Kundan Sivashanmugan

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 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.

Intense Raman scattering on hybrid Au/Ag nanoplatforms for the distinction of MMP-9-digested collagen type-I fiber detection

Well-ordered Au-nanorod arrays were fabricated using the focused ion beam method (denoted as fibAu_NR). Au or Ag nanoclusters (NCs) of various sizes and dimensions were then deposited on the fibAu_NR arrays using electron beam deposition to improve the surface-enhanced Raman scattering (SERS) effect, which was verified using a low concentration of crystal violet (10(-)(5)M) as the probe molecule. An enhancement factor of 6.92 × 10(8) was obtained for NCsfibAu_NR, which is attributed to the combination of intra-NC and NR localized surface plasmon resonance. When 4-aminobenzenethiol (4-ABT)-coated Au or Ag nanoparticles (NPs) were attached to NCsfibAu_NR, the small gaps between 4-ABT-coated NPs and intra-NCs allowed detection at the single-molecule level. Hotspots formed at the interfaces of NCs/NRs and NPs/NCs at a high density, producing a strong local electromagnetic effect. Raman spectra from as-prepared type I collagen (Col-I) and Ag-NP-coated Col-I fibers on NCsfibAu_NR were compared to determine the quantity of amino acids in their triple helix structure. Various concentrations of matrix-metalloproteinase-9-digested Col-I fibers on NCsfibAu_NR were qualitatively examined at a Raman laser wavelength of 785nm to determine the changes of amino acids in the Col-I fiber structure. The results can be used to monitor the growth of healing Col-I fibers in a micro-environment.

Nanovoids embedded in FIB-fabricated Au/Ag nanorod arrays for ultrasensitive SERS-active substrate

A focused ion beam (FIB) was employed to fabricate Au/Ag nanorod (NR) arrays (fibAu/Ag_NR). After an annealing process, the fibAu/Ag_NR exhibited a Au/Ag diffused structure or nanovoids (NVs) embedded in NRs preferentially at the Au/Ag interface. With crystal violet (CV) used as the probe molecule, NV_Au/Ag_NRs were found to show an increase in the effect of surface-enhanced Raman scattering. An enhancement of 7 orders of magnitude was obtained at low concentrations of CV. It is most likely that the embedded NVs increase the effective surface area for the interactions between CV molecules and laser light. A strong electromagnetic field effect is presumably generated inside NVs and around NRs.

Enhancement of Inverted Polymer Solar Cells Performances Using Cetyltrimethylammonium-Bromide Modified ZnO

In this study, the performance and stability of inverted bulk heterojunction (BHJ) polymer solar cells (PSCs) is enhanced by doping zinc oxide (ZnO) with 0–6 wt % cetyltrimethylammonium bromide (CTAB) in the sol-gel ZnO precursor solution. The power conversion efficiency (PCE) of the optimized 3 wt % CTAB-doped ZnO PSCs was increased by 9.07%, compared to a PCE of 7.31% for the pristine ZnO device. The 0–6 wt % CTAB-doped ZnO surface roughness was reduced from 2.6 to 1 nm and the number of surface defects decreased. The X-ray photoelectron spectroscopy binding energies of Zn 2p3/2 (1021.92 eV) and 2p1/2 (1044.99 eV) shifted to 1022.83 and 1045.88 eV, respectively, which is related to strong chemical bonding via bromide ions (Br−) that occupy oxygen vacancies in the ZnO lattice, improving the PCE of PSCs. The concentration of CTAB in ZnO significantly affected the work function of PSC devices; however, excessive CTAB increased the work function of the ZnO layer, resulting from the aggregation of CTAB molecules. In addition, after a 120-hour stability test in the atmosphere with 40% relative humidity, the inverted device based on CTAB-doped ZnO retained 92% of its original PCE and that based on pristine ZnO retained 68% of its original PCE. The obtained results demonstrate that the addition of CTAB into ZnO can dramatically influence the optical, electrical, and morphological properties of ZnO, enhancing the performance and stability of BHJ PSCs.

Biocompatible 3D SERS substrate for trace detection of amino acids and melamine

A novel, low-cost and biocompatible three-dimensional (3D) substrate for surface-enhanced Raman spectroscopy (SERS) is fabricated using gold nanoparticles (AuNPs) loaded on cellulose paper for detection of amino acids and melamine. Dysosma pleiantha rhizome (Dp-Rhi) capped AuNPs (Dp-Rhi_AuNPs) were prepared by in situ using aqueous extract of Dp-Rhi and in situ functionalized Dp-Rhi on AuNPs surface was verified by Fourier transform infrared spectroscopy and zeta potentials analysis shows a negative (-18.4mV) surface charges, which confirm that presence of Dp-Rhi on AuNPs. The biocompatibility of Dp-Rhi_AuNPs is also examined by cell viability of FaDu cells using MTS assay and compared to control group. In conclusion, the SERS performance of AuNPs@cellulose paper substrates were systematically demonstrated and examined with different excitation wavelengths (i.e. 532, 632.8 and 785nm lasers) and the as-prepared 3D substrates provided an enhancement factor approaching 7 orders of magnitude compared with conventional Raman intensity using para-nitrothiophenol (p-NTP), para-aminothiophenol (p-ATP) and para-mercaptobenzoic acid (p-MBA) as probe molecules. The strong electromagnetic effect was generated at the interface of AuNPs and pre-treated roughened cellulose paper is also investigated by simulation in which the formation of possible Raman hot-spot zone in fiber-like microstructure of cellulose paper decorated with AuNPs. Notably, with optimized condition of as-prepared 3D AuNPs@cellulose paper is highly sensitive in the SERS detection of aqueous tyrosine (10-10M) and melamine (10-9M).

