{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T13:02:18Z","timestamp":1790168538524,"version":"4.1.0"},"reference-count":34,"publisher":"MDPI AG","issue":"20","license":[{"start":{"date-parts":[[2019,10,10]],"date-time":"2019-10-10T00:00:00Z","timestamp":1570665600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100003329","name":"Ministerio de Econom\u00eda y Competitividad","doi-asserted-by":"publisher","award":["MAT2017-89207-R"],"award-info":[{"award-number":["MAT2017-89207-R"]}],"id":[{"id":"10.13039\/501100003329","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The mixed-ligand strategy was selected as an approach to tailor a metal\u2013organic framework (MOF) with microextraction purposes. The strategy led to the synthesis of up to twelve UiO-66-based MOFs with different amounts of functionalized terephthalate ligands (H-bdc), including nitro (-NO2) and amino (-NH2) groups (NO2-bdc and NH2-bdc, respectively). Increases of 25% in ligands were used in each case, and different pore environments were thus obtained in the resulting crystals. Characterization of MOFs includes powder X-ray diffraction, infrared spectroscopy, and elemental analysis. The obtained MOFs with different degrees and natures of functionalization were tested as sorbents in a dispersive miniaturized solid-phase extraction (D-\u00b5SPE) method in combination with high-performance liquid chromatography (HPLC) and diode array detection (DAD), to evaluate the influence of mixed functionalization of the MOF on the analytical performance of the entire microextraction method. Eight organic pollutants of different natures were studied, using a concentration level of 5 \u00b5g\u00b7 L\u22121 to mimic contaminated waters. Target pollutants included carbamazepine, 4-cumylphenol, benzophenone-3, 4-tert-octylphenol, 4-octylphenol, chrysene, indeno(1,2,3-cd)pyrene, and triclosan, as representatives of drugs, phenols, polycyclic aromatic hydrocarbons, and disinfectants. Structurally, they differ in size and some of them present polar groups able to form H-bond interactions, either as donors (-NH2) or acceptors (-NO2), permitting us to evaluate possible interactions between MOF pore functionalities and analytes\u2019 groups. As a result, extraction efficiencies can reach values of up to 60%, despite employing a microextraction approach, with four main trends of behavior being observed, depending on the analyte and the MOF.<\/jats:p>","DOI":"10.3390\/molecules24203656","type":"journal-article","created":{"date-parts":[[2019,10,11]],"date-time":"2019-10-11T03:07:11Z","timestamp":1570763231000},"page":"3656","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":26,"title":["Mixed Functionalization of Organic Ligands in UiO-66: A Tool to Design Metal\u2013Organic Frameworks for Tailored Microextraction"],"prefix":"10.3390","volume":"24","author":[{"given":"Gabriel","family":"Gonz\u00e1lez-Rodr\u00edguez","sequence":"first","affiliation":[{"name":"Departamento de Qu\u00edmica, Unidad Departamental de Qu\u00edmica Anal\u00edtica, Universidad de La Laguna (ULL), Tenerife, 38206 La Laguna, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Iv\u00e1n","family":"Taima-Mancera","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica, Unidad Departamental de Qu\u00edmica Anal\u00edtica, Universidad de La Laguna (ULL), Tenerife, 38206 La Laguna, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5884-528X","authenticated-orcid":false,"given":"Ana B.","family":"Lago","sequence":"additional","affiliation":[{"name":"Laboratorio de Rayos X y Materiales Moleculares (MATMOL), Departamento de F\u00edsica, Universidad de La Laguna (ULL), Tenerife, 38206 La Laguna, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8982-2662","authenticated-orcid":false,"given":"Juan H.","family":"Ayala","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica, Unidad Departamental de Qu\u00edmica Anal\u00edtica, Universidad de La Laguna (ULL), Tenerife, 38206 La Laguna, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9012-723X","authenticated-orcid":false,"given":"Jorge","family":"Pas\u00e1n","sequence":"additional","affiliation":[{"name":"Laboratorio de Rayos X y Materiales Moleculares (MATMOL), Departamento de F\u00edsica, Universidad de La Laguna (ULL), Tenerife, 38206 La Laguna, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1698-5524","authenticated-orcid":false,"given":"Ver\u00f3nica","family":"Pino","sequence":"additional","affiliation":[{"name":"Departamento de Qu\u00edmica, Unidad Departamental de Qu\u00edmica Anal\u00edtica, Universidad de La Laguna (ULL), Tenerife, 38206 La Laguna, Spain"},{"name":"University Institute of Tropical Diseases and Public Health, Universidad de La Laguna (ULL), Tenerife, 38206 La Laguna, Spain"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2019,10,10]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"114","DOI":"10.1016\/j.trac.2017.03.002","article-title":"Metal-organic frameworks as novel sorbents in dispersive-based microextraction approaches","volume":"90","author":"Pino","year":"2017","journal-title":"Trac Trends Anal. Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"142","DOI":"10.1016\/j.trac.2017.03.004","article-title":"Magnetic solid-phase extraction using metal-organic frameworks (MOFs) and their derived carbons","volume":"90","author":"Maya","year":"2017","journal-title":"Trac Trends Anal. Chem."