Photosynthetic hydrogen production

Among various technologies for hydrogen production, the use of oxygenic natural photosynthesis has a great potential as can use clean and cheap sources—water and solar energy. In oxygenic photosynthetic microorganisms electrons and protons produced from water and redirected by the photosynthetic electron-transport chain via ferredoxin to the hydrogen-producing enzymes hydrogenase or nitrogenase. By these enzymes, e^? and H⁺ recombine and form molecular hydrogen. Hydrogenase activity can be very high but is extremely sensitive to the photosynthetically evolved O₂ that leads to reduced and unstable H₂ production. However, presently, several approaches are developed to improve the energetic efficiency to generate H₂. This review examines the main available pathways to improve the photosynthetic H₂ production.     

Bioinspired Artificial Photosynthetic Systems

Mimicking photosynthesis using artificial systems, as a means for solar energy conversion and green fuel generation, is one of the holy grails of modern science. This perspective presents recent advances towards developing artificial photosynthetic systems. In one approach, native photosystems are interfaced with electrodes to yield photobioelectrochemical cells that transform light energy into electrical power. This is exemplified by interfacing photosystem I (PSI) and photosystem II (PSII) as an electrically contacted assembly mimicking the native Z-scheme, and by the assembly of an electrically wired PSI/glucose oxidase biocatalytic conjugate on an electrode support. Illumination of the functionalized electrodes led to light-induced generation of electrical power, or to the generation of photocurrents using glucose as the fuel. The second approach introduces supramolecular photosensitizer nucleic acid/electron acceptor complexes as functional modules for effective photoinduced electron transfer stimulating the subsequent biocatalyzed generation of NADPH or the Pt-nanoparticle-catalyzed evolution of molecular hydrogen. Application of the DNA machineries for scaling-up the photosystems is demonstrated. A third approach presents the integration of artificial photosynthetic modules into dynamic nucleic acid networks undergoing reversible reconfiguration or dissipative transient operation in the presence of auxiliary triggers. Control over photoinduced electron transfer reactions and photosynthetic transformations by means of the dynamic networks is demonstrated.     

Photosynthetic oxygen evolution in mesoporous silica material: adsorption of photosystem II reaction center complex into 23 nm nanopores in SBA

An oxygen-evolving photosynthetic reaction center complex (PSII) was adsorbed into nanopores in SBA, a mesoporous silica compound. We purified the dimer of PSII complex from a thermophilic cyanobacterium, Thermosynechococcus vulcanus, which grows optimally at 57 °C. The thermally stable PSII dimeric complex has a diameter of 20 nm and a molecular mass of 756 kDa and binds more than 60 chlorophylls. The SBA particles, with average internal pore diameters of 15 nm (SBA(15)) and 23 nm (SBA(23)), adsorbed 4.7 and 15 mg of PSII/g SBA, respectively. Measurement with a confocal laser-scanning microscope indicated the adsorption of PSII to the surface and the inner space of the SBA(23) particles, indicating the adsorption of PSII into the 23 nm silica nanopores. PSII did not bind to the inner pores of SBA(15). PSII bound to SBA(23) showed the high and stable activity of a photosynthetic oxygen-evolving reaction, indicating the light-driven electron transport from water to the quinone molecules added in the outer medium. The PSII-SBA conjugate can be a new material for photosensors and artificial photosynthetic systems.     

光合放氧复合物结构及其放氧机理的研究

光合水氧化是地球上最重要的生化过程之一.光合放氧生物包括光系统Ⅰ(PSⅠ)和光系统Ⅱ(PSⅡ)两种类型反应中心,光系统Ⅱ反应中心能以水作为电子给体,利用光能氧化水产生质子和氧气.对于水如何被氧化这个难题前人已做了大量的工作,但到目前为止放氧复合物(OEC)的结构及水氧化的机理仍不清楚.本文结合当前研究结果,就光合放氧复合物的结构及光合放氧机理进行了综述,希望能有助于推进这方面的工作.     

Different Photosynthetic Responses of Pyropia yezoensis to Ultraviolet Radiation Under Changing Temperature and Photosynthetic Active Radiation Regimes

Macroalgae play a crucial role in coastal marine ecosystems, but they are also subject to multiple challenges due to tidal and seasonal alterations. In this work, we investigated the photosynthetic response of Pyropia yezoensis to ultraviolet radiation (PAR: 400–700 nm; PAB: 280–700 nm) under changing temperatures (5, 10 and 15°C) and light intensities (200, 500 and 800 μmol photons m^?2 s^?1). Under low light intensity (200 μmol photons m^?2 s^?1), P. yezoensis showed the lowest sensitivity to ultraviolet radiation, regardless of temperature. However, higher temperatures inhibited the repair rates (r) and damage rates (k) of photosystem II (PSII) in P. yezoensis. However, under higher light intensities (500 and 800 μmol photons m^?2 s^?1), P. yezoensis showed higher sensitivity to UV radiation. Both r and the ratio of repair rate to damage rate (r:k) were significantly inhibited in P. yezoensis by PAB, regardless of temperature. In addition, higher temperatures significantly decreased the relative UV‐inhibition rates, while an increased carbon fixation rate was found. Our study suggested that higher light intensities enhanced the sensitivity to UV radiation, while higher temperatures could relieve the stress caused by high light intensity and UV radiation.     

