{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T23:20:45Z","timestamp":1788391245336,"version":"build-2803163510"},"reference-count":34,"publisher":"American Chemical Society (ACS)","issue":"17","license":[{"start":{"date-parts":[[2017,10,4]],"date-time":"2017-10-04T00:00:00Z","timestamp":1507075200000},"content-version":"vor","delay-in-days":168,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_ccbyncnd_termsofuse.html"}],"funder":[{"DOI":"10.13039\/100007479","name":"Fondazione Cassa di Risparmio di Padova e Rovigo","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/100007479","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001712","name":"Stichting voor Fundamenteel Onderzoek der Materie","doi-asserted-by":"publisher","award":["03BMP03"],"award-info":[{"award-number":["03BMP03"]}],"id":[{"id":"10.13039\/501100001712","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003246","name":"Nederlandse Organisatie voor Wetenschappelijk Onderzoek","doi-asserted-by":"publisher","award":["700.58.014"],"award-info":[{"award-number":["700.58.014"]}],"id":[{"id":"10.13039\/501100003246","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2017,5,4]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>We address the interpretation, via an integrated computational approach, of the experimental continuous-wave electron paramagnetic resonance (cw-EPR) spectra of a complete set of conformationally highly restricted, stable 310-helical peptides from hexa- to nonamers, each bis-labeled with nitroxide radical-containing TOAC (4-amino-1-oxyl-2,2,6,6-tetramethylpiperidine-4-carboxylic acid) residues. The usefulness of TOAC for this type of analysis has been shown already to be due to its cyclic piperidine side chain, which is rigidly connected to the peptide backbone \u03b1-carbon. The TOAC \u03b1-amino acids are separated by two, three, four, and five intervening residues. This set of compounds has allowed us to modulate both the radical\u00b7\u00b7\u00b7radical distance and the relative orientation parameters. To further validate our conclusion, a comparative analysis has been carried out on three singly TOAC-labeled peptides of similar main-chain length.<\/jats:p>","DOI":"10.1021\/acs.jpcb.7b01050","type":"journal-article","created":{"date-parts":[[2017,4,19]],"date-time":"2017-04-19T14:48:55Z","timestamp":1492613335000},"page":"4379-4387","source":"Crossref","is-referenced-by-count":4,"title":["Integrated Computational Approach\nto the Electron\nParamagnetic Resonance Characterization of Rigid 310-Helical\nPeptides with TOAC Nitroxide Spin Labels"],"prefix":"10.1021","volume":"121","author":[{"given":"Marco","family":"Gerolin","sequence":"first","affiliation":[{"name":"University of Padova , , ,","place":["Padova, Italy, 35131"]},{"name":"UPMC University of Paris 06, CNRS, Laboratory of Biomolecules , , ,","place":["Paris, France, 75005"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mirco","family":"Zerbetto","sequence":"additional","affiliation":[{"name":"University of Padova , , ,","place":["Padova, Italy, 35131"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Alessandro","family":"Moretto","sequence":"additional","affiliation":[{"name":"University of Padova , , ,","place":["Padova, Italy, 35131"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fernando","family":"Formaggio","sequence":"additional","affiliation":[{"name":"University of Padova , , ,","place":["Padova, Italy, 35131"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Claudio","family":"Toniolo","sequence":"additional","affiliation":[{"name":"University of Padova , , ,","place":["Padova, Italy, 35131"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Martin","family":"van Son","sequence":"additional","affiliation":[{"name":"Leiden University , , ,","place":["Leiden, The Netherlands, 2300RA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Maryam Hashemi","family":"Shabestari","sequence":"additional","affiliation":[{"name":"Leiden University , , ,","place":["Leiden, The Netherlands, 