Wei-Lung Tseng

Colorimetric Sensing of Silver(I) and Mercury(II) Ions Based on an Assembly of Tween 20-Stabilized Gold Nanoparticles

We have developed a rapid and homogeneous method for the highly selective detection of Hg(2+) and Ag(+) using Tween 20-modified gold nanoparticles (AuNPs). Citrate ions were found to still be adsorbed on the Au surface when citrate-capped AuNPs were modified with Tween 20, which stabilizes the citrate-capped AuNPs against conditions of high ionic strength. When citrate ions had reduced Hg(2+) and Ag(+) to form Hg-Au alloys and Ag on the surface of the AuNPs, Tween 20 was removed from the NP surface. As a result, the AuNPs were unstable under a high-ionic-strength solution, resulting in NP aggregation. The formation of Hg-Au alloys or Ag on the surface of the AuNPs was demonstrated by means of inductively coupled plasma mass spectroscopy and energy-dispersive X-ray spectroscopy. Tween 20-AuNPs could selectively detect Hg(2+) and Ag(+) at concentrations as low as 0.1 and 0.1 microM in the presence of NaCl and EDTA, respectively. Moreover, the probe enables the analysis of AgNPs with a minimum detectable concentration that corresponds to 1 pM. This probe was successfully applied to detect Hg(2+) in drinking water and seawater, Ag(+) in drinking water, and AgNPs in drinking water.

Ultrasensitive sensing of Hg2+ and CH3Hg+ based on the fluorescence quenching of lysozyme type VI-stabilized gold nanoclusters.

This study presents a one-step approach to prepare lysozyme type VI-stabilized gold nanoclusters (Lys VI-AuNCs) for the ultrasensitive detection of Hg(2+) and CH(3)Hg(+) based on fluorescence quenching. The optical properties and size of Lys VI-AuNCs are highly dependent on the concentration of Lys VI, which acts as both a reducing and a stabilizing agent. With an increase in the concentration of Lys VI, we observed a systematic blue shift in the fluorescence maxima, an increase in the quantum yields, and a reduction in the particle size. When using 25 mg/mL Lys VI as a reducing agent, the formed Lys VI-AuNCs (denoted as Au-631) were found to be highly stable in a high-concentration glutathione or NaCl. Additionally, the Au-631 were capable of sensing Hg(2+) and CH(3)Hg(+) through the interaction between Hg(2+)/CH(3)Hg(+) and Au(+) on the Au surface; the limits of detection (LODs) for Hg(2+) and CH(3)Hg(+) were 3 pM and 4 nM, respectively. The selectivity of this probe is more than 500-fold for Hg(2+) over any metal ions. As compared to bovine serum albumin-stabilized AuNCs, Au-631 provided an approximately 330-fold improvement in the detection of Hg(2+). To the best of our knowledge, Au-631 not only provide the first example for detecting CH(3)Hg(+) but also have the lowest LOD value for Hg(2+) when compared to other AuNC-based Hg(2+) sensors. Importantly, this probe was successfully applied to the determination of Hg(2+) and CH(3)Hg(+) in seawater.

Sensitivity enhancement in the colorimetric detection of lead(II) ion using gallic acid-capped gold nanoparticles: improving size distribution and minimizing interparticle repulsion.

We have developed a colorimetric assay for the highly sensitive and selective detection of Pb(2+) by narrowing the size distribution of gallic acid-capped gold nanoparticles (GA-AuNPs) and minimizing electrostatic repulsion between each GA-AuNP. We unveil that the particle size and size distribution of GA-AuNPs could be controlled by varying the pH of HAuCl(4) with fixed concentrations of HAuCl(4) and GA. When the pH of the precursor solution (i.e., HAuCl(4)) was adjusted from 2.2 to 11.1, the average diameter of GA-AuNPs was decreased from 75.1 nm to 9.3 nm and their size distribution was reduced from 56.6-93.6 nm to 9.0-9.6 nm. The colorimetric sensitivity of the Pb(2+)-induced aggregation of GA-AuNPs could be improved using narrow size distribution of GA-AuNPs. Moreover, further enhancement of the colorimetric sensitivity of GA-AuNPs toward Pb(2+) could be achieved by adding NaClO(4) to minimize electrostatic repulsion between GA-AuNPs, which provide a small energy barrier for Pb(2+) to overcome. Under the optimum conditions (1.0 mM NaClO(4) and 20 mM formic acid at pH 4.5), the selectivity of 9.3 nm GA-AuNPs for Pb(2+) over other metal ions in aqueous solutions is remarkably high, and its minimum detectable concentration for Pb(2+) is 10nM. We demonstrate the practicality of 9.3 nm GA-AuNPs for the determination of Pb(2+) in drinking water. This approach offers several advantages, including simplicity (without temperature control), low cost (no enzyme or DNA), high sensitivity, high selectivity, and a large linear range (10.0-1000.0 nM).