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"65","DOI":"10.1016\/j.trac.2017.08.015","article-title":"Metal-organic frameworks as advanced sorbents for the extraction and determination of pollutants from environmental, biological, and food media","volume":"97","author":"Hashemi","year":"2017","journal-title":"Trac Trends Anal. Chem."},{"key":"ref_4","unstructured":"Mittal, V. (2019). Micro-Solid-Phase Extraction Using Metal-Organic Frameworks. Metal Organic Frameworks, Hardcover Central West Publishing."},{"key":"ref_5","doi-asserted-by":"crossref","unstructured":"Guti\u00e9rrez-Serpa, A., Pacheco-Fern\u00e1ndez, I., Pas\u00e1n, J., and Pino, V. (2019). Metal-organic frameworks as key materials for solid-phase microextraction devices\u2014A review. Separations, 6, in press.","DOI":"10.3390\/separations6040047"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"169","DOI":"10.1016\/j.jes.2018.12.010","article-title":"Recent advances on porous organic frameworks for the adsorptive removal of hazardous materials","volume":"80","author":"Lv","year":"2019","journal-title":"J. Environ. Sci."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"10575","DOI":"10.1021\/cr5002589","article-title":"Water Stability and Adsorption in Metal-Organic Frameworks","volume":"114","author":"Burtch","year":"2014","journal-title":"Chem. Rev."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"226","DOI":"10.1016\/j.trac.2018.12.005","article-title":"Dispersive micro-solid phase extraction","volume":"112","author":"Chisvert","year":"2019","journal-title":"Trac Trends Anal. Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"99","DOI":"10.1016\/j.trac.2017.01.004","article-title":"Development of dispersive micro-solid phase extraction based on micro and nano sorbents","volume":"89","author":"Khezeli","year":"2017","journal-title":"Trac Trends Anal. Chem."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"26","DOI":"10.1016\/j.trac.2014.03.011","article-title":"Recent advances in solid-phase sorbents for sample preparation prior to chromatographic analysis","volume":"59","author":"Wen","year":"2014","journal-title":"Trac Trends Anal. Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"775","DOI":"10.1016\/j.talanta.2017.12.012","article-title":"Insights in the analytical performance of neat metal-organic frameworks in the determination of pollutants of different nature from waters using dispersive miniaturized solid-phase extraction and liquid chromatography","volume":"179","author":"Pino","year":"2018","journal-title":"Talanta"},{"key":"ref_12","doi-asserted-by":"crossref","unstructured":"Taima-Mancera, I., Roc\u00edo-Bautista, P., Pas\u00e1n, J., Ayala, J.H., Ruiz-P\u00e9rez, C., Afonso, A.M., Lago, A.B., and Pino, V. (2018). Influence of Ligand Functionalization of UiO-66-Based Metal-Organic Frameworks When Used as Sorbents in Dispersive Solid-Phase Analytical Microextraction for Different Aqueous Organic Pollutants. Molecules, 23.","DOI":"10.3390\/molecules23112869"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"14044","DOI":"10.1002\/chem.201802343","article-title":"Monitoring the Effect of Different Metal Centers in Metal-Organic Frameworks and Their Adsorption of Aromatic Molecules using Experimental and Simulation Studies","volume":"24","author":"Lirio","year":"2018","journal-title":"Chem. Eur. J."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"735","DOI":"10.1007\/s10337-018-3498-0","article-title":"Amine-Functionalized Metal-Organic Framework as a New Sorbent for Vortex-Assisted Dispersive Micro-Solid Phase Extraction of Phenol Residues in Water Samples Prior to HPLC Analysis: Experimental and Computational Studies","volume":"81","author":"Boontongto","year":"2018","journal-title":"Chromatographia"},{"key":"ref_15","first-page":"57","article-title":"Computational screening of metal-organic frameworks for CO2 separation","volume":"16","author":"Jiang","year":"2019","journal-title":"Curr. Opin. Green Sust. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1704792","DOI":"10.1002\/adma.201704792","article-title":"A Metal-Organic Framework with Optimized Porosity and Functional Sites for High Gravimetric and Volumetric Methane Storage Working Capacities","volume":"30","author":"Wen","year":"2018","journal-title":"Adv. Mater."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"160","DOI":"10.1016\/j.jcat.2017.12.007","article-title":"Computational screening of MOF-supported transition metal catalysts for activity and selectivity in ethylene dimerization","volume":"360","author":"Ye","year":"2018","journal-title":"J. Catal."