nanozymes and the development of novel nanomaterials with enzyme mimicking activities.

Nanozymes: Classification, Catalytic Mechanisms, Activity Regulation, and Applications

Recent Trends in Macro-, Micro-, and Nanomaterial-Based Tools and Strategies for Heavy-Metal Detection Gemma Aragay, Josefina Pons, and Arben Merkoc-i* Nanobioelectronics & Biosensors Group, Institut Catal a de Nanotecnologia (CIN2, ICN-CSIC), 08193, Bellaterra, Barcelona, Spain Departament of Chemistry, Universitat Aut onoma de Barcelona, 08193, Bellaterra, Barcelona, Spain ICREA, Barcelona, Spain

Recent trends in macro-, micro-, and nanomaterial-based tools and strategies for heavy-metal detection.

Recent developments in paper-based microfluidic devices.

Colorimetric assay based on the unique surface plasmon resonance properties of metallic nanoparticles has received considerable attention in bioassay due to its simplicity, high sensitivity, and low cost. Most of colorimetric methods previously reported employed gold nanoparticles (GNPs) as sensing elements. In this work, we develop a sensitive, selective, simple, and label-free colorimetric assay using unmodified silver nanoparticle (AgNP) probes to detect enzymatic reactions. Enzymatic reactions concerning adenosine triphosphate (ATP) dephosphorylation by calf intestine alkaline phosphatase (CIAP) and peptide phosphorylation by protein kinase A (PKA) were studied. In the absence of the enzymes, unreacted ATP could protect AgNPs from salt-induced aggregation, whereas in the presence of the enzymes, the reaction product of ATP (i.e., adenosine for CIAP and ADP for PKA) could not. Via our method, dephosphorylation and phosphorylation could be readily detected by the color change of AgNPs, with a detection ...

Enzyme colorimetric assay using unmodified silver nanoparticles.

Aptamers, which are artificial oligonucleotides selected in vitro, have been employed to design novel biosensors (i.e., aptasensors). In this work, we first constructed a label-free electrochemical aptasensor introducing a probe immobilization technique by the use of a layer-by-layer (LBL) self-assembled multilayer with ferrocene-appended poly(ethyleneimine) (Fc-PEI) on an indium tin oxide (ITO) array electrode for detection of cocaine. The Fc-PEI and gold nanoparticles (AuNPs) were LBL assembled on the electrode surface via electrostatic interaction. Then, cocaine aptamer fragments, SH-C2, were covalently labeled onto the outermost AuNP layer. When the target cocaine and cocaine aptamer C1 were present simultaneously, the SH-C2 layer hybridized partly with C1 to bind the cocaine, which led to a decreased differential pulse voltammetry (DPV) signal of Fc-PEI. This DPV signal change could be used to sensitively detect cocaine with the lowest detectable concentration down to 0.1 microM and the detection range up to 38.8 microM, which falls in the the expected range for medical use of detecting drug abuse involving cocaine. Meanwhile, the sensor was specific to cocaine in complex biologic fluids such as human plasma, human saliva, etc. The sensing strategy had general applicability, and the detection of thrombin could also be realized, displayed a low detection limit, and exhibited worthiness to other analytes. The aptasensor based on the array electrode held promising potential for integration of the sensing ability in multianalysis for simultaneous detection.

Solid-State Probe Based Electrochemical Aptasensor for Cocaine: A Potentially Convenient, Sensitive, Repeatable, and Integrated Sensing Platform for Drugs

This communication demonstrates for the first time the controlled power release of biofuel cells (BFCs) by aptamer logic systems processed according to the Boolean logic operations "programmed" into the biocomputing systems. On the basis of the built-in Boolean NAND logic, the fabricated aptamer-based BFCs logically controlled by biochemical signals enabled us to construct self-powered and intelligent logic aptasensors that can determine whether the two specific targets are both present in a sample.

Aptamer-controlled biofuel cells in logic systems and used as self-powered and intelligent logic aptasensors.

Au NPs-enhanced surface plasmon resonance for sensitive detection of mercury(II) ions.

In this work, a novel style of a microfluidic-based bipolar system with two-direction driving electrodes and dual-channel configuration was described for the first time, which could reach 100% current efficiency in theory. More importantly, the background signal from the integrated driving electrodes was completely eliminated, when this unique design was used to construct an electrochemiluminescence (ECL) sensing platform. First, universal pH indicator was employed to study the mechanism and demonstrate that this new bipolar system possessed 100% current efficiency theoretically. Then, the Ru(bpy)32+/TPrA ECL system was introduced to construct the dual-channel bipolar ECL sensing platform, and the results of visual ECL experiments proved that the background signals from the driving electrodes were completely dispelled with our design. To illustrate the promising applications of this dual-channel device, TPrA, dopamine (DA), H2O2, and K3Fe(CN)6 were detected as model targets under different principles.

Chaogui Chen

Papers

Enzyme colorimetric assay using unmodified silver nanoparticles.

Solid-State Probe Based Electrochemical Aptasensor for Cocaine: A Potentially Convenient, Sensitive, Repeatable, and Integrated Sensing Platform for Drugs

Aptamer-controlled biofuel cells in logic systems and used as self-powered and intelligent logic aptasensors.

Au NPs-enhanced surface plasmon resonance for sensitive detection of mercury(II) ions.

New Insight into a Microfluidic-Based Bipolar System for an Electrochemiluminescence Sensing Platform