(Lysozyme Type VI)‐Stabilized Au8 Clusters: Synthesis Mechanism and Application for Sensing of Glutathione in a Single Drop of Blood

This paper presents a one-pot approach for preparing highly fluorescent Au(8) clusters by reacting the Au(3+) precursor solution with lysozyme type VI (Lys VI) at pH 3. The fluorescence band of (Lys VI)-stabilized Au(8) clusters is centered at 455 nm on the excitation at 380 nm. Blue-emitting Au(8) clusters have a high quantum yield (∼56%), two fluorescence lifetimes, and a rare amount of Au(+) on the surface of the Au core. When the pH of a solution of Au(8) clusters increases suddenly to 12, the Au(8) clusters gradually convert to Au(25) clusters over time. This conversion is also observed in the case of (Lys VI)-directed synthesis of Au(25) clusters at pH 12. The pH-induced conversion of Au(8) to Au(25) clusters suggests that the size of (Lys VI)-stabilized gold nanoclusters (AuNCs) relies on the secondary structure of Lys VI, which is susceptible to pH change. Based on these results and previous literature, this paper proposes the possible mechanism for growing (Lys VI)-stabilized Au(8) and Au(25) clusters. Additionally, (Lys VI)-stabilized Au(8) clusters could sense glutathione (GSH) through GSH-induced core-etching of Au(8) clusters; the limit of detection at a signal-to-noise ratio of 3 for GSH is determined to be 20 nm. Except for cysteine, the selectivity of (Lys VI)-stabilized Au(8) clusters for GSH over amino acids is remarkably high. The practicality of using Au(8) clusters to determine the concentration of GSH in a single drop of blood is also validated.

Colorimetric Detection of Mercury(II) in a High-Salinity Solution Using Gold Nanoparticles Capped with 3-Mercaptopropionate Acid and Adenosine Monophosphate

A new colorimetric sensor for sensing Hg2+ in a high-salinity solution has been developed using gold nanoparticles (AuNPs) decorated with 3-mercaptopropionate acid (MPA) and adenosine monophosphate (AMP). Because of the high negative charge density of AMP on each AuNP surface, MPA/AMP-capped AuNPs are well dispersed in a high-salt solution. In contrast, the aggregation of MPA-capped AuNPs was induced by sodium ions, which shield the negative charges of the carboxylic groups of MPA. Through the coordination between the carboxylic group of MPA and Hg2+, the selectivity of MPA/AMP-capped AuNPs for Hg2+ in a high-salt solution is remarkably high over that of the other metals without the addition of a masking agent or a change in the temperature. We have carefully investigated the effect of the AMP concentration on the stability and sensitivity of MPA/AMP-capped AuNPs. Under optimum conditions, the lowest detectable concentration of Hg2+ using this probe was 500 nM on the basis of the measurement of the ratio of absorption at 620 nm to that at 520 nm. The sensitivity to Hg2+ can be further improved by modifying the MPA/AMP-capped AuNPs with highly fluorescent rhodamine 6G (R6G). By monitoring the fluorescence enhancement, the lowest detectable concentration of Hg2+ using R6G/MPA/AMP-capped AuNPs was 50 nM.

Colorimetric Detection of Lysozyme Based on Electrostatic Interaction with Human Serum Albumin-Modified Gold Nanoparticles

In this study, an aqueous solution of 13-nm gold nanoparticles (AuNPs) covalently bonded with human serum albumin (HSA) was used for sensing lysozyme (Lys). HSA molecules were good stabilizing agents for AuNPs in high-salt solution and exhibited the ability to bond with Lys electrostatically. The aggregation of HSA-AuNPs was achieved upon the addition of high-pI proteins, such as Lys, alpha-chymotrypsinogen A, and conalbumin. Not the same was achieved, however, when low-pI proteins such as ovalbumin, bovine serum albumin, and alpha-lactalbumin were added. Matrix-assisted desorption/ionization mass spectrometry was used to demonstrate the interaction between HSA-AuNPs and Lys. It was found that the sensitivity of HSA-AuNPs for Lys was highly dependent on the HSA concentration. The Lys-induced aggregation of HSA-AuNPs was suggested based on the London-van der Waals attractive force. We further improved the selectivity of the probe by adjusting the pH solution to 8.0. Under the optimum conditions, the selectivity of this system for Lys over other proteins in high-salt solutions was remarkably high, even when their pI was very close to the Lys. The lowest detectable concentration of Lys in this approach was 50 nM. The applicability of the method was validated through the analyses of Lys in chicken egg white.

Effective adsorption of chromium(vi)/Cr(iii) from aqueous solution using ionic liquid functionalized multiwalled carbon nanotubes as a super sorbent

