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Cheah, M. H., Zhang, M., Shevela, D., Mamedov, F., Zouni, A. & Messinger, J. (2020). Assessment of the manganese cluster’s oxidation state via photoactivation of photosystem II microcrystals. Proceedings of the National Academy of Sciences of the United States of America, 117(1), 141-145
Open this publication in new window or tab >>Assessment of the manganese cluster’s oxidation state via photoactivation of photosystem II microcrystals
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2020 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 117, no 1, p. 141-145Article in journal (Refereed) Published
Abstract [en]

Knowledge of the manganese oxidation states of the oxygen-evolving Mn4CaO5 cluster in photosystem II (PSII) is crucial toward understanding the mechanism of biological water oxidation. There is a 4 decade long debate on this topic that historically originates from the observation of a multiline electron paramagnetic resonance (EPR) signal with effective total spin of S = 1/2 in the singly oxidized S2 state of this cluster. This signal implies an overall oxidation state of either Mn(III)3Mn(IV) or Mn(III)Mn(IV)3 for the S2 state. These 2 competing assignments are commonly known as “low oxidation (LO)” and “high oxidation (HO)” models of the Mn4CaO5 cluster. Recent advanced EPR and Mn K-edge X-ray spectroscopy studies converge upon the HO model. However, doubts about these assignments have been voiced, fueled especially by studies counting the number of flash-driven electron removals required for the assembly of an active Mn4CaO5 cluster starting from Mn(II) and Mn-free PSII. This process, known as photoactivation, appeared to support the LO model since the first oxygen is reported to evolve already after 7 flashes. In this study, we improved the quantum yield and sensitivity of the photoactivation experiment by employing PSII microcrystals that retained all protein subunits after complete manganese removal and by oxygen detection via a custom built thin-layer cell connected to a membrane inlet mass spectrometer. We demonstrate that 9 flashes by a nanosecond laser are required for the production of the first oxygen, which proves that the HO model provides the correct description of the Mn4CaO5 cluster’s oxidation states.

Place, publisher, year, edition, pages
Proceedings of the National Academy of Sciences, 2020
Keywords
photosynthesis, oxygen evolving cluster, photoassembly, manganese oxidation state, mechanism of water oxidation
National Category
Physical Chemistry
Research subject
biological chemistry; Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-167235 (URN)10.1073/pnas.1915879117 (DOI)000506001200027 ()
Available from: 2020-01-13 Created: 2020-01-13 Last updated: 2020-02-25Bibliographically approved
Boniolo, M., Shylin, S. I., Chernev, P., Cheah, M. H., Heizmann, P. A., Huang, P., . . . Messinger, J. (2020). Spin transition in a ferrous chloride complex supported by a pentapyridine ligand. Chemical Communications, 56(18), 2703-2706
Open this publication in new window or tab >>Spin transition in a ferrous chloride complex supported by a pentapyridine ligand
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2020 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 56, no 18, p. 2703-2706Article in journal (Refereed) Published
Abstract [en]

Ferrous chloride complexes [FeIILxCl] commonly attain a high-spin state independently of the supporting ligand(s) and temperature. Herein, we present the first report of a complete spin crossover with T1/2 = 80 K in [FeII(Py5OH)Cl]+ (Py5OH = pyridine-2,6-diylbis[di(pyridin-2-yl)methanol]). Both spin forms of the complex are analyzed by X-ray spectroscopy and DFT calculations.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2020
National Category
Physical Chemistry Theoretical Chemistry
Identifiers
urn:nbn:se:umu:diva-170805 (URN)10.1039/c9cc09630b (DOI)000528510000032 ()32057045 (PubMedID)
Funder
Swedish Energy Agency, 45421-1Stiftelsen Olle Engkvist Byggmästare, 198-0369
Available from: 2020-05-27 Created: 2020-05-27 Last updated: 2020-05-27Bibliographically approved
Kawde, A., Annamalai, A., Sellstedt, A., Glatzel, P., Wågberg, T. & Messinger, J. (2019). A microstructured p-Si photocathode outcompetes Pt as a counter electrode to hematite in photoelectrochemical water-splitting. Dalton Transactions, 48(4), 1166-1170
Open this publication in new window or tab >>A microstructured p-Si photocathode outcompetes Pt as a counter electrode to hematite in photoelectrochemical water-splitting
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2019 (English)In: Dalton Transactions, ISSN 1477-9226, E-ISSN 1477-9234, Vol. 48, no 4, p. 1166-1170Article in journal (Refereed) Published
Abstract [en]

