Comparative analysis of surface-enhanced Raman spectroscopy of daidzein and formononetin

Phytoestrogens daidzein (4′,7-dihydroxy-isoflavone) and formononetin (4′-methoxy-7-hydroxy-isoflavone) have been studied by surface-enhanced Raman (SER) spectroscopy. Spectra were acquired in the presence of citratereduced silver colloids, over a range of pH and concentrations. Density functional theory calculations were used to assist assignment of the normal Raman spectra and help determine the mode of interaction of isoflavones with the silver nanoparticles. Formononetin does not show SER activity unless the 7-OH group is deprotonated, and accordingly, the interaction with the silver surface occurs via the deprotonated site. Daidzein, on the other hand, appears to contain multiple species at the surface, interacting via both the hydroxyl groups at 7-OH and 4′-OH, after deprotonation. This is an important result that points to potential future SERS applications in phytoestrogen analysis and provides a foundation for understanding the SER spectra of isoflavones.

Analysis of 5-hydroxyisoflavones by surface-enhanced Raman spectroscopy : genistein and methoxy derivatives

A series of 5-hydroxy-isoflavones—genistein, biochanin A, prunetin, and 4′,7-dimethoxygenistein—have been studied by surface-enhanced Raman spectroscopy (SERS). Citrate reduced silver colloids were employed as a standard technique to measure SER spectra over a range of pH and concentrations. Density functional theory calculations were used to assist in determining the mode of interaction of isoflavones with the silver nanoparticles. It is revealed that biochanin A and prunetin interact with the silver nanoparticles upon deprotonation of the 7- and the 4′-OH groups, respectively, to show SERS activity. Correlations of their spectra with SERS of genistein strongly support the presence of multiple interaction modes involving both of the OH groups in genistein, in a similar manner to daidzein. Surprisingly, however, under these conditions, the 5-OH group was found to be noninteractive as revealed by attempts to measure SERS of 4′,7-dimethoxygenistein. This was attributed partly to the low solubility and, more importantly, to the influence of steric hindrance, caused by the position of the pendant phenyl ring, which prevented interaction with the Ag colloid surface. These results complement recent work on daidzein and formononetin and provide further insight into understanding the SER spectra of isoflavones.

Modeling and simulation of a periodic grating coupled configuration for surface plasmon excitation

The deficiencies in the design of surface plasmon resonance (SPR) systems that are reported in numerous published works consistently identify the optics assembly as the main problem in the miniaturization of SPR sensors for integration into biosensor systems. This paper presents a novel design of a grating coupled optical waveguide surface plasmon (SP) excitation mechanism, investigated with the intention of addressing the problems associated with using the traditional prism input-output light coupling approach. Computational multiphysics modeling and simulation of the design is carried out. The results are presented and discussed.

Variable incidence angle localized surface plasmon resonance graphene biosensor

This paper investigates the enhancement of sensitivity of variable incidence angle LSPR biosensor by monitoring biomolecular interactions of biotin-streptavidin with gold thin film. The investigation is carried out by means of introducing an additional layer of graphene sheet on top of gold layer (graphene biosensor) and using different coupling configuration of laser beam. The sensitivity, which is indicated by the shift of plasmon resonance angle, increases with graphene deposited onto the gold layers and is linearly related with the number of graphene layers. In addition, an investigation of the shift of plasmon dip is carried out for two different analyte interfaces: air and water. It is found that graphene biosensor has better sensitivity for triangular prism, higher prism angle, and water interface. The evaluation approach involves a plot of a reflectivity curve as a function of the angle of incidence while the operating wavelength is kept fixed.

