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Determination of chlorothalonil levels through inhibitory effect on papain activity at protein-decorated liquid crystal interfaces.

ABSTRACT: A liquid crystal (LC)-based assay was developed to detect chlorothalonil (CHL). The detection principle is based on (i) the electrostatic interaction between the positively charged protein protamine (PRO) with the negatively charged phospholipid dioleoyl-sn-glycero-3-phospho-rac-(1-glycerol) sodium salt (DOPG) and (ii) the CHL-mediated inhibition of papain (PAP) activity. The aqueous/LC interface was decorated with a monolayer of DOPG and PRO that self-assembled via electrostatic interactions. PAP can hydrolyze PRO, resulting in the realignment of an LC by DOPG, inducing a shift in the LC response from bright to dark. The addition of CHL can inhibit the activity of PAP, leading to the attraction of PRO to DOPG and the consequent disruption of the LC orientation. The orientation change of the LC in the presence or absence of CHL can be observed from the changes in its optical appearance using a polarized light microscope. Under optimal conditions, the developed assay achieved a detection limit of 0.196 pg mL^-1 within a range of determination of 0.65-200 pg mL^-1. The selectivity of the assay was verified in the presence of carbendazim and imidacloprid. The practical application of the proposed assay was demonstrated by its use to determine the levels of CHL in food extracts and environmental samples, which yielded recoveries and relative standard deviations (RSD) in the ranges of 87.39-99.663% and 1.03-6.32%, respectively.

SUBMITTER: Duong DST

PROVIDER: S-EPMC9313939 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:We demonstrate that the assembly of an amphiphilic polyamine on the interfaces of micrometer-sized droplets of a thermotropic liquid crystal (LC) dispersed in aqueous solutions can be used to facilitate the immobilization of LC droplets on chemically functionalized surfaces. Polymer 1 was designed to contain both hydrophobic (alkyl-functionalized) and hydrophilic (primary and tertiary amine-functionalized) side chain functionality. The assembly of this polymer at the interfaces of aqueous dispersions of LC droplets was achieved by the spontaneous adsorption of polymer from aqueous solution. Polymer adsorption triggered transitions in the orientational ordering of the LCs, as observed by polarized light and bright-field microscopy. We demonstrate that the presence of polymer 1 on the interfaces of these droplets can be exploited to immobilize LC droplets on planar solid surfaces through covalent bond formation (e.g., for surfaces coated with polymer multilayers containing reactive azlactone functionality) or through electrostatic interactions (e.g., for surfaces coated with multilayers containing hydrolyzed azlactone functionality). The characterization of immobilized LC droplets by polarized, fluorescence, and laser scanning confocal microscopy revealed the general spherical shape of the polymer-coated LC droplets to be maintained after immobilization, and that immobilization led to additional ordering transitions within the droplets that were dependent on the nature of the surfaces with which they were in contact. Polymer 1-functionalized LC droplets were not immobilized on polymer multilayers treated with poly(ethylene imine) (PEI). We demonstrate that the ability to design surfaces that promote or prevent the immobilization of polymer-functionalized LC droplets can be exploited to pattern the immobilization of LC droplets on surfaces. The results of this investigation provide the basis of an approach that could be used to tailor the properties of dispersed LC emulsions and to immobilize these droplets on functional surfaces of interest in a broad range of fundamental and applied contexts.

Project description:We reported recently that amphiphilic polymers can be assembled at interfaces created between aqueous phases and thermotropic liquid crystals (LCs) in ways that: (i) couple the organization of the polymer to the order of the LC and (ii) respond to changes in the properties of aqueous phases that can be characterized as changes in the optical appearance of the LC. This investigation sought to characterize the behavior of aqueous-LC interfaces decorated with uniaxially compressed thin films of polymers transferred by Langmuir-Schaefer (LS) transfer. Here, we report physicochemical characterization of interfaces created between aqueous phases and the thermotropic LC 4-cyano-4'-pentylbiphenyl (5CB) decorated with Langmuir films of a novel amphiphilic polymer (polymer 1), synthesized by the addition of hydrophobic and hydrophilic side chains to poly(2-vinyl-4,4'-dimethylazlactone). Initial characterization of this system resulted in the unexpected observation of uniform azimuthal alignment of 5CB after LS transfer of the polymer films to aqueous-5CB interfaces. This paper describes characterization of Langmuir films of polymer 1 hosted at aqueous-5CB interfaces as well as the results of our investigations into the origins of the uniform ordering of the LC observed upon LS transfer. Our results, when combined, support the conclusion that uniform azimuthal alignment of 5CB is the result of long-range ordering of polymer chains in the Langmuir films (in a preferred direction orthogonal to the direction of compression) that is generated during uniaxial compression of the films prior to LS transfer. Although past studies of Langmuir films of polymers at aqueous-air interfaces have demonstrated that in-plane alignment of polymer backbones can be induced by uniaxial compression, these past reports have generally made use of polymers with rigid backbones. One important outcome of this current study is thus the observation of anisotropy and long-range order in Langmuir films of a novel flexible polymer. A second important outcome is the observation that the existence, extent, and dynamics of this order can be identified and characterized optically by transfer of the Langmuir film to a thin film of LC. Additional characterization of Langmuir films of two other flexible polymers [poly(methyl methacrylate) and poly(vinyl stearate)] using this method also resulted in uniform azimuthal alignment of 5CB, suggesting that the generation of long-range order in uniaxially compressed Langmuir films of polymers may also occur more generally over a broader range of polymers with flexible backbones.

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Determination of chlorothalonil levels through inhibitory effect on papain activity at protein-decorated liquid crystal interfaces.

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