University of Groningen

Polymeric surfactants based on the chemical modification of alternating aliphatic polyketonesAraya Hermosilla, Esteban Alejand

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Polymeric surfactants based on the chemical modification of

alternating aliphatic polyketones

PhD thesis

to obtain the degree of PhD at the University of Groningen on the authority of the

Rector Magnificus prof. E. Sterken and in accordance with

the decision by the College of Deans.

This thesis will be defended in public on

Monday 6 May 2019 at 11.00 hours

by

Esteban Alejandro Araya Hermosilla

born on 10 February 1984 in Providencia, Chili

Supervisor

Prof. F. Picchioni

Assessment Committee

Prof. M. Kobrak

Prof. G.J.W. Euverink

Prof. R. Rossi

Polymeric Surfactants Based on theChemical Modification of Alternating

Aliphatic Polyketones

Esteban Alejandro Araya Hermosilla

ii

Dedicated to my beloved family.

iv

Contents***

1 Introduction 11.1 Supramolecular systems . . . . . . . . . . . . . . . . . . . . . . . 1

1.1.1 Supramolecular systems . . . . . . . . . . . . . . . . . . . 11.1.2 Self-Assembly . . . . . . . . . . . . . . . . . . . . . . . . 21.1.3 Active molecules . . . . . . . . . . . . . . . . . . . . . . . 31.1.4 Antibiotics . . . . . . . . . . . . . . . . . . . . . . . . . . 41.1.5 Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41.1.6 Redox-active molecules . . . . . . . . . . . . . . . . . . . 6

1.2 Polymeric surfactants . . . . . . . . . . . . . . . . . . . . . . . . . 71.3 Polyketones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

1.3.1 The Paal-Knorr reaction . . . . . . . . . . . . . . . . . . . 101.4 Aim of the thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

2 Novel polyketone with pendant imidazolium groups as nanodispersantsof hydrophobic antibiotics 132.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162.3 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . 182.4 Final remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

3 Amphiphilic modified polyketones as stabilizers of the tetra-anionic formof 5,10,15,20-Tetrakis-(4-sulfonatophenyl)porphyrin in aqueous acid con-ditions 273.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303.3 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . 323.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41

v

vi CONTENTS

4 Supramolecular structures based on pH-sensitive surfactant polyketonesand 5,10,15,20-tetrakis-(sulfonatophenyl)porphyrin 454.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 464.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 484.3 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . 514.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65

5 Totally organic redox-active pH-sensitive nanoparticles stabilized by am-phiphilic aromatic polyketones 775.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 785.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 805.3 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . 825.4 Final remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 885.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90

6 Functionalization of polyketones: beyond the synthesis of polymeric sur-factants 916.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 916.2 Polymeric emulsifiers based on polyketones . . . . . . . . . . . . . 93

6.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . 936.2.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . 946.2.3 Results and discussion . . . . . . . . . . . . . . . . . . . . 956.2.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . 99

6.3 Catalysts Based on Polyketones . . . . . . . . . . . . . . . . . . . 996.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . 996.3.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . 1036.3.3 Results and discussion . . . . . . . . . . . . . . . . . . . . 1066.3.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . 112

A Appendix 115

Bibliography 123

List of Figures***

1.1 Schematic representation of the components of an organic dye molecule,4-Hydroxyazobenzene. . . . . . . . . . . . . . . . . . . . . . . . . 5

1.2 Scheme of aliphatic polyketone. . . . . . . . . . . . . . . . . . . . 91.3 Schematic representation of polyketones chemical modification via

the Paal-Knorr reaction. . . . . . . . . . . . . . . . . . . . . . . . . 111.4 Schematic representation of the Paal-Knorr reaction . . . . . . . . . 11

2.1 Schematic representation of the chemical modification of polyke-tones (PK50) via Paal-Knorr reaction with histamine. . . . . . . . . 15

