Colm Delaney

Glucose Sensing for Diabetes Monitoring: Recent Developments

This review highlights recent advances towards non-invasive and continuous glucose monitoring devices, with a particular focus placed on monitoring glucose concentrations in alternative physiological fluids to blood.

Solvato-morphologically controlled, reversible NIPAAm hydrogel photoactuators

Photo-actuator hydrogels were generated using a N-isopropylacrylamide-co-acrylated spiropyran-co-acrylic acid (p(NIPAAm-co-SP-co-AA)) copolymer, in 100–1–5 mole ratio. Different ratios of deionised water : organic solvent (tetrahydrofuran, dioxane and acetone) were used as the polymerisation solvent. By changing the polymerisation solvent, the pore size and density of the hydrogels were altered, which in turn had an impact on the diffusion path-length of water molecules, thus influencing the swelling and photo-induced shrinking kinetics of the hydrogel. We successfully demonstrated that the polymerisation solvent has a significant effect on the curing time, the elasticity and morphology of the resulting hydrogel. The highest shrinking ratio was obtained for hydrogels produced using 4 : 1 acetone : deionised water (CI) as the polymerisation solvent, with the hydrogel reaching 39.56% (±2.37% (n = 3)) of its hydrated area after 4 min of white light irradiation followed by reswelling in the dark to 61.95% (±5.76% (n = 3)) after 11 min. Conversely, the best reswelling capabilities were obtained for the hydrogels produced using 1 : 1 tetrahydrofuran : deionised water (AIII), when the shrunk hydrogel (61.78 ± 0.26% (n = 3)) regained 91.31% (±0.22% (n = 3)) of its original size after 11 min in the dark. To our knowledge, this is the largest reported photo-induced area change for self-protonated spiropyran containing hydrogels. The shrinking/reswelling process was completely reversible in DI water with no detectable hysteresis over three repeat irradiation cycles.

Micro-Capillary Coatings Based on Spiropyran Polymeric Brushes for Metal Ion Binding, Detection, and Release in Continuous Flow

Micro-capillaries, capable of light-regulated binding and qualitative detection of divalent metal ions in continuous flow, have been realised through functionalisation with spiropyran photochromic brush-type coatings. Upon irradiation with UV light, the coating switches from the passive non-binding spiropyran form to the active merocyanine form, which binds different divalent metal ions (Zn2+, Co2+, Cu2+, Ni2+, Cd2+), as they pass through the micro-capillary. Furthermore, the merocyanine visible absorbance spectrum changes upon metal ion binding, enabling the ion uptake to be detected optically. Irradiation with white light causes reversion of the merocyanine to the passive spiropyran form, with simultaneous release of the bound metal ion from the micro-capillary coating.

Photoswitchable layer-by-layer coatings based on photochromic polynorbornenes bearing spiropyran side groups

Herein, we present the synthesis of linear photochromic norbornene polymers bearing spiropyran side groups (poly(SP-R)) and their assembly into layer-by-layer (LbL) films on glass substrates when converted to poly(MC-R) under UV irradiation. The LbL films were composed of bilayers of poly(allylamine hydrochloride) (PAH) and poly(MC-R), forming (PAH/poly(MC-R)) n coatings. The merocyanine (MC) form presents a significant absorption band in the visible spectral region, which allowed tracking of the LbL deposition process by UV-vis spectroscopy, which showed a linear increase of the characteristic MC absorbance band with increasing number of bilayers. The thickness and morphology of the (PAH/poly(MC-R)) n films were characterized by ellipsometry and scanning electron microscopy, respectively, with a height of ∼27.5 nm for the first bilayer and an overall height of ∼165 nm for the (PAH/poly(MC-R))5 multilayer film. Prolonged white light irradiation (22 h) resulted in a gradual decrease of the MC band by 90.4 ± 2.9% relative to the baseline, indicating the potential application of these films as coatings for photocontrolled delivery systems.

Fluorescent Probes for Sugar Detection

Herein, a new class of polymerizable boronic acid (BA) monomers are presented, which are used to generate soft hydrogels capable of accurate determination of saccharide concentration. By exploiting the interaction of these cationic BAs with an anionic fluorophore, 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (pyranine), a two-component sugar-sensing system was realized. In the presence of such cationic BAs ( o-BA, m-BA, and p-BA), the fluorescence of pyranine becomes quenched because of the formation of a nonfluorescent BA-fluorophore complex. Upon addition of saccharides, formation of a cyclic boronate ester results in dissociation of the nonfluorescent complex and recovery of the pyranine fluorescence. The response of this system was examined in solution with common monosaccharides, such as glucose, fructose, and galactose. Subsequent polymerization of the BA monomers yielded cross-linked hydrogels which showed similar reversible recovery of fluorescence in the presence of glucose.

CHAPTER 9:Applications of Ionic Liquid Materials in Microfluidic Devices

“Lab-on-a-chip” (LOC) and microfluidics enable the manipulation of fluids at small length scales (from micrometers to millimeters). These systems often have well-defined fabrication processes and are capable of integrating multiple functional elements, to provide complete sample-in/answer-out systems. Nevertheless, the development of fully integrated microfluidic devices still faces some considerable obstacles, including fluidic control, miniaturisation and high costs. Due to their unique properties, ionic liquids have arisen as smart solutions to circumvent some of the hurdles facing current LOC technologies. They can directly benefit microfluidic devices by aiding miniaturised fabrication and passive microfluidic elements for fluid control, sensing and sample storage. Improved chemical reactions and separation, in addition to power generation, temperature control, and electrowetting show potential for reducing manufacturing costs and widening market possibilities. In this chapter we will review and discuss the fundamental applications of ionic liquids within microfluidic systems.

Precise Flow-Control Using Photo-Actuated Hydrogel Valves and Pid-controlled LED Actuation

Herein we demonstrate remarkable control of flow within fluidic channels using photo-actuated hydrogel valves. By polymerizing the valves in situ it has been possible to create highly- reproducible valves. Through the use of an LED platform and a PID algorithm we have generated extremely accurate flow control and created prototype devices to document their potential application within the microfluidics field.

Stimuli-Controlled Manipulation of Synthetic Micrometre-Sized Vehicles for Bio-Inspired Fluidics

Controlled movement in fluids is essential to the function of living systems. The desire of [...]

Stimuli-controlled fluid control and microvehicle movement in microfluidic channels

Integration of stimuli-responsive materials into microfluidic systems provides a means to locally manipulate flow at the microscale, in a noninvasive manner, while also reducing system complexity. In recent years, several modes of stimulation have been applied, including electrical, magnetic, light and temperature, among others. To achieve remote control of flow in microfluidics using external stimulation, two main approaches have emerged in the recent years: