Reader-friendly Edible Binarycodes and Sensors Based on Smart Hydrogel

Abstract

Food and medicines are two of the most essential categories of goods for human beings, providing vital nourishment and healthcare. However, as these products are commercialized and distributed on a global scale, consumers face the threat of counterfeit and deteriorated products. In response, this dissertation presents four prototypes consisting of On-Dose-Authentication (ODA) binarycodes and battery-less indicators based on smart hydrogel that are edible and reader-friendly to address these issues.

First, a microfluidic platform for continuous synthesis of hydrogel microparticles with superparamagnetic colloids (SPCs) embedded at prescribed positions has been established. The shape of the cross-linked microparticle is independently controlled by stop-flow lithography, whereas the position of trapped SPCs is dictated by virtual magnetic molds made of 2D nickel patches facilitating magnetic trapping. The spatial positions of trapped SPCs collectively function as a binary code matrix for product authentication. The proposed magnetic microparticles will contribute to the development of soft matter-inspired product quality control, tracking, and anti-counterfeiting technologies. (Chapter 2)

Second, a Physical Unclonable Functions (PUF) algorithm was developed to enhance the ODA binary codes' safety level. This algorithm exploits the diameter and coordinates of spheres as input, abandoning color and intensity as inputs, enabling imaging using common illumination and low-magnification microscopy hence lifting the reading constraints to advanced labs that are usually found in other current graphical PUF systems. Two sets of Poly(ethylene glycol) diacrylate ODA-PUF tags that can be read out via this algorithm were fabricated. The sets are single-diameter PUF leveraging random distributed superparamagnetic colloids of identical diameters and multiple-diameter PUF utilizing vortexed sunflower oil drops of various diameters, respectively. The performance of the single-diameter system was investigated. It passed NIST Statistical tests, demonstrating sufficient randomness, ideal bit uniformity, Hamming distance, and device uniqueness. The encoding capacity of the single-diameter system was found to be $9.2 imes10^{18}$, which can satisfy labeling the annual output of Aspirin. (Chapter 3)

Third, a humidity indicator has been created that mechanically bends and rolls itself irreversibly upon exposure to high humidity conditions. The indicator is made of two food-grade polymer films with distinct ratios of a milk protein, casein, and a plasticizer, glycerol, that are physically attached to each other. Based on the thermogravimetric analysis and microstructural characterization, the bending mechanism is a result of hygroscopic swelling and consequent counter diffusion of water and glycerol. Guided by this mechanism, the rolling behavior, including response time and final curvature, can be tuned by the geometric dimensions of the indicator. As the proposed indicator is made of food-grade ingredients, it can be placed directly in contact with perishable products to report exposure to undesirable humidity inside the package, without the risk of contaminating the product or causing oral toxicity in case of accidental ingestion - features that commercial inedible electronic and chemo-chromatic sensors cannot provide presently. (Chapter 4)

Finally, an alginate TTI bead that encapsulates betacyanin, a natural colorant extracted from purple pitaya, is proposed to continuously monitor and reflect the temperature history of the perishable products to diagnose the storage conditions. The instability of betacyanin is exploited to demonstrate undesirable temperature abuse through visual color changes. The thermochromic change of the purple pitaya extract and the pitaya-extract-encapsulated bead was investigated under various temperatures, pH, and gaseous atmosphere conditions. Experimental results show that the proposed TTI exhibits an irreversible thermochromic change under a wide operation temperature range up to at least 100 extdegree C with negligible disturbance from the gaseous composition. (Chapter 5)