Direct Laser Writing of Silica Nanoparticle Nanocomposites: Probing Mechanical Reinforcement and Understanding Structural Color from Design Parameters.

Nanocomposite materials have been thoroughly exploited in additive manufacturing, as a means to alter physical, chemical, and optical properties of resulting structures. Herein, nanocomposite materials suitable for direct laser writing (DLW) by two-photon polymerization are presented. These materials, comprising silica nanoparticles, bring significant added value to the technology through physical reinforcement and controllable photonic properties.

Liquid Crystalline Network Microstructures for Stimuli Responsive Labels with Multi-Level Encryption.

Two-photon direct laser writing enables the fabrication of shape-changing microstructures that can be exploited in stimuli responsive micro-robotics and photonics. The use of Liquid Crystalline Networks (LCN) allows to realize 3D micrometric objects that can contract along a specific direction in response to stimuli, such as temperature or light. In this paper, the fabrication of free-standing LCN microstructures is demonstrated as graphical units of a smart tag for simple physical and optical encryption.

Controlled degradation of polycaprolactone-based micropillar arrays.

Herein we demonstrate the fabrication of arrays of micropillars, achieved through the combination of direct laser writing and nanoimprint lithography. By combining two diacrylate monomers, polycaprolactone dimethacrylate (PCLDMA) and 1,6-hexanediol diacrylate (HDDA), two copolymer formulations that, owing to the varying ratios of the hydrolysable ester functionalities present in the polycaprolactone moiety, can be degraded in the presence of base in a controllable manner. As such, the degradation of the micropillars can be tuned over several days as a function of PCLDMA concentration within the copolymer formulations, and the topography greatly varied over a short space of time, as visualised using scanning electron microscopy and atomic force microscopy.

Direct laser writing of vapour-responsive photonic arrays.

Using direct laser writing, arrays of optically responsive ionogel structures were fabricated. To demonstrate their responsive nature, visible colour changes in the presence of different solvent vapours were investigated. This represents a new departure for photonic structural colouration, in which the fabricating structure shows a programmable, controllable, and dynamic stimuli response.

Big data and machine learning for materials science.

Herein, we review aspects of leading-edge research and innovation in materials science that exploit big data and machine learning (ML), two computer science concepts that combine to yield computational intelligence. ML can accelerate the solution of intricate chemical problems and even solve problems that otherwise would not be tractable. However, the potential benefits of ML come at the cost of big data production; that is, the algorithms demand large volumes of data of various natures and from different sources, from material properties to sensor data.

Magnetic movement under the spotlight.

Composite hydrogel robots can achieve programmable locomotion using light and magnetic fields.

Direct Laser Writing of Four-Dimensional Structural Color Microactuators Using a Photonic Photoresist.

With the advent of direct laser writing using two-photon polymerization, the generation of high-resolution three-dimensional microstructures has increased dramatically. However, the development of stimuli-responsive photoresists to create four-dimensional (4D) microstructures remains a challenge. Herein, we present a supramolecular cholesteric liquid crystalline photonic photoresist for the fabrication of 4D photonic microactuators, such as pillars, flowers, and butterflies, with submicron resolution.

3D Printed Sugar-Sensing Hydrogels.

The ability of boronic acids (BAs) to reversibly bind diols, such as sugars, has been widely studied in recent years. In solution, through the incorporation of additional fluorophores, the BA-sugar interaction can be monitored by changes in fluorescence. Ultimately, a practical realization of this technology requires a transition from solution-based methodologies.

Silicon Microcantilever Sensors to Detect the Reversible Conformational Change of a Molecular Switch, Spiropyan.

The high sensitivity of silicon microcantilever sensors has expanded their use in areas ranging from gas sensing to bio-medical applications. Photochromic molecules also represent promising candidates for a large variety of sensing applications. In this work, the operating principles of these two sensing methods are combined in order to detect the reversible conformational change of a molecular switch, spiropyran.

Dual Droplet Functionality: Phototaxis and Photopolymerization.

The use of phototaxis to move droplets in liquids offers the opportunity to emulate natural processes such as the controlled transport of materials in fluidic environments and to undertake chemistry at specific locations. We have developed a photoactive organic droplet, whose movement in aqueous solution is driven by a photoinitiator, as a result of a light-induced reaction within the droplet generating a Marangoni flow. The photoinitiator not only drives the droplet motion but can also be used to initiate polymerization following transfer of the droplet to a specific location and its merging with a monomer-containing droplet.

Paper based electronic tongue - a low-cost solution for the distinction of sugar type and apple juice brand.

This work reports on a low cost microfluidic electronic tongue (e-tongue) made with carbon interdigitated electrodes, printed on paper, and coated with boronic acid-containing hydrogels. Using capacitance measurements, the e-tongue was capable of distinguishing between different types of sugars (e.g.

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.

Moving Droplets in 3D Using Light.

The emulation of the complex cellular and bacterial vesicles used to transport materials through fluids has the potential to add revolutionary capabilities to fluidic platforms. Although a number of artificial motile vesicles or microdroplets have been demonstrated previously, control over their movement in liquid in 3D has not been achieved. Here it is shown that by adding a chemical "fuel," a photoactive material, to the droplet, it can be moved in any direction (3D) in water using simple light sources without the need for additives in the water.

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 (Zn, Co, Cu, Ni, Cd), 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.

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)) 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.

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.

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).

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.

Self-propelled chemotactic ionic liquid droplets.

Herein we report the chemotactic behaviour of self-propelled droplets composed solely of the ionic liquid trihexyl(tetradecyl)phosphonium chloride ([P(6,6,6,14)][Cl]). These droplets spontaneously move along an aqueous-air boundary in the direction of chloride gradients to specific destinations due to asymmetric release of [P(6,6,6,14)](+) cationic surfactant from the droplet into the aqueous phase.

Photo-chemopropulsion--light-stimulated movement of microdroplets.

The controlled movement of a chemical container by the light-activated expulsion of a chemical fuel, named here "photo-chemopropulsion", is an exciting new development in the array of mechanisms employed for controlling the movement of microvehicles, herein represented by lipid-based microdroplets. This "chemopropulsion" effect can be switched on and off, and is fully reversible.

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.

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.

Ionic liquid modulation of swelling and LCST behavior of N-isopropylacrylamide polymer gels.

The physicochemical properties of free-standing cross-linked poly(N-isopropylacrylamide) (pNIPAAM) gels, generated in the presence of the Ionic liquids (ILs), 1-ethyl-3-methylimidazolium [C2mIm](+) salts of ethylsulfate [EtSO4](-), dicyanamide [DCA](-), bis(trifluoromethylsulfonyl)imide [NTf2](-), and trihexyltetradecylphosphonium dicyanamide ([P(6,6,6,14)][DCA]) are described. The Lower Critical Solution Temperature (LCST) of the resulting ionogel was found to vary between 24-31 °C. The behaviour of swelling is found to be as high as 31.

Self-assembled solvato-morphologically controlled photochromic crystals.

Here we describe, for the first time, intriguing solvato-morphological control of spiropyran-based microcrystalline structures. These microstructures exhibit reversible photoisomerization upon light irradiation (UV/Vis) in the solid-state. Finally, light-guided aggregation of these microstructures at the liquid/air interface is also demonstrated.

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.