Similar to its popular older cousins the fullerene, the carbon nanotube, and graphene, the latest form of nanocarbon, the carbon nanodot, is inspiring intensive research efforts in its own right. These surface-passivated carbonaceous quantum dots, so-called C-dots, combine several favorable attributes of traditional semiconductor-based quantum dots (namely, size- and wavelength-dependent luminescence emission, resistance to photobleaching, ease of bioconjugation) without incurring the burden of intrinsic toxicity or elemental scarcity and without the need for stringent, intricate, tedious, costly, or inefficient preparation steps. C-dots can be produced inexpensively and on a large scale (frequently using a one-step pathway and potentially from biomass waste-derived sources) by many approaches, ranging from simple candle burning to in situ dehydration reactions to laser ablation methods. In this Review, we summarize recent advances in the synthesis and characterization of C-dots. We also speculate on their future and discuss potential developments for their use in energy conversion/storage, bioimaging, drug delivery, sensors, diagnostics, and composites.

Luminescent Carbon Nanodots: Emergent Nanolights

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.

Carbon nanodots (C-dots) have generated enormous excitement because of their superiority in water solubility, chemical inertness, low toxicity, ease of functionalization and resistance to photobleaching. In this review, by introducing the synthesis and photo- and electron-properties of C-dots, we hope to provide further insight into their controversial emission origin (particularly the upconverted photoluminescence) and to stimulate further research into their potential applications, especially in photocatalysis, energy conversion, optoelectronics, and sensing.

Carbon nanodots: synthesis, properties and applications

A simple, one-pot, "green" synthetic route, based on the "biomineralization" capability of a common commercially available protein, bovine serum albumin (BSA), has been developed for the preparation of highly stable Au nanocrystals (NCs) with red emission and high quantum yield.

Protein-directed synthesis of highly fluorescent gold nanoclusters.

Electrogenerated chemiluminescence (also called electrochemiluminescence and abbreviated ECL) is the process whereby species generated at electrodes undergo high-energy electron-transfer reactions to form excited states that emit light. The first detailed ECL studies were described by Hercules and Bard et al. in the mid-1960s, although reports concerning light emission during electrolysis date back to the 1920s by Harvey. After about 40 years study, ECL has now become a very powerful analytical technique and been widely used in the areas of, for example, immunoassay, food and water testing, and biowarfare agent detection. ECL has also been successfully exploited as a detector of flow injection analysis (FIA), high-performance liquid chromatography (HPLC), capillary electrophoresis, and micro total analysis (μTAS). Figure 1 illustrates a time line of various events in the development of ECL. A literature survey using SciFinder Scholar reveals that more than 2000 journal articles, book chapters, and patents on various topics of ECL have been published. The overall number of publications, as shown in Figure 2, has increased exponentially over the past 20 years, of which 40–50% were biorelated. Similar amounts of ECL papers could be also found from the Thomson ISI Web of Science as well as † Telephone (601) 266 4716; fax (601) 266 6075; e-mail wujian.miao@ usm.edu. Wujian Miao received his undergraduate diploma in chemistry from Nantong University (Nantong, China) in 1982, his M.Sc. degree in analytical chemistry from Zhongshan University (Guangzhou, China, with Jinyuan Mo) in 1991, and his Ph.D. degree in electrochemistry from Monash University (Melbourne, Australia, with Alan M. Bond) in 2000. He then served as a Research Scientist in CSIRO (Melbourne, Australia), followed by a postdoctoral fellowship at the University of Texas at Austin with Allen J. Bard in 2001. Since 2004 he has served as an assistant professor of chemistry at the University of Southern Mississippi.

