Electron Paramagnetic Resonance as a Probe for Metal Ions and Radicals in Paper
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Alfonso Zoleo
Alfonso Zoleo gained his first degree in 1995 at the Department of Chemical Sciences of the University of Padova, under the supervision of Prof. Marina Brustolon, with a work in the field of the Electron Paramagnetic Resonance (EPR). In 2000, he received a Ph.D degree in Chemical Sciences at the same Department, under the supervision of Prof. Marina Brustolon, concerning advanced EPR techniques (CW and pulsed EPR). In 2000, he took part as Post-Doc Fellow to the TMR (Training and Mobility Research) European research program at the Max Volmer Institut of the Technische Universität, Berlin. Since 2008, it has been active in the study and application of EPR to Cultural Heritage materials, and specifically to cellulose and paper materials from historic books, working in cooperation with national and international experts in the field, and crossing the results with data from canonical spectroscopies (IR, Raman, UV-Vis) and other analytical techniques (HPIC, HPLC, MS).Laura Speri gained her Bachelor’s degree in “Sciences and Technologies applied on Cultural Heritage” at the University of Padua under the supervision of Dr. Alfonso Zoleo in 2013, with a thesis entitled “EPR characterization of paper degradation by-products in a 16th century book and comparison with model systems.” At the moment, she is graduating in “Conservation and Restoration” at University Ca’ Foscari of Venice: her Master’s degree thesis internship deals with the optimization of Restoration plasters for walls affected by capillary salt ascent by means of statistical methods.Maddalena Bronzato graduated in 2011 with full marks cum laude in Chemistry at the University of Padua, with a Master’s thesis entitled “Spectroscopic analyses of ancient paper degradation products. A 16th century codex.” From January 2012 to March 2015, she was active as a PhD student in the Physical Chemistry Department of the same university. The research, developed during the thesis internship and the PhD studies, was focused on the characterization of degradation by-products present in ancient papers by means of chemical, spectroscopic and separative techniques. From May to October 2015, she worked as a Post-Doc fellow at the Environmental and Analytical Chemistry Department of the same institution, developing a project regarding the detection and quantification of Cr(III) ligands, in particular polyamino carboxylic acids, in tannery waste waters. At the moment, she is working on a distinct project in cooperation with the Physical Chemistry Department, involving the restoration of a precious ancient manuscript.
Abstract
Electron Paramagnetic Resonance (EPR) is a technique devoted to the identification and characterization of paramagnetic species, i.e. chemical species with unpaired electrons. Very common paramagnetic species which can be detected through EPR in historic paper are Fe(III), Mn(II), Cu(II) ions and radicals, where Fe(III), Cu(II) and radicals play a relevant role in paper degradation. Specifically, Fe(III) is almost ubiquitous in historic paper. Here we propose an overview of the EPR signals in historic and artificially aged paper, and in particular, we would like to show how a deep analysis of EPR signals from paper could provide useful information about the paper’s origin and unique indications of the degradation and oxidation level of the paper.
Zusammenfassung
Elektronenspinresonanz als Untersuchung für Metallionen und Radikale im Papier
Elektronenspinresonanz (ESR) ist eine Technik, die eine Identifizierung und Charakterisierung von paramagnetischen Spezies, d.h. chemischer Spezies mit ungepaarten Elektronen, ermöglicht. Unter den üblichen paramagnetischen Spezies, die mit EPR in historischen und modernen Papieren detektiert werden können, befinden sich auch Fe(III), Mn(II) und Cu(II) Ionen, sowie Radikale, wobei Fe(III), Cu(II) und Radikale eine entscheidende Rolle beim Papierabbau spielen. Insbesondere Fe(III) ist eigentlich immer in historischen Papieren enthalten. In diesem Beitrag geben wir einen Überblick über EPR Signale von historischen und künstlich gealterten Papieren. Wir wollen zeigen, dass eine gründliche Analyse von EPR-Signalen von Papieren nützliche Informationen über den Ursprung des Papiers und einzigartige Merkmale von Papierabbau und Ausmaß der Oxidation ergeben.
