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Enrichment of biologically active compounds from selected plants using adsorptive bubble separation [Elektronische Ressource] / Leonor Thompson

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TECHNISCHE UNIVERSITÄT MÜNCHEN Lehrstuhl für Chemisch-Technische Analyse und Chemische Lebensmitteltechnologie Enrichment of Biologically Active Compounds from Selected Plants Using Adsorptive Bubble Separation Leonor Thompson Vollständiger Abdruck der von der Fakultät Wissenschaftszentrum Weihenstephan für Ernährung, Landnutzung und Umwelt der Technische Universität München zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.) genehmigten Dissertation. Vorsitzender: Univ.-Prof. Dr. K. Sommer Prüfer der Dissertation: 1. Univ.-Prof. Dr. H. Parlar 2. Univ.-Prof. Dr. K.-H. Engel Die Dissertation wurde am 16.06.2004 bei der Technischen Universität München eingereicht und durch die Fakultät Wissenschaftszentrum Weihenstephan für Ernährung, Landnutzung und Umwelt am 22.09.2004 angenommen. Dedicated to the memory of my late father, for instilling in me the desire to learn and the praise for the good values of Life Acknowledgements The research work presented in this PhD thesis was realised at the Chair for Chemical and Technical Analysis and Chemical Food Technology of the Technical University of Munich, in Freising, Weihenstephan. I would like to express my gratitude to: Prof. Dr.

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Published 01 January 2004
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TECHNISCHE UNIVERSITÄT MÜNCHEN
Lehrstuhl für Chemisch-Technische Analyse
und Chemische Lebensmitteltechnologie

Enrichment of Biologically Active Compounds from Selected
Plants Using Adsorptive Bubble Separation


Leonor Thompson


Vollständiger Abdruck der von der Fakultät Wissenschaftszentrum Weihenstephan für
Ernährung, Landnutzung und Umwelt der Technische Universität München zur Erlangung des
akademischen Grades eines

Doktors der Naturwissenschaften (Dr. rer. nat.)


genehmigten Dissertation.



Vorsitzender: Univ.-Prof. Dr. K. Sommer
Prüfer der Dissertation: 1. Univ.-Prof. Dr. H. Parlar
2. Univ.-Prof. Dr. K.-H. Engel



Die Dissertation wurde am 16.06.2004 bei der Technischen Universität München eingereicht
und durch die Fakultät Wissenschaftszentrum Weihenstephan für Ernährung, Landnutzung
und Umwelt am 22.09.2004 angenommen.












Dedicated to the memory of my late father, for instilling in me the desire to learn
and the praise for the good values of Life

Acknowledgements

The research work presented in this PhD thesis was realised at the Chair for Chemical and
Technical Analysis and Chemical Food Technology of the Technical University of Munich, in
Freising, Weihenstephan. I would like to express my gratitude to:

Prof. Dr. Harun Parlar, the Head of the Chair and my supervisor, for providing me with an
interesting topic for the thesis, for the freedom to implement my ideas and the availability of
funds for the financing of three years of work.

Dr. Mehmet Coelhan, the head of my working group, for providing that the required means
for the pursuance of my work were met, for the practical hints, particularly in relation with the
HPLC and GC-MS analysis, as well as the interesting discussions regarding chemistry.

Ms. Florence Beaume, for the good atmosphere in the laboratory, the interesting discussions
on chemistry and themes other than science, for a great companionship during the time of
hard work and sporadic pleasant breaks.

Dr. Carsten Wattenbach, for the help given with the NMR analysis and the readiness for the
innumerable and challenging discussions concerning chemistry.

Mr. Albrecht Friess, for the kind, untiring and timely help in the improvement of the linguis-
tics and presentation aspects of this thesis, as well as for sorting out administrative details of
the thesis.

Mr. Kurt Sholz, for the prompt production of special glass apparatus for the Foam Fractiona-
tion.

Ms. Johanna Strohmeier, for the good atmosphere in the laboratory and companionship. Ms.
Bettina Zimmerman, for the help with the GC-ECNI/MS analysis. Ms. Mareike Wenning
from the Microbial Ecology Group, Technical University of Munich, for the help with the
FTIR analysis.

Prof. Dr. Matthias Hamburger, Friedrich-Schiller University, Jena, for the kind supply of the
tryptanthrin standard. The Raps Institute in Freising, Weihenstephan, the Thuringian State
Institute for Agriculture, Thuringia and the firma BAFA, Malsch, for the kind supply of plant
raw materials.

