Jiunn Der Liao

Nanofabricated SERS-active substrates for single-molecule to virus detection in vitro: a review.

The surface-enhanced Raman scattering (SERS) method has great potential for the detection of Raman-active species, ranging from single molecules to biomolecules. In the last five years, various approaches have been developed to fabricate SERS-active substrates with high sensitivity using noble metal nanostructures via top-down, bottom-up, combination, or template-assisted routes. Nanostructured substrates with high average SERS enhancement factors (EFs) can now be easily produced, with the EF depending strongly on the size and shape of the nanostructures that give rise to the effect. For SERS substrates to be used as a platform for applications such as trace detection and bio-sensing, several issues, including sensitivity, intensity-concentration dependency, and selectivity, need to be addressed. Although several challenges remain before SERS-active substrates become consistent analytical tools, many successful examples have been demonstrated with promising results.

Focused ion beam-fabricated Au micro/nanostructures used as a surface enhanced Raman scattering-active substrate for trace detection of molecules and influenza virus

The focused ion beam (FIB) technique was used to precisely fabricate patterned Au micro/nanostructures (fibAu). The effects of surface enhanced Raman scattering (SERS) on the fibAu samples were investigated by adjusting the geometrical, dimensional, and spacing factors. The SERS mechanism was evaluated using low-concentration rhodamine 6G (R6G) molecules, physically adsorbed or suspended on/within the micro/nanostructures. The results indicated that for detecting R6G molecules, hexagon-like micro/nanostructures induced a higher electromagnetic mechanism (EM) due to the availability of multiple edges and small curvature. By decreasing the dimensions from 300 to 150 nm, the laser-focused area contained an increasing number of micro/nanostructures and therefore intensified the excitation of SERS signals. Moreover, with an optimized geometry and dimensions of the micro/nanostructures, the relative intensity/surface area value reached a maximum as the spacing was 22 nm. An exponential decrease was found as the spacing was increased, which most probably resulted from the loss of EM. The spacing between the micro/nanostructures upon the fibAu was consequently regarded as the dominant factor for the detection of R6G molecules. By taking an optimized fibAu to detect low-concentration influenza virus, the amino acids from the outermost surface of the virus can be well distinguished through the SERS mechanism.

Synthesis and Characterization of Cu (InxB1-x) Se2 Nanocrystals for Low-Cost Thin Film Photovoltaics

Chalcopyrite quaternary semiconductor Cu(In(x)B(1-x))Se(2) nanocrystals have been successfully prepared via a relatively simple and convenient solvothermal route. The effect of different solvents on the formation of the product also indicates that diethylenetriamine is the optimal solvent for this reaction. The device parameters for a single junction Cu(In(x)B(1-x))Se(2) solar cell under AM1.5G are as follows: an open circuit voltage of 265 mV, a short-circuit current of 25.90 mA/cm(2), a fill factor of 34%, and a power conversion efficiency of 2.34%. Based on a series of comparative experiments under different reaction conditions, the probable formation mechanism of crystal Cu(In(x)B(1-x))Se(2) nanorods is proposed.

Plasma-Synthesized Silver Nanoparticles on Electrospun Chitosan Nanofiber Surfaces for Antibacterial Applications

Chitosan nanofibers have been electrospun with poly(ethylene oxide) and silver nitrate, as a coelectrospinning polymer and silver nanoparticle precursor, respectively. The average diameter of the as-spun chitosan nanofibers with up to 2 wt % silver nitrate loading was approximately 130 nm, and there was no evidence of bead formation or polymer agglomeration. Argon plasma was then applied for surface etching and synthesis of silver nanoparticles via precursor decomposition. Plasma surface bombardment induced nanoparticle formation primarily on the chitosan nanofiber surfaces, and the moderate surface plasma etching further encouraged maximum exposure of silver nanoparticles. UV-vis spectra showed the surface plasmon resonance signature of silver nanoparticles. The surface-immobilized nanoparticles were visualized by TEM and were found to have average particle diameters as small as 1.5 nm. Surface analysis by infrared spectroscopy and X-ray photoelectron spectroscopy confirmed the interactions between the silver nanoparticles and chitosan molecules, as well as the effect of plasma treatment on the nanofiber surfaces. Finally, a bacteria inhibition study revealed that the antibacterial activity of the electrospun chitosan nanofibers correspondingly increased with the plasma-synthesized silver nanoparticles.

