Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II

Abstract The redox-active tyrosine residue ($ Y_{Z} $) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced $ Y_{Z} $· in magnetic interaction with the $ CaMn_{4} $-cluster in the particular S-state, $...
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Autor*in:	Havelius, Kajsa G. V. [verfasserIn] Sjöholm, Johannes [verfasserIn] Ho, Felix M. [verfasserIn] Mamedov, Fikret [verfasserIn] Styring, Stenbjörn [verfasserIn]

Format:	E-Artikel
Sprache:	Englisch

Erschienen:	2009

Schlagwörter:	Electron Paramagnetic Resonance Electron Paramagnetic Resonance Spectrum Electron Paramagnetic Resonance Signal Cryogenic Temperature Kinetic Isotope Effect

Übergeordnetes Werk:	Enthalten in: Applied magnetic resonance - Wien [u.a.] : Springer, 1990, 37(2009), 1-4 vom: 19. Nov.
Übergeordnetes Werk:	volume:37 ; year:2009 ; number:1-4 ; day:19 ; month:11

Links:	Volltext

DOI / URN:	10.1007/s00723-009-0045-z

Katalog-ID:	SPR007598009

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520			\|a Abstract The redox-active tyrosine residue ($ Y_{Z} $) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced $ Y_{Z} $· in magnetic interaction with the $ CaMn_{4} $-cluster in the particular S-state, $ Y_{Z} $·$ S_{X} $ intermediates, have been found in intact photosystem II. These so-called split EPR signals are induced by illumination at cryogenic temperatures and provide means to both study the otherwise transient $ Y_{Z} $· and to probe the S-states with EPR spectroscopy. The illumination used for signal induction grouped the observed split EPR signals in two categories: (i) $ Y_{Z} $ in the lower S-states was oxidized by $ P680^{+} $ formed via charge separation, while (ii) $ Y_{Z} $ in the higher S-states was oxidized by an excited, highly oxidizing Mn species. Applied mechanistic studies of the $ Y_{Z} $·$ S_{X} $ intermediates in the different S-states are reviewed and compared to investigations in photosystem II at physiological temperature. Addition of methanol induced S-state characteristic changes in the split signals’ formation which reflect changes in the magnetic coupling within the $ CaMn_{4} $-cluster due to methanol binding. The pH titration of the split EPR signals, on the other hand, could probe the proton-coupled electron transfer properties of the $ Y_{Z} $ oxidation. The apparent pKas found for decreased split signal induction were interpreted in the fate of the phenol proton.
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650		4	\|a Cryogenic Temperature \|7 (dpeaa)DE-He213
650		4	\|a Kinetic Isotope Effect \|7 (dpeaa)DE-He213
700	1		\|a Sjöholm, Johannes \|e verfasserin \|4 aut
700	1		\|a Ho, Felix M. \|e verfasserin \|4 aut
700	1		\|a Mamedov, Fikret \|e verfasserin \|4 aut
700	1		\|a Styring, Stenbjörn \|e verfasserin \|4 aut
773	0	8	\|i Enthalten in \|t Applied magnetic resonance \|d Wien [u.a.] : Springer, 1990 \|g 37(2009), 1-4 vom: 19. Nov. \|w (DE-627)271596589 \|w (DE-600)1480644-7 \|x 1613-7507 \|7 nnns
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matchkey_str	article:16137507:2009----::ealrdclpsgasrmhyzsaenemda
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publishDate	2009
allfields	10.1007/s00723-009-0045-z doi (DE-627)SPR007598009 (SPR)s00723-009-0045-z-e DE-627 ger DE-627 rakwb eng 530 620 ASE 33.00 bkl Havelius, Kajsa G. V. verfasserin aut Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II 2009 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The redox-active tyrosine residue ($ Y_{Z} $) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced $ Y_{Z} $· in magnetic interaction with the $ CaMn_{4} $-cluster in the particular S-state, $ Y_{Z} $·$ S_{X} $ intermediates, have been found in intact photosystem II. These so-called split EPR signals are induced by illumination at cryogenic temperatures and provide means to both study the otherwise transient $ Y_{Z} $· and