Stimulated and co-operative electron transfer in energy conversion and catalysis.

A new mechanism of electron transfer, stimulated electron transfer, is postulated, in which an electronic feedback is drastically increasing both the rate of electron transfer and the propagation of free energy along electron transferring molecular pathways. In principle, the idea of pushing a system far from equilibrium to achieve a high reaction rate and co-operative phenomena is applied to molecular electron transfer. The effect is calculated from a semiclassical kinetic model of a chain redox reaction with autocatalytic feedback on individual rate constants, where the steps have subsequently been minimized to obtain a continuous electron transfer pathway with electronic feedback. The influence of inhomogeneities and asymmetries in the electron transfer path and of vectorial components (electrical field, gradient of redox potential) are discussed as well as the acceleration of individual and multiple electron transfer as a function of feedback. Examples of autocatalytic feedback are provided including mechanisms involving electron transfer proteins and multi-centre electron transfer catalysts. Such a phenomenon can be described for molecular and interfacial electron transfer in analogy to stimulated and coherent light emission. The results suggest that autocatalytic or stimulated electron transfer may be a key to the understanding of efficient electron transfer and co-operative multi-electron transfer catalysis in biology and a challenge for fuel production mechanisms in artificial photosynthesis and fuel cycles.     

The three-dimensional structures of bacterial reaction centers

This review presents a broad overview of the research that enabled the structure determination of the bacterial reaction centers from Blastochloris viridis and Rhodobacter sphaeroides, with a focus on the contributions from Duysens, Clayton, and Feher. Early experiments performed in the laboratory of Duysens and others demonstrated the utility of spectroscopic techniques and the presence of photosynthetic complexes in both oxygenic and anoxygenic photosynthesis. The laboratories of Clayton and Feher led efforts to isolate and characterize the bacterial reaction centers. The availability of well-characterized preparations of pure and stable reaction centers allowed the crystallization and subsequent determination of the structures using X-ray diffraction. The three-dimensional structures of reaction centers revealed an overall arrangement of two symmetrical branches of cofactors surrounded by transmembrane helices from the L and M subunits, which also are related by the same twofold symmetry axis. The structure has served as a framework to address several issues concerning bacterial photosynthesis, including the directionality of electron transfer, the properties of the reaction center-cytochrome c ₂ complex, and the coupling of proton and electron transfer. Together, these research efforts laid the foundation for ongoing efforts to address an outstanding question in oxygenic photosynthesis, namely the molecular mechanism of water oxidation.     

Solar‐to‐Hydrogen Energy Conversion Based on Water Splitting

Artificial photosynthesis provides a blueprint to harvest solar energy to sustain the future energy demands. Solar‐driven water splitting, converting solar energy into hydrogen energy, is the prototype of photosynthesis. Various systems have been designed and evaluated to understand the reaction pathways and/or to meet the requirements of potential applications. In solar‐to‐hydrogen conversion, electrocatalytic hydrogen and oxygen evolution reactions are key research areas that are meaningful both theoretically and practically. To utilize hydrogen energy, fuel cell technology has been extensively investigated because of its high efficiency in releasing chemical energy. In this review, general concepts of the photosynthesis in green plants are discussed, different strategies for the light‐driven water splitting proposed in laboratories are introduced, the progress of electrocatalytic hydrogen and oxygen evolution reactions are reviewed, and finally, the reactions in hydrogen fuel cells are briefly discussed. Overall, the mass and energy circulation in the solar‐hydrogen‐electricity circle are delineated. The authors conclude that attention from scientists and engineers of relevant research areas is still highly needed to eliminate the wide disparity between the aspirations and realities of artificial photosynthesis.     

光合作用研究进展:从分子机理到绿色革命

根据国际科学期刊Nature,Science和PhotosynthesisResearch等近年发表的60多篇文献评论了过去5年来光合作用研究领域的研究进展.这篇评论由光合机构的精细结构与光合作用的反应机理、光合作用的调节机制与环境胁迫和光合机理知识的应用与绿色革命三部分组成.第一部分包括天线和反应中心的结构、放氧机理和ATP合成的分子机理;第二部分涉及二磷酸核酮糖羧化酶/加氧酶,光抑制,氧化还原调节和光合作用的高温抑制;第三部分讨论新绿色革命的特点和艰巨性,指出新绿色革命的中心问题是作物光合效率的改善,锐利武器是基因工程,新绿色革命的成功有赖于对光合作用的深入理解和分子生物学家、植物生理学家、生物化学家与农学家们的协同努力.     

