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Surface plasmon resonance

Explanation

Surface plasmons, also known as surface plasmon polaritons, are surface electromagnetic waves that propagate in a direction parallel to the metal/dielectric (or metal/vacuum) interface. Since the wave is on the boundary of the metal and the external medium (air or water for example), these oscillations are very sensitive to any change of this boundary, such as the adsorption of molecules to the metal surface.

To describe the existence and properties of surface plasmons, one can choose from various models (quantum theory, Drude model, etc.). The simplest way to approach the problem is to treat each material as a homogeneous continuum, described by a frequency-dependent relative permittivity between the external medium and the surface. This quantity, hereafter referred to as the materials' "dielectric constant," is complex-valued. In order for the terms which describe the electronic surface plasmons to exist, the real part of the dielectric constant of the metal must be negative and its magnitude must be greater than that of the dielectric. This condition is met in the IR-visible wavelength region for air/metal and water/metal interfaces (where the real dielectric constant of a metal is negative and that of air or water is positive).

Realisation

Otto configuration

Kretschmann configuration

In order to excite surface plasmons in a resonant manner, one can use an electron or light beam (visible and infrared are typical). The incoming beam has to match its impulse to that of the plasmon. In the case of p-polarized light (polarization occurs parallel to the plane of incidence), this is possible by passing the light through a block of glass to increase the wavenumber (and the impulse), and achieve the resonance at a given wavelength and angle. S-polarized (polarization occurs perpendicular to the plane of incidence) light cannot excite electronic surface plasmons. Electronic and magnetic surface plasmons obey the following dispersion relation:

where stands for the dielectric constant, and for the magnetic permeability of the materials (1: the glass block, 2: the metal film).

Typical metals that support surface plasmons are silver and gold, but metals such as copper, titanium or chromium are also known to be applicable.

Using light to excite SP waves, there are two constructions which are well known. In the Otto setup, the light is shone on the wall of a glass block, typically a prism, and totally reflected. A thin metal (for example gold) film is positioned close enough, that the evanescent waves can interact with the plasma waves on the surface and excite the plasmons.

In the Kretschmann configuration, the metal film is evaporated onto the glass block. The light is again illuminating from the glass, and an evanescent wave penetrates through the metal film. The plasmons are excited at the outer side of the film. This configuration is used in most practical applications.

SPR emission

When the surface plasmon wave hits a local particle or irregularityike on a rough surface, part of the energy can be reemitted as light. This emitted light can be detected behind the metal film in various directions.

Applications

Surface plasmons have been used to enhance the surface sensitivity of several spectroscopic measurements including fluorescence, Raman scattering, and second harmonic generation. However, in their simplest form, SPR reflectivity measurements can be used to detect molecular adsorption, such as polymers, DNA or proteins, etc. Technically, it is common, that the angle of the reflection minimum (absorption maximum) is measured. This angle changes in the order of 0.1 during thin (about nm thickness) film adsorption. (See also the Examples.) In other cases the changes in the absorption wavelength is followed. The mechanism of detection is based on that the adsorbing molecules cause changes in the local index of refraction, changing the resonance conditions of the surface plasmon waves.

If the surface is patterned with different biopolymers, using adequate optics and imaging sensors (i.e. a camera), the technique can be extended to surface plasmon resonance imaging (SPRI). This method provides a high contrast of the images based on the adsorbed amount of molecules, somewhat similar to Brewster angle microscopy (this latter is most commonly used together with a Langmuir-Blodgett trough).

For nanoparticles, localized surface plasmon oscillations can give rise to the intense colors of suspensions or sols containing the nanoparticles. Nanoparticles or nanowires of noble metals exhibit strong absorption bands in the ultraviolet-visible light regime that are not present in the bulk metal. This extraordinary absorption increase has been exploited to increase light absorption in photovoltaic cells by depositing metal nanoparticles on the cell surface. The energy (color) of this absorption differs when the light is polarized along or perpendicular to the nanowire. Shifts in this resonance due to changes in the local index of refraction upon adsorption to the nanoparticles can also be used to detect biopolymers such as DNA or proteins. Related complementary techniques include plasmon waveguide resonance, QCM, extraordinary optical transmission, and Dual Polarisation Interferometry

Data interpretation

The most common data interpretation is based on the Fresnel formulas, which treat the formed thin films as infinite, continuous dielectric layers. This interpretation may result multiple possible refractive index and thickness values. However, usually only one solution is within the reasonable data range.

Metal particle plasmons are usually modeled using the Mie scattering theory.

In many cases no detailed models are applied, but the sensors are calibrated for the specific application, and used with interpolation within the calibration curve.

Examples

Layer-by-layer self-assembly

SPR curves measured during the adsorption of a polyelectrolyte and then a clay mineral self-assembled film onto a thin (ca. 38 nanometers) gold sensor.

One of the first common applications of surface plasmon resonance spectroscopy was the measurement of the thickness (and refractive index) of adsorbed self-assembled nanofilms on gold substrates. The resonance curves shift to higher angles as the thickness of the adsorbed film increases. This example is a 'static SPR' measurement.

