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ApcE plays an important role in light-induced excitation energy dissipation in the Synechocystis PCC6803 phycobilisomes. ApcE 在 Synechocystis PCC6803 植物体的光诱导激发能量耗散中发挥着重要作用。
IF 3.7 3区 生物学 Q2 PLANT SCIENCES Pub Date : 2024-04-01 Epub Date: 2024-02-26 DOI: 10.1007/s11120-024-01078-6
Gonfa Tesfaye Assefa, Joshua L Botha, Bertus van Heerden, Farooq Kyeyune, Tjaart P J Krüger, Michal Gwizdala

Phycobilisomes (PBs) play an important role in cyanobacterial photosynthesis. They capture light and transfer excitation energy to the photosynthetic reaction centres. PBs are also central to some photoprotective and photoregulatory mechanisms that help sustain photosynthesis under non-optimal conditions. Amongst the mechanisms involved in excitation energy dissipation that are activated in response to excessive illumination is a recently discovered light-induced mechanism that is intrinsic to PBs and has been the least studied. Here, we used single-molecule spectroscopy and developed robust data analysis methods to explore the role of a terminal emitter subunit, ApcE, in this intrinsic, light-induced mechanism. We isolated the PBs from WT Synechocystis PCC 6803 as well as from the ApcE-C190S mutant of this strain and compared the dynamics of their fluorescence emission. PBs isolated from the mutant (i.e., ApcE-C190S-PBs), despite not binding some of the red-shifted pigments in the complex, showed similar global emission dynamics to WT-PBs. However, a detailed analysis of dynamics in the core revealed that the ApcE-C190S-PBs are less likely than WT-PBs to enter quenched states under illumination but still fully capable of doing so. This result points to an important but not exclusive role of the ApcE pigments in the light-induced intrinsic excitation energy dissipation mechanism in PBs.

叶绿体(PB)在蓝藻的光合作用中发挥着重要作用。它们捕捉光并将激发能量转移到光合反应中心。它们也是一些光保护和光调节机制的核心,有助于在非最佳条件下维持光合作用。在参与激发能量耗散的机制中,最近发现的一种光诱导机制在过度光照下被激活,这种机制是 PBs 固有的,但研究得最少。在这里,我们使用单分子光谱学并开发了稳健的数据分析方法来探索末端发射器亚基 ApcE 在这种内在的光诱导机制中的作用。我们从 WT Synechocystis PCC 6803 以及该菌株的 ApcE-C190S 突变体中分离出了 PBs,并比较了它们的荧光发射动态。从突变体(即 ApcE-C190S-PBs)中分离出的 PBs 尽管没有结合复合物中的一些红移色素,但却显示出与 WT-PBs 相似的全局发射动态。然而,对核心动态的详细分析显示,ApcE-C190S-PBs 在光照下进入淬灭态的可能性比 WT-PBs 小,但仍完全有能力进入淬灭态。这一结果表明,ApcE 色素在 PBs 的光诱导本征激发能量耗散机制中扮演着重要但并非唯一的角色。
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引用次数: 0
On the Pelletier and Caventou (1817, 1818) papers on chlorophyll and beyond. 关于叶绿素及其他的 Pelletier 和 Caventou(1817 年和 1818 年)论文。
IF 3.7 3区 生物学 Q2 PLANT SCIENCES Pub Date : 2024-04-01 Epub Date: 2024-03-15 DOI: 10.1007/s11120-024-01081-x
Govindjee Govindjee, Alexandrina Stirbet, Jonathan S Lindsey, Hugo Scheer

The first use of the word 'chlorophyll' (chlorophile or chlorophyle in the French original) appeared in two papers by Pierre-Joseph Pelletier and Joseph Bienaimé Caventou, pharmacists in Paris who isolated and studied the green pigment from plants. Here, we provide English translations of their 1818 note and the slightly longer 1817 paper. Historical context is provided including a timeline of key discoveries in chlorophyll chemistry pertaining to photosynthesis.

