Nguyen Hoang Ly

Silver Nanoparticle-Enhanced Resonance Raman Sensor of Chromium(III) in Seawater Samples

Tris(hydroxymethyl)aminomethane ethylenediaminetetraacetic acid (Tris-EDTA), upon binding Cr(III) in aqueous solutions at pH 8.0 on silver nanoparticles (AgNPs), was found to provide a sensitive and selective Raman marker band at ~563 cm−1, which can be ascribed to the metal-N band. UV-Vis absorption spectra also supported the aggregation and structural change of EDTA upon binding Cr(III). Only for Cr(III) concentrations above 500 nM, the band at ~563 cm−1 become strongly intensified in the surface-enhanced Raman scattering spectra. This band, due to the metal-EDTA complex, was not observed in the case of 50 μM of K+, Cd2+, Mg2+, Ca2+, Mn2+, Co2+, Na+, Cu2+, NH4+, Hg2+, Ni2+, Fe3+, Pb2+, Fe2+, and Zn2+ ions. Seawater samples containing K, Mg, Ca, and Na ion concentrations higher than 8 mM also showed the characteristic Raman band at ~563 cm−1 above 500 nM, validating our method. Our approach may be useful in detecting real water samples by means of AgNPs and Raman spectroscopy.

Detection of Copper(II) Ions Using Glycine on Hydrazine-Adsorbed Gold Nanoparticles via Raman Spectroscopy

A facile, selective, and sensitive detection method for the Cu2+ ions in environmental and biological solutions has been newly developed by observing the unique CN stretching peaks at ~2108 cm−1 upon the dissociative adsorption of glycine (GLY) in hydrazine buffer on gold nanoparticles (AuNPs). The relative abundance of Cu species on AuNPs was identified from X-ray photoelectron spectroscopy analysis. UV-Vis spectra also indicated that the Au particles aggregated to result in the color change owing to the destabilization induced by the GLY-Cu2+ complex. The CN stretching band at ~2108 cm−1 could be observed to indicate the formation of the CN species from GLY on the hydrazine-covered AuNP surfaces. The other ions of Fe3+, Fe2+, Hg2+, Mg2+, Mn2+, Ni2+, Zn2+, Cr3+, Co2+, Cd2+, Pb2+, Ca2+, NH4+, Na+, and K+ at high concentrations of 50 µM did not produce such spectral changes. The detection limit based on the CN band for the determination of the Cu2+ ion could be estimated to be as low as 500 nM in distilled water and 1 µM in river water, respectively. We attempted to apply our method to estimate intracellular ion detection in cancer cells for more practical purposes.

Highly Luminescent Folate-Functionalized Au22 Nanoclusters for Bioimaging

Gold nanoclusters are emerging as new materials for biomedical applications because of promises offered by their ultrasmall size and excellent biocompatibility. Here, the synthesis and optical and biological characterizations of a highly luminescent folate-functionalized Au22 cluster (Au22 -FA) are reported. The Au22 -FA clusters are synthesized by functionalizing the surface of Au22 (SG)18 clusters, where SG is glutathione, with benzyl chloroformate and folate. The functionalized clusters are highly water-soluble and exhibit remarkably bright luminescence with a quantum yield of 42%, significantly higher than any other water-soluble gold clusters protected with thiolate ligands. The folate groups conjugated to the gold cluster give rise to additional luminescence enhancement by energy transfer sensitization. The brightness of Au22 -FA is found to be 4.77 mM-1 cm-1 , nearly 8-fold brighter than that of Au22 (SG)18 . Further biological characterizations have revealed that the Au22 -FA clusters are well-suited for bioimaging. The Au22 -FA clusters exhibit excellent photostability and low toxicity; nearly 80% cell viability at 1000 ppm of the cluster. Additionally, the Au22 -FA clusters show target specificity to folate-receptor positive cells. Finally, the time-course in vivo luminescence images of intravenous-injected mice show that the Au22 -FA clusters are renal-clearable, leaving only 8% of them remained in the body after 24 h post-injection.

Hg(II) Raman sensor of poly-L-lysine conformation change on gold nanoparticles

In order to develop optical Hg(II) sensors, the adsorption characteristics of poly-L-lysine (PLL) after the conjugation of various ions on gold nanoparticles (AuNPs) were examined by means of Raman spectroscopy, UV-Vis absorption, and quasi-elastic light scattering (QELS). The intensities of the two bands at 458 and 1115 cm-1 appeared to decrease, in comparison with that at 1150 cm-1 in the presence of 100 μM of Hg(II). The other ions of Cr3+, Pb2+, Mn2+, Zn2+, Co2+, Ni2+, Cd2+, Fe2+, Na+, K+, Ca2+, Mg2+, Cu2+, NH4+, and Fe3+ did not show such spectral changes. The prominent band at 1150 cm-1, which may be ascribed to the C-N or γ (NH3 +) band, suggests that a conformational change of poly-L-lysine (PLL) occurs after its interaction with Hg(II) ions. The Hg(II) concentration-dependent SERS spectra indicated that the relative intensities of the two bands at 458 and 1115 cm-1 decreased and that at 1150 cm-1 increased above 1 μM. These vibrational fingerprints may be useful to discriminate the Hg(II) ion above 1 μM using AuNPs and Raman spectroscopy. On the basis of the presented spectroscopic study, we plan to develop an efficient method of detecting the Hg(II) ion at lower concentrations by introducing a variety of SERS platforms.

