Mo2C@3D ultrathin macroporous carbon realizing efficient and stable nitrogen fixation
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In this article the affiliation ‘State Key Laboratory of Soil and Sustainable Agriculture, Institute of Soil Science, Chinese Academy of Sciences, Nanjing 210008, China’ for Xinhua Peng was missing. The original article has been corrected.
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Progress is reported for research on the following: (1) magnetically shielded test facility studies; (2) electrochemistry of B10C2H12, B9CH10(-), and preparation of tumor specific boron containing materials for use in cancer therapy; (3) histochemical method for determining lead in living plant tissue; (4) diamond cementing; (5) analysis of solar wind using the washings of lunar fines; and (6) environmental engineering.
The reported analysis implies that the number of molecules of NO produced per joule of discharge varies with input energy. The calculations assume a cylindrical symmetry but the results are consistent with equivalent calculations using spherical symmetry. If NO yield does vary with input energy, extrapolation of laboratory experiments using small sparks is not as straightforward as has previously been assumed. Calculated curves for the yield of NO as a function of discharge energy are presented and are compared with experimental values and other theoretical values.
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Nitrogenases (N 2 ases) and nitrogen fixation-like (NFL) systems play distinct roles in nitrogen, carbon, sulfur, and energy metabolism based on their fundamental differences in structure and metallocofactor identity. As new NFL systems have recently been identified and characterized, striking parallels and differences compared to N 2 ase structure, catalysis, and regulation have emerged. NFL systems use metallocofactors that span from simple [4Fe-4S] clusters to complex clusters akin to FeMo-co, previously only thought to occur in N 2 ase. This review describes the present state of knowledge on the function, structure, catalytic mechanisms, and regulation of NFL systems that perform distinct biological roles across all three domains of life. Recent advancements in N 2 ase spectroscopic techniques for probing metallocofactor structure and electronic states guide current and future work on how each NFL system catalyzes its specific biological reaction(s). Key knowledge gaps and needed areas of research for uncovering the specific metallocofactors and structural motifs that are at the heart of NFL system reaction specificity, along with how these systems are regulated, are discussed.
Atmospheric CO 2 concentration is increasing, largely due to anthropogenic activities. Previous studies of individual free-air CO 2 enrichment (FACE) experimental sites have shown significant impacts of elevated CO 2 (eCO 2 ) on soil microbial communities; however, no common microbial response patterns have yet emerged, challenging our ability to predict ecosystem functioning and sustainability in the future eCO 2 environment. Here we analyzed 66 soil microbial communities from five FACE sites, and showed common microbial response patterns to eCO 2 , especially for key functional genes involved in carbon and nitrogen fixation (e.g., pcc/acc for carbon fixation, nifH for nitrogen fixation), carbon decomposition (e.g., amyA and pulA for labile carbon decomposition, mnp and lcc for recalcitrant carbon decomposition), and greenhouse gas emissions (e.g., mcrA for methane production, norB for nitrous oxide production) across five FACE sites. Also, the relative abundance of those key genes was generally increased and directionally associated with increased biomass, soil carbon decomposition, and soil moisture. In addition, a further literature survey of more disparate FACE experimental sites indicated increased biomass, soil carbon decay, nitrogen fixation, methane and nitrous oxide emissions, plant and soil carbon and nitrogen under eCO 2 . A conceptual framework was developed to link commonly responsive functional genes with ecosystem processes, such as pcc/acc vs. soil carbon storage, amyA/pulA/mnp/lcc vs. soil carbon decomposition, and nifH vs. nitrogen availability, suggesting that such common responses of microbial functional genes may have the potential to predict ecosystem functioning and sustainability in the future eCO 2 environment.
Biological nitrogen fixation, the microbial reduction of atmospheric nitrogen to bioavailable ammonia, represents both a major limitation on biological productivity and a highly desirable engineering target for synthetic biology. However, the engineering of nitrogen fixation requires an integrated understanding of how the gene regulatory dynamics of host diazotrophs respond across sequence-function space of its central catalytic metalloenzyme, nitrogenase. Here, we interrogate this relationship by analyzing the transcriptome of Azotobacter vinelandii engineered with a phylogenetically inferred ancestral nitrogenase protein variant. The engineered strain exhibits reduced cellular nitrogenase activity but recovers wild-type growth rates following an extended lag period. We find that expression of genes within the immediate nitrogen fixation network is resilient to the introduced nitrogenase sequence-level perturbations. Rather the sustained physiological compatibility with the ancestral nitrogenase variant is accompanied by reduced expression of genes that support trace metal and electron resource allocation to nitrogenase. Our results spotlight gene expression changes in cellular processes adjacent to nitrogen fixation as productive engineering considerations to improve compatibility between remodeled nitrogenase proteins and engineered host diazotrophs.