to probe the S-states with EPR spectroscopy. The illumination used for signal induction grouped the observed split EPR signals in two categories: (i) $ Y_{Z} $ in the lower S-states was oxidized by $ P680^{+} $ formed via charge separation, while (ii) $ Y_{Z} $ in the higher S-states was oxidized by an excited, highly oxidizing Mn species. Applied mechanistic studies of the $ Y_{Z} $·$ S_{X} $ intermediates in the different S-states are reviewed and compared to investigations in photosystem II at physiological temperature. Addition of methanol induced S-state characteristic changes in the split signals’ formation which reflect changes in the magnetic coupling within the $ CaMn_{4} $-cluster due to methanol binding. The pH titration of the split EPR signals, on the other hand, could probe the proton-coupled electron transfer properties of the $ Y_{Z} $ oxidation. The apparent pKas found for decreased split signal induction were interpreted in the fate of the phenol proton. Electron Paramagnetic Resonance (dpeaa)DE-He213 Electron Paramagnetic Resonance Spectrum (dpeaa)DE-He213 Electron Paramagnetic Resonance Signal (dpeaa)DE-He213 Cryogenic Temperature (dpeaa)DE-He213 Kinetic Isotope Effect (dpeaa)DE-He213 Sjöholm, Johannes verfasserin aut Ho, Felix M. verfasserin aut Mamedov, Fikret verfasserin aut Styring, Stenbjörn verfasserin aut Enthalten in Applied magnetic resonance Wien [u.a.] : Springer, 1990 37(2009), 1-4 vom: 19. Nov. (DE-627)271596589 (DE-600)1480644-7 1613-7507 nnns volume:37 year:2009 number:1-4 day:19 month:11 https://dx.doi.org/10.1007/s00723-009-0045-z lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 33.00 ASE AR 37 2009 1-4 19 11
spelling	10.1007/s00723-009-0045-z doi (DE-627)SPR007598009 (SPR)s00723-009-0045-z-e DE-627 ger DE-627 rakwb eng 530 620 ASE 33.00 bkl Havelius, Kajsa G. V. verfasserin aut Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II 2009 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The redox-active tyrosine residue ($ Y_{Z} $) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced $ Y_{Z} $· in magnetic interaction with the $ CaMn_{4} $-cluster in the particular S-state, $ Y_{Z} $·$ S_{X} $ intermediates, have been found in intact photosystem II. These so-called split EPR signals are induced by illumination at cryogenic temperatures and provide means to both study the otherwise transient $ Y_{Z} $· and to probe the S-states with EPR spectroscopy. The illumination used for signal induction grouped the observed split EPR signals in two categories: (i) $ Y_{Z} $ in the lower S-states was oxidized by $ P680^{+} $ formed via charge separation, while (ii) $ Y_{Z} $ in the higher S-states was oxidized by an excited, highly oxidizing Mn species. Applied mechanistic studies of the $ Y_{Z} $·$ S_{X} $ intermediates in the different S-states are reviewed and compared to investigations in photosystem II at physiological temperature. Addition of methanol induced S-state characteristic changes in the split signals’ formation which reflect changes in the magnetic coupling within the $ CaMn_{4} $-cluster due to methanol binding. The pH titration of the split EPR signals, on the other hand, could probe the proton-coupled electron transfer properties of the $ Y_{Z} $ oxidation. The apparent pKas found for decreased split signal induction were interpreted in the fate of the phenol proton. Electron Paramagnetic Resonance (dpeaa)DE-He213 Electron Paramagnetic Resonance Spectrum (dpeaa)DE-He213 Electron Paramagnetic Resonance Signal (dpeaa)DE-He213 Cryogenic Temperature (dpeaa)DE-He213 Kinetic Isotope Effect (dpeaa)DE-He213 Sjöholm, Johannes verfasserin aut Ho, Felix M. verfasserin aut Mamedov, Fikret verfasserin aut Styring, Stenbjörn verfasserin aut Enthalten in Applied magnetic resonance Wien [u.a.] : Springer, 1990 37(2009), 1-4 vom: 19. Nov. (DE-627)271596589 (DE-600)1480644-7 1613-7507 nnns volume:37 year:2009 number:1-4 day:19 month:11 https://dx.doi.org/10.1007/s00723-009-0045-z lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 33.00 ASE AR 37 2009 1-4 19 11
