Although gold is the subject of one of the most ancient themes of investigation in science, its renaissance now leads to an exponentially increasing number of publications, especially in the context of emerging nanoscience and nanotechnology with nanoparticles and self-assembled monolayers (SAMs). We will limit the present review to gold nanoparticles (AuNPs), also called gold colloids. AuNPs are the most stable metal nanoparticles, and they present fascinating aspects such as their assembly of multiple types involving materials science, the behavior of the individual particles, size-related electronic, magnetic and optical properties (quantum size effect), and their applications to catalysis and biology. Their promises are in these fields as well as in the bottom-up approach of nanotechnology, and they will be key materials and building block in the 21st century. Whereas the extraction of gold started in the 5th millennium B.C. near Varna (Bulgaria) and reached 10 tons per year in Egypt around 1200-1300 B.C. when the marvelous statue of Touthankamon was constructed, it is probable that “soluble” gold appeared around the 5th or 4th century B.C. in Egypt and China. In antiquity, materials were used in an ecological sense for both aesthetic and curative purposes. Colloidal gold was used to make ruby glass 293 Chem. Rev. 2004, 104, 293−346

Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology.

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.

Gold nanorods with aspect ratios of 4.6 ± 1.2, 13 ± 2, and 18 ± 2.5 (all with 16 ± 3 nm short axis) are prepared by a seeding growth approach in the presence of an aqueous miceller template. Citrate-capped 3.5 nm diameter gold particles, prepared by the reduction of HAuCl4 with borohydride, are used as the seed. The aspect ratio of the nanorods is controlled by varying the ratio of seed to metal salt. The long rods are isolated from spherical particles by centrifugation.

Wet Chemical Synthesis of High Aspect Ratio Cylindrical Gold Nanorods

12.2.2. Four-Wave Mixing (FWM) 4849 12.2.3. Dye Aggregation 4850 12.2.4. Optoelectronic Nanodevices 4850 12.3. Sensor 4851 12.3.1. Chemical Sensor 4851 12.3.2. Biological Sensor 4851 12.4. Catalysis 4852 13. Conclusion and Perspectives 4852 14. Abbreviations 4853 15. Acknowledgements 4854 16. References 4854 * Corresponding author E-mail: tpal@chem.iitkgp.ernet.in. † Raidighi College. § Indian Institute of Technology. 4797 Chem. Rev. 2007, 107, 4797−4862

Interparticle Coupling Effect on the Surface Plasmon Resonance of Gold Nanoparticles: From Theory to Applications

A simple one-step NaCl-assisted microwave-solvothermal method has been developed for the preparation of monodisperse α-Fe2O3 mesoporous microspheres. In this approach, Fe(NO3)3 · 9H2O is used as the iron source, and polyvinylpyrrolidone (PVP) acts as a surfactant in the presence of NaCl in mixed solvents of H2O and ethanol. Under the present experimental conditions, monodisperse α-Fe2O3 mesoporous microspheres can form via oriented attachment of α-Fe2O3 nanocrystals. One of the advantages of this method is that the size of α-Fe2O3 mesoporous microspheres can be adjusted in the range from ca. 170 to ca. 260 nm by changing the experimental parameters. High photocatalytic activities in the degradation of salicylic acid are observed for α-Fe2O3 mesoporous microspheres with different specific surface areas.

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Monodisperse α-Fe2O3 Mesoporous Microspheres: One-Step NaCl-Assisted Microwave-Solvothermal Preparation, Size Control and Photocatalytic Property

New fields of research in chemistry and physics require improved synthetic techniques for colloidal metal particles. This paper reports a generally applicable technique for synthesizing colloidal Au particles of mean diameters between 20 and 100 nm that exhibit improved monodispersity relative to previously published methods. In this approach (called “seeding”) Au3+ is reduced on the surface of preformed 12-nm-diameter Au nanoparticles by introduction of boiling sodium citrate, producing particles highly uniform in size and shape. A similar procedure, utilizing the reductant NH2OH at room temperature, produces two populations of particles; the larger population is even more spherical than citrate-reduced particles of similar size, while the smaller population is very distinctly rod-shaped.

