Deciphering the near-field response with the far-field wavelength-scanned SERS spectra of 4-mercaptopyridine adsorbed on gold nanocolloidal particles entrapped in Langmuir Reverse Schaefer film of 5CB liquid crystal molecules.

Herein, we have reported the wavelength-scanned (WS) SERS spectra of 4-mercaptopyridine molecules (4-MPy) adsorbed on gold nanoparticles immobilised in a Langmuir Reverse Schaefer (L-RSh) film matrix of 5CB molecules. The WS-SERS spectral profile exhibited an increment in the intensity of the enhanced Raman bands of 4-MPy with an increase in the wavelength of the excitation laser source. The rationale behind the experimental observations was supported by the simulated extinction spectra and the enhancement factor measurements of the modelled systems using the T-matrix formalism. The SERS intensity fluctuations in the band located at 1000 cm-1 for the 4-MPy molecule, as obtained from three different locations in the L-RSh film substrate, were also analyzed. Surprisingly, depending on the spatial locations of the substrates, the intensity fluctuations of the abovementioned band exhibit both Poisson and Gaussian distributions but the maximum number of probe molecules that can reside in the scattering areas under investigation cannot exceed sixteen. These observations suggest that the origin of SERS from single/few molecules or from the ensemble-averaged system cannot be inferred from the statistical distributions of the Raman intensity fluctuations. The present experimental observations also revealed the relation between the near-field plasmonic behaviors of the substrate with the corresponding far-field SERS spectra of the 4-MPy molecule.

Charge Transfer-Mediated Blue Luminescence in Plasmonic Ag-Cu2O Quantum Nanoheterostructures.

Metal-semiconductor hybrid nanoheterostructures have the possibility to exhibit new synergic properties other than the combination of properties from discrete components due to the interaction of metal and semiconductor components at the interfaces. Here, we have synthesized Ag-Cu2O eyeball-shaped quantum nanoheterostructures with diameter ranging between 8 and 12 nm using a single-step low-cost solvothermal process. It is observed that the presence of a minimum 3% of Ag is required for the formation of Ag-Cu2O quantum nanoheterostructures. The formation of nanoheterostructures has introduced new synergic properties like intense blue luminescence and surface-enhanced Raman scattering due to the interactions between Ag and Cu2O atoms at the interfaces. The significant presence of charge transfer through the interfaces is identified from the peak shift of Raman modes. The increase in the electron density at the metal surface due to the charge transfer and the recombination of these electrons with sp- or d-band holes of Ag could be the effective mechanism of the observed blue luminescence. The blue luminescence of Ag-Cu2O quantum nanoheterostructures together with its low band gap value (≈2.3 eV) is believed to have important applications in optoelectronic devices.

Investigation of the Origin of Voltage Generation in Potentized Homeopathic Medicine through Raman Spectroscopy.

BACKGROUND: For the study of homeopathic medicines in proper perspective, emerging techniques in material science are being used. Vibrational spectroscopy is one such tool for providing information on different states of hydrogen bonding as an effect of potentization. The associated change in electrical properties is also correlated with this effect. OBJECTIVE: From the vibrational spectra, the changes in hydrogen bonding due to dilution followed by unidirectional vigorous shaking (together termed potentization) of 91% ethanol and two homeopathic medicines Chininum purum and Acidum benzoicum have been studied. The aim was to correlate the result with the change in the electrical properties of the system. METHODS: Raman spectroscopy was used to study the vibrational spectra. A U-shaped glass tube (electrochemical cell), where one arm contained bi-distilled water and the other arm alcohol/homeopathic medicine (the arms being separated by a platinum foil), was used to measure the voltage generated across two symmetrically placed platinum electrodes. RESULTS: For all samples, it was observed that potentization affected the intensity of OH stretching bands at the frequencies 3240 cm-1, 3420 cm-1 and 3620 cm-1, corresponding to strong hydrogen bond, weak hydrogen bond and broken hydrogen bond, respectively. With the increase in potency, in the presence and absence of the two medicines in ethanol, the number of OH groups linked by strong hydrogen bonds decreased, while the number of OH groups with weak hydrogen bonds increased. With the increase in potentization, the number of OH groups with broken hydrogen bonds showed a difference in the presence and absence of the medicine.The voltage measurements for ethanol show that, with succussion, the magnitude of voltage increased with the two medicines at lower potencies, but not at higher potency where the voltage is lower. Acidum benzoicum, which is acidic in nature, had higher voltage values (113mV, 130 mV and 118 mV at 6C, 30C and 200C, respectively), compared with Chininum purum, which is basic in nature (20 mV, 85 mV and 65 mV at 6C, 30C and 200C, respectively). CONCLUSION: The experimental results indicate a correlation between the vibrational and electrical properties of the homeopathic medicines Acidum benzoicum and Chininum purum at different potencies.

