Sergiy Patskovsky

Phase and amplitude sensitivities in surface plasmon resonance bio and chemical sensing

We consider amplitude and phase characteristics of light reflected under the Surface Plasmon Resonance (SPR) conditions and study their sensitivities to refractive index changes associated with biological and chemical sensing. Our analysis shows that phase can provide at least two orders of magnitude better detection limit due to the following reasons: (i) Maximal phase changes occur in the very dip of the SPR curve where the vector of probing electric field is maximal, whereas maximal amplitude changes are observed on the resonance slopes: this provides a one order of magnitude larger sensitivity of phase to refractive index variations; (ii) Under a proper design of a detection scheme, phase noises can be orders of magnitude lower compared to amplitude ones, which results in a much better signal-to-noise ratio; (iii) Phase offers much better possibilities for signal averaging and filtering, as well as for image treatment. Applying a phase-sensitive SPR polarimetry scheme and using gas calibration model, we experimentally demonstrate the detection limit of 10(-8) RIU, which is about two orders of magnitude better compared to amplitude-sensitive schemes. Finally, we show how phase can be employed for filtering and treatment of images in order to improve signal-to-noise ratio even in relatively noisy detection schemes. Combining a much better physical sensitivity and a possibility of imaging and sensing in micro-arrays, phase-sensitive methodologies promise a substantial upgrade of currently available SPR technology.

Properties and sensing characteristics of surface-plasmon resonance in infrared light

Conditions of surface-plasmon resonance (SPR) production with use of IR pumping light (800-2300 nm) in the Kretschmann-Raether prism arrangement were investigated. Both calculations and experimental data showed that SPR characteristics in the IR are strongly influenced by the properties of the coupling prism material. Indeed, quite different regularities of plasmon excitation, polarity of sensing response, and sensitivity are observed for two different glasses and silicon. The observed differences in SPR properties are related to essentially different behavior of dispersion characteristics of materials near the SPR coupling point. Methods for improving sensor performance and miniaturizing the SPR technique using novel coupling materials (silicon) are discussed.

Phase-sensitive time-modulated surface plasmon resonance polarimetry for wide dynamic range biosensing

A novel polarimetry scheme is proposed to improve the performance of phase-sensitive Surface Plasmon Resonance (SPR) biosensors. The scheme uses s-polarized light, not affected by SPR, as a reference beam, while information on the phase of the p-polarized component is obtained from an analysis of phase-polarization state of light of mixed polarization. We utilize temporal modulation of the beam reflected under SPR by a photo-elastic modulator and show that, under certain birefringent geometry, the signals at the 2nd and 3rd harmonics of modulated frequency can provide ultra-sensitive phase-based response to changes of the refractive index (thickness) of thin films on gold. We also show that the proposed configuration significantly improves detection limit compared to conventional intensity-sensitive SPR, yet enables to maintain wide dynamic range of measurements, which is normally difficult with phase-sensitive SPR schemes. Biosensing applications of the proposed scheme are illustrated in a biological model reaction of avidin - biotin binding on gold.

Intensity based surface plasmon resonance sensor using a nanohole rectangular array

We show high resolution measurements of a surface plasmon resonance (SPR) sensor based on a rectangular nanohole array in a metal film. This SPR setup uses balanced intensity detection between two orthogonal polarizations of a He-Ne laser beam, which allows for sensitivity improvement, noise reduction and rejection of any uncorrelated variation in the intensity signal. A bulk sensitivity resolution of 6.4 x 10(-6) RIU is demonstrated. The proposed methodology is promising for applications in portable nanoplasmonic multisensing and imaging.

Silicon-based surface plasmon resonance sensing with two surface plasmon polariton modes.

Surface plasmon resonance (SPR) sensing on a silicon-based platform is considered. We have studied properties of SPR in a combined silicon-dielectric layer-gold film-sample medium structure and established conditions of the simultaneous excitation of two plasmon polariton modes that provide narrow and well-separated minima of the reflected intensity. It has been shown that the external mode over the gold-sample medium interface demonstrates a highly sensitive response to a change in the refractive index of the sample medium, whereas the internal mode over the dielectric-gold interface is almost insensitive to medium parameters. We propose that the internal mode can be used as an effective reference zero point for miniature and portable SPR-based systems designed for field and multichannel sensing.

