M ETHODS IN MOLECULAR BIOLOGY™ Series Editor John M. Walker School of Life Sciences University of Hertfordshire Hatfield, Hertfordshire, AL10 9AB, UK For further volumes: http://www.springer.com/series/7651 Amino Acid Analysis Methods and Protocols Edited by Michail A. Alterman Tumor Vaccines and Biotechnology Branch, CBER, FDA, Bethesda, MD, USA Peter Hunziker Functional Genomics Center, University of Zűrich, Zűrich, Switzerland Editors Michail A. Alterman Peter Hunziker Tumor Vaccines and Biotechnology Branch Functional Genomics Center CBER, FDA University of Zürich Bethesda, MD, USA Zürich, Switzerland [email protected] [email protected] ISSN 1064-3745 e-ISSN 1940-6029 ISBN 978-1-61779-444-5 e-ISBN 978-1-61779-445-2 DOI 10.1007/978-1-61779-445-2 Springer New York Dordrecht Heidelberg London Library of Congress Control Number: 2011941583 © Springer Science+Business Media, LLC 2012 All rights reserved. This work may not be translated or copied in whole or in part without the written permission of the publisher (Humana Press, c/o Springer Science+Business Media, LLC, 233 Spring Street, New York, NY 10013, USA), except for brief excerpts in connection with reviews or scholarly analysis. Use in connection with any form of information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed is forbidden. The use in this publication of trade names, trademarks, service marks, and similar terms, even if they are not identified as such, is not to be taken as an expression of opinion as to whether or not they are subject to proprietary rights. Printed on acid-free paper Humana Press is part of Springer Science+Business Media (www.springer.com) Preface Amino Acid Analysis (AAA) has been an integral part of analytical biochemistry for almost 60 years. AAA was originally developed by Moore and Stein and was at the very heart of their work on the mechanism of enzyme catalysis for which they were awarded a Nobel Prize in Chemistry in 1972. In a relatively short time since the previous AAA book in this series has been published (10 years), the variety of AAA methods changed dramatically with more methods shifting to the use of mass spectrometry (MS) as a detection method. At the same time, a number of old techniques acquired a new make-up, like combination of AccQ-Tag with UPLC and MS, instead of HPLC and fl uorescence. Another new aspect is miniaturization. One of the chapters in this book describes an AAA in a single cell. However, the most important aspect is that AAA in this day and age should be viewed in the context of Metabolomics as a part of Systems Biology. Historically, analysis of amino acids (AA) includes derivatization (pre, on-, or post- column) coupled with chromatographic separation. A wide variety of separation techniques were applied to separation of AA over the years. This list includes ion-exchange LC, reverse- phase HPLC, gas chromatography (GC), and capillary electrophoresis (CE). Recent advances in mass spectrometry (MS) led to the application of electrospray ionization cou- pled with LC or CE for AA detection which may also allow the analysis of underivatized AA. Two most recent technological advances in AAA include the application of MALDI TOF MS and TOF/TOF MS/MS and microfl uidics. AAA techniques evolve and follow the bioanalytical technological advances. Sample preparation for AAA plays a critical role in the successful implementation of AAA. Correspondingly, in this book a reader can fi nd chapters describing general as well as specifi c approaches to the sample preparation. A number of chapters describe different applications of AAA. Some chapters describe specifi c applications of AAA in clinical chem- istry as well as in food analysis, microbiology, and other biomedical fi elds. Separate chapters are devoted to the application of AAA for protein quantitation and chiral AAA. Our goal was to present a spectrum of all available methods for readers to choose the method that most suits particular laboratory and needs. And, at the same time we attempted to present more than one method for each application or detection/separation approach so that again the readers can fi nd the one that most suits their needs and available laboratory conditions. What is unique about this book, and in essence about AAA itself, is that it is related and is of interest to anyone involved in biomedical research or, in general, in life sciences. One can fi nd here techniques essential in medicine, or in drug metabolism, or cell biology, even in archeology, in meat industry, in marine biology, in agriculture, and the list goes on. All of the described techniques are multifaceted and in many cases can serve as a blueprint for the analysis of other chemically related classes of metabolites. Bethesda, MD, USA Michail A. Alterman Zürich, Switzerland Peter Hunziker v Contents Preface. v Contributors. xi 1 Rapid LC–MS/MS Profiling of Protein Amino Acids and Metabolically Related Compounds for Large-Scale Assessment of Metabolic Phenotypes. 