Modeling Nonlinear Dynamics of Functionalization Layers: Enhancing Gas Sensor Sensitivity for Piezoelectrically Driven Microcantilever.

This article presents a parametrized response model that enhances the limit of detection (LOD) of piezoelectrically driven microcantilever (PD-MC) based gas sensors by accounting for the adsorption-induced variations in elastic properties of the functionalization layer (binder) and the nonlinear motional dynamics of the PD-MC. The developed model is demonstrated for quantifying cadaverine, a volatile biogenic diamine whose concentration is used to assess the freshness of meat. At low concentrations of cadaverine, an increase in the resonance frequency is observed, contrary to the expected reduction due to mass added by adsorption. The study explores the variations in the elastic modulus vis-à-vis the adsorbed mass of cadaverine and derives the resonance frequency to the adsorbed mass response function. We advance a blended technique involving the analysis of atomic force microscopy (AFM) force-distance (f-d) curves and fitting of the quartz crystal microbalance (QCM) impedance response spectrum to deduce the adsorption-induced changes in the viscoelastic properties of the functionalization layer. The findings obtained are subsequently employed in modeling the response function for a structurally nonhomogenous PD-MC, highlighting the significance of the functionalization layer to the global elastic properties. The structural composition of the PD-MC beam adopted herein features a trapezoidal base hosting the actuating piezoelectric stratum and a rectangular free end with a functionalization layer. The Euler-Bernoulli beam theory coupled with Hamilton's principle is used to develop the equation of motion, which is subsequently discretized into a set of nonlinear ordinary differential equations via Galerkin expansion, and the solutions to the first fundamental mode of vibration are determined using the method of multiple scales. The obtained solutions provide a basis for deducing the nonlinear response function model to the adsorbed mass. The derived model is validated by recorded resonance frequency changes resulting from exposure to known concentrations of cadaverine. We demonstrate that the increase in resonance frequency for low concentrations of cadaverine is due to the dominance of the variation of the elastic modulus of the functionalization layer originating from the initial binder-analyte interactions over damping due to added mass. It is concluded that the developed nonlinear response function model can reliably be used to quantify the cadaverine concentration at low concentrations with an elevated Limit of Detection.

Gas Adsorption Response of Piezoelectrically Driven Microcantilever Beam Gas Sensors: Analytical, Numerical, and Experimental Characterizations.

This work presents an approach for the estimation of the adsorbed mass of 1,5-diaminopentane (cadaverine) on a functionalized piezoelectrically driven microcantilever (PD-MC) sensor, using a polynomial developed from the characterization of the resonance frequency response to the known added mass. This work supplements the previous studies we carried out on the development of an electronic nose for the measurement of cadaverine in meat and fish, as a determinant of its freshness. An analytical transverse vibration analysis of a chosen microcantilever beam with given dimensions and desired resonance frequency (>10 kHz) was conducted. Since the beam is considered stepped with both geometrical and material non-uniformity, a modal solution for stepped beams, extendable to clamped-free beams of any shape and structure, is derived and used for free and forced vibration analyses of the beam. The forced vibration analysis is then used for transformation to an equivalent electrical model, to address the fact that the microcantilever is both electronically actuated and read. An analytical resonance frequency response to the mass added is obtained by adding simulated masses to the free end of the beam. Experimental verification of the resonance frequency response is carried out, by applying known masses to the microcantilever while measuring the resonance frequency response using an impedance analyzer. The obtained response is then transformed into a resonance frequency to the added mass response polynomial using a polynomial fit. The resulting polynomial is then verified for performance using different masses of cantilever functionalization solution. The functionalized cantilever is then exposed to different concentrations of cadaverine while measuring the resonance frequency and mass of cadaverine adsorbed estimated using the previously obtained polynomial. The result is that there is the possibility of using this approach to estimate the mass of cadaverine gas adsorbed on a functionalized microcantilever, but the effectiveness of this approach is highly dependent on the known masses used for the development of the response polynomial model.

Novel cadaverine non-invasive biosensor technology for the prediction of shelf life of modified atmosphere packed pork cutlets.

Food waste in perishable products calls for the development of cost-efficient and real-time freshness and shelf life assessment tools. The current study evaluated a newly developed cadaverine biosensor for its ability to assess the sensory freshness stage and microbial quality of modified atmosphere packed (MAP) pork cutlets under a realistic supply chain scenario. The experiment compared the cadaverine levels measured by the biosensor to liquid chromatography - tandem mass spectrometry (LC-MS/MS) cadaverine concentrations, and associated these to the shelf life estimation and freshness states determined by sensory and microbial evaluations during an 18-day storage period (5 °C). Results underlined the potential of cadaverine as a freshness biomarker as well as the applicability of the biosensor as a shelf life prediction tool. This is supported by the correlations obtained between sensory odour freshness evaluation and total viable counts with biosensor cadaverine levels for which the r obtained were 0.97 (<0.001) and 0.95 (<0.001), respectively.

Surface Modification Enabling Reproducible Cantilever Functionalization for Industrial Gas Sensors.

Micro-cantilever sensors are a known reliable tool for gas sensing in industrial applications. We have demonstrated the application of cantilever sensors on the detection of a meat freshness volatile biomarker (cadaverine), for determination of meat and fish precise expiration dates. For achieving correct target selectivity, the cantilevers need to be functionalized with a cadaverine-selective binder, based on a cyclam-derivative. Cantilever surface properties such as surface energy strongly influence the binder morphology and material clustering and, therefore, target binding. In this paper, we explore how chemical and physical surface treatments influence cantilever surface, binder morphology/clustering and binding capabilities. Sensor measurements with non-controlled surface properties are presented, followed by investigations on the binder morphology versus surface energy and cadaverine capture. We demonstrated a method for hindering binder crystallization on functionalized surfaces, leading to reproducible target capture. The results show that cantilever surface treatment is a promising method for achieving a high degree of functionalization reproducibility for industrial cantilever sensors, by controlling binder morphology and uniformity.