2-Phosphoglycolate

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2-Phosphoglycolate
Phosphoglycolat.svg
Names
IUPAC name
2-phosphonatooxyacetate
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.032.789 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • acid:236-084-2
PubChem CID
UNII
  • InChI=1S/C2H5O6P/c3-2(4)1-8-9(5,6)7/h1H2,(H,3,4)(H2,5,6,7)/p-3
    Key: ASCFNMCAHFUBCO-UHFFFAOYSA-K
  • acid:InChI=1S/C2H5O6P/c3-2(4)1-8-9(5,6)7/h1H2,(H,3,4)(H2,5,6,7)
    Key: ASCFNMCAHFUBCO-UHFFFAOYSA-N
  • C(C(=O)[O-])OP(=O)([O-])[O-]
  • acid:C(C(=O)O)OP(=O)(O)O
Properties
C2H2O6P−3
Molar mass 153.007 g·mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Infobox references

2-Phosphoglycolate (chemical formula C2H2O6P3-; also known as phosphoglycolate, 2-PG, or PG) is a natural metabolic product of the oxygenase reaction mediated by the enzyme ribulose 1,5-bisphosphate carboxylase (RuBisCo).

Contents

Photorespiration serves as a salvage pathway that converts 2-PG into non-toxic metabolites. Contrary to the Calvin cycle, this pathway is responsible a net loss of previously fixed carbon. It also serves as sink for ATP and NADH. Photorespiration eng.png
Photorespiration serves as a salvage pathway that converts 2-PG into non-toxic metabolites. Contrary to the Calvin cycle, this pathway is responsible a net loss of previously fixed carbon. It also serves as sink for ATP and NADH.

Synthesis

RuBisCo catalyzes the fixation of atmospheric carbon dioxide in the chloroplasts of plants.[ citation needed ] It uses ribulose 1,5-bisphosphate (RuBP) as substrate and facilitates carboxylation at the C2 carbon via an endiolate intermediate. The two three-carbon products (3-phosphoglycerate) are subsequently fed into the Calvin cycle. Atmospheric oxygen competes with this reaction. In a process called photorespiration RuBisCo can also catalyze addition of atmospheric oxygen to the C2 carbon of RuBP forming a high energy hydroperoxide intermediate that decomposes into 2-phosphoglycolate and 3-phosphoglycerate. [1] Despite a higher energy barrier for the oxygenation reaction compared to carboxylation, photorespiration accounts for up to 25% of RuBisCo turnover in C3 plants. [2]

Biological role

Plants

In plants, 2-phosphoglycolate has a potentially toxic effect as it inhibits a number of metabolic pathways. [3] The activities of important enzymes in the central carbon metabolism of the chloroplast such as triose-phosphate isomerase, phosphofructokinase, or sedoheptulose 1,7-bisphosphate phosphatase show a significant decrease in the presence of 2-PG. Therefore, degradation of 2-PG during photorespiration is important for cellular homeostasis.

Photorespiration is the main way of chloroplasts to rid themselves of 2-PG. [4] However, this pathway comes at a decreased return on investment ratio as 2-PG is transformed to 3-phosphoglycerate in an elaborate salvage pathway at the cost of one equivalent of NADH and ATP, respectively. In addition, this salvage pathway loses ½ equivalent of previously fixed carbon dioxide and releases ½ equivalent of toxic ammonia per molecule of 2-PG. This leads to a net loss of carbon in photorespiration, making it much less efficient than the Calvin cycle.

However, this salvage pathway can also act as a cellular energy sink, preventing the chloroplastidal electron transport chain from over reduction. [4] It is believed that this pathway also plays a role in improving the abiotic stress response of plants.

Bacteria

2-PG is similarly a toxic product in bacteria. Bacteria remove this substance using a glycerate pathway. This shorter pathway branches out from photorespiration after the formation of glyoxylate, proceeding to use glycoxylate carboxylase and tartronic semialdehyde reductase to rejoin at the formation of glycerate. Some Cyanobacteria can use a combination of photorespiration and glycerate pathways. [5]

Transferring the shorter glycerate pathway into plant chloroplasts, combined with stopping chloroplastic export of glycolate, results in higher photosynthetic efficiency. In tobacco, the biomass increases by 13%, not as good a result as a designed pathway. [6]

Animals

Although mainly produced in plants, 2-PG also plays a role in mammalian metabolism, [3] though the source of 2-PG in mammals remains incompletely understood. It is thought that the processing of breaks in the DNA-strand produces small amounts of 2-PG, but other processes may yield 2-PG as well. The phosphatase subunit of bisphosphoglycerate mutase, an enzyme found in red blood cells, shows an increase in activity by up three orders of magnitude in the presence of 2-PG, resulting in an increase of the oxygen affinity of hemoglobin.

