Related Titles

Schlüter, D. A., Hawker, C.,
Sakamoto, J. (eds.)
Synthesis of Polymers
New Structures and Methods
Hardcover
ISBN: 978-3-527-32757-7

Harada, A. (ed.)
Supramolecular Polymer Chemistry
Hardcover
ISBN: 978-3-527-32321-0

Lendlein, A., Sisson, A. (eds.)
Handbook of Biodegradable Polymers
Isolation, Synthesis, Characterization and Applications
Hardcover
ISBN: 978-3-527-32441-5

Knoll, W., Advincula, R. C. (eds.)
Functional Polymer Films
2 Volume Set
2011
Hardcover
ISBN: 978-3-527-32190-2

Chujo, Y. (ed.)
Conjugated Polymer Synthesis
Methods and Reactions
2011
Hardcover
ISBN: 978-3-527-32267-1

Mathers, Robert T., Meier, Michael A. R.
(eds.)
Green Polymerization Methods
Renewable Starting Materials, Catalysis and Waste Reduction
2011
Hardcover
ISBN: 978-3-527-32625-9

Loos, K. (ed.)
Biocatalysis in Polymer Chemistry
2011
Hardcover
ISBN: 978-3-527-32618-1

Xanthos, Marino (ed.)
Functional Fillers for Plastics
Second, updated and enlarged edition
2010
Hardcover
ISBN: 978-3-527-32361-6

Leclerc, Mario, Morin,
Jean-Francois (eds.)
Design and Synthesis of Conjugated Polymers
2010
Hardcover
ISBN: 978-3-527-32474-3

Cosnier, S., Karyakin, A. (eds.)
Electropolymerization
Concepts, Materials and Applications
2010
Hardcover
ISBN: 978-3-527-32414-9

All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No.: applied for

British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library.

Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at .

© 2012 Wiley-VCH Verlag & Co. KGaA, Boschstr. 12, 69469 Weinheim, Germany

All rights reserved (including those of translation into other languages). No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.

Cover Design Formgeber, Eppelheim

Typesetting Thomson Digital, Noida, India

Printing Fabulous Printers Pte Ltd, Singapore

Binding Fabulous Printers Pte Ltd, Singapore

Print ISBN: 978-3-527-32924-3

ePDF ISBN: 978-3-527-64184-0

oBook ISBN: 978-3-527-64182-6

ePub ISBN: 978-3-527-64183-3

Mobi ISBN: 978-3-527-64185-7

List of Contributors

Grayna Adamus
Polish Academy of Sciences
Center of Polymer and Carbon Materials
34 M. Curie-Sklodowska Street
41-800 Zabrze
Poland

 

Christopher Barner-Kowollik
Karlsruhe Institute of Technology (KIT)
Institut für Technische Chemie und Polymerchemie
Macromolecular Chemistry
Engesserstr. 18
76128 Karlsruhe
Germany

 

Stephen J. Blanksby
School of Chemistry
University of Wollongong
Wollongong, NSW 2522
Australia

 

Michael Buback
Georg-August-Universität GÖttingen
Institut für Physikalische Chemie
Tammannstr. 6
37077 GÖttingen
Germany

 

Sabrina Carroccio
National Research Council (CNR)
Institute of Chemistry and Technology of Polymers (ICTP)
Via Paolo Gaifami 18
95126 Catania
Italy

 

Anna C. Crecelius
Friedrich-Schiller-University Jena
Laboratory of Organic and Macromolecular Chemistry (IOMC)
Humboldtstr. 10
07743 Jena
Germany

 

Guillaume Delaittre
Karlsruhe Institute of Technology (KIT)
Institut für Technische Chemie und Polymerchemie
Macromolecular Chemistry
Engesserstr. 18
76128 Karlsruhe
Germany

 

Jana Falkenhagen
Bundesanstalt für Materialforschung und -prüfung (BAM)
Federal Institute for Materials Research and Testing
Richard-Willstätter-Strasse 11
12489 Berlin
Germany

Anthony P. Gies
Vanderbilt University
Department of Chemistry
7330 Stevenson Center
Station B 351822
Nashville, TN 37235
USA

 

Till Gruendling
Karlsruhe Institute of Technology (KIT)
Institut für Technische Chemie und Polymerchemie
Macromolecular Chemistry
Engesserstr. 18
76128 Karlsruhe
Germany

 

Charles M. Guttman
National Institute of Standards and Technology
Polymers Division
Gaithersburg, MD 20899
USA

 

Scott D. Hanton
Intertek ASA
7201 Hamilton Blvd. RD1, Dock #5
Allentown, PA 18195
USA