叶绿素"(法文原文为chlorophile或chlorophyle)一词的首次使用出现在巴黎药剂师皮埃尔-约瑟夫-佩勒蒂埃(Pierre-Joseph Pelletier)和约瑟夫-比耶梅-卡文托(Joseph Bienaimé Caventou)的两篇论文中,他们从植物中分离并研究了这种绿色色素。在此,我们提供了他们 1818 年的说明和篇幅稍长的 1817 年论文的英文译文。我们还提供了历史背景,包括与光合作用有关的叶绿素化学重要发现的时间轴。
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引用次数: 0
Modulating spectral response of raw photosynthetic pigments via ternary cadmium chalcogenide quantum dots: simultaneous enhancement at green spectrum and inhibition at UV region. 通过三元铬化镉量子点调节原始光合色素的光谱响应:同时增强绿色光谱和抑制紫外线区域。
IF 3.7 3区 生物学 Q2 PLANT SCIENCES Pub Date : 2024-04-01 Epub Date: 2024-02-26 DOI: 10.1007/s11120-024-01085-7
Sümeyye Aykut, Nida Ük, İbrahim Yağız Coşkun, Sultan Şahin Keskin, Ilgın Nar, Levent Trabzon, Caner Ünlü

Photosynthesis relies on the absorption of sunlight by photosynthetic pigments (PPs) such as chlorophylls and carotenoids. While these pigments are outstanding at harvesting light, their natural structure restricts their ability to harvest light at specific wavelengths. In this study, Oleic acid-capped CdSeS and CdTeS ternary quantum dots (QDs) were synthesized using a novel two-phase synthesis method. Then, these QDs were used to interact with raw PPs, a mixture of chlorophylls and carotenoids isolated from spinach. Our findings revealed the following: (1) Interacting QDs with raw PPs effectively inhibited the chlorophyll fluorescence of the pigments upon excitation in UV light region (250-400 nm) without causing any damage to their structure. (2) By forming an interaction with QDs, the chlorophyll fluorescence of raw PPs could be induced through excitation with green-light spectrum. (3) The composition of the QDs played a fundamental role in their interaction with PPs. Our study demonstrated that the photophysical properties of isolated PPs could be modified by using cadmium-based QDs by preserving the structure of the pigments themselves.

光合作用依赖于叶绿素和类胡萝卜素等光合色素(PP)对阳光的吸收。虽然这些色素在采光方面表现出色,但它们的天然结构限制了它们在特定波长采光的能力。本研究采用一种新颖的两相合成法合成了油酸封端的 CdSeS 和 CdTeS 三元量子点(QDs)。然后,这些 QDs 与从菠菜中分离出来的叶绿素和类胡萝卜素混合物--原始 PPs 进行了相互作用。我们的研究结果表明了以下几点:(1) 在紫外光区(250-400 nm)激发下,QDs 与未加工的 PPs 相互作用可有效抑制叶绿素荧光,而不会对其结构造成任何破坏。(2)通过与 QDs 形成相互作用,在绿光光谱的激发下可诱导未加工 PPs 的叶绿素荧光。(3) QDs 的组成对其与 PPs 的相互作用起着根本性的作用。我们的研究表明,使用镉基 QDs 可以改变分离的 PPs 的光物理特性,同时保留色素本身的结构。
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引用次数: 0
In vitro demetalation of central magnesium in various chlorophyll derivatives using Mg-dechelatase homolog from the chloroflexi Anaerolineae. 利用叶绿素植物 Anaerolineae 中的镁脱螯酶同源物对各种叶绿素衍生物中的中心镁进行体外脱金属。
IF 3.7 3区 生物学 Q2 PLANT SCIENCES Pub Date : 2024-04-01 Epub Date: 2024-03-26 DOI: 10.1007/s11120-024-01088-4
Soma Sato, Mitsuaki Hirose, Ryouichi Tanaka, Hisashi Ito, Hitoshi Tamiaki

