Shasha Wang

Colorimetric sensing of copper(II) based on catalytic etching of gold nanoparticles

Based on the catalytic etching of gold nanoparticles (AuNPs), a label-free colorimetric probe was developed for the detection of Cu(2+) in aqueous solutions. AuNPs were first stabilized by hexadecyltrimethylammonium bromide in NH3-NH4Cl (0.6M/0.1M) solutions. Then thiosulfate (S2O3(2-)) ions were introduced and AuNPs were gradually dissolved by dissolved oxygen. With the further addition of Cu(2+), Cu(NH3)4(2+) oxidized AuNPs to produce Au(S2O3)2(3-) and Cu(S2O3)3(5-), while the later was oxid-ized to Cu(NH3)4(2+) again by dissolved oxygen. The dissolving rate of AuNPs was thereby remarkably promoted and Cu(2+) acted as the catalyst. The process went on due to the sufficient supply of dissolved oxygen and AuNPs were rapidly etched. Meanwhile, a visible color change from red to colorless was observed. Subsequent tests confirmed such a non-aggregation-based method as a sensitive (LOD=5.0 nM or 0.32 ppb) and selective (at least 100-fold over other metal ions except for Pb(2+) and Mn(2+)) way for the detection of Cu(2+) (linear range, 10-80 nM). Moreover, our results show that the color change induced by 40 nM Cu(2+) can be easily observed by naked eyes, which is particularly applicable to fast on-site investigations.

Label-free colorimetric sensing of copper(II) ions based on accelerating decomposition of H2O2 using gold nanorods as an indicator.

A novel label-free colorimetric strategy was reported for sensitive detection of copper ions (Cu(2+)) by using the decelerating etching of gold nanorods (GNRs). H2O2 was employed as the oxidant for corrosion of GNRs, leading to the decrease of the aspect ratio of GNRs. In the absence of Cu(2+), the redox corrosion of GNRs by H2O2 occurred rapidly, causing the distinct color change of GNRs from bluish green to purplish red. By virtue of the strong and specific catalysis by Cu(2+) of the decomposition of H2O2, the rate of redox corrosion can be decelerated. Relevant experimental parameters, including pH value, concentrations of NaSCN and H2O2, incubation temperature and time were evaluated. Under optimal conditions, our method gave a good linear range of 10-300 nM (R = 0.9985) for Cu(2+) and the detection limit with the naked eye is as low as 10 nM. Thus, the proposed colorimetric sensor is simple, sensitive (4.96 nM) and selective, and it has been successfully applied to detect Cu(2+) in shellfish samples. Moreover, the potential mechanism was also discussed.

Iodine-Mediated Etching of Gold Nanorods for Plasmonic ELISA Based on Colorimetric Detection of Alkaline Phosphatase

Here, we propose a plasmonic enzyme-linked immunosorbent assay (ELISA) based on highly sensitive colorimetric detection of alkaline phosphatase (ALP), which is achieved by iodine-mediated etching of gold nanorods (AuNRs). Once the sandwich-type immunocomplex is formed, the ALP bound on the polystyrene microwells will hydrolyze ascorbic acid 2-phosphate into ascorbic acid. Subsequently, iodate is reduced to iodine, a moderate oxidant, which etches AuNRs from rod to sphere in shape. The shape change of AuNRs leads to a blue-shift of longitudinal localized surface plasmon resonance. As a result, the solution of AuNRs changes from blue to red. Benefiting from the highly sensitive detection of ALP, the proposed plasmonic ELISA has achieved an ultralow detection limit (100 pg/mL) for human immunoglobulin G (IgG). Importantly, the visual detection limit (3.0 ng/mL) allows the rapid differential diagnosis with the naked eye. The further detection of human IgG in fetal bovine serum indicates its applicability to the determination of low abundance protein in complex biological samples.

On-Site Visual Detection of Hydrogen Sulfide in Air Based on Enhancing the Stability of Gold Nanoparticles

We have described a simple and low-cost visual method for on-site detection of hydrogen sulfide (H2S) in air based on the antiaggregation of gold nanoparticles (AuNPs). The bubbling of H2S into a weak alkaline buffer solution leads to the formation of HS-, which can stabilize the AuNPs and ensure the AuNPs maintain their red color even in a Tris buffer solution containing 80 mM NaCl with the presence of Tween 80. The stabilization of the AuNPs is attributed to the adsorption of negatively charged S2- on the AuNPs surface. In contrast, without the bubbling of H2S, AuNPs aggregate and change color from red to blue. Under optimal conditions, the proposed method exhibits excellent visual sensitivity with a naked-eye detectable limit of 0.5 ppm (v/v), making the on-site detection of H2S possible. This method also possesses good selectivity toward H2S over other gases by using a simple SO2 removal device. The successful determination of the concentrations of H2S in local air indicates the potential application of this cost-effective method.

The Interactions Between Engineered Nanomaterials and Biomolecules

With the development and wide applications of engineered nanomaterials (ENMs), their impacts on human health have received increasing concerns. ENMs can enter human body through respiratory pathway, digestive tract, skin penetration, intravenous injection, and implantation, and then they are carried to distal organs via bloodstream and lymphatic functions to perturb physiological systems. It is very important to investigate the interactions between ENMs and biomolecules (the basic building blocks of the human body) such as phospholipid, protein, DNA, and some other small biological molecules. The chapter intends to discuss the chemical basis of interactions between ENMs and biomolecules, and the effects of the differences in surface morphology, composition, and modified groups of ENMs. The in-depth understanding of interactions between ENMs and biomolecules could lay foundations for further elucidating the effects of ENMs on human cells, organs, and physiological systems, which paves the way for human and environmental friendliness in the production and usage of ENMs.

Nanomaterial-based optical sensors for sensitive detection of heavy metal ions

Nanometerial-based optical nanoprobes have been extensively developed because of their high sensitivity, good specificity, and potential for easy quantification of species in chemical and biological analysis. With the development of nanotechnology, various kinds of nanomaterials with novel optical properties have heen generated, laying the foundation of optical nanoprobes. By further integrating receptors (chemical ligand, aptamer, molecular imprinting polymer, etc.), the information of binding specific targets will transform into analytically optical signals by employing different detection techniques including colorimetry/UV-Vis spectra, fluorometry and surface enhanced Raman scattering (SERS). In this presentation, firstly, we introduced a simple, rapid and ultrasensitive SERS nanosensor for mercury ion (Hg2+) detection based on the 4-mercaptopyridine (4-MPY) functionalized silver nanoparticles (AgNPs) in the presence of spermine; then, a novel colorimetric nanosensor for mercury species was developed for the first time due to the analyte-induced aggregation of gold nanoparticles (AuNPs) with the assistance of a thiol-containing ligand of diethyldithiocarbamate (DDTC); finally, the sensitive and selective recognition and detection of trypsin was realized in a SERS strategy by using anti-aggregation of 4-MPY-functionalized AgNPs on the basis of the interaction between protamine and trypsin.