{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,8]],"date-time":"2026-10-08T20:26:53Z","timestamp":1791491213019,"version":"4.3.4"},"reference-count":42,"publisher":"MDPI AG","issue":"8","license":[{"start":{"date-parts":[[2022,4,8]],"date-time":"2022-04-08T00:00:00Z","timestamp":1649376000000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22176111"],"award-info":[{"award-number":["22176111"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"name":"Young Scholars Program of Shandong University","award":["2018WLJH54"],"award-info":[{"award-number":["2018WLJH54"]}]},{"name":"Taishan Scholars","award":["Ts201712003"],"award-info":[{"award-number":["Ts201712003"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Heavy metals are non-biodegradable and carcinogenic pollutants with great bio-accumulation potential. Their ubiquitous occurrence in water and soils has caused serious environmental concerns. Effective strategies that can eliminate the heavy metal pollution are urgently needed. Here the adsorption potential of seven heavy metal cations (Cd2+, Cu2+, Fe3+, Hg2+, Mn2+, Ni2+ and Zn2+) with 20 amino acids was systematically investigated with Density Functional Theory method. The binding energies calculated at B3LYP-D3\/def2TZVP level showed that the contribution order of amino acid side chains to the binding affinity was carboxyl &gt; benzene ring &gt; hydroxyl &gt; sulfhydryl &gt; amino group. The affinity order was inversely proportional to the radius and charge transfer of heavy metal cations, approximately following the order of: Ni2+ &gt; Fe3+ &gt; Cu2+ &gt; Hg2+ &gt; Zn2+ &gt; Cd2+ &gt; Mn2+. Compared to the gas-phase in other researches, the water environment has a significant influence on structures and binding energies of the heavy metal and amino acid binary complexes. Collectively, the present results will provide a basis for the design of a chelating agent (e.g., adding carboxyl or a benzene ring) to effectively remove heavy metals from the environment.<\/jats:p>","DOI":"10.3390\/molecules27082407","type":"journal-article","created":{"date-parts":[[2022,4,9]],"date-time":"2022-04-09T05:13:08Z","timestamp":1649481188000},"page":"2407","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":62,"title":["Interaction Structure and Affinity of Zwitterionic Amino Acids with Important Metal Cations (Cd2+, Cu2+, Fe3+, Hg2+, Mn2+, Ni2+ and Zn2+) in Aqueous Solution: A Theoretical Study"],"prefix":"10.3390","volume":"27","author":[{"given":"Xinning","family":"Liu","sequence":"first","affiliation":[{"name":"Environment Research Institute, Shandong University, Qingdao 266237, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Menghan","family":"Wu","sequence":"additional","affiliation":[{"name":"State Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chenchen","family":"Li","sequence":"additional","affiliation":[{"name":"School of Management, Ocean University of China, Qingdao 266101, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Peng","family":"Yu","sequence":"additional","affiliation":[{"name":"State Key Joint Laboratory of Environmental Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shanshan","family":"Feng","sequence":"additional","affiliation":[{"name":"School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yanwei","family":"Li","sequence":"additional","affiliation":[{"name":"Environment Research Institute, Shandong University, Qingdao 266237, China"},{"name":"Shenzhen Research Institute, Shandong University, Shenzhen 518057, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qingzhu","family":"Zhang","sequence":"additional","affiliation":[{"name":"Environment Research Institute, Shandong University, Qingdao 266237, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2022,4,8]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"142811","DOI":"10.1016\/j.scitotenv.2020.142811","article-title":"Pb2+, Cd2+ and Hg2+ removal by designed functionalized swelling high-charged micas","volume":"764","author":"Osuna","year":"2020","journal-title":"Sci. Total Environ."