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Multi-parametric surface plasmon resonance (MP-SPR) is based on surface plasmon resonance (SPR), an established real-time label-free method for biomolecular interaction analysis, but it uses a different optical setup, a goniometric SPR configuration. While MP-SPR provides same kinetic information as SPR (equilibrium constant, dissociation constant, association constant), it provides also structural information (refractive index, layer thickness). Hence, MP-SPR measures both surface interactions and nanolayer properties.^[1]

History

The goniometric SPR method was researched alongside focused beam SPR and Otto configurations at VTT Technical Research Centre of Finland since 1980s by Dr. Janusz Sadowski.^[2] The goniometric SPR optics was commercialized by Biofons Oy for use in point-of-care applications. Introduction of additional measurement laser wavelengths and first thin film analyses were performed in 2011 giving way to MP-SPR method.

Principle

The MP-SPR optical setup measures at multiple wavelengths simultaneously (similarly to spectroscopic SPR), but instead of measuring at a fixed angle, it rather scans across a wide range of θ angles (for instance 40 degrees). This results in measurements of full SPR curves at multiple wavelengths providing additional information about structure and dynamic conformation of the film.^[3]

Measured values

The measured full SPR curves (x-axis: angle, y-axis: reflected light intensity) can be transcribed into sensograms (x-axis: time, y-axis: selected parameter such as peak minimum, light intensity, peak width).^[4] The sensograms can be fitted using binding models to obtain kinetic parameters including on- and off-rates and affinity. The full SPR curves are used to fit Fresnel equations to obtain thickness and refractive index of the layers. Also due to the ability of scanning the whole SPR curve, MP-SPR is able to separate bulk effect and analyte binding from each other using parameters of the curve.

Molecular interactions	Layer properties
Kinetics, PureKinetics (k_on, k_off)	Refractive index (n)
Affinity (K_D)	Thickness (d)
Concentration (c)	Extinction coefficient (k)
Adsorption/Absorption	Density (ρ)
Desorption	Surface coverage (Γ)
Adhesion	Swelling (Δd)
Electrochemistry (E, I, omega)	Optical dispersion (n(λ))

While QCM-D measures wet mass, MP-SPR and other optical methods measure dry mass, which enables analysis of water content of nanocellulose films.

Applications

The method has been used in life sciences, material sciences and biosensor development. In life sciences, the main applications focus on pharmaceutical development including small-molecule, antibody or nanoparticle interactions with target with a biomembrane^[5] or with a living cell monolayer.^[4] As first in the world, MP-SPR is able to separate transcellular and paracellular drug uptake^[4] in real-time and label-free for targeted drug delivery. In biosensor development, MP-SPR is used for assay development for point-of-care applications.^[3]^[6]^[7]^[8] Typical developed biosensors include electrochemical printed biosensors, ELISA and SERS. In material sciences, MP-SPR is used for optimization of thin solid films from Ångströms to 100 nanometers (graphene, metals, oxides),^[9] soft materials up to microns (nanocellulose, polyelectrolyte) including nanoparticles. Applications including thin film solar cells, barrier coatings including anti-reflective coatings, antimicrobial surfaces, self-cleaning glass, plasmonic metamaterials, electro-switching surfaces, layer-by-layer assembly, and graphene.^[10]^[11]^[12]^[13]