I finally express my deepest gratitude to my wonderful family to whom I owe so much:

My mother Mrs. Lucia Thompson, for the support, encouragement, caring and for being a
source of strength during the difficult moments. My siblings, in particular Prof. Dr. Rachael
Thompson, Prof. Dr. Gertrude Thompson and Dr. Ricardo Thompson, for the support, en-
couragement, and wise advice.

My husband Dr. Michael Lutze, for helping with the linguistic improvement of this thesis, for
always standing by me both for the happy and difficult moments, for the understanding, en-
couragement and loving. My small daughter Michelle Thompson Lutze, for being such a
lovely child, a source of inspiration and for her contagious joy.







Contents
______________________________________________________________________________
Contents

1. INTRODUCTION------------------------------------------------------------------------------ 1
2. THEORETICAL BACKGROUND ---------------------------------------------------- 5
2.1 Non-Foaming Adsorptive Bubble Separation and Foam Separation ------------------- 6
2.2 Foam Fractionation ------------------------------------------------------------------------------- 7
2.2.1 Adsorption ------------------------------------------------------------------------------------- 8
2.2.2 Foams ------------------------------------------------------------------------------------------13
2.2.2.2 Drainage and Thinning ---------------------------------------------------------------15
2.2.2.3 Gas Diffusion Coalescence and Bubble size---------------------------------------16
2.2.3.1 Foam Fractionation Devices ---------------------------------------------------------17
2.2.4 Efficiency of Foam Fractionation --------------------------------------------------------20
2.2.5 Parameters Influencing the Efficiency of Foam Fractionation---------------------22
2.2.5.1 Concentration of Solute and Surfactant -------------------------------------------22
2.2.5.2 Addition of Organic Solvents22
2.2.5.3 Addition of Electrolytes and Polyelectrolytes ------------------------------------23
2.2.5.4 Addition of Viscosity Enhancers ----------------------------------------------------23
2.2.5.5 pH of Solution---------------------------------------------------------------------------24
2.2.5.6 Ionic Strength24
2.2.5.7 Gas Flow Rate --------------------------------------------------------------------------24
2.2.5.8 Height of Liquid Pool------------------------------------------------------------------25
2.2.5.9 Height of Foam Tower ----------------------------------------------------------------25
2.2.5.10 Internal Reflux Ratio25
2.3 Plant Materials Under Investigation----------------------------------------------------------26
2.3.1 Calendula Officinalis L. --------------------------------------------------------------------27
2.3.1.1 General -----------------------------------------------------------------------------------27
2.3.1.2 Chemical Composition ----------------------------------------------------------------28
2.3.1.3 Active Principles------------------------------------------------------------------------29
2.3.1.4 Other Components---------------------------------------------------------------------33
2.3.1.5 Biological and Pharmacological Activity ------------------------------------------34
2.3.1.6 Toxicology -------------------------------------------------------------------------------34 Contents
______________________________________________________________________________
2.3.2 Camellia Sinensis L.-------------------------------------------------------------------------35
2.3.2.1 General -----------------------------------------------------------------------------------35
2.3.2.2 Chemical Composition ----------------------------------------------------------------36
2.3.2.3 Active Principle36
2.3.2.4 Other compounds ----------------------------------------------------------------------39
2.3.3 Isatis Tinctoria L. ----------------------------------------------------------------------------44
2.3.3.1 General44
2.3.3.2 Chemical Composition45
2.3.3.3 Active Principle-------------------------------------------------------------------------45
2.3.3.5 Important Conversions of the Main Components -------------------------------46
2.3.3.6 Biological and Pharmacological Activity ------------------------------------------47
2.3.3.7 Toxicity-----------------------------------------------------------------------------------47
2.3.4 Cannabis Sativa L. --------------------------------------------------------------------------48
2.3.4.1 General48
2.3.4.2 Chemical Composition ----------------------------------------------------------------49
2.3.4.3 Active Principle-------------------------------------------------------------------------50
2.3.4.4 Other components----------------------------------------------------------------------52
2.3.4.5 Important Reactions of Active Cannabinoids ------------------------------------52
2.3.4.6 Biological and Pharmacological Activity ------------------------------------------53
2.3.4.7 Toxicology -------------------------------------------------------------------------------54
3. MATERIALS EQUIPMENTS AND METHODS -------------------------------------------55
3.1 Materials -------------------------------------------------------------------------------------------55