2300RA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7632-1968","authenticated-orcid":true,"given":"Martina","family":"Huber","sequence":"additional","affiliation":[{"name":"Leiden University , , ,","place":["Leiden, The Netherlands, 2300RA"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7614-8931","authenticated-orcid":true,"given":"Paolo","family":"Calligari","sequence":"additional","affiliation":[{"name":"University of Padova , , ,","place":["Padova, Italy, 35131"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Antonino","family":"Polimeno","sequence":"additional","affiliation":[{"name":"University of Padova , , ,","place":["Padova, Italy, 35131"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2017,4,19]]},"reference":[{"key":"2026090219060907400_cit1","doi-asserted-by":"publisher","first-page":"107","DOI":"10.1007\/BF03161886","article-title":"Pulsed Electron Double Resonance\n(PELDOR) and Its Applications in Free-Radicals Research","volume":"15","author":"Milov","year":"1998","journal-title":"Appl. Magn. Reson."},{"key":"2026090219060907400_cit2","doi-asserted-by":"publisher","first-page":"72","DOI":"10.1006\/jmre.2001.2498","article-title":"Direct Conversion of\nEPR Dipolar Time Evolution Data to Distance Distributions","volume":"155","author":"Jeschke","year":"2002","journal-title":"J. Magn. Reson."},{"key":"2026090219060907400_cit3","doi-asserted-by":"publisher","first-page":"2668","DOI":"10.1021\/jp066908e","article-title":"Ab Initio\nModeling of CW-ESR Spectra of the Double Spin Labeled Peptide Fmoc-(Aib\u2013Aib\u2013TOAC)2-Aib-OMe in Acetonitrile","volume":"111","author":"Zerbetto","year":"2007","journal-title":"J. Phys. Chem.\nB"},{"key":"2026090219060907400_cit4","doi-asserted-by":"publisher","first-page":"13026","DOI":"10.1021\/jp2063645","article-title":"In Silico\nInterpretation of CW-ESR at 9 and 95 GHz of Mono- and Bis TOAC-Labeled\nAib-Homo Peptides in Fluid and Frozen Acetonitrile","volume":"115","author":"Carlotto","year":"2011","journal-title":"J. Phys. Chem. B"},{"key":"2026090219060907400_cit5","doi-asserted-by":"publisher","first-page":"244","DOI":"10.1002\/bip.22467","article-title":"Conformation and EPR Characterization\nof Rigid, 310-Helical Peptides with TOAC Spin Labels: Models\nfor Short Distances","volume":"102","author":"Hashemi Shabestari","year":"2014","journal-title":"Biopolymers (Pept. Sci.)"},{"key":"2026090219060907400_cit6","doi-asserted-by":"publisher","first-page":"153","DOI":"10.1002\/(SICI)1097-0282(1998)47:2&lt;153::AID-BIP4&gt;3.0.CO;2-T","article-title":"TOAC, a Nitroxide\nSpin-Labeled, Achiral\nC\u03b1-Tetrasubstituted \u03b1-Amino Acid, Is an Excellent\nTool in Materials Science and Biochemistry","volume":"47","author":"Toniolo","year":"1998","journal-title":"Biopolymers (Pept. Sci.)"},{"key":"2026090219060907400_cit7","doi-asserted-by":"publisher","first-page":"396","DOI":"10.1002\/1097-0282(2001)60:6&lt;396::AID-BIP10184&gt;3.0.CO;2-7","article-title":"Control of Peptide\nConformation by the Thorpe-Ingold Effect (C\u03b1-Tetrasubstitution)","volume":"60","author":"Toniolo","year":"2001","journal-title":"Biopolymers (Pept. Sci.)"},{"key":"2026090219060907400_cit8","doi-asserted-by":"publisher","first-page":"6747","DOI":"10.1021\/bi00481a001","article-title":"Structural Characteristics\nof \u03b1-Helical Peptide\nMolecules Containing Aib Residues","volume":"29","author":"Karle","year":"1990","journal-title":"Biochemistry"},{"key":"2026090219060907400_cit9","doi-asserted-by":"publisher","first-page":"7618","DOI":"10.1021\/ja961025u","article-title":"ESR Characterization\nof Hexameric, Helical Peptides Using Double TOAC Labeling","volume":"118","author":"Hanson","year":"1996","journal-title":"J. Am. Chem. Soc."},{"key":"2026090219060907400_cit10","doi-asserted-by":"publisher","first-page":"4609","DOI":"10.1039\/b607998a","article-title":"Toward an Integrated Computational Approach to CW-ESR\nSpectra of Free Radicals","volume":"8","author":"Barone","year":"2006","journal-title":"Phys. Chem. Chem.\nPhys."