New optical nanoresonance effects enabled us to study the effect of ions on nanometric carbohydrate thin layers on chips. Immobilization was done via spin coating of the derivatized carbohydrate polymer at a metallized chip surface forming ultrathin films (about 50-300 nm thick) followed by photochemical cross-linking. Deposition of metal-nanoclusters, synthesized by chemical means and sputter coating on top of the polymer, induced an optical resonance effect, which transduced changes of polymer structure quantitatively into an optical signal that can be observed directly as resonance shift of a narrow optical peak. The response of the sensor chip even visible to the eye was quantified spectroscopically in the visible and ir range of the spectrum. The lifetime of thin film was good, and thus application as a sensor was limited only by the mechanical stability of the reactive matrix, but not by photobleaching or molecular leakage. Due to the inherent hydrophilic nature of the alginate polymer, the response time of this new sensor is governed by simple aqueous diffusion of the ionic calcium for up to 300 nm completed within less than one second. Monitoring of calcium fluctuations in a high background of magnesium and even serum was demonstrated with a dynamic range optimal for physiological measurements and a linear response up to 5 mM. Surface and alignment of polymer chain were influenced by the nanostructure of the supporting metal film-contrary to alginic acid, chitosan was deposited well aligned to the nanocrystals of the support.
Copyright 2003 Wiley Periodicals, Inc. Biopolymers 69: 333-342, 2003