Fast, real‐time detection of gases and volatile organic compounds (VOCs) is an emerging research field relevant to most aspects of modern society, from households to health facilities, industrial units, and military environments. Sensor features such as high sensitivity, selectivity, fast response, and low energy consumption are essential. Liquid crystal (LC)‐based sensors fulfill these requirements due to their chemical diversity, inherent self‐assembly potential, and reversible molecular order, resulting in tunable stimuli‐responsive soft materials. Sensing platforms utilizing thermotropic uniaxial systems—nematic and smectic—that exploit not only interfacial phenomena, but also changes in the LC bulk, are demonstrated. Special focus is given to the different interaction mechanisms and tuned selectivity toward gas and VOC analytes. Furthermore, the different experimental methods used to transduce the presence of chemical analytes into macroscopic signals are discussed and detailed examples are provided. Future perspectives and trends in the field, in particular the opportunities for LC‐based advanced materials in artificial olfaction, are also discussed.
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.
Liquid crystals (LCs) are prime examples of dynamic supramolecular soft materials. Their autonomous self-assembly at the nanoscale level and the further nanoscale events that give rise to unique stimuli-responsive properties have been exploited for sensing purposes. One of the key features to employ LCs as sensing materials derives from the fine-tuning between stability and dynamics. This challenging task was addressed in this work by studying the effect of the alkyl chain length of cyanobiphenyl LCs on the molecular self-assembled compartments organized in the presence of ionic liquid molecules and gelatin. The resulting multicompartment nematic and smectic gels were further used as volatile organic compound chemical sensors. The LC structures undergo a dynamic sequence of phase transitions, depending on the nature of the LC component, yielding a variety of optical signals, which serve as optical fingerprints. In particular, the materials incorporating smectic compartments resulted in unexpected and rich optical textures that have not been reported previously. Their sensing capability was tested in an in-house-assembled electronic nose and further assessed via signal collection and machine-learning algorithms based on support vector machines, which classified 12 different gas analytes with high accuracy scores. Our work expands the knowledge on controlling LC self-assembly to yield fast and autonomous accurate chemical-sensing systems based on the combination of complex nanoscale sensing events with artificial intelligence tools.
The phase behaviour of mixtures between two symmetric dimers, CBC9CB and the ether-linked analogue CBOC9OCB was investigated by Polarizing Optical Microscopy (POM), Differential Scanning Calorimetry (DSC) and X-Ray Diffraction (XRD) studies. The dimeric constituents are fully miscible and the construction of a temperature-composition phase diagram reveals a surprising amplification of the stability of the Nx phase in compositions of up to 37 wt% of CBOC9OCB in CBC9CB. The origin for this enhancement of stability is discussed and an explanation based on chiral recognition is developed.
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