},{"key":"2026090219060907400_cit11","doi-asserted-by":"publisher","first-page":"2680","DOI":"10.1016\/j.cpc.2009.06.017","article-title":"Simulation\nof Electron Spin Resonance\nSpectroscopy in Diverse Environments: an Integrated Approach","volume":"180","author":"Zerbetto","year":"2009","journal-title":"Comput. Phys. Commun."},{"key":"2026090219060907400_cit12","doi-asserted-by":"publisher","first-page":"387","DOI":"10.1002\/9780470141229.ch10","article-title":"Spin Relaxation and Motional Dynamics","volume":"73","author":"Schneider","year":"1989","journal-title":"Adv.\nChem. Phys."},{"key":"2026090219060907400_cit13","doi-asserted-by":"publisher","first-page":"309","DOI":"10.1021\/acs.jctc.6b00702","article-title":"Decomposition of Proteins\ninto Dynamic Units from Atomic Cross-Correlation Functions","volume":"13","author":"Calligari","year":"2017","journal-title":"J. Chem. Theory Comput."},{"key":"2026090219060907400_cit14","doi-asserted-by":"publisher","first-page":"11248","DOI":"10.1021\/ja073516s","article-title":"Unraveling Solvent-Driven\nEquilibria between \u03b1-\nand 310-Helices through an Integrated Spin Labeling and\nComputational Approach","volume":"129","author":"Carlotto","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"2026090219060907400_cit15","doi-asserted-by":"publisher","first-page":"024501","DOI":"10.1063\/1.2812280","article-title":"On the Interpretation\nof Continuous Wave Electron Spin Resonance Spectra of Tempo-Palmitate\nin 5-Cyanobiphenyl","volume":"128","author":"Zerbetto","year":"2008","journal-title":"J. Chem. Phys."},{"key":"2026090219060907400_cit16","doi-asserted-by":"publisher","first-page":"11202","DOI":"10.1021\/jp804675q","article-title":"Modeling of\ncw-EPR Spectra of Propagating Radicals in Methacrylic Polymerization\nat Different Temperatures","volume":"112","author":"Hermosilla","year":"2008","journal-title":"J. Phys. Chem. B"},{"key":"2026090219060907400_cit17","doi-asserted-by":"publisher","first-page":"1064","DOI":"10.1002\/qua.25132","article-title":"Quantum Chemical\nCalculation of Exchange Interactions in Supramolecularly Arranged\nN,N\u2019-dioxy-2,6-diazaadamantane Organic Biradical","volume":"116","author":"Khafizov","year":"2016","journal-title":"Int. J. Quantum Chem."},{"key":"2026090219060907400_cit18","doi-asserted-by":"publisher","first-page":"5504","DOI":"10.1039\/c2cp23845d","article-title":"Magnetic Exchange\nCoupling in Bis-Nitroxides: a Theoretical Analysis of the Solvent\nEffects","volume":"14","author":"Coulaud","year":"2012","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026090219060907400_cit19","doi-asserted-by":"publisher","first-page":"265","DOI":"10.1007\/s002140000133","article-title":"Magnetic Coupling in\nBiradicals, Binuclear Complexes and Wide-Gap Insulators: a Survey\nof Ab Initio Wave Function and Density Functional Theory Approaches","volume":"104","author":"Illas","year":"2000","journal-title":"Theor. Chem. Acc."},{"key":"2026090219060907400_cit20","doi-asserted-by":"publisher","first-page":"33","DOI":"10.1016\/0301-0104(93)80104-H","article-title":"Specific CI Calculation\nof Energy Differences: Transition Energies and Bond Energies","volume":"172","author":"Miralles","year":"1993","journal-title":"Chem. Phys."},{"key":"2026090219060907400_cit21","doi-asserted-by":"publisher","first-page":"4129","DOI":"10.1103\/PhysRevB.55.4129","article-title":"Ab Initio Theoretical Comparative\nStudy of Magnetic Coupling in KNiF3 and K2NiF4","volume":"55","author":"Moreira","year":"1997","journal-title":"Phys.\nRev. B"},{"key":"2026090219060907400_cit22","doi-asserted-by":"publisher","first-page":"1511","DOI":"10.1007\/s11172-013-0217-8","article-title":"Combined Calculation Method of Weak\nExchange Interactions in Biradicals","volume":"62","author":"Umanskii","year":"2013","journal-title":"Russ. Chem.\nBull."