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.

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Self-assembled monolayers of thiolates on metals as a form of 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.

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New approaches to nanofabrication: molding, printing, and other techniques.

Initially poorly conducting PbSe nanocrystal solids (quantum dot arrays or superlattices) can be chemically "activated" to fabricate n- and p-channel field effect transistors with electron and hole mobilities of 0.9 and 0.2 square centimeters per volt-second, respectively; with current modulations of about 10(3) to 10(4); and with current density approaching 3 x 10(4) amperes per square centimeter. Chemical treatments engineer the interparticle spacing, electronic coupling, and doping while passivating electronic traps. These nanocrystal field-effect transistors allow reversible switching between n- and p-transport, providing options for complementary metal oxide semiconductor circuits and enabling a range of low-cost, large-area electronic, optoelectronic, thermoelectric, and sensing applications.

PbSe Nanocrystal Solids for n- and p-Channel Thin Film Field-Effect Transistors

Molecular electronics is commonly conceived as reproducing diode or transistor action at the molecular level. The quantum-dot cellular automata (QCA) approach offers an attractive alternative in which binary information is encoded in the configuration of charge among redox-active molecular sites. The Coulomb interaction between neighboring molecules provides device-device coupling. No current flow between molecules is required. We present an ab initio analysis of a simple molecular system which acts as a molecular QCA cell. The intrinsic bistability of the charge configuration results in dipole or quadrupole fields which couple strongly to the state of neighboring molecules. We show how logic gates can be implemented. We examine the role of the relaxation of nuclear coordinates in the molecular charge reconfiguration.

Molecular quantum-dot cellular automata

The ability to efficiently utilize solar thermal energy to enable liquid-to-vapor phase transition has great technological implications for a wide variety of applications, such as water treatment and chemical fractionation Here, we demonstrate that functionalizing graphene using hydrophilic groups can greatly enhance the solar thermal steam generation efficiency Our results show that specially functionalized graphene can improve the overall solar-to-vapor efficiency from 38% to 48% at one sun conditions compared to chemically reduced graphene oxide Our experiments show that such an improvement is a surface effect mainly attributed to the more hydrophilic feature of functionalized graphene, which influences the water meniscus profile at the vapor–liquid interface due to capillary effect This will lead to thinner water films close to the three-phase contact line, where the water surface temperature is higher since the resistance of thinner water film is smaller, leading to more efficient evaporation Th

Functionalized Graphene Enables Highly Efficient Solar Thermal Steam Generation.

Ultrasmooth octadecyltrichlorosilane (OTS) monolayers (2.6 ± 0.2 nm thick, RMS roughness ∼1.0 A) can be obtained reproducibly by exposing clean native SiO2 surfaces to a dry solution of OTS in Isop...

Growth of Ultrasmooth Octadecyltrichlorosilane Self-Assembled Monolayers on SiO2

We investigate poly(methylmethacrylate) (PMMA) development processing with cold developers (4–10 °C) for its effect on resolution, resist residue, and pattern quality of sub-10 nm electron beam lithography (EBL). We find that low-temperature development results in higher EBL resolution and improved feature quality. PMMA trenches of 4–8 nm are obtained reproducibly at 30 kV using cold development. Fabrication of single-particle-width Au nanoparticle lines was performed by lift-off. We discuss key factors for formation of PMMA trenches at the sub-10 nm scale.

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Marya Lieberman

Papers

Molecular quantum-dot cellular automata

Functionalized Graphene Enables Highly Efficient Solar Thermal Steam Generation.

Growth of Ultrasmooth Octadecyltrichlorosilane Self-Assembled Monolayers on SiO2

Sub-10 nm electron beam lithography using cold development of poly(methylmethacrylate)

Iron(ii) organizes a synthetic peptide into three-helix bundles