Larisa Florea

Self-protonating spiropyran-co-NIPAM-co-acrylic acid hydrogel photoactuators

Up to now, photoresponsive hydrogels and ionogels based on poly(N-isopropylacrylamide) copolymerised with pendant spiropyran groups require exposure to external acidic solution (usually milimolar HCl) to generate the swollen gel prior to photo-triggered contraction. This serious functional limitation has been solved by copolymerising acrylic acid into the gel matrix, to provide an internal source of protons. Due to the relative pKa values of acrylic acid and the spiropyran and merocyanine isomers, the protonation and deprotonation occurs internally within the gel and there is no need for an external source of protons. Furthermore, the shrinking–expansion cycles of these gels in deionised water are repeatable, as protonation throughout the gel does not rely on movement of protons from an external acidic solution into the bulk gel. In contrast to previous formulations, these gels do not show degradation of their photo-induced shrinking ability after multiple washings in deionised water and repeated switching over a 2 month period.

Spiropyran polymeric microcapillary coatings for photodetection of solvent polarity.

Fused silica microcapillaries were functionalized with spiropyran-polymer brushes using surface-initiated ring-opening metathesis polymerization. Based on the inherited spiropyran properties, the functionalized capillaries were successfully used to photoidentify solvents of different polarity when passing through the microcapillary in continuous flow. In the present study, six different solvents (toluene, tetrahydrofuran, acetone, acetonitrile, ethanol, and methanol) can be easily detected while passing through the modified microcapillary by simply irradiating a portion of it with UV light (365 nm). This converts the closed spiropyran moiety to the open merocyanine form, and as a consequence, the microcapillary gains a distinct color and spectral response depending on the polarity of the solvent. The rate of ring-opening of the spiropyran-polymer brushes coatings has been determined in situ in the presence of different solvents, showing that the coloration rate is also influenced by the solvent polarity and therefore can be used as an additional parameter for solvent sensing.

Photoswitchable ratchet surface topographies based on self protonating spiropyran-NIPAAM hydrogels

In this work, self-protonating spiropyran-based poly(N-isopropylacrylamide) polymer networks are prepared. These photoresponsive hydrogel coatings can change their surface topography upon exposure with visible light in a neutral environment. Photoresponsive surface-constrained films have been fabricated for which the swelling behavior can be controlled in a reversible manner. In a first step, symmetrical switchable surface topologies with varying cross-link density are obtained by polymerization-induced diffusion. Under light exposure, the areas with low cross-link density swell more than the areas with high cross-link density, thus forming a corrugated surface. Asymmetric ratchet-like photoresponsive surfaces have been prepared on prestructured asymmetric substrates. As a result of thickness variation of the surface-confined hydrogel layer, an asymmetric swelling behavior is obtained. Depending on the cross-link density of the hydrogel, it is possible to switch between a ratchet and flat surface topography or even an inverse ratchet surface by light.

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.

Poly(Ionic Liquid) Semi-Interpenetrating Network Multi-Responsive Hydrogels.

Herein we describe poly(ionic liquid) hydrogel actuators that are capable of responding to multiple stimuli, namely temperature, ionic strength and white light irradiation. Using two starting materials, a crosslinked poly ionic liquid (PIL) and a linear poly(N-isopropylacrylamide-co-spiropyran-co-acrylic acid), several semi-interpenetrating (sIPN) hydrogels were synthesised. The dimensions of hydrogels discs were measured before and after applying the stimuli, to quantify their response. Samples composed of 100% crosslinked PIL alone showed an average area reduction value of ~53% when the temperature was raised from 20 °C to 70 °C, ~24% when immersed in 1% w/w NaF salt solution and no observable photo-response. In comparison, sIPNs containing 300% w/w linear polymer showed an average area reduction of ~45% when the temperature was raised from 20 °C to 70 °C, ~36% when immersed in 1% NaF w/w salt solution and ~10% after 30 min exposure to white light irradiation, respectively. Moreover, by varying the content of the linear component, fine-control over the photo-, thermo- and salt response, swelling-deswelling rate and mechanical properties of the resulting sIPN was achieved.

Wearable Bio and Chemical Sensors

Wearable chemical and biochemical sensors are a relatively new area of sensor research that poses unique challenges to the field of wearable sensing. The reason is that chemical sensors have a different mode of operation compared to physical transducers, and thus must be directly exposed, and interact with, specific molecular components in (usually liquid) samples. Wearable chemical and biochemical sensing has the potential to provide new sources of non-invasive physiological information through interaction with a variety of body fluids, such as sweat and interstitial fluids. This information may be used to enhance personal health through early detection of illness that in turn can trigger early interventions. There is also the potential to ensure personal safety by monitoring hazardous substances in the individual’s external environment. This chapter explains the design issues of wearable chemical sensors. Some of the main application areas of this novel technology are discussed with examples of the latest research developments.

