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.

/pdf/gold-nanoparticles-in-chemical-and-biological-sensing-5e2qojkdzn.pdf

Gold nanoparticles in chemical and biological sensing.

http://users.encs.concordia.ca/~mojtaba/elec6271/silver%20nanoparticles.pdf

Silver nanoparticles: green synthesis and their antimicrobial activities.

Within the field of nanotechnology, nanoparticles are one of the most prominent and promising candidates for technological applications. Self-assembly of nanoparticles has been identified as an important process where the building blocks spontaneously organize into ordered structures by thermodynamic and other constraints. However, in order to successfully exploit nanoparticle self-assembly in technological applications and to ensure efficient scale-up, a high level of direction and control is required. The present review critically investigates to what extent self-assembly can be directed, enhanced, or controlled by either changing the energy or entropy landscapes, using templates or applying external fields.

Directed Self-Assembly of Nanoparticles

Design and fabrication of magnetic nanoparticles for targeted drug delivery and imaging

Atomically precise pieces of matter of nanometer dimensions composed of noble metals are new categories of materials with many unusual properties. Over 100 molecules of this kind with formulas such as Au25(SR)18, Au38(SR)24, and Au102(SR)44 as well as Ag25(SR)18, Ag29(S2R)12, and Ag44(SR)30 (often with a few counterions to compensate charges) are known now. They can be made reproducibly with robust synthetic protocols, resulting in colored solutions, yielding powders or diffractable crystals. They are distinctly different from nanoparticles in their spectroscopic properties such as optical absorption and emission, showing well-defined features, just like molecules. They show isotopically resolved molecular ion peaks in mass spectra and provide diverse information when examined through multiple instrumental methods. Most important of these properties is luminescence, often in the visible–near-infrared window, useful in biological applications. Luminescence in the visible region, especially by clusters prot...

Atomically Precise Clusters of Noble Metals: Emerging Link between Atoms and Nanoparticles

Magnetite nanoparticles of nearly uniform size have been prepared by precipitating ferrous ions in the presence of two different polyelectrolytes, viz., poly(acrylic acid) and the sodium salt of carboxymethyl cellulose at high pH (∼13). The size of the magnetite nanoparticles can be controlled easily by varying the concentration of the polyelectrolyte in the medium. Transmission electron microscopy study indicates that the average particle size varies from 5 to 15 nm, depending on the concentration and the nature of the polyelectrolyte. X-ray diffraction study shows the presence of only magnetite phase. FTIR spectroscopy and thermogravimetric analysis confirmed the presence of polyelectrolyte on the magnetite surface. The magnetization and Mossbauer studies were performed on two samples with mean diameters 7.0 and 14.7 nm. Magnetization measurements suggest that both of these particles are of single magnetic domain. The measurements also estimate the superparamagnetic blocking temperature, TB = 145 K for ...

Size-Controlled Synthesis of Magnetite Nanoparticles in the Presence of Polyelectrolytes

Synthetic oligopeptides with a tryptophan residue at the C-terminus have been used for the synthesis of gold and silver nanoparticles at pH 11. The tryptophan residue in the peptides is responsible for the reduction of metal ions to the respective metals, possibly through electron transfer. A mechanistic pathway has been proposed to explain the reductive properties of the tryptophan moiety of the peptide based on some spectroscopic techniques, such as UV-visible and fluorescence spectroscopy. This study reveals that some of the peptide molecules are converted to its corresponding ditryptophan, kynurenine form and some cross-linked products, all of which are highly fluorescent species. The resultant peptide-functionalized metal nanoparticles have also been characterized by UV-visible spectroscopy, transmission electron microscopy, and Fourier transform IR spectroscopy and thermogravimatric analysis.

Tryptophan-based peptides to synthesize gold and silver nanoparticles: a mechanistic and kinetic study.

Synthetic oligopeptides containing redox-active tyrosine residues have been employed to prepare gold and silver nanoparticles. In this reduction process an electron from the tyrosinate ion of the peptide is transferred to the metal ion at basic pH through the formation of a tyrosyl radical, which is eventually converted to its dityrosine form during the reaction. This reaction mechanism was confirmed from UV-visible, fluorescence, and EPR spectroscopy and was found to be pH-dependent. Transmission electron microscopy measurement shows that the average size and the monodispersity of gold nanoparticles increase as the number of tyrosine residues in the peptide increases. The kinetic study, based on spectrophotometric measurements of the surface plasmon resonance optical property, shows that the rate of formation of gold nanoparticles was much faster at higher pH than at lower pH and was also dependent on the number of tyrosine residues present in the peptide. The dityrosine form of the peptide was found to retain reducing properties like those of tyrosine in basic medium.

A mechanistic and kinetic study of the formation of metal nanoparticles by using synthetic tyrosine-based oligopeptides

Carboxylated peptide-functionalized gold nanoparticles (peptide−GNPs) were self-assembled into networks of one-dimensional (1D) chains in the presence of mercury ion (Hg2+) at room temperature without use of any template. Transmission electron microscopy (TEM) confirmed the formation of a 1D array of gold nanoparticle (GNP) chains and revealed that the length of the chain can be tuned by varying the Hg2+ ion concentration in the medium. Dynamic light scattering (DLS) measurements showed that the assembly of peptide−GNPs actually occurred in the medium and not during TEM specimen preparation. The assembly of peptide−GNPs resulted in a change of color of the suspension from red to purple to blue. This color change is due to the development of a new surface plasmon resonance (SPR) band at 670 nm. A mechanistic pathway is suggested for this 1D assembly on the basis of some control experiments, and we believe that the main driving force for the 1D array of GNPs is dipole−dipole interactions. The change of colo...

One-Dimensional Assembly of Peptide-Functionalized Gold Nanoparticles: An Approach Toward Mercury Ion Sensing

The assembly/disassembly process of carboxylated peptide-functionalized gold nanoparticles (peptide-GNPs) was studied within the pH interval of 2.5 to 10. The assembly process was not well controlled at pH 2.5, leading to the formation of 3D structures of GNPs, whereas at pH 4 we observed controlled assembly with the formation of only a network of 1D chains. In the pH range of 2.5 to 4, the assembly proceeded with the formation of a combination of two extremes (i.e., having both 1D and 2D nanostructures). The assembly process was reversed on changing the pH of the medium to 10. The assembly/disassembly process was monitored using UV−vis spectroscopy and finally confirmed by TEM analysis. This assembly resulted from the intermolecular H-bonding between two carboxylic acid groups of peptides bound to the two adjacent GNPs and were confirmed by FTIR spectroscopy.

Satyabrata Si

Papers

Size-Controlled Synthesis of Magnetite Nanoparticles in the Presence of Polyelectrolytes

Tryptophan-based peptides to synthesize gold and silver nanoparticles: a mechanistic and kinetic study.

A mechanistic and kinetic study of the formation of metal nanoparticles by using synthetic tyrosine-based oligopeptides

One-Dimensional Assembly of Peptide-Functionalized Gold Nanoparticles: An Approach Toward Mercury Ion Sensing

pH-controlled reversible assembly of peptide-functionalized gold nanoparticles.