{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T01:03:49Z","timestamp":1760403829388,"version":"build-2065373602"},"reference-count":69,"publisher":"Wiley","issue":"2","license":[{"start":{"date-parts":[[2005,1,20]],"date-time":"2005-01-20T00:00:00Z","timestamp":1106179200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2005,2,11]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:italic>The interaction of Cu<\/jats:italic><jats:sup><jats:italic>II<\/jats:italic><\/jats:sup> <jats:italic>with 6\u2010formylamino\u20103\u03b1\u2010carboxypenam and 6\u2010acetylamino\u20103\u03b1\u2010carboxypenam was investigated by means of DFT calculations with the UB3LYP functional. Nine different modes of complexation between Cu<\/jats:italic><jats:sup><jats:italic>II<\/jats:italic><\/jats:sup> <jats:italic>and 6\u2010formylamino\u2010<\/jats:italic>3<jats:italic>\u03b1\u2010carboxypenam were located. When two water molecules directly bonded to Cu<\/jats:italic><jats:sup><jats:italic>II<\/jats:italic><\/jats:sup> <jats:italic>are included in the calculations on 6\u2010acetylamino\u20103\u03b1\u2010carboxypenam as penicillin model, only six Cu<\/jats:italic><jats:sup><jats:italic>II<\/jats:italic><\/jats:sup><jats:italic>(H<jats:sub>2<\/jats:sub>O)<jats:sub>2<\/jats:sub>\u20136\u2010acetylamino\u20103\u03b1\u2010carboxypenam complexes (<jats:bold>1\u2009S<\/jats:bold>\u2013<jats:bold>6\u2009S<\/jats:bold>) are found. In solution the four most stable complexes obtained from our calculations, <jats:bold>6\u2009S<\/jats:bold>, <jats:bold>1\u2009S<\/jats:bold>, <jats:bold>2\u2009S<\/jats:bold>, and <jats:bold>3\u2009S<\/jats:bold>, exhibit Cu<\/jats:italic><jats:sup><jats:italic>II<\/jats:italic><\/jats:sup> <jats:italic>in square\u2010planar coordination with at least one bond to the carboxylate group, in agreement with experimental evidence. Complexes <jats:bold>6\u2009S<\/jats:bold>, <jats:bold>1\u2009S<\/jats:bold>, and <jats:bold>3\u2009S<\/jats:bold> were previously suggested by available experimental evidence. In three of the most stable complexes (<jats:bold>6\u2009S<\/jats:bold>, <jats:bold>2\u2009S<\/jats:bold>, and <jats:bold>3\u2009S<\/jats:bold>) the \u03b2\u2010lactam C\uf8ffN bond is remarkably activated and displays C\uf8ffN bond lengths similar to those found in some tetrahedral intermediates located for the hydrolysis of 2\u2010azetidinones. This suggests that these kinds of complexes belong to the reaction coordinate for the degradation of<\/jats:italic> \u03b2<jats:italic>\u2010lactam antibiotics in the presence of Cu<\/jats:italic><jats:sup><jats:italic>II<\/jats:italic><\/jats:sup>.<\/jats:p>","DOI":"10.1002\/cphc.200400280","type":"journal-article","created":{"date-parts":[[2005,1,20]],"date-time":"2005-01-20T07:28:51Z","timestamp":1106206131000},"page":"344-351","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["A Theoretical Analysis of the Coordination Modes of Cu<sup>II<\/sup> with Penicillins: Activation of the \u03b2\u2010Lactam C\uf8ffN Bond"],"prefix":"10.1002","volume":"6","author":[{"given":"Pablo","family":"Campomanes","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"M. Isabel","family":"Men\u00e9ndez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ram\u00f3n","family":"L\u00f3pez","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Tom\u00e1s L.","family":"Sordo","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2005,2,4]]},"reference":[{"volume-title":"The Chemistry of \u03b2\u2010Lactams","year":"1992","key":"e_1_2_5_1_2"},{"key":"e_1_2_5_2_2","first-page":"199","volume-title":"\u03b2\u2010Lactamase: Mechanism of Action in The Chemistry of \u03b2\u2010Lactams","author":"Waley S. G.","year":"1992"},{"key":"e_1_2_5_3_2","doi-asserted-by":"publisher","DOI":"10.1039\/a803578d"},{"key":"e_1_2_5_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1367-5931(99)00017-4"},{"key":"e_1_2_5_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/jps.2600581210"},{"key":"e_1_2_5_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/p29780000335"},{"key":"e_1_2_5_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/P29800001725"},{"key":"e_1_2_5_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/jps.2600720402"},{"key":"e_1_2_5_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar00100a005"},{"key":"e_1_2_5_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/DT9890000197"},{"key":"e_1_2_5_11_2","doi-asserted-by":"publisher","DOI":"10.1039\/P29890000227"},{"key":"e_1_2_5_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/P29900000043"},{"key":"e_1_2_5_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/p29900000393"},{"key":"e_1_2_5_14_2","doi-asserted-by":"publisher","DOI":"10.1248\/cpb.40.3228"},{"key":"e_1_2_5_15_2","doi-asserted-by":"publisher","DOI":"10.1016\/0378-5173(93)90189-M"},{"key":"e_1_2_5_16_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00098a002"},{"key":"e_1_2_5_17_2","unstructured":"\u00a0"},{"key":"e_1_2_5_18_2","doi-asserted-by":"publisher","DOI":"10.1038\/194474a0"},{"key":"e_1_2_5_19_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-2836(64)80163-7"},{"volume-title":"Metal