{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,1,19]],"date-time":"2026-01-19T13:48:17Z","timestamp":1768830497804,"version":"3.49.0"},"reference-count":104,"publisher":"MDPI AG","issue":"6","license":[{"start":{"date-parts":[[2022,3,12]],"date-time":"2022-03-12T00:00:00Z","timestamp":1647043200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>Copper(II) azacyclam complexes (azacyclam = 1,3,5,8,12-pentaazacyclotetradecane) containing naphthyl or dansyl subunits can be prepared by template synthesis involving proper sulfonamide derivatives as locking fragments. The macrocyclic complexes are very poorly emissive due to the fluorescence-quenching behavior displayed by Cu2+ ions. However, the fluorescence can be recovered as a result of the decomposition of the complexes, which induces the release of free light-emitting subunits to the solution. This reaction takes place very slowly in neutral water but its rate is increased by the presence of sulfite. Therefore, [Cu(azacyclam)]2+ derivatives have been investigated as simple chemical probes for the fluorogenic detection of sulfite both on laboratory and real samples. Preliminary tests performed on samples of white wine provided sulfite concentration values that are in agreement with those obtained by a standard analytical method.<\/jats:p>","DOI":"10.3390\/molecules27061852","type":"journal-article","created":{"date-parts":[[2022,3,13]],"date-time":"2022-03-13T22:29:43Z","timestamp":1647210583000},"page":"1852","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["Fluorogenic Detection of Sulfite in Water by Using Copper(II) Azacyclam Complexes"],"prefix":"10.3390","volume":"27","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-4954-866X","authenticated-orcid":false,"given":"Carlo","family":"Ciarrocchi","sequence":"first","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Pavia, Via Taramelli 12, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Donatella","family":"Sacchi","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Pavia, Via Taramelli 12, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4991-145X","authenticated-orcid":false,"given":"Massimo","family":"Boiocchi","sequence":"additional","affiliation":[{"name":"Centro Grandi Strumenti, Universit\u00e0 di Pavia, Via Bassi 21, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8936-0891","authenticated-orcid":false,"given":"Maduka Lankani","family":"Weththimuni","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Pavia, Via Taramelli 12, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5463-1444","authenticated-orcid":false,"given":"Alessio","family":"Orbelli Biroli","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Pavia, Via Taramelli 12, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9276-1530","authenticated-orcid":false,"given":"Maurizio","family":"Licchelli","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica, Universit\u00e0 di Pavia, Via Taramelli 12, 27100 Pavia, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2022,3,12]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"433","DOI":"10.1080\/02652039009373907","article-title":"A Review of Sulphites in Foods: Analytical Methodology and Reported Findings","volume":"7","author":"Fazio","year":"1990","journal-title":"Food Addit. Contam."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"139","DOI":"10.1007\/s00216-011-5237-3","article-title":"Challenges and Trends in the Determination of Selected Chemical Contaminants and Allergens in Food","volume":"402","author":"Krska","year":"2012","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_3","first-page":"16","article-title":"Adverse Reactions to the Sulphite Additives","volume":"5","author":"Vally","year":"2012","journal-title":"Gastroenterol. Hepatol. Bed Bench"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"243","DOI":"10.1007\/BF00429112","article-title":"Sulfite Formation by Wine Yeasts","volume":"118","author":"Heinzel","year":"1978","journal-title":"Arch. Microbiol."