2.2 Structure of oxolinic acid and flumequine. . . . . . . . . . . . . . . 162.3 OA precipitation pH at 1 ⋅ 10−3 M and 2 ⋅ 10−4 M. . . . . . . . . . . 192.4 FLU precipitation pH at 1 ⋅ 10−3 M and 2 ⋅ 10−4 M. . . . . . . . . . 192.5 Correlograms obtained by DLS of PK-Im at concentration of 1 ⋅ 10−3,

1 ⋅ 10−4, and 1 ⋅ 10−5 M at different values of pH. . . . . . . . . . . 212.6 Size and zeta potential of particles composed of OA, PK-Im, and

FLU and PK-Im as a function of their relative concentration. . . . . 222.7 Size and zeta potential of OA/PK-Im nanoparticles as a function of

time for OA/PK-Im at different molar ratios. . . . . . . . . . . . . . 222.8 Size and zeta potential of FLU/PK-Im nanoparticles as a function of

time for FLU/PK-Im a different molar ratios. . . . . . . . . . . . . 23

3.1 Acid and basic forms of TPPS. . . . . . . . . . . . . . . . . . . . . 293.2 Schematic representation of the chemical modification of polyketone

50 via Paal-Knorr reaction with N-(2-hydroxyethyl)ethylenediamine(HEDA). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30

3.3 1H-NMR spectra of pyrrole-HEDA model compound. . . . . . . . . 333.4 1H-NMR spectra of PK50 modified with HEDA at different x. . . . 343.5 FT-IR spectra of PK50 modified with HEDA at different x. . . . . . 353.6 Surface tension graph of PK50-HEDA80 as a functions of pH and

concentration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 363.7 Transition pH of TPPS at a concentration of 1 ⋅ 10−6 M. . . . . . . . 37

vii

viii LIST OF FIGURES

3.8 Normalized UV-vis spectra of 1 ⋅ 10−6 M TTPS at different pHs. . . 373.9 Schematic structure of J-aggregates and H-aggregates formed by TPPS. 383.10 Normalized UV-vis spectra of 1 ⋅ 10−6 M TTPS in the presence of

PK50-HEDA80 1 ⋅ 10−4 M at different pHs. . . . . . . . . . . . . . 393.11 Fluorescence spectra of 1 ⋅ 10−6 TTPS in the presence of PK50-

HEDA80 1 ⋅ 10−4 at different pHs. . . . . . . . . . . . . . . . . . . 403.12 Transition pH shift of TPPS at 1 ⋅ 10−6 in presence of the polymer at

1 ⋅ 10−4: PK50-HEDA80, PK50-HEDA60, and PK50-HEDA40. . . 413.13 Normalized visible spectra of 1 ⋅ 10−6 M TTPS in presence of PK50-

HEDA60 and PK50-HEDA40 at different pHs. . . . . . . . . . . . 423.14 Fluorescence spectra of 1⋅10−6 M TTPS in presence of PK50-HEDA60. 433.15 Fluorescence spectra of 1⋅10−6 M TPPS in presence of PK50-HEDA40. 44

4.1 Acid and base form of TPPS. . . . . . . . . . . . . . . . . . . . . . 474.2 Schematic structure of J-aggregates and H-aggregates formed by TPPS. 474.3 Schematic representation of Paal-Knorr reaction on polyketones with

the amines used in this study. . . . . . . . . . . . . . . . . . . . . . 484.4 1H-NMR spectra of pyrrole-IM, pyrrole-PI, and pyrrole-HEDA model

compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 524.5 1H-NMR and FT-IR spectra of polyketones before and after modifi-

cation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 544.6 Surface tension of PK50-IM, PK50-PI and PK50-HEDA as a func-

tion of the concentration at various pH values. . . . . . . . . . . . . 564.7 Correlograms, size and zeta potential of the polymer solutions at a

concentration of 1 ⋅ 10−4 M of functional groups and at different val-ues of pH. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58

