{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,16]],"date-time":"2026-10-16T03:42:50Z","timestamp":1792122170699,"version":"4.4.0"},"reference-count":53,"publisher":"MDPI AG","issue":"17","license":[{"start":{"date-parts":[[2020,8,24]],"date-time":"2020-08-24T00:00:00Z","timestamp":1598227200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"National Science Centre Poland","award":["DEC-2014\/13\/B\/NZ7\/02352"],"award-info":[{"award-number":["DEC-2014\/13\/B\/NZ7\/02352"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Materials"],"abstract":"<jats:p>The structure of the Zn(II) complex of 5-caffeoylquinic acid (chlorogenic acid, 5-CQA) and the type of interaction between the Zn(II) cation and the ligand were studied by means of various experimental and theoretical methods, i.e., electronic absorption spectroscopy UV\/Vis, infrared spectroscopy FT-IR, elemental, thermogravimetric and density functional theory (DFT) calculations at B3LYP\/6-31G(d) level. DPPH (2,2-diphenyl-1-picrylhydrazyl), ABTS (2,2\u2032-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), FRAP (ferric reducing antioxidant power), CUPRAC (cupric reducing antioxidant power) and trolox oxidation assays were applied in study of the anti-\/pro-oxidant properties of Zn(II) 5-CQA and 5-CQA. The antimicrobial activity of these compounds against Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, Staphylococcus aureus, Salmonella enteritidis and Candida albicans was tested. An effect of Zn(II) chelation by chlorogenic acid on the anti-\/pro-oxidant and antimicrobial activities of the ligand was discussed. Moreover, the mechanism of the antioxidant properties of Zn(II) 5-CQA and 5-CQA were studied on the basis of the theoretical energy descriptors and thermochemical parameters. Zn(II) chlorogenate showed better antioxidant activity than chlorogenic acid and commonly applied natural (L-ascorbic acid) and synthetic antioxidants (butylated hydroxyanisol (BHA) and butylated hydroxytoluene (BHT)). The pro-oxidant activity of Zn(II) 5-CQA was higher than the ligand and increased with the rise of the compound concentration The type of Zn(II) coordination by the chlorogenate ligand strongly affected the antioxidant activity of the complex.<\/jats:p>","DOI":"10.3390\/ma13173745","type":"journal-article","created":{"date-parts":[[2020,8,24]],"date-time":"2020-08-24T10:37:32Z","timestamp":1598265452000},"page":"3745","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":75,"title":["Zn(II) Complex of Plant Phenolic Chlorogenic Acid: Antioxidant, Antimicrobial and Structural Studies"],"prefix":"10.3390","volume":"13","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0839-9891","authenticated-orcid":false,"given":"Monika","family":"Kalinowska","sequence":"first","affiliation":[{"name":"Department of Chemistry, Biology and Biotechnology, Institute of Civil Engineering and Energetics, Faculty of Civil Engineering and Environmental Sciences, Bialystok University of Technology, Wiejska 45E Street, 15-351 Bialystok, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4956-300X","authenticated-orcid":false,"given":"Justyna","family":"Sienkiewicz-Gromiuk","sequence":"additional","affiliation":[{"name":"Department of General and Coordination Chemistry and Crystallography, Institute of Chemical Sciences, Faculty of Chemistry, Maria Curie-Sklodowska University, Maria Curie-Sklodowska Sq. 2, 20-031 Lublin, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4442-6348","authenticated-orcid":false,"given":"Grzegorz","family":"\u015awiderski","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Biology and Biotechnology, Institute of Civil Engineering and Energetics, Faculty of Civil Engineering and Environmental Sciences, Bialystok University of Technology, Wiejska 45E Street, 15-351 Bialystok, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8820-5216","authenticated-orcid":false,"given":"Anna","family":"Pietryczuk","sequence":"additional","affiliation":[{"name":"Department of Water Ecology, Faculty of Biology, University of Bialystok, Ciolkowskiego 1J Street, 15-245 