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"829","DOI":"10.1007\/s11746-004-0987-3","article-title":"Intrinsic Sulfite Content of Isolated Soy Proteins","volume":"81","author":"Stine","year":"2004","journal-title":"J. Am. Oil Chem. Soc."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1643","DOI":"10.1111\/j.1365-2222.2009.03362.x","article-title":"Clinical Effects of Sulphite Additives","volume":"39","author":"Vally","year":"2009","journal-title":"Clin. Exp. Allergy"},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"229","DOI":"10.1080\/07315724.1995.10718500","article-title":"Sulfite Sensitivity: Significance in Human Health","volume":"14","author":"Lester","year":"1995","journal-title":"J. Am. Coll. Nutr."},{"key":"ref_8","unstructured":"U.S. Food and Drug Administration (2022, January 31). Code of Federal Regulations, 21CFR130.9, Available online: https:\/\/www.accessdata.fda.gov\/scripts\/cdrh\/cfdocs\/cfcfr\/cfrsearch.cfm?fr=130.9."},{"key":"ref_9","first-page":"77","article-title":"Comparison of Three Liquid Chromatographic Methods with FDA Optimized Monier-Williams Method for Determination of Total Sulfite in Foods","volume":"73","author":"Lawrence","year":"1990","journal-title":"J. Assoc. Off. Anal. Chem."},{"key":"ref_10","unstructured":"(2022, January 31). European Commission (EC) Directive 2000\/13\/EC on the Approximation of the Laws of the Member States Relating to the Labeling, Presentation, and Advertising of Foodstuffs; EC. Available online: https:\/\/www.fsai.ie\/uploadedFiles\/Consol_Dir2000_13.pdf."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"187","DOI":"10.1080\/19440049.2013.857048","article-title":"Comparison of Four Different Methods for the Determination of Sulfites in Foods Marketed in South Korea","volume":"31","author":"Lim","year":"2014","journal-title":"Food Addit. Contam. Part A"},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"650","DOI":"10.1080\/03067319.2011.637198","article-title":"A New Voltammetric Sensor for the Determination of Sulfite in Water and Wastewater Using Modified-Multiwall Carbon Nanotubes Paste Electrode","volume":"93","author":"Ensafi","year":"2013","journal-title":"Int. J. Environ. Anal. Chem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"751","DOI":"10.1016\/0043-1354(84)90171-4","article-title":"A Low Level Spectrophotometric Method for the Determination of Sulfite in Water","volume":"18","author":"Haskins","year":"1984","journal-title":"Water Res."},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"975","DOI":"10.1016\/j.foodcont.2005.07.008","article-title":"Simple Methods for Rapid Determination of Sulfite in Food Products","volume":"17","author":"Li","year":"2006","journal-title":"Food Control."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"1755","DOI":"10.1021\/ac00190a032","article-title":"Cycling Technique for the Determination of Femtomole Amounts of Sulfite","volume":"61","author":"Keil","year":"1989","journal-title":"Anal. Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"3049","DOI":"10.1007\/s00216-013-6753-0","article-title":"Determination of Sulfite with Emphasis on Biosensing Methods: A Review","volume":"405","author":"Pundir","year":"2013","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"1513","DOI":"10.1021\/jf025693c","article-title":"Sulfite Analysis of Fruits and Vegetables by High-Performance Liquid Chromatography (HPLC) with Ultraviolet Spectrophotometric Detection","volume":"51","author":"McFeeters","year":"2003","journal-title":"J. Agric. Food Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"5126","DOI":"10.1021\/jf505525z","article-title":"Development of a Liquid Chromatography-Tandem Mass Spectrometry Method for the Determination of Sulfite in Food","volume":"63","author":"Robbins","year":"2015","journal-title":"J. Agric. Food Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"1360","DOI":"10.1111\/j.1365-2621.1986.tb13122.x","article-title":"Analysis of Free and Total Sulfites in Food by Ion Chromatography with Electrochemical Detection","volume":"51","author":"Kim","year":"2006","journal-title":"J. Food Sci."