On-site detection of sub-mg/kg melamine mixed in powdered infant formula and chocolate using sharp-edged gold nanostar substrates

ABSTRACT We report a facile method for sample preparation and sensitive on-site detection of melamine in powdered infant formula and chocolate using Raman spectroscopy on sharp-edged gold nanostars (AuNSs). The aggregation of AuNSs by sodium chloride (1.2 M) facilitates the more sensitive detection of melamine in comparison with spherical gold nanoparticles (AuNPs). Density functional theory quantum mechanical calculations were performed to determine the energetic stability on gold cluster atoms. Our spectroscopic data indicated that AuNSs are an efficient platform for detecting melamine in food mixtures. The detection limits of melamine in powdered infant formula and chocolate were found to be ~0.1 mg/kg and ~1 mg/kg, respectively, on AuNPs, whereas they were observed to be ~0.01 mg/kg and ~0.1 mg/kg, respectively, on AuNSs. Using a handheld Raman spectrometer, a sub-mg/kg detection of melamine in both powdered infant formula and chocolate could be achieved within a few minutes. GRAPHICAL ABSTRACT

Unique Energy Transfer in Fluorescein-Conjugated Au22 Nanoclusters Leading to 160-Fold pH-Contrasting Photoluminescence

Accurate measurements of intracellular pH are of crucial importance in understanding the cellular activities and in the development of intracellular drug delivery systems. Here we report a highly sensitive pH probe based on a fluorescein-conjugated Au22 nanocluster. Steady-state photoluminescence (PL) measurements have shown that, when conjugated to Au22, fluorescein exhibits more than 160-fold pH-contrasting PL in the pH range of 4.3-7.8. Transient absorption measurements show that there are two competing ultrafast processes in the fluorescein-conjugated Au22 nanocluster: the intracore-state relaxation and the energy transfer from the nonthermalized states of Au22 to fluorescein. The latter becomes predominant at a higher pH, leading to dramatic PL enhancement of fluorescein. In addition to the intrinsically low toxicity, fluorescein-conjugated Au22 nanoclusters exhibit high pH sensitivity, wide dynamic range, and excellent photostability, providing a powerful tool for the study of intracellular processes.

Electrostatically Self-assembled Quinazoline-based Anticancer Drugs on Negatively-charged Nanodiamonds for Overcoming the Chemoresistances in Lung Cancer Cells

The nanodiamond (ND) conjugates of gefitinib (GF) and erlotinib (EL) were assembled for in vitro lung cancer treatments. The carboxylate infrared bands along with the negative surface charge of -28.3 (±2.1) mV were found efficient to conjugate the nitrogen-containing quinazoline ring drugs, due to the electrostatic interactions, resulting from the surface changes to -12.0 (±1.2) mV and -9.1 (±1.2) mV after adsorption of GF and EL on NDs, respectively. The physicochemical properties of NDs were characterized by transmission electron microcopy, X-ray diffraction, X-ray photoelectron, infrared and Raman spectroscopic tools. The size distributions of NDs after the self-assembly of GF and EL could be checked by dynamic light scattering measurements. The uptake of NDs in cancer cells was estimated by fluorescence microscopy. Cell viability appeared to decrease by 30-50% at 50 and 100 nM of GF and EL, respectively, after the treatment of PEG-assembled NDs compared to the cases using free drugs. Our ND conjugates may be potentially useful for overcoming the chemoresistances in lung cancer cells.

Interaction between Diethyldithiocarbamate and Cu(II) on Gold in Non-Cyanide Wastewater

A surface-enhanced Raman scattering (SERS) detection method for environmental copper ions (Cu2+) was developed according to the vibrational spectral change of diethyldithiocarbamate (DDTC) on gold nanoparticles (AuNPs). The ultraviolet-visible (UV-Vis) absorption spectra indicated that DDTC formed a complex with Cu2+, showing a prominent peak at ~450 nm. We found Raman spectral changes in DDTC from ~1490 cm−1 to ~1504 cm−1 on AuNPs at a high concentration of Cu2+ above 1 μM. The other ions of Zn2+, Pb2+, Ni2+, NH4+, Mn2+, Mg2+, K+, Hg2+, Fe2+, Fe3+, Cr3+, Co2+, Cd2+, and Ca2+ did not produce such spectral changes, even after they reacted with DDTC. The electroplating industrial wastewater samples were tested under the interference of highly concentrated ions of Fe3+, Ni2+, and Zn2+. The Raman spectroscopy-based quantification of Cu2+ ions was able to be achieved for the wastewater after treatment with alkaline chlorination, whereas the cyanide-containing water did not show any spectral changes, due to the complexation of the cyanide with the Cu2+ ions. A micromolar range detection limit of Cu2+ ions could be achieved by analyzing the Raman spectra of DDTC in the cyanide-removed water.