In the metabolic pathway of chlorophylls (Chls), an enzyme called STAY-GREEN or SGR catalyzes the removal of the central magnesium ion of Chls and their derivatives to their corresponding free bases, including pheophytins. The substrate specificity of SGR has been investigated through in vitro reactions using Chl-related molecules. However, information about the biochemical properties and reaction mechanisms of SGR and its substrate specificity remains elusive. In this study, we synthesized various Chl derivatives and investigated their in vitro dechelations using an SGR enzyme. Chl-a derivatives with the C3-vinyl group on the A-ring, which is commonly found as a substituent in natural substrates, and their analogs with ethyl, hydroxymethyl, formyl, and styryl groups at the C3-position were prepared as substrates. In vitro dechelatase reactions of these substrates were performed using an SGR enzyme derived from an Anaerolineae bacterium, allowing us to investigate their specificity. Reactivity was reduced for substrates with an electron-withdrawing formyl or sterically demanding styryl group at the C3-position. Furthermore, the Chl derivative with the C8-styryl group on the B-ring was less reactive for SGR dechelation than the C3-styryl substrate. These results indicate that the SGR enzyme recognizes substituents on the B-ring of substrates more than those on the A-ring.

在叶绿素(Chls)的代谢途径中,一种名为 STAY-GREEN 或 SGR 的酶催化去除叶绿素及其衍生物的中心镁离子,将其转化为相应的游离碱,包括叶绿素。通过使用 Chl 相关分子进行体外反应,对 SGR 的底物特异性进行了研究。然而,有关 SGR 的生化性质和反应机制及其底物特异性的信息仍不明确。在本研究中,我们合成了多种 Chl 衍生物,并利用 SGR 酶研究了它们的体外脱螯反应。我们制备了 A 环上带有 C3-乙烯基(天然底物中常见的取代基)的 Chl-a 衍生物以及 C3 位上带有乙基、羟甲基、甲酰基和苯乙烯基的类似物作为底物。这些底物的体外脱螯酶反应是利用一种来自厌氧菌的 SGR 酶进行的,从而使我们能够研究它们的特异性。当底物的 C3 位上带有抽电子的甲酰基或立体要求较高的苯乙烯基时,反应活性会降低。此外,与 C3-苯乙烯基底物相比,B 环上带有 C8-苯乙烯基的 Chl 衍生物对 SGR 脱螯的反应性更低。这些结果表明,SGR 酶识别底物 B 环上取代基的能力强于 A 环上的取代基。
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引用次数: 0
Excitation transfer and quenching in photosystem II, enlightened by carotenoid triplet state in leaves 叶片中类胡萝卜素三重态启示下的光系统 II 的激发传递和淬灭
IF 3.7 3区 生物学 Q2 PLANT SCIENCES Pub Date : 2024-03-19 DOI: 10.1007/s11120-024-01086-6
Agu Laisk, Richard B. Peterson, Vello Oja

Accumulation of carotenoid (Car) triplet states was investigated by singlet–triplet annihilation, measured as chlorophyll (Chl) fluorescence quenching in sunflower and lettuce leaves. The leaves were illuminated by Xe flashes of 4 μs length at half-height and 525–565 or 410–490 nm spectral band, maximum intensity 2 mol quanta m−2 s−1, flash photon dose up to 10 μmol m−2 or 4–10 PSII excitations. Superimposed upon the non-photochemically unquenched Fmd state, fluorescence was strongly quenched near the flash maximum (minimum yield Fe), but returned to the Fmd level after 30–50 μs. The fraction of PSII containing a 3Car in equilibrium with singlet excitation was calculated as Te = (FmdFe)/Fmd. Light dependence of Te was a rectangular hyperbola, whose initial slope and plateau were determined by the quantum yields of triplet formation and annihilation and by the triplet lifetime. The intrinsic lifetime was 9 μs, but it was strongly shortened by the presence of O2. The triplet yield was 0.66 without nonphotochemical quenching (NPQ) but approached zero when NP-Quenched fluorescence approached 0.2 Fmd. The results show that in the Fmd state a light-adapted charge-separated PSIIL state is formed (Sipka et al., The Plant Cell 33:1286–1302, 2021) in which PheoP680+ radical pair formation is hindered, and excitation is terminated in the antenna by 3Car formation. The results confirm that there is no excitonic connectivity between PSII units. In the PSIIL state each PSII is individually turned into the NPQ state, where excess excitation is quenched in the antenna without 3Car formation.

