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Metal (Mo, W, Ti) Carbide Catalysts: Synthesis and Application as Alternative Catalysts for Dry Reforming of Hydrocarbons-A Review.
Czaplicka, N, Rogala, A, Wysocka, I
International journal of molecular sciences. 2021;(22)
Abstract
Dry reforming of hydrocarbons (DRH) is a pro-environmental method for syngas production. It owes its pro-environmental character to the use of carbon dioxide, which is one of the main greenhouse gases. Currently used nickel catalysts on oxide supports suffer from rapid deactivation due to sintering of active metal particles or the deposition of carbon deposits blocking the flow of gases through the reaction tube. In this view, new alternative catalysts are highly sought after. Transition metal carbides (TMCs) can potentially replace traditional nickel catalysts due to their stability and activity in DR processes. The catalytic activity of carbides results from the synthesis-dependent structural properties of carbides. In this respect, this review presents the most important methods of titanium, molybdenum, and tungsten carbide synthesis and the influence of their properties on activity in catalyzing the reaction of methane with carbon dioxide.
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Synthetic Enzyme-Catalyzed CO2 Fixation Reactions.
Aleku, GA, Roberts, GW, Titchiner, GR, Leys, D
ChemSusChem. 2021;(8):1781-1804
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Abstract
In recent years, (de)carboxylases that catalyze reversible (de)carboxylation have been targeted for application as carboxylation catalysts. This has led to the development of proof-of-concept (bio)synthetic CO2 fixation routes for chemical production. However, further progress towards industrial application has been hampered by the thermodynamic constraint that accompanies fixing CO2 to organic molecules. In this Review, biocatalytic carboxylation methods are discussed with emphases on the diverse strategies devised to alleviate the inherent thermodynamic constraints and their application in synthetic CO2 -fixation cascades.
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Novel technologies for emission reduction complement conservation agriculture to achieve negative emissions from row-crop production.
Northrup, DL, Basso, B, Wang, MQ, Morgan, CLS, Benfey, PN
Proceedings of the National Academy of Sciences of the United States of America. 2021;(28)
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Plants remove carbon dioxide from the atmosphere through photosynthesis. Because agriculture's productivity is based on this process, a combination of technologies to reduce emissions and enhance soil carbon storage can allow this sector to achieve net negative emissions while maintaining high productivity. Unfortunately, current row-crop agricultural practice generates about 5% of greenhouse gas emissions in the United States and European Union. To reduce these emissions, significant effort has been focused on changing farm management practices to maximize soil carbon. In contrast, the potential to reduce emissions has largely been neglected. Through a combination of innovations in digital agriculture, crop and microbial genetics, and electrification, we estimate that a 71% (1,744 kg CO2e/ha) reduction in greenhouse gas emissions from row crop agriculture is possible within the next 15 y. Importantly, emission reduction can lower the barrier to broad adoption by proceeding through multiple stages with meaningful improvements that gradually facilitate the transition to net negative practices. Emerging voluntary and regulatory ecosystems services markets will incentivize progress along this transition pathway and guide public and private investments toward technology development. In the difficult quest for net negative emissions, all tools, including emission reduction and soil carbon storage, must be developed to allow agriculture to maintain its critical societal function of provisioning society while, at the same time, generating environmental benefits.
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Natural genetic variation in photosynthesis: an untapped resource to increase crop yield potential?
Faralli, M, Lawson, T
The Plant journal : for cell and molecular biology. 2020;(3):518-528
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Raising crop yield potential is a major goal to ensure food security for the growing global population. Photosynthesis is the primary determinant of crop productivity and any gain in photosynthetic CO2 assimilation per unit of leaf area (A) has the potential to increase yield. Significant intraspecific variation in A is known to exist in various autotrophic organs that represent an unexploited target for crop improvement. However, the large number of factors that influence photosynthetic rates often makes it difficult to measure or estimate A under dynamic field conditions (i.e. fluctuating light intensities or temperatures). This complexity often results in photosynthetic capacity, rather than realized photosynthetic rates being used to assess natural variation in photosynthesis. Here we review the work on natural variation in A, the different factors determining A and their interaction in yield formation. A series of drawbacks and perspectives are presented for the most common analyses generally used to estimate A. The different yield components and their determination based on different photosynthetic organs are discussed with a major focus on potential exploitation of various traits for crop improvement. To conclude, an example of different possibilities to increase yield in wheat through enhancing A is illustrated.
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Comparing Molecular Mechanisms in Solar NH3 Production and Relations with CO2 Reduction.
Mallamace, D, Papanikolaou, G, Perathoner, S, Centi, G, Lanzafame, P
International journal of molecular sciences. 2020;(1)
Abstract
Molecular mechanisms for N2 fixation (solar NH3) and CO2 conversion to C2+ products in enzymatic conversion (nitrogenase), electrocatalysis, metal complexes and plasma catalysis are analyzed and compared. It is evidenced that differently from what is present in thermal and plasma catalysis, the electrocatalytic path requires not only the direct coordination and hydrogenation of undissociated N2 molecules, but it is necessary to realize features present in the nitrogenase mechanism. There is the need for (i) a multi-electron and -proton simultaneous transfer, not as sequential steps, (ii) forming bridging metal hydride species, (iii) generating intermediates stabilized by bridging multiple metal atoms and (iv) the capability of the same sites to be effective both in N2 fixation and in COx reduction to C2+ products. Only iron oxide/hydroxide stabilized at defective sites of nanocarbons was found to have these features. This comparison of the molecular mechanisms in solar NH3 production and CO2 reduction is proposed to be a source of inspiration to develop the next generation electrocatalysts to address the challenging transition to future sustainable energy and chemistry beyond fossil fuels.