Biological nitrogen fixation, the microbial reduction of atmospheric nitrogen to bioavailable ammonia, represents both a major limitation on biological productivity and a highly desirable engineering target for synthetic biology. However, the engineering of nitrogen fixation requires an integrated understanding of how the gene regulatory dynamics of host diazotrophs respond across sequence-function space of its central catalytic metalloenzyme, nitrogenase. Here, we interrogate this relationship by analyzing the transcriptome of Azotobacter vinelandii engineered with a phylogenetically inferred ancestral nitrogenase protein variant. The engineered strain exhibits reduced cellular nitrogenase activity but recovers wild-type growth rates following an extended lag period. We find that expression of genes within the immediate nitrogen fixation network is resilient to the introduced nitrogenase sequence-level perturbations. Rather the sustained physiological compatibility with the ancestral nitrogenase variant is accompanied by reduced expression of genes that support trace metal and electron resource allocation to nitrogenase. Our results spotlight gene expression changes in cellular processes adjacent to nitrogen fixation as productive engineering considerations to improve compatibility between remodeled nitrogenase proteins and engineered host diazotrophs.
The demand for energy from biofuel production is increasing, prompting concerns about the environmental impact and long-term sustainability of bioenergy cropping systems. These cropping systems will make up much of our future landscapes, and threaten to take the place of food cropping systems. Many life cycle analyses of bioenergy sustainability focus on carbon accrual and budgets, since they want to maximize carbon accrual while producing alternative fuel. Less attention has been given to nitrogen (N) dynamics in these systems. N is the most commonly limiting nutrient for plants, but applying nitrogen fertilizer- as we do for most cropping systems – is harmful to the environment, energetically costly, and produces greenhouse gases. In other words, adding nitrogen by fertilizer bioenergy systems could add to the very problems (climate change) it is trying to address. This is especially true for the areas that are proposed for bioenergy systems: marginal lands. These more degraded lands do not complete with food crops, but do have limited nitrogen. If we are to use these marginal lands for bioenergy, we need to understand the mechanisms regulating nutrient acquisition, and identify ways that bioenergy crops can get nitrogen in sustainable ways. Nutrient acquisition in the soil is performed by microbes in the root zone, or rhizosphere. Microbes can either mineralize nitrogen in the soil (from organic forms) or fix nitrogen from the air, in a process called nitrogen fixation. The goal of our project was thus to understand how the rhizosphere microbiome provides nutrients to bioenergy crops on marginal lands. We focus especially on the process of nitrogen fixation, since it has potential to get “fertilizer for free” that has much less environmental harm. We investigated this goal using sites from the DOE Great Lakes Bioenergy Research Center (GLBRC) in the upper Midwest, and associated lab and ‘omics methods. We group our findings into three major areas. First, we showed that nitrogen fixation, the conversion of N2 gas from the air to ammonium that is usable by plants, is performed in bioenergy soils, and benefits switchgrass crops. While more well-studied in leguminous plants, free-living nitrogen fixation can occur in some systems, and represents a potential opportunity to gain ‘free’ sustainable nitrogen source. We identified the nitrogen fixing bacteria that were most active in providing switchgrass with N, and showed that the drivers of nitrogen fixation occurred at a microscale; it is not well-predicted by bulk variables like soil moisture or plant phenology. Second, we showed that nitrogen fixation is not suppressed by long-term fertilizer. We expected that plentiful nitrogen would reduce the symbiotic relationship between nitrogen fixers and plants, and ‘downregulate’ fixation. We did not find evidence for this, either after long-term fertilizer in the field, or short-term fertilizer in the greenhouse. Finally, we identified the root exudates, carbon compounds that are emitted from the root, that best stimulate nitrogen fixation. We found that carbohydrates were better at stimulating fixation than organic acids. We expected these exudates to be emitted from the plant in periods of high N demand, but we found they are emitted when N is plentiful. This suggests that the stimulation of N fixation by plants is a passive process. Overall, we show that nitrogen fixation has potential to support bioenergy cropping system, and future management could develop ways to maximize it. However, this may not be best achieved via the plant – we found very little evidence of a ‘transactional’ system by which plants are controlling when and where nitrogen fixation is stimulated. It will be better to understand how management practices like planting and fertilizer application affect the microscale soil dynamics, which will determine nitrogen fixation rates.
