Table of Contents

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The Editor

Prof. Dr. Sebastian Schlücker

Department of Physics

University of Osnabrück

Barbarastraße 7

49076 Osnabrück

Germany

Cover

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.

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ISBN: 978-3-527-32567-2

Foreword

More than 80 years since the discovery of the Raman effect have passed and Raman spectroscopy has become one of the most important methods within the various methods of analysis and structural determinations. Certainly, the discovery of the laser in 1960 has opened up new horizons for Raman spectroscopy and brought several new useful techniques. One of the most interesting and significant findings in this field is undoubtedly surface-enhanced Raman scattering (SERS) which was discovered in 1977. Within this phenomenon, molecules adsorbed onto metal surfaces under certain conditions exhibit an anomalously large interaction cross section for the Raman effect. It might be thought that a subject originated more than three decades ago would be virtually exhausted by now, but nothing could be farther from truth. The recent developments in SERS have led to large increases in the sensitivity of SERS measurements and have enabled new phenomena to be observed and applied. SERS measurements are expected to become increasingly important in chemistry, biochemistry, and biophysics.

In the 14 chapters of this book, an authoritative, up-to-date account of the principles and fundamentals of SERS is given including many examples for its applications. The book includes the basic theory for SERS; summarizes the various SERS substrates; discusses quantitative SERS methods with emphasis on reproducibility, stability and sensitivity up to single molecule detection; and describes SERS microscopy, electrochemical SERS, surface enhanced resonance Raman scattering (SERRS), and surface-enhanced hyper Raman scattering (SEHRS), as well as surface- and tip-enhanced coherent anti-Stokes Raman scattering (SE-CARS, TE-CARS). Applications of SERS include the detection of organic pollutants and pharmaceuticals; studies of electron transfer of proteins at membrane models; investigations of microfluidics, quantitative DNA analysis, biomedical applications by means of SERS microscopy, SERS as an intracellular probe; and coupling of SERS with various separation methods (e.g. liquid or gas chromatography).

The abundant references provide ready access to the original research literature. As the field of SERS has sufficiently matured during the past decades, the danger of rapid obsolescence for this book is less. The subject matter, however, still offers plenty of opportunity for further exploration and exploitation. In my opinion this book, which clearly expresses the current excitement in this extremely active research area, will make a substantial contribution to the further growth of an increasingly important subfield of vibrational spectroscopy.

Professor Schlücker, editor of this volume, is one of the leading researchers working currently in the SERS field. As chemist at the University of Würzburg, Germany, and the National Institutes of Health, Bethesda, USA, and now as physicist at the University of Osnabrück, Germany, he has played a major role in introducing a few important new experimental techniques of SERS (e.g. the direct and label-free SERS detection of solid-phase bound compounds; immuno-SERS microscopy with nanoparticle probes). He is well qualified to present this book to the scientific community.

Wolfgang Kiefer

University of Würzburg and Eisingen

Laboratory for Applied Raman Spectroscopy (ELARS)

Preface

The field of surface-enhanced Raman scattering (SERS) is currently undergoing a very dynamic development and many novel directions are rapidly emerging. The aim of this book is to provide an overview of current exciting topics in SERS, focusing on analytical, biophysical and life science applications. International leaders in their respective research areas have contributed to this volume. Their original scientific background and training is quite diverse, ranging from bioorganic chemistry to physical chemistry and solid state physics — in my opinion, this directly reflects the highly multidisciplinary nature of SERS applications, a prerequisite for original and pioneering research between the boundaries of traditionally distinct disciplines. The selection of the scientific topics covered in the 14 chapters is naturally subjective and I must certainly apologize to those who have not received the opportunity to contribute to this edition.

This monograph is intended to be useful for both the newcomer with no or little background in Raman/SERS spectroscopy as well as for the experts in the field who are interested in achieving a quick overview as well as in-depth information on specific subjects.

The first part of this book (Chapters 1–3) lays the foundation for the entire book by providing important theoretical and practical background. Topics are the basic electromagnetic theory of SERS, various aspects of metal colloids as plasmonic nanostructures and practical considerations for quantitative SERS. The second part (Chapters 4–14) covers various analytical, biophysical and life science applications of SERS. Chapters 4 through 8 describe analytical applications of SERS, including single-molecule and trace detection, sensors for detecting organic pollutants based on host–guest systems as well as the detection of pharmaceuticals. Two chapters describe the promising combination of SERS with other analytical techniques such as separation methods and microfluidic platforms for lab-on-a chip detection. Chapters 9 and 10 cover spectroelectrochemistry as a classical and important topic in SERS. After an introduction into the theory and experimental setups for combining SERS with electrochemistry, applications to several biological molecules are summarized. Biophysical applications of spectroelectrochemistry with SERS are focused on the electron transfer in membrane models, in particular cytochrome c on coated electrodes. Chapters 11 through 14 report on recent life science applications of SERS. Quantitative DNA analysis with immense multiplexing and ultrasensitive detection capabilities is demonstrated by surface-enhanced resonance Raman scattering (SERRS). Selective protein localization in cells and tissue specimens via SERS microscopy requires the design and fabrication of functionalized metal colloids for labeling target-specific ligands such as antibodies. Information on intracellular biochemical composition and physiological conditions is accessible via one- or two-photon excited SERS in a label-free approach in conjunction with microscopy. Surface- and tip-enhanced coherent anti-Stokes Raman scattering (CARS) as advanced microspectroscopic techniques with sub-diffraction limited spatial resolution together with first applications to DNA are discussed in the last chapter.

I would like to thank all authors for their hard work and commitment to contribute their chapters. This international and multidisciplinary book project would not have been possible without their dedication. The support from Lesley Belfit (Wiley-VCH) and Manfred Köhl (now Thieme) is greatly appreciated. Thanks to Wolfgang Kiefer for his foreword – many of his former students including the editor have contributed to this book. Finally, I would like to thank my wife Uta-Maria, our sons Jan and Henrik, my parents Marianne and Eberhard as well as my group members for their continuous support.

Osnabrück, August 2010

Sebastian Schlücker

List of Contributors