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"358","DOI":"10.1016\/j.talanta.2017.12.071","article-title":"A combination of computational-experimental study on metal-organic frameworks MIL-53(Al) as sorbent for simultaneous determination of estrogens and glucocorticoids in water and urine samples by dispersive micro-solid-phase extraction coupled to UPLC-MS\/MS","volume":"180","author":"Gao","year":"2018","journal-title":"Talanta"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"13","DOI":"10.1016\/j.talanta.2015.02.032","article-title":"The metal-organic framework HKUST\u22121 as efficient sorbent in a vortex-assisted dispersive micro solid-phase extraction of parabens from environmental waters, cosmetic creams, and human urine","volume":"139","author":"Pino","year":"2015","journal-title":"Talanta"},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"236","DOI":"10.1016\/j.talanta.2018.11.049","article-title":"Use of Basolite\u00ae F300 metal-organic framework for the dispersive solid-phase extraction of phthalic acid esters from water samples prior to LC-MS determination","volume":"195","year":"2019","journal-title":"Talanta"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"139","DOI":"10.1016\/j.mtchem.2018.12.004","article-title":"Understanding the modifications and applications of highly stable porous frameworks via UiO-66","volume":"12","author":"Zou","year":"2019","journal-title":"Mater. Today Chem."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"2327","DOI":"10.1039\/C5CS00837A","article-title":"Zr-based metal-organic frameworks: Design, synthesis, structure, and applications","volume":"45","author":"Bai","year":"2016","journal-title":"Chem. Soc. Rev."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"19018","DOI":"10.1039\/C5DT03359D","article-title":"De facto methodologies toward the synthesis and scale-up production of UiO-66-type metal-organic frameworks and membrane materials","volume":"44","author":"Hu","year":"2015","journal-title":"Dalton Trans."},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Roc\u00edo-Bautista, P., Taima-Mancera, I., Pas\u00e1n, J., and Pino, V. (2019). Metal-Organic Frameworks in Green Analytical Chemistry. Separations, 6.","DOI":"10.3390\/separations6030033"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"23","DOI":"10.1016\/j.talanta.2019.03.072","article-title":"Gallic acid functionalized UiO-66 for the recovery of ribosylated metabolites from human urine samples","volume":"201","author":"Mohyuddin","year":"2019","journal-title":"Talanta"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"179","DOI":"10.1016\/j.micromeso.2019.03.017","article-title":"Simultaneous adsorption of methyl orange and methylene blue from aqueous solution using amino functionalized Zr-based MOFs","volume":"282","author":"Lv","year":"2019","journal-title":"Microporous Mesoporous Mat."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"160","DOI":"10.1016\/j.molliq.2019.03.100","article-title":"Effect of free carboxylic acid groups in UiO-66 analogues on the adsorption of dyes from water: Plausible mechanisms for adsorption and gate-opening behavior","volume":"283","author":"Zhang","year":"2019","journal-title":"J. Mol. Liq."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"3623","DOI":"10.1039\/c0ce00568a","article-title":"Mixed-component metal-organic frameworks (MC-MOFs): Enhancing functionality through solid solution formation and surface modifications","volume":"13","author":"Burrows","year":"2011","journal-title":"CrystEngComm."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1551","DOI":"10.1039\/C6CP07801J","article-title":"Mixed-linker UiO-66: Structure-property relationships revealed by a combination of high-resolution powder X-ray diffraction and density theory calculations","volume":"19","author":"Taddei","year":"2017","journal-title":"Phys. Chem. Chem. Phys."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"7700","DOI":"10.1039\/c0cc02990d","article-title":"Isoreticular synthesis and modification of frameworks with the UiO-66 topology","volume":"46","author":"Garibay","year":"2010","journal-title":"Chem. Commun."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"9509","DOI":"10.1021\/ic500607a","article-title":"Synthesis and Characterization of Amine-Functionalized Mixed-Ligand Metal-Organic Frameworks of UiO-66 Topology","volume":"53","author":"Chavan","year":"2014","journal-title":"Inorg. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"9449","DOI":"10.1039\/c3cc46105j","article-title":"A facile synthesis of UiO-66, UiO-67 and their derivatives","volume":"49","author":"Katz","year":"2013","journal-title":"Chem. Commun."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"13850","DOI":"10.1021\/ja8057953","article-title":"A New Zirconium Inorganic Building Brick Forming Metal Organic Frameworks with Exceptional Stability","volume":"130","author":"Cavka","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref_34","unstructured":"Nakamoto, K. (2006). Infrared and raman spectra of inorganic and coordination compounds, theory and applications in inorganic chemistry. Infrared and Raman Spectra of Inorganic and Coordination Compounds, Wiley. [5th ed.]."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/20\/3656\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T13:29:08Z","timestamp":1760189348000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/20\/3656"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,10,10]]},"references-count":34,"journal-issue":{"issue":"20","published-online":{"date-parts":[[2019,10]]}},"alternative-id":["molecules24203656"],"URL":"https:\/\/doi.org\/10.3390\/molecules24203656","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,10,10]]}}}