3.1.1 Samples of Plant Materials ----------------------------------------------------------------55
3.1.2 Standards -------------------------------------------------------------------------------------56
3.1.3 Chemicals and Solvents--------------------------------------------------------------------58
3.1.4 Miscellaneous Materials59
3.2 Foam Fractionation Unit and Equipments --------------------------------------------------59
3.2.1 Foam Fractionation Unit-------------------------------------------------------------------59
3.2.2 High Performance Liquid Chromatography ------------------------------------------60
3.2.3 Gas Chromatography ----------------------------------------------------------------------61
3.2.3 UV-Vis Spectroscopy -----------------------------------------------------------------------61
3.2.4 Nuclear Magnetic Resonance Spectroscopy--------------------------------------------61 Contents
______________________________________________________________________________
3.2.5 Fourier Transform Infrared Microspectroscopy -------------------------------------61
3.2.6 Other Equipments---------------------------------------------------------------------------62
3.3 Methods---------------------------------------------------------------------------------------------62
3.3.1 Analytical Characterisation and Quantification --------------------------------------62
3.3.1.1 Faradiol Esters--------------------------------------------------------------------------62
3.3.1.2 Catechins---------------------------------------------------------------------------------64
3.3.1.3 Tryptanthrin ----------------------------------------------------------------------------65
3.3.1.4 Cannabinoids66
3.3.2 Extraction-------------------------------------------------------------------------------------67
3.3.2.1 Extraction of Faradiol Esters -------------------------------------------------------67
3.3.2.2 Extraction of Catechins ---------------------------------------------------------------68
3.3.2.3 Extraction of Tryptanthrin-----------------------------------------------------------68
3.3.2.4 Extraction of Cannabinoids----------------------------------------------------------68
3.3.3 Foam Fractionation -------------------------------------------------------------------------69
3.3.3.1 Foam Fractionation of Faradiol Esters---------------------------------------------70
3.3.3.2 Foam Fractionation of Catechins ---------------------------------------------------74
3.3.3.3 Foam Fractionation of Tryptanthrin-----------------------------------------------76
4. RESULTS-----------------------------------------------------------------------------------------82
4.1 Accuracy of Measurements and Quantification of Active Principles by HPLC -----82
4.2 Calendula Officinalis------------------------------------------------------------------------------85
4.2.1 Analytical Characterisation of Lupeol Acetate ---------------------------------------85
4.2.1.1 UV-Vis Characterisation -------------------------------------------------------------85
4.2.1.2 HRGC-EI/MS Characterisation -------------------------------------------------------85
4.2.2 Extraction of Faradiol Esters86
4.2.3 Enrichment of Faradiol Esters-----------------------------------------------------------87
4.2.3.1 Influence of Surfactant and Additives ---------------------------------------------88
4.2.3.2 Influence of Solute Concentration and pH ----------------------------------------89
4.2.3.3 Influence of Height of Foam Tower and Height of Liquid Pool --------------91
4.2.3.4 Influence of Time of Foaming and Gas Flow Rates -----------------------------92
4.2.3.5 Optimised Overall Enrichment Process -------------------------------------------93
4.3 Camellia Sinensis----------------------------------------------------------------------------------95 Contents
______________________________________________________________________________
4.3.1 Analytical Characterisation of Catechins ----------------------------------------------95
4.3.1.1 UV-Vis Characterisation -------------------------------------------------------------95
4.3.1.2 Nuclear Magnetic Resonance Characterisation ---------------------------------96
4.3.2 Extraction of Catechins --------------------------------------------------------------------96
4.3.3 Enrichment of Catechins-------------------------------------------------------------------97
4.3.3.1 Influence of Solute Concentration, Additives and pH ---------------------------98
4.3.3.2 Influence of Consecutive Foaming and Gas Flow Rate----------------------- 100
4.3.3.3 Optimised Overall Enrichment Process ----------------------------------------- 101
4.4 Isatis Tinctoria----------------------------------------------------------------------------------- 104
4.4.1 Analytical Characterisation of Tryptanthrin ---------------------------------------- 104
4.4.1.1 UV-Vis Characterisation ------------------------------------------------------------ 104
4.4.1.2 Fourier Transform Infrared Characterisation--------------------------------- 104
4.4.2 Extraction of Tryptanthrin-------------------------------------------------------------- 105
4.4.3 Enrichment of Tryptanthrin------------------------------------------------------------- 106
4.4.3.1 Influence of Solute Concentration, Surfactants and Additives-------------- 107