Focused-ion-beam-fabricated homogeneous acute-angled Au nanorods for surface-enhanced Raman scattering

Well-ordered acute-angled Au nanorod (NR) arrays were fabricated using a focused ion beam (FIB) (fibAu_NR). The angle between the NRs and the substrate was tilted at 30–90°. A fibAu_NR with an angle of less than 90° significantly increased the effect of surface-enhanced Raman scattering, which was evaluated using low-concentration rose bengal (<10−5 M) as the molecular test probe. The results show that an angled NR surface produces a strong local electromagnetic effect owing to a large number of Raman active sites. In addition, an optimized fibAu_NR was found to distinguish cyanuric acid in milk solution with good reproducibility.

Probed adhesion force of living lung cells with a tip-modified atomic force microscope.

The mechanical properties of the extracellular matrix play an important role in bio-microenvironment activities. Herein, atomic force microscope (AFM) was used to measure the interaction between Au and Ag nanoparticle (NP) clusters on the surface of human fetal lung cells. Using (3-mercapto-propyl) triethoxysilane (MPTMS), NP clusters were grafted onto the apex of AFM tip, and then, the adhesion force between the tip and the cell was analyzed. The measured adhesion force increased from 92 pN for AFM tip to 332 pN for that modified with MPTMS. The increase is most probably contributed by the nonspecific interactions between the apex of the modified AFM tip and the surface of the cells. The adhesion forces between the surface of NPs clusters grafted AFM tip and that of lung cells were dramatically reduced as NPs clusters were replaced by MPTMS. For the former, as the Au NPs cluster was applied, the adhesion force reached to 122 pN, whereas it significantly augmented with the addition of the clusters size and dimension on the AFM tip. For the case of Ag cluster grafted on AFM tip, its adhesion force with the surface of the cells significantly lowered and reduced to 56 pN. Presumably, the electrostatic or van der Waals force between the two surfaces results in the variation of measurements. It is also very likely that the cell-surface interactions are probably varied by the nature of the contact surfaces, like the force-distance of attraction. The result is significant for understanding the the nature of the interactions between the surface of NPs and the membrane of lung cells.

AuGa2 on focused Ga ion beam-fabricated Au nanorod array for trace detection of melamine cyanurate in milk solution

Au nanorod arrays were fabricated using a focused gallium (Ga) ion beam (fibAu_NRs) with various levels of Ga ion energy. The formation of AuGa2 on fibAu_NRs was controlled by adjusting the level of Ga ion energy and subsequent heat treatment in order to increase the effect of surface-enhanced Raman scattering (SERS). The SERS enhancement factor of the substrates was evaluated using crystal violet as a molecular test probe. The results show that low-density AuGa2 formation on fibAu_NRs increases the SERS effect, which is likely due to the interjunction charge transfer between Au and AuGa2. An optimized AuGa2 on fibAu_NRs was applied to the trace detection of melamine cyanurate in milk solution with high measured sensitivity.

Gold Nanoparticle-Coated ZrO2-Nanofiber Surface as a SERS-Active Substrate for Trace Detection of Pesticide Residue

Trace detection of common pesticide residue is necessary to assure safety of fruit and vegetables, given that the potential health risk to consumers is attributed to the contamination of the sources. A simple, rapid and effective means of finding the residue is however required for household purposes. In recent years, the technique in association with surface-enhanced Raman scattering (SERS) has been well developed in particular for trace detection of target molecules. Herein, gold nanoparticles (Au NPs) were integrated with sol-gel spin-coated Zirconia nanofibers (ZrO2 NFs) as a chemically stable substrate and used for SERS application. The morphologies of Au NPs/ZrO2 NFs were adjusted by the precursor concentrations (_X, X = 0.05–0.5 M) and the effect of SERS on Au NPs/ZrO2 NFs_X was evaluated by different Raman laser wavelengths using rhodamine 6G as the probe molecule at low concentrations. The target pesticides, phosmet (P1), carbaryl (C1), permethrin (P2) and cypermethrin (C2) were thereafter tested and analyzed. Au NPs/ZrO2 NFs_0.3 exhibited an enhancement factor of 2.1 × 107, which could detect P1, C1, P2 and C2 at the concentrations down to 10−8, 10−7, 10−7 and 10−6 M, respectively. High selectivity to the organophosphates was also found. As the pesticides were dip-coated on an apple and then measured on the diluted juice containing sliced apple peels, the characteristic peaks of each pesticide could be clearly identified. It is thus promising to use NPs/ZrO2 NFs_0.3 as a novel SERS-active substrate for trace detection of pesticide residue upon, for example, fruits or vegetables.