Interaction of amino acids with different ionogenic groups [Elektronische Ressource] / Olesya Evgen'evna Kister. Betreuer: Frank Rößner

Informations

• Publié par: carl_von_ossietzky_universitat_oldenburg
• Publié le: 01 janvier 2012
• Nombre de lectures: 7
• Langue: English
• Poids de l'ouvrage: 2 Mo

Extrait

Interaction of amino acids
with differennt ionoggenic grroups


VVon der Fakkultät für Maathematik uund Naturwiissenschafteen
der Carl von Ossietzky Universität Oldenburg zur Erlangung des Grades und Titels eines



Doctor rerum naturalium
((Dr. rer. natt.)



angenommene Dissertation



von Frau M.Sc. Olesya Evgen‘evna Kister, geb. Fomenko

geboren am 9. Januar 1984 in Woronesch, Russland















Gutachter: Prof. Dr. Frank Rößner
Carl von Ossietzky Universität Oldenburg
Zweitgutachter: Prof. Dr. Axel Brehm
Carl von Ossietzky Universität Oldenburg

Tag der Disputation: 29. November 2011


























Published with the support of DAAD








For Max and my Parents






























Acknowledgements
The completion of this thesis would not have been possible without the support of
numerous people. I would like to use this opportunity to thank all of them.

First of all I would like to thank Professor Frank Rößner for giving me the
opportunity of the completion of this thesis at the University of Oldenburg at the
Department of Industrial Chemistry II and for the specification of the research topic. I
also would like to thank him for his motivation and spiritual support.

I would like to thank the members of the groups for Industrial Chemistry II of the
Carl von Ossietzky University of Oldenburg for many inspiring talks and social hours. I
also would like all of them for the warm welcome and for the support during my study in
Oldenburg.

I would like to thank Dr. Philipp Adryan, Dr. Oliver Meyer, Dr. Wojciech
Supronowicz and Dipl.-Chem. Robert Henkel for allowing me to call for their help
whenever needed, for great cooperation and critical discussions.

Many thanks to the members of the Departments of Physical, Analytical and
Organic Chemistry for helping me to characterize developed composite materials and
adsorption of amino acids of them.

I thank DAAD (German Academic Exchange Service) for the financial support
during the whole period of my PhD work.