Herein, we communicate about an Earth-abundant semiconductor photocathode (p-Si/TiO2/NiOx) as an alternative for the rare and expensive Pt as a counter electrode for overall photoelectrochemical water splitting. The proposed photoelectrochemical (PEC) water-splitting device mimics the "Z"-scheme observed in natural photosynthesis by combining two photoelectrodes in a parallelillumination mode. A nearly 60% increase in the photocurrent density (Jph) for pristine α-Fe2Oand a 77% increase in the applied bias photocurrent efficiency (ABPE) were achieved by replacing the conventionally used Pt cathode with an efficient, cost effective p-Si/TiO2/NiOx photocathode under parallel illumination. The resulting photocurrent density of 1.26 mA cm−2 at 1.23VRHE represents a new record performance for hydrothermally grown pristine α-Fe2O3 nanorod photoanodes in combination with a photocathode, which opens the prospect for further improvement by doping α-Fe2O3 or by its decoration with co-catalysts. Electrochemical impedance spectroscopy measurements suggest that this significant performance increase is due to the enhancement of the space-charge field in α-Fe2O3. 

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Materials Chemistry
Identifiers
urn:nbn:se:umu:diva-153415 (URN)10.1039/c8dt03653e (DOI)000459625900002 ()30534760 (PubMedID)
Available from: 2018-11-20 Created: 2018-11-20 Last updated: 2019-03-27Bibliographically approved
Shevela, D., Ananyev, G., Vatland, A. K., Arnold, J., Mamedov, F., Eichacker, L. A., . . . Messinger, J. (2019). 'Birth defects' of photosystem II make it highly susceptible to photodamage during chloroplast biogenesis. Physiologia Plantarum: An International Journal for Plant Biology, 166(1), 165-180
Open this publication in new window or tab >>'Birth defects' of photosystem II make it highly susceptible to photodamage during chloroplast biogenesis
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2019 (English)In: Physiologia Plantarum: An International Journal for Plant Biology, ISSN 0031-9317, E-ISSN 1399-3054, Vol. 166, no 1, p. 165-180Article in journal (Refereed) Published
Abstract [en]

High solar flux is known to diminish photosynthetic growth rates, reducing biomass productivity and lowering disease tolerance. Photosystem II (PSII) of plants is susceptible to photodamage (also known as photoinactivation) in strong light, resulting in severe loss of water oxidation capacity and destruction of the water‐oxidizing complex (WOC). The repair of damaged PSIIs comes at a high energy cost and requires de novo biosynthesis of damaged PSII subunits, reassembly of the WOC inorganic cofactors and membrane remodeling. Employing membrane‐inlet mass spectrometry and O2‐polarography under flashing light conditions, we demonstrate that newly synthesized PSII complexes are far more susceptible to photodamage than are mature PSII complexes. We examined these ‘PSII birth defects’ in barley seedlings and plastids (etiochloroplasts and chloroplasts) isolated at various times during de‐etiolation as chloroplast development begins and matures in synchronization with thylakoid membrane biogenesis and grana membrane formation. We show that the degree of PSII photodamage decreases simultaneously with biogenesis of the PSII turnover efficiency measured by O2‐polarography, and with grana membrane stacking, as determined by electron microscopy. Our data from fluorescence, QB‐inhibitor binding, and thermoluminescence studies indicate that the decline of the high‐light susceptibility of PSII to photodamage is coincident with appearance of electron transfer capability QA− → QB during de‐etiolation. This rate depends in turn on the downstream clearing of electrons upon buildup of the complete linear electron transfer chain and the formation of stacked grana membranes capable of longer‐range energy transfer.

