Insights into Plasmon-Induced Dimerization of Rhodanine-A Surface-Enhanced Raman Scattering Study.

Plasmon-mediated chemical reactions (PMCRs) have attracted considerable interest in recent times. The PMCR initiated by hot carriers is known to be influenced by the type of metals and the excitation wavelength. Herein, we have carried out the surface-enhanced Raman scattering (SERS) investigation of rhodanine (Rd), an important pharmacologically active heterocyclic compound, adsorbed on silver and gold nanoparticles (AgNP and AuNP) using 514.5 and 632.8 nm lasers. The prominent Raman band at 1566 cm-1 observed in the SERS spectra is attributed to the characteristic ν(C═C) stretching vibration of the Rd dimer and not of Rd tautomers. The chemical transformation of Rd to Rd dimer on metal surfaces is plausibly triggered by the indirect transfer of energetic hot electrons generated during the non-radiative decay of plasmon. The mechanism involved in the dimerization of Rd via the indirect transfer of hot electrons is also presented. The effect of wavelength on the dimerization of Rd is also observed on the AgNP surface, which indicates that the dimerization occurs more efficiently on the AgNP surface with excitation at 514.5 nm wavelength.

Measurement of dose enhancement factor for Xoft Axxent electronic brachytherapy device using nanoparticle-embedded alginate film and radiochromic film.

Aim: Inw nanoparticles-aided radiotherapy, the radiation sensitivity of tumor is increased with the infusion of nanoparticles in tumor. This therapeutic modality is capable of delivering enhanced dose to tumor, without exceeding the normal tissue tolerance dose. Further, the quantification of the enhanced dose using suitable dosimeter is important. The present study is aimed at measuring the dose enhancement factors (DEFs) using the combination of nanoparticles-embedded alginate (Alg) film and unlaminated Gafchromic EBT3 film. Materials and Methods: Gold nanoparticles (AuNPs)- and silver nanoparticles (AgNPs)-embedded Alg polymer films were synthesized and characterized using standard techniques. Further, a customized version of the Gafchromic EBT3 film, i.e., unlaminated EBT3 film, was specially fabricated. The DEFs were measured using Xoft Axxent electronic brachytherapy device. Results: The surface plasmon resonance (SPR) and particle size of AuNPs were found to be 550 and 15 ± 2 nm, respectively. In the case of AgNPs, the SPR and particle size were recorded as 400 and 13 ± 2 nm, respectively. The DEFs measured, using unlaminated EBT3 film, for Xoft Axxent electronic brachytherapy using AuNPs and AgNPs were 1.35 ± 0.02 and 1.20 ± 0.01, respectively. Conclusion: The increase in dose enhancement during nanoparticles-aided electronic brachytherapy can be attributed to dominance of photoelectric effect, due to the presence of low-energy X-rays. The investigation indicates that the Xoft Axxent electronic brachytherapy device is suitable for nanoparticles-aided brachytherapy.

Conformational Selectivity of Merocyanine on Nanostructured Silver Films: Surface Enhanced Resonance Raman Scattering (SERRS) and Density Functional Theoretical (DFT) Study.

In this study, detailed structural and vibrational analysis of merocyanine has been investigated using Raman, surface enhanced Raman scattering (SERS) and surface-enhanced resonance Raman scattering (SERRS). The Raman, SERS and SERRS studies aided by density functional theoretical (DFT) calculations clearly established the prevalence of the trans- and cis-conformers of the protonated form of merocyanine (MCH+) in solid and acetonitrile solution. The binding characteristics of merocyanine adsorbed on nanostructured silver-coated films (SCFs) were investigated using excitation-dependent SERS, concentration-dependent SERRS and DFT studies. The conformers of merocyanine involved in the surface adsorption processes were recognized. The prominent marker bands observed at 1538 (ethylenic C=C stretch) and 1133 cm-1 (pyridinium C-N stretch) in the Raman spectrum of merocyanine in acetonitrile shifted to 1540 and 1126 cm-1, respectively on the nanostructured SCFs. The shift in the marker bands is associated with either the preferential binding of selective conformer or change in resonance equilibrium between the benzenoid and quinoid forms. The excitation wavelength dependent SERS spectrum infers that in addition to the major contribution from the electromagnetic enhancement, chemical (resonance) effect leads to the amplification of the 1540 cm-1 band. The concentration-dependent SERRS study showed maximum enhancement for the nanostructured SCFs functionalized with 1 µM concentration of merocyanine, indicative of monolayer coverage. For lower concentrations of merocyanine, the SERRS signal intensity reduced without any alteration in the peak positions. The SERRS study thus, revealed sub-nanomolar (0.1 nM) sensing of merocyanine using nanostructured SCFs with the analytical enhancement factor (AEF) of ∼ 1010 for the 1126 cm-1 and 1540 cm-1 Raman bands for MC concentration of 0.1 nM. In this study, combination of SERRS and DFT have clearly established the predominance of trans-MCH+ on the nanostructured silver surface with minor contribution from cis-MCH+, which remain exclusively bound to the surface via the phenoxyl ring O atom. This conformational surface selectivity of geometrical isomers of merocyanine using nanostructured surfaces can be further explored for energy efficient and economical separation of geometrical isomers.

