Chia-Wei Wang

Fluorescent Gold Nanoclusters: Recent Advances in Sensing and Imaging

F gold nanoclusters (Au NCs) or nanodots (NDs) with sizes smaller than 3 nm are a specific type of gold nanomaterials. In this review, Au NCs are used to represent fluorescent Au nanomaterials with sizes smaller than 3 nm. Unlike the most popular and well-known spherical, large gold nanoparticles, Au NCs do not exhibit surface plasmon resonance (SPR) absorption in the visible region but have fluorescence in the visible to near-infrared (NIR) region. With advantages of long lifetime, large Stokes shift, and biocompatibility, Au NCs have become interesting sensing and imaging materials. Although Au NCs prepared from Au in the presence of small thiol compounds such as 2-phenylethanethiol (PhCH2CH2SH) have been reported over the past decade, 5 their use for bioapplications have not been well recognized, mainly because of their low quantum yield (usually less than 1%), poor water dispersibility, photo and chemical instability, and difficulty for conjugation. In the past decade, many strategies for the preparation of stable, water dispersible, highly fluorescent, and biocompatible Au NCs have been reported. There are two major categories elucidating the recent advanced techniques for the preparation of Au NCs. The first category is through etching of larger sizes of nonfluorescent gold nanoparticles (Au NPs) by thiol compounds such as mercaptopropionic acid. The second category is from reduction of Au in the presence of a ligand or template (protein) such as bovine serum albumin (BSA). The optical properties of biocompatible Au NCs are dependent on their size, surface ligand or template, and the surrounding medium, and thus they can be studied to develop sensitive and selective sensing and imaging systems for the detection of various analytes. The growing popularity of Au NCs in analytical applications has been realized in these few years. Several excellent review papers dealing with Au NCs from the viewpoint of analytical chemistry have been reported to highlight their potential for the analysis of environmental and biological samples. This review focuses on recent advances in Au NCs based sensing and imaging systems between 2012 and 2014. Current challenges and future prospects of Au NCs for fundamental studies and analytical applications will be provided.

Detection of Mercury(II) Ions Using Colorimetric Gold Nanoparticles on Paper-Based Analytical Devices

An on-field colorimetric sensing strategy employing gold nanoparticles (AuNPs) and a paper-based analytical platform was investigated for mercury ion (Hg(2+)) detection at water sources. By utilizing thymine-Hg(2+)-thymine (T-Hg(2+)-T) coordination chemistry, label-free detection oligonucleotide sequences were attached to unmodified gold nanoparticles to provide rapid mercury ion sensing without complicated and time-consuming thiolated or other costly labeled probe preparation processes. Not only is this strategys sensing mechanism specific toward Hg(2+), rather than other metal ions, but also the conformational change in the detection oligonucleotide sequences introduces different degrees of AuNP aggregation that causes the color of AuNPs to exhibit a mixture variance. To eliminate the use of sophisticated equipment and minimize the power requirement for data analysis and transmission, the color variance of multiple detection results were transferred and concentrated on cellulose-based paper analytical devices, and the data were subsequently transmitted for the readout and storage of results using cloud computing via a smartphone. As a result, a detection limit of 50 nM for Hg(2+) spiked pond and river water could be achieved. Furthermore, multiple tests could be performed simultaneously with a 40 min turnaround time. These results suggest that the proposed platform possesses the capability for sensitive and high-throughput on-site mercury pollution monitoring in resource-constrained settings.

Porous palladium copper nanoparticles for the electrocatalytic oxidation of methanol in direct methanol fuel cells

A facile method has been demonstrated for the preparation of PdCu nanoparticles (NPs) with various morphologies from Pd2+ and Cu2+ reduced by ascorbate in the presence of dodecyltrimethylammonium chloride (DTAC) at 95 °C. We have found that DTAC is important to assist the growth of PdCu with high-energy surfaces through the etching and capping of certain surfaces of Pd and PdCu seeds. By varying the Pd2+/Cu2+ molar ratio, different morphologies of PdCu NPs have been prepared. Cubic PdCu NPs have a dominant Pd3Cu composition when prepared at a high Pd2+/Cu2+ molar ratio (20/1), while porous PdCu NPs have a dominant PdCu3 composition when prepared at a low Pd2+/Cu2+ molar ratio (1/10). The copper content not only controls the morphology, but also affects the catalytic activity toward the methanol oxidation reaction (MOR) in alkaline media. Upon increasing the copper content, the catalytic activity toward the MOR increases, mainly due to the advantages of the electroactive surface area, more direct cathodic oxide reduction (lower onset potential for the formation of Pd–OH), and synergistic effects. Porous PdCu NP-modified electrodes provide a higher catalytic activity (363 A g−1) toward the MOR at a more negative onset potential (−0.62 V vs. Ag/AgCl) on the porous PdCu electrodes than commercial Pd/C-modified ones do (180 A g−1) at −0.52 V. To the best of our knowledge, this is the first example using porous PdCu NP-modified electrodes as anodes under alkaline conditions in direct methanol fuel cells (DMFCs). With the advantages of high electrochemical activity, stability, and cost effectiveness, the porous PdCu NPs have great potential as anode catalysts for DMFCs.

