aminated polyelectrolytes – advanced concepts for their modification and application

199 Pages·2013·6.94 MB·English

AMINATED POLYELECTROLYTES – ADVANCED
CONCEPTS FOR THEIR MODIFICATION AND
APPLICATION

Von der Fakultät für Mathematik, Informatik und Naturwissenschaften
der RWTH Aachen University zur Erlangung des akademischen Grades eines
Doktors der Naturwissenschaften genehmigte Dissertation

vorgelegt von

Master of Science

Metodi Ivanov Bozukov
Aus Sliven, Bulgaria

Berichter: Universitätsprofessor Dr. rer. nat. Martin Möller
Universitätsprofessor Dr. rer. nat. Uwen Beginn

Tag der mündlichen Prüfung: 16. Mai 2013

Diese Dissertation ist auf den Internetseiten der Hochschulbibliothek online verfügbar.
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“I know that I know nothing”
Socrates

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To my family

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Table of contents ……………………………………………………………………………. 5
List of abbreviations ………………………………………………………………………. 11
Acknowledgment ………………………………………………………………………….. 15
Summary …………………………………………………………………………………… 17
Zusammenfassung …………………………………………………………………………. 19
Chapter I General introduction ………………………………………………………... 21
1.1) Polyelectrolytes – definition, classification, structure, origin ……………… 22
1.1.1) Classification of polyelectrolytes in respect to their electrochemical charge . 22
1.1.2) Classification of polyelectrolytes in respect to their molecular architecture .. 22
1.1.3) Classification of polyelectrolytes in respect to their origin …………………. 24
1.2) Polyelectrolyte in solution ……………………………………………….….. 31
1.3) Osmotic pressure of semidilute polyelectrolyte solutions ………………….. 34
1.4) Viscosimetry …...…………………………………………………………… 35
1.5) “Salting in” and “Salting out” interactions. Hofmeister series ……………... 36
1.6) Light scattering and molecular weight measurements of polyelectrolyte
solutions ………………………………………………………………….…. 39
1.7) Applications of polyelectrolyte aqueous solutions for fiber formation ….…. 42
1.8) Polyelectrolytes on surfaces …………………………………………….….. 44
1.8.1) Polyelectrolytes on oppositely charged surfaces …………………………… 44
1.8.2) Effect of polyelectrolyte bulk concentration ……………………….………. 46
1.8.3) Effect of polyelectrolyte ionic strength ……………………………………... 46
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1.8.4) Effect of polyelectrolyte charge density …………………………………….. 47
1.8.5) Effect of surface charge density …………………………………………….. 47
1.8.6) Polyelectrolytes on similarly charged surfaces ……………………………... 47
1.8.7) Polyelectrolytes on uncharged surfaces ………………………………….…. 48
1.8.8) Grafted polyelectrolytes ……………………………………………………. 50
1.9) Industrial and biomedical applications of polyamines ……………………… 52
1.10) Electrospinning of polyamines ……………………………………………… 57
1.11) Atmospheric pressure glow discharge plasma jet …………………………... 61
1.12) Physicochemical characterization of modified surfaces ……………….……. 63
1.12.1) X-ray photoelectron spectroscopy (XPS) …………………………………… 63
1.12.2) Water-drop contact angle …………………………………………………… 64
1.13) Aims of the thesis …………………………………………………………… 65
1.14) References …………………………………………..………………………. 66
Chapter II Electrospinning of polyvynylamine: antibacterial polyelectrolyte water-
resistant mats ………………………………………………………………... 77
2.1) Introduction ……………………………………………………………….… 78
2.2) Experimental part …………………………………………………………… 79
2.2.1) Materials ………………………………………………………………….…. 79
2.2.2) Analytical techniques ………………………………………………….……. 79
2.2.3) Synthesis of p-(6-bromohexyloxy)benzophenone (BHBP) ………………… 80
2.2.4) Functionalization of PVAm with BHBP (P1) ………………………………. 81
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2.2.5) Strategy I: Modification of PVAm-BHBP with MAC (P2) ………………… 81
2.2.6) Strategy II: Modification of PVAm- BHBP with GtMAC (P3) and MAC (P4)
2.2.7) Electrospinning ……………………………………………………………… 82
2.2.8) Crosslink stabilization of electrospun nanofibers ………………………..…. 85
2.2.9) Antibacterial assessment with Escherichia coli ……………………………. 85
2.3) Results and discussion ………………………………………………………………. 85
2.3.1) Synthesis of PVAm derivatives ……………………………………………... 88
2.3.2) Electrospinning of polyvinylamine ……………………………………….… 93
2.3.2.1) Influence of the solution concentration ………………………….….. 93