},{"key":"2026090219060907400_cit23","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1134\/S1990793115010121","article-title":"Weak Exchange\nInteractions in Biradicals: A Pseudopotential for Unpaired Electrons\nand an Asymptotic Method for Calculating the Exchange Integral","volume":"9","author":"Umanskii","year":"2015","journal-title":"Russ. J. Phys. Chem. B"},{"key":"2026090219060907400_cit24","doi-asserted-by":"publisher","first-page":"084108","DOI":"10.1063\/1.2436888","article-title":"Gaussian-4\nTheory","volume":"126","author":"Curtiss","year":"2007","journal-title":"J. Chem. Phys."},{"key":"2026090219060907400_cit25","doi-asserted-by":"publisher","first-page":"4734","DOI":"10.1021\/ja057414i","article-title":"Stochastic\nModeling of CW-ESR Spectroscopy of [60]Fulleropyrrolidine Bisadducts\nwith Nitroxide Probes","volume":"128","author":"Polimeno","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"2026090219060907400_cit26","doi-asserted-by":"publisher","first-page":"3915","DOI":"10.1063\/1.444346","article-title":"Electron-Spin\nRelaxation and Ordering in Smetic and Supercooled Nematic Liquid Crystals","volume":"77","author":"Meirovitch","year":"1982","journal-title":"J. Chem. Phys."},{"key":"2026090219060907400_cit27","volume-title":"Gaussian\n03","author":"Frisch","year":"2004","edition":"Revision C.02"},{"key":"2026090219060907400_cit28","first-page":"469","article-title":"Finite Elements Molecular\nSurfaces in Continuum Solvent Models for Large Chemical Systems","volume":"2","author":"Scalmani","year":"2002","journal-title":"J. Comput. Methods Sci. Eng."},{"key":"2026090219060907400_cit29","doi-asserted-by":"publisher","first-page":"1231","DOI":"10.1021\/cr960085f","article-title":"Interplay of Electronic, Environmental, and Vibrational\nEffects in Determining the Hyperfine Coupling Constants of Organic\nFree Radicals","volume":"104","author":"Improta","year":"2004","journal-title":"Chem. Rev."},{"key":"2026090219060907400_cit30","doi-asserted-by":"publisher","first-page":"2","DOI":"10.1002\/jcc.21007","article-title":"Hydrodynamic\nModeling of Diffusion\nTensor Properties of Flexible Molecules","volume":"30","author":"Barone","year":"2009","journal-title":"J.\nComput. Chem."},{"key":"2026090219060907400_cit31","doi-asserted-by":"publisher","first-page":"167","DOI":"10.1016\/0301-0104(87)87034-9","article-title":"Coupling of\nthe Overall Molecular Motion with the Conformational Transitions.\nI. The Model System of Two Coupled Rotors","volume":"118","author":"Moro","year":"1987","journal-title":"Chem.\nPhys."},{"key":"2026090219060907400_cit32","doi-asserted-by":"publisher","first-page":"181","DOI":"10.1016\/0301-0104(87)87035-0","article-title":"Coupling of\nthe Overall Molecular Motion with the Conformational Transitions.\nII. The Full Rotational Problem","volume":"118","author":"Moro","year":"1987","journal-title":"Chem. Phys."},{"key":"2026090219060907400_cit33","volume-title":"CRC Handbook of Chemistry\nand Physics","author":"Haynes","year":"2012","edition":"93"},{"key":"2026090219060907400_cit34","doi-asserted-by":"crossref","first-page":"133","DOI":"10.1016\/B978-0-12-092350-2.50009-6","volume-title":"Spin Labeling,Theory\nand Applications","author":"Luckhurst","year":"1976"}],"container-title":["The Journal of Physical Chemistry B"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpcb.7b01050","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/121\/17\/4379\/67045543\/acs.jpcb.7b01050.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article-pdf\/121\/17\/4379\/67045543\/acs.jpcb.7b01050.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T23:06:15Z","timestamp":1788390375000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpcbfk\/article\/121\/17\/4379\/858800\/Integrated-Computational-Approach-to-the-Electron"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2017,4,19]]},"references-count":34,"journal-issue":{"issue":"17","published-online":{"date-parts":[[2017,4,19]]},"published-print":{"date-parts":[[2017,5,4]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpcb.7b01050","relation":{},"ISSN":["1520-6106","1520-5207"],"issn-type":[{"value":"1520-6106","type":"print"},{"value":"1520-5207","type":"electronic"}],"subject":[],"published":{"date-parts":[[2017,4,19]]}}}