Application of unlaminated EBT3 film dosimeter for quantification of dose enhancement using silver nanoparticle-embedded alginate film.

Purpose.The paper describes the application of unlaminated Gafchromic EBT3 film dosimeter for quantification of dose enhancement using locally synthesized silver nanoparticle-embedded alginate film (AgNPs-Alg film) for nanoparticles-aided radiotherapy.Materials and Methods.AgNPs-Alg film was synthesized and characterized using standard techniques. The unlaminated Gafchromic EBT3 film was specially customized for dosimetric measurement. The dose enhancements due to AgNPs-Alg film was experimentally determined for ISO wide spectrum x-rays series (average energy ranging from 57-137 keV) and 6 and 10 MV x-rays using laminated and unlaminated Gafchromic EBT3 film. The radiation dose of 1 Gy was delivered to a combination of AgNPs-Alg films and EBT3 film.Results.Ultraviolet-Visible spectroscopy of silver nanoparticles shows a surface plasmon resonance peak at 400 nm. The average particle size of 13 ± 2 nm was measured using Atomic Force Microscopy. For unlaminated film, the dose enhancements of 29%, 23%, 14% and 2% was observed for ISO wide spectrum x-rays having average energy of 57, 79, 104 and 137 keV, respectively. The dose enhancement was negligible for 6 and 10 MV x-rays. In the case of laminated film, no significant dose enhancement was measured for all the x-ray energies.Conclusion.The unlaminated Gafchromic EBT3 film can be a suitable choice for the measurement of dose enhancement. Further, silver nanoparticles can be used during nanoparticle-aided radiotherapy when irradiated at low x-ray energy.

Phase evolution in sonochemically synthesized Fe(3+) doped BaTiO3 nanocrystallites: structural, magnetic and ferroelectric characterisation.

The properties of nanomaterials are highly dependent on their size, morphology, crystal phase, etc., which in turn depend on the method of synthesis. We report here the electrical and magnetic characterisation of sonochemically synthesized Fe(3+) doped nano BaTiO3 samples. The dopant ion concentration has been optimized and the coexistence of ferromagnetism and ferroelectricity has been observed in the sample. With increase in Fe(3+) doping from 0 to 20 mol%, a gradual phase change from tetragonal to hexagonal occurred in these sonochemically synthesized BaTiO3 nanomaterials. Below 15 mol% Fe concentration the material displays ferroelectric behaviour with the absence of any magnetic ordering, while at an Fe concentration of ∼15 mol% the material exhibits both room temperature ferromagnetism and ferroelectricity. Ferromagnetism as well as relaxor type behaviour has been observed in the BaTiO3:Fe(3+)(20%) sample. We have studied the ferromagnetic and ferroelectric ordering in these sonochemically synthesized Fe(3+) doped BaTiO3 nanomaterials and have tried to correlate the results with their crystal structure and morphology. The origin of ferromagnetism in these materials has been attributed to both intrinsic as well as extrinsic factors.

Investigating structural aspects to understand the putative/claimed non-toxicity of the Hg-based Ayurvedic drug Rasasindura using XAFS.

XANES- and EXAFS-based analysis of the Ayurvedic Hg-based nano-drug Rasasindura has been performed to seek evidence of its non-toxicity. Rasasindura is determined to be composed of single-phase α-HgS nanoparticles (size ∼24 nm), free of Hg(0) or organic molecules; its structure is determined to be robust (<3% defects). The non-existence of Hg(0) implies the absence of Hg-based toxicity and establishes that chemical form, rather than content of heavy metals, is the correct parameter for evaluating the toxicity in these drugs. The stable α-HgS form (strong Hg-S covalent bond and robust particle character) ensures the integrity of the drug during delivery and prevention of its reduction to Hg(0) within the human body. Further, these comparative studies establish that structural parameters (size dispersion, coordination configuration) are better controlled in Rasasindura. This places the Ayurvedic synthesis method on par with contemporary techniques of nanoparticle synthesis.

Synthesis of pH sensitive gold nanoparticles for potential application in radiosensitization.

Synthesis of gold nanoparticles (GNPs) for in-vivo applications involves reduction of chloroauric acid by a biologically important molecule which itself undergoes redox reaction during physiological processes in human body. But the GNPs often prepared by this method are not stable enough. In order to stabilize these particles, surfactants are used which may or may not be compatible for in-vivo applications. Is there any other way to stabilize these particles in solution? In this work, the answer to this question is explored and a detailed study of the mechanism of the formation of GNPs is done to understand the basis of stabilization of nanoparticles without using a stabilizer. Chloroauric acid is reduced by L-tryptophan (Trp) in buffered medium and the formation mechanism is studied both visually and by UV-vis spectroscopy. The pH dependent structure of Trp was found to play an important role not only in the formation of stable GNPs but also in the stabilization of redispersed nanoparticles. pH sensitive property of the synthesized GNPs was utilized to make the GNPs accumulate at polar-non-polar liquid-liquid interface similar to hypoxic tumor tissue environment. Mechanistic study of the formation of GNPs by gas chromatography throws light on intermediate decarboxylation process. On the other hand, fluorescence study gives information about the interaction of Trp with GNPs.