Place, publisher, year, edition, pages
Wiley-Blackwell, 2019
Keywords
Practice variation, Bronchopulmonary dysplasia, Preterm infants, Ventilation
National Category
Biophysics
Identifiers
urn:nbn:se:umu:diva-158931 (URN)10.1111/ppl.12932 (DOI)000466108300014 ()30693529 (PubMedID)
Funder
Swedish Research CouncilSwedish Research Council
Note

Special Issue: SI

Available from: 2019-05-15 Created: 2019-05-15 Last updated: 2019-06-10Bibliographically approved
Kwong, W. L., Lee, C. C., Shchukarev, A. & Messinger, J. (2019). Cobalt- doped hematite thin films for electrocatalytic water oxidation in highly acidic media. Chemical Communications, 55(34), 5017-5020
Open this publication in new window or tab >>Cobalt- doped hematite thin films for electrocatalytic water oxidation in highly acidic media
2019 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 55, no 34, p. 5017-5020Article in journal (Refereed) Published
Abstract [en]

Earth-abundant cobalt-doped hematite thin-film electrocatalysts were explored for acidic water oxidation. The strategically doped hematite produced a stable geometric current density of 10 mA cm(-2) for up to 50 h at pH 0.3, as a result of Co-enhanced intrinsic catalytic activity and charge transport properties across the film matrix.

Place, publisher, year, edition, pages
The Royal Society of Chemistry, 2019
National Category
Materials Chemistry
Identifiers
urn:nbn:se:umu:diva-159862 (URN)10.1039/c9cc01369e (DOI)000468618000025 ()30968887 (PubMedID)
Available from: 2019-06-10 Created: 2019-06-10 Last updated: 2019-09-05Bibliographically approved
Chrysina, M., Heyno, E., Kutin, Y., Reus, M., Nilsson, H., Nowaczyk, M. M., . . . Cox, N. (2019). Five-coordinate Mn-IV intermediate in the activation of nature's water splitting cofactor. Proceedings of the National Academy of Sciences of the United States of America, 116(34), 16841-16846
Open this publication in new window or tab >>Five-coordinate Mn-IV intermediate in the activation of nature's water splitting cofactor
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2019 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 116, no 34, p. 16841-16846Article in journal (Refereed) Published
Abstract [en]

Nature's water splitting cofactor passes through a series of catalytic intermediates (S-0-S-4) before O-O bond formation and O-2 release. In the second last transition (S-2 to S-3) cofactor oxidation is coupled to water molecule binding to Mn1. It is this activated, water-enriched all Mn-IV form of the cofactor that goes on to form the O-O bond, after the next light-induced oxidation to S-4. How cofactor activation proceeds remains an open question. Here, we report a so far not described intermediate (S-3') in which cofactor oxidation has occurred without water insertion. This intermediate can be trapped in a significant fraction of centers (> 50%) in (i) chemical-modified cofactors in which Ca2+ is exchanged with Sr2+; the Mn4O5Sr cofactor remains active, but the S-2-S-3 and S-3-S-0 transitions are slower than for the Mn4O5Ca cofactor; and (ii) upon addition of 3% vol/vol methanol; methanol is thought to act as a substrate water analog. The S-3' electron paramagnetic resonance (EPR) signal is significantly broader than the untreated S-3 signal (2.5 T vs. 1.5 T), indicating the cofactor still contains a 5-coordinate Mn ion, as seen in the preceding S-2 state. Magnetic double resonance data extend these findings revealing the electronic connectivity of the S-3' cofactor is similar to the high spin form of the preceding S-2 state, which contains a cuboidal Mn3O4Ca unit tethered to an external, 5-coordinate Mn ion (Mn-4). These results demonstrate that cofactor oxidation regulates water molecule insertion via binding to Mn-4. The interaction of ammonia with the cofactor is also discussed.

