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Title: Redox-Triggered Orientational Responses of Liquid Crystals to Chlorine Gas

Abstract

Surface-supported liquid crystals (LCs) that exhibit orientational and thus optical responses upon exposure to ppb concentrations of Cl 2 gas are reported. Computations identified Mn cations as candidate surface binding sites that undergo redox-triggered changes in the strength of binding to nitrogen-based LCs upon exposure to Cl 2 gas. Guided by these predictions, μm-thick films of nitrile- or pyridine-containing LCs were prepared on surfaces decorated with Mn 2+ binding sites as perchlorate salts. Following exposure to Cl 2, formation of Mn 4+ (in the form of MnO 2 microparticles) was confirmed and an accompanying change in the orientation and optical appearance of the supported LC films was measured. In unoptimized systems, the LC orientational transitions provided the sensitivity and response times needed for monitoring human exposure to Cl 2 gas. Finally, the response was also selective to Cl 2 over other oxidizing agents such as air or NO 2 and other chemical targets such as organophosphonates.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [2];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States). Dept. of Chemical and Biological Engineering
  2. Kent State Univ., Kent, OH (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of California, Oakland, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1543473
Grant/Contract Number:  
AC02-05CH11231; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 57; Journal Issue: 31; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; anchoring transitions; Cl2 detection; liquid crystals; redox chemistry; sensors

Citation Formats

Szilvási, Tibor, Bao, Nanqi, Nayani, Karthik, Yu, Huaizhe, Rai, Prabin, Twieg, Robert J., Mavrikakis, Manos, and Abbott, Nicholas L. Redox-Triggered Orientational Responses of Liquid Crystals to Chlorine Gas. United States: N. p., 2018. Web. doi:10.1002/anie.201803194.
Szilvási, Tibor, Bao, Nanqi, Nayani, Karthik, Yu, Huaizhe, Rai, Prabin, Twieg, Robert J., Mavrikakis, Manos, & Abbott, Nicholas L. Redox-Triggered Orientational Responses of Liquid Crystals to Chlorine Gas. United States. doi:10.1002/anie.201803194.
Szilvási, Tibor, Bao, Nanqi, Nayani, Karthik, Yu, Huaizhe, Rai, Prabin, Twieg, Robert J., Mavrikakis, Manos, and Abbott, Nicholas L. Fri . "Redox-Triggered Orientational Responses of Liquid Crystals to Chlorine Gas". United States. doi:10.1002/anie.201803194. https://www.osti.gov/servlets/purl/1543473.
@article{osti_1543473,
title = {Redox-Triggered Orientational Responses of Liquid Crystals to Chlorine Gas},
author = {Szilvási, Tibor and Bao, Nanqi and Nayani, Karthik and Yu, Huaizhe and Rai, Prabin and Twieg, Robert J. and Mavrikakis, Manos and Abbott, Nicholas L.},
abstractNote = {Surface-supported liquid crystals (LCs) that exhibit orientational and thus optical responses upon exposure to ppb concentrations of Cl2 gas are reported. Computations identified Mn cations as candidate surface binding sites that undergo redox-triggered changes in the strength of binding to nitrogen-based LCs upon exposure to Cl2 gas. Guided by these predictions, μm-thick films of nitrile- or pyridine-containing LCs were prepared on surfaces decorated with Mn2+ binding sites as perchlorate salts. Following exposure to Cl2, formation of Mn4+ (in the form of MnO2 microparticles) was confirmed and an accompanying change in the orientation and optical appearance of the supported LC films was measured. In unoptimized systems, the LC orientational transitions provided the sensitivity and response times needed for monitoring human exposure to Cl2 gas. Finally, the response was also selective to Cl2 over other oxidizing agents such as air or NO2 and other chemical targets such as organophosphonates.},
doi = {10.1002/anie.201803194},
journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 31,
volume = 57,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
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Cited by: 2 works
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Figures / Tables:

Figure 1 Figure 1: (a) Computational model used to predict the orientation of 5CB on Mn2+-decorated surfaces (perchlorate salts). (b) Model hydroxylated MnO2 (110) surface used to assess the orientation of 5CB on Mn4+ surfaces. (c) Schematic representation of the orientation of 5CB and optical image (crossed polars) of 5CB hosted inmore » a copper grid (lateral size of grid square is 300 μm) on surfaces decorated with 10.8±0.3 pmol/mm2 Mn(ClO4)2. (d) Schematic representation of the orientation of 5CB and optical image of 5CB (crossed polars) in a copper grid supported on a surface decorated with 10.8±0.3 pmol/mm2 Mn(ClO4)2 and exposed to 5 ppm Cl2 (1 hr at 35 % RH) prior to contact with the 5CB.« less

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    Works referencing / citing this record:

      Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.