1 Liping Gu, A. Daniel Jones, and Robert L. Last 2 Combination of an AccQ·Tag-Ultra Performance Liquid Chromatographic Method with Tandem Mass Spectrometry for the Analysis of Amino Acids. 13 Carolina Salazar, Jenny M. Armenta, Diego F. Cortés, and Vladimir Shulaev 3 Isotope Dilution Liquid Chromatography-Tandem Mass Spectrometry for Quantitative Amino Acid Analysis. 29 David M. Bunk and Mark S. Lowenthal 4 Analysis of Underivatized Amino Acids: Zwitterionic Hydrophilic Interaction Chromatography Combined with Triple Quadrupole Tandem Mass Spectrometry . 39 Madeleine Dell’mour, Gunda Koellensperger, and Stephan Hann 5 Amino Acid Analysis via LC–MS Method After Derivatization with Quaternary Phosphonium . 47 Shinsuke Inagaki and Toshimasa Toyo’oka 6 Amino Acid Analysis by Hydrophilic Interaction Chromatography Coupled with Isotope Dilution Mass Spectrometry . 55 Megumi Kato and Akiko Takatsu 7 A Universal HPLC-MS Method to Determine the Stereochemistry of Common and Unusual Amino Acids . 63 Sonja Hess 8 Amino Acid Analysis by Capillary Electrophoresis-Mass Spectrometry . 77 Akiyoshi Hirayama and Tomoyoshi Soga 9 New Advances in Amino Acid Profiling by Capillary Electrophoresis-Electrospray Ionization-Mass Spectrometry . 83 Philip Britz-McKibbin 10 Optimal Conditions for the Direct RP-HPLC Determination of Underivatized Amino Acids with Online Multiple Detection . 101 A. Pappa-Louisi, P. Agrafiotou, and S. Sotiropoulos vii viii Contents 11 Absolute Quantitation of Proteins by Acid Hydrolysis Combined with Amino Acid Detection by Mass Spectrometry . 115 Olga A. Mirgorodskaya, Roman Körner, Yuri P. Kozmin, and Peter Roepstorff 12 Amino Acid Analysis by Means of MALDI TOF Mass Spectrometry or MALDI TOF/TOF Tandem Mass Spectrometry . 121 Natalia V. Gogichaeva and Michail A. Alterman 13 Heptafluorobutyl Chloroformate-Based Sample Preparation Protocol for Chiral and Nonchiral Amino Acid Analysis by Gas Chromatography . 137 Petr Šimek, Petr Hušek, and Helena Zahradníčková 14 The EZ:Faast Family of Amino Acid Analysis Kits: Application of the GC-FID Kit for Rapid Determination of Plasma Tryptophan and Other Amino Acids . 153 Abdulla A.-B. Badawy 15 Amino Acid Analysis in Physiological Samples by GC–MS with Propyl Chloroformate Derivatization and iTRAQ–LC–MS/MS . 165 Katja Dettmer, Axel P. Stevens, Stephan R. Fagerer, Hannelore Kaspar, and Peter J. Oefner 16 Automated Analysis of Primary Amino Acids in Plasma by High-Performance Liquid Chromatography . 183 Durk Fekkes 17 RP-LC of Phenylthiocarbamyl Amino Acid Adducts in Plasma Acetonitrile Extracts: Use of Multiple Internal Standards and Variable Wavelength UV Detection. 201 Lionella Palego, Gino Giannaccini, and Antonio Lucacchini 18 Quantification of Underivatised Amino Acids on Dry Blood Spot, Plasma, and Urine by HPLC–ESI–MS/MS. 219 Giuseppe Giordano, Iole Maria Di Gangi, Antonina Gucciardi, and Mauro Naturale 19 Capillary Electrophoresis of Free Amino Acids in Physiological Fluids Without Derivatization Employing Direct or Indirect Absorbance Detection. 243 Gordana D. Žunić, Slavica Spasić, and Zorana Jelić-Ivanović 20 Measurement of 3-Nitro-Tyrosine in Human Plasma and Urine by Gas Chromatography-Tandem Mass Spectrometry . 255 Dimitrios Tsikas, Anja Mitschke, and Frank-Mathias Gutzki 21 Analysis of Hydroxyproline in Collagen Hydrolysates . 271 Tobias Langrock and Ralf Hofmann 22 Innovative and Rapid Procedure for 4-Hydroxyproline Determination in Meat-Based Foods . 281 Maria Cristina Messia and Emanuele Marconi Contents ix 23 Multiple Reaction Monitoring for the Accurate Quantification of Amino Acids: Using Hydroxyproline to Estimate Collagen Content . 291 Michelle L. Colgrave, Peter G. Allingham, Kerri Tyrrell, and Alun Jones 24 Sequential Injection Chromatography for Fluorimetric Determination of Intracellular Amino Acids in Marine Microalgae. 305 Marilda Rigobello-Masini and Jorge C. Masini 25 Direct Analysis of Underivatized Amino Acids in Plant Extracts by LC-MS-MS. 317 Björn Thiele, Nadine Stein, Marco Oldiges, and Diana Hofmann 26 Wheat Gluten Amino Acid Analysis by High-Performance Anion-Exchange Chromatography with Integrated Pulsed Amperometric Detection. 329 Ine Rombouts, Bert Lagrain, Lieve Lamberts, Inge Celus, Kristof Brijs, and Jan A. Delcour 27 Preparative HPLC Separation of Underivatized Amino Acids for Isotopic Analysis . 339 Jennifer A. Tripp and James S.O. McCullagh 28 Quantification of Amino Acids in a Single Cell by Microchip Electrophoresis