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Automated Analysis of Amino Sugars Using the Elson-Morgan Reaction Lee Van Lenten

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Automated Analysis of Amino Sugars Using the Elson-Morgan Reaction Lee Van Lenten Yale University EliScholar – A Digital Platform for Scholarly Publishing at Yale Yale Medicine Thesis Digital Library School of Medicine Spring 5-31-1966 Automated Analysis of Amino Sugars using the Elson-Morgan Reaction Lee Van Lenten Follow this and additional works at: https://elischolar.library.yale.edu/ymtdl Part of the Biochemistry Commons Recommended Citation Van Lenten, Lee, "Automated Analysis of Amino Sugars using the Elson-Morgan Reaction" (1966). Yale Medicine Thesis Digital Library. 6. https://elischolar.library.yale.edu/ymtdl/6 This Open Access Thesis is brought to you for free and open access by the School of Medicine at EliScholar – A Digital Platform for Scholarly Publishing at Yale. It has been accepted for inclusion in Yale Medicine Thesis Digital Library by an authorized administrator of EliScholar – A Digital Platform for Scholarly Publishing at Yale. For more information, please contact [email protected]. ABSTRACT A combined chromatographic and analytical system is described for the specific determination of amino sugars. An adaptation of the Elson-Morgan reaction has been made using the equipment of the Technicon AutoAnalyzer. The colorimetric procedure is based partly on the work of Lewy and McAllan . The Elson-Morgan reaction is a two-stage reaction which involves first 2 the reaction of the amino sugar with acetic anhydride or ,4pentane- dione and the formation of cyclic intermediates by heating in an al kaline medium. In the second stage, the medium is acidifed and the intermediates coupled with p_-dimethylaminobenzaldehyde to give a colored product. In the automated procedure developed, acetylation is performed with an acetic acid - N,N-dimethylacetamide reagent and the cycliza- tion is accomplished at elevated temperatures in a basic borate solu tion. The reaction mixture is then acidified by the addition of an acetic acid - formic acid - HC1 - water reagent and the p-dimethyl- aminobenzaldehyde is added in an alcoholic solution. All reagents are stable for several weeks. Two chromatographic systems have been developed for the separation of amino sugars without modification of the chromatographic section of the Technicon Amino Acid Analyzer. These systems have distinctly different elution patterns. It is possible to carry out simultaneous ninhydrin and Elson-Morgan analyses of the chromatographic effluents. AN AUTOMATED ANALYSIS OF AMINO SUGARS USING THE ELSON-MORGAN REACTION by Lee Van Lenten A.B., Colgate University, i960 A Thesis Submitted to the Faculty of the Yale University School of Medicine in Candidacy for the Degree of Doctor of Medicine Department of Biochemistry Yale University 1966 J 7 / 7 ACKNOWLEDGMENTS This investigation was carried out in the laboratory of Dr. Fritz Lipmann at the Rockefeller University under the guidance of Dr. John D. Gregory. I wish to thank Dr. Detlev W. Bronk, President of the Rockefeller University, for the opportunities made available in the stimulating atmosphere of the University and Dr. Lipmann for the opportunity of working in his well-appointed laboratory. Dr. Gregory has been most generous with his teaching, by precept and example, his encouragement and friendship, and his willingness to let me wander down blind alleys and make my own mistakes. At Yale University Dr. Joseph S. Fruton has been kind enough to sponsor this thesis and has given me skilled assistance in the preparation of this manuscript. My thanks also go to Mr. George D. Winter of the Technicon Chromatography Corporation for his technical advice and assistance. Last, but by no means least, I thank my wife, Beth, for her moral support without which this investigation would never have been completed, my sister, Ellen, for the art work in the figures, and my parents, who are what parents should be. TABLE OF CONTENTS Page INTRODUCTION 1 A. Amino Sugars and Their Biological Role 1 B. Hydrolysis of Amino Sugar Containing Material 2 C. Methods for Amino Sugar Analysis 9 D. Elson-Morgan Reaction 10 E. Mechanism of the Morgan-Elson Reaction 12 F. Mechanism of the Elson-Morgan Reaction 19 G. Purpose of This Investigation 22 MATERIALS AND METHODS 23 A. Materials 23 B. Manual Elson-Morgan Methods 24 C. Technicon Amino Acid Analyzer 24 D. Automated Chromatography of Amino Sugars 27 E. Automated Elson-Morgan Analysis 28 F. Automated Ninhydrin Analysis 33 G. Calculation of the Plateau Height 35 H. Calculation of the Peak Area 36 I. Comparison of Areas Obtained in Different Chromatographic Runs 36 J . Spectra 38 K. pH Determinations 38 ANALYTICAL SYSTEM FOR THE AUTOMATED ANALYSIS OF AMINO SUGARS 39 Page A, Advantages and Limitations of the Technicon Amino Acid Analyzer 39 B. Choice of Reagents ^0 C. Development of the Specific Manifold and Reaction Conditons 43 1. Choice of solvent for coupling the cyclic intermediates with p-dimethylaminobenzal dehyde (Stage II) 