allfields_unstemmed	10.1007/s00723-009-0045-z doi (DE-627)SPR007598009 (SPR)s00723-009-0045-z-e DE-627 ger DE-627 rakwb eng 530 620 ASE 33.00 bkl Havelius, Kajsa G. V. verfasserin aut Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II 2009 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The redox-active tyrosine residue ($ Y_{Z} $) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced $ Y_{Z} $· in magnetic interaction with the $ CaMn_{4} $-cluster in the particular S-state, $ Y_{Z} $·$ S_{X} $ intermediates, have been found in intact photosystem II. These so-called split EPR signals are induced by illumination at cryogenic temperatures and provide means to both study the otherwise transient $ Y_{Z} $· and to probe the S-states with EPR spectroscopy. The illumination used for signal induction grouped the observed split EPR signals in two categories: (i) $ Y_{Z} $ in the lower S-states was oxidized by $ P680^{+} $ formed via charge separation, while (ii) $ Y_{Z} $ in the higher S-states was oxidized by an excited, highly oxidizing Mn species. Applied mechanistic studies of the $ Y_{Z} $·$ S_{X} $ intermediates in the different S-states are reviewed and compared to investigations in photosystem II at physiological temperature. Addition of methanol induced S-state characteristic changes in the split signals’ formation which reflect changes in the magnetic coupling within the $ CaMn_{4} $-cluster due to methanol binding. The pH titration of the split EPR signals, on the other hand, could probe the proton-coupled electron transfer properties of the $ Y_{Z} $ oxidation. The apparent pKas found for decreased split signal induction were interpreted in the fate of the phenol proton. Electron Paramagnetic Resonance (dpeaa)DE-He213 Electron Paramagnetic Resonance Spectrum (dpeaa)DE-He213 Electron Paramagnetic Resonance Signal (dpeaa)DE-He213 Cryogenic Temperature (dpeaa)DE-He213 Kinetic Isotope Effect (dpeaa)DE-He213 Sjöholm, Johannes verfasserin aut Ho, Felix M. verfasserin aut Mamedov, Fikret verfasserin aut Styring, Stenbjörn verfasserin aut Enthalten in Applied magnetic resonance Wien [u.a.] : Springer, 1990 37(2009), 1-4 vom: 19. Nov. (DE-627)271596589 (DE-600)1480644-7 1613-7507 nnns volume:37 year:2009 number:1-4 day:19 month:11 https://dx.doi.org/10.1007/s00723-009-0045-z lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 33.00 ASE AR 37 2009 1-4 19 11
allfieldsGer	10.1007/s00723-009-0045-z doi (DE-627)SPR007598009 (SPR)s00723-009-0045-z-e DE-627 ger DE-627 rakwb eng 530 620 ASE 33.00 bkl Havelius, Kajsa G. V. verfasserin aut Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II 2009 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The redox-active tyrosine residue ($ Y_{Z} $) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced $ Y_{Z} $· in magnetic interaction with the $ CaMn_{4} $-cluster in the particular S-state, $ Y_{Z} $·$ S_{X} $ intermediates, have been found in intact photosystem II. These so-called split EPR signals are induced by illumination at cryogenic temperatures and provide means to both study the otherwise transient $ Y_{Z} $· and to probe the S-states with EPR spectroscopy. The illumination used for signal induction grouped the observed split EPR signals in two categories: (i) $ Y_{Z} $ in the lower S-states was oxidized by $ P680^{+} $ formed via charge separation, while (ii) $ Y_{Z} $ in the higher S-states was oxidized by an excited, highly oxidizing Mn species. Applied mechanistic studies of the $ Y_{Z} $·$ S_{X} $ intermediates in the different S-states are reviewed and compared to investigations in photosystem II at physiological temperature. Addition of methanol induced S-state characteristic changes in the split signals’ formation which reflect changes in the magnetic coupling within the $ CaMn_{4} $-cluster due to methanol binding. The pH titration of the split EPR signals, on the other hand, could probe the proton-coupled electron transfer properties of the $ Y_{Z} $ oxidation. The apparent pKas found for decreased split signal induction were interpreted in the fate of the phenol proton. Electron Paramagnetic Resonance (dpeaa)DE-He213 Electron Paramagnetic Resonance Spectrum (dpeaa)DE-He213 Electron Paramagnetic Resonance Signal (dpeaa)DE-He213 Cryogenic Temperature (dpeaa)DE-He213 Kinetic Isotope Effect (dpeaa)DE-He213 Sjöholm, Johannes verfasserin aut Ho, Felix M. verfasserin aut Mamedov, Fikret verfasserin aut Styring, Stenbjörn verfasserin aut Enthalten in Applied magnetic resonance Wien [u.a.] : Springer, 1990 37(2009), 1-4 vom: 19. Nov. (DE-627)271596589 (DE-600)1480644-7 1613-7507 nnns volume:37 year:2009 number:1-4 day:19 month:11 https://dx.doi.org/10.1007/s00723-009-0045-z lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 33.00 ASE AR 37 2009 1-4 19 11
allfieldsSound	10.1007/s00723-009-0045-z doi (DE-627)SPR007598009 (SPR)s00723-009-0045-z-e DE-627 ger DE-627 rakwb eng 530 620 ASE 33.00 bkl Havelius, Kajsa G. V. verfasserin aut Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II 2009 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier Abstract The redox-active tyrosine residue ($ Y_{Z} $) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced $ Y_{Z} $· in magnetic interaction with the $ CaMn_{4} $-cluster in the particular S-state, $ Y_{Z} $·$ S_{X} $ intermediates, have been found in intact photosystem II. These so-called split EPR signals are induced by illumination at cryogenic temperatures and provide means to both study the otherwise transient $ Y_{Z} $· and to probe the S-states with EPR spectroscopy. The illumination used for signal induction grouped the observed split EPR signals in two categories: (i) $ Y_{Z} $ in the lower S-states was oxidized by $ P680^{+} $ formed via charge separation, while (ii) $ Y_{Z} $ in the higher S-states was oxidized by an excited, highly oxidizing Mn species. Applied mechanistic studies of the $ Y_{Z} $·$ S_{X} $ intermediates in the different S-states are reviewed and compared to investigations in photosystem II at physiological temperature. Addition of methanol induced S-state characteristic changes in the split signals’ formation which reflect changes in the magnetic coupling within the $ CaMn_{4} $-cluster due to methanol binding. The pH titration of the split EPR signals, on the other hand, could probe the proton-coupled electron transfer properties of the $ Y_{Z} $ oxidation. The apparent pKas found for decreased split signal induction were interpreted in the fate of the phenol proton. Electron Paramagnetic Resonance (dpeaa)DE-He213 Electron Paramagnetic Resonance Spectrum (dpeaa)DE-He213 Electron Paramagnetic Resonance Signal (dpeaa)DE-He213 Cryogenic Temperature (dpeaa)DE-He213 Kinetic Isotope Effect (dpeaa)DE-He213 Sjöholm, Johannes verfasserin aut Ho, Felix M. verfasserin aut Mamedov, Fikret verfasserin aut Styring, Stenbjörn verfasserin aut Enthalten in Applied magnetic resonance Wien [u.a.] : Springer, 1990 37(2009), 1-4 vom: 19. Nov. (DE-627)271596589 (DE-600)1480644-7 1613-7507 nnns volume:37 year:2009 number:1-4 day:19 month:11 https://dx.doi.org/10.1007/s00723-009-0045-z lizenzpflichtig Volltext GBV_USEFLAG_A SYSFLAG_A GBV_SPRINGER GBV_ILN_11 GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_32 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_90 GBV_ILN_95 GBV_ILN_100 GBV_ILN_101 GBV_ILN_105 GBV_ILN_110 GBV_ILN_120 GBV_ILN_138 GBV_ILN_150 GBV_ILN_151 GBV_ILN_152 GBV_ILN_161 GBV_ILN_170 GBV_ILN_171 GBV_ILN_187 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_250 GBV_ILN_281 GBV_ILN_285 GBV_ILN_293 GBV_ILN_370 GBV_ILN_602 GBV_ILN_636 GBV_ILN_702 GBV_ILN_2001 GBV_ILN_2003 GBV_ILN_2004 GBV_ILN_2005 GBV_ILN_2006 GBV_ILN_2007 GBV_ILN_2008 GBV_ILN_2009 GBV_ILN_2010 