We report an interesting interaction between oxidized multiwalled carbon nanotubes (oxi-MWCNTs), tetra n-heptylammonium bromide (ionic liquid) and total chromium ((Cr(VI)/Cr(III)) in this study. The interaction between the IL and oxidized MWCNTs primarily involves electrostatic affinity between the quaternary ammonium cation, and surface carboxyl and hydroxyl groups in oxi-MWCNTs. The IL-oxi-MWCNT adsorbent acts as a host in welcoming the incoming guest hydrochromate anions and several interesting interactions such as cation–π interactions, electrostatic interactions as well as anion–π interactions could be conceptualized in this process. The abundant oxygen-containing functional groups on the surfaces of oxi-MWCNTs play an important role in Cr(VI)/Cr(III) sorption. Characterization of the adsorbent was performed using various characterization techniques such as cross polarization magic angle spinning nuclear magnetic resonance (13CPMAS-NMR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), powder-X-ray diffraction (Powder-XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy analysis (TEM), Brunauer–Emmett–Teller (BET) isotherm studies, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). The capability of inductively coupled plasma mass spectrometry (ICP-MS) for Cr(VI) adsorption was extensively studied under different optimal parameters and the maximum adsorption capacity was found to be 85.83 mg g−1 from a nonlinear Langmuir isotherm model. A kinetic study confirms a pseudo second order model and the process could be upgraded by column studies to a sample volume of 2000 mL. Effective regeneration of the adsorbent could be accomplished with sodium hydroxide and the potential of this novel adsorbent has been examined in the removal of Cr(VI)/Cr(III) from aqueous solutions.

Skp2 overexpression increases the expression of MMP-2 and MMP-9 and invasion of lung cancer cells.

Skp2 is one of the components of the E3 ubiquitin ligase which is required for the degradation of tumor suppressor p27. Overexpression of this oncogene is frequently found in human cancers and has been shown to be associated with poor prognosis. In addition to induce p27 degradation and enhance cellular proliferation, Skp2 also plays a role in promoting tumor metastasis. However, the underlying mechanism is unclear. In this study, we established Skp2-overexpressing stable transfectants from A549 human lung cancer cells. We found that these stable transfectants exhibited increased migratory and invasive abilities. In addition, expression of matrix metalloproteinase-2 (MMP-2) and MMP-9 was up-regulated. Enzymatic assay and gelatin zymography confirmed the increase of MMP-2 and MMP-9 activity and neutralization of these two MMPs by antibodies reduced cell invasion. Our results also revealed that Sp1 was involved in the induction of MMP-2 and MMP-9 by Skp2 because treatment of mithramycin or knockdown of Sp1 by small interference RNA attenuated their expressions. Collectively, we provide the first evidence that up-regulation of MMP-2 and MMP-9 is one of the mechanisms by which Skp2 promotes cell invasion.

Gold Nanoparticles as Assisted Matrices for the Detection of Biomolecules in a High-Salt Solution through Laser Desorption/Ionization Mass Spectrometry

Citrate-capped gold nanoparticles (AuNPs) serve as matrices for the determination of biomolecules in a high-salt solution through matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). In the case of using 2,5-dihydroxybenzoic acid (2,5-DHB) as a matrix, the signal intensities of neutral steroids were severely suppressed in a high-salt solution. A high concentration of NaCl caused the formation of the sodium adduct ions during the desorption/ionization process, resulting in a decrease of the signal intensities of the protonated ions. In comparison, by applying AuNP-assisted LDI-TOF-MS, the signal intensities of neutral steroids remained almost constant when the concentration of NaCl was increased to 500 mM. Because the use of citrate-capped AuNPs as matrices primarily offers alkali metal ion adducts, AuNP matrices have a higher tolerance to high NaCl concentrations relative to that of 2,5-DHB matrices. The relevant phenomena are also discovered in the case of analysis of neutral carbohydrate, monosialoganglioside, indolamine, and angiotensin I. The quantification of small molecules in a high-salt solution has been accomplished by AuNP-assisted LDI-TOF-MS coupled to a unique sample preparation, in which samples are deposited onto the sample plate before AuNPs. The present method has been further applied to the determination of urea, creatinine, uric acid, and glucose in a urine sample.

One-Step Synthesis of White-Light-Emitting Quantum Dots at Low Temperature

Alloyed Zn(x)Cd(1-x)Se quantum dots (QDs) have been successfully prepared at low temperatures by reacting a mixture of Cd(ClO(4))(2) and Zn(ClO(4))(2) with NaHSe using 3-mercaptopropionic acid as a surface-stabilizing agent. The optical properties and composition of the alloyed QDs were highly dependent on the molar ratio of Zn(2+) to Cd(2+). With an increase in the Zn content, a systematic blue shift in the first exciton absorption and band-edge emission indicated the formation of the alloyed QDs. Moreover, X-ray diffraction peaks of the alloyed QDs systematically shifted to larger angles as the Zn molar fraction of the Zn(x)Cd(1-x)Se QDs was increased. This systematic shift further confirmed the appearance of alloyed QDs. Interestingly, among these alloyed QDs, the Zn(0.93)Cd(0.07)Se QDs exhibited white-light emission with quantum yields of 12%. In addition, we discovered that we could adjust the Zn(0.93)Cd(0.07)Se QD intensity ratio of the band-edge (431 nm) to trap-state (499 nm) emissions by controlling the reaction time. Careful control of the reaction time allowed us to balance the relative strength of the band-edge and trap-state emissions, thereby attaining white-light-emitting QDs. The Zn(0.93)Cd(0.07)Se QDs offer unique advantages, including one-step synthesis, tunable white-light emission, easy manipulation, a low-temperature requirement, and low fabrication costs.