4.2.3.2 Influence of pH ----------------------------------------------------------------------- 108
4.4.3.3 Influence of Height of Foam Tower and Height of Liquid Pool ------------- 109
4.4.3.4. Influence of Consecutive Foaming and Gas Flow Rates---------------------- 110
4.4.3.5 Optimised Overall Enrichment Process ----------------------------------------- 111
4.5 Cannabis Sativa --------------------------------------------------------------------------------- 113
4.5.1 Analytical Characterisation of Cannabinoids --------------------------------------- 113
4.5.1.1 UV-Vis Characterisation ----------------------------------------------------------- 113
4.5.2.2. HRGC-EI/MS Characterisation-------------------------------------------------- 114
4.5.2 Extraction of Cannabinoids ---------------------------------------------------------- 115
4.5.3 Enrichment of Caids 115
4.5.3.1 Influence of Solute Concentration, Surfactants and Additives-------------- 116
4.5.3.2 Influence of pH ----------------------------------------------------------------------- 117
4.5.3.3 Influence of Height of Foam Tower and Height of Liquid Pool ------------- 119
4.5.3.4. Influence of Consecutive Foaming and Gas Flow Rates---------------------- 120
4.2.3.5 Optimised Overall Enrichment Process ----------------------------------------- 121
5. DISCUSSION --------------------------------------------------------------------------------- 124
5.1 Calendula Officinalis --------------------------------------------------------------------------- 124 Contents
______________________________________________________________________________
5.1.1 Characterisation of Lupeol Acetate ---------------------------------------------------- 124
5.1.2 Extraction of Faradiol Esters ----------------------------------------------------------- 124
5.1.3 Enrichment of Faradiol Esters--------------------------------------------------------- 125
5.1.3.1 Influence of Surfactants and Additives ------------------------------------------ 126
5.1.3.2. Influence of Solute Concentration and pH ------------------------------------- 127
5.1.3.3 Influence of Height of Foam Tower and Height of Liquid Pool------------ 128
5.1.3.4 Influence of Time of Foaming and Gas Flow Rates --------------------------- 129
5.1.3.5 Optimised Overall Enrichment--------------------------------------------------- 130
5.2 Camellia Sinensis-------------------------------------------------------------------------------- 131
5.2.1 Characterisation of Catechins ---------------------------------------------------------- 131
5.2.2 Extraction of Catechins ------------------------------------------------------------------ 131
5.2.3 Enrichment of Catechins----------------------------------------------------------------- 132
5.2.3.1 Influence of Solute Concentration, Additives and pH ------------------------ 134
5.2.3.2 Influence of Consecutive Foaming and Gas Flow Rates ---------------------- 135
5.2.3.3 Optimised Overall Enrichment---------------------------------------------------- 136
5.3 Isatis Tinctoria----------------------------------------------------------------------------------- 137
5.3.1 Characterisation of Tryptanthrin------------------------------------------------------- 137
5.3.2 Extraction of Tryptanthrin-------------------------------------------------------------- 138
5.3.3 Enrichment of Tryptanthrin ------------------------------------------------------------ 138
5.3.3.1 Influence of Solute Concentration, Surfactants and Additives-------------- 139
5.3.3.2. Influence of pH----------------------------------------------------------------------- 140
5.3.3.3 Influence of Height of Foam Tower and Height of the Liquid Pool-------- 141
5.3.3.4 Influence of Consecutive Foaming and Gas Flow Rates -------------------- 142
5.3.3.5 Overall Optimised Enrichment ---------------------------------------------------- 142
5.4 Cannabis Sativa --------------------------------------------------------------------------------- 143
5.4.1 Characterisation of Cannabinoids ------------------------------------------------------ 143
5.4.2 Extraction of Cannabinoids ------------------------------------------------------------- 143
5.4.3 Enrichment of Cannabinoids ----------------------------------------------------------- 144
5.4.3.1 Influence of Solute Concentration, Surfactants and Additives-------------- 145
5.4.3.2 Influence of pH ----------------------------------------------------------------------- 146
5.4.3.3 Influence of Height of Foam Tower and Height of Liquid Pool ------------ 147
5.4.3.4 Influence of Consecutive Foaming and Gas Flow Rates---------------------- 148
5.4.3.5 Optimised Overall Enrichment---------------------------------------------------- 148 Contents
______________________________________________________________________________
6. CONCLUSIONS AND RECOMMENDATIONS ------------------------------- 149
6.1 Conclusions -------------------------------------------------------------------------------------- 149
6.2 Recommendations ------------------------------------------------------------------------------ 150
7. SUMMARY------------------------------------------------------------------------------------- 151
8. LITERATURE ------------------------------------------------------------------------------- 154
9. ANNEXES--------------------------------------------------------------------------------------- 166