Ching-Hsiang Chen

Metal carbonyl-gold nanoparticle conjugates for highly sensitive SERS detection of organophosphorus pesticides

The binding of organometallic osmium carbonyl clusters onto the surface of gold nanoparticles (10OsCO-Au NPs) greatly enhanced the CO stretching vibration signal at ~2100cm-1, which is relatively free from interference due to the absorbance of biomolecules. By utilizing the acetylcholinesterase (AChE) mediated hydrolysis of acetylthiocholine to thiocholine where the activity of AChE is inhibited by the presence of organophosphate pesticides (OPPs), the subsequent thiocholine-induced aggregation of 10OsCO-Au NPs can be monitored by the change in color of the NPs solution and the variation in intensity of the SERS CO signal. The change in color offers a fast pre-screening method, whereas monitoring via SERS is used for greater accuracy and lower limit of detection (0.1 ppb) for quantitative detection. Its potential as a quick and accurate method of OPPs monitoring in consumer products was demonstrated in the detection of OPPs in real spiked samples such as beer.

Local Electronic Structures and Electrical Characteristics of Well-Controlled Nitrogen-Doped ZnO Thin Films Prepared by Remote Plasma In situ Atomic Layer Doping

Nitrogen-doped ZnO (ZnO:N) films were prepared by remote plasma in situ atomic layer doping. X-ray photoelectron and absorption near-edge spectroscopies reveal the presence of Zn-N bond and a decrease in strength of the O 2p hybridized with Zn 4s states, which are consistent with the decrease of electron concentration in ZnO:N films with increasing nitrogen content and indicate the formation of acceptor states by occupation of oxygen sites with nitrogen. Linear dependence between the nitrogen content and the atomic layer doping percentage indicates the electrical properties and local electronic structures can be precisely controlled using this atomic layer doping technique.

Innovative fabrication of a Au nanoparticle-decorated SiO2 mask and its activity on surface-enhanced Raman scattering

Surface-enhanced Raman scattering (SERS) utilizing the well-defined localized surface plasmon resonance (LSPR) of Ag and Au nanoparticles (NPs) under resonant irradiation has emerged as a promising spectroscopy technique for providing vibrational information on trace molecules. The Raman scattering intensity from molecules close to the surface of these finely divided metals can be significantly enhanced by a factor of more than 10(6). In addition to the high sensitivity, the reproducibility of the SERS signal is also an important parameter for its reliable application. In this work, we report on the innovative and facile fabrication of a Au NP-decorated SiO2 mask coated on indium tin oxide (ITO) glass as a SERS array substrate. First, a highly ordered porous SiO2 mask with pore sizes of 350 nm in diameter and wall thickness of 60 nm was deposited on ITO glass by using spin coating. Then, Au NPs were controllably decorated into the pores of the conductive ITO glass-bottomed SiO2 mask by using sonoelectrochemical deposition-dissolution cycling (SEDDC). Experimental results indicate that the SERS effect of Rhodamine 6G (R6G) observed on this developed substrate increases with an increase in the deposition time of Au NPs in SEDDC. The corresponding optimal enhancement factor (EF) that is obtained is ca. 6.5 × 10(7). Significantly, this system achieves an optimal reproducibility under a medium-length deposition time of Au NPs in SEDDC with a relative standard deviation (RSD) of 12% for measurements of five spots on different areas. The low RSD of the SERS signal and the large EF suggest that the developed array system can serve as an excellent spectroscopy platform for practical applications in analytical chemistry.

Direct electron transfer of glucose oxidase and dual hydrogen peroxide and glucose detection based on water-dispersible carbon nanotubes derivative

A water-dispersible multi-walled carbon nanotubes (MWCNTs) derivative, MWCNTs-1-one-dihydroxypyridine (MWCNTs-Py) was synthesis via Friedel-Crafts chemical acylation. Raman spectra demonstrated the conjugated level of MWCNTs-Py was retained after this chemical modification. MWCNTs-Py showed dual hydrogen peroxide (H2O2) and glucose detections without mutual interference by adjusting pH value. It was sensitive to H2O2 in acidic solution and displayed the high performances of sensitivity, linear range, response time and stability; meanwhile it did not respond to H2O2 in neutral solution. In addition, this positively charged MWCNTs-Py could adsorb glucose oxidase (GOD) by electrostatic attraction. MWCNTs-Py-GOD/GC electrode showed the direct electron transfer (DET) of GOD with a pair of well-defined redox peaks, attesting the bioactivity of GOD was retained due to the non-destroyed immobilization. The high surface coverage of active GOD (3.5×10(-9) mol cm(-2)) resulted in exhibiting a good electrocatalytic activity toward glucose. This glucose sensor showed high sensitivity (68.1 μA mM(-1) cm(-2)) in a linear range from 3 μM to 7 mM in neutral buffer solution. The proposed sensor could distinguish H2O2 and glucose, thus owning high selectivity and reliability.