Metal‐Free Artificial Photosynthesis of Carbon Monoxide Using N‐Doped ZnTe Nanorod Photocathode Decorated with N‐Doped Carbon Electrocatalyst Layer

An artificial photosynthesis system based on N‐doped ZnTe nanorods decorated with an N‐doped carbon electrocatalyst layer is fabricated via an all‐solution process for the selective conversion of CO₂ to CO. Substitutional N‐doping into the ZnTe lattice decreases the bandgap slightly and improves the charge transfer characteristics, leading to enhanced photoelectrochemical activity. Remarkable N‐doping effects are also demonstrated by the N‐doped carbon layer that promotes selective CO₂‐to‐CO conversion instead of undesired water‐to‐H₂ reduction by providing active sites for CO₂ adsorption and activation, even in the absence of metallic redox centers. The photocathode shows promising performance in photocurrent generation (?1.21 mA cm^?2 at ?0.11 V_RHE), CO selectivity (dominant CO production of ≈72%), minor H₂ reduction (≈20%), and stability (corrosion suppression). The metal‐free electrocatalyst/photocatalyst combination prepared via a cost‐effective solution process exhibits high performance due to synergistic effects between them, and thus may find application in practical solar fuel production.     

Towards artificial photosynthesis: ruthenium-manganese chemistry mimicking photosystem II reactions

The reaction center Photosystem II is a key component of the most successful solar energy converting machinery on earth: the oxygenic photosynthesis. Photosystem II uses light to drive the reduction of plastoquinone and the oxidation of water. Water-oxidation is catalyzed by a manganese cluster and gives the organism an abundant source of electrons. The principles of photosynthesis have inspired chemists to mimic these reactions in artificial molecular assemblies. Synthetic light-harvesting antennae and light-induced charge separation systems have been demonstrated by several groups. More recently, there has been an increasing effort to mimic Photosystem II by coupling light-driven charge separation to water oxidation, catalyzed by synthetic manganese complexes.     

Challenges and opportunities for photochemists on the verge of solar energy conversion.

Has photochemistry missed the boat on solar energy conversion? Certainly not, but it is time to reach out and make a difference if we do not want to have to choose between feeding our families or our thirst for fuel. Compared to other initiatives, such as biofuels or nuclear fusion, direct conversion of solar energy into electricity or fuels is lagging behind in terms of funding, and this is slowing progress on overcoming critical bottlenecks. This perspective outlines some of the key fundamental issues in solar energy conversion based on organic photovoltaic devices or artificial photosynthesis where being a photochemist can make a difference.     

PHOTOSYNTHETIC AND GROWTH RESPONSES TO SALINITY IN A MARINE ISOLATE OF NANNOCHLORIS BACILLARIS (CHLOROPHYCEAE)1

A marine unicellular alga, Nannochloris bacillaris Naumann, was studied with respect to growth, viability and photosynthesis during the steady-state and also subsequent to changes in the concentration of artificial seawater medium. Cells grew exponentially over the range of 2% to 300% artificial seawater, but more rapidly at lower salinities. In contrast to growth, photosynthesis as measured by both oxygen evolution and bicarbonate photoassimilation was not obviously inhibited for cells adapted within the range of 7% to 200% artificial seawater. In 300% artificial seawater, photosynthesis, especially bicarbonate photoassimilation, was inhibited. Osmotic shocks caused by transferring cells from 200% to 7% artificial seawater had little if any effect on growth, viability or photosynthesis. However, equal shocks in the upward direction (from 7% to 200% artificial seawater) caused long lag phases in growth, totally inhibited photosynthesis and very often led to cell death. Intermediate upward shocks were less deleterious, but did result in lags in growth.     

Thirty years of fun with antenna pigment-proteins and photochemical reaction centers: A tribute to the people who have influenced my career

The author summarizes the research contributions to photosynthesis made by him, his graduate and postdoctoral students, visiting scientists and by his collaboration with other photosynthesis workers during 1964–1994. The development of isolation procedures and biochemical/biophysical characterization of antenna pigment-proteins and photochemical reaction centers are described together with the author's education and experiences as a scientific researcher. Some anecdotes hopefully add insight into what it was like to be in this area of science during the period.     