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2015 GBV_ILN_2020 GBV_ILN_2021 GBV_ILN_2025 GBV_ILN_2026 GBV_ILN_2027 GBV_ILN_2031 GBV_ILN_2034 GBV_ILN_2037 GBV_ILN_2038 GBV_ILN_2039 GBV_ILN_2044 GBV_ILN_2048 GBV_ILN_2049 GBV_ILN_2050 GBV_ILN_2055 GBV_ILN_2057 GBV_ILN_2059 GBV_ILN_2061 GBV_ILN_2064 GBV_ILN_2065 GBV_ILN_2068 GBV_ILN_2070 GBV_ILN_2086 GBV_ILN_2088 GBV_ILN_2093 GBV_ILN_2106 GBV_ILN_2107 GBV_ILN_2108 GBV_ILN_2110 GBV_ILN_2111 GBV_ILN_2112 GBV_ILN_2113 GBV_ILN_2116 GBV_ILN_2118 GBV_ILN_2119 GBV_ILN_2122 GBV_ILN_2129 GBV_ILN_2143 GBV_ILN_2144 GBV_ILN_2147 GBV_ILN_2148 GBV_ILN_2152 GBV_ILN_2153 GBV_ILN_2188 GBV_ILN_2190 GBV_ILN_2232 GBV_ILN_2336 GBV_ILN_2446 GBV_ILN_2470 GBV_ILN_2472 GBV_ILN_2507 GBV_ILN_2522 GBV_ILN_2548 GBV_ILN_4035 GBV_ILN_4037 GBV_ILN_4046 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4242 GBV_ILN_4246 GBV_ILN_4249 GBV_ILN_4251 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4326 GBV_ILN_4333 GBV_ILN_4334 GBV_ILN_4335 GBV_ILN_4336 GBV_ILN_4338 GBV_ILN_4393 GBV_ILN_4700 33.00 ASE AR 37 2009 1-4 19 11
language	English
source	Enthalten in Applied magnetic resonance 37(2009), 1-4 vom: 19. Nov. volume:37 year:2009 number:1-4 day:19 month:11
sourceStr	Enthalten in Applied magnetic resonance 37(2009), 1-4 vom: 19. Nov. volume:37 year:2009 number:1-4 day:19 month:11
format_phy_str_mv	Article
institution	findex.gbv.de
topic_facet	Electron Paramagnetic Resonance Electron Paramagnetic Resonance Spectrum Electron Paramagnetic Resonance Signal Cryogenic Temperature Kinetic Isotope Effect
dewey-raw	530
isfreeaccess_bool	false
container_title	Applied magnetic resonance
authorswithroles_txt_mv	Havelius, Kajsa G. V. @@aut@@ Sjöholm, Johannes @@aut@@ Ho, Felix M. @@aut@@ Mamedov, Fikret @@aut@@ Styring, Stenbjörn @@aut@@
publishDateDaySort_date	2009-11-19T00:00:00Z
hierarchy_top_id	271596589
dewey-sort	3530
id	SPR007598009
language_de	englisch
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author	Havelius, Kajsa G. V.
spellingShingle	Havelius, Kajsa G. V. ddc 530 bkl 33.00 misc Electron Paramagnetic Resonance misc Electron Paramagnetic Resonance Spectrum misc Electron Paramagnetic Resonance Signal misc Cryogenic Temperature misc Kinetic Isotope Effect Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II
authorStr	Havelius, Kajsa G. V.
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topic_title	530 620 ASE 33.00 bkl Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II Electron Paramagnetic Resonance (dpeaa)DE-He213 Electron Paramagnetic Resonance Spectrum (dpeaa)DE-He213 Electron Paramagnetic Resonance Signal (dpeaa)DE-He213 Cryogenic Temperature (dpeaa)DE-He213 Kinetic Isotope Effect (dpeaa)DE-He213
topic	ddc 530 bkl 33.00 misc Electron Paramagnetic Resonance misc Electron Paramagnetic Resonance Spectrum misc Electron Paramagnetic Resonance Signal misc Cryogenic Temperature misc Kinetic Isotope Effect
topic_unstemmed	ddc 530 bkl 33.00 misc Electron Paramagnetic Resonance misc Electron Paramagnetic Resonance Spectrum misc Electron Paramagnetic Resonance Signal misc Cryogenic Temperature misc Kinetic Isotope Effect
topic_browse	ddc 530 bkl 33.00 misc Electron Paramagnetic Resonance misc Electron Paramagnetic Resonance Spectrum misc Electron Paramagnetic Resonance Signal misc Cryogenic Temperature misc Kinetic Isotope Effect
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title	Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II
ctrlnum	(DE-627)SPR007598009 (SPR)s00723-009-0045-z-e
title_full	Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II
author_sort	Havelius, Kajsa G. V.
journal	Applied magnetic resonance
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author_browse	Havelius, Kajsa G. V. Sjöholm, Johannes Ho, Felix M. Mamedov, Fikret Styring, Stenbjörn
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class	530 620 ASE 33.00 bkl
format_se	Elektronische Aufsätze
author-letter	Havelius, Kajsa G. V.