通过向日葵和莴苣叶片中的单线态-三线态湮灭(以叶绿素(Chl)荧光淬灭测量),研究了类胡萝卜素(Car)三线态的积累。向日葵和莴苣叶片在半高和 525-565 或 410-490 nm 光谱波段上受到长度为 4 μs 的 Xe 闪光灯照射,最大强度为 2 mol quanta m-2 s-1,闪光灯光子剂量高达 10 μmol m-2 或 4-10 PSII 激发。叠加在非光化学未淬灭的 Fmd 状态上,荧光在闪光最大值附近被强烈淬灭(最小产量 Fe),但在 30-50 μs 后又恢复到 Fmd 水平。含有与单子激发平衡的 3Car 的 PSII 部分的计算公式为 Te = (Fmd-Fe)/Fmd。Te 的光依赖性是一个矩形双曲线,其初始斜率和高原由三重子形成和湮灭的量子产率以及三重子寿命决定。本征寿命为 9 μs,但由于 O2 的存在,寿命大大缩短。在没有非光化学淬灭(NPQ)的情况下,三重子产率为 0.66,但当 NP-Quenched 荧光接近 0.2 Fmd 时,三重子产率接近零。结果表明,在 Fmd 状态下形成了光适应电荷分离 PSIIL 状态(Sipka 等人,The Plant Cell 33:1286-1302, 2021),其中 Pheo-P680+ 自由基对的形成受到阻碍,激发在天线中通过 3Car 的形成而终止。结果证实,PSII 单元之间不存在激子连接。在 PSIIL 状态下,每个 PSII 都单独进入 NPQ 状态,过量的激发在天线中被淬灭,而不会形成 3Car。
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引用次数: 0
International conference on “Photosynthesis and Hydrogen Energy Research for Sustainability-2023”: in honor of Robert Blankenship, Győző Garab, Michael Grätzel, Norman Hüner and Gunnar Öquist 光合作用和氢能研究促进可持续性-2023 年 "国际会议:纪念 Robert Blankenship、Győző Garab、Michael Grätzel、Norman Hüner 和 Gunnar Öquist
IF 3.7 3区 生物学 Q2 PLANT SCIENCES Pub Date : 2024-03-19 DOI: 10.1007/s11120-024-01087-5

Abstract

The 11th International Photosynthesis Conference on Hydrogen Energy Research and Sustainability 2023 was organized in honor of Robert Blankenship, Győző Garab, Michael Grätzel, Norman Hüner, and Gunnar Öquist, in Istanbul, Türkiye at Bahçeşehir University Future Campus from 03 to 09 July 2023. It was jointly supported by the International Society of Photosynthesis Research (ISPR) and the International Association for Hydrogen Energy (IAHE). In this article we provide brief details of the conference, its events, keynote speakers, and the scientific contribution of scientists honored at this conference. Further, we also describe the participation of young researchers, their talks, and their awards.

摘要 为纪念 Robert Blankenship、Győző Garab、Michael Grätzel、Norman Hüner 和 Gunnar Öquist,2023 年 7 月 3 日至 9 日在土耳其伊斯坦布尔 Bahçeşehir 大学未来校区举办了第 11 届氢能研究与可持续性 2023 年国际光合作用会议。会议得到了国际光合作用研究学会(ISPR)和国际氢能协会(IAHE)的联合支持。在本文中,我们将简要介绍此次会议的详细情况、会议活动、主旨发言人以及受表彰科学家的科学贡献。此外,我们还介绍了青年研究人员的参与情况、他们的演讲和获奖情况。
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引用次数: 0
The influence of cationic antiseptics on the processes of light energy conversion in various photosynthetic pigment-protein complexes 阳离子防腐剂对各种光合色素-蛋白质复合物中光能转换过程的影响
IF 3.7 3区 生物学 Q2 PLANT SCIENCES Pub Date : 2024-03-11 DOI: 10.1007/s11120-024-01082-w

Abstract

The widespread use of disinfectants and antiseptics, and consequently their release into the environment, determines the relevance of studying their potential impact on the main producers of organic matter on the planet—photosynthetic organisms. The review examines the effects of some biguanides and quaternary ammonium compounds, octenidine, miramistin, chlorhexidine, and picloxidine, on the functioning of the photosynthetic apparatus of various organisms (Strakhovskaya et al. in Photosynth Res 147:197–209, 2021; Knox et al. in Photosynth Res 153:103, 2022; Paschenko et al. in Photosynth Res 155:93–105, 2023a, Photosynth Res 2023b). A common feature of these antiseptics is the combination of hydrophobic and hydrophilic regions in the molecules, the latter carrying a positive charge(s). The comparison of the results obtained with intact bacterial membrane vesicles (chromatophores) and purified pigment-protein complexes (photosystem II and I) of oxygenic organisms allows us to draw conclusions about the mechanisms of the cationic antiseptic action on the functional properties of the components of the photosynthetic apparatus.

