Design of Chemoresponsive Soft Matter Using Hydrogen-Bonded Liquid Crystals

Abstract

Soft matter that undergoes programmed macroscopic responses to molecular analytes has potential utility in a range of health and safety-related contexts. In this study, we report the design of a nematic liquid crystal (LC) composition that forms through dimerization of carboxylic acids and responds to the presence of vapors of organoamines by undergoing a visually distinct phase transition to an isotropic phase. Specifically, we screened mixtures of two carboxylic acids, 4-butylbenzoic acid and trans-4-pentylcyclohexanecarboxylic acid, and found select compositions that exhibited a nematic phase from 30.6 to 111.7 °C during heating and 110.6 to 3.1 °C during cooling. The metastable nematic phase formed at ambient temperatures was found to be long-lived (>5 days), thus enabling the use of the LC as a chemoresponsive optical material. By comparing experimental infrared (IR) spectra of the LC phase with vibrational frequencies calculated using density functional theory (DFT), we show that it is possible to distinguish between the presence of monomers, homodimers and heterodimers in the mixture, leading us to conclude that a one-to-one heterodimer is the dominant species within this LC composition. Further support for this conclusion is obtained by using differential scanning calorimetry. Exposure of the LC to 12 ppm triethylamine (TEA) triggers a phase transition to an isotropic phase, which we show by IR spectroscopy to be driven by an acid-base reaction, leading to the formation of ammonium carboxylate salts. We characterized the dynamics of the phase transition and found that it proceeds via a characteristic spatiotemporal pathway involving the nucleation, growth, and coalescence of isotropic domains, thus amplifying the atomic-scale acid-base reaction into an information-rich optical output. In contrast to TEA, we determined via both experiment and computation that neither hydrogen bonding donor or acceptor molecules, such as water, dimethyl methylphosphonate, ethylene oxide or formaldehyde, disrupt the heterodimers formed in the LC, hinting that the phase transition (including spatial-temporal characteristics of the pathway) induced in this class of hydrogen bonded LC may offer the basis of a facile and chemically selective way of reporting the presence of volatile amines. This proposal is supported by exploratory experiments in which we show that it is possible to trigger a phase transition in the LC by exposure to volatile amines emitted from rotting fish. Overall, these results provide new principles for the design of chemoresponsive soft matter based on hydrogen bonded LCs that may find use as the basis of low-cost visual indicators of chemical environments.

Recent Progress in Droplet Structure Machining for Advanced Optics

“…The standard technical strategy involves employing specially designed stimulus-responsive polymers to solidify periodic structures within the droplets. Consequently, the variations in the structural color of these droplets can be harnessed for detecting parameters like temperature, pressure, pH, specific components in solutions (e.g., metal ions, proteins, DNA), and even volatile gases, among others [ 100 , 101 , 102 , 103 , 104 , 105 , 106 , 107 , 108 , 109 ]. Such applications necessitate the utilization of smart materials, such as polymers or surfactants, to accomplish the mentioned functions.…”

Innovative use of liquid crystalline acids as color developers in leuco dye-based temperature sensors

“…It is known that some carboxylic acids, such as 4-butylbenzoic acid, characterized by an elongated structure, exhibit a nematic phase stabilized by hydrogen-bonded dimers between acid molecules. 23 This implies that the protons needed for leuco dye development are not accessible in the temperature range corresponding to the occurrence of the nematic phase. Temperature sensors designed in this way could be capable of detecting three different temperature ranges, allowing them to identify the optimal temperature range through its discoloration.…”