References

^ Korhonen, Kristiina; Granqvist, Niko; Ketolainen, Jarkko; Laitinen, Riikka (October 2015). "Monitoring of drug release kinetics from thin polymer films by multi-parametric surface plasmon resonance". International Journal of Pharmaceutics. 494 (1): 531–536. doi:10.1016/j.ijpharm.2015.08.071. PMID 26319634.
^ Sadowski, J. W.; Korhonen, I.; Peltonen, J. (1995). "Characterization of thin films and their structures in surface plasmon resonance measurements". Optical Engineering. 34 (9): 2581–2586. Bibcode:1995OptEn..34.2581S. doi:10.1117/12.208083.
^ ^a ^b Wang, Huangxian Ju, Xueji Zhang, Joseph (2011). NanoBiosensing : principles, development, and application. New York: Springer. p. chapter 4. ISBN 978-1-4419-9621-3.{{cite book}}: CS1 maint: multiple names: authors list (link)
^ ^a ^b ^c Viitala, Tapani; Granqvist, Niko; Hallila, Susanna; Raviña, Manuela; Yliperttula, Marjo; van Raaij, Mark J. (27 August 2013). "Elucidating the Signal Responses of Multi-Parametric Surface Plasmon Resonance Living Cell Sensing: A Comparison between Optical Modeling and Drug–MDCKII Cell Interaction Measurements". PLOS ONE. 8 (8): e72192. Bibcode:2013PLoSO...872192V. doi:10.1371/journal.pone.0072192. PMC 3754984. PMID 24015218.
^ Garcia-Linares, Sara; Palacios-Ortega, Juan; Yasuda, Tomokazu; Åstrand, Mia; Gavilanes, Jose G.; Martinez-del-Pozo, Alvaro; Slotte, J.Peter (2016). "Toxin-induced pore formation is hindered by intermolecular hydrogen bonding in sphingomyelin bilayers". Biomembranes. 1858 (6): 1189–1195. doi:10.1016/j.bbamem.2016.03.013. PMID 26975250.
^ Souto, Dênio E.P.; Fonseca, Aliani M.; Barragan, José T.C.; Luz, Rita de C.S.; Andrade, Hélida M.; Damos, Flávio S.; Kubota, Lauro T. (August 2015). "SPR analysis of the interaction between a recombinant protein of unknown function in Leishmania infantum immobilised on dendrimers and antibodies of the visceral leishmaniasis: A potential use in immunodiagnosis". Biosensors and Bioelectronics. 70: 275–281. doi:10.1016/j.bios.2015.03.034. PMID 25829285.
^ Sonny, Susanna; Virtanen, Vesa; Sesay, Adama M. (2010). "Development of diagnostic SPR based biosensor for the detection of pharmaceutical compounds in saliva". SPIE Laser Applications in Life Sciences. 7376 (5): 737605. Bibcode:2010SPIE.7376E..05S. doi:10.1117/12.871116. S2CID 95200834.
^ Ihalainen, Petri; Majumdar, Himadri; Viitala, Tapani; Törngren, Björn; Närjeoja, Tuomas; Määttänen, Anni; Sarfraz, Jawad; Härmä, Harri; Yliperttula, Marjo; Österbacka, Ronald; Peltonen, Jouko (27 December 2012). "Application of Paper-Supported Printed Gold Electrodes for Impedimetric Immunosensor Development". Biosensors. 3 (1): 1–17. doi:10.3390/bios3010001. PMC 4263588. PMID 25587396.
^ Taverne, S.; Caron, B.; Gétin, S.; Lartigue, O.; Lopez, C.; Meunier-Della-Gatta, S.; Gorge, V.; Reymermier, M.; Racine, B.; Maindron, T.; Quesnel, E. (2018-01-12). "Multispectral surface plasmon resonance approach for ultra-thin silver layer characterization: Application to top-emitting OLED cathode". Journal of Applied Physics. 123 (2): 023108. Bibcode:2018JAP...123b3108T. doi:10.1063/1.5003869. ISSN 0021-8979.
^ Jussila, Henri; Yang, He; Granqvist, Niko; Sun, Zhipei (5 February 2016). "Surface plasmon resonance for characterization of large-area atomic-layer graphene film". Optica. 3 (2): 151. Bibcode:2016Optic...3..151J. doi:10.1364/OPTICA.3.000151.
^ Emilsson, Gustav; Schoch, Rafael L.; Feuz, Laurent; Höök, Fredrik; Lim, Roderick Y. H.; Dahlin, Andreas B. (15 April 2015). "Strongly Stretched Protein Resistant Poly(ethylene glycol) Brushes Prepared by Grafting-To". ACS Applied Materials & Interfaces. 7 (14): 7505–7515. doi:10.1021/acsami.5b01590. PMID 25812004.
^ Vuoriluoto, Maija; Orelma, Hannes; Johansson, Leena-Sisko; Zhu, Baolei; Poutanen, Mikko; Walther, Andreas; Laine, Janne; Rojas, Orlando J. (10 December 2015). "Effect of Molecular Architecture of PDMAEMA–POEGMA Random and Block Copolymers on Their Adsorption on Regenerated and Anionic Nanocelluloses and Evidence of Interfacial Water Expulsion". The Journal of Physical Chemistry B. 119 (49): 15275–15286. doi:10.1021/acs.jpcb.5b07628. PMID 26560798.
^ Granqvist, Niko; Liang, Huamin; Laurila, Terhi; Sadowski, Janusz; Yliperttula, Marjo; Viitala, Tapani (9 July 2013). "Characterizing Ultrathin and Thick Organic Layers by Surface Plasmon Resonance Three-Wavelength and Waveguide Mode Analysis". Langmuir. 29 (27): 8561–8571. doi:10.1021/la401084w. PMID 23758623.