Keywords
Photosystem II, WOC/OEC, EPR, EDNMR, methanol
National Category
Organic Chemistry
Identifiers
urn:nbn:se:umu:diva-163062 (URN)10.1073/pnas.1817526116 (DOI)000481935500034 ()31391299 (PubMedID)
Funder
Swedish Research Council, 2016-05183
Available from: 2019-10-17 Created: 2019-10-17 Last updated: 2019-10-17Bibliographically approved
Krieger-Liszkay, A., Spetea, C. & Messinger, J. (2019). Photosynthesis - European Congress on Photosynthesis Research. Physiologia Plantarum: An International Journal for Plant Biology, 166(1), 4-6
Open this publication in new window or tab >>Photosynthesis - European Congress on Photosynthesis Research
2019 (English)In: Physiologia Plantarum: An International Journal for Plant Biology, ISSN 0031-9317, E-ISSN 1399-3054, Vol. 166, no 1, p. 4-6Article in journal, Editorial material (Other academic) Published
Place, publisher, year, edition, pages
Wiley-Blackwell, 2019
National Category
Biological Sciences
Identifiers
urn:nbn:se:umu:diva-159868 (URN)10.1111/ppl.12968 (DOI)000466108300001 ()31012147 (PubMedID)
Available from: 2019-06-10 Created: 2019-06-10 Last updated: 2019-06-10Bibliographically approved
Chatterjee, R., Lassalle, L., Gul, S., Fuller, F. D., Young, I. D., Ibrahim, M., . . . Yano, J. (2019). Structural isomers of the S-2 state in photosystem II: do they exist at room temperature and are they important for function?. Paper presented at 1st European Congress on Photosynthesis Research (EPS), JUN 25-28, 2018, Uppsala, SWEDEN. Physiologia Plantarum: An International Journal for Plant Biology, 166(1), 60-72
Open this publication in new window or tab >>Structural isomers of the S-2 state in photosystem II: do they exist at room temperature and are they important for function?
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2019 (English)In: Physiologia Plantarum: An International Journal for Plant Biology, ISSN 0031-9317, E-ISSN 1399-3054, Vol. 166, no 1, p. 60-72Article in journal (Refereed) Published
Abstract [en]

In nature, an oxo‐bridged Mn4CaO5 cluster embedded in photosystem II (PSII), a membrane‐bound multi‐subunit pigment protein complex, catalyzes the water oxidation reaction that is driven by light‐induced charge separations in the reaction center of PSII. The Mn4CaO5 cluster accumulates four oxidizing equivalents to enable the four‐electron four‐proton catalysis of two water molecules to one dioxygen molecule and cycles through five intermediate S‐states, S0 – S4 in the Kok cycle. One important question related to the catalytic mechanism of the oxygen‐evolving complex (OEC) that remains is, whether structural isomers are present in some of the intermediate S‐states and if such equilibria are essential for the mechanism of the O‐O bond formation. Here we compare results from electron paramagnetic resonance (EPR) and X‐ray absorption spectroscopy (XAS) obtained at cryogenic temperatures for the S2state of PSII with structural data collected of the S1, S2 and S3 states by serial crystallography at neutral pH (∼6.5) using an X‐ray free electron laser at room temperature. While the cryogenic data show the presence of at least two structural forms of the S2 state, the room temperature crystallography data can be well‐described by just one S2 structure. We discuss the deviating results and outline experimental strategies for clarifying this mechanistically important question.

Place, publisher, year, edition, pages
Wiley-Blackwell, 2019
National Category
Physical Chemistry Biological Sciences
Identifiers
urn:nbn:se:umu:diva-159873 (URN)10.1111/ppl.12947 (DOI)000466108300007 ()30793319 (PubMedID)
Conference
1st European Congress on Photosynthesis Research (EPS), JUN 25-28, 2018, Uppsala, SWEDEN
Funder
NIH (National Institute of Health), GM110501NIH (National Institute of Health), GM126289NIH (National Institute of Health), GM055302Swedish Research Council, 2016-05183
Note

Special Issue: SI

Available from: 2019-06-10 Created: 2019-06-10 Last updated: 2019-06-10Bibliographically approved
Conlan, B. l., Govindjee, . & Messinger, J. (2019). Thomas John Wydrzynski (8 July 1947-16 March 2018). Photosynthesis Research, 140(3), 253-261
Open this publication in new window or tab >>Thomas John Wydrzynski (8 July 1947-16 March 2018)
2019 (English)In: Photosynthesis Research, ISSN 0166-8595, E-ISSN 1573-5079, Vol. 140, no 3, p. 253-261Article in journal (Refereed) Published
Abstract [en]

With this Tribute, we remember and honor Thomas John (Tom) Wydrzynski. Tom was a highly innovative, independent and committed researcher, who had, early in his career, defined his life-long research goal. He was committed to understand how Photosystem II produces molecular oxygen from water, using the energy of sunlight, and to apply this knowledge towards making artificial systems. In this tribute, we summarize his research journey, which involved working on soft money' in several laboratories around the world for many years, as well as his research achievements. We also reflect upon his approach to life, science and student supervision, as we perceive it. Tom was not only a thoughtful scientist that inspired many to enter this field of research, but also a wonderful supervisor and friend, who is deeply missed (see footnote*).