Bialystok, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8783-454X","authenticated-orcid":false,"given":"Adam","family":"Cudowski","sequence":"additional","affiliation":[{"name":"Department of Water Ecology, Faculty of Biology, University of Bialystok, Ciolkowskiego 1J Street, 15-245 Bialystok, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"W\u0142odzimierz","family":"Lewandowski","sequence":"additional","affiliation":[{"name":"Department of Chemistry, Biology and Biotechnology, Institute of Civil Engineering and Energetics, Faculty of Civil Engineering and Environmental Sciences, Bialystok University of Technology, Wiejska 45E Street, 15-351 Bialystok, Poland"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"1968","published-online":{"date-parts":[[2020,8,24]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"3025","DOI":"10.1021\/acs.jafc.6b00331","article-title":"Polyphenol\u2013Aluminum Complex Formation: Implications for Aluminum Tolerance in Plants","volume":"64","author":"Zhang","year":"2016","journal-title":"J. Agric. Food Chem."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"123","DOI":"10.1007\/s00374-011-0653-2","article-title":"Plant-borne flavonoids released into the rhizosphere: Impact on soil bio-activities related to plant nutrition. A review","volume":"48","author":"Cesco","year":"2012","journal-title":"Boil. Fertil. Soils"},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"4","DOI":"10.4161\/psb.5.1.10197","article-title":"Iron and its complexation by phenolic cellular metabolites: From oxidative stress to chemical weapons","volume":"5","author":"Chobot","year":"2010","journal-title":"Plant Signal. Behav."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"134","DOI":"10.1016\/j.ecoenv.2018.11.004","article-title":"Phenolic metabolism and related heavy metal tolerance mechanism in Kandelia Obovata under Cd and Zn stress","volume":"169","author":"Chen","year":"2019","journal-title":"Ecotoxicol. Environ. Saf."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"359","DOI":"10.1080\/00380768.2001.10408399","article-title":"The plasma membrane strength of the root-tip cells and root phenolic compounds are correiated with Al tolerance in several common woody plants","volume":"47","author":"Wagatsuma","year":"2001","journal-title":"Soil Sci. Plant Nutr."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"549","DOI":"10.1016\/j.plaphy.2016.10.027","article-title":"Phenolic compounds responding to zinc and\/or cadmium treatments in Gynura pseudochina (L.) DC. extracts and biomass","volume":"109","author":"Mongkhonsin","year":"2016","journal-title":"Plant Physiol. Biochem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"147","DOI":"10.1016\/j.plantsci.2006.03.005","article-title":"Phenolics metabolism and lignin synthesis in root suspension cultures of Panax ginseng in response to copper stress","volume":"171","author":"Ali","year":"2006","journal-title":"Plant Sci."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"169","DOI":"10.1016\/j.plaphy.2014.09.006","article-title":"Apples: Content of phenolic compounds vs. variety, part of apple and cultivation model, extraction of phenolic compounds, biological properties","volume":"84","author":"Kalinowska","year":"2014","journal-title":"Plant Physiol. Biochem."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Gan, R.-Y., Zhang, D., Wang, M., and Corke, H. (2018). Health Benefits of Bioactive Compounds from the Genus Ilex, a Source of Traditional Caffeinated Beverages. Nutrients, 10.","DOI":"10.3390\/nu10111682"},{"key":"ref_10","doi-asserted-by":"crossref","unstructured":"Kalinowska, M., Bajko, E., Matejczyk, M., Kaczy\u0144ski, P., \u0141ozowicka, B., and Lewandowski, W. (2018). The Study of Anti-\/Pro-Oxidant, Lipophilic, Microbial and Spectroscopic Properties of New Alkali Metal Salts of 5-O-Caffeoylquinic Acid. Int. J. Mol. Sci., 19.","DOI":"10.3390\/ijms19020463"},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"1235","DOI":"10.1007\/s00468-019-01837-2","article-title":"Characterization of bioactive compounds in the biomass of black locust, poplar and willow","volume":"33","author":"Konkol","year":"2019","journal-title":"Trees"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"471","DOI":"10.1016\/j.lwt.2015.08.024","article-title":"5-O-Caffeoylquinic