4.8 Size and zeta potential of PK50-IM interacting with TPPS at differ-ent concentrations. . . . . . . . . . . . . . . . . . . . . . . . . . . 60

4.9 Size and zeta potential PK50PI interacting with TPPS at differentconcentrations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60

4.10 Size and zeta potential PK50-HEDA interacting with TPPS at differ-ent concentrations. . . . . . . . . . . . . . . . . . . . . . . . . . . 61

4.11 Normalized UV-vis spectra of TTPS at different concentrations inthe presence of PK50- IM80 1 ⋅ 10−4 M at different pH. . . . . . . . 63

4.12 Normalized UV-vis spectra of TPPS at a different concentrations inthe presence of PK50-PI 1 ⋅ 10−4 M at different pH. . . . . . . . . . 64

4.13 Normalized UV-vis spectra of TTPS at different concentrations inthe presence of PK50-HEDA 1 ⋅ 10−4 M at different pH. . . . . . . . 65

4.14 Fluorescence spectra of TTPS at 1 ⋅ 10−6 M in presence of PK50-IMat 1 ⋅ 10−4 M at different pHs. . . . . . . . . . . . . . . . . . . . . . 67

4.15 Fluorescence spectra of TTPS at 5 ⋅ 10−6 M in presence of PK50-IMat 1 ⋅ 10−4 M at different pHs. . . . . . . . . . . . . . . . . . . . . . 68

LIST OF FIGURES ix

4.16 Fluorescence spectra of TTPS at 1 ⋅ 10−5 M in presence of PK50-IMat 1 ⋅ 10−4 M at different pHs. . . . . . . . . . . . . . . . . . . . . . 69

4.17 Fluorescence spectra of TTPS at 1 ⋅ 10−6 M in presence of PK50-PIat 1 ⋅ 10−4 M at different pHs. . . . . . . . . . . . . . . . . . . . . . 70

4.18 Fluorescence spectra of TTPS at 5 ⋅ 10−6 M in presence of PK50-PIat 1 ⋅ 10−4 M at different pHs. . . . . . . . . . . . . . . . . . . . . . 71

4.19 Fluorescence spectra of TTPS at 1 ⋅ 10−5 M in presence of PK50-PIat 1 ⋅ 10−4 M at different pHs. . . . . . . . . . . . . . . . . . . . . . 72

4.20 Fluorescence spectra of TTPS at 1 ⋅ 10−6 M in presence of PK50-HEDA at 1 ⋅ 10−4 M at different pHs. . . . . . . . . . . . . . . . . . 73

4.21 Fluorescence spectra of TTPS at 5⋅10−6 M in presence of PK50HEDA80at 1 ⋅ 10−4 M at different pHs. . . . . . . . . . . . . . . . . . . . . . 74

4.22 Fluorescence spectra of TTPS at 1⋅10−5 M in presence of PK50HEDA80at 1 ⋅ 10−4 M at different pHs. . . . . . . . . . . . . . . . . . . . . . 75

5.1 Functionalization of aliphatic polyketones with ABA via the Paal-Knorr reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79

5.2 1H-NMR and ATR FT-IR spectra of PK50ABAx at different valuesof x. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83

5.3 Optical images of 10−3 M of PK50ABAx at basic and acid pH, andcorrelograms obtained upon titration of the corresponding basic so-lutions with HCl, for different values of x. . . . . . . . . . . . . . . 83

5.4 1H-NMR spectra in D2O of TTC 10−3 M, PK50ABAx 10−2 M, andtheir corresponding mixtures at different x values . . . . . . . . . . 85

5.5 600 MHz NOESY spectra in D2O of 10−3 M of TTC in the presencePK50ABA37, PK50ABA53, and PK50ABA69. . . . . . . . . . . . 86

5.6 Optical images of samples containing 10−2 M of PK50ABA37, PK50-ABA53, and PK50ABA69. . . . . . . . . . . . . . . . . . . . . . . 87