摘要 消毒剂和防腐剂的广泛使用及其在环境中的释放,决定了研究它们对地球上主要有机物生产者--光合生物--的潜在影响具有现实意义。本综述研究了一些双胍类和季铵化合物、辛烯啶、米拉米星、洗必泰和吡咯西丁对各种生物光合装置功能的影响(Strakhovskaya 等人,发表于《Photosynth Res》147:197-209, 2021 年;Knox 等人,发表于《Photosynth Res》153:103, 2022 年;Paschenko 等人,发表于《Photosynth Res》155:93-105, 2023 年a,《Photosynth Res》2023 年b)。这些防腐剂的共同特点是分子中疏水和亲水区域的结合,后者带有正电荷。通过对完整的细菌膜囊(色素体)和纯化的含氧生物色素-蛋白质复合物(光合系统 II 和 I)的研究结果进行比较,我们可以得出阳离子防腐剂对光合装置各组成部分的功能特性产生作用的机制。
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引用次数: 0
Three-state mathematical model for the assessment of DCMU-treated photosystem II heterogeneity 评估经 DCMU 处理的光系统 II 异质性的三态数学模型
IF 3.7 3区 生物学 Q2 PLANT SCIENCES Pub Date : 2024-03-11 DOI: 10.1007/s11120-024-01077-7
Tatiana Yu. Plyusnina, Sergei S. Khruschev, Natalia S. Degtereva, Elena N. Voronova, Alena A. Volgusheva, Galina Yu. Riznichenko, Andrew B. Rubin

Photosystem II (PSII) is one of the main pigment-protein complexes of photosynthesis which is highly sensitive to unfavorable environmental factors. The heterogeneity of PSII properties is essential for the resistance of autotrophic organisms to stress factors. Assessment of the PSII heterogeneity may be used in environmental monitoring for on-line detection of contamination of the environment. We propose an approach to assess PSII oxygen-evolving complex and light-harvesting antenna heterogeneity that is based on mathematical modeling of the shape of chlorophyll a fluorescence rise of 3-(3,4-dichlorophenyl)-1,1-dimethylurea-treated samples. The hierarchy of characteristic times of the processes considered in the model makes it possible to reduce the model to a system of three ordinary differential equations. The analytic solution of the reduced three-state model is expressed as a sum of two exponential functions, and it exactly reproduces the solution of the complete system within the time range from microseconds to hundreds of milliseconds. The combination of several such models for reaction centers with different properties made it possible to use it as an instrument to study PSII heterogeneity. PSII heterogeneity was studied for Chlamydomonas at different intensities of actinic light, for Scenedesmus under short-term heating, and for Chlorella grown in nitrate-enriched and nitrate-depleted media.

光系统 II(PSII)是光合作用的主要色素-蛋白质复合物之一,对不利的环境因素高度敏感。PSII 特性的异质性对于自养生物抵抗压力因素至关重要。对 PSII 异质性的评估可用于环境监测,对环境污染进行在线检测。我们提出了一种评估 PSII 氧发生复合体和光收集天线异质性的方法,该方法基于对 3-(3,4-二氯苯基)-1,1-二甲基脲处理样品的叶绿素 a 荧光上升形状的数学建模。模型中考虑的过程特征时间的层次结构使得将模型简化为三个常微分方程系统成为可能。简化后的三态模型的解析解用两个指数函数之和表示,在从微秒到数百毫秒的时间范围内完全再现了完整系统的解析解。将具有不同性质的反应中心的多个此类模型组合在一起,就有可能将其用作研究 PSII 异质性的工具。研究了不同光照强度下衣藻的 PSII 异质性、短期加热下的 Scenedesmus 以及在富硝酸盐和贫硝酸盐培养基中生长的小球藻的 PSII 异质性。
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引用次数: 0
Inverted region in the reaction of the quinone reduction in the A1-site of photosystem I from cyanobacteria. 蓝藻光系统 I A1 位点醌还原反应中的反转区域。
IF 3.7 3区 生物学 Q2 PLANT SCIENCES Pub Date : 2024-03-01 Epub Date: 2023-04-24 DOI: 10.1007/s11120-023-01020-2
Dmitry Cherepanov, Arseny Aybush, T Wade Johnson, Ivan Shelaev, Fedor Gostev, Mahir Mamedov, Victor Nadtochenko, Alexey Semenov