2.3.2.2) Influence of the applied voltage (V) ……………………………… 96
2.3.2.3) Choice of the working distance (D) and the flow rate (F) .................. 98
2.3.3) Fiber diameter (d) at various processing parameters …………………… 100
f
2.4) Electrospinning of polyvinylamine derivatives ………………………….. 101
2.4.1) Electrospinning of PVAm-BHBP-MAC derivatives (P2) ……………….. 101
2.4.2) Electrospinning of PVAm-BHBP-MAC-GtMAC ………………………... 104
2.5) Antibacterial tests with Escherichia coli ………………………………….. 105
2.6) Conclusions ………………………………………………………………... 107
2.7) Reference …………………………………………………………………. 107
Chapter 3 Easy-to-apply stable coating for polytetrafluoreethylene vascular grafts
……………………………………………………………………………. 109
3.1) Introduction ……………………..………………………………………. 110
3.2) Experimental part ……………………………….………………………. 112
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3.2.1) Materials ………………………………………………….…………….… 112
3.2.2) Analytical methods ………..…………………………………………….. 113
3.2.3) Synthesis of methacrylate grafted polyethylenimine (PEI-GMA, M1 and M2)
………………………………………..………………….………………... 113
3.2.4) Preparation of isocyanate-terminated star PEG ………….………..……. 114
3.2.5) Modification of PTFE vascular grafts ………………….………...……… 114
3.2.6) In vitro protein adsorption test ………….………………………………. 116
3.3) Results and discussion …………………………………………………… 116
3.3.1) Synthesis of methacrylate grafted polyethylenimine (PEIMA, M1 and M2)
………………………………………..…………………………………… 116
3.3.2) Modification of PTFE vascular grafts …………..……………..…….….. 118
3.3.3) BSA absorption tests ……………………………………….……….…… 131
3.4) Conclusions ……………………………………………….………….….. 133
3.5) References …………………………………….………………………..... 134
Chapter IV Surface activation of polypropylene films by atmospheric pressure plasma jet
4.1) Introduction …………………………………….……………….……..…... 138
4.2) Experimental part ……………………….…………………….……..…….. 139
4.2.1) Materials …………………………………….………………….…….……. 139
4.2.2) Analytical techniques …………………………………….……………… 139
4.2.3) Plasma treatment technique ………………………….………….………… 140
4.3) Results and discussion ………………………………….………….…….... 144
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4.3.1) Influence of the forward power, gas flow rate and gas flow composition on the
plasma temperature ………………………………………………………… 146
4.3.2) Hydrophilicity of PP substrate after plasma activation with Ar, Ar/N and
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Ar/NH gas flow mixtures …………………………………………………. 151
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4.3.3) ATR-IR spectroscopy ……………………………………………………. 153
4.3.4) X-ray photoelectron spectroscopy ……………………………………….. 155
4.3.5) Zeta potential …………………………………………………………….. 160
4.3.6) Visual proof for the surface activation ……………………….………….. 162
4.3.7) Atomic Force Microscopy ……………………………………………….. 163
4.4) Conclusions ………..……………………………………………………… 167
4.5) References ………………………………………………………………… 168
Chapter V Atmospheric pressure glow discharge plasma jet solution activated coating
process towards functional polycation antibacterial coatings activity …… 171
5.1) Introduction ……………………..…………………………………….….. 172
5.2) Experimental part …………………….……….………………………….. 173
5.2.1) Materials …………………………………….…………………………… 173
5.2.3) Characterization …………………………………….……………………. 174
5.2.4) PEI functionalization by GMA …………………………….…………….. 174
5.2.5) PEI functionalization by MAC and –NH + …………………...…….… 175
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5.2.6) Dip-coating modification of PP films ………………………………….… 175
5.2.7) APGPJ solution-activated surface modification of PP films ….…………. 176
5.2.8) Antibacterial testing ………………………………………….………….. 176
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5.3) Results and discussion ………………………………………………..…..... 177
5.3.1) Characterization of the chemical composition – CA, XPS and ATR-IR …...177
5.3.1.1) Dip-coating ………………………………………………………… 177
5.3.1.2) APGPJ solution-activeted modification ..…………………....….…. 181
5.3.2) Characterization of the surface morphology – FE-SEM & SPM .…………. 187
5.3.3) Antibacterial properties against S. aureus Gram-positive bacteria ………... 190
5.4) Conclusions ………………………………………………….…………….. 193
5.5) References ……………………………………………………………..…... 194
General conclusions and perspectives …………………………………………………... 197

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