acid: A spectroscopic study and biological screening for antimicrobial activity","volume":"65","author":"Bajko","year":"2016","journal-title":"LWT"},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"16","DOI":"10.3390\/nu8010016","article-title":"Role of Chlorogenic Acids in Controlling Oxidative and Inflammatory Stress Conditions","volume":"8","author":"Liang","year":"2015","journal-title":"Nutrients"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"112063","DOI":"10.1016\/j.phytochem.2019.112063","article-title":"Should I stay or should I go: Are chlorogenic acids mobilized towards lignin biosynthesis?","volume":"166","author":"Silvia","year":"2019","journal-title":"Phytochem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1","DOI":"10.3389\/fpls.2016.01563","article-title":"Salinity Stress Is Beneficial to the Accumulation of Chlorogenic Acids in Honeysuckle (Lonicera japonica Thunb.)","volume":"7","author":"Yan","year":"2016","journal-title":"Front. Plant Sci."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"97","DOI":"10.1016\/j.pmpp.2017.04.003","article-title":"A simplified technique to detect variations of leaf chlorogenic acid levels between and within plants caused by maturation or biological stress","volume":"98","author":"Baker","year":"2017","journal-title":"Physiol. Mol. Plant Pathol."},{"key":"ref_17","first-page":"1","article-title":"UV-B pre-treatment alters phenolics response to Monilinia fructicola infection in a structure-dependent way in peach skin","volume":"9","author":"Santin","year":"2018","journal-title":"Front. Plant Sci."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"813","DOI":"10.1007\/s13765-016-0229-9","article-title":"Responses of the phenolic compounds of Zea mays under heavy metal stress","volume":"59","author":"Elmastas","year":"2016","journal-title":"Appl. Biol. Chem."},{"key":"ref_19","first-page":"523","article-title":"Phenolic compounds and their antioxidant activity in plants growing under heavy metal stress","volume":"15","author":"Michalak","year":"2006","journal-title":"Pol. J. Environ. Stud."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"86","DOI":"10.1016\/j.jinorgbio.2014.02.013","article-title":"Promising antioxidant and anticancer (human breast cancer) oxidovanadium(IV) complex of chlorogenic acid. Synthesis, characterization and spectroscopic examination on the transport mechanism with bovine serum albumin","volume":"135","author":"Naso","year":"2014","journal-title":"J. Inorg. Biochem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"245","DOI":"10.1016\/j.cbi.2017.06.016","article-title":"Hydroxyflavone metal complexes\u2014Molecular structure, antioxidant activity and biological effects","volume":"273","author":"Samsonowicz","year":"2017","journal-title":"Chem. Interact."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"742","DOI":"10.1016\/j.jscs.2017.12.006","article-title":"A new calcium 2,5-dihydroxybenzoate: Synthesis, characterization and antioxidant studies and stress mediated cytotoxity in MCF-7 cells","volume":"22","author":"Kalinowska","year":"2018","journal-title":"J. Saudi Chem. Soc."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"377","DOI":"10.1016\/S0014-5793(98)00048-9","article-title":"EPR detection of phenoxyl radicals stabilized by zinc ions: Evidence for the redox coupling of plant phenolics with ascorbate in the H2O2-peroxide system","volume":"422","author":"Yamasaki","year":"1998","journal-title":"FEBS Lett."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1051\/agro:2002073","article-title":"Effect of Metal Toxicity on Plant Growth and Metabolism: I. Zinc","volume":"23","author":"Rout","year":"2003","journal-title":"Agronomy"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"273","DOI":"10.1007\/s11101-018-9592-y","article-title":"Recent advances in extraction and analysis procedures of natural chlorogenic acids","volume":"18","author":"Wianowska","year":"2018","journal-title":"Phytochem. Rev."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"67","DOI":"10.1016\/j.biopha.2017.10.064","article-title":"Chlorogenic acid (CGA): A pharmacological review and call for further research","volume":"97","author":"Naveed","year":"2017","journal-title":"Biomed. Pharmacother."