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"2439","DOI":"10.1002\/1522-2683(200208)23:15<2439::AID-ELPS2439>3.0.CO;2-Z","article-title":"Capillary Electrophoretic Determination of Thiosulfate, Sulfide and Sulfite Using in-Capillary Derivatization with Iodine","volume":"23","author":"Daunoravicius","year":"2002","journal-title":"Electrophoresis"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"67","DOI":"10.1016\/S0021-9673(01)01295-X","article-title":"Capillary Electrophoretic Determination of Sulfite Using the Zone-Passing Technique of in-Capillary Derivatization","volume":"934","author":"Jankovskiene","year":"2001","journal-title":"J. Chromatogr. A"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"343","DOI":"10.1039\/an9275200343","article-title":"Ministry of Health. The Determination of Sulphur Dioxide in Foods","volume":"52","year":"1927","journal-title":"Analyst"},{"key":"ref_23","first-page":"194","article-title":"Ripper Procedure for Determining Sulfur Dioxide in Wine: Collaborative Study","volume":"63","author":"Vahl","year":"1980","journal-title":"J.-Assoc. Off. Anal. Chem."},{"key":"ref_24","unstructured":"AOAC (2019). Optimized Monier-Williams Method. Official Methods of Analysis, AOAC Int."},{"key":"ref_25","unstructured":"AOAC (2019). Sulfite (Free) in Wines. Official Methods of Analysis, AOAC Int."},{"key":"ref_26","unstructured":"AOAC (2019). Sulfite (Total) in Foods and Beverages. Official Methods of Analysis, AOAC Int.. Method 990.29."},{"key":"ref_27","unstructured":"AOAC (2019). Sulfites in Foods and Beverages. Official Methods of Analysis, AOAC Int.. Method 990.31."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"537","DOI":"10.1016\/j.foodchem.2019.02.042","article-title":"Comparison and Optimization of Three Commercial Methods with an LC-MS\/MS Method for the Determination of Sulfites in Food and Beverages","volume":"286","author":"Carlos","year":"2019","journal-title":"Food Chem."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"2","DOI":"10.1016\/j.ccr.2017.05.003","article-title":"Fluorescent and Colorimetric Sensors for Anionic Species","volume":"354","author":"Gale","year":"2018","journal-title":"Coord. Chem. Rev."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"98","DOI":"10.1016\/j.ccr.2017.06.020","article-title":"Luminescent\/Colorimetric Probes and (Chemo-) Sensors for Detecting Anions Based on Transition and Lanthanide Ion Receptor\/Binding Complexes","volume":"354","author":"Aletti","year":"2018","journal-title":"Coord. Chem. Rev."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"4849","DOI":"10.1021\/jo900573v","article-title":"Selective Colorimetric Sensing of Anions in Aqueous Media through Reversible Covalent Bonding","volume":"74","author":"Kim","year":"2009","journal-title":"J. Org. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"7840","DOI":"10.1021\/cr5005524","article-title":"Recent Advances in Supramolecular Analytical Chemistry Using Optical Sensing","volume":"115","author":"You","year":"2015","journal-title":"Chem. Rev."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"7863","DOI":"10.1039\/C7NJ04699E","article-title":"A Dual Channel Sulphur-Containing a Macrocycle Functionalised BODIPY Probe for the Detection of Hg(Ii) in a Mixed Aqueous Solution","volume":"42","author":"Batista","year":"2018","journal-title":"New J. Chem"},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"9921","DOI":"10.1002\/anie.201805316","article-title":"Sensing Uranyl(VI) Ions by Coordination and Energy Transfer to a Luminescent Europium(III) Complex","volume":"57","author":"Harvey","year":"2018","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"192","DOI":"10.1021\/cr2004103","article-title":"Luminescent Chemodosimeters for Bioimaging","volume":"113","author":"Yang","year":"2013","journal-title":"Chem. Rev."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"418","DOI":"10.1002\/open.201500053","article-title":"Gated Silica Mesoporous Materials in Sensing Applications","volume":"4","author":"Pascual","year":"2015","journal-title":"ChemistryOpen"},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"2069","DOI":"10.1002\/chem.201805244","article-title":"Highly Sensitive and Selective Molecular Probes for Chromo-Fluorogenic Sensing of Carbon Monoxide in Air, Aqueous Solution and Cells","volume":"25","author":"Toscani","year":"2019","journal-title":"Chem. Eur. J."