http://pubs.acs.org/doi/pdf/10.1021/cr400546e

Fluorescent Sensors for Measuring Metal Ions in Living Systems

Anisotropic gold nanoparticles (AuNPs) have attracted the interest of scientists for over a century, but research in this field has considerably accelerated since 2000 with the synthesis of numerous 1D, 2D, and 3D shapes as well as hollow AuNP structures. The anisotropy of these nonspherical, hollow, and nanoshell AuNP structures is the source of the plasmon absorption in the visible region as well as in the near-infrared (NIR) region. This NIR absorption is especially sensitive to the AuNP shape and medium and can be shifted towards the part of the NIR region in which living tissue shows minimum absorption. This has led to crucial applications in medical diagnostics and therapy ("theranostics"), especially with Au nanoshells, nanorods, hollow nanospheres, and nanocubes. In addition, Au nanowires (AuNWs) can be synthesized with longitudinal dimensions of several tens of micrometers and can serve as plasmon waveguides for sophisticated optical devices. The application of anisotropic AuNPs has rapidly spread to optical, biomedical, and catalytic areas. In this Review, a brief historical survey is given, followed by a summary of the synthetic modes, variety of shapes, applications, and toxicity issues of this fast-growing class of nanomaterials.

Anisotropic gold nanoparticles: synthesis, properties, applications, and toxicity

Gold nanorods have received much attention due to their unique optical and electronic properties which are dependent on their shape, size, and aspect ratio. This article covers in detail the synthesis, functionalization, self-assembly, and sensing applications of gold nanorods. The synthesis of three major types of rods is discussed: single-crystalline and pentahedrally-twinned rods, which are synthesized by wet chemistry methods, and polycrystalline rods, which are synthesized by templated deposition. Functionalization of these rods is usually necessary for their applications, but can often be problematic due to their surfactant coating. Thus, general strategies are provided for the covalent and noncovalent functionalization of gold nanorods. The review will then examine the significant progress that has been made in controllable assembly of nanorods into various arrangements. This assembly can have a large effect on measurable properties of rods, making it particularly applicable towards sensing of a variety of analytes. Other types of sensing not dependent on nanorod assembly, such as refractive-index based sensing, are also discussed.

Functional Gold Nanorods: Synthesis, Self-Assembly, and Sensing Applications

DNAzyme-based biosensors and nanodevices

Fluorescent nanoprobes for sensing and imaging of metal ions: recent advances and future perspectives.

Sensitive detection of endonuclease activity and inhibition using gold nanorods.

In this paper, we have reported a sensitive assay for fluorescence “turn-on” detection of Pb2+ in aqueous solutions based on FRET between gold nanorods (GNRs) and the FAM-labeled substrate strand of 8-17DNAzyme. The fluorescence of the FAM-labeled substrate strand is quenched when 8-17DNAzyme is adsorbed on GNRs surface through electrostatic interaction. In the presence of lead ions, the fluorescence is restored due to the decrease of FRET efficiency caused by the specific cleavage of the FAM-labeled substrate strand by the enzyme, which weakens the electrostatic interaction between the GNRs and short FAM-labeled DNA fragment. The interference of eleven common metal ions has been tested, indicating that Pb2+ can be selectively detected. This method exhibits a high sensitivity for Pb2+ with a detection limit of 61.8 pM and a linear range from 0.1 nM to 100 nM. It is a simple, sensitive, and selective method for Pb2+ detection. Moreover, this sensing system obtained satisfying results for Pb2+ detection in tap water samples.

Gold nanorods-based FRET assay for sensitive detection of Pb2+ using 8-17DNAzyme

DNA cleavage reaction catalyzed by nucleases is essential in many important biological processes and medicinal chemistry. Therefore, it is important to develop reliable and facile methods to assay nuclease activity. With this goal in mind, we report a fluorescent assay for label-free, facile, and real-time monitoring of DNA cleavage by EcoRI endonuclease using SYBR Green I (SGI) as a signal probe. The fluorescence of SGI dramatically increased when the free SGI was mixed with double-stranded DNA (dsDNA) substrate. Upon interacting with EcoRI, which cleaves the dsDNA into small fragments, the weakened interaction between SGI and the shortened DNA fragments caused a decrease in fluorescence of SGI. EcoRI–DNA interaction was real-time studied by monitoring fluorescence change with the prolonging of interaction time. The important kinetic parameters, including Michaelis–Menten constant (KM) and maximum initial velocity (Vmax), were accurately calculated, which is consistent with previously reported studies. Site-specific DNA cleavage by EcoRI endonuclease has also been verified by gel electrophoresis analysis, which indicated that this method is a simple and effective approach to assay DNA cleavage reaction. Specificity investigation demonstrated that EcoRI–DNA interactions can be studied with high selectivity. Compared with previously reported methods, this approach is selective, simple, convenient and cost-efficient without any labeling of the probe or of the target.

Label-free fluorescent assay for real-time monitoring site-specific DNA cleavage by EcoRI endonuclease.

The G-rich overhang of human telomere tends to form a G-quadruplex structure, and G-quadruplex formation can effectively inhibit telomerase activity in most cancer cells. Therefore, it is important to identify the formation and properties of the G-quadruplex, with the particular aim of selecting G-quadruplex-binding ligands that could potentially lead to the development of anticancer therapeutic agents. With this goal in mind, we report a fluorescence resonance energy transfer (FRET) assay system for the identification of G-quadruplex ligands using DNA-functionalized gold nanoparticles (DNA-GNPs) as the fluorescence quencher and a carboxyfluorescein (FAM)-tagged human telomeric sequence (F-GDNA) as the recognition probe. A thiolated complementary strand of human telomeric DNA (cDNA), which first adheres to the surface of the GNPs and then hybridizes with F-GDNA, results in the fluorescence quenching of F-GDNA by the GNPs. However, fluorescence is restored when single-stranded F-GDNA folds into a G-quadruplex structure upon the binding of quadruplex ligands, leading to the release of F-GDNA from the surface of the GNPs. Combined data from fluorescence measurements and CD spectroscopy indicated that ligands selected by this FRET method could induce GDNA to form a G-quadruplex. Therefore, this FRET G-quadruplex assay is a simple and effective approach to identify quadruplex-binding ligands, and, as such, it promises to provide a solid foundation for the development of novel anticancer therapeutic agents.

Identifying G-quadruplex-binding ligands using DNA-functionalized gold nanoparticles

Gold nanorods-based FRET assay for ultrasensitive detection of Hg2+

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