Ethnobotany of pre-altiplanic community in the Andes of northern Chile

The perception of the surrounding environment and use of the flora by the inhabitants of Toconce, a Pre-Altiplanic community in the Andes of northern Chile, were investigated. Six ecological units, which are given the local names of Pampa, Tolar, Medano, Pajonal, Hoyada, and Paniso, are recognized by the people of Toconce on the basis of their different dominant plants, geomorphology and microclimate. These units are in turn integrated into 3 units of landscape utilization: Cerro, Campo and Chacra. The latter is an artificial unit, corresponding to the man-made terraces located on the steep slopes of the Andean canyons. The Campo is a pastoral area, mainly for llamas. The Cerro, situated at higher elevation, has ritual as well as economic importance. This altitudinal sector is the place for the gathering of llareta, the most valuable vegetal fuel in Toconce. Seven categories of plant use are defined: forage, medicinal, food, fuel, crafts, ritual and construction. The inhabitants of Toconce have maximized the use of the plant resources in each altitudinal level. This long-lasting cultural pattern is being gradually modified due to the influence of industrial development and growth of the neighboring urban centers.     

Photosynthesis research: advances through molecular biology – the beginnings, 1975–1980s and on...

Restriction endonuclease recognition sites and genes for rRNAs were first mapped on chloroplast chromosomes in 1975–1976. This marked the beginning of the application of molecular biology tools to photosynthesis research. In the first phase, knowledge about proteins involved in photosynthesis was used to identify plastid and nuclear genes encoding these proteins on cloned segments of DNA. Soon afterwards the DNA sequences of the cloned genes revealed the full primary sequences of the proteins. Knowledge of the primary amino acid sequences provided deeper understanding of the functioning of the protein and interactions among proteins of the photosynthetic apparatus. Later, as chloroplast DNA sequencing proceeded, genes were discovered that encoded proteins that had not been known to be part of the photosynthetic apparatus. This more complete knowledge of the composition of reaction centers and of the primary amino acid sequences of individual proteins comprising the reaction centers opened the way to determining the three-dimensional structures of reaction centers. At present, the availability of cloned genes, knowledge of the gene sequences and systems developed to genetically manipulate photosynthetic organisms is permitting experimental inquiries to be made into crucial details of the photosynthetic process. This revised version was published online in August 2006 with corrections to the Cover Date.     

Artificial leaf aids analysis of chlorophyll fluorescence and P700 absorbance in studies involving microalgae

Measuring chlorophyll fluorescence and P700 absorbance has been widely used to study photosynthesis in both terrestrial plants and algae. However, in order to apply these measurement techniques to study microalgae, a concentrated suspension of algae, which is usually prepared by centrifugation, is required. In this study, instead of using centrifugation, we concentrated microalgae on a nitrocellulose membrane using filtration to create an ‘artificial leaf’ before analysis. Overall, we were able to generate values of the appropriate photosynthetic parameters that were comparable to those obtained when chlorophyll fluorescence and P700 absorbance were measured following centrifugation. There were no statistically significant differences (P > 0.05) between the artificial leaf method and the traditional cuvette method for determining chlorophyll fluorescence or P700 absorbance at appropriate chlorophyll concentrations. We were also able to reduce background noise by using a filter membrane as a carrier. Therefore, an artificial leaf has the potential to be a valuable tool for phycologists interested in studying microalgal photosynthesis by enabling them to eliminate tedious centrifugation steps. In addition, fluorometers commonly used for studying the leaves of higher plants will also be suitable for studying microalgae.     

A quest for the artificial leaf

It has been estimated that the energy captured in one hour of sunlight that reaches our planet is equivalent to annual energy production by human population globally. To efficiently capture the practically inexhaustible solar energy and convert it into high energy density solar fuels provides an attractive ‘green’ alternative to running our present day economies on rapidly depleting fossil fuels, especially in the context of ever growing global energy demand. Natural photosynthesis represents one of the most fundamental processes that sustain life on Earth. It provides nearly all the oxygen we breathe, the food we consume and fossil fuels that we so much depend on. Imitating the reactions that occur at the early stages of photosynthesis represents the main challenge in the quest for construction of an efficient, robust, self-renewing and cost-effective ‘artificial leaf’. In this review we summarize the main molecular features of the natural solar energy converters, photosystem I and photosystem II, that allow them to operate at high quantum efficiencies, and thus inspire the smart matrix design of the artificial solar-to-fuel devices. We also discuss the main challenges that face the field and overview selected recent technological advances that have tremendously accelerated the race for a fully operational artificial leaf that could serve as a viable alternative to fossil fuels for energy production.     