Electrogenerated Chemiluminescence and Its Biorelated Applications

Differential pulse voltammetry (DPV) of TOPO-capped CdTe nanoparticles (NPs) in dichloromethane and a mixture of benzene and acetonitrile showed two anodic and one cathodic peaks of the NPs themselves and an additional anodic peak resulting from the oxidation of reduced NPs. The electrochemical band gap (∼2.1 eV) between the first anodic and cathodic DPV peaks was close to the value (2 eV) obtained from the absorption spectrum. Electrogenerated chemiluminescence (ECL) of CdTe NPs was highly intense for scans into the negative potential region in dichloromethane. The fact that the ECL peak occurs at about the same wavelength as the band-edge photoluminescence (PL) peak indicates that, in contrast to CdSe NPs, the CdTe NPs as synthesized had no deep surface traps that can cause a substantially red shifted ECL.

Electrochemistry and electrogenerated chemiluminescence of CdTe nanoparticles

A product showing strong blue photoluminescence was obtained by oxidation of OH-terminated PAMAM dendrimers, such as G4-OH, G2-OH, and G0-OH, with HAuCl4 or (NH4)2S2O8. The fluorescence emission spectrum peaked at 450 nm, while the excitation maximum was at 380 nm, independent of the generation of dendrimer. The product also shows two weak electrogenerated chemiluminescence (ECL) signals upon cycling the potential between about 1.2 and −1.7 V.

Strong blue photoluminescence and ECL from OH-terminated PAMAM dendrimers in the absence of gold nanoparticles.

The electrogenerated chemiluminescence (ECL) spectrum of CdSe/ZnSe nanocrystals (NCs) dispersed in a CH2Cl2 solution containing 0.1 M TBAP was obtained by stepping the potential between +2.3 and −2...

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Effect of Surface Passivation on the Electrogenerated Chemiluminescence of CdSe/ZnSe Nanocrystals

An unusual enhancement of photoluminescence from CdSe nanocrystals (NCs) dispersed in air-saturated CHCl3 was observed as a function of time. Within two weeks, for samples kept in the dark, the photoluminescence intensity increased by as much as a factor of 6, based on the peak height, with no change in peak position or width. This enhancement can be attributed to the reaction of nanocrystals with dissolved oxygen, which results in surface passivation. CdSe NCs kept in the growth solution (TOP/TOPO) showed no photoluminescence increase.

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Enhancement of the Photoluminescence of CdSe Nanocrystals Dispersed in CHCl3 by Oxygen Passivation of Surface States

Films of octadecyl-capped Si nanoparticles (NPs) (diameter, 3.4 ± 0.7 nm) prepared by drop-coating on indium tin oxide (ITO) showed electrogenerated chemiluminescence (ECL) for both cathodic and anodic potential sweeps in KOH solutions containing peroxydisulfate. The redox potentials of the Si NPs can be estimated as approximately −0.9 and +0.95 V (versus Ag|AgCl) based on the anodic potential for the onset of ECL minus the ECL peak energy. The ECL exhibits a relatively broad spectrum (FWHM = 160 nm) with a peak wavelength of ~670 nm (1.85 eV), similar to the photoluminescence spectra. In electrochemical studies in KOH solution in the absence of peroxydisulfate, an anodic current peak appears at about −1 V (versus Ag|AgCl) following a scan to negative potentials. A similar peak has been observed during the etching of a bulk single crystal Si electrode in alkaline aqueous solution. Unpassivated surface sites of Si NPs seem to be etched at potentials negative of the anodic oxidation peak.

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Yoonjung Bae

Papers

Electrochemistry and electrogenerated chemiluminescence of CdTe nanoparticles

Strong blue photoluminescence and ECL from OH-terminated PAMAM dendrimers in the absence of gold nanoparticles.

Effect of Surface Passivation on the Electrogenerated Chemiluminescence of CdSe/ZnSe Nanocrystals

Enhancement of the Photoluminescence of CdSe Nanocrystals Dispersed in CHCl3 by Oxygen Passivation of Surface States

Electrochemistry and electrogenerated chemiluminescence of films of silicon nanoparticles in aqueous solution