Agricultural significance

RuBisCo has been a potential target for bioengineers for agricultural purposes. A decrease in the oxygenation of RuBP may result in a boost in the efficiency of carbon assimilation in crops such as rice or wheat and therefore increase their net biomass production. Attempts have been made to artificially alter the protein structure of RuBisCo to enhance its catalytic turnover rate. Mutations in the L-subunit of the enzyme, for example, have been shown to increase both the catalytic turnover rate and RuBisCos affinity for carbon dioxide [7]

Related Research Articles

Photosynthesis Biological process to convert light into chemical energy

Photosynthesis is a process used by plants and other organisms to convert light energy into chemical energy that, through cellular respiration, can later be released to fuel the organism's activities. Some of this chemical energy is stored in carbohydrate molecules, such as sugars and starches, which are synthesized from carbon dioxide and water – hence the name photosynthesis, from the Greek phōs, "light", and sunthesis, "putting together". In most cases, oxygen is also released as a waste product that stores three times more chemical energy than the carbohydrates. Most plants, algae, and cyanobacteria perform photosynthesis; such organisms are called photoautotrophs. Photosynthesis is largely responsible for producing and maintaining the oxygen content of the Earth's atmosphere, and supplies most of the energy necessary for life on Earth.

RuBisCO Key enzyme of the photosynthesis involved in carbon fixation

Ribulose-1,5-bisphosphate carboxylase-oxygenase, commonly known by the abbreviations RuBisCo, rubisco, RuBPCase, or RuBPco, is an enzyme involved in the first major step of carbon fixation, a process by which atmospheric carbon dioxide is converted by plants and other photosynthetic organisms to energy-rich molecules such as glucose. In chemical terms, it catalyzes the carboxylation of ribulose-1,5-bisphosphate. It is probably the most abundant enzyme on Earth.

C<sub>4</sub> carbon fixation Photosynthetic process in some plants

C4 carbon fixation or the Hatch–Slack pathway is one of three known photosynthetic processes of carbon fixation in plants. It owes the names to the 1960's discovery by Marshall Davidson Hatch and Charles Roger Slack that some plants, when supplied with 14CO2, incorporate the 14C label into four-carbon molecules first.

Photorespiration

Photorespiration (also known as the oxidative photosynthetic carbon cycle or C2 cycle) refers to a process in plant metabolism where the enzyme RuBisCO oxygenates RuBP, wasting some of the energy produced by photosynthesis. The desired reaction is the addition of carbon dioxide to RuBP (carboxylation), a key step in the Calvin–Benson cycle, but approximately 25% of reactions by RuBisCO instead add oxygen to RuBP (oxygenation), creating a product that cannot be used within the Calvin–Benson cycle. This process reduces the efficiency of photosynthesis, potentially reducing photosynthetic output by 25% in C3 plants. Photorespiration involves a complex network of enzyme reactions that exchange metabolites between chloroplasts, leaf peroxisomes and mitochondria.

Ribulose 1,5-bisphosphate Chemical compound

Ribulose 1,5-bisphosphate (RuBP) is an organic substance that is involved in photosynthesis, notably as the principal CO2 acceptor in plants. It is a colourless anion, a double phosphate ester of the ketopentose called ribulose. Salts of RuBP can be isolated, but its crucial biological function happens in solution. RuBP occurs not only in plants but in all domains of life, including Archaea, Bacteria, and Eukarya.

C<sub>3</sub> carbon fixation Most common pathway in photosynthesis

C3 carbon fixation is the most common of three metabolic pathways for carbon fixation in photosynthesis, along with C4 and CAM. This process converts carbon dioxide and ribulose bisphosphate (RuBP, a 5-carbon sugar) into two molecules of 3-phosphoglycerate through the following reaction:

Calvin cycle Light-independent reactions in photosynthesis

The Calvin cycle,light-independent reactions, bio synthetic phase,dark reactions, or photosynthetic carbon reduction (PCR) cycle of photosynthesis are the chemical reactions that convert carbon dioxide and hydrogen-carrier compounds into glucose. The Calvin cycle is present in all photosynthetic eukaryotes and also many photosynthetic bacteria. In plants, these reactions occur in the stroma, the fluid-filled region of a chloroplast outside the thylakoid membranes. These reactions take the products of light-dependent reactions and perform further chemical processes on them. The Calvin cycle uses the chemical energy of ATP and reducing power of NADPH from the light dependent reactions to produce sugars for the plant to use. These substrates are used in a series of reduction-oxidation reactions to produce sugars in a step-wise process; there is no direct reaction that converts several molecules of CO2 to a sugar. There are three phases to the light-independent reactions, collectively called the Calvin cycle: carboxylation, reduction reactions, and ribulose 1,5-bisphosphate (RuBP) regeneration.