Effect of SDS concentration on colloidal suspensions of Ag and Au nanoparticles.

We present a kinetic study of the effects of sodium dodecyl sulfate (SDS) concentration on reduction and aggregation of Ag(+) and Au(3+) ions in aqueous solutions. There are distinct differences between the surface plasmon absorption bands of Ag nanoparticles at different concentrations of SDS. The results reveal the existence of two competing SDS-induced processes: stabilization of the Ag nanoparticles due to adsorption and aggregation of the Ag nanoparticles due to increase in ionic strength. However, SDS induced aggregation of Au nanoparticles is negligible because of less surface passivity as evident from eaq(-) reaction with AuCl4(-). Nevertheless, the average size of the Ag and Au nanoparticles remains almost similar at all SDS concentrations. UV-Vis spectrophotometry and transmission electron microscopy are used to characterize the nanoparticles. Moreover, it is shown that these SDS-capped Ag, Au and Au/Ag bimetallic nanoparticles could function as catalysts for the reduction of o-nitro aniline in the presence of NaBH4.

Adsorption and sub-nanomolar sensing of thioflavin T on colloidal gold nanoparticles, silver nanoparticles and silver-coated films studied using surface-enhanced Raman scattering.

Raman and surface-enhanced Raman scattering (SERS) studies of thioflavin T (ThT) in solid, solution, gold nanoparticles (GNPs), silver nanoparticles (SNPs) and silver-coated films (SCFs) were investigated. Concentration-dependent SERS spectrum of ThT in GNPs and SNPs indicated the existence of two possible structures, one with the torsional angle (φ) between benzothiazole and dimethylaminobenzene rings being 37° and the other with φ=90°. The SERS spectrum of ThT in SCFs were similar to the Raman spectrum of solid and solution that suggests φ=37°. In this paper, the high sensitivity of the SERS technique was employed for sub-nanomolar (picomolar) sensing of ThT.

Binding of a cyclic organoselenium compound with gold nanoparticles (GNP) and its effect on electron transfer properties.

Binding of a cyclic organoselenium compound, DL-trans-3,4-dihydroxy-1-selenolane (DHSred) with gold nanoparticles (GNP) of different sizes was studied by absorption spectroscopy, dynamic light scattering (DLS), transmission electron microscope (TEM), surface enhanced Raman spectroscopy (SERS) and zeta-potential (ζ) measurements. GNP of different size were synthesized by varying the reaction conditions and their size was determined by DLS and TEM techniques. The absorption spectral data showed red shift in the surface plasmon resonance (SPR) band indicating increase in the size of GNP on binding to DHSred. SERS studies confirmed that the binding of DHSred with GNP is through selenium center with planar orientation of DHSred on the GNP surface. The product of the number of binding sites (n) in GNP and the binding constant (K) was estimated for GNP of different particle size. The zeta potential (ζ) value of GNP decreased marginally in the presence of DHSred. Further, the binding of DHSred with GNP was found to enhance its reactivity with 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) radicals (ABTS(·-)) and the reactivity increased with decrease in the GNP size. Such enhancement in the reducing ability may have a greater impact on the antioxidant activity of DHSred.

Reduction and aggregation of silver ions in aqueous citrate solutions.

Radiolytic reduction of Ag(+) ions and the subsequent formation of Ag clusters were studied in aqueous citrate solutions. Pulse-radiolysis studies show that the presence of citrate in the solution affects the early processes, via complexation of Ag(+) ions with the carboxyl moieties of the citrate. The ratio of citrate to Ag(+) determines the kinetic consequences of the reduction and agglomeration processes. The complexation reduces somewhat the rate of reduction by hydrated electrons. However, when all the ions are complexed to the citrate, the surface plasmon absorption band becomes broader, albeit small, but nevertheless it provides extreme stability to the formed nanoparticles.

DFT and surface-enhanced Raman scattering study of tryptophan-silver complex.

Surface-enhanced Raman scattering (SERS) study of tryptophan was carried out in silver hydrosol. The surface adsorption properties of tryptophan were investigated due to its biological importance. Tryptophan is an essential amino acid needed for the normal growth in infants and for nitrogen balance in adults. DFT calculations using B3LYP functional with LANL2DZ basis set was carried out to support the experimental Raman and SERS data. The strong enhancement of 1343 cm(-1) band, assigned to the CO(2) sym. stretching vibration in the SERS spectrum along with a red shift of 63 cm(-1), manifests that chemical mechanism contributes to the SERS activity. Moreover, the observed features in the SERS spectrum as well as theoretical calculations infer that tryptophan is chemisorbed to the silver surface directly through the oxygen and nitrogen atoms of the carboxylate and amino groups with an edge-on orientation with the indole ring lying nearly perpendicular to the silver surface. The SERS enhancement factors for various Raman vibrations of tryptophan were found to be of the order of 10(5)-10(6).