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"2440","DOI":"10.1038\/s41467-019-10472-x","article-title":"Remediation of heavy metal contaminated soil by asymmetrical alternating current electrochemistry","volume":"10","author":"Xu","year":"2019","journal-title":"Nat. Commun."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1016\/j.envpol.2007.11.015","article-title":"The use of chelating agents in the remediation of metal-contaminated soils: A review","volume":"153","author":"Luo","year":"2008","journal-title":"Environ. Pollut."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"485","DOI":"10.1007\/BF03326158","article-title":"Removal of heavy metals from a contaminated soil using organic chelating acids","volume":"7","author":"Wuana","year":"2010","journal-title":"Int. J. Environ. Sci. Technol."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1161","DOI":"10.1016\/j.chemosphere.2012.02.032","article-title":"Remediation of toxic metal contaminated soil by washing with biodegradable aminopolycarboxylate chelants","volume":"87","author":"Begum","year":"2012","journal-title":"Chemosphere"},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"132","DOI":"10.1016\/j.scitotenv.2013.11.049","article-title":"Effect of EDTA washing of metal polluted garden soils. Part I: Toxicity hazards and impact on soil properties","volume":"475","author":"Jelusic","year":"2014","journal-title":"Sci. Total Environ."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"149060","DOI":"10.1016\/j.scitotenv.2021.149060","article-title":"Demonstrational gardens with EDTA-washed soil. Part I: Remediation efficiency, effect on soil properties and toxicity hazards","volume":"792","author":"Gluhar","year":"2021","journal-title":"Sci. Total Environ."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"49040","DOI":"10.1039\/C4RA08155B","article-title":"Influence of metal ions (Zn2+, Cu2+, Ca2+, Mg2+ and Na+) on the water coordinated neutral and zwitterionicl-histidine dimer","volume":"4","author":"Umadevi","year":"2014","journal-title":"RSC Adv."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"1983","DOI":"10.1021\/acs.jpcb.8b11967","article-title":"Experimental and Computational Study of the Group 1 Metal Cation Chelates with Lysine: Bond Dissociation Energies, Structures, and Structural Trends","volume":"123","author":"Clark","year":"2019","journal-title":"J. Phys. Chem. B"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"109140","DOI":"10.1016\/j.envres.2020.109140","article-title":"Natural amino acids as potential chelators for soil remediation","volume":"183","author":"Dolev","year":"2020","journal-title":"Environ. Res."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"2258","DOI":"10.1021\/jp711237g","article-title":"Infrared Multiphoton Dissociation Spectroscopy of Cationized Threonine: Effects of Alkali-Metal Cation Size on Gas-Phase Conformation","volume":"112","author":"Rodgers","year":"2008","journal-title":"J. Phys. Chem. A"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"389","DOI":"10.1016\/j.jclepro.2017.04.023","article-title":"Influence of different factors in the life cycle assessment of mixed municipal solid waste management systems\u2014A comparison of case studies in Finland and China","volume":"154","author":"Liikanen","year":"2017","journal-title":"J. Clean. Prod."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1002","DOI":"10.1002\/jccs.202000383","article-title":"Theoretical study on the interaction of phenylalaninal with group IA (Li+, Na+, K+) and IIA (Be2+, Mg2+, Ca2+) metal cations","volume":"68","author":"Alirezapour","year":"2021","journal-title":"J. Chin. Chem. Soc."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"3989","DOI":"10.1021\/jp3012766","article-title":"Metal Cation Dependence of Interactions with Amino Acids: Bond Energies of Cs+ to Gly, Pro, Ser, Thr, and Cys","volume":"116","author":"Armentrout","year":"2012","journal-title":"J. Phys. Chem. A"},{"key":"ref_15","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Petersson, G.A., and Nakatsuji, H. (2010). Gaussian 09, Gaussian Inc.. Revision B.01."},{"key":"ref_16","unstructured":"Dennington, R., Keith, T., and Millam, J. (2009). GAUSSVIEW, Semichem Inc.. VERSION 5."