Glyceraldehyde 3-phosphate Chemical compound

Glyceraldehyde 3-phosphate, also known as triose phosphate or 3-phosphoglyceraldehyde and abbreviated as G3P, GA3P, GADP, GAP, TP, GALP or PGAL, is the metabolite that occurs as an intermediate in several central pathways of all organisms. With the chemical formula H(O)CCH(OH)CH2OPO32-, this anion is a monophosphate ester of glyceraldehyde.

Methylotrophs are a diverse group of microorganisms that can use reduced one-carbon compounds, such as methanol or methane, as the carbon source for their growth; and multi-carbon compounds that contain no carbon-carbon bonds, such as dimethyl ether and dimethylamine. This group of microorganisms also includes those capable of assimilating reduced one-carbon compounds by way of carbon dioxide using the ribulose bisphosphate pathway. These organisms should not be confused with methanogens which on the contrary produce methane as a by-product from various one-carbon compounds such as carbon dioxide. Some methylotrophs can degrade the greenhouse gas methane, and in this case they are called methanotrophs. The abundance, purity, and low price of methanol compared to commonly used sugars make methylotrophs competent organisms for production of amino acids, vitamins, recombinant proteins, single-cell proteins, co-enzymes and cytochromes.

Carboxysome Bacterial microcompartment containing the enzyme RuBisCo

Carboxysomes are bacterial microcompartments (BMCs) consisting of polyhedral protein shells filled with the enzymes ribulose-1,5-bisphosphate carboxylase/oxygenase (RuBisCO)—the predominant enzyme in carbon fixation and the rate limiting enzyme in the Calvin cycle—and carbonic anhydrase.

3-Phosphoglyceric acid Chemical compound

3-Phosphoglyceric acid (3PG, 3-PGA, or PGA) is the conjugate acid of 3-phosphoglycerate or glycerate 3-phosphate (GP or G3P). This glycerate is a biochemically significant metabolic intermediate in both glycolysis and the Calvin-Benson cycle. The anion is often termed as PGA when referring to the Calvin-Benson cycle. In the Calvin-Benson cycle, 3-phosphoglycerate is typically the product of the spontaneous scission of an unstable 6-carbon intermediate formed upon CO2 fixation. Thus, two equivalents of 3-phosphoglycerate are produced for each molecule of CO2 that is fixed. In glycolysis, 3-phosphoglycerate is an intermediate following the dephosphorylation (reduction) of 1,3-bisphosphoglycerate.

Phosphoenolpyruvate carboxylase Class of enzymes

Phosphoenolpyruvate carboxylase (also known as PEP carboxylase, PEPCase, or PEPC; EC 4.1.1.31, PDB ID: 3ZGE) is an enzyme in the family of carboxy-lyases found in plants and some bacteria that catalyzes the addition of bicarbonate (HCO3) to phosphoenolpyruvate (PEP) to form the four-carbon compound oxaloacetate and inorganic phosphate:

Carboxylation is a chemical reaction in which a carboxylic acid is produced by treating a substrate with carbon dioxide. The opposite reaction is decarboxylation. In chemistry, the term carbonation is sometimes used synonymously with carboxylation, especially when applied to the reaction of carbanionic reagents with CO2. More generally, carbonation usually describes the production of carbonates.

Fructose-bisphosphate aldolase

Fructose-bisphosphate aldolase, often just aldolase, is an enzyme catalyzing a reversible reaction that splits the aldol, fructose 1,6-bisphosphate, into the triose phosphates dihydroxyacetone phosphate (DHAP) and glyceraldehyde 3-phosphate (G3P). Aldolase can also produce DHAP from other (3S,4R)-ketose 1-phosphates such as fructose 1-phosphate and sedoheptulose 1,7-bisphosphate. Gluconeogenesis and the Calvin cycle, which are anabolic pathways, use the reverse reaction. Glycolysis, a catabolic pathway, uses the forward reaction. Aldolase is divided into two classes by mechanism.

Ribose-5-phosphate isomerase

Ribose-5-phosphate isomerase (Rpi) encoded by the RPIA gene is an enzyme that catalyzes the conversion between ribose-5-phosphate (R5P) and ribulose-5-phosphate (Ru5P). It is a member of a larger class of isomerases which catalyze the interconversion of chemical isomers. It plays a vital role in biochemical metabolism in both the pentose phosphate pathway and the Calvin cycle. The systematic name of this enzyme class is D-ribose-5-phosphate aldose-ketose-isomerase.

Phosphoglycolate phosphatase

Phosphoglycolate phