{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,7]],"date-time":"2026-04-07T10:18:59Z","timestamp":1775557139635,"version":"3.50.1"},"reference-count":45,"publisher":"MDPI AG","issue":"19","license":[{"start":{"date-parts":[[2023,9,26]],"date-time":"2023-09-26T00:00:00Z","timestamp":1695686400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"Deputyship for Research &amp; Innovation, \u201cMinistry of Education\u201d","award":["IFKSUOR3\u2013303-1"],"award-info":[{"award-number":["IFKSUOR3\u2013303-1"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Quartz tuning forks (QTFs), which were coated with gold and with self-assembled monolayers (SAM) of a lower-rim functionalized calix[4]arene methoxy ester (CME), were used for the detection of benzene, toluene, and ethylbenzene in water samples. The QTF device was tested by measuring the respective frequency shifts obtained using small (100 \u00b5L) samples of aqueous benzene, toluene, and ethylbenzene at four different concentrations (10\u221212, 10\u221210, 10\u22128, and 10\u22126 M). The QTFs had lower limits of detection for all three aromatic hydrocarbons in the 10\u221214 M range, with the highest resonance frequency shifts (\u00b15%) being shown for the corresponding 10\u22126 M solutions in the following order: benzene (199 Hz) &gt; toluene (191 Hz) &gt; ethylbenzene (149 Hz). The frequency shifts measured with the QTFs relative to that in deionized water were inversely proportional to the concentration\/mass of the analytes. Insights into the effects of the alkyl groups of the aromatic hydrocarbons on the electronic interaction energies for their hypothetical 1:1 supramolecular host\u2013guest binding with the CME sensing layer were obtained through density functional theory (DFT) calculations of the electronic interaction energies (\u0394IEs) using B3LYP-D3\/GenECP with a mixed basis set: LANL2DZ and 6-311++g(d,p), CAM-B3LYP\/LANL2DZ, and PBE\/LANL2DZ. The magnitudes of the \u0394IEs were in the following order: [Au4-CME\u2283[benzene] &gt; [Au4-CME]\u2283[toluene] &gt; [Au4-CME]\u2283[ethylbenzene]. The gas-phase BSSE-uncorrected \u0394IE values for these complexes were higher, with values of \u221296.86, \u221287.80, and \u221279.33 kJ mol\u22121, respectively, and \u221286.39, \u221277.23, and \u221267.63 kJ mol\u22121, respectively, for the corresponding BSSE-corrected values using B3LYP-D3\/GenECP with LANL2dZ and 6-311++g(d,p). The computational findings strongly support the experimental results, revealing the same trend in the \u0394IEs for the proposed hypothetical binding modes between the tested analytes with the CME SAMs on the Au-QTF sensing surfaces.<\/jats:p>","DOI":"10.3390\/molecules28196808","type":"journal-article","created":{"date-parts":[[2023,9,26]],"date-time":"2023-09-26T08:58:17Z","timestamp":1695718697000},"page":"6808","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Detection of Aromatic Hydrocarbons in Aqueous Solutions Using Quartz Tuning Fork Sensors Modified with Calix[4]arene Methoxy Ester Self-Assembled Monolayers: Experimental and Density Functional Theory Study"],"prefix":"10.3390","volume":"28","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4219-4758","authenticated-orcid":false,"given":"Shofiur","family":"Rahman","sequence":"first","affiliation":[{"name":"Biological and Environmental Sensing Research Unit, King Abdullah Institute for Nanotechnology, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mahmoud A.","family":"Al-Gawati","sequence":"additional","affiliation":[{"name":"Biological and Environmental Sensing Research Unit, King Abdullah Institute for Nanotechnology, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia"},{"name":"Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Fatimah S.","family":"Alfaifi","sequence":"additional","affiliation":[{"name":"Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Wadha Khalaf","family":"Alenazi","sequence":"additional","affiliation":[{"name":"Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Nahed","family":"Alarifi","sequence":"additional","affiliation":[{"name":"Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Hamad","family":"Albrithen","sequence":"additional","affiliation":[{"name":"Biological and Environmental Sensing Research Unit, King Abdullah Institute for Nanotechnology, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia"},{"name":"Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0202-8712","authenticated-orcid":false,"given":"Abdullah N.","family":"Alodhayb","sequence":"additional","affiliation":[{"name":"Biological and Environmental Sensing Research Unit, King Abdullah Institute for Nanotechnology, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia"},{"name":"Department of Physics and Astronomy, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9435-6857","authenticated-orcid":false,"given":"Paris E.","family":"Georghiou","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Memorial University of Newfoundland, St. John\u2019s, NL A1C 5S7, Canada"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2023,9,26]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"60","DOI":"10.1016\/j.trac.2011.08.011","article-title":"Determination of volatile organic compounds in drinking and environmental waters","volume":"32","author":"Chary","year":"2012","journal-title":"Trends Anal. 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A"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/19\/6808\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T20:58:45Z","timestamp":1760129925000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/28\/19\/6808"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,9,26]]},"references-count":45,"journal-issue":{"issue":"19","published-online":{"date-parts":[[2023,10]]}},"alternative-id":["molecules28196808"],"URL":"https:\/\/doi.org\/10.3390\/molecules28196808","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,9,26]]}}}