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"553","DOI":"10.1002\/poc.1786","article-title":"Interaction studies of cysteine with Li+, Na+, K+, Be2+, Mg2+, and Ca2+ metal cation complexes","volume":"24","author":"Shankar","year":"2011","journal-title":"J. Phys. Org. Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"6378","DOI":"10.1021\/jp810292n","article-title":"Universal Solvation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions","volume":"113","author":"Marenich","year":"2009","journal-title":"J. Phys. Chem. B"},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"211","DOI":"10.1002\/wcms.30","article-title":"Density functional theory with London dispersion corrections","volume":"1","author":"Grimme","year":"2011","journal-title":"WIREs Comput. Mol. Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"93","DOI":"10.1016\/j.cplett.2018.12.021","article-title":"An ab iniio study on the micro-solvation of amino acids: On the number of water molecules necessary to stabilize the zwitter ion","volume":"716","author":"Gochhayat","year":"2019","journal-title":"Chem. Phys. Lett."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"362","DOI":"10.1016\/j.jcis.2019.06.086","article-title":"pH-dependent adsorption of \u03b1-amino acids, lysine, glutamic acid, serine and glycine, on TiO2 nanoparticle surfaces","volume":"554","author":"Ustunol","year":"2019","journal-title":"J. Colloid Interface Sci."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"4746","DOI":"10.1021\/acs.langmuir.6b00563","article-title":"Adsorption of Lysine on Na-Montmorillonite and Competition with Ca2+: A Combined XRD and ATR-FTIR Study","volume":"32","author":"Yang","year":"2016","journal-title":"Langmuir"},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"14","DOI":"10.1016\/j.ab.2019.05.016","article-title":"Solid-state vibrational circular dichroism studies of L- and D-serine","volume":"580","author":"Kawamura","year":"2019","journal-title":"Anal. Biochem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"2229","DOI":"10.1007\/s00894-014-2229-1","article-title":"Deducing the molecular properties of zwitterionic, protonated, deprotonated, and double-deprotonated forms of L-cysteine from vibrational spectroscopy (IR, Raman, VCD) and quantum chemical calculations","volume":"20","year":"2014","journal-title":"J. Mol. Model."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1537","DOI":"10.1016\/j.tetasy.2013.09.025","article-title":"Conformational landscape of l-threonine in neutral, acid and basic solutions from vibrational circular dichroism spectroscopy and quantum chemical calculations","volume":"24","year":"2013","journal-title":"Tetrahedron Asymmetry"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"5810","DOI":"10.1021\/jp411734j","article-title":"Molecular Interaction of Amino Acids with Acidic Zeolite BEA: The Effect of Water","volume":"118","author":"Merz","year":"2014","journal-title":"J. Phys. Chem. C"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"7177","DOI":"10.1021\/jp303289p","article-title":"Extensive Computational Study on Coordination of Transition Metal Cations and Water Molecules to Glutamic Acid","volume":"116","author":"Meng","year":"2012","journal-title":"J. Phys. Chem. A"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1733","DOI":"10.1002\/cphc.201200964","article-title":"Interaction Modes and Absolute Affinities of \u03b1-Amino Acids for Mn2+: A Comprehensive Picture","volume":"14","author":"Khodabandeh","year":"2013","journal-title":"ChemPhysChem"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.comptc.2014.04.016","article-title":"Complexations of alkali\/alkaline earth metal cations with gaseous glutamic acid","volume":"1039","author":"Meng","year":"2014","journal-title":"Comput. Theor. Chem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"17628","DOI":"10.1021\/jp047213l","article-title":"The Coupling Character of Ca2+ with Glutamic Acid: Implication for the Conformational Behavior and Transformation of Ca2+-ATPase in Transmembrane Ca2+ Channel","volume":"108","author":"Xiang","year":"2004","journal-title":"J. Phys. Chem. B"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"12056","DOI":"10.1021\/jp802427n","article-title":"Experimental