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The use of silicon dioxide (SiO(2) ) nanosprings as supports for immobilized enzymes in a continuous microreactor is described. A nanospring mat (2.2 cm(2) × 60 μm thick) was functionalized with γ-aminopropyltriethoxysilane, then treated with N-succinimidyl-3-(2-pyridyldithio)-propionate (SPDP) and dithiothreitol (DTT) to produce surface thiol (--SH) groups. SPDP-modified β-galactosidase from Aspergillus oryzae was immobilized on the thiolated nanosprings by reversible disulfide linkages. The enzyme-coated nanospring mat was placed into a 175-μm high microchannel, with the mat partially occluding the channel. The kinetics and steady-state conversion of hydrolysis of o-nitrophenyl β-D-galactosylpyranoside at various substrate flow rates and concentrations were measured. Substantial flow was observed through the nanosprings, for which the Darcy permeability κ ≈ 3 × 10(-6) cm(2) . A simple, one-parameter numerical model coupling Navier-Stokes and Darcy flow with a pseudo-first-order reaction was used to fit the experimental data. Simulated reactor performance was sensitive to changes in κ and the height of the nanospring mat. Permeabilities lower than 10(-8) cm(2) practically eliminated convective flow through the nanosprings, and substantially decreased conversion. Increasing the height of the mat increased conversion in simulations, but requires more enzymes and could cause sealing issues if grown above channel walls. Preliminary results indicate that in situ regeneration by reduction with DTT and incubation with SPDP-modified β-galactosidase is possible. Nanosprings provide high solvent-accessible surface area with good permeability and mechanical stability, can be patterned into existing microdevices, and are amenable to immobilization of biomolecules. Nanosprings offer a novel and useful support for enzymatic microreactors, biosensors, and lab-on-chip devices.

Chemiresistors were constructed using 3-D silica nanospring mats coated with a contiguous film of ZnO nanocrystals. Chemiresistors with an average ZnO nanocrystal radius <3 nm, or >20 nm, were found to exhibit a relative change in conductance of a factor of 50 upon exposure to a gas flow of 20% O2 and 80% N2 with ∼500 ppm of toluene and an operational temperature of 400 °C. Samples with an average ZnO nanocrystal radius of 15 nm were found to be the most responsive with a relative conductance change of a factor of 1000. The addition of metal nanoparticles (average radius equal to 2.4 nm) onto the surface of the ZnO nanocrystals (average radius equal to 15 nm) produced a relative change in conductance of a factor of 1500. For the optimum conditions (T = 400 °C, grain size ∼15 nm) well-defined spikes in conductance to explosive vapors (TNT, TATP) were obtained for 0.1 ms exposure time at ppb levels.

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Chemiresistors (conductometric sensor) were fabricated on the basis of novel nanomaterials—silica nanosprings ALD coated with ZnO. The effects of high temperature and UV illumination on the electronic and gas sensing properties of chemiresistors are reported. For the thermally activated chemiresistors, a discrimination mechanism was developed and an integrated sensor-array for simultaneous real-time resistance scans was built. The integrated sensor response was tested using linear discriminant analysis (LDA). The distinguished electronic signatures of various chemical vapors were obtained at ppm level. It was found that the recovery rate at high temperature drastically increases upon UV illumination. The feasibility study of the activation method by UV illumination at room temperature was conducted.