Photosynthetic Electron Transport in an Anoxygenic Photosynthetic Bacterium Afifella (Rhodopseudomonas) marina Measured Using PAM Fluorometry

Blue diode‐based pulse amplitude modulation (PAM) technology can be used to measure the photosynthetic electron transport rate (ETR) in a purple nonsulfur anoxygenic photobacterium, Afifella (Rhodopseudomonas) marina. Rhodopseudomonads have a reaction center light harvesting antenna complex containing an RC‐2 type bacteriochlorophyll a protein (BChl a RC‐2‐LH1) which has a blue absorption peak and variable fluorescence similar to PSII. Absorptance of cells filtered onto glass fiber disks was measured using a blue–diode‐based absorptance meter (Blue‐RAT) so that absolute ETR could be calculated from PAM experiments. Maximum quantum yield (Y) was ≈0.6, decreasing exponentially as irradiance increased. ETR vs irradiance (P vs E) curves fitted the waiting‐in‐line model (ETR = (ETR_max × E/E_opt) × exp(1 ? E/E_opt)). Maximum ETR (ETR_max) was ≈1000–2000 μmol e^? mg^?1 BChl a h^?1. Fe²⁺, bisulfite and thiosulfate act as photosynthetic electron donors. Optimum irradiance was ≈100 μmol m^?2 s^?1 PPFD even in Afifella grown in sunlight. Quantum efficiencies (α) were ≈0.3–0.4 mol e^? mol hλ^?1; or ≈11.8 ± 2.9 mol e^? mol hλ^?1 m² μg^?1 BChl a). An underlying layer of Afifella in a constructed algal/photosynthetic bacterial mat has little effect on the measured ETR of the overlying oxyphotoautotroph (Chlorella).     

Engineering Photosynthetic Microbial Consortia for Carbon-Negative Biosynthesis

Microbial consortia consisting of phototrophs and heterotrophs have raised extensive attention due to their potential in sustainable biotechnology. The challenge remains in the selection of appropriate partners since most heterotrophic microorganisms cannot naturally use the intermediate carbohydrates secreted by autotrophic partners. In a recent study, the Ni Lab has developed a highly compatible autotrophic-heterotrophic symbiotic system comprising Synechococcus elongatus and Vibrio natriegens. V. natriegens (the sucrose utilization module) shows a high degree of nutritional complementarity and culturing compatibility with the engineered S. elongatus (the CO₂ sequestration module). The combination of both species channels CO₂ into various valuable chemicals, enabling carbon-negative biosynthesis.     

How Quantum Coherence Assists Photosynthetic Light Harvesting

This perspective examines how hundreds of pigment molecules in purple bacteria cooperate through quantum coherence to achieve remarkable light harvesting efficiency. Quantum coherent sharing of excitation, which modifies excited state energy levels and combines transition dipole moments, enables rapid transfer of excitation over large distances. Purple bacteria exploit the resulting excitation transfer to engage many antenna proteins in light harvesting, thereby increasing the rate of photon absorption and energy conversion. We highlight here how quantum coherence comes about and plays a key role in the photosynthetic apparatus of purple bacteria.     

Photosynthetic reactions in fullerene based donor-acceptor complexes

Donor-acceptor interaction changes essentially the terms of the ground state of binary complexes imparting them a multi-well, in particular, two-well form. A quantum chemical analysis of formation conditions for the amine derivatives of fullerenes depending on the type of the term has been performed by the example of binary complexes, including fullerenes C₆₀ and C₇₀ as acceptors of electrons and amines as donors,. It is found that the addition reaction of amines to fullerene hampered between neutral molecules can occur when the latter are ionized by light.     