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"4400","DOI":"10.1039\/C4CS00346B","article-title":"Synthetic Fluorescent Probes for Studying Copper in Biological Systems","volume":"44","author":"Cotruvo","year":"2015","journal-title":"Chem. Soc. Rev."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"8","DOI":"10.1016\/j.snb.2010.09.066","article-title":"A Rhodamine-Based Fluorescent Probe Selective for Bisulfite Anion in Aqueous Ethanol Media","volume":"152","author":"Yang","year":"2011","journal-title":"Sens. Actuators B Chem."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"3430","DOI":"10.1039\/c2an35512d","article-title":"A Fluorescent Turn-on Probe for Bisulfite Based on Hydrogen Bond-Inhibited C\u2014N Isomerization Mechanism","volume":"137","author":"Sun","year":"2012","journal-title":"Analyst"},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"274","DOI":"10.1016\/j.snb.2013.04.070","article-title":"\u201cReactive\u201d Probe for Hydrogen Sulfite: Good Ratiometric Response and Bioimaging Application","volume":"184","author":"Cheng","year":"2013","journal-title":"Sens. Actuators B Chem."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"615","DOI":"10.1016\/j.snb.2017.02.127","article-title":"A New Fluorescent Material and Its Application in Sulfite and Bisulfite Bioimaging","volume":"246","author":"Yin","year":"2017","journal-title":"Sens. Actuators B Chem."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"2637","DOI":"10.1039\/c3cc39161b","article-title":"Fluorescent Probe for Biological Gas SO2 Derivatives Bisulfite and Sulfite","volume":"49","author":"Sun","year":"2013","journal-title":"Chem. Commun."},{"key":"ref_44","doi-asserted-by":"crossref","first-page":"5452","DOI":"10.1021\/acsomega.0c00063","article-title":"Red-Emission Probe for Ratiometric Fluorescent Detection of Bisulfite and Its Application in Live Animals and Food Samples","volume":"5","author":"Zhou","year":"2020","journal-title":"ACS Omega"},{"key":"ref_45","doi-asserted-by":"crossref","first-page":"3018","DOI":"10.1039\/c3an00172e","article-title":"A Real-Time Colorimetric and Ratiometric Fluorescent Probe for Sulfite","volume":"138","author":"Wu","year":"2013","journal-title":"Analyst"},{"key":"ref_46","doi-asserted-by":"crossref","first-page":"13957","DOI":"10.1002\/ange.201306688","article-title":"Selective and Sensitive Chromofluorogenic Detection of the Sulfite Anion in Water Using Hydrophobic Hybrid Organic\u2013Inorganic Silica Nanoparticles","volume":"125","author":"Agostini","year":"2013","journal-title":"Angew. Chem."},{"key":"ref_47","doi-asserted-by":"crossref","first-page":"322","DOI":"10.1016\/j.dyepig.2015.04.038","article-title":"A Simple Pyrene-Pyridinium-Based Fluorescent Probe for Colorimetric and Ratiometric Sensing of Sulfite","volume":"120","author":"Xu","year":"2015","journal-title":"Dyes Pigment."},{"key":"ref_48","doi-asserted-by":"crossref","first-page":"377","DOI":"10.1016\/j.snb.2015.01.122","article-title":"A Near-Infrared Fluorescent Probe for Rapid, Colorimetric and Ratiometric Detection of Bisulfite in Food, Serum, and Living Cells","volume":"211","author":"Zhang","year":"2015","journal-title":"Sens. Actuators B Chem."},{"key":"ref_49","doi-asserted-by":"crossref","first-page":"4637","DOI":"10.1039\/c4ob00132j","article-title":"A Coumarin-Quinolinium-Based Fluorescent Probe for Ratiometric Sensing of Sulfite in Living Cells","volume":"12","author":"Tan","year":"2014","journal-title":"Org. Biomol. Chem."},{"key":"ref_50","doi-asserted-by":"crossref","first-page":"5624","DOI":"10.1021\/ol102298b","article-title":"Chromogenic and Fluorogenic Signaling of Sulfite by Selective Deprotection of Resorufin Levulinate","volume":"12","author":"Choi","year":"2010","journal-title":"Org. Lett."},{"key":"ref_51","doi-asserted-by":"crossref","first-page":"11935","DOI":"10.1021\/jf2032928","article-title":"A Boron-Dipyrromethene-Based Fluorescent Probe for Colorimetric and Ratiometric Detection of Sulfite","volume":"59","author":"Gu","year":"2011","journal-title":"J. Agric. Food Chem."},{"key":"ref_52","doi-asserted-by":"crossref","first-page":"10869","DOI":"10.1039\/c2ra21471g","article-title":"A Highly Sulfite-Selective Ratiometric Fluorescent Probe Based on ESIPT","volume":"2","author":"Chen","year":"2012","journal-title":"RSC Adv."},{"key":"ref_53","doi-asserted-by":"crossref","first-page":"1196","DOI":"10.1016\/j.snb.2013.08.007","article-title":"A Fluorescein-Based Probe with High Selectivity and Sensitivity for Sulfite Detection in Aqueous Solution","volume":"188","author":"Ma","year":"2013","journal-title":"Sens. Actuators B Chem."},{"key":"ref_54","doi-asserted-by":"crossref","first-page":"1628","DOI":"10.1016\/j.ccr.2009.12.002","article-title":"Template Synthesis of Azacyclam Metal Complexes Using Primary Amides as Locking Fragments","volume":"254","author":"Fabbrizzi","year":"2010","journal-title":"Coord. Chem. Rev."},{"key":"ref_55","doi-asserted-by":"crossref","first-page":"1366","DOI":"10.1021\/ic00085a026","article-title":"Nickel(II) Complexes of Azacyclams: Oxidation and Reduction Behavior and Catalytic Effects in the Electroreduction of Carbon Dioxide","volume":"33","author":"Fabbrizzi","year":"1994","journal-title":"Inorg. Chem."},{"key":"ref_56","doi-asserted-by":"crossref","first-page":"455","DOI":"10.1351\/pac199365030455","article-title":"Novel Routes to Functionalized Cyclam-like Macrocycles","volume":"65","author":"Fabbrizzi","year":"1993","journal-title":"Pure Appl. Chem."},{"key":"ref_57","doi-asserted-by":"crossref","first-page":"2355","DOI":"10.1021\/acs.cgd.1c00011","article-title":"Coordination Polymers of the Macrocyclic Nickel(II) and Copper(II) Complexes with Isomeric Benzenedicarboxylates: The Case of Spatial Complementarity between the Bis-Macrocyclic Complexes and o-Phthalate","volume":"21","author":"Tsymbal","year":"2021","journal-title":"Cryst. Growth Des."},{"key":"ref_58","doi-asserted-by":"crossref","first-page":"237","DOI":"10.1007\/s10847-018-0855-4","article-title":"Structural Diversity of Metal\u2013Organic Frameworks via Employment of Azamacrocycles as a Building Block","volume":"92","author":"Lee","year":"2018","journal-title":"J. Incl. Phenom. Macrocycl. Chem."},{"key":"ref_59","doi-asserted-by":"crossref","first-page":"10976","DOI":"10.1021\/ja017560y","article-title":"A Metal\u2212Organic Bilayer Open Framework with a Dynamic Component: Single-Crystal-to-Single-Crystal Transformations","volume":"124","author":"Suh","year":"2002","journal-title":"J. Am. Chem. Soc."},{"key":"ref_60","doi-asserted-by":"crossref","first-page":"1820","DOI":"10.1039\/c3cc38519a","article-title":"An Unprecedented Dynamic Porous Metal\u2013Organic Framework Assembled from Fivefold Interlocked Closed Nanotubes with Selective Gas Adsorption Behaviors","volume":"49","author":"Ju","year":"2013","journal-title":"Chem Commun"},{"key":"ref_61","doi-asserted-by":"crossref","first-page":"154","DOI":"10.1016\/j.poly.2018.01.036","article-title":"Azamacrocyclic-Based Metal Organic Frameworks: Design Strategies and Applications","volume":"145","author":"Stackhouse","year":"2018","journal-title":"Polyhedron"},{"key":"ref_62","doi-asserted-by":"crossref","unstructured":"Savastano, M., Monini, V., Bazzicalupi, C., and Bianchi, A. (2022). Bidimensional Polyiodide Netting Stabilized by a Cu(II) Macrocyclic Complex. Inorganics, 10.","DOI":"10.3390\/inorganics10010012"},{"key":"ref_63","doi-asserted-by":"crossref","first-page":"368","DOI":"10.1021\/acs.inorgchem.1c02967","article-title":"Assembly of Polyiodide Networks with Cu(II) Complexes of Pyridinol-Based Tetraaza Macrocycles","volume":"61","author":"Savastano","year":"2022","journal-title":"Inorg. Chem."