The availability of fixed nitrogen limits overall agricultural crop production worldwide. The so-called modern “green revolution” catalyzed by the widespread application of nitrogenous fertilizer has propelled global population growth. It has led to imbalances in global biogeochemical nitrogen cycling, resulting in a “nitrogen problem” that is growing at a similar trajectory to the “carbon problem”. As a result of the increasing imbalances in nitrogen cycling and additional environmental problems such as soil acidification, there is renewed and increasing interest in increasing the contributions of biological nitrogen fixation to reduce the inputs of nitrogenous fertilizers in agriculture. Interestingly, biological nitrogen fixation, or life’s ability to convert atmospheric dinitrogen to ammonia, is restricted to microbial life and not associated with any known eukaryotes. It is not clear why plants never evolved the ability to fix nitrogen and rather form associations with nitrogen-fixing microorganisms. Perhaps it is because of the large energy demand of the process, the oxygen sensitivity of the enzymatic apparatus, or simply failure to encounter the appropriate selective pressure. Whatever the reason, it is clear that this ability of crop plants, especially cereals, would transform modern agriculture once again. Successfully engineering plants will require creating an oxygen-free niche that can supply ample energy in a tightly regulated manner to minimize energy waste and ensure the ammonia produced is assimilated. Nitrogen-fixing aerobic bacteria can perhaps provide a blueprint for engineering nitrogen-fixing plants. This short review discusses the key features of robust nitrogen fixation in the model nitrogen-fixing aerobe, gamma proteobacteria Azotobacter vinelandii, in the context of the basic requirements for engineering nitrogen-fixing plants.
Biological nitrogen fixation is the process by which certain bacteria and archaea use the enzyme nitrogenase to reduce atmospheric nitrogen into bioavailable ammonium. Engineering non‐nitrogen‐fixing organisms, like plants, to use nitrogenase could reduce dependency on synthetic fertilizer and mitigate the environmental impacts of industrial fertilizer production. However, nitrogenase activity requires delivery of reducing power by small electron carrying proteins known as ferredoxins and flavodoxins, and successfully engineering nitrogenase into new systems will require a mechanistic understanding of electron delivery by these proteins. Most organisms often have multiple ferredoxins, raising the question of which ferredoxin can support nitrogenase activity. The purpose of this study is to gain insight into how we can predict which ferredoxin is compatible with the Fe protein, the component of nitrogenase that interacts with ferredoxin or flavodoxin. Our in silico protein–protein docking simulations reveal that most ferredoxins and flavodoxins involved in nitrogen fixation have the shortest distance (≤10 Å) between their redox cofactor and the [4Fe‐4S] cluster of the Fe protein. We found shorter cofactor distance contributes to faster intermolecular electron tunneling rates. Bacterial ferredoxins that play a role in nitrogen fixation also exhibit more complementary interactions with the Fe protein than bacterial and plant ferredoxins not involved in this process. Heterologous expression of a set of ferredoxins from both nitrogen‐fixing and non‐nitrogen‐fixing bacteria in the diazotroph Rhodopseudomonas palustris supports our model‐derived prediction that shorter distances between the electron‐carrying cofactors favor nitrogenase compatibility. These findings offer a framework to predict and potentially enhance ferredoxin–nitrogenase compatibility, which will help to improve our ability to engineer nitrogen fixation into non‐nitrogen‐fixing organisms like plants.
Photocatalytic nitrogen fixation has the potential to provide a greener route for producing nitrogen-based fertilizers under ambient conditions. Computational screening is a promising route to discover new materials for the nitrogen fixation process, but requires identifying “descriptors” that can be efficiently computed. In this work, we argue that selectivity toward the adsorption of molecular nitrogen and oxygen can act as a key descriptor. A catalyst that can selectively adsorb nitrogen and resist poisoning of oxygen and other molecules present in air has the potential to facilitate the nitrogen fixation process under ambient conditions. Here we provide a framework for active site screening based on multifidelity density functional theory (DFT) calculations for a range of metal oxides, oxyborides, and oxyphosphides. The screening methodology consists of initial low-fidelity fixed geometry calculations and a second screening in which more expensive geometry optimizations were performed. The approach identifies promising active sites on several TiO 2 polymorph surfaces and a VBO 4 surface, and the full nitrogen reduction pathway is studied with the BEEF-vdW and HSE06 functionals on two active sites. The findings suggest that metastable TiO 2 polymorphs may play a role in photocatalytic nitrogen fixation, and that VBO 4 may be an interesting material for further studies.
Recent detection of nitrate on Mars indicates that nitrogen fixation processes occurred in early martian history. Data collected by the Sample Analysis at Mars (SAM) instrument on the Curiosity Rover can be integrated with Mars analog work in order to better understand the fixation and mobility of nitrogen on Mars, and thus its availability to putative biology. In particular, the relationship between nitrate and other soluble salts may help reveal the timing of nitrogen fixation and post-depositional behavior of nitrate on Mars. In addition, in situ measurements of nitrogen abundance and isotopic composition may be used to model atmospheric conditions on early Mars.
Legume crops establish beneficial associations with rhizobial bacteria that perform biological nitrogen fixation, providing nitrogen to plants without the economic and greenhouse gas emission costs of chemical nitrogen inputs. Here, we examine the influence of three environmental factors that vary in agricultural fields on strain relative fitness in nodules.