Résumé
La Résonance Paramagnétique Electronique comme moyen d’exploration des ions métalliques et des radicaux dans le papier
La résonance paramagnétique électronique (RPE) est une technique consacrée à l‘identification et à la caractérisation d’espèces paramagnétiques, c’est à dire des espèces chimiques avec des électrons non appariés. Les espèces paramagnétiques communes qui peuvent être détectés grâce à l’RPE dans les papiers anciens et modernes sont les ions et radicaux Fe (III), Mn (II), Cu (II), où Fe (III), Cu (II) et les radicaux jouent un rôle significatif dans la dégradation du papier. Plus précisément, l’ion Fe (III) est presque omniprésent dans les papiers anciens. Les auteurs proposent dans cet article un aperçu des signaux RPE obtenus avec des papiers anciens et artificiellement vieillis, et tiennent en particulier à montrer comment une analyse profonde des signaux RPE obtenus à partir de ces papiers pourrait fournir des informations utiles quant à l‘origine du papier et des indications uniques sur la dégradation du papier et le niveau d‘oxydation.
About the authors
Alfonso Zoleo gained his first degree in 1995 at the Department of Chemical Sciences of the University of Padova, under the supervision of Prof. Marina Brustolon, with a work in the field of the Electron Paramagnetic Resonance (EPR). In 2000, he received a Ph.D degree in Chemical Sciences at the same Department, under the supervision of Prof. Marina Brustolon, concerning advanced EPR techniques (CW and pulsed EPR). In 2000, he took part as Post-Doc Fellow to the TMR (Training and Mobility Research) European research program at the Max Volmer Institut of the Technische Universität, Berlin. Since 2008, it has been active in the study and application of EPR to Cultural Heritage materials, and specifically to cellulose and paper materials from historic books, working in cooperation with national and international experts in the field, and crossing the results with data from canonical spectroscopies (IR, Raman, UV-Vis) and other analytical techniques (HPIC, HPLC, MS).
Laura Speri gained her Bachelor’s degree in “Sciences and Technologies applied on Cultural Heritage” at the University of Padua under the supervision of Dr. Alfonso Zoleo in 2013, with a thesis entitled “EPR characterization of paper degradation by-products in a 16th century book and comparison with model systems.” At the moment, she is graduating in “Conservation and Restoration” at University Ca’ Foscari of Venice: her Master’s degree thesis internship deals with the optimization of Restoration plasters for walls affected by capillary salt ascent by means of statistical methods.
Maddalena Bronzato graduated in 2011 with full marks cum laude in Chemistry at the University of Padua, with a Master’s thesis entitled “Spectroscopic analyses of ancient paper degradation products. A 16th century codex.” From January 2012 to March 2015, she was active as a PhD student in the Physical Chemistry Department of the same university. The research, developed during the thesis internship and the PhD studies, was focused on the characterization of degradation by-products present in ancient papers by means of chemical, spectroscopic and separative techniques. From May to October 2015, she worked as a Post-Doc fellow at the Environmental and Analytical Chemistry Department of the same institution, developing a project regarding the detection and quantification of Cr(III) ligands, in particular polyamino carboxylic acids, in tannery waste waters. At the moment, she is working on a distinct project in cooperation with the Physical Chemistry Department, involving the restoration of a precious ancient manuscript.
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©2015 by De Gruyter
Articles in the same Issue
- Frontmatter
- Editorial
- The Effect of Iron Ions from Prussian Blue Pigment on the Deterioration of Japanese Paper
- Electron Paramagnetic Resonance as a Probe for Metal Ions and Radicals in Paper
- Evaluation of Treatments for Stabilization of Verdigris and Malachite Containing Paper Documents
- Aqueous Washing Treatment Aids: How to Remove Ionic Fixatives from Paper
- Cellulose Acetate Lamination: A Literature Review and Survey of Paper-Based Collections in the United States
Articles in the same Issue
- Frontmatter
- Editorial
- The Effect of Iron Ions from Prussian Blue Pigment on the Deterioration of Japanese Paper
- Electron Paramagnetic Resonance as a Probe for Metal Ions and Radicals in Paper
- Evaluation of Treatments for Stabilization of Verdigris and Malachite Containing Paper Documents
- Aqueous Washing Treatment Aids: How to Remove Ionic Fixatives from Paper
- Cellulose Acetate Lamination: A Literature Review and Survey of Paper-Based Collections in the United States
