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Porphyrins and Heme in Microorganisms

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Porphyrins and Heme in Microorganisms ! "#$ #%## & ' () * ( +,-% . ( / % / 0 1 2 ( % 3 4 % 4 ( / % 1 / %3 4 / 56( / / 78# (/ / 2 % / %3 ( / / / % / / // % / "$ %3 2 / 1 % 9 / / / / %3 / 8":/ / / % 4 ( % / 7#8 ;"%$!< " / 4 %- " 8;%,!< / =8# %3 / % > / / 78# 56 % / ( / % 9/ ( / / % > ( / % ( 2 ( % "#; ?<< %% < @ A ? ? ?? 7 7#8 >-B ;$ ;; ;#; $ >-B ;$ ;; ;#$#7 (#, PORPHYRINS AND HEME IN MICROORGANISMS Jonas Fyrestam Porphyrins and heme in microorganisms Porphyrin content and its relation to phototherapy and antimicrobial treatments in vivo and in vitro Jonas Fyrestam ©Jonas Fyrestam, Stockholm University 2018 ISBN print 978-91-7797-079-8 ISBN PDF 978-91-7797-080-4 Printed in Sweden by Universitetsservice US-AB, Stockholm 2017 Distributor: Department of Environmental Science and Analytical Chemistry List of papers This thesis is based on the following papers, which will be referred to by Roman numerals, I. Fyrestam, J., Bjurshammar, N., Paulsson, E., Johannsen, A., & Östman, C. (2015). Determination of porphyrins in oral bacteria by liquid chromatography electrospray ionization tandem mass spectrometry. Analytical and bioanalytical chemistry, 407(23), 7013-7023. II. Fyrestam, J., Bjurshammar, N., Paulsson, E., Mansouri, N., Johannsen, A., & Östman, C. (2017). Influence of culture conditions on porphyrin production in Aggregatibacter actinomycetemcomitans and Porphyromonas gingivalis. Photodiagnosis and photodynamic therapy, 17, 115-123. III. Fyrestam, J., & Östman, C. (2017). Determination of heme in microorganisms using HPLC-MS/MS and cobalt(III) protoporphyrin IX inhibition of heme acquisition in Escherichia coli. Analytical and Bioanalytical Chemistry, [Epub ahead of print]. IV. Fyrestam, J., & Östman, C. (2017). Escherichia coli is killed by 405 nm blue light due to its endogenous porphyrins induced by 5- aminolevulinic acid. Manuscript. V. Bjurshammar, N., Malmqvist, S., Johannsen, G., Boström, EA., Fyrestam, J., Östman, C., & Johannsen, A. The Effect of Local Phototherapy on Gingival Inflammation - A Randomized Controlled Study. Manuscript. The contribution of Jonas Fyrestam to the papers in this thesis was as follows: I. The respondent was responsible for design of the study, parts of the experimental work, all data analysis, and significant parts of the writing. II. The respondent was responsible for generating the idea, design of the study, parts of the experimental work, all data analysis, and significant parts of the writing. III. The respondent was responsible for generating the idea, design of the study, all of the experimental work, all data analysis and significant parts of the writing. IV. The respondent was responsible for generating the idea, design of the study, all of the experimental work, all data analysis and all of the writing. V. The respondent was involved in generating the idea, parts of the design of the study and minor parts of the writing. Contents List of papers................................................................................................. vii Abbrebrevations ............................................................................................11 Populärvetenskaplig sammanfattning ...........................................................13 Introduction and aims....................................................................................16 Part 1. Background .......................................................................................19 Phototherapy...............................................................................................................19 Porphyrins and heme ..................................................................................................19 Porphyrins as photosensitizers in phototherapy ..........................................................22 Biosynthesis of porphyrins and heme in bacteria ........................................................25 Heme acquisition as a potential drug target ................................................................30 Oral bacteria ...............................................................................................................31 Aggregatibacter actinomycetemcomitans ..............................................................31 Porphyromonas gingivalis......................................................................................32 Part 2. Determination of porphyrins and heme .............................................34 Samples and sampling................................................................................................34 Cell lysis......................................................................................................................35 Extraction and clean-up ..............................................................................................36 Solid phase extraction of porphyrins ......................................................................37 Optimization of heme extraction ............................................................................39 Protein precipitation...............................................................................................42 Salting-out assisted liquid-liquid extraction ............................................................45 Liquid chromatography of porphyrins ..........................................................................45 HPLC columns.......................................................................................................46 Mobile phases .......................................................................................................48 Mass spectrometry of porphyrins ................................................................................50 Stability of porphyrins and heme in solution ................................................................53 Part 3. Applications .......................................................................................56 Photo inactivation of bacteria ......................................................................................56 Pilot study..............................................................................................................56 In vitro experiments ...............................................................................................57 Porphyrin content in microorganisms ..........................................................................59 Influence of culture conditions.....................................................................................60 Time of culturing ....................................................................................................61 Passage ................................................................................................................62 Cultivation medium ................................................................................................63 Influence of different additives on E. coli .....................................................................64 5-aminolaevulinic acid ...........................................................................................64 Hemin ....................................................................................................................67 Cobalt protoporphyrin IX........................................................................................67 Singlet oxygen production of porphyrins .....................................................................68 Clinical study...............................................................................................................71 Conclusions and future perspectives ............................................................74 References....................................................................................................77 Acknowledgements.......................................................................................86 HapPhy Days? A cohort study of the happiness during PhD studies ..........................86 Abbrebrevations 5-ALA 5-aminolaevulinic acid 5-ALA-S 5-aminolaevulinic acid synthase aPT Antimicrobial phototherapy BOP Bleeding on probing CCF Central composite face design CFU Colony forming unit COP-O Coproporphyrinogen oxidase Co-PPIX Cobalt(III) protoporphyrin IX EDTA Ethylenediaminetetraacetic acid FECH Ferrochelatase GC Gas chromatography GI Gingival index HILIC Hydrophilic interaction chromatography His L-histidine HMB Hydroxymethylbilane HPLC High performance liquid chromatography IC Internal conversion ISC Inter system crossing LED Light emitting diode LLE Liquid-liquid extraction LOD Limit of detection logD Octanol-water partition coefficient at a specific pH logP Octanol-water partition coefficient
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