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.

Background Since at least 400 C.E., when the Mayans first used layered clays to make dyes, people have been harnessing the properties of layered materials. This gradually developed into scientific research, leading to the elucidation of the laminar structure of layered materials, detailed understanding of their properties, and eventually experiments to exfoliate or delaminate them into individual, atomically thin nanosheets. This culminated in the discovery of graphene, resulting in a new explosion of interest in two-dimensional materials. Layered materials consist of two-dimensional platelets weakly stacked to form three-dimensional structures. The archetypal example is graphite, which consists of stacked graphene monolayers. However, there are many others: from MoS 2 and layered clays to more exotic examples such as MoO 3 , GaTe, and Bi 2 Se 3 . These materials display a wide range of electronic, optical, mechanical, and electrochemical properties. Over the past decade, a number of methods have been developed to exfoliate layered materials in order to produce monolayer nanosheets. Such exfoliation creates extremely high-aspect-ratio nanosheets with enormous surface area, which are ideal for applications that require surface activity. More importantly, however, the two-dimensional confinement of electrons upon exfoliation leads to unprecedented optical and electrical properties. Liquid exfoliation of layered crystals allows the production of suspensions of two-dimensional nanosheets, which can be formed into a range of structures. (A) MoS 2 powder. (B) WS 2 dispersed in surfactant solution. (C) An exfoliated MoS 2 nanosheet. (D) A hybrid material consisting of WS 2 nanosheets embedded in a network of carbon nanotubes. Advances An important advance has been the discovery that layered crystals can be exfoliated in liquids. There are a number of methods to do this that involve oxidation, ion intercalation/exchange, or surface passivation by solvents. However, all result in liquid dispersions containing large quantities of nanosheets. This brings considerable advantages: Liquid exfoliation allows the formation of thin films and composites, is potentially scaleable, and may facilitate processing by using standard technologies such as reel-to-reel manufacturing. Although much work has focused on liquid exfoliation of graphene, such processes have also been demonstrated for a host of other materials, including MoS 2 and related structures, layered oxides, and clays. The resultant liquid dispersions have been formed into films, hybrids, and composites for a range of applications. Outlook There is little doubt that the main advances are in the future. Multifunctional composites based on metal and polymer matrices will be developed that will result in enhanced mechanical, electrical, and barrier properties. Applications in energy generation and storage will abound, with layered materials appearing as electrodes or active elements in devices such as displays, solar cells, and batteries. Particularly important will be the use of MoS 2 for water splitting and metal oxides as hydrogen evolution catalysts. In addition, two-dimensional materials will find important roles in printed electronics as dielectrics, optoelectronic devices, and transistors. To achieve this, much needs to be done. Production rates need to be increased dramatically, the degree of exfoliation improved, and methods to control nanosheet properties developed. The range of layered materials that can be exfoliated must be expanded, even as methods for chemical modification must be developed. Success in these areas will lead to a family of materials that will dominate nanomaterials science in the 21st century.

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Liquid Exfoliation of Layered Materials

https://cyberleninka.org/article/n/1018032.pdf

Polymer nanotechnology: Nanocomposites

Graphene oxide: preparation, functionalization, and electrochemical applications.

We developed two-step solution-phase reactions to form hybrid materials of Mn3O4 nanoparticles on reduced graphene oxide (RGO) sheets for lithium ion battery applications. Mn3O4 nanoparticles grown selectively on RGO sheets over free particle growth in solution allowed for the electrically insulating Mn3O4 nanoparticles wired up to a current collector through the underlying conducting graphene network. The Mn3O4 nanoparticles formed on RGO show a high specific capacity up to ~900mAh/g near its theoretical capacity with good rate capability and cycling stability, owing to the intimate interactions between the graphene substrates and the Mn3O4 nanoparticles grown atop. The Mn3O4/RGO hybrid could be a promising candidate material for high-capacity, low-cost, and environmentally friendly anode for lithium ion batteries. Our growth-on-graphene approach should offer a new technique for design and synthesis of battery electrodes based on highly insulating materials.

Mn3O4-Graphene Hybrid as a High Capacity Anode Material for Lithium Ion Batteries

Polyaniline (PANI)/Au composite hollow spheres were successfully synthesized using polystyrene/sulfonated polystyrene core/shell gel particle templates. The PANI shell thickness and the number of Au nanoparticles decorating the PANI could be controlled effectively by adjusting the experimental conditions. The morphology, composition, and optical properties of the resulting products were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and ultraviolet-visible absorption spectra. It was found that the electrical conductivity of the PANI/Au composite hollow spheres was more than 3 times higher than that of the pure PANI hollow spheres. Furthermore, PANI/Au composites were immobilized on the surface of a glassy carbon electrode (GCE) and applied to construct a sensor. The obtained PANI/Au-modified GCEs showed one pair of redox peaks and high catalytic activity for the oxidation of dopamine. The possible formation mechanism of the PANI/Au composite hollow spheres was also discussed.

