Novel metallo-porphyrin based colourimetric amine sensors and their processing via plasma ...

238 Pages·2014·9.7 MB·English

by  Heier, Philip

Novel metallo-porphyrin based
colourimetric amine sensors and their
processing via plasma enhanced chemical
vapour deposition at atmospheric pressure
– synthesis, characterisation and
mechanistic studies
Dissertation
zur Erlangung des Grades
„Doktor der Naturwissenschaften”
im Promotionsfach Chemie

am Fachbereich Chemie, Pharmazie und Geowissenschaften der
Johannes Gutenberg-Universität Mainz

Philip Christoph Heier
geboren in Oldenburg

Mainz, 2014

Die vorliegende Arbeit wurde unter der Betreuung von Prof. Dr. Katja Heinze in der Zeit
vom Oktober 2010 bis Juli 2014 am Institut für Anorganische und Analytische Chemie
der Johannes Gutenberg-Universität in Mainz, Deutschland und am Centre de
Recherche Public – Gabriel Lippmann in Belvaux, Luxemburg angefertigt.
Mainz, Juli 2014

Dekan: Prof. Dr. Holger Frey
Erster Berichterstatter: Prof. Dr. Katja Heinze
Zweiter Berichterstatter: Prof. Dr. Karl W. Klinkhammer

Tag der mündlichen Prüfung: 15. August 2014

D77

Abstract
Volatile amines are prominent indicators of food freshness, as they are produced
during many microbiological food degradation processes. Monitoring and indicating
the volatile amine concentration within the food package by intelligent packaging
solutions might therefore be a simple yet powerful way to control food safety
throughout the distribution chain.
In this context, this work aims to the formation of colourimetric amine sensing surfaces
on different substrates, especially transparent PET packaging foil. The colour change of
the deposited layers should ideally be discernible by the human eye to facilitate the
determination by the end-user. The associated research topics addressed in this work
can be summarised in three fields as shown in Figure 1.

Figure 1 Graphical abstract of the research topics addressed in this work.
Different tailored zinc(II) and chromium(III) metalloporphyrins have been used as
chromophores for the colourimetric detection of volatile amines (Figure 1, A). A new
concept to increase the porphyrins absorbance change upon exposure to amines is
introduced. Moreover, the novel porphyrins’ processability during the deposition
process is increased by their enhanced solubility in non-polar solvents.
The porphyrin chromophores have successfully been incorporated into polysiloxane
matrices on different substrates via a dielectric barrier discharge enhanced chemical
vapour deposition (B). This process allows the use of nitrogen as a cheap and abundant
plasma gas, produces minor amounts of waste and by-products and can be easily
introduced into (existing) roll-to-roll production lines. The formed hybrid sensing layers
tightly incorporate the porphyrins and moreover form a porous structure to facilitate
the amines diffusion to and interaction with the chromophores.
The work is completed with the thorough analysis of the porphyrins’ amine sensing
performance in solution as well as in the hybrid coatings (C). To reveal the underlying
interaction mechanisms, the experimental results are supported by DFT calculations.
The deposited layers could be used for the detection of NEt concentrations below
3
10 ppm in the gas phase. Moreover, the coated foils have been tested in preliminary
food storage experiments.
The mechanistic investigations on the interaction of amines with chromium(III)
porphyrins revealed a novel pathway to the formation of chromium(IV) oxido
porphyrins. This has been used for electrochemical epoxidation reactions with
dioxygen as the formal terminal oxidant.
Contents
1. Introduction ............................................................................................. 1
1.1 Smart Food Packaging ................................................................................................ 2
1.1.1 Intelligent Packaging .................................................................................................... 3
1.1.2 Food Quality Indicators ................................................................................................ 5
1.2 Sensing of Amines ..................................................................................................... 6
1.2.1 Biogenic and Volatile Amines ....................................................................................... 7
1.2.2 Optical Amine Sensing.................................................................................................. 9
1.3 (Metallo)Porphyrins................................................................................................. 17
1.3.1 Synthesis of Artificial Porphyrins ............................................................................... 18
1.3.2 Photophysical Properties of Porphyrins ..................................................................... 19
1.3.3 Tuning of Porphyrin Absorption Spectra.................................................................... 21
1.4 Porphyrins in Sensing Applications ........................................................................... 27
1.4.1 Porphyrin Based Gas Sensing Layers .......................................................................... 29
1.5 Atmospheric Pressure Plasmas ................................................................................. 34
1.5.1 Dielectric Barrier Discharge Plasmas .......................................................................... 37
1.5.2 DBD Enhanced Chemical Vapour Deposition ............................................................. 39
1.6 Epoxidation of Olefins.............................................................................................. 43
1.7 Bibliography Introduction ........................................................................................ 46
2. Aim of the work ...................................................................................... 55
3. Results and Discussion ............................................................................ 57
3.1 Plasma Polymer Membranes for Immobilising Metalloporphyrins ............................. 59
Introduction ........................................................................................................................ 61
Experimental Section .......................................................................................................... 62
Results and Discussion ........................................................................................................ 64
Discussion ............................................................................................................................ 71
Conclusion ........................................................................................................................... 72
References ........................................................................................................................... 73
3.2 Atmospheric pressure plasma polymerisation of metalloporphyrins containing
mesoporous membranes for gas sensing applications .................................................... 75
Introduction ........................................................................................................................ 77
I
Experimental ....................................................................................................................... 78
Results and discussion ......................................................................................................... 79
Conclusions .......................................................................................................................... 85
References ........................................................................................................................... 86
3.3 Optical Sensing Responses of CrIIICl(TPP)(H O)-based Coatings Obtained by an
2
Atmospheric Pressure Plasma Method –
Application to the Detection of Volatile Amines ............................................................. 89
Introduction ......................................................................................................................... 91
Experimental ....................................................................................................................... 92
Results and Discussion ........................................................................................................ 95
Conclusions ........................................................................................................................ 103
References ......................................................................................................................... 103
3.4- and -Zinc-meso-tetraarylporphyrins with large optical responses to
triethylamine .............................................................................................................. 107
Introduction ....................................................................................................................... 109
Results and discussion ....................................................................................................... 110
Conclusions ........................................................................................................................ 125
Experimental section ......................................................................................................... 126
Notes and references ........................................................................................................ 129
3.5 New class of ZnII and CrIII porphyrins incorporated into mesoporous polymer matrixes
via an atmospheric pressure plasma enhanced CVD to form gas sensing layers ............. 133
Introduction ....................................................................................................................... 135
Experimental Section ......................................................................................................... 136
Plasma Deposition of Sensor Coatings .............................................................................. 139
Amine Sensing Experiments .............................................................................................. 146
Influence of CrIII Porphyrin Concentration on the Sensor Properties ............................... 150
Conclusions ........................................................................................................................ 152
Notes and References ....................................................................................................... 153
3.6 Dual Application of (Aqua)(Chlorido)(Porphyrinato)Chromium(III) as Hypersensitive ON
Switch Amine Detector and for Dioxygen Activation ..................................................... 155
Introduction………………………………………………………………………………………………………………….157
Results and Discussion…………………………………………………………………………………………………..158
Conclusion…………………………………………………………………………………………………………………….171
II
References…………………………………………………………………………………………………………………….172
4. Summary .............................................................................................. 177
5. Outlook ................................................................................................ 179
6. Supporting Information ........................................................................ 181
7. Acknowledgments ................................................................................ 215
8. Curriculum Vitae ................................................................................... 217
8.1 List of Publications .................................................................................................. 219
8.2 Conference contributions ........................................................................................ 220

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