Towards spin torch experiments and artificial reaction centers

Harvesting solar energy for human use has long been a cherished dream of scientists. Especially when unprecedented potentials of biological systems are explored, they could shift the paradigm in the field of development of bio-electronic devices. Hence artificial photosynthetic reaction centers can be potential ‘photovoltaic cells at molecular dimensions’. Understanding the chemical environment, structure and dynamics plays an important role towards the effort of achieving an ‘artificial reaction center’. Let us see how S. Karthick Babu, an EMBO student describes how ‘spin torch’ experiments are designed to chase this dream.     

同源建模在纤维素酶分子改造中的应用

同源建模技术(homology modeling)给蛋白质的研究带来了新的希望,在理论上解决了结构预测和功能分析以及蛋白质工程实施方面所面临的难题.纤维素酶(cellulase)是能水解纤维素生成纤维二糖和葡萄糖的一组酶的总称.对纤维素酶的研究目前已经发展到结构功能分析、理性设计等方面.由于实验方法不能胜任全部纤维素酶结构的测定工作,故以计算机为依托的同源建模技术便发挥着重要作用,它在纤维素酶分子改造中的应用主要有:家族同源分析、研究功能氨基酸的作用机理、基于分子结构的理性设计、预测突变体结构和新功能等.随着同源建模技术自身的不断完善,以及分子对接、分子动力学模拟等技术的发展,计算机模拟技术将在酶分子的改造过程中显示出巨大的生命力.     

Molecular Design of Single‐Atom Catalysts for Oxygen Reduction Reaction

Fuel cells are highly attractive for direct chemical‐to‐electrical energy conversion and represent the ultimate mobile power supply solution. However, presently, fuel cells are limited by the sluggish kinetics of the cathodic oxygen reduction reaction (ORR), which requires the use of Pt as a catalyst, thus significantly increasing the overall cost of the cells. Recently, nonprecious metal single‐atom catalysts (SACs) with high ORR activity under both acidic and alkaline conditions have been recognized as promising cost‐effective alternatives to replace Pt in fuel cells. Considerable efforts have been devoted to further improving the ORR activity of SACs, including tailoring the coordination structure of the metal centers, enriching the concentration of the metal centers, and engineering the electronic structure and porosity of the substrate. Herein, a brief introduction to fuel cells and fundamentals of the ORR parameters of SACs and the origin of their high activity is provided, followed by a detailed review of the recently developed strategies used to optimize the ORR activity of SACs in both rotating disk electrode and membrane electrode assembly tests. Remarks and perspectives on the remaining challenges and future directions of SACs for the development of commercial fuel cells are also presented.     

冷冻电镜技术在分子植物学研究中的应用

植物体的各项生理活动依赖于分子水平上多种植物蛋白质/蛋白质复合体的相互作用和动态变化,了解这些蛋白质/蛋白质复合体的结构和功能对于研究相关植物生理活动的分子机理至关重要.得益于最近的技术进步——包括直接电子探测器的发展和先进的图像处理算法,冷冻电镜技术已经逐步发展成为研究蛋白质/蛋白质复合体的重要技术手段,这也为深入理...     

Picosecond fluorometry in primary events of photosynthesis.

Many laboratories in different countries are involved in the study of the mechanism of conversion of light energy into chemical energy, namely photosynthesis. As is evident from the literature, the initial phases of photosynthesis, which determine the character of this process, proceed at time intervals of 10(-8) and 10(-13) s. They are associated with absorption of light quanta and energy transfer from the molecules of light-harvesting antenna (LHA) chlorophyll and accesory pigments to the reaction centers (RC), where the key reaction of photosynthesis occurs: photo-induced charge separation. Evidently it is of importance to study experimentally the process that occurs within the 10(-8) -10(-13)s time domain.     

Flight and dispersal of periodical cicadas

Summary Periodical cicadas (Magicicada spp.) rarely flew distances greater than 50 m across an open field or along a forest edge. Most cicadas caught after flying 50 m or more were females and all of these females had mated. Flights were most common when adults were 2 to 3 weeks old. Among insects in general, most dispersing individuals are barely post-teneral or extremely young. Cicadas are discussed as an exception to this generality. Both sexes of cicadas are attracted by the male song to chorusing centers for mating (Alexander and Moore 1958). Trees which were chorusing centers had more eggnests than those which were not, suggesting a lack of postmating dispersal from the chorusing trees.