Ions in Biological Systems","year":"1985","key":"e_1_2_5_20_2"},{"volume-title":"Handbook of Metal\u2010Ligand Interactions in Biological Fluids","year":"1995","key":"e_1_2_5_21_2"},{"key":"e_1_2_5_22_2","first-page":"388","volume-title":"Bioorganic Chemistry. A Chemical Approach to Enzyme Action","author":"Dugas H.","year":"1996"},{"key":"e_1_2_5_23_2","doi-asserted-by":"publisher","DOI":"10.1042\/bj1430129"},{"volume-title":"The Use of Antibiotics","year":"1988","author":"Kucers A.","key":"e_1_2_5_24_2"},{"key":"e_1_2_5_25_2","doi-asserted-by":"publisher","DOI":"10.1039\/p29750000567"},{"key":"e_1_2_5_26_2","doi-asserted-by":"publisher","DOI":"10.1016\/0378-5173(93)90353-H"},{"key":"e_1_2_5_27_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0378-5173(96)04844-2"},{"key":"e_1_2_5_28_2","doi-asserted-by":"publisher","DOI":"10.1016\/S1386-1425(01)00401-2"},{"key":"e_1_2_5_29_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0277-5387(00)86068-4"},{"key":"e_1_2_5_30_2","doi-asserted-by":"publisher","DOI":"10.1126\/science.291.5505.856"},{"key":"e_1_2_5_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja001265g"},{"key":"e_1_2_5_32_2","unstructured":"To confirm C\uf8ffN activation in solution we reoptimized3\u2009Swith a continuum model (Poisson\u2013Boltzmann) implemented in the Jaguar program (Jaguar 5.0 edit. Schr\u00f6dinger Inc. Portland OR 2003). This optimization failed with the PCM method implemented in Gaussian\u200998. In solution the C\uf8ffN bond (1.521 \u00c5) is even more stretched than in the gas phase (1.487 \u00c5)."},{"key":"e_1_2_5_33_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3765(20020215)8:4<859::AID-CHEM859>3.0.CO;2-I"},{"key":"e_1_2_5_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp963387u"},{"key":"e_1_2_5_35_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp036573q"},{"key":"e_1_2_5_36_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00038a040"},{"key":"e_1_2_5_37_2","unstructured":"Gaussian\u200998 (Revision\u2009A.7) M. J. Frisch G. W. Trucks H. B. Schlegel G. E. Scuseria M. A. Robb J. R. Cheeseman V. G. Zakrzewski J. A. Montgomery Jr. R. E. Stratmann J. C. Burant S. Dapprich J. M. Millam A. D. Daniels K. N. Kudin M. C. Strain O. Farkas J. Tomasi V. Barone M. Cossi R. Cammi B. Mennucci C. Pomelli C. Adamo S. Clifford J. Ochterski G. A. Petersson P. Y. Ayala Q. Cui K. Morokuma D. K. Malick A. D. Rabuck K. Raghavachari J. B. Foresman J. Cioslowski J. V. Ortiz B. B. Stefanov G. Liu A. Liashenko P. Piskorz I. Komaromi R. Gomperts R. L. Martin D. J. Fox T. Keith M. A. Al\u2010Laham C. Y. Peng A. Nanayakkara C. Gonzalez M. Challacombe P. M. W. Gill B. Johnson W. Chen M. W. Wong J. L. Andres C. Gonzalez M. Head\u2010Gordon E. S. Replogle J. A. Pople Gaussian Inc. Pittsburgh PA 1998."},{"key":"e_1_2_5_38_2","unstructured":"\u00a0"},{"key":"e_1_2_5_39_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.38.3098"},{"key":"e_1_2_5_40_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.37.785"},{"key":"e_1_2_5_41_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_5_42_2","unstructured":"\u00a0"},{"key":"e_1_2_5_43_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00267a063"},{"key":"e_1_2_5_44_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.476673"},{"key":"e_1_2_5_45_2","unstructured":"\u00a0"},{"key":"e_1_2_5_46_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.1673095"},{"key":"e_1_2_5_47_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.433731"},{"key":"e_1_2_5_48_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.438955"},{"key":"e_1_2_5_49_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.438980"},{"key":"e_1_2_5_50_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.457230"},{"key":"e_1_2_5_51_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.540030212"},{"key":"e_1_2_5_52_2","doi-asserted-by":"publisher","DOI":"10.1039\/a903018b"},{"key":"e_1_2_5_53_2","unstructured":"To check the reliability of the geometry provided by the UB3LYP method we reoptimized complex1at the UHF\/6\u201031G* and UMP2\/6\u201031G* levels (no significant spin contamination took place in the calculations). The three structures are quite similar. The largest discrepancy between the UHF and the UB3LYP geometries is 0.035 \u00c5 for the distance between the \u03b2\u2010lactam carbonyl oxygen atom and CuII and the largest discrepancy between UMP2 and UB3LYP is 0.027 \u00c5 for the C6\uf8ffC7 bond."},{"volume-title":"Statistical Mechanics","year":"1976","author":"McQuarrie D. 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