Use of electrochemical impedance spectroscopy for study of CO2 corrosion prevention by batch treatment inhibitor films

Electrochemical impedance spectroscopy (EIS) was used to study and evaluate commercial batch treatment inhibitors which are used for protecting oil wells, gas wells, and pipelines from CO2 corrosion, focusing on the evaluation of inhibitor film persistency. It was found that theformation and deterioration of batch treatment inhibitor films were accompanied by typical impedance spectral changes. During the formation of inhibitor films, electrode impedance showed a rapid increase and the Bode phase angle plots also showed a sudden change. Thus, the formation of inhibitor film was a very fast process. During the deterioration of inhibitor films, electrode impedance showed a gradual decrease and the Bode phase angle plots showed changes which characterised the three stages of the inhibitor film deterioration process. The relationships between EIS and corrosion rate are discussed, including comparisons with weight loss measurements. Based on the experimental findings in the present work, a method is suggested for estimating the persistency of inhibitor films by monitoring the characteristic changes in the Bode phase angle plots and by measuring electrochemical charge transfer resistance at the second and third stages of the inhibitor film deterioration process.

Design and analysis of a multilayer localized surface plasmon resonance graphene biosensor

This paper describes a multilayer localized surface plasmon resonance (LSPR) graphene biosensor that includes a layer of graphene sheet on top of the gold layer, and the use of different coupled configuration of a laser beam. The study also investigates the enhancement of the sensitivity and detection accuracy of the biosensor through monitoring biomolecular interactions of biotin-streptavidin with the graphene layer on the gold thin film. Additionally, the role of thin films of gold, silver, copper and aluminum in the performance of the biosensor is separately investigated for monitoring the binding of streptavidin to the biotin groups. The performance of the LSPR graphene biosensor is theoretically and numerically assessed in terms of sensitivity, adsorption efficiency, and detection accuracy under varying conditions, including the thickness of biomolecule layer, number of graphene layers and operating wavelength. Enhanced sensitivity and improved adsorption efficiency are obtained for the LSPR graphene biosensor in comparison with its conventional counterpart; however, detection accuracy under the same resonance condition is reduced by 5.2% with a single graphene sheet. This reduction in detection accuracy (signal to noise ratio) can be compensated for by introducing an additional layer of silica doped B2O3 (sdB2O3) placed under the graphene layer. The role of prism configuration, prism angle and the interface medium (air and water) is also analyzed and it is found that the LSPR graphene biosensor has better sensitivity with triangular prism, higher prism angle, lower operating wavelength and larger number of graphene layers. The approach involves a plot of a reflectivity curve as a function of the incidence angle. The outcomes of this investigation highlight the ideal functioning condition corresponding to the best design parameters.

Sensitivity analysis of a sub-wavelength localized surface plasmon resonance graphene biosensor

Localized surface plasmon resonance (LSPR) is a promising detection method for label-free sensing of biomolecules. In this paper, a multilayer design for a LSPR biosensor is presented. In the proposed design, a periodic array of dielectric grating is incorporated on top of a graphene layer in the biosensor. The aim is to improve sensitivity of the LSPR biosensor through monitoring biomolecular interactions of biotin-streptavidin. Sensitivity improvement is obtained for the proposed LSPR biosensor compared with conventional SPR counterparts. In addition, to optimize the design, we have investigated grating geometry including volume factor and grating depth. The outcome of this investigation identifies ideal functioning conditions corresponding to the best design parameters.

Localized surface plasmon resonance: nano-sinusoid arrays

A new nano-sinusoid shape has recently been proposed, which offers the advantage of more resonance wavelength tunability than that offered by other sharp-tip nano-particles. In this paper, a one-dimensional (1D) chain of the nano-sinusoids is modelled, and results are compared with those describing chains of nano-triangles and nano-diamonds. It is demonstrated that the chain of nano-sinusoids provides more enhancement at hot spots than other examined nano-particle shapes. This enhancement is analytically quantified using the coupling constant values used in the electrostatic eigenmode method for analytically solving Maxwell's equations for the nano-plasmonic devices. In addition, investigating LSPR spectrum of two-dimensional (2D) arrays of NPs demonstrates existence of enhanced surface electric fields on hot spots of the outer rows of the array.

Design and analysis of a multilayer surface plasmon resonance biosensor

Designed a multilayer SPR biosensor to improve the detection sensitivity and accuracy simultaneously. Developed a design procedure to identify optimum design parameters for SPR biosensing. Devised a new detection measurement technique based on S-parameters for SPR biosensing.