Seeding of Colloidal Au Nanoparticle Solutions. 2. Improved Control of Particle Size and Shape

Covalent attachment of nanometer-scale colloidal Au particles to organosilane-coated substrates is a flexible and general approach to formation of macroscopic Au surfaces that have well-defined nanostructure. Variations in substrate (glass, metal, Al2O3), geometry (planar, cylindrical), functional group (−SH, −P(C6H5)2, −NH2, −CN), and particle diameter (2.5−120 nm) demonstrate that each component of these assemblies can be changed without adverse consequences. Information about particle coverage and interparticle spacing has been obtained using atomic force microscopy, field emission scanning electron microscopy, and quartz crystal microgravimetry. Bulk surface properties have been probed with UV−vis spectroscopy, cyclic voltammetry, and surface enhanced Raman scattering. Successful application of the latter two techniques indicates that these substrates may have value for Raman and electrochemical measurements. The assembly method described herein is compared with previous methods for controlling the na...

Two-dimensional arrays of colloidal gold particles : A flexible approach to macroscopic metal surfaces

Reversible electrochemistry of horse heart cytochrome c (Cc) has been obtained at SnO2 electrodes modified with 12-nm-diameter colloidal Au particles. Previous experiments had demonstrated electrochemical addressability of these particle ensembles; the high current densities and small peak-to-peak separations observed for Cc are indicative of facile electron transfer. In contrast to previously described modified electrodes for Cc, these data were acquired without polishing and without any modification of the Au particle surface. Quasireversible voltammetry was obtained with surfaces comprising monodisperse 36-nm-diameter and polydisperse 6-nm-diameter Au particles, but no voltammetric wave for Cc was seen at surfaces composed of aggregates of 12-nm-diameter or 22-nm-diameter Au particles. These data indicate that nanometer-scale morphology of metals plays a key role in protein electrochemistry, and suggest that isolated, surface-confined colloidal Au particles may be useful building blocks for macroscopic...

Morphology-dependent electrochemistry of cytochrome c at au colloid-modified sno2 electrodes

Atomic force microscopy (AFM), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and near-field scanning optical microscopy (NSOM) have been used to characterize the nanostructure of Au colloid-based surfaces. Because these substrates are composed of particles whose dimensions are known prior to assembly, they are well-suited for a critical comparison of the capabilities and limitations of each nanoscale imaging technique. The three criteria for this comparison, which are relevant to the field of nanoparticle assemblies in general, are (i) accuracy in establishing particle size, particle coverage, and interparticle spacing; (ii) accuracy in delineating surface topography; and (iii) ease of sample preparation, data acquisition, and image analysis. For colloidal Au arrays, TEM gives the most reliable size and spacing information but exhibits the greatest constraints with regard to sample preparation; in contrast, AFM is widely applicable but yields data that are t...

Nanoscale characterization of gold colloid monolayers: a comparison of four techniques.

An approach to enlarge preformed colloidal Au nanoparticles in solution based on the Au colloidal surface-catalyzed reduction of Au3+ by NH2OH (“seeding”) has been adapted to 12-nm-diameter colloidal Au nanoparticles immobilized in monolayers and multilayers. Bulk characterization of the ensuing films was carried out by atomic absorption, UV−vis−near-IR optical spectroscopy, cyclic voltammetry, and dc resistance measurements. Exposure of a 12-nm-diameter Au colloid monolayer on organosilane-modified glass surfaces to NH2OH/Au3+ leads to rapid particle growth and coalescence:  after roughly 5−10 min, the optical and electrical properties closely resemble that of conductive Au thin films prepared by evaporation. Evolution of the nanometer-scale architecture was followed using atomic force microscopy (AFM), surface-enhanced Raman scattering (SERS), surface plasmon resonance (SPR), and field emission scanning electron microscopy (FE-SEM), leading to the following key findings:  (i) Seeding of surface-confined...

Kenneth R. Brown

Papers

Seeding of Colloidal Au Nanoparticle Solutions. 2. Improved Control of Particle Size and Shape

Two-dimensional arrays of colloidal gold particles : A flexible approach to macroscopic metal surfaces

Morphology-dependent electrochemistry of cytochrome c at au colloid-modified sno2 electrodes

Nanoscale characterization of gold colloid monolayers: a comparison of four techniques.

Hydroxylamine Seeding of Colloidal Au Nanoparticles. 3. Controlled Formation of Conductive Au Films