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"2935","DOI":"10.1002\/elan.201100476","article-title":"A Polarographic Study of Chlorogenic Acid and Its Interaction with Some Heavy Metal Ions","volume":"23","author":"Potkonjak","year":"2011","journal-title":"Electroanalysis"},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"24197","DOI":"10.1021\/jp0549430","article-title":"Radical Scavenging and Catalytic Activity of Metal\u2212Phenolic Complexes","volume":"109","author":"Mahal","year":"2005","journal-title":"J. Phys. Chem. B"},{"key":"ref_29","first-page":"243","article-title":"Thermodynamic stability of copper (II), manganese (II), zinc 9II) and iron(III) complexes with chlorogenic acid","volume":"133","author":"Ameziane","year":"1996","journal-title":"Bull. Soc. Fr."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"2345","DOI":"10.1016\/S0277-5387(00)80295-8","article-title":"Cupric ion binding by dihydroxybenzoic acids","volume":"8","author":"Kiss","year":"1989","journal-title":"Polyhedron"},{"key":"ref_31","unstructured":"Rice-Evans, C.A., and Diplock, A.T. (1991). Symons MCR. Techniques in Free Radical Research, Elsevier."},{"key":"ref_32","doi-asserted-by":"crossref","unstructured":"Zeraik, M.L., Petr\u00f4nio, M.S., Coelho, D., Regasini, L.O., Silva, D.H.S., Da Fonseca, L.M., Machado, S.A.S., Bolzani, V.D.S., and Ximenes, V.F. (2014). Improvement of Pro-Oxidant Capacity of Protocatechuic Acid by Esterification. PLoS ONE, 9.","DOI":"10.1371\/journal.pone.0110277"},{"key":"ref_33","unstructured":"Ogliaro, F., Bearpark, M.J., Heyd, J.J., Brothers, E.N., Kudin, K.N., Staroverov, V.N., Keith, T.A., Kobayashi, R., Normand, J., and Raghavachari, K. (2016). Gaussian 16, Revision C.01, Gaussian, Inc."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"4184","DOI":"10.1021\/jp0225774","article-title":"Ionization Potential, Electron Affinity, Electronegativity, Hardness, and Electron Excitation Energy: Molecular Properties from Density Functional Theory Orbital Energies","volume":"107","author":"Zhan","year":"2003","journal-title":"J. Phys. Chem. A"},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"1609","DOI":"10.1351\/pac199971081609","article-title":"Substituent effects on the O-H bond dissociation enthalpies in phenolic compounds: Agreements and controversies","volume":"71","author":"Bizarro","year":"1999","journal-title":"Pure Appl. Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"1173","DOI":"10.1021\/ja002455u","article-title":"Predicting the activity of phenolic antioxidants: Theoretical method, analysis of substituent effects, and application to major families of antioxidants","volume":"123","author":"Wright","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"3433","DOI":"10.1021\/jo026917t","article-title":"Abnormal Solvent Effects on Hydrogen Atom Abstractions. 1. The Reactions of Phenols with 2,2-Diphenyl-1-picrylhydrazyl (DPPH) in Alcohols","volume":"68","author":"Litwinienko","year":"2003","journal-title":"J. Org. Chem."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"5888","DOI":"10.1021\/jo049254j","article-title":"Abnormal Solvent Effects on Hydrogen Atom Abstraction. 2. Resolution of the Curcumin Antioxidant Controversy. The Role of Sequential Proton Loss Electron Transfer","volume":"69","author":"Litwinienko","year":"2004","journal-title":"J. Org. Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"2309","DOI":"10.1021\/jo035758q","article-title":"Electron-Transfer Reaction of Cinnamic Acids and Their Methyl Esters with the DPPH Radical in Alcoholic Solutions","volume":"69","author":"Foti","year":"2004","journal-title":"J. Org. Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"8765","DOI":"10.1021\/acs.jafc.5b03839","article-title":"Use and Abuse of the DPPH Radical","volume":"63","author":"Foti","year":"2015","journal-title":"J. Agric. Food Chem."