Selective Colorimetric Detection of Hydrogen Sulfide Based on Primary Amine-Active Ester Cross-Linking of Gold Nanoparticles

Hydrogen sulfide (H2S) is a highly toxic environmental pollutant and also an important gaseous transmitter. Therefore, selective detection of H2S is very important, and visual detection of it with the naked eye is preferred in practical applications. In this study, thiolated azido derivates and active esters functionalized gold nanoparticles (AE-AuNPs)-based nanosensors have been successfully prepared for H2S perception. The sensing principle consists of two steps: first, H2S reduces the azide group to a primary amine; second, a cross-linking reaction between the primary amine and active ester induces the aggregation of AuNPs. The AE-AuNPs-based nanosensors show high selectivity toward H2S over other anions and thiols due to the specific azide-H2S chemistry. Under optimal conditions, 0.2 μM H2S is detectable using a UV-vis spectrophotometer, and 4 μM H2S can be easily detected by the naked eye. In addition, the practical application of the designed nanosensors was evaluated with lake water samples.

Optical and electrochemical applications of silicon-carbon dots/silicon dioxide nanocomposites.

Various colors of photoluminescent SiC-dots/SiO2 prepared through a simple heating process have been employed for optical and electrochemical applications. Blue (B)-, green (G)-, and tan (T)-SiC-dots/SiO2 powders have been prepared from SiC-dots that had been prepared from 3-aminopropyl trimethoxysilane through a hydrothermal route by simply controlling heating at 60 °C for 60 min and 300 °C for 10 and 20 min, respectively. The B-, G-, and T-SiC-dots/SiO2 nanocomposites emit at 455, 534, and 574 nm, respectively, under excitation at 360 nm. B-, G-, and T-SiC-dots/SiO2 glass films show at least seven colors when excited at 360, 460, and 520 nm. Through a heat-induced photoluminescence (PL) change, a representative lithographic pattern of B-SiC-dots/SiO2 films has been fabricated using a near-infrared laser. The B-, G-, and T-SiC-dots/SiO2 also possess high electrocatalytic activity for the oxygen reduction reaction. Having such interesting PL and electrical properties, the stable, low-toxic, and cost-effective B-, G-, and T-SiC-dots/SiO2 nanocomposites show great economic potential in many applications such as light-emitting diodes, photoluminescent windows, and fuel cells.

Immobilization of aptamer-modified gold nanoparticles on BiOCl nanosheets: Tunable peroxidase-like activity by protein recognition.

A self-assembled nanocomposite is prepared from an aqueous mixture of aptamer-modified gold nanoparticles (Apt-Au NPs), bismuth ions and chloride ions. The Apt-Au NPs are immobilized on bismuth oxychloride (BiOCl) nanosheets in situ to form Apt-Au NPs/BiOCl nanocomposites. The as-prepared nanocomposites exhibit high peroxidase-like activity for the catalytic conversion of Amplex Red (AR) to fluorescent resorufin in the presence of H2O2. The catalytic activity of Apt-Au NPs/BiOCl nanocomposites is at least 90-fold higher than that of Apt-Au NPs or BiOCl nanosheets, revealing synergistic effects on their activity. The catalytic activity of Apt-Au NPs/BiOCl nanocomposites is suppressed by vascular endothelial growth factor-A165 (VEGF-A165) molecules that specifically interact with the aptamer units (Del-5-1 and v7t-1) on the nanocomposite surface. The AR/H2O2-Apt-Au NPs/BiOCl nanocomposites probe shows high selectivity (>1000-fold over other proteins) and sensitivity (detection limit ~0.5nM) for the detection of VEGF-A165. Furthermore, the probe is employed for the detection of VEGF isoforms and for the study of interactions between VEGF and VEGF receptors. The practicality of this simple, rapid, cost-effective probe is validated by the analysis of VEGF-A165 in cell culture media, showing its great potential for the analysis of VEGF in biological samples.

Sensitive detection of platelet-derived growth factor through surface-enhanced Raman scattering.

