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Artificial Mn4Ca-cluster with Exchangeable Solvent Molecules Mimicking the Oxygen-Evolving Center in Photosynthesis
摘要： The natural Mn4Ca-cluster in photosystem II serves as a blueprint to develop artificial water-splitting catalysts in artificial photosynthesis. Although significant advances have recently been achieved, it remains great challenges to prepare robust artificial Mn4Ca-cluster to precisely mimic the structure and function of the biological catalyst in the laboratory. Here, we report the isolation and structural characterization of two Mn4CaO4-complexes from polar solvents acetonitrile or N, N-dimethylformamide, which closely mimics the two water molecules on calcium ion, as well as, the oxidation states of the four manganese ions and the main geometric structure of the natural Mn4Ca-cluster. These new artificial Mn4Ca-complexes provide important chemical clues to understand the structure and mechanism of its biological paragon.
关键词： bioinorganic chemistry,photosynthesis,manganese,heterometallic complexes,water splitting
更新于2025-09-23 15:22:29
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Measurement of Photosynthesis Using PAM Technology in a Purple Sulfur Bacterium <i>Thermochromatium tepidum</i> (Chromatiaceae)
摘要： We demonstrate that Blue-diode-based pulse amplitude modulation (PAM) technology can be used to measure the photosynthetic electron transport rate (ETR) of purple sulfur bacteria (Thermochromatium tepidum, Chromatiaceae). Previous studies showed that PAM technology could be used to estimate photosynthesis in purple nonsulfur bacteria and so PAM technology can be used to estimate photosynthesis of both kinds of purple photosynthetic bacteria. The absorptance of Thermochromatium films on glass fiber disks was measured and used to calculate actual ETR. ETR vs Irradiance curves fitted the waiting-in-line model (ETR = (ETRmax * E/Eopt) * exp (1-E/Eopt)). Yield (Y) was only 0.3–0.4. Thermochromatium saturates at 325 ± 13.8 μmol photons m?2 s?1 or ~15% sunlight and shows photoinhibition at high irradiances. A pond of Thermochromatium would exhibit classic surface inhibition. Photosynthesis is extremely low in the absence of an electron source: ETR increases in the presence of acetate (5 mol m?3) provided as an organic carbon source and also increases in the presence of sulfite (3 mol m?3) but not sulfide and is only marginally increased by the presence of Fe2?. Nonphotochemical quenching does occur in Thermochromatium but at very low levels compared to oxygenic photo-organisms or Rhodopseudomonads.
关键词： photosynthesis,PAM technology,photoinhibition,absorptance,Thermochromatium tepidum,purple sulfur bacteria,electron transport rate
更新于2025-09-23 15:22:29
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Recent Improvements in the Production of Solar Fuels: From CO <sub/>2</sub> Reduction to Water Splitting and Artificial Photosynthesis
摘要： This account deals with recent trends and challenges regarding photo(electro)chemical solar fuels produced by CO2 reduction and water splitting. The CO2 reduction process is limited by product selectivity, catalyst stability, and its complex reaction mechanism. A variety of catalysts—including thermocatalysts, photocatalysts, electrocatalysts, and combinations of photo- and electrocatalysts—have been employed to facilitate selective and durable CO2 reduction. In addition, the roles of the supporting electrolyte, pH, reaction temperature, chemical environment, and catalyst surface chemistry in efficient CO2 reduction have been thoroughly studied in recent years. Effective use of solar light is a significant part of realizing efficient solar-to-hydrogen conversion during the water splitting process, and so the response of photo(electro)systems to visible light is key. To this end, several strategies have been studied in detail, including band engineering of photocatalysts, photocatalytic systems that mimic natural photosynthesis, and the development of photoanodes and their combination with photovoltaic systems. Here, we summarize recent developments surrounding the CO2-reduction and water-splitting reactions and progress towards achieving artificial photosynthesis.