},{"key":"ref_64","doi-asserted-by":"crossref","first-page":"100034","DOI":"10.1016\/j.enchem.2020.100034","article-title":"Non-Noble Metal-Based Molecular Complexes for CO2 Reduction: From the Ligand Design Perspective","volume":"2","author":"Liu","year":"2020","journal-title":"EnergyChem"},{"key":"ref_65","doi-asserted-by":"crossref","first-page":"225","DOI":"10.1016\/j.ccr.2018.09.003","article-title":"Artificial Photosynthesis: Catalytic Water Oxidation and CO2 Reduction by Dinuclear Non-Noble-Metal Molecular Catalysts","volume":"377","author":"Wang","year":"2018","journal-title":"Coord. Chem. Rev."},{"key":"ref_66","doi-asserted-by":"crossref","first-page":"2670","DOI":"10.1002\/asia.201701130","article-title":"Capped Mesoporous Silica Nanoparticles for the Selective and Sensitive Detection of Cyanide","volume":"12","author":"Sayed","year":"2017","journal-title":"Chem. Asian J."},{"key":"ref_67","doi-asserted-by":"crossref","first-page":"7002","DOI":"10.1002\/chem.201500360","article-title":"Hexametaphosphate-Capped Silica Mesoporous Nanoparticles Containing CuII Complexes for the Selective and Sensitive Optical Detection of Hydrogen Sulfide in Water","volume":"21","author":"Milani","year":"2015","journal-title":"Chem.-Eur. J."},{"key":"ref_68","doi-asserted-by":"crossref","first-page":"1582","DOI":"10.1021\/ic950841k","article-title":"Template Synthesis of a Tetraaza Macrocycle Which Involves Benzaldehyde Rather Than Formaldehyde as a Building Block. Isolation and Structure Determination of the Open-Chain Schiff Base Intermediate Complex","volume":"35","author":"Fabbrizzi","year":"1996","journal-title":"Inorg. Chem."},{"key":"ref_69","doi-asserted-by":"crossref","unstructured":"Fabbrizzi, L., Lanfredi, A.M.M., Pallavicini, P., Perotti, A., Taglietti, A., and Ugozzoli, F. (1991). Crystal and Molecular Structure and Solution Behaviour of Low-Spin (3-Methyl-1,3,5,8,12-Pentaazacyclotetradecane)\u039a4N1,N5,N8,N12)Nickel(II) Diperchlorate. J. Chem Soc. Dalton Trans., 3263\u20133269.","DOI":"10.1039\/DT9910003263"},{"key":"ref_70","doi-asserted-by":"crossref","unstructured":"Rosokha, S.V., and Lampeka, Y.D. (1991). A New One-Pot Synthesis of Bis(Macrocyclic) Complexes: Preparation and Characterization of Nickel Complexes with Bis(Pentaazamacrocyclic) Ligands. J. Chem. Soc. Chem. Commun., 1077\u20131079.","DOI":"10.1039\/c39910001077"},{"key":"ref_71","doi-asserted-by":"crossref","first-page":"2777","DOI":"10.1016\/S0277-5387(97)00030-2","article-title":"Padlock Macrocyclic Complexes. The Synthesis of a Range of Nickel(II) Complexes of N-Alkyl Azacyclams and the Crystal Structure of (3-Ethyl-1,3,5,8,12-Penta-Azacyclotetradecane) Nickel(II) Perchlorate","volume":"16","author":"Hay","year":"1997","journal-title":"Polyhedron"},{"key":"ref_72","doi-asserted-by":"crossref","first-page":"269","DOI":"10.1016\/S0013-4686(98)00118-2","article-title":"Electrochemical and Spectral Properties of Novel Dinickel(II) and Dicopper(II) Complexes with N,N-Linked Bis(Pentaazacyclotetradecane)","volume":"44","author":"Ohsaka","year":"1998","journal-title":"Electrochim. Acta"},{"key":"ref_73","doi-asserted-by":"crossref","first-page":"4214","DOI":"10.1021\/ic980243g","article-title":"Aminotriazines as Locking Fragments in Macrocyclic Synthesis","volume":"37","author":"Bernhardt","year":"1998","journal-title":"Inorg. Chem."},{"key":"ref_74","doi-asserted-by":"crossref","unstructured":"De Blas, A., De Santis, G., Fabbrizzi, L., Licchelli, M., Lanfredi, A.M.M., Morosini, P., Pallavicini, P., and Ugozzoli, F. (1993). Amides and Sulfonamides: Efficient Molecular Padlocks for the Template Synthesis of Azacyclam (1,3,5,8,12-Pentaazacyclotetradecane) Macrocycles. J. Chem. Soc. Dalton Trans., 1411\u20131416.","DOI":"10.1039\/dt9930001411"},{"key":"ref_75","doi-asserted-by":"crossref","first-page":"3385","DOI":"10.1021\/ic00067a034","article-title":"The Copper(I) Complex of a Metallocyclam-Functionalized Phenanthroline: A Poorly Stable Species That Is Very Resistant to Oxidation","volume":"32","author":"Fabbrizzi","year":"1993","journal-title":"Inorg. Chem."},{"key":"ref_76","doi-asserted-by":"crossref","first-page":"106","DOI":"10.1021\/ic00053a018","article-title":"Pyridines with an Appended Metallocyclam Subunit. Versatile Building Blocks to Supramolecular Multielectron Redox Systems","volume":"32","author":"Fabbrizzi","year":"1993","journal-title":"Inorg. Chem."