A surface-enhanced Raman scattering (SERS) assay using two different nanomaterials has been demonstrated for highly sensitive and selective detection of platelet-derived growth factor (PDGF). Gold nanoparticles (Au NPs; 13 nm) are conjugated with aptamer (Apt) and 4-mercaptobenzoic acid (MBA) as the recognition element and reporter, respectively, while Au pearl necklace nanomaterials (Au PNNs) are used for generating reproducible and enhanced SERS signal of 4-MBA. The Apt/MBA-Au NPs bind PDGF through a specific interaction between Apt and PDGF in a fashion of 2:1, leading to concentration of the analyte and removal of the sample matrix. Through electrostatic interaction, the PDGF-Apt/MBA-Au NPs complexes form aggregates with Au PNNs, leading to an enhanced Raman signal of 4-MBA. Au PNNs allow enhancement factors up to 1.3 × 10(7) and relative standard deviations of Raman signals for 4-MBA down to 15% (five measurements). The assay allows detection of PDGF BB down to 0.5 pM, with linearity of the Raman signal of 4-MBA against the concentration of PDGF over 1-50 pM. Having advantages of sensitivity and reproducibility, this assay has been further applied for the determination of the concentration of PDGF in urine samples, showing its great potential for ultrasensitive analysis of target proteins in biological samples.

Unibody core-shell smart polymer as a theranostic nanoparticle for drug delivery and MR imaging.

Developing novel multifunctional nanoparticles (NPs) with robust preparation, low cost, high stability, and flexible functionalizability is highly desirable. This study provides an innovative platform, termed unibody core-shell (UCS), for this purpose. UCS is comprised of two covalent-bonded polymers differed only by the functional groups at the core and the shell. By conjugating Gd(3+) at the stable core and encapsulating doxorubicin (Dox) at the shell in a pH-sensitive manner, we developed a theranostic NPs (UCS-Gd-Dox) that achieved a selective drug release (75% difference between pH 7.4 and 5.5) and MR imaging (r1 = 0.9 and 14.5 mm(-1) s(-1) at pH 7.4 and 5.5, respectively). The anti-cancer effect of UCS-Gd-Dox is significantly better than free Dox in tumor-bearing mouse models, presumably due to enhanced permeability and retention effect and pH-triggered release. To the best of our knowledge, this is the simplest approach to obtain the theranostic NPs with Gd-conjugation and Dox doping.

Detection of mercury ions using silver telluride nanoparticles as a substrate and recognition element through surface-enhanced Raman scattering.

In this paper we unveil a new sensing strategy for sensitive and selective detection of Hg2+ through surface-enhanced Raman scattering (SERS) using Ag2Te nanoparticles (NPs) as a substrate and recognition element and rhodamine 6G (R6G) as a reporter. Ag2Te NPs prepared from tellurium dioxide and silver nitrate and hydrazine in aqueous solution containing sodium dodecyl sulfate at 90°C with an average size of 26.8 ± 4.1 nm (100 counts) have strong SERS activity. The Ag2Te substrate provides strong SERS signals of R6G with an enhancement factor of 3.6 × 105 at 1360 cm−1, which is comparable to Ag NPs. After interaction of Ag2Te NPs with Hg2+, some HgTe NPs are formed, leading to decreases in the SERS signal of R6G, mainly because HgTe NPs relative to Ag2Te NPs have weaker SERS activity. Under optimum conditions, this SERS approach using Ag2Te as substrates is selective for the detection of Hg2+, with a limit of detection of 3 nM and linearity over 10–150 nM. The practicality of this approach has been validated for the determination of the concentrations of spiked Hg2+ in a pond water sample.

Control of pH for separated quantitation of nitrite and cyanide ions using photoluminescent copper nanoclusters

A dual sensing probe has been developed for the detection of nitrite (NO2−) and cyanide (CN−) ions based on the analyte-induced photoluminescence (PL) quenching of thiosalicylic acid (TA) capped-copper (Cu) nanocluster (NC) aggregates. The TA–Cu NC aggregates prepared from Cu2+ and TA emit at 420 nm when excited at 338 nm, with a quantum yield of 13.2%. The PL quenching of the TA–Cu NC aggregates by NO2− is through a redox reaction between HNO2 and TA under acidic conditions, while that by CN− ions in a basic solution is through an etching process. By controlling pH values at 5.0 and then at 8.0, the probe allows consecutive quantitation of NO2− and CN− ions in water samples, with limits of detection of 5 μM and 5 nM, respectively, at a signal-to-noise ratio of 3. The practicality of this probe has been validated through the determination of the concentrations of NO2− and CN− ions in representative lake water samples.