关键词： Artificial photosynthesis,CO2 reduction,Water splitting
更新于2025-09-23 15:22:29
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Production of Methanol from Aqueous CO <sub/>2</sub> by Using Co <sub/>3</sub> O <sub/>4</sub> Nanostructures as Photocatalysts
摘要： In this work, we report for the first time the photocatalytic activity of Co3O4 nanostructures for the reduction of aqueous CO2 to methanol (MeOH). This could be considered a simple example of artificial photosynthesis. The photocatalysis experiments were developed under simulated solar light of 100 mW/cm2 and without using any sacrificial agent. To carry out this study, nanostructured mixed valence cobalt oxide (Co3O4) powders, with porous nanoparticle aggregates of different morphologies, have been prepared by two synthesis methods. The characterization of structural (PXRD, XPS, SEM, and TEM) and optical (UV-vis-NIR, Raman, and FT-IR) properties, magnetization curves, and surface area (BET) was accomplished.
关键词： Co3O4,photocatalysis,artificial photosynthesis,CO2 reduction,nanostructures,methanol
更新于2025-09-23 15:22:29
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"Two-in-One" Strategy of o-Amino and Aromatic Nitrogen in Biomimetic Metal-Organic Frameworks for Efficient CO2 Photoconversion
摘要： Visible-light driven photoconversion of CO2 into energy carriers is highly important to the natural carbon balance and sustainable development. Herein, we demonstrate the biological nucleobase adenine-dependent CO2 photoreduction performance in green biomimetic metal-organic frameworks. Photocatalytic results indicate that AD-MOF-2 exhibited a very high HCOOH production rate of 443.2 μmol g-1 h-1 in pure aqueous solution, which is more than two times higher than that of AD-MOF-1 (179.0 μmol hour?1 g?1) in acetonitrile solution. Significantly, experimental and theoretical evidences reveal that CO2 photoreduction reaction mainly takes place on biological adenine molecules by unique o-amino assisted active aromatic nitrogen atom rather than traditional metal center. This work not only serves as an important case study for the development of green biomimetic photocatalysts used for artificial photosynthesis, but also proposes a new catalytic strategy for efficient CO2 photoconversion.
关键词： photosensitivity,hydrophobicity,biomimetic catalysis,green MOFs,artificial photosynthesis
更新于2025-09-23 15:22:29
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Use of Sun-Induced Chlorophyll Fluorescence Obtained by OCO-2 and GOME-2 for GPP Estimates of the Heihe River Basin, China
摘要： Sun-induced chlorophyll ?uorescence (SIF) provides a new method for monitoring vegetation photosynthesis from space and has been widely used to estimate gross primary productivity (GPP). However, the ability of SIF obtained from the Orbital Carbon Observatory 2 (OCO-2 SIF) and Global Ozone Monitoring Experiment-2 (GOME-2) to estimate GPP in the cold and arid region of Heihe River Basin remains unclear because previous comparisons were insuf?cient. Here, we choose maize and alpine meadow to evaluate the performance of SIF obtained by OCO-2 and GOME-2 in GPP estimations. The results of this study show that daily SIF757 had stronger correlations with daily tower GPP than daily SIF771, and the correlation between daily SIF757 and daily tower GPP was stronger than the correlation between 16-d averaged SIF740 and 16-d averaged tower GPP. The 16-d averaged absorbed photosynthetically active radiation (APAR) and reconstructed sun-induced ?uorescence (RSIF) had the strongest linear correlations with 16-d averaged tower GPP. GPP_VPM and GPP_RSIF exhibited the best performance in GPP estimation, closely followed by GPP_SIF757, then GPP_SIF771 and GPP_ SIF740. We also found that the robustness of the correlation coef?cients of OCO-2 SIF with GOME-2 SIF was highly dependent on the size of their spatial footprint overlaps, indicating that the spatial differences between OCO-2 and GOME-2 footprints contribute to the differences in GPP estimates between OCO-2 and GOME-2. In addition, the differences of viewing zenith angle (VZA), cloud contamination, scale effects, and environmental scalars (Tscalar × Wscalar) can result in differences between OCO-2 SIF and GOME-2 SIF.