Stability of sputter-deposited gold nanoparticles in imidazolium ionic liquids

The stability of gold nanoparticles synthesised by sputter deposition has been studied in situ in 1-butyl-3-methylimidazolium ionic liquids with bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate and dicyanamide anions with UV-VIS absorption spectroscopy and transmission electron microscopy. Besides the growth of the gold nanoparticles, two other processes were observed after sputtering, namely aggregation and sedimentation of these nanoparticles. To model the absorption spectra of the sputtered gold nanoparticles, generalized multiparticle Mie calculations were performed. These theoretical calculations confirm the increase in absorbance at longer wavelength for larger aggregates and are in agreement with the experimental observations. It was found that the kinetics of aggregation and sedimentation scale with the viscosity of the ionic liquid. Small amounts of water were found to have a large detrimental influence on the stability of the colloidal suspensions of the gold nanoparticles in ionic liquids. From the large discrepancy between the theoretical and the experimentally observed stability of the NPs, it was concluded that structural forces stabilize the gold nanoparticles. This was also borne out by AFM measurements.

Self-noise-filtering phase-sensitive surface plasmon resonance biosensing

Emerged as an upgrade of currently available Surface Plasmon Resonance (SPR) biosensing in terms of sensitivity, phase-sensitive SPR technology still requires the minimization of instrumental noises to profit from its projected ultra-low detection limit (10(-8) refractive index units and lower). We present a polarimetry-based methodology for the efficient reduction of main instrumental noises in phase-sensitive measurements. The proposed approach employs a sinusoidal phase modulation of pumping light and is based on selection of proper modulation amplitude and initial phase relation for the first two modulation harmonics (F1 and F2), which enables to subtract amplitude drifts in the difference (F1 - F2) signal while doubling the phase response. The resulting effect can be called self-noise-filtering, since it implies an inherent noise subtraction in every phase sensing measurement. This methodology allows one to tackle drifts related to instabilities of light sources and optical elements and thus drastically lower the detection limit of phase-sensitive SPR sensing even in relatively simple and noisy experimental implementations.

Mechanical modulation method for ultrasensitive phase measurements in photonics biosensing.

A novel polarimetry methodology for phase-sensitive measurements in single reflection geometry is proposed for applications in optical transduction-based biological sensing. The methodology uses altering step-like chopper-based mechanical phase modulation for orthogonal s- and p- polarizations of light reflected from the sensing interface and the extraction of phase information at different harmonics of the modulation. We show that even under a relatively simple experimental arrangement, the methodology provides the resolution of phase measurements as low as 0.007 deg. We also examine the proposed approach using Total Internal Reflection (TIR) and Surface Plasmon Resonance (SPR) geometries. For TIR geometry, the response appears to be strongly dependent on the prism material with the best values for high refractive index Si. The detection limit for Si-based TIR is estimated as 10(-5) in terms Refractive Index Units (RIU) change. SPR geometry offers much stronger phase response due to a much sharper phase characteristics. With the detection limit of 3.2*10(-7) RIU, the proposed methodology provides one of best sensitivities for phase-sensitive SPR devices. Advantages of the proposed method include high sensitivity, simplicity of experimental setup and noise immunity as a result of a high stability modulation.

Hyperspectral darkfield microscopy of PEGylated gold nanoparticles targeting CD44‐expressing cancer cells

We present a new hyperspectral darkfield imaging system with a scanned broadband supercontinuum light source. We observed the specific attachment of the functionalized gold plasmonic nanoparticles (AuNPs) targeting CD44(+) human breast cancer cells by conventional and by proposed hyperspectral darkfield microscopy. This wide-field and low phototoxic hyperspectral imaging system has been successful for performing spectral three-dimensional (3D) localization and spectroscopic identification of CD44-targeted PEGylated AuNPs in fixed cell preparations. Such spatial and spectral information is essential for the improvement of nanoplasmonic-based imaging, disease detection and treatment in complex biological environment. Presented system capability for 3D NP tracking will also enable investigation of specific sub-cellular activity with the use of NPs as spectral sensors.

Phase-sensitive silicon-based total internal reflection sensor

A concept of phase-sensitive Si-based Total Internal Reflection bio- and chemical sensor is presented. The sensor uses the reflection of light from an internal edge of a Si prism, which is in contact with analyte material changing its index of refraction (thickness). Changes of the refractive index are monitored by measuring the differential phase shift between p- and s-polarized components of light reflected from the system. We show that due to a high refractive index of Si, such methodology leads to a high sensitivity and dynamic range of measurements. Furthermore, the Si-based platform offers an easy bioimmobilization step and excellent opportunities for the development of multi-channel microsensors taking advantage of the advanced state of development of Si-based microfabrication technologies.