 

Gene Hart-Smith
School of Biotechnology and Biomolecular Sciences
University of New South Wales
Sydney, NSW 2052
Australia

 

Anthony J. Kearsley
National Institute of Standards and Technology
Applied and Computational Mathematics Division
Gaithersburg, MD 20899
USA

 

Marek Kowalczuk
Polish Academy of Sciences
Center of Polymer and Carbon Materials
34 M. Curie-Sklodowska Street
41-800 Zabrze
Poland

 

Christopher B. Lietz
Wayne State University
Department of Chemistry
5101 Cass Ave
Detroit, MI 48202
USA

 

Christine M. Mahoney
National Institute of Standards and Technology
Material Measurement Laboratory
Surface and Microanalysis Science Division
100 Bureau Drive, Mail Stop 6371
Gaithersburg, MD 20899-6371

 

Darrell D. Marshall
Wayne State University
Department of Chemistry
5101 Cass Ave
Detroit, MI 48202
USA

 

Kevin G. Owens
Drexel University
Chemistry Department
3141 Chestnut Street
Philadelphia, PA 19104

 

Thomas PaulÖhrl
Karlsruhe Institute of Technology (KIT)
Institut für Technische Chemie und Polymerchemie
Macromolecular Chemistry
Engesserstr. 18
76128 Karlsruhe
Germany

 

Concetto Puglisi
National Research Council (CNR)
Institute of Chemistry and Technology of Polymers (ICTP)
Via Paolo Gaifami 18
95126 Catania
Italy

 

Yue Ren
Wayne State University
Department of Chemistry
5101 Cass Ave
Detroit, MI 48202
USA

 

Alicia L. Richards
Wayne State University
Department of Chemistry
5101 Cass Ave
Detroit, MI 48202
USA

 

Paola Rizzarelli
National Research Council (CNR)
Institute of Chemistry and Technology of Polymers (ICTP)
Via Paolo Gaifami 18
95126 Catania
Italy

 

Gregory T. Russell
Department of Chemistry
University of Canterbury
20 Kirkwood Ave.
Upper Riccarton, Christchurch 8041
New Zealand

 

Ulrich S. Schubert
Friedrich-Schiller-University Jena
Laboratory of Organic and Macromolecular Chemistry (IOMC)
Humboldtstr. 10
07743 Jena
Germany

 

Vincenzo Scionti
University of Akron
Department of Chemistry
302 Buchtel Common
Akron, OH 44325
USA

 

Sarah Trimpin
Wayne State University
Department of Chemistry
5101 Cass Avenue
Detroit, MI 48202
USA

 

Philipp Vana
Georg-August-Universität GÖttingen
Institut für Physikalische Chemie
Tammannstr. 6
37077 GÖttingen
Germany

 

William E. Wallace
National Institute of Standards and Technology
Chemical and Biochemical Reference Data Division
Gaithersburg, MD 20899
USA

 

Steffen M. Weidner
Bundesanstalt für Materialforschung und -prüfung (BAM)
Federal Institute for Materials Research and Testing
Richard-Willstätter-Strasse 11
12489 Berlin
Germany

 

Chrys Wesdemiotis
University of Akron
Department of Chemistry
302 Buchtel Common
Akron, OH 44325
USA

Introduction

Christopher Barner-Kowollik, Jana Falkenhagen, Till Gruendling, and Steffen Weidner

The first mass spectrometric experiment was arguably conducted by J. J. Thomson in the late 19th century, when he measured mass-to-charge ratios (m/z) in experiments that would eventually lead to the discovery of the electron [1]. By 1912, Thomson's investigations into the mass of charged atoms resulted in the publication of details of what could be called the first mass spectrometer [2, 3]. Interestingly, Thomson also employed one of the first man-made polymeric materials in his design of the parabola spectrograph: a material with trade name Ebonite or Vulcanite, a highly crosslinked natural rubber, which, although it was fairly brittle, provided an excellent electrical insulator and could easily be milled into shape. At the time, Thomson was most likely unaware of its chemical identity, as Staudinger's ground breaking macromolecular hypothesis was not to be established until a few years later [4]. By 1933 – the same year in which German chemist Otto Röhm patented and registered Plexiglas as a brand name – F. W. Aston had firmly established mass spectrometry as a field of analytical chemistry. Using the technique, he ascertained the isotopic abundances of essentially all of the chemical elements [5]. Thomson, Aston, and Staudinger were later to receive the Nobel Prize for their individual achievements.