关键词： vegetation photosynthesis model,eddy covariance,sun-induced ?uorescence,gross primary productivity,carbon cycle
更新于2025-09-23 15:22:29
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AIP Conference Proceedings [Author(s) PROCEEDINGS OF THE 3RD INTERNATIONAL SYMPOSIUM ON CURRENT PROGRESS IN MATHEMATICS AND SCIENCES 2017 (ISCPMS2017) - Bali, Indonesia (26–27 July 2017)] - Bismuth vanadate (BiVO4) as counter electrode in the newly developed catalysis zone of modified cadmium sulfide (CdS) sensitized solar cell for hydrogen production
摘要： Recently we developed a modified quantum dot dyes sensitized solar cell (QD-DSSC) having catalysis zone extension for hydrogen production. The DSSC section comprised of CdS sensitized highly order Titanium dioxidenanotube (CdS-HOTN) immobilized on Ti plate, Na2S/S containing electrolyte, and Pt covered SnO-F (fluorine doped tin oxide) glass plate (hence Pt/SnO-F/Glass). While the catalysis zone comprised of an extension of Ti support, as cathode, and the respected counter electrode was an extension of SnO-F glass, which was covered by BiVO4 film, both from respected DSSC section. In this presentation, we will focus on the role of the BiVO4 in our newly developed system. The bismuth vanadate was prepared by co-precipitation method with ammonia and calcination to obtain a fine powder. The BiVO4 fine powder were then deposited onto SnO-F glass plate and characterized by FT-IR, UV–vis diffused reflectance spectroscopy, SEM and X-ray diffraction. The characterization results revealed that the BiVO4 film, typically, has a band gap of 2.35 eV, characteristic of IR peaks represent the –V-O-, and –Bi-O-V- bonds, having a crystal phase as BiVO4 monoclinic scheelite with a typically crystallite size of 74.06 nm. The photo-electro-chemical properties of the BiVO4 film photo-anode was investigated by a linear sweep voltammetry and multi pulse amperometry, which revealed that the current response under the visible light was 0.03 mA/cm2. Further investigation when the BiVO4 film was incorporated into the modified QD-DSSC, the system (catalysis zone section), under solely visible light, was able to split the water into hydrogen and molecular oxygen. A brief discussion of the newly developed modified QD-DSSC, especially on the role of BiVO4 counter electrode in the catalysis zone will be presented, to gain a better insight in our new type artificial photosynthesis.
关键词： water splitting,titanium dioxide nanotubes,cadmium sulfide,artificial photosynthesis,modified dyes sensitized solar cell,Bismuth vanadate
更新于2025-09-23 15:21:21
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Oxidation of P700 Ensures Robust Photosynthesis
摘要： In the light, photosynthetic cells can potentially suffer from oxidative damage derived from reactive oxygen species. Nevertheless, a variety of oxygenic photoautotrophs, including cyanobacteria, algae, and plants, manage their photosynthetic systems successfully. In the present article, we review previous research on how these photoautotrophs safely utilize light energy for photosynthesis without photo-oxidative damage to photosystem I (PSI). The reaction center chlorophyll of PSI, P700, is kept in an oxidized state in response to excess light, under high light and low CO2 conditions, to tune the light utilization and dissipate the excess photo-excitation energy in PSI. Oxidation of P700 is co-operatively regulated by a number of molecular mechanisms on both the electron donor and acceptor sides of PSI. The strategies to keep P700 oxidized are diverse among a variety of photoautotrophs, which are evolutionarily optimized for their ecological niche.