Lastly, my special thanks go to my parents, grandparents and my husband Max for
their support, patience and love. Table of contents
1. Introduction 1
2. Literature view 4
2.1 Silica gel 5
2.2 The hydroxylated surface 7
2.3 Infrared study of the silica surface 8
2.4 Use 10
2.5 MC-41 3
2.6 Stability of MCM-41 15
2.7 Ordered mesoporous materials in catalysis 17
2.8 Functionalization of silicates 18
2.9 Silica gel and M41S materials in adsorption and separation processes 23
2.9.1 Silica gel 23
2.9.2 MC-41 25
2.9.3 Adsorption capacity and kinetics 26
2.9.4 Biomolecule separations 27
2.10 Amino acids 9
2.10.1 Industrial applications of amino acids 29
2.10.2 Structure and some properties of amino acids 29
2.10.3 Hydration of amino acids in aqueous solutions 32
2.11 Adsorption of amino acids on mineral surfaces 34
2.11.1 Investigation methods 34
2.11.2 Adsorption mechanism 35
3. Experimental part 41
3.1 Preparation of silicate composites 41
3.1.1 Chemicals and reagents 41
3.1.2 Synthesis of the composites
3.2 Characterization 46
3.2.1 Infrared spectroscopy (DRIFTS) 46 3.2.2 Nitrogen adsorption / desorption (BET) 47
3.2.3 X-Ray difraction 48
3.2.4 Solid state Nuclear Magnetic Resonance (NMR) 48
3.2.5 Rastro Electron Microscopy (REM) 48
3.2.6 Transmission Electron (TEM) 49
3.2.7 Catalytic test reaction: conversion of methylbutynol (MBOH) 49
3.2.8 Study of the thermal stability of the materials (TGA / DTA) 50
3.2.9 Adsorption of amino acids 51
3.2.10 Study of amino acids solutions by UV-Vis spectroscopy 55
3.2.11 Mathematic description of amino acids adsorption. Adsorption
isotherm 60
4. Results and discussion 62
4.1 Modification and characterization of the composite materials 62
4.1.1 Silylation 62
4.1.2 Characterization of the silylized materials 67
4.1.2.1 Structural characteristics 67
4.1.2.2 BET 70
4.1.2.3 Nuclear Magnetic Resonance 75
4.1.2.4 TEM and REM 81
4.1.2.5 Catalytic test reaction 83
4.1.2.6 Thermal stability of the materials 86
4.1.3 Sulfonation 95
4.1.4 Characterization of the sulfonated silicate compounds 95
4.1.4.1 Infrared spectroscopy 95
4.1.4.2 Structural characteristics 97
4.1.4.3 BET 99
4.1.4.4 NMR 102
4.1.4.5 Catalytic test reaction 105
4.1.4.6 Thermal stability of the sulfonated materials 108
4.2 Adsorption of amino acids from aqueous solutions 113
4.2.1 Adsorption of amino acids of mesoporous materials based on
MCM-41 113
4.2.2 Adsorption of phenylalanine on the MCM-41 composites 113
4.2.3 Adsorption of tryptophan and tyrosine on MCM-41 based materials 119
4.2.4 Influence of an adsorbent structure on the adsorption of amino
acids: adsorption experiments on amorphous silica gel materials 126
5. Conclusion 128
6. References 32
7. Apendix 40 1. Introduction
Silica is one of the most widely spread materials; and the silicates are one of the
biggest classes of solids. Different types of the structures are characteristic for them and
so, the variety of properties. Silica is naturally occurring in minerals (quartz, flint) and in
plants, as, for example, bamboo, rice and barley. However, silica materials, mostly used
in chemical applications, have a synthetic origin. Different phases can be formed,
depending on temperature, pressure and degree of hydration. Here is just a short list of the
materials based on silica: colloidal silicas, silica gel, pyrogenic silica, precipitated silicas,
porosils. Due to variable properties, these materials have found application in a broad
range of areas: as desiccants, in adsorption, in microelectronics, in catalysis as catalyst
and catalyst carriers, as active filler in silicone rubber, as antisettling agents, dispersants
and many others [1].
Relatively new class of silicon oxide based materials is the M41S class. These
materials were invented in early 1990s [2]. They were prepared by templating silica
species with surfactant, which resulted in the formation of silica oxides with ordered
mesoporous structure. This invention extended the range of pore sizes accessible in the
form of an ordered pore system. MCM-41, which is the most known member of M41S
family, possesses a hexagonal array of uniform mesopores. This material, as well as many
others of the M41S class, has attracted attention of numerous research groups all over the
world in the last years. Promising results of their application in catalysis and in adsorption
processes were demonstrated [3-12].
The applications of amorphous silica, as well as mesoporous MCM-41, can be
extended by the variation of properties of the materials, in the case of MCM-41 – also by
the improvement of its hydrothermal stability. The qualities of the compounds can be
adjusted by the incorporation of the metal ions in their structures, what also changes the
acid-base properties. This method was often used to synthesize materials, which can be
effectively used in catalytic processes [3, 13-14]. Another possible technique for the
modification of properties of mentioned substances is grafting of organic functional
groups on their surface. The qualities of the resulting compound vary depending on the
type of introduced groups. Such kind of modifications, called silylation, is often used to
synthesize materials for catalytic purposes, as well as for their application in adsorption,
1 
 and particularly in the adsorption of the biologically active molecules [7, 15-21]. Peptides
and their building blocks - amino acids, can be attributed to such a kind of molecules. The
investigation of their adsorption is very important, because of several reasons: 1) the
study of their adsorption on the biomaterial surfaces can lead to the understanding of the
biomolecular adsorption; 2) amino acids are widely used as stock feed and in food
technology. Regardless of the way of the production, the separation techniques for the
recovery and purification of amino acids always have to be applied.
The object of the presented research is the study of amorphous silica gel and
mesoporous siliceous MCM-41. These materials have similarities, as well as differences
in their structures. The biggest difference is in the absence (silica gel) / presence (MCM-
41) of the order in the po