When higher speed observation is desired, one can select an angle right below the resonance point (the angle of minimum reflectance), and measure the reflectivity changes at that point. This is the so called 'dynamic SPR' measurement. The interpretation of the data assumes, that the structure of the film does not change significantly during the measurement.

Binding constant determination

Association and dissociation signal

Example of output from Biacore

When the affinity of two ligands has to be determined, the binding constant must be determined. It is the equilibrium value for the product quotient. This value can also be found using the dynamical SPR parameters and, as in any chemical reaction, it is the association rate divided by the dissociation rate.

For this, a so-called bait ligand is immobilized on the dextran surface of the SPR crystal. Through a microflow system, a solution with the prey analyte is injected over the bait layer. As the prey analyte binds the bait ligand, an increase in SPR signal (expressed in response units, RU) is observed. After desired association time, a solution without the prey analyte (usually the buffer) is injected on the microfluidics that dissociates the bound complex between bait ligand and prey analyte. Now as the prey analyte dissociates from the bait ligand, a decrease in SPR signal (expressed in response units, RU) is observed. From these association ('on rate', von) and dissociation rates ('off rate', voff), the binding constant can be calculated.

The actual SPR signal can be explained by the electromagnetic 'coupling' of the incident light with the surface plasmon of the gold layer. This plasmon can be influenced by the layer just a few nanometer across the gold-solution interface i.e. the bait protein and possibly the prey protein. Binding makes the reflection angle change;

Magnetic plasmon resonance

Recently, there has been an interest in magnetic surface plasmons. These require materials with large negative magnetic permeability, a property that has only recently been made available with the construction of metamaterials.

References

^ H. M. Hiep et al. (2007). "A localized surface plasmon resonance based immunosensor for the detection of casein in milk" (free download pdf). Sci. Technol. Adv. Mater. 8: 331. doi:10.1016/j.stam.2006.12.010. 

^ S. Pillai, K. R. Catchpole, T. Trupke and M. A. Green (2007). J. Appl. Phys. 101: 093105. 

^ K. Locharoenrat et al. (2007). "Phenomenological studies of optical properties of Cu nanowires" (free download pdf). Sci. Technol. Adv. Mater. 8: 277. doi:10.1016/j.stam.2007.02.001. 

Further reading

A selection of free-download papers on Plasmonics in New Journal of Physics

Heinz Raether (1988). Surface plasmons on smooth and rough surfaces and on gratings. Springer Verlag, Berlin. ISBN 978-3540173632. 

Stefan Maier (2007). Plasmonics: Fundamentals and Applications. Springer. ISBN 978-0387331508. 

Richard B M Schasfoort (Editor) and Anna J Tudos (Editor) (2008). Handbook of Surface Plasmon Resonance. RSC publishing. ISBN 978-0-85404-267-8. 

Hutter E, Fendler J. Exploitation of Localized Surface Plasmon Resonance. Adv. Mater. 2004, 16, 19, 1685-1706.

Aslan K, Lakowicz JR, Geddes C. Plasmon light scattering in biology and medicine: new sensing approaches, visions and perspectives. Current Opinion in Chemical Biology 2005, 9:538544

Smith EA, Corn RM. Surface Plasmon Resonance Imaging as a Tool to Monitor Biomolecular Interactions in an Array Based Format. Appl. Spectroscopy, 2003, 57, 320A-332A.

J. N. Gollub, D. R. Smith, D. C. Vier, T. Perram, J. J. Mock, Phys. Rev. B 71, 195402 (2005)

http://www.astbury.leeds.ac.uk/facil/SPR/spr_intro2004.htm (a short detailed synopsis of how surface plasmon resonance works in practice)

Cheng, S.-F.; Chau, L.-K. olloidal Gold Modified Optical Fiber for Chemical and Biochemical Sensing, Anal. Chem. 2003, 75, 16.

Chau, L.-K.; Lin, Y.-F.; Cheng, S.-F.; Lin, T.-J. iber-optic chemical and biochemical probes based on localized surface plasmon resonance. Sens. Actuators B 2006, 113, 100-105.

Chen, C.-D.; Cheng, S.-F.; Chau, L.-K.; Wang, C. R. C. ensing Capability of the Localized Surface Plasmon Resonance of Gold Nanorods. Biosens. Bioelectron. 2007, 22, 926-932.

Lai, N.-S.; Wang, C.-C.; Chiang, H.-L.; Chau, L.-K. etection of antinuclear antibodies by a colloidal gold-modified optical fiber: Comparison with ELISA. Anal. Bioanal. Chem. 2007, 388, 901-907.

External links

The affinity and valence of an antibody can be determined by equilibrium dialysis (ncbi.nlm.nih.gov)

Plasmon Enhanced Photonics

See also

Waves in plasmas

plasmon

Plasma oscillation

Spinplasmonics

Hydrogen sensor

Nano-optics

Biosensor

Dual Polarization Interferometry

Categories: Electromagnetism | Nanotechnology | Spectroscopy | Biochemistry methods | Biophysics | Forensic techniques
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