关键词： photosynthesis,reactive oxygen species,photoinhibition,P700 oxidation,photosystem I
更新于2025-09-23 15:21:21
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Strong pH-Dependent Near-Infrared Fluorescence in a Microbial Rhodopsin Reconstituted with a Red-Shifting Retinal Analogue
摘要： Near-infrared (NIR)-driven rhodopsins are of great interest in optogenetics and other optobiotechnological developments such as artificial photosynthesis and deep-tissue voltage imaging. Here we report the proton pump proteorhodopsin (PR) containing a NIR-active retinal analogue (PR:MMAR) exhibits intense NIR fluorescence at a quantum yield of 3.3%. This is 130 times higher than native PR (Lenz, M. O.; et al. Biophys J. 2006, 91, 255?262) and 3?8 times higher than the QuasAr and PROPS voltage sensors (Kralj, J.; et al. Science 2011, 333, 345?348; Hochbaum, D. R.; et al. Nat. Methods 2014, 11, 825?833). The NIR fluorescence strongly depends on the pH in the range of 6?8.5, suggesting potential application of MMAR-binding proteins as ultrasensitive NIR-driven pH and/or voltage sensors. Femtosecond transient absorption spectroscopy showed that upon near-IR excitation, PR:MMAR features an unusually long fluorescence lifetime of 310 ps and the absence of isomerized photoproducts, consistent with the high fluorescence quantum yield. Stimulated Raman analysis indicates that the NIR-absorbing species develops upon protonation of a conserved aspartate, which promotes charge delocalization and bond length leveling due to an additional methylamino group in MMAR, in essence providing a secondary protonated Schiff base. This results in much smaller bond length alteration along the conjugated backbone, thereby conferring significant single-bond character to the C13C14 bond and structural deformation of the chromophore, which interferes with photoinduced isomerization and extends the lifetime for fluorescence. Hence, our studies allow for a molecular understanding of the relation between absorption/emission wavelength, isomerization, and fluorescence in PR:MMAR. As acidification enhances the resonance state, this explains the strong pH dependence of the NIR emission.
关键词： stimulated Raman analysis,fluorescence,voltage sensor,rhodopsins,optogenetics,artificial photosynthesis,proteorhodopsin,femtosecond transient absorption spectroscopy,pH sensor,Near-infrared,voltage imaging
更新于2025-09-23 15:21:01
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Regionalization and Dynamic Parameterization of Quantum Yield of Photosynthesis to Improve the Ocean Primary Production Estimates From Remote Sensing
摘要： Quantum yield of photosynthesis (φ) expresses the efficiency of phytoplankton carbon fixation given certain amount of absorbed light. This photophysiological parameter is key to obtaining reliable estimates of primary production (PPsat) in the ocean based on remote sensing information. Several works have shown that φ changes temporally, vertically, and horizontally in the ocean. One of the primary factors ruling its variability is light intensity and thereby, it can be modeled as a function of Photosynthetically Available Radiation (PAR). We estimated φ utilizing long time-series collected in the North Subtropical Oligotrophic Gyres, at HOT and BATS stations (Pacific and Atlantic oceans, respectively). Subsequently the maximum quantum yield (φm) and Kφ (PAR value at half φm) were calculated. Median φm values were ～0.040 and 0.063 mol C mol photons?1 at HOT and BATS, respectively, with higher values in winter. Kφ values were ～8.0 and 10.8 mol photons m?2 d?1 for HOT and BATS, respectively. Seasonal variability in Kφ showed its peak in summer. Dynamical parameterizations for both regions are indicated by their temporal behaviors, where φm is related to temperature at BATS while Kφ to PAR, in both stations. At HOT, φm was weakly related to temperature and its median annual value was used for the whole data series. Differences in the study areas, even though both belong to Subtropical Gyres, reinforced the demand for regional parameterizations in PPsat models. Such parameterizations were finally included in a PPsat model based on phytoplankton absorption (PPsat?aphy?based), where results showed that the PPsat?aphy?based model coupled with dynamical parameterization improved PPsat estimates. Compared with PPsat estimates from the widely used VGPM, a model based on chlorophyll concentration (PPsat?chl?based), PPsat?aphy?based reduced model-measurement differences from ～62.8 to ～8.3% at HOT, along with well-matched seasonal cycle of PP (R2 = 0.76). There is not significant reduction in model-measurement differences between PPsat?chl?based and PPsat?aphy?based PP at BATS though (37.8 vs. 36.4%), but much better agreement in seasonal cycles with PPsat?aphy?based (R2 increased from 0.34 to 0.71). Our results point to improved estimation of PPsat by parameterized quantum yield along with phytoplankton absorption coefficient at the core.
关键词： quantum yield of photosynthesis,ocean color,phytoplankton primary production,in situ measurements,dynamical parameterization,marine seasonal variability
更新于2025-09-23 15:21:01