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. Incorporation into acrylate photoresists, via a one-step fabrication process, enables the formation of complex structures with large overhangs. The inclusion of 150 nm silica nanoparticles in DLW photoresists at high concentrations, allows for the fabrication of composite microstructures that show reflected color, a product of the relative contributions from the quasi-ordering and random scattering. Using common DLW design parameters, such as slicing distance and structure dimension, a wide gamut of structural color, in solution, using a set concentration of nanoparticles is demonstrated. Numerical modeling is employed to predict the reflected wavelength of the pixel arrays, across the visible spectrum, and this information is used to encode reflected colors into different pixel arrays.

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. Using an array of identical pixels, information can be hidden to the observer and revealed only upon application of a specific stimulus. The reading mechanism is based on the shape-change of each pixel under stimuli and their color that combine together in a two-level encryption label. Once the stimulus is removed, the pixels recover their original shape and the message remains completely hidden. Therefore, an opto-mechanical equivalent of an "invisible ink" is realized. This new concept paves the way for introducing enhanced functionalities in smart micro-systems within a single lithography step, spanning from storage devices with physical encryption to complex motion actuators.

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. Herein, the first example of 3D-printed sugar-sensing hydrogels, achieved through the incorporation of a BA-fluorophore pair in a gelatin methacrylamide-based matrix is presented. Through optimization of monomeric cocktails, it is possible to use extrusion printing to generate structured porous hydrogels which show a measurable and reproducible linear fluorescence response to glucose and fructose up to 100 mm.

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. Thus, arrays of silicon microcantilever sensors were functionalized with spiropyran on the gold covered side and used as test microcantilevers. The microcantilever deflection response was observed, in five sequential cycles, as the transition from the spiropyran (SP) (CLOSED) to the merocyanine (MC) (OPEN) state and vice-versa when induced by UV and white light LED sources, respectively, proving the reversibility capabilities of this type of sensor. The microcantilever deflection direction was observed to be in one direction when changing to the MC state and in the opposite direction when changing back to the SP state. A tensile stress was induced in the microcantilever when the SP to MC transition took place, while a compressive stress was observed for the reverse transition. These different type of stresses are believed to be related to the spatial conformational changes induced in the photochromic molecule upon photo-isomerisation.

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. glucose, fructose and sucrose), in addition to distinguishing between commercial brands of apple juice using a small volume of sample (6 µL). The channels of the microfluidic e-tongue were made using a wax printer, and were modified with hydrogels containing acrylamide copolymerized with 5 or 20 mol% 3-(acrylamido) phenyl boronic acid (Am-PBA), or a crosslinked homopolymeric hydrogel based on N-(2-boronobenzyl)-2-hydroxy-N,N-dimethylethan-1-aminium-3-sulfopropyl acrylate (DMA-PBA). Such hydrogels, containing a phenyl boronic acid (PBA) moiety, can bind saccharides. Combining various hydrogels of this nature in an e-tongue device enabled discrimination between apple juices, which are known to contain higher amounts of fructose compared to glucose or sucrose. Changes in capacitance were captured with impedance spectroscopy in the frequency range from 0.1 to 10 MHz for solutions with varying concentrations of glucose, fructose and sucrose (from 0 to 0.056 g mL-1). The capacitance data were treated with Principal Component Analysis (PCA) and Interactive Document Map (IDMAP), which then correlated overall sugar content from different brands of apple juice. This low-cost, easy-to-use, disposable e-tongue offers great potential in the routine analysis of food and beverages, while offering comparative performance to alternatives in the literature.

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.

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.

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.

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 31.55% (±0.47, n = 3) from the initial dehydrated state, while 28.04% (±0.42, n = 3) shrinking from the hydrated swollen state is observed. For ionogels based on the [DCA](-) anion an unexpected complete loss of the shrinking behaviour occurs, attributed to water interactions with the nitrile group of the [DCA](-) anion. Scanning Electron Microscopy also reveals distinct morphological changes, for example [C2mIm][EtSO4] displays a highly porous, nodule type morphology, efficiently pre-disposed for water uptake.

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.

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.

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. Crosslinked neat HDDA was used as a control material, demonstrating that the presence of the PCL was responsible for the ability of the microstructures to degrade in the controlled manner. In addition, the mass loss of the crosslinked materials was minimal, demonstrating the degradation of microstructured surfaces without loss of bulk properties was possible. Moreover, the compatibility of these crosslinked materials with mammalian cells was explored. The influence of both indirect and direct contact of the materials with A549 cells was assessed by profiling indices reflective of cytotoxicity such as morphology, adhesion, metabolic activity, oxidative balance, and release of injury markers. No significant changes in the aforementioned profile were observed in the cells cultured under these conditions for up to 72 h, with the cell-material interaction suggesting these materials may have potential in microfabrication contexts towards biomedical application purposes.

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. In the survey, we propose a roadmap for future developments with emphasis on computer-aided discovery of new materials and analysis of chemical sensing compounds, both prominent research fields for ML in the context of materials science. In addition to providing an overview of recent advances, we elaborate upon the conceptual and practical limitations of big data and ML applied to materials science, outlining processes, discussing pitfalls, and reviewing cases of success and failure.

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. These micron-sized features display structural color and shape changes triggered by a variation of humidity or temperature. These findings serve as a roadmap for the design and creation of high-resolution 4D photonic microactuators.

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. The same light is used to control the transport of the droplet and the polymerization. The efficacy of this droplet transport and reactor system has been demonstrated by the site-specific underwater polymerization of N-isopropylacrylamide to repair a leaking vessel and the adhesion of two materials together.

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.

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. The droplets can be made up of a range of solvents and move with speeds as high as 10.4 mm s-1 toward or away from the irradiation source as a result of a light-induced isothermal change in interfacial tension (Marangoni flow). It is further demonstrated that more complex functions can be accomplished by merging a photoactive droplet with a droplet carrying a "cargo" and moving the new larger droplet to a "reactor" droplet where the cargo undergoes a chemical reaction. The control and versatility of this light-activated, motile droplet system will open up new possibilities for fluidic chemical transport and applications.