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Photorespiration in the context of Rubisco biochemistry, CO2 diffusion and metabolism.
Busch, FA
The Plant journal : for cell and molecular biology. 2020;(4):919-939
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Photorespiratory metabolism is essential for plants to maintain functional photosynthesis in an oxygen-containing environment. Because the oxygenation reaction of Rubisco is followed by the loss of previously fixed carbon, photorespiration is often considered a wasteful process and considerable efforts are aimed at minimizing the negative impact of photorespiration on the plant's carbon uptake. However, the photorespiratory pathway has also many positive aspects, as it is well integrated within other metabolic processes, such as nitrogen assimilation and C1 metabolism, and it is important for maintaining the redox balance of the plant. The overall effect of photorespiratory carbon loss on the net CO2 fixation of the plant is also strongly influenced by the physiology of the leaf related to CO2 diffusion. This review outlines the distinction between Rubisco oxygenation and photorespiratory CO2 release as a basis to evaluate the costs and benefits of photorespiration.
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Constraining estimates of terrestrial carbon uptake: new opportunities using long-term satellite observations and data assimilation.
Smith, WK, Fox, AM, MacBean, N, Moore, DJP, Parazoo, NC
The New phytologist. 2020;(1):105-112
Abstract
The response of terrestrial carbon uptake to increasing atmospheric [CO2 ], that is the CO2 fertilization effect (CFE), remains a key area of uncertainty in carbon cycle science. Here we provide a perspective on how satellite observations could be better used to understand and constrain CFE. We then highlight data assimilation (DA) as an effective way to reconcile different satellite datasets and systematically constrain carbon uptake trends in Earth System Models. As a proof-of-concept, we show that joint DA of multiple independent satellite datasets reduced model ensemble error by better constraining unobservable processes and variables, including those directly impacted by CFE. DA of multiple satellite datasets offers a powerful technique that could improve understanding of CFE and enable more accurate forecasts of terrestrial carbon uptake.
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Characterization of Carbonic Anhydrase In Vivo Using Magnetic Resonance Spectroscopy.
Tomar, JS, Shen, J
International journal of molecular sciences. 2020;(7)
Abstract
Carbonic anhydrase is a ubiquitous metalloenzyme that catalyzes the reversible interconversion of CO2/HCO3-. Equilibrium of these species is maintained by the action of carbonic anhydrase. Recent advances in magnetic resonance spectroscopy have allowed, for the first time, in vivo characterization of carbonic anhydrase in the human brain. In this article, we review the theories and techniques of in vivo 13C magnetization (saturation) transfer magnetic resonance spectroscopy as they are applied to measuring the rate of exchange between CO2 and HCO3- catalyzed by carbonic anhydrase. Inhibitors of carbonic anhydrase have a wide range of therapeutic applications. Role of carbonic anhydrases and their inhibitors in many diseases are also reviewed to illustrate future applications of in vivo carbonic anhydrase assessment by magnetic resonance spectroscopy.
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Exploring the Relationship between Crassulacean Acid Metabolism (CAM) and Mineral Nutrition with a Special Focus on Nitrogen.
Pereira, PN, Cushman, JC
International journal of molecular sciences. 2019;(18)
Abstract
Crassulacean acid metabolism (CAM) is characterized by nocturnal CO2 uptake and concentration, reduced photorespiration, and increased water-use efficiency (WUE) when compared to C3 and C4 plants. Plants can perform different types of CAM and the magnitude and duration of CAM expression can change based upon several abiotic conditions, including nutrient availability. Here, we summarize the abiotic factors that are associated with an increase in CAM expression with an emphasis on the relationship between CAM photosynthesis and nutrient availability, with particular focus on nitrogen, phosphorus, potassium, and calcium. Additionally, we examine nitrogen uptake and assimilation as this macronutrient has received the greatest amount of attention in studies using CAM species. We also discuss the preference of CAM species for different organic and inorganic sources of nitrogen, including nitrate, ammonium, glutamine, and urea. Lastly, we make recommendations for future research areas to better understand the relationship between macronutrients and CAM and how their interaction might improve nutrient and water-use efficiency in order to increase the growth and yield of CAM plants, especially CAM crops that may become increasingly important as global climate change continues.
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Net photosynthetic CO2 assimilation: more than just CO2 and O2 reduction cycles.
Tcherkez, G, Limami, AM
The New phytologist. 2019;(2):520-529
Abstract
Net photosynthetic assimilation in C3 plants is mostly viewed as a simple balance between CO2 fixation by Rubisco-catalyzed carboxylation and CO2 production by photorespiration (and to a lower extent, by day respiration) that can be easily manipulated during gas exchange experiments using the CO2 : O2 ratio of the environment. However, it now becomes clear that it is not so simple, because the photosynthetic response to gaseous conditions involves 'ancillary' metabolisms, even in the short-term. That is, carbon and nitrogen utilization by pathways other than the Calvin cycle and the photorespiratory cycle, as well as rapid signaling events, can influence the observed rate of net photosynthesis. The potential impact of such ancillary metabolisms is assessed as well as how it must be taken into account to avoid misinterpretation of photosynthetic CO2 response curves or low O2 effects in C3 leaves.