Place, publisher, year, edition, pages
Springer Netherlands, 2019
Keywords
Water oxidation, Photosystem II, Manganese, Chloride, Artificial photosynthesis
National Category
Botany
Identifiers
urn:nbn:se:umu:diva-159594 (URN)10.1007/s11120-018-0606-9 (DOI)000467577100001 ()30478710 (PubMedID)
Available from: 2019-06-17 Created: 2019-06-17 Last updated: 2019-06-17Bibliographically approved
Pham, L. V., Olmos, J. D., Chernev, P., Kargul, J. & Messinger, J. (2019). Unequal misses during the flash-induced advancement of photosystem II: effects of the S state and acceptor side cycles. Paper presented at 8th International Conference on Photosynthesis and Hydrogen Energy Research for Sustainability in honor of Agepati S Raghavendra, William A Cramer, and Govindjee, 2017, Hyderabad, India. Photosynthesis Research, 139(1-3), 93-106
Open this publication in new window or tab >>Unequal misses during the flash-induced advancement of photosystem II: effects of the S state and acceptor side cycles
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2019 (English)In: Photosynthesis Research, ISSN 0166-8595, E-ISSN 1573-5079, Vol. 139, no 1-3, p. 93-106Article in journal (Refereed) Published
Abstract [en]

Photosynthetic water oxidation is catalyzed by the oxygen-evolving complex (OEC) in photosystem II (PSII). This process is energetically driven by light-induced charge separation in the reaction center of PSII, which leads to a stepwise accumulation of oxidizing equivalents in the OEC (S-i states, i=0-4) resulting in O-2 evolution after each fourth flash, and to the reduction of plastoquinone to plastoquinol on the acceptor side of PSII. However, the S-i-state advancement is not perfect, which according to the Kok model is described by miss-hits (misses). These may be caused by redox equilibria or kinetic limitations on the donor (OEC) or the acceptor side. In this study, we investigate the effects of individual S state transitions and of the quinone acceptor side on the miss parameter by analyzing the flash-induced oxygen evolution patterns and the S-2, S-3 and S-0 state lifetimes in thylakoid samples of the extremophilic red alga Cyanidioschyzon merolae. The data are analyzed employing a global fit analysis and the results are compared to the data obtained previously for spinach thylakoids. These two organisms were selected, because the redox potential of Q(A)/Q(A)(-) in PSII is significantly less negative in C. merolae (E-m=-104mV) than in spinach (E-m=-163mV). This significant difference in redox potential was expected to allow the disentanglement of acceptor and donor side effects on the miss parameter. Our data indicate that, at slightly acidic and neutral pH values, the E-m of Q(A)(-)/Q(A) plays only a minor role for the miss parameter. By contrast, the increased energy gap for the backward electron transfer from Q(A)(-) to Pheo slows down the charge recombination reaction with the S-3 and S-2 states considerably. In addition, our data support the concept that the S-2 S-3 transition is the least efficient step during the oxidation of water to molecular oxygen in the Kok cycle of PSII.

Place, publisher, year, edition, pages
Springer, 2019
Keywords
Photosynthesis, Photosystem II, Mechanism of water oxidation, Flash-induced oxygen oscillation pattern (FIOP), Unequal miss parameter, Cyanidioschyzon merolae
National Category
Physical Chemistry
Identifiers
urn:nbn:se:umu:diva-156869 (URN)10.1007/s11120-018-0574-0 (DOI)000458553100008 ()30191436 (PubMedID)
Conference
8th International Conference on Photosynthesis and Hydrogen Energy Research for Sustainability in honor of Agepati S Raghavendra, William A Cramer, and Govindjee, 2017, Hyderabad, India
Available from: 2019-03-12 Created: 2019-03-12 Last updated: 2019-06-17Bibliographically approved
Projects
Water-binding and water-splitting by photosystem II and artificial catalysts [2009-03722_VR]; Umeå UniversityTRANSFORMERS - Integrated biomass production using Swedish microorganisms, local wastewaters and flue gases [2015-92_Formas]; Umeå UniversityMechanism and assembly of the water oxidation catalyst in photosystem II [2016-05183_VR]; Umeå University
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0003-2790-7721

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