Focused-ion-beam-fabricated Au nanorods coupled with Ag nanoparticles used as surface-enhanced Raman scattering-active substrate for analyzing trace melamine constituents in solution

A well-ordered Au-nanorod array with a controlled tip ring diameter (Au_NRsd) was fabricated using the focused ion beam method. Au_NRsd was then coupled with Ag nanoparticles (Ag NPs) to bridge the gaps among Au nanorods. The effect of surface-enhanced Raman scattering (SERS) on Au_NRsd and Ag NPs/Au_NRsd was particularly verified using crystal violet (CV) as the molecular probe. Raman intensity obtained from a characteristic peak of CV on Au_NRsd was estimated by an enhancement factor of ≈10(7) in magnitude, which increased ≈10(12) in magnitude for that on Ag NPs/Au_NRsd. A highly SERS-active Ag NPs/Au_NRsd was furthermore applied for the detection of melamine (MEL) at very low concentrations. Raman-active peaks of MEL (10(-3) to 10(-12)M) in water or milk solution upon Au_NRsd or Ag NPs/Au_NRsd were well distinguished. The peaks at 680 and 702 cm(-1) for MEL molecules were found suitable to be used as the index for sensing low-concentration MEL in a varied solution, while that at 1051 cm(-1) was practical to interpret MEL molecules in water or milk solution bonded with Au (i.e., Au_NRsd) or Ag (i.e., Ag NPs/Au_NRsd) surface. At the interface of Ag NPs/Au_NRsd and MEL molecules in milk solution, a laser-induced electromagnetic field or hotspot effect was produced and competent to sense low-concentration MEL molecules interacting with Ag and Au surfaces. Accordingly, Ag NPs/Au_NRsd is very promising to be used as a fast and sensitive tool for screening MEL in complex matrices such as adulteration in e.g., food and pharmaceutical products.

Submerged Liquid Plasma for the Synthesis of Unconventional Nitrogen Polymers

Glow discharge polymerization is not well understood due to the rapid/complex reaction at the plasma/gas precursor interface. Plasma reaction in a submerged condition allows post-plasma-polymerization, leading to further polymer growth and thus a stable structure. Electron collision with acetonitrile at the interface initiates the formation of radical monomers, which undergoes further rearrangement to form low-molecular (LM) nitrogen polymers (NPs). The radical-rich LM NPs go through further polymerization, forming stable high-molecular (HM) NPs (as determined using liquid chromatography/mass spectrometry). LM NPs absorb light at a wavelength of 270 nm (λ max) whereas HM NPs show absorption at 420 nm (λ max), as determined from ultraviolet-visible absorption spectra. The fluorescence spectra of HM NPs show characteristic emission at 430 nm, which indicates the presence of nitrogen functional groups with external conjugation. The proposed structure of HM NPs is verified with different analytical instruments.