43 2. Heating conditons for the acetylation and cyclization (Stage I) 49 3. Reaction conditions for coupling the cyclic intermediates with p_-dimethylaminobenz aldehyde (Stage II) 50 4. Optimal boric acid concentration and pH in Stage I and the resulting optimal HC1 concentration in Stage II 6l 5. Spectrum of the colored product(s) in the automated procedure 65 6. Linearity of the automated analytical system 68 D. Summary 70 AUTOMATED CHROMATOGRAPHY AND ANALYSIS OF AMINO SUGARS 73 A. Chromatographic Systems 73 B. The Relationship between the Peak Areas and the Amount of Amino Sugar in the Combined Chromatography and Elson-Morgan Analysis 77 C. Color Yields 81 D. Summary 81 CONCLUSION 84 APPENDICES 87 APPENDIX I Directions for the Chromatography of Amino Sugars 88 Page A. Chromatographic Conditions 88 B. Chromatographic Buffers 88 C. Standard Amino Sugar Solutions 89 APPENDIX II Directions for the Elson-Morgan Analytical System 91 A. Manifold for the Elson-Morgan Reaction 91 B. Reagents for the Elson-Morgan Reaction 96 APPENDIX III Directions for the Ninhydrin Analytical System 99 A. Manifold for the Ninhydrin Reaction 99 B. Reagents for the Ninhydrin Reaction 101 REFERENCES 10 5 LIST OF FIGURES Figure Title Page 1. The chromatographic section of the Technicon Amino Acid Analyzer 26 2 . The analytical section for the Elson-Morgan reaction 29 3. The displacement bottle for the acetylating reagent 31 4. The filter for the "acids" pumping line 32 5. The analytical section for the ninhydrin reaction 3^ 6, The size and span of the expanded and unex- panded ranges 37 7. The effect of acetic and formic acids on the stability of pumping rates 46 8. The effect of mixtures of glacial acetic acid, formic acid, water and concentrated HCl on the stability of the pumping rates 48 9. The effect of variations in pH and concentra tion of the boric acid buffer and "acids" composition on the amount of color formed in the automated method using the phosphate chromatographic buffer (System B) 62 10. The effect of variations in pH of the 0.80 M boric acid buffer on the amount of color formed in the automated method using the phosphate chromatgraphic buffer ( System B ) 63 11. The effect of NaOH concentration on the amount of color formed in the automated method using the borate chromatographic buffer ( System A ) 64 12. The effect of HCl concentration on the amount of color formed using 0.160 N NaOH in the automated method using the borate chromato graphic buffer ( System A ) 66 Figure Title Page 13. Spectrum of the color produced by glucosamine in the automated method 67 14. Absorbance of standard glucosamine solutions in chromatographic buffers A and B 69 15. Composite tracings of chromatograms of amino sugars in the borate and phosphate chromato graphic systems 7^ 16, A typical chromato gram using the borate chromatographic system and simultaneous Elson-Morgan and ninhydrin analyses 75 17. A typical chromato gram using the phosphate chromatographic system and simultaneous Elson-Morgan and ninhydrin analyses 76 18. The relationship between sample size and peak areas obtained after chromatography and analysis using the borate chromatographic system 78 19. The relationship between sample size and peak areas obtained after chromatography and analysis using the phosphate chromatographic system 79 20. A chromatogram of a hydrolyzed mucoprotein product 85 21. The analytical section for the Elson-Morgan reaction 92 22. The filter for the "acids" pumping line 94 23, The displacement bottle for the acetylating reagent 95 24. The analytical section for the ninhydrin reaction 100 25. The apparatus for preparation and storage of the ninhydrin reagent 102 LIST OF TABLES Title Pag Amino sugars from natural sources 3 The relative color yields produced in a manual Elson-Morgan reaction using various solvents in the second stage of the reaction 44 The effect of the amount of air introduced in the first stage on the color yield in an automated procedure 51 The effect of incubation temperature in Stage II on the color yield in a manual Elson-Morgan reaction 53 The effect of incubation time in Stage II on the color yield in a manual Elson-Morgan reaction 5^ The effect of the resample : "acids" ratio in Stage II on the color yield in a manual Elson- Morgan reaction 56 The effect of the resample : "acids" ratio in Stage II on the color yield in an automated Elson-Morgan reaction 58 The effect of the incubation time in Stage II on the color yield in an automated Elson- Margan reaction 60 The relative Elson-Morgan color yields and ratios to ninhydrin color yields for various amino sugars 82 1 INTRODUCTION A. Amino Sugars and Their Biological Role Amino sugars are those compounds of the sugar series which contain in their molecule an amino group, either free or substituted, replacing any hydroxyl group except the hemiacetal hydroxyl group. They are known to occur widely in nature. For a long time the 2-amino- 2-deoxy-hexoses, glucosamine (I), galactosamine (II), and mannosamine (III), were the principal naturally occuring amino sugars known.
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