Au nanoparticles functionalized 3D-MoS2 nanoflower: An efficient SERS matrix for biomolecule sensing.

Fabrication of Molybdenum disulfide (MoS2) nanostructures and surface functionalization with noble metal nano particles is an emerging field of research as it has potential applications in electronic devices and chemical sensing. Here we report application of gold nanoparticles (AuNPs) decorated MoS2 nanoflowers (Au-MoS2 NFs) as an efficient bio-sensor. MoS2 NFs, synthesized using green synthesis process, are further functionalized with AuNPs to tune their physical properties and make them more appropriate for biological applications. The abundant 'hot-spots' created by AuNPs through localization of electromagnetic field endows the Au-MoS2 hybrid structure as an excellent substrate for biochemical sensing through surface enhanced Raman scattering (SERS). The sensing efficiency of the SERS substrate is examined using Rh6G as probe molecule with concentration as low as 10-12 M. Main emphasis is given in detecting free bilirubin, an important component of human blood, using SERS technique. Au-MoS2 NF SERS substrate exhibits high sensitivity, stability and excellent reproducibility in sensing bilirubin from high level (10-3 M) to picomolar level. The concentration (C) dependent SERS intensity (I) is found to follow the general relationship I = Cα, with α ranging from 0.09 to 0.12. The substrate shows excellent selectivity and reliability while sensing of free bilirubin performed in human serum in the presence of crucial interferences such as dextrose, cholesterol and phosphate. In the present study, this Au-MoS2 hybrid offers a new potential biosensing technology for free bilirubin detection and is anticipated to be applied for clinic diagnosis.

Hygroscopic Coating of Sulfuric Acid Shields Oxidant Attack on the Atmospheric Pollutant Benzo(a)pyrene Bound to Model Soot Particles.

Substantial impacts on climate have been documented for soot‒sulfuric acid (H2SO4) interactions in terms of optical and hygroscopic properties of soot aerosols. However, the influence of H2SO4 on heterogeneous chemistry on soot remains unexplored. Additionally, oxidation rate coefficients for polycyclic aromatic hydrocarbons intrinsic to the atmospheric particles evaluated in laboratory experiments seem to overestimate their degradation in ambient atmosphere, possibly due to matrix effects which are hitherto not mimicked in laboratory experiments. For the first time, our kinetics study reports significant influence of H2SO4 coating on heterogeneous ozonation of benzo(a)pyrene (BaP) deposited on model soot, representative to atmospheric particles. The approximate specific surface area of model soot (5 m2g-1) was estimated as a measure of the availability of surface molecules to a typical gaseous atmospheric oxidant. Heterogeneous bimolecular reaction kinetics and Raman spectroscopy studies suggested plausible reasons for decreased BaP ozonation rate in presence of H2SO4: 1. decreased partitioning of O3 on soot surface and 2. shielding of BaP molecules to gaseous O3 by acid-BaP reaction or O3 oxidation products.

Directional growth of Ag nanorod from polymeric silver cyanide: A potential substrate for concentration dependent SERS signal enhancement leading to melamine detection.

Attention has been directed to prepare exclusive one-dimensional silver nanostructure from the linear inorganic polymer AgCN. Successive color change from yellow to orange, to red and finally to green reflects the evolution of high yielding Ag nanorods (NRs) from well-known -[Ag-CN]- chains of polymeric AgCN at room temperature. The parental 1D morphology of AgCN is retained within the as-synthesized Ag NRs. So we could successfully exploit the Ag NR for surface-enhanced Raman scattering (SERS) studies for sensing a popular milk adulterant melamine down to picomolar level. We observed interesting concentration dependent selective SERS band enhancement of melamine. The enhanced ~1327cm-1 SERS signal intensity at lower concentration (10-9 and 10-12M) of melamine speaks for the preferential participation of -C-N of melamine molecule with Ag surface. On the other hand, '-NH2' group together with ring 'N' participation of melamine molecule onto Ag surface suggested an adsorptive stance at higher (10-3-10-7M) concentration range. Thus the binding modes of the molecule at the Ag surface justify its fluxional behavior.