Today, mass spectrometry provides the synthetic polymer chemist with one of the most powerful analytical tools to investigate the molecular structure of intact macromolecules. The development of technology that would be able to achieve this task was not realized until the late 1980s. Indeed, the mass analyzers themselves were not the key problem, as they were already fairly advanced at the time. An ionization technique that allowed the entire synthetic macromolecule to be transferred into the gas phase as ions without fragmentation could, however, only be realized in the late 1980s. The application of traditional MS ionization techniques requiring thermal evaporation of the sample to the large and entwined macromolecules was considered quite impossible, although notable attempts existed at employing the more traditional ionization techniques to polymeric material [6–8]. This perception had to undergo a drastic revision in 1988 and thereafter, the years in which electrospray ionization mass spectrometry (ESI) [9] and matrix assisted laser desorption and ionization (MALDI) [10, 11] were first reported of being capable to ionize proteins and synthetic polymers. Largely on the back of the work of four researchers, Karas [12–14], Hillenkamp [10, 12, 13], Tanaka [11], and Fenn [9, 15, 16], these new soft ionization mass spectrometry techniques commenced their success story initially in the field of biochemistry and later in synthetic polymer chemistry. Since the early 1990s, soft ionization mass spectrometry techniques have become an important part of polymer chemistry, ranging from unraveling polymerization mechanisms, assessing copolymer structures to studying the degradation of polymeric materials on a molecular level. However, a case can nevertheless be made that mass spectrometry is an underutilized tool in polymer chemistry compared to its high potential [17]. Such a notion is underpinned by an analysis of the current literature: of the approximately 10 000 studies conducted upon – for example – polyacrylates (which are readily ionizable) from 2000 until 2010, NMR spectroscopy played a significant role in 15% of these studies, whereas soft ionization mass spectrometry played a significant role in only about 3% of these studies. This is despite of the fact that soft ionization mass spectrometry technology has – due to its dominance as a highly applicable analytical tool in the biological sciences – become almost as readily available as NMR. To date, mass spectrometry remains the only technique with the power to isolate (provided the correct mass analyzer is employed) and image individual polymer chains on a routine basis.

Although there have been some notable books addressing the field of mass spectrometry applied to synthetic polymers [18–20], no publication especially dedicated to the needs of synthetic polymer chemists exists, which could aid in the selection of appropriate mass spectrometric tools. Specifically, most books on polymer mass spectrometry do not engage with the topics of living/controlled radical polymerization methods and their mechanistic underpinnings or the mass spectrometric investigation of polymerization processes in general. In addition, an up-date on the current situation of polymer mass spectrometry is required. With the present compilation, we wish to close this critical gap in the literature and provide a state-of-the-art overview on the applications of mass spectrometry in molecular polymer chemistry to the reader. In this edited publication, a series of leading researchers in the field will present their expert perspectives on several – in our view – important topics in contemporary mass spectrometry. It is thus no surprise that the large majorities of authors contributing to the present book are chemists by training, as we have attempted to provide a book that addresses the analytical requirements posed in contemporary polymer chemistry.

The book opens with an overview of the available mass analyzers. Special consideration is given by the authors Steven Blanksby and Gene Hart-Smith to their uses in polymer chemistry. Various ionization techniques applicable in polymer mass spectrometry are then explored in-depth by Anthony Gies. Chrys Wesdemiotis subsequently takes a close look at tandem mass spectrometry, a highly important tool for the elucidation of polymer structure and one of the major contemporary fields of development in the mass spectrometry sector. Sarah Trimpin and colleagues follow with their contribution, describing gas-phase ion-separation procedures as applied to synthetic polymers. The ionization process of polymers via the MALDI approach requires a careful design of the sample preparation procedures. Scott Hanton and Kevin Owens therefore provide a close look at how polymer samples are best prepared. Synthetic polymers are not only important materials in their own right, but are also frequently employed to (covalently) modify variable surfaces. Surface analysis is notoriously challenging and a range of techniques have to be employed to map the chemical characteristics of surface-bound macromolecules. Christine Mahoney and Steffen Weidner provide a detailed description of the part which surface-sensitive mass spectrometric techniques play in elucidating a polymer surface's structure.

Soft ionization mass spectrometry techniques can be especially powerful when combined with chromatographic techniques such as size exclusion chromatography (SEC), liquid adsorption chromatography at critical conditions (LACCCs) or both. Jana Falkenhagen and Steffen Weidner explore the wide variety of so-called hyphenated techniques and impressively demonstrate the information depth that can be attained by employing such technologies. While arguably the majority of molecular weight determination is carried out via SEC often equipped with refractive index as well as light scattering detectors, Till Gruendling, William Wallace, and colleagues demonstrate how MALDI-MS as well as SEC coupled to ESI-MS can be employed to deduce absolute molecular weight distributions. The chapter also provides an overview of contemporary automated data processing techniques for mass spectrometric data. Most polymers generated are arguably copolymers and it thus is mandatory to dedicate an entire chapter to the analysis of copolymers via mass spectrometry – Ulrich Schubert and Anna Crecelius provide an in-depth analysis. The field of living/controlled radical polymerization provides fascinating high precision avenues for the construction of complex macromolecular architectures and enables the generation of polymers with a high degree of end-group fidelity, which are often employed in cross-discipline applications (e.g., in biosynthetic conjugates). Soft ionization mass spectrometry plays an integral part in unraveling the mechanism of living/controlled radical polymerization processes as well as in the characterization of macromolecular building blocks: Christopher Barner-Kowollik and colleagues take a close look at the current state-of-the-art. Similarly, polymers generated via conventional radical polymerization can be readily investigated via mass spectrometry. Here, especially the investigation of the initiation process and of the generated end-group type is of high importance – Michael Buback, Greg Russell, and colleagues report. Finally, Grazyna Adamus and Marek Kowalczuk survey the field of mass spectrometry applied to polymers prepared via nonradical methods such as coordination polymerization, polycondensation, and polyaddition. The question of polymer stability and a detailed understanding of polymer degradation processes on a molecular level are of paramount importance for an evaluation of the performance of a polymer in chemical applications or as a material. Sabrina Carroccio and colleagues survey the field of soft ionization mass spectrometry applied to the molecular study of degradation processes at the book's conclusion.

With the above spectrum, we hope to have covered most of what constitutes modern mass spectrometry applied to questions of organic polymer chemistry. The final chapter provides an outlook and evaluation – from our perspective – of what the important advances in mass spectrometry technology related to polymer chemistry could be and which important chemical questions are yet to be addressed by soft ionization techniques.

Karlsruhe and Berlin, February 2011

Christopher Barner-Kowollik

Jana Falkenhagen

Till Gruendling

Steffen Weidner

References

1 Thomson, J.J. (1897) Philos. Mag., 5, 293.

2 Thomson, J.J. (1912) Philos. Mag., 24, 209.

3 Thomson, J.J. (1913) Proc. R. Soc. Lond. A, 89, 1.

4 Staudinger, H. (1920) Ber. Dtsch. Chem. Ges., 53, 1073.

5 Aston, F.W. (1933) Mass Spectra and Isotopes, Edward Arnold, London.

6 Achhammer, B.G., Reiney, M.J., Wall, L.A., and Reinhart, F.W. (1952) J. Polym. Sci., 8, 555.

7 Hummel, D.O., Düssel, H.J., and Rübenacker, K. (1971) Makromol. Chem., 145, 267.

8 Lattimer, R.P., Harmon, D.J., and Hansen, G.E. (1980) Anal. Chem., 52, 1808.

9 Meng, C.K., Mann, M., and Fenn, J.B. (1988) Z. Phys. D: At. Mol. Clusters, 10, 361.

10 Karas, M. and Hillenkamp, F. (1988) Anal. Chem., 60, 2299.

11 Tanaka, K., Waki, H., Idao, Y., Akita, S., Yoshida, Y., and Yoshida, T. (1988) Rapid Commun. Mass Spectrom., 2, 151.

12 Karas, M., Bachmann, D., Bahr, U., and Hillenkamp, F. (1987) Int. J. Mass Spectr. Ion Proc., 78, 53.

13 Karas, M., Bachmann, D., and Hillenkamp, F. (1985) Anal. Chem., 57, 2935.

14 Karas, M. and Bahr, U. (1985) Trends Anal. Chem., 5, 90.

15 Yamashita, M. and Fenn, J.B. (1984) J. Phys. Chem., 88, 4451.

16 Yamashita, M. and Fenn, J.B. (1984) J. Phys. Chem., 88, 4671.

17 Hart-Smith, G. and Barner-Kowollik, C. (2010) Macromol. Chem. Phys., 211, 1507.

18 Li, L. (2010) MALDI Mass Spectrometry for Synthetic Polymer Analysis (Chemical Analysis: A Series of Monographs on Analytical Chemistry and Its Applications), John Wiley & Sons, Hoboken, NJ.

19 Pasch, H. and Schrepp, W. (2003) MALDI-TOF Mass Spectrometry of Synthetic Polymers, Springer, Berlin.

20 Montaudo, G. and Lattimer, R.P. (2001) Mass Spectrometry of Polymers, CRC Press, Boca Raton, FL.