Spin-coated Au-nanohole arrays engineered by nanosphere lithography for a Staphylococcus aureus 16S rRNA electrochemical sensor

The nanopatterning of gold nanoparticle (AuNP) arrays on an indium tin oxide (ITO) electrode using efficient and low-cost methods is described. This process used nanosphere lithography (NSL) encompassing the deposition of monolayered Polystyrene (PS) followed by a convective self-assembly drop coating protocol onto the ITO substrate that further acted as the mask after the AuNP assembly. The results showed that spin-coating allowed AuNPs to follow the contour and adhere to the PS nanospheres. The final products, after etching the PS, generated a highly ordered Au-nanohole array on an ITO substrate. The Au-nanohole arrays on the ITO electrode provided a greater surface area and successfully enhanced the peak current of electrochemical measurements by 82% compared with bare ITO and was used to detect Staphylococcus aureus 16S rRNA hybridization. In contrast to non-templated AuNP structures, the Au-nanohole arrays on the ITO electrode contributed to an optimum sensitivity improvement in DNA hybridization detection by 23%, along with an impressive limit of detection (LOD) of 10 pM. The high specificity of this distinguished structure was also achieved in the hybridization measurements of multi-analyte pathogens. These findings indicate that the combination of PS nanosphere lithography, followed by the spin-coating of AuNPs, leads to an inexpensive and simple engineering process that effectively generates uniform Au-nanohole arrays on ITO, which provides a greater surface area to optimize the electrochemical performance of the DNA biosensor.

Surface enhanced Raman scattering and localized surface plasmon resonance of nanoscale ultrathin films prepared by atomic layer deposition

An approach was proposed to characterize nanoscale ultrathin films using surface enhanced Raman scattering (SERS). Raman spectroscopy of the TiO2 film as thin as ∼2 nm, which was prepared by atomic layer deposition, was obtained by depositing a nanostructured Au layer on the film surface. Red-shift in the extinction spectrum of the nanostructured Au layer was observed with increasing TiO2 film thickness, ascribed to the increase in effective refractive index of the substrate slab and coupled plasmon resonance. This SERS technique can be applied to investigate a variety of solid-state ultrathin films in nanosclae materials and devices in future studies.

Improved Solar-Driven Photocatalytic Performance of Highly Crystalline Hydrogenated TiO 2 Nanofibers with Core-Shell Structure

Hydrogenated titanium dioxide has attracted intensive research interests in pollutant removal applications due to its high photocatalytic activity. Herein, we demonstrate hydrogenated TiO2 nanofibers (H:TiO2 NFs) with a core-shell structure prepared by the hydrothermal synthesis and subsequent heat treatment in hydrogen flow. H:TiO2 NFs has excellent solar light absorption and photogenerated charge formation behavior as confirmed by optical absorbance, photo-Kelvin force probe microscopy and photoinduced charge carrier dynamics analyses. Photodegradation of various organic dyes such as methyl orange, rhodamine 6G and brilliant green is shown to take place with significantly higher rates on our novel catalyst than on pristine TiO2 nanofibers and commercial nanoparticle based photocatalytic materials, which is attributed to surface defects (oxygen vacancy and Ti3+ interstitial defect) on the hydrogen treated surface. We propose three properties/mechanisms responsible for the enhanced photocatalytic activity, which are: (1) improved absorbance allowing for increased exciton generation, (2) highly crystalline anatase TiO2 that promotes fast charge transport rate, and (3) decreased charge recombination caused by the nanoscopic Schottky junctions at the interface of pristine core and hydrogenated shell thus promoting long-life surface charges. The developed H:TiO2 NFs can be helpful for future high performance photocatalysts in environmental applications.

Internal structure of tunable ternary CdSexS1−x quantum dots unraveled by x-ray absorption spectroscopy

CdSexS1−xquantum dots(QDs) were synthesized by a simple one-injection non-coordinate solvent method. The composition distribution of Se and S and the internal structures of the CdSexS1−xQDs can be tuned by the Se/S molar ratio. To investigate the internal structure of CdSexS1−xQD,x-ray absorption spectroscopy was used to examine the distribution of Se and S inside CdSexS1−xQDs.

Depth profile of alloying extent and composition in bimetallic nanoparticles investigated by in situ x-ray absorption spectroscopy

The authors report a general methodology for probing the depth profile of alloying extent and composition in bimetallic nanoparticles (NPs) by a combined in situ x-ray absorption spectroscopy (XAS) and electrochemical strategy. The XAS results of Pt-richcore–Ru-richshell NPs during methanol electro-oxidation revealed that the alloying extent of Pt (JPt) and Ru (JRu) is higher in the core region compared to those in the shell region. An average decrease in the JPt and JRu is observed when the cluster undergoes reduction. By controlling the cluster oxidation degree it is possible to probe the depth profile of the alloying extent in bimetallic NPs.

Optical Interference-Free Surface-Enhanced Raman Scattering CO-Nanotags for Logical Multiplex Detection of Vascular Disease-Related Biomarkers

Matrix metalloproteinases (MMPs), specifically MMP-2, MMP-7, and MMP-9, have been discovered to be linked to many forms of vascular diseases such as stroke, and their detection is crucial to facilitate clinical diagnosis. In this work, we prepared a class of optical interference-free SERS nanotags (CO-nanotags) that can be used for the purpose of multiplex sensing of different MMPs. Multiplex detection with the absence of cross-talk was achieved by using CO-nanotags with individual tunable intrinsic Raman shifts of CO in the 1800-2200 cm-1 region determined by the metal core and ligands of the metal carbonyl complex. Boolean logic was used as well to simultaneously probe for two proteolytic inputs. Such nanotags offer the advantages of convenient detection of target nanotags and high sensitivity as validated in the ischemia rat model.