and Theoretical Studies of Potassium Cation Interactions with the Acidic Amino Acids and Their Amide Derivatives","volume":"112","author":"Heaton","year":"2008","journal-title":"J. Phys. Chem. B"},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"3328","DOI":"10.1021\/jp800439j","article-title":"Experimental and Theoretical Studies of Sodium Cation Complexes of the Deamidation and Dehydration Products of Asparagine, Glutamine, Aspartic Acid, and Glutamic Acid","volume":"112","author":"Heaton","year":"2008","journal-title":"J. Phys. Chem. A"},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"4107","DOI":"10.1021\/jp101264m","article-title":"Metal Cation Dependence of Interactions with Amino Acids: Bond Energies of Rb+ to Gly, Ser, Thr, and Pro","volume":"114","author":"Bowman","year":"2010","journal-title":"J. Phys. Chem. B"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"1377","DOI":"10.1002\/1521-3765(20020315)8:6<1377::AID-CHEM1377>3.0.CO;2-D","article-title":"Alkali Metal Ion Binding to Amino Acids Versus Their Methyl Esters: Affinity Trends and Structural Changes in the Gas Phase","volume":"8","author":"Talley","year":"2002","journal-title":"Chem.\u2014A Eur. J."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"499","DOI":"10.1016\/j.saa.2014.11.084","article-title":"Interaction between transition metals and phenylalanine: A combined experimental and computational study","volume":"138","author":"Hossain","year":"2015","journal-title":"Spectrochim. Acta Part A Mol. Biomol. Spectrosc."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"3771","DOI":"10.1021\/jp401366g","article-title":"Metal Cation Dependence of Interactions with Amino Acids: Bond Energies of Rb+ and Cs+ to Met, Phe, Tyr, and Trp","volume":"117","author":"Armentrout","year":"2013","journal-title":"J. Phys. Chem. B"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"14600","DOI":"10.1021\/ja048297e","article-title":"Cation\u2212\u03c0 Interactions: Structures and Energetics of Complexation of Na+ and K+ with the Aromatic Amino Acids, Phenylalanine, Tyrosine, and Tryptophan","volume":"126","author":"Ruan","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"8578","DOI":"10.1021\/jp803121w","article-title":"Alkali Metal Ion Binding to Glutamine and Glutamine Derivatives Investigated by Infrared Action Spectroscopy and Theory","volume":"112","author":"Bush","year":"2008","journal-title":"J. Phys. Chem. A"},{"key":"ref_39","unstructured":"Harvey, K.B., Porter, G.B., and Porter, G.B. (1963). Introduction to Physical Inorganic Chemistry, American Chemical Society. [3rd ed.]."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"6441","DOI":"10.1039\/b805860a","article-title":"A comparison of the binding affinity of the common amino acids with different metal cations","volume":"45","author":"Jover","year":"2008","journal-title":"Dalton Trans."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"24666","DOI":"10.1021\/jp0645972","article-title":"Structural and Electronic Characterization of the Complexes Obtained by the Interaction between Bare and Hydrated First-Row Transition-Metal Ions (Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+) and Glycine","volume":"110","author":"Marino","year":"2006","journal-title":"J. Phys. Chem. B"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"4300","DOI":"10.1021\/jp5001754","article-title":"Metal Cation Dependence of Interactions with Amino Acids: Bond Dissociation Energies of Rb+ and Cs+ to the Acidic Amino Acids and Their Amide Derivatives","volume":"118","author":"Armentrout","year":"2014","journal-title":"J. Phys. Chem. B"}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/8\/2407\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T22:50:27Z","timestamp":1760136627000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/8\/2407"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,4,8]]},"references-count":42,"journal-issue":{"issue":"8","published-online":{"date-parts":[[2022,4]]}},"alternative-id":["molecules27082407"],"URL":"https:\/\/doi.org\/10.3390\/molecules27082407","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,4,8]]}}}