},{"key":"ref_77","doi-asserted-by":"crossref","first-page":"854","DOI":"10.1021\/ic00058a017","article-title":"Ferrocene-Metallocyclam Conjugates: New Redox Systems Whose Two-Electron Activity Can Be Modulated through the Medium","volume":"32","author":"Fabbrizzi","year":"1993","journal-title":"Inorg. Chem."},{"key":"ref_78","doi-asserted-by":"crossref","first-page":"1243","DOI":"10.1002\/chem.19960021010","article-title":"Fluorescence Redox Switching Systems Operating through Metal Centres: The NiIII\/NiII Couple","volume":"2","author":"Fabbrizzi","year":"1996","journal-title":"Chem. Eur. J."},{"key":"ref_79","doi-asserted-by":"crossref","first-page":"11288","DOI":"10.1002\/chem.200901364","article-title":"Templated Synthesis of Copper(II) Azacyclam Complexes Using Urea as a Locking Fragment and Their Metal-Enhanced Binding Tendencies towards Anions","volume":"15","author":"Boiocchi","year":"2009","journal-title":"Chem. Eur. J."},{"key":"ref_80","doi-asserted-by":"crossref","first-page":"273","DOI":"10.1016\/j.ccr.2005.04.022","article-title":"Light-Emitting Molecular Devices Based on Transition Metals","volume":"250","author":"Amendola","year":"2006","journal-title":"Coord. Chem. Rev."},{"key":"ref_81","doi-asserted-by":"crossref","unstructured":"Boiocchi, M., Fabbrizzi, L., Licchelli, M., Sacchi, D., V\u00e1zquez, M., and Zampa, C. (2003). A Two-Channel Molecular Dosimeter for the Optical Detection of Copper (II). Chem. Commun., 1812\u20131813.","DOI":"10.1039\/B305456J"},{"key":"ref_82","doi-asserted-by":"crossref","first-page":"18003","DOI":"10.1021\/ja207851s","article-title":"Development of a Highly Selective Fluorescence Probe for Hydrogen Sulfide","volume":"133","author":"Sasakura","year":"2011","journal-title":"J. Am. Chem. Soc."},{"key":"ref_83","doi-asserted-by":"crossref","first-page":"41","DOI":"10.1002\/ejic.201301306","article-title":"Highly Selective Fluorescence Detection of Hydrogen Sulfide by Using an Anthracene-Functionalized Cyclam\u2013CuII Complex","volume":"2014","author":"Costero","year":"2014","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_84","doi-asserted-by":"crossref","first-page":"3900","DOI":"10.1002\/ejic.201700623","article-title":"A Cyclam-Based Fluorescent Ligand as a Molecular Beacon for Cu2+ and H2S Detection","volume":"2017","author":"Mirra","year":"2017","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_85","doi-asserted-by":"crossref","unstructured":"Hathaway, B.J. (1984). A new look at the stereochemistry and electronic properties of complexes of the copper(II) ion. Structure and Bonding, Springer.","DOI":"10.1007\/BFb0111454"},{"key":"ref_86","doi-asserted-by":"crossref","first-page":"210","DOI":"10.1016\/j.ica.2011.12.001","article-title":"Synthesis of Novel Diazacyclam Copper(II) Complexes by Template Reaction Involving Sulphonamides as Locking Fragments","volume":"384","author":"Licchelli","year":"2012","journal-title":"Inorg. Chim. Acta"},{"key":"ref_87","doi-asserted-by":"crossref","first-page":"3198","DOI":"10.1021\/ja00323a023","article-title":"Origin of the High Ligand Field Strength and Macrocyclic Enthalpy in Complexes of Nitrogen-Donor Macrocycles","volume":"106","author":"Thoem","year":"1984","journal-title":"J. Am. Chem. Soc."},{"key":"ref_88","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1107\/S2052520616003954","article-title":"The Cambridge Structural Database","volume":"72","author":"Groom","year":"2016","journal-title":"Acta Crystallogr. Sect. B"},{"key":"ref_89","doi-asserted-by":"crossref","first-page":"2151","DOI":"10.1021\/ja00710a068","article-title":"Effect of Macrocyclic Structures on the Rate of Formation and Dissociation of Copper(II) Complexes","volume":"92","author":"Cabbiness","year":"1970","journal-title":"J. Am. Chem. Soc."},{"key":"ref_90","doi-asserted-by":"crossref","first-page":"392","DOI":"10.1021\/ar50130a005","article-title":"Distinctive Coordination Chemistry and Biological Significance of Complexes with Macrocyclic Ligands","volume":"11","author":"Busch","year":"1978","journal-title":"Acc. Chem. Res."