5.7 Apparent size (left) and zeta potential (right) of TF nanoparticle sam-ples containing PK50ABA37, PK50ABA53, and PK50ABA69 afterreduction of variable amounts of TTC with ASC. . . . . . . . . . . 88

5.8 Optical images after reduction of 5 ⋅ 10−4 M of TTC with ASC in thepresence of PK50ABA37, PK50ABA53, and PK50ABA69 at acidand basic pH. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89

6.1 Polyketones modified with HEDA and ABA. . . . . . . . . . . . . 946.2 Surface tension graph of PK50-HEDA and of PK50-ABA as a func-

tions of pH and concentration. . . . . . . . . . . . . . . . . . . . . 966.3 Emulsion stability in a function of the concentration of PK50-HEDA

and pH. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 976.4 Stability of the emulsions produced with PK50ABA at a concentra-

tion of 3.0 mg/mL. . . . . . . . . . . . . . . . . . . . . . . . . . . 97

x LIST OF FIGURES

6.5 Phase inversion point of emulsions assisted by PK50HEDA at differ-ent concentrations. . . . . . . . . . . . . . . . . . . . . . . . . . . 98

6.6 Possible products of the reaction CO2 with epoxides. . . . . . . . . 1006.7 Scheme of a catalytic cycle via the cooperative activation of epoxide

with a Lewis acid (Mg) and a nucleophile (Br− ion). . . . . . . . . . 1016.8 Schematic representation of a polyketones about to undergo a Paal-

Knorr reaction with IM and the alkylation of imidazole group. . . . 1026.9 Schematic representation of a polyketones about to undergo a Paal-

Knorr reaction with IM, FU and the alkylation of imidazole group. . 1036.10 1H-NMR spectrum of pyrrole-imidazole model compound and after

the alkylation of the imidazole group. . . . . . . . . . . . . . . . . 1076.11 1H-NMR spectrum of PK50, PK30 modified with IM and PK50

modified with IM and FU. . . . . . . . . . . . . . . . . . . . . . . 1096.12 Mechanism proposed for synthesis of cyclic carbonates through the

cyclic intermediate using inonic liquids immobilized onto polyketones.1106.13 1H-NMR spectrum of a reaction aliquot from the reaction of CO2

with styrene oxide, CO2 with 1,2-epoxyhexane. . . . . . . . . . . . 1136.14 FT-IR spectrum of a reaction aliquot from the reaction of CO2 with

styrene oxide, CO2 with 1,2-epoxyhexane. . . . . . . . . . . . . . . 113

List of Tables***

2.1 Size, PDI values, and zeta potential of PK-Im aggregates at differentpHs at a PK-Im concentration of 1 ⋅ 10−3 M. . . . . . . . . . . . . . 25

2.2 Size, PDI values, and zeta potential of PK-Im aggregates at differentpHs at a PK-Im concentration of 1 ⋅ 10−4 M. . . . . . . . . . . . . . 25

2.3 Size, PDI values, and zeta potential of PK-Im aggregates at differentpHs at a PK-Im concentration of 1 ⋅ 10−5 M. . . . . . . . . . . . . . 26

2.4 Final pH and component concentration of the formulation containingOA and PK-Im. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

2.5 Final pH and component concentration of the formulation containingOA and PK-Im. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

3.1 Amounts in the feed and carbonyl conversion (x) in the Paal-Knorrreaction between PK50 and HEDA. . . . . . . . . . . . . . . . . . 32

4.1 Functionalization of PK50 with HEDA, IM, and PI . . . . . . . . . 50

5.1 PK50 and ABA feed ratios and the corresponding x. . . . . . . . . . 81

6.1 Functionalization of PK50 and PK30 with IM. . . . . . . . . . . . . 1056.2 Alkylation of PK50IM and PK30IM. . . . . . . . . . . . . . . . . . 1056.3 Cyclic carbonates conversion by PK50IM and PK30IM. . . . . . . . 111

xi

xii LIST OF TABLES