Polyaniline/Au composite hollow spheres: synthesis, characterization, and application to the detection of dopamine.

Single crystalline MoO3 nanobelts with width of 200–300 nm and the length up to several tens of micrometres were prepared by a facile hydrothermal method and characterized. Based on time- and temperature-dependent experiments, a solid–solution–solid transformation mechanism was proposed for the formation of crystalline MoO3 nanobelts. The as-prepared MoO3 nanobelts were used as a photocatalyst to degrade methylene blue (MB) under visible light irradiation and demonstrated a dramatic activity, indicating that the as-prepared MoO3 nanobelts were promising candidates for the photodegradation of organic dyes. A self-sensitization photocatalytic mechanism was suggested based on the experimental results.

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Single-crystalline orthorhombic molybdenum oxide nanobelts: synthesis and photocatalytic properties

A new and convenient sonoelectrochemical method was used to synthesize uniform three-dimensional (3D) dendritic Pt nanostructures (DPNs) at room temperature. The size and morphology of the final product could be controlled via simply adjusting the experiment parameters. The morphology and structure of the DPNs were characterized by transmission electron microscopy, high resolution transmission electron microscopy, field emission scanning electron microscopy, energy-dispersive X-ray, and X-ray diffraction. The formation process of the DPNs was carefully studied, and a spontaneous assembly mechanism was proposed based on the experimental results. Additionally, the electrocatalytic activity of the DPNs was evaluated using methanol and glucose as model molecules. The DPNs showed improved electrocatalytic activity toward methanol oxidation with respect to the monodisperse Pt nanoparticles; this improvement is due to the porosity structure and the greatly enhanced effective surface area. In addition, a sensitive enzyme-free biosensor can be easily developed for the detection of glucose in pH 7.4 phosphate buffer solution. The present method provides a new and simple strategy toward the fabrication of 3D DPNs with extensive applications.

Three-dimensional Dendritic Pt Nanostructures: Sonoelectrochemical Synthesis and Electrochemical Applications

ZnO/CdS hierarchical nanospheres were prepared for photoelectrochemical selective sensing of Cu2+. Hierarchical ZnO nanospheres were first synthesized by the hydrolysis of zinc salt under ultrasound irradiation, and then CdS nanocrystals were selectively grown on the hierarchical ZnO nanospheres. The light scattering of ZnO nanospheres and the heterointerfaces between CdS and ZnO provided significant advantages for enhanced light absorption and charge separation, thus resulting in an improvement in the photocurrent intensity. A photoelectrochemical sensor was developed based on the interaction between Cu2+ and CdS. The results showed that this sensor has a good selectivity and high sensitivity for Cu2+ detection.

ZnO/CdS Hierarchical Nanospheres for Photoelectrochemical Sensing of Cu2+

Polypyrrole (PPy)-coated Ag composites were synthesized through an immiscible organic/inorganic biphasic system in the presence of polyvinylpyrrolidone (PVP). Highly dispersed PPy/Ag was obtained by using interface polymerization and controlling the reactive conditions. The presence of PVP could realize the effective coating of PPy on the surface of Ag. The core−shell structure was directly confirmed by transmission electron microscopy and also characterized by techniques such as Fourier transform infrared spectroscopy and X-ray diffraction. Furthermore, three-layered Au-modified PPy-coated Ag nanocomposite was prepared through the reaction of Au colloidal solution and PPy/Ag. Moreover, Au/PPy/Ag nanocomposite was immobilized on the surface of a glassy carbon electrode and applied to construct a dopamine (DA) biosensor. The biosensor exhibited a fast amperometric response to DA with the linear range from 1 × 10-4 to 5 × 10-3 mol/L.

Wenhua Hou

Papers

Polyaniline/Au composite hollow spheres: synthesis, characterization, and application to the detection of dopamine.

Single-crystalline orthorhombic molybdenum oxide nanobelts: synthesis and photocatalytic properties

Three-dimensional Dendritic Pt Nanostructures: Sonoelectrochemical Synthesis and Electrochemical Applications

ZnO/CdS Hierarchical Nanospheres for Photoelectrochemical Sensing of Cu2+

Ag/Polypyrrole Core-Shell Nanostructures: Interface Polymerization, Characterization, and Modification by Gold Nanoparticles