},{"key":"ref_91","doi-asserted-by":"crossref","first-page":"15950","DOI":"10.1039\/C4DT02366H","article-title":"Crystal Structure, DFT, Spectroscopic and Biological Activity Evaluation of Analgin Complexes with Co(Ii), Ni(II) and Cu(II)","volume":"43","author":"Mansour","year":"2014","journal-title":"Dalton Trans."},{"key":"ref_92","doi-asserted-by":"crossref","unstructured":"Borman, P., and Elder, D. (2017). Q2(R1) Validation of Analytical Procedures. ICH Qual. Guidel., 127\u2013166.","DOI":"10.1002\/9781118971147.ch5"},{"key":"ref_93","doi-asserted-by":"crossref","first-page":"1627","DOI":"10.1021\/ac60214a047","article-title":"Smoothing and Differentiation of Data by Simplified Least Squares Procedures","volume":"36","author":"Savitzky","year":"1964","journal-title":"Anal. Chem."},{"key":"ref_94","doi-asserted-by":"crossref","first-page":"261","DOI":"10.1038\/s41592-019-0686-2","article-title":"SciPy 1.0: Fundamental Algorithms for Scientific Computing in Python","volume":"17","author":"Virtanen","year":"2020","journal-title":"Nat. Methods"},{"key":"ref_95","doi-asserted-by":"crossref","first-page":"90","DOI":"10.1109\/MCSE.2007.55","article-title":"Matplotlib: A 2D Graphics Environment","volume":"9","author":"Hunter","year":"2007","journal-title":"Comput. Sci. Eng."},{"key":"ref_96","doi-asserted-by":"crossref","first-page":"22","DOI":"10.1109\/MCSE.2011.37","article-title":"The NumPy Array: A Structure for Efficient Numerical Computation","volume":"13","author":"Colbert","year":"2011","journal-title":"Comput. Sci. Eng."},{"key":"ref_97","doi-asserted-by":"crossref","first-page":"21","DOI":"10.1109\/MCSE.2007.53","article-title":"IPython: A System for Interactive Scientific Computing","volume":"9","author":"Perez","year":"2007","journal-title":"Comput. Sci. Eng."},{"key":"ref_98","unstructured":"Newville, M., Otten, R., Nelson, A., Ingargiola, A., Stensitzki, T., Allan, D., Fox, A., Carter, F., and Pustakhod, D. (2022, January 31). Lmfit\/Lmfit-Py 0.9.13. Available online: https:\/\/doi.org\/10.5281\/zenodo.2620617."},{"key":"ref_99","doi-asserted-by":"crossref","first-page":"849","DOI":"10.1107\/S0021889812029111","article-title":"WinGX and It ORTEP for Windows: An Update","volume":"45","author":"Farrugia","year":"2012","journal-title":"J. Appl. Crystallogr."},{"key":"ref_100","doi-asserted-by":"crossref","first-page":"351","DOI":"10.1107\/S0567739468000707","article-title":"A Semi-Empirical Method of Absorption Correction","volume":"24","author":"North","year":"1968","journal-title":"Acta Crystallogr. Sect. A"},{"key":"ref_101","unstructured":"Brucker (2003). SAINT Software Reference Manual, Version 6, Bruker AXS Inc."},{"key":"ref_102","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1107\/S1600576714022985","article-title":"Comparison of Silver and Molybdenum Microfocus X-Ray Sources for Single-Crystal Structure Determination","volume":"48","author":"Krause","year":"2015","journal-title":"J. Appl. Crystallogr."},{"key":"ref_103","doi-asserted-by":"crossref","first-page":"115","DOI":"10.1107\/S0021889898007717","article-title":"SIR97: A New Tool for Crystal Structure Determination and Refinement","volume":"32","author":"Altomare","year":"1999","journal-title":"J. Appl. Crystallogr."},{"key":"ref_104","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1107\/S2053229614024218","article-title":"Crystal Structure Refinement with SHELXL","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr. Sect. C Struct. Chem."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/6\/1852\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,10]],"date-time":"2025-10-10T22:35:33Z","timestamp":1760135733000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/27\/6\/1852"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2022,3,12]]},"references-count":104,"journal-issue":{"issue":"6","published-online":{"date-parts":[[2022,3]]}},"alternative-id":["molecules27061852"],"URL":"https:\/\/doi.org\/10.3390\/molecules27061852","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2022,3,12]]}}}