Swelling and shrinking properties of thermo-responsive polymeric ionic liquid hydrogels with embedded linear pNIPAAM.

In this study, varying concentrations of linear pNIPAAM have been incorporated for the first time into a thermo-responsive polymeric ionic liquid (PIL) hydrogel, namely tributyl-hexyl phosphonium 3-sulfopropylacrylate (P-SPA), to produce semi-interpenetrating polymer networks. The thermal properties of the resulting hydrogels have been investigated along with their thermo-induced shrinking and reswelling capabilities. The semi-interpenetrating networks (IPN) hydrogels were found to have improved shrinking and reswelling properties compared with their PIL counterpart. At elevated temperatures (50–80 °C), it was found that the semi-IPN with the highest concentration of hydrophobic pNIPAAM exhibited the highest shrinking percentage of ~40% compared to the conventional P-SPA, (27%). This trend was also found to occur for the reswelling measurements, with semi-IPN hydrogels producing the highest reswelling percentage of ~67%, with respect to its contracted state. This was attributed to an increase in water affinity due to the presence of hydrophilic pNIPAAM. Moreover, the presence of linear pNIPAAM in the polymer matrix leads to improved shrinking and reswelling response compared to the equivalent PIL.

Temperature and pH triggered release characteristics of water/fluorescein from 1-ethyl-3-methylimidazolium ethylsulfate based ionogels

A crosslinked poly(N-isopropylacrylamide) ionogel encapsulating an ionic liquid exhibits improved transmittance properties, enhanced water uptake/release, greater thermal actuation behaviour and distinct solvatomorphology over its hydrogel equivalent. It was also found that the rate of release of fluorescein pre-loaded into membranes was considerably enhanced for ionogels compared to equivalent hydrogels, and could be triggered through changes in pH and temperature.

Thiol-Ene Photo-Click Collagen-PEG Hydrogels: Impact of Water-Soluble Photoinitiators on Cell Viability, Gelation Kinetics and Rheological Properties

Thiol-ene photo-click hydrogels were prepared via step-growth polymerisation using thiol-functionalised type-I collagen and 8-arm poly(ethylene glycol) norbornene-terminated (PEG-NB), as a potential injectable regenerative device. Type-I collagen was thiol-functionalised by a ring opening reaction with 2-iminothiolane (2IT), whereby up to 80 Abs. % functionalisation and 90 RPN% triple helical preservation were recorded via 2,4,6-Trinitrobenzenesulfonic acid (TNBS) colorimetric assay and circular dichroism (CD). Type, i.e., either 2-Hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-propanone (I2959) or lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP), and concentration of photoinitiator were varied to ensure minimal photoinitiator-induced cytotoxicity and to enable thiol-ene network formation of collagen-PEG mixtures. The viability of G292 cells following 24 h culture in photoinitiator-supplemented media was largely affected by the photoinitiator concentration, with I2959-supplemented media observed to induce higher toxic response (0.1 → 0.5% (w/v) I2959, cell survival: 62 → 2 Abs. %) compared to LAP-supplemented media (cell survival: 86 → 8 Abs. %). In line with the in vitro study, selected photoinitiator concentrations were used to prepare thiol-ene photo-click hydrogels. Gelation kinetics proved to be largely affected by the specific photoinitiator, with LAP-containing thiol-ene mixtures leading to significantly reduced complete gelation time (τ: 187 s) with respect to I2959-containing mixtures (τ: 1683 s). Other than the specific photoinitiator, the photoinitiator concentration was key to adjusting the hydrogel storage modulus (G’), whereby 15-fold G’ increase (232 → 3360 Pa) was observed in samples prepared with 0.5% (w/v) compared to 0.1% (w/v) LAP. Further thiol-ene formulations with 0.5% (w/v) LAP and varied content of PEG-NB were tested to prepare photo-click hydrogels with porous architecture, as well as tunable storage modulus (G’: 540–4810 Pa), gelation time (τ: 73–300 s) and swelling ratio (SR: 1530–2840 wt %). The photoinitiator-gelation-cytotoxicity relationships established in this study will be instrumental to the design of orthogonal collagen-based niches for regenerative medicine.

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.