doi_str_mv	10.1007/s00723-009-0045-z
dewey-full	530 620
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title_sort	metalloradical epr signals from the $ y_{z} $·s-state intermediates in photosystem ii
title_auth	Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II
abstract	Abstract The redox-active tyrosine residue ($ Y_{Z} $) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced $ Y_{Z} $· in magnetic interaction with the $ CaMn_{4} $-cluster in the particular S-state, $ Y_{Z} $·$ S_{X} $ intermediates, have been found in intact photosystem II. These so-called split EPR signals are induced by illumination at cryogenic temperatures and provide means to both study the otherwise transient $ Y_{Z} $· and to probe the S-states with EPR spectroscopy. The illumination used for signal induction grouped the observed split EPR signals in two categories: (i) $ Y_{Z} $ in the lower S-states was oxidized by $ P680^{+} $ formed via charge separation, while (ii) $ Y_{Z} $ in the higher S-states was oxidized by an excited, highly oxidizing Mn species. Applied mechanistic studies of the $ Y_{Z} $·$ S_{X} $ intermediates in the different S-states are reviewed and compared to investigations in photosystem II at physiological temperature. Addition of methanol induced S-state characteristic changes in the split signals’ formation which reflect changes in the magnetic coupling within the $ CaMn_{4} $-cluster due to methanol binding. The pH titration of the split EPR signals, on the other hand, could probe the proton-coupled electron transfer properties of the $ Y_{Z} $ oxidation. The apparent pKas found for decreased split signal induction were interpreted in the fate of the phenol proton.
abstractGer	Abstract The redox-active tyrosine residue ($ Y_{Z} $) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced $ Y_{Z} $· in magnetic interaction with the $ CaMn_{4} $-cluster in the particular S-state, $ Y_{Z} $·$ S_{X} $ intermediates, have been found in intact photosystem II. These so-called split EPR signals are induced by illumination at cryogenic temperatures and provide means to both study the otherwise transient $ Y_{Z} $· and to probe the S-states with EPR spectroscopy. The illumination used for signal induction grouped the observed split EPR signals in two categories: (i) $ Y_{Z} $ in the lower S-states was oxidized by $ P680^{+} $ formed via charge separation, while (ii) $ Y_{Z} $ in the higher S-states was oxidized by an excited, highly oxidizing Mn species. Applied mechanistic studies of the $ Y_{Z} $·$ S_{X} $ intermediates in the different S-states are reviewed and compared to investigations in photosystem II at physiological temperature. Addition of methanol induced S-state characteristic changes in the split signals’ formation which reflect changes in the magnetic coupling within the $ CaMn_{4} $-cluster due to methanol binding. The pH titration of the split EPR signals, on the other hand, could probe the proton-coupled electron transfer properties of the $ Y_{Z} $ oxidation. The apparent pKas found for decreased split signal induction were interpreted in the fate of the phenol proton.
abstract_unstemmed	Abstract The redox-active tyrosine residue ($ Y_{Z} $) plays a crucial role in the mechanism of the water oxidation. Metalloradical electron paramagnetic resonance (EPR) signals reflecting the light-induced $ Y_{Z} $· in magnetic interaction with the $ CaMn_{4} $-cluster in the particular S-state, $ Y_{Z} $·$ S_{X} $ intermediates, have been found in intact photosystem II. These so-called split EPR signals are induced by illumination at cryogenic temperatures and provide means to both study the otherwise transient $ Y_{Z} $· and to probe the S-states with EPR spectroscopy. The illumination used for signal induction grouped the observed split EPR signals in two categories: (i) $ Y_{Z} $ in the lower S-states was oxidized by $ P680^{+} $ formed via charge separation, while (ii) $ Y_{Z} $ in the higher S-states was oxidized by an excited, highly oxidizing Mn species. Applied mechanistic studies of the $ Y_{Z} $·$ S_{X} $ intermediates in the different S-states are reviewed and compared to investigations in photosystem II at physiological temperature. Addition of methanol induced S-state characteristic changes in the split signals’ formation which reflect changes in the magnetic coupling within the $ CaMn_{4} $-cluster due to methanol binding. The pH titration of the split EPR signals, on the other hand, could probe the proton-coupled electron transfer properties of the $ Y_{Z} $ oxidation. The apparent pKas found for decreased split signal induction were interpreted in the fate of the phenol proton.
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container_issue	1-4
title_short	Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II
url	https://dx.doi.org/10.1007/s00723-009-0045-z
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author2	Sjöholm, Johannes Ho, Felix M. Mamedov, Fikret Styring, Stenbjörn
author2Str	Sjöholm, Johannes Ho, Felix M. Mamedov, Fikret Styring, Stenbjörn
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doi_str	10.1007/s00723-009-0045-z
up_date	2024-07-03T13:57:30.007Z
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Metalloradical EPR Signals from the $ Y_{Z} $·S-State Intermediates in Photosystem II

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