ABSTRACT
Improved chemical- and bio-sensing with Surface Enhanced Raman Spectroscopy (SERS) requires nanostuctures that can be flexibly designed and fabricated with different physical and optical properties. Here, we present nano-pillar arrays ranging from 200 nm to 600 nm as SERS substrates for mycotoxin detection that are fabricated by means of two-photon polymerization. We built a nominal shape and a voxel-based model for simulating the enhancement of the electric field of the nano-pillar arrays using the Finite-Difference Time-Domain (FDTD) method. A new model was built based on the Atomic Force Microscopy (AFM) data obtained from the fabricated nanostructures and introduced into a FDTD model. We demonstrated the enhancement behavior by measuring the Raman spectrum of Rhodamine B solutions. Both the simulations and experimental results suggest that the 200 nm nano-pillar array has the highest Enhancement Factor (EF). Besides, we determined the limit of detection of the 200 nm pillar array by performing Raman measurements on Rhodamine B solutions with different concentrations. The detection limit of our 200 nm nano-pillar array is 0.55 µM. Finally we discriminated 1 ppm deoxynivalenol and 1.25 ppm fumonisin b1 in acetonitrile solutions by our SERS substrate in combination with principal component analysis. This versatile approach for SERS substrates fabrication gives new opportunities for material characterization in chemical and biological applications.
ABSTRACT
Thermosensitive chitosan hydrogels containing sodium beta-glycerophosphate (ß-GP), whose gelation is induced by increasing temperature to body temperature, were functionalized by incorporation of alkaline phosphatase (ALP), an enzyme involved in mineralization of bone. ALP incorporation led to acceleration of gelation upon increase of temperature for four different chitosan preparations of differing molecular weight, as demonstrated by rheometric time sweeps at 37 °C. Hydrogels containing ALP were subsequently incubated in calcium glycerophosphate (Ca-GP) solution to induce their mineralization with calcium phosphate (CaP) in order to improve their suitability as materials for bone replacement. Incorporated ALP retained its bioactivity and induced formation of CaP mineral, as confirmed by SEM, FTIR, Raman spectroscopy, XRD, ICP-OES, and increases in dry mass percentage, which rose with increasing ALP concentration and incubation time in Ca-GP solution. The results demonstrate that ALP accelerates formation of thermosensitive chitosan/ß-GP hydrogels and induces their mineralization with CaP, which paves the way for applications as injectable bone replacement materials.