Nano-indentation at the surface contact level: applying a harmonic frequency for measuring contact stiffness of self-assembled monolayers adsorbed on Au

In this study, the well-ordered alkanethiolate self-assembled monolayers (SAMs) of varied chain lengths and tail groups were employed as examples for nano-characterization on their mechanical properties. A novel nano-indentation technique with a constant harmonic frequency was applied on SAMs chemically adsorbed on Au to explore their contact mechanics, and furthermore to interpret how SAM molecules respond to an infinitesimal oscillation force without pressing them. Experimental results demonstrated that the harmonic contact stiffness along with the measured displacement of SAMs/Au was distinguishable using a dynamic contact modulus with the distinct feature of phase angles. Phase angles resulted from the relaxing continuation of an applied harmonic frequency and mostly influenced by the outermost tail group of SAM molecules. The harmonic contact stiffness of SAM molecules obviously increased with the densely packed alkyl chains and relatively intense agglomeration of the head group at the anchoring site. As a consequence, the result of this work is relevant to contact mechanics at the surface contact level for the distinction of molecular substances attached on a solid surface. Furthermore it is particularly anticipated to identify biological molecules of variable qualities under a fluid-like micro-environment.

Fabrication of nano-indented cavities on Au for the detection of chemically-adsorbed DTNB molecular probes through SERS effect

Micro/nano-lithographic techniques are usually employed as a straightforward process for roughening a thin-film Au surface for surface-enhanced Raman scattering (SERS). However, a topographical pattern with deepened edges is difficult to control in a rapid and environmental-friendly way. In this study, a simple physical procedure is proposed for tailoring a thin-film Au surface with triangular nanostructures using nano-indentation technique. The as-fabricated nano-indented cavities on Au (nAu) were structured as a characterization substrate for SERS. By calculating the geometries of nAu and the increase of surface area as a function of the concentration of chemically adsorbed 2-nitro-5-thiobenzoic acid (NTB), a combined chemical and electromagnetic effect was estimated. Particularly-made nAu was adjusted for examining chemically adsorbed NTB molecules with differently intensified Raman-active groups by tuning the indentation depth and the tip-to-tip displacement. SERS enhancement factor on a specific NTB/nAu could be increased to 2.1×10(6).

Characterization of cholesterol-depleted or -restored cell membranes by depth-sensing nano-indentation

Cholesterol is a major component of eukaryotic cell membranes. It is well-accepted that cholesterol depletion triggers a complicated cascade of biochemical reactions which may affect many cell processes. However, the effect of cholesterol depletion on the deformability of cell membranes is still controversial. In this study, depth-sensing nano-indentation is performed on the lamellipodium of adherent NIH-3T3 fibroblast cells with normal, depleted, and restored membrane cholesterol contents. By extracting data from contact stiffness measurement, nano-mechanical characterizations are focused at a depth within the superficial 20 nm of the tested cells. Our results show that cholesterol depletion indeed decreases membrane stiffness, while the membrane stiffness decreases exponentially with the increase of cholesterol-depletion time. In addition, the effect of cholesterol restoration following depletion is further examined, showing that cholesterol restoration reverses the effect of cholesterol depletion on both cellular morphology and membrane stiffness. This is the first study, focused on nano-mechanical characterization of cellular outermost layers, demonstrating the effect of altered cholesterol content on the stiffness of cell membranes.

Ultra-thin phospholipid layers physically adsorbed upon glass characterized by nano-indentation at the surface contact level

Dipalmitoylphosphatic acid was chosen as a model to interpret how molecules physically adsorbed upon glass responded to an infinitesimal oscillation force at the surface contact level. Oscillation of a nano-indentation tip toward the phospholipid layers was driven by a dynamic contact module at a constant harmonic frequency; the phase angle of the oscillation frequency was exponentially relaxed along the nano-scale displacement. The tip-on-molecule contact was thereafter identified and influenced by the characteristic of the physically adsorbed phospholipids. By applying the harmonic displacement of the nano-indentation tip and making a distinction between full contact displacements, the thickness of the phospholipid layers was thereafter estimated. Moreover, the additional force required to penetrate through the physically adsorbed molecules was minor compared to the analogous process for the chemically adsorbed ones. The importance of recognizing the physically adsorbed molecules is relevant to applications of contact mechanics for the distinction of various phospholipids. Furthermore it is very promising to interpret the mechanism by which cells convert mechanical stimuli into biochemical responses on the channels of phospholipids.