Photosystem I from the menB strain of Synechocystis sp. PCC 6803 containing foreign quinones in the A1 sites was used for studying the primary steps of electron transfer by pump-probe femtosecond laser spectroscopy. The free energy gap (- ΔG) of electron transfer between the reduced primary acceptor A0 and the quinones bound in the A1 site varied from 0.12 eV for the low-potential 1,2-diamino-anthraquinone to 0.88 eV for the high-potential 2,3-dichloro-1,4-naphthoquinone, compared to 0.5 eV for the native phylloquinone. It was shown that the kinetics of charge separation between the special pair chlorophyll P700 and the primary acceptor A0 was not affected by quinone substitutions, whereas the rate of A0 → A1 electron transfer was sensitive to the redox-potential of quinones: the decrease of - ΔG by 400 meV compared to the native phylloquinone resulted in a ~ fivefold slowing of the reaction The presence of the asymmetric inverted region in the ΔG dependence of the reaction rate indicates that the electron transfer in photosystem I is controlled by nuclear tunneling and should be treated in terms of quantum electron-phonon interactions. A three-mode implementation of the multiphonon model, which includes modes around 240 cm-1 (large-scale protein vibrations), 930 cm-1 (out-of-plane bending of macrocycles and protein backbone vibrations), and 1600 cm-1 (double bonds vibrations) was applied to rationalize the observed dependence. The modes with a frequency of at least 1600 cm-1 make the predominant contribution to the reorganization energy, while the contribution of the "classical" low-frequency modes is only 4%.

利用泵浦探针飞秒激光光谱法研究了在 A1 位点含有外来醌类化合物的 Synechocystis sp.还原主受体 A0 与结合在 A1 位点上的醌类化合物之间电子转移的自由能隙(- ΔG)从低电位的 1,2- 二氨基蒽醌的 0.12 eV 到高电位的 2,3- 二氯-1,4-萘醌的 0.88 eV 不等,而原生植物醌的自由能隙为 0.5 eV。研究表明,特殊配对叶绿素 P700 与主受体 A0 之间的电荷分离动力学不受醌取代的影响,而 A0 → A1 电子转移的速率对醌的氧化还原电位很敏感:反应速率随 ΔG 变化的不对称倒置区域的存在表明,光系统 I 中的电子转移受核隧道控制,应从量子电子-声子相互作用的角度来处理。为了合理解释观察到的依赖关系,我们采用了多声子模型的三模式实现方法,其中包括 240 cm-1 附近的模式(大规模蛋白质振动)、930 cm-1 附近的模式(大环的平面外弯曲和蛋白质骨架振动)和 1600 cm-1 附近的模式(双键振动)。频率至少为 1600 cm-1 的模式对重组能的贡献最大,而 "经典 "低频模式的贡献仅为 4%。
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引用次数: 0
Chlorophyll triplet states in thylakoid membranes of Acaryochloris marina. Evidence for a triplet state sitting on the photosystem I primary donor populated by intersystem crossing. 叶绿素三重态在钝叶藻类(Acaryochloris marina)的类叶绿体膜中的表现。证明三重态位于光系统 I 初级供体上,由系统间交叉填充。
IF 3.7 3区 生物学 Q2 PLANT SCIENCES Pub Date : 2024-03-01 Epub Date: 2023-05-16 DOI: 10.1007/s11120-023-01023-z
Stefano Santabarbara, Alessandro Agostini, Anastasia A Petrova, Marco Bortolus, Anna Paola Casazza, Donatella Carbonera