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"797","DOI":"10.1016\/j.cell.2007.06.049","article-title":"A Common Mechanism of Cellular Death Induced by Bactericidal Antibiotics","volume":"130","author":"Kohanski","year":"2007","journal-title":"Cell"},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"482","DOI":"10.1016\/j.mib.2009.06.018","article-title":"Role of reactive oxygen species in antibiotic action and resistance","volume":"12","author":"Dwyer","year":"2009","journal-title":"Curr. Opin. Microbiol."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"315","DOI":"10.1126\/science.1219192","article-title":"Oxidation of the Guanine Nucleotide Pool Underlies Cell Death by Bactericidal Antibiotics","volume":"336","author":"Foti","year":"2012","journal-title":"Science"},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"12147","DOI":"10.1073\/pnas.1203735109","article-title":"Eradication of bacterial persisters with antibiotic-generated hydroxyl radicals","volume":"109","author":"Grant","year":"2012","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1155\/2013\/392058","article-title":"In Vitro Antibacterial and Antibiofilm Activities of Chlorogenic Acid against Clinical Isolates of Stenotrophomonas maltophilia including the Trimethoprim\/Sulfamethoxazole Resistant Strain","volume":"2013","author":"Karunanidhi","year":"2012","journal-title":"BioMed Res. Int."},{"key":"ref_46","doi-asserted-by":"crossref","unstructured":"Kot, B., Kwiatek, K., Janiuk, J., Witeska, M., and P\u0119kala-Safi\u0144ska, A. (2019). Antibacterial Activity of Commercial Phytochemicals against Aeromonas Species Isolated from Fish. Pathogens, 8.","DOI":"10.3390\/pathogens8030142"},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"1697","DOI":"10.1111\/ijfs.14051","article-title":"Antibacterial activity and mechanism of cinnamic acid and chlorogenic acid against Alicyclobacillus acidoterrestris vegetative cells in apple juice","volume":"54","author":"Cai","year":"2018","journal-title":"Int. J. Food Sci. Technol."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"M398","DOI":"10.1111\/j.1750-3841.2011.02213.x","article-title":"Antibacterial Activity and Mechanism of Action of Chlorogenic Acid","volume":"76","author":"Lou","year":"2011","journal-title":"J. Food Sci."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"1","DOI":"10.3389\/fmicb.2015.01031","article-title":"The therapeutic effect of chlorogenic acid against Staphylococcus aureus infection through sortase A inhibition","volume":"6","author":"Wang","year":"2015","journal-title":"Front. Microbiol."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"334","DOI":"10.1080\/00958972.2012.756480","article-title":"Synthesis, crystal structure, spectroscopic properties, and antimicrobial studies of a zinc(II) complex of p-coumaric acid","volume":"66","author":"Kalinowska","year":"2013","journal-title":"J. Coord. Chem."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"631","DOI":"10.1016\/j.saa.2013.11.089","article-title":"Spectroscopic (FT-IR, FT-Raman, 1H, 13C NMR, UV\/VIS), thermogravimetric and microbiological studies of Ca(II), Mn(II), Cu(II), Zn(II) and Cd(II) complexes of ferulic acid","volume":"122","author":"Kalinowska","year":"2014","journal-title":"Spectrochim. Acta A Mol. Biomol. Spectrosc."},{"key":"ref_52","unstructured":"Ur-Rahman, A. (2016). Frontiers in Clinical Drug Research, Bentham Science Publishers."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"222","DOI":"10.1021\/ar0682029","article-title":"Solvent effects on the rates and mechanisms of reaction of phenols with free radicals","volume":"40","author":"Litwinienko","year":"2007","journal-title":"Acc. Chem. Res."}],"container-title":["Materials"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1996-1944\/13\/17\/3745\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T10:05:56Z","timestamp":1760177156000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1996-1944\/13\/17\/3745"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2020,8,24]]},"references-count":53,"journal-issue":{"issue":"17","published-online":{"date-parts":[[2020,9]]}},"alternative-id":["ma13173745"],"URL":"https:\/\/doi.org\/10.3390\/ma13173745","relation":{},"ISSN":["1996-1944"],"issn-type":[{"value":"1996-1944","type":"electronic"}],"subject":[],"published":{"date-parts":[[2020,8,24]]}}}