Effect of Polymer Hydrophobicity in the Performance of Hybrid Gel Gas Sensors for E-Noses.

Relative humidity (RH) is a common interferent in chemical gas sensors, influencing their baselines and sensitivity, which can limit the performance of e-nose systems. Tuning the composition of the sensing materials is a possible strategy to control the impact of RH in gas sensors. Hybrid gel materials used as gas sensors contain self-assembled droplets of ionic liquid and liquid crystal molecules encapsulated in a polymeric matrix. In this work, we assessed the effect of the matrix hydrophobic properties in the performance of hybrid gel materials for VOC sensing in humid conditions (50% RH). We used two different polymers, the hydrophobic PDMS and the hydrophilic bovine gelatin, as polymeric matrices in hybrid gel materials containing imidazolium-based ionic liquids, [BMIM][Cl] and [BMIM][DCA], and the thermotropic liquid crystal 5CB. Better accuracy of VOC prediction is obtained for the hybrid gels composed of a PDMS matrix combined with the [BMIM][Cl] ionic liquid, and the use of this hydrophobic matrix reduces the effect of humidity on the sensing performance when compared to the gelatin counterpart. VOCs interact with all the moieties of the hybrid gel multicomponent system; thus, VOC correct classification depends not only on the polymeric matrix used, but also on the IL selected, which seems to be key to achieve VOCs discrimination at 50% RH. Thus, hybrid gels' tunable formulation offers the potential for designing complementary sensors for e-nose systems operable under different RH conditions.

Tackling Humidity with Designer Ionic Liquid-Based Gas Sensing Soft Materials.

Relative humidity is simultaneously a sensing target and a contaminant in gas and volatile organic compound (VOC) sensing systems, where strategies to control humidity interference are required. An unmet challenge is the creation of gas-sensitive materials where the response to humidity is controlled by the material itself. Here, humidity effects are controlled through the design of gelatin formulations in ionic liquids without and with liquid crystals as electrical and optical sensors, respectively. In this design, the anions [DCA]- and [Cl]- of room temperature ionic liquids from the 1-butyl-3-methylimidazolium family tailor the response to humidity and, subsequently, sensing of VOCs in dry and humid conditions. Due to the combined effect of the materials formulations and sensing mechanisms, changing the anion from [DCA]- to the much more hygroscopic [Cl]- , leads to stronger electrical responses and much weaker optical responses to humidity. Thus, either humidity sensors or humidity-tolerant VOC sensors that do not require sample preconditioning or signal processing to correct humidity impact are obtained. With the wide spread of 3D- and 4D-printing and intelligent devices, the monitoring and tuning of humidity in sustainable biobased materials offers excellent opportunities in e-nose sensing arrays and wearable devices compatible with operation at room conditions.

Optical Gas Sensing with Liquid Crystal Droplets and Convolutional Neural Networks.

Liquid crystal (LC)-based materials are promising platforms to develop rapid, miniaturised and low-cost gas sensor devices. In hybrid gel films containing LC droplets, characteristic optical texture variations are observed due to orientational transitions of LC molecules in the presence of distinct volatile organic compounds (VOC). Here, we investigate the use of deep convolutional neural networks (CNN) as pattern recognition systems to analyse optical textures dynamics in LC droplets exposed to a set of different VOCs. LC droplets responses to VOCs were video recorded under polarised optical microscopy (POM). CNNs were then used to extract features from the responses and, in separate tasks, to recognise and quantify the vapours exposed to the films. The impact of droplet diameter on the results was also analysed. With our classification models, we show that a single individual droplet can recognise 11 VOCs with small structural and functional differences (F1-score above 93%). The optical texture variation pattern of a droplet also reflects VOC concentration changes, as suggested by applying a regression model to acetone at 0.9-4.0% (v/v) (mean absolute errors below 0.25% (v/v)). The CNN-based methodology is thus a promising approach for VOC sensing using responses from individual LC-droplets.

Effect of film thickness in gelatin hybrid gels for artificial olfaction.

Artificial olfaction is a fast-growing field aiming to mimic natural olfactory systems. Olfactory systems rely on a first step of molecular recognition in which volatile organic compounds (VOCs) bind to an array of specialized olfactory proteins. This results in electrical signals transduced to the brain where pattern recognition is performed. An efficient approach in artificial olfaction combines gas-sensitive materials with dedicated signal processing and classification tools. In this work, films of gelatin hybrid gels with a single composition that change their optical properties upon binding to VOCs were studied as gas-sensing materials in a custom-built electronic nose. The effect of films thickness was studied by acquiring signals from gelatin hybrid gel films with thicknesses between 15 and 90 µm when exposed to 11 distinct VOCs. Several features were extracted from the signals obtained and then used to implement a dedicated automatic classifier based on support vector machines for data processing. As an optical signature could be associated to each VOC, the developed algorithms classified 11 distinct VOCs with high accuracy and precision (higher than 98%), in particular when using optical signals from a single film composition with 30 µm thickness. This shows an unprecedented example of soft matter in artificial olfaction, in which a single gelatin hybrid gel, and not an array of sensing materials, can provide enough information to accurately classify VOCs with small structural and functional differences.

Enhanced Gas Sensing with Soft Functional Materials.

The materials described in this work result from the self-assembly of liquid crystals and ionic liquids into droplets, stabilized within a biopolymeric matrix. These systems are extremely versatile gels, in terms of composition, and offer potential for fine tuning of both structure and function, as each individual component can be varied. Here, the characterization and application of these gels as sensing thin films in gas sensor devices is presented. The unique supramolecular structure of the gels is explored for molecular recognition of volatile organic compounds (VOCs) by employing gels with distinct formulations to yield combinatorial optical and electrical responses used in the distinction and identification of VOCs.