Protein Ligation of the Photosynthetic Oxygen-Evolving Center

Photosynthetic water oxidation is catalyzed by a unique Mn(4)Ca cluster in Photosystem II. The ligation environment of the Mn(4)Ca cluster optimizes the cluster's reactivity at each step in the catalytic cycle and minimizes the release of toxic, partly oxidized intermediates. However, our understanding of the cluster's ligation environment remains incomplete. Although the recent X-ray crystallographic structural models have provided great insight and are consistent with most conclusions of earlier site-directed mutagenesis studies, the ligation environments of the Mn(4)Ca cluster in the two available structural models differ in important respects. Furthermore, while these structural models and the earlier mutagenesis studies agree on the identity of most of the Mn(4)Ca cluster's amino acid ligands, they disagree on the identity of others. This review describes mutant characterizations that have been undertaken to probe the ligation environment of the Mn(4)Ca cluster, some of which have been inspired by the recent X-ray crystallographic structural models. Many of these characterizations have involved Fourier Transform Infrared (FTIR) difference spectroscopy because of the extreme sensitivity of this form of spectroscopy to the dynamic structural changes that occur during an enzyme's catalytic cycle.     

Challenges and Perspectives in Designing Artificial Photosynthetic Systems

The development of artificial photosynthetic systems for water splitting and CO₂ reduction on a large scale for practical applications is the ultimate goal towards worldwide sustainability. This Concept highlights the state‐of‐the‐art research trends of artificial photosynthesis concepts and designs from some new perspectives. Particularly, it is focused on five important aspects for the design of promising artificial photosynthetic systems: 1) catalyst development, 2) architecture design, 3) device buildup 4) mechanism exploration, and 5) theoretical investigations. Some typical progress and challenges, the most significant milestones achieved to date, as well as possible future directions are illustrated and discussed. This Concept article presents a selection of new developments to highlight new trends and possibilities, main barriers, or challenges; with this, we hope to inspire more advances in the field of artificial photosynthesis.     

光合放氧复合物锰簇光组装

在光系统II水氧化过程中, 由锰簇及其附近一个具氧化还原活性的酪氨酸Y_Z组成的光合放氧复合物通过4个连续的氧化还原反应将水裂解为质子和氧气。在光系统II的功能性组装过程中,光合放氧复合物锰簇是通过一个被称作光组装的过程形成的。结合当前的研究进展,本文详尽地介绍了光合放氧复合物锰簇光组装的动力学模型、与锰簇形成相关的蛋白及锰簇的外围配体、锰与去锰光系统II的结合特性、其它辅助因子对锰簇光组装的影响及锰簇光组装的机理。此外,结合我们的研究结果,对人工合成的锰化合物与去锰光系统II放氧复合物的光组装进行了综述和讨论。本文最后介绍了目前光合放氧复合物锰簇结构及功能研究中存在的一些问题,并对光合放氧复合物锰簇结构及功能研究的应用前景进行了展望。     

Immobilization of Photosynthetic Pigments into Silica-Surfactant Nanocomposite Films

Highly transparent silica-surfactant nanocomposite films containing photosynthetic pigments have been successfully formed through the solubilization of chlorophyll a (Chl a) into surfactant micelles. The UV-vis absorption spectra indicated that a large amount of Chl a were transformed into pheophytin a in the films. These photosynthetic pigments were well dispersed in the surfactant assemblies and their chlorin rings were exposed to the surface of silica layers. Even under an air atmosphere, the photostability of immobilized pigments was largely improved in comparison with that in a homogeneous Chl a solution. Because both Chl a and pheophytin a molecules are effective for the photosensitive charge separation, the present film system is very suitable for heterogeneous immobilizing media for photosynthetic pigments from the viewpoint of in vitro biomimetic devices for solar energy conversion.     

Silyl-substituted 1,3-butadienes for Diels-Alder reaction, ene reaction and allylation reaction

Silyl-substituted 1,3-butadienes are useful building blocks and are readily applied in several types of reactions such as Diels-Alder reaction, ene reaction and allylation. They can also participate in different tandem reactions such as Diels-Alder/allylation, ene/allylation, ene/allylation/Diels-Alder reaction, ene/allylation/ene reaction and ene/allylation/Diels-Alder/allylation reaction. This feature article reviews the synthesis of silyl-substituted 1,3-butadienes, and their applications in the reaction types mentioned above, involving a tandem Diels-Alder/ene/allylation process. This article also introduces some reactions of alkenylsilanes and allylsilanes for comparison and discussion about the tandem reaction. The tandem reactions described in this article are a powerful tool to construct complicated multicyclic compounds with high selectivity and high efficiency.     

An anamolous reaction product in vilsmeier-haack reaction

A Vilsmeier-Haack formylation is reported in which reduction has occurred with the methyl group of the reagent functioning as hydrogen donor.     

高效光催化分解水制氢的人工光合组装体

<正>自组装是组装基元通过非共价键的相互作用自发形成特定结构的过程,是创造新物质和产生新功能的重要手段。自然界光合作用中心的原初反应是由集成在光合膜中的功能分子组装体高效完成。通过分子设计和组装手段构筑人工光合组装体不仅可以从结构和功能上模拟自然界光合作用中心制氢放氧的反应过程,而且能够为设计具有高效光催化分解水功能的人工光合组装体开辟新途径。