Photo-induced triplet states in the thylakoid membranes isolated from the cyanobacterium Acaryocholoris marina, that harbours Chlorophyll (Chl) d as its main chromophore, have been investigated by Optically Detected Magnetic Resonance (ODMR) and time-resolved Electron Paramagnetic Resonance (TR-EPR). Thylakoids were subjected to treatments aimed at poising the redox state of the terminal electron transfer acceptors and donors of Photosystem II (PSII) and Photosystem I (PSI), respectively. Under ambient redox conditions, four Chl d triplet populations were detectable, identifiable by their characteristic zero field splitting parameters, after deconvolution of the Fluorescence Detected Magnetic Resonance (FDMR) spectra. Illumination in the presence of the redox mediator N,N,N',N'-Tetramethyl-p-phenylenediamine (TMPD) and sodium ascorbate at room temperature led to a redistribution of the triplet populations, with T3 (|D|= 0.0245 cm-1, |E|= 0.0042 cm-1) becoming dominant and increasing in intensity with respect to untreated samples. A second triplet population (T4, |D|= 0.0248 cm-1, |E|= 0.0040 cm-1) having an intensity ratio of about 1:4 with respect to T3 was also detectable after illumination in the presence of TMPD and ascorbate. The microwave-induced Triplet-minus-Singlet spectrum acquired at the maximum of the |D|-|E| transition (610 MHz) displays a broad minimum at 740 nm, accompanied by a set of complex spectral features that overall resemble, despite showing further fine spectral structure, the previously reported Triplet-minus-Singlet spectrum attributed to the recombination triplet of PSI reaction centre, 3 P 740 [Schenderlein M, Çetin M, Barber J, et al. Spectroscopic studies of the chlorophyll d containing photosystem I from the cyanobacterium Acaryochloris marina. Biochim Biophys Acta 1777:1400-1408]. However, TR-EPR experiments indicate that this triplet displays an eaeaea electron spin polarisation pattern which is characteristic of triplet sublevels populated by intersystem crossing rather than recombination, for which an aeeaae polarisation pattern is expected instead. It is proposed that the observed triplet, which leads to the bleaching of the P740 singlet state, sits on the PSI reaction centre.

我们利用光检测磁共振(ODMR)和时间分辨电子顺磁共振(TR-EPR)研究了从以叶绿素(Chl)d 为主要发色团的蓝藻 Acaryocholoris marina 中分离出来的叶绿体膜中光诱导的三重态。对葡萄体进行了处理,目的是分别调节光系统 II(PSII)和光系统 I(PSI)末端电子传递受体和供体的氧化还原状态。在环境氧化还原条件下,对荧光检测磁共振(FDMR)光谱进行解卷积后,可检测到四种 Chl d 三重粒子群,并可通过其特征零场分裂参数进行识别。室温下,在氧化还原介质 N,N,N',N'-四甲基对苯二胺(TMPD)和抗坏血酸钠的存在下进行光照,三重子群重新分布,T3(|D|= 0.0245 cm-1,|E|= 0.0042 cm-1)成为主要的三重子群,与未处理的样品相比,其强度不断增加。在有 TMPD 和抗坏血酸存在的情况下,还可以检测到第二个三重子群(T4,|D|= 0.0248 cm-1,|E|= 0.0040 cm-1),与 T3 相比,其强度比约为 1:4。在|D|-|E|转变的最大值(610 MHz)处获得的微波诱导三重子减星光光谱在 740 nm 处显示出一个宽广的最小值,并伴有一系列复杂的光谱特征,尽管显示出更精细的光谱结构,但总体上类似于之前报道的归因于 PSI 反应中心重组三重子的三重子减星光光谱 3 P 740 [Schenderlein M, Çetin M, Barber J, et al.来自蓝藻 Acaryochloris marina 的含叶绿素 d 光系统 I 的光谱研究。Biochim Biophys Acta 1777:1400-1408].然而,TR-EPR 实验表明,这种三重子显示出一种 eaeaea 电子自旋极化模式,这是通过系统间交叉而非重组填充的三重子级的特征,而对于系统间交叉,预计会出现 aeeaae 极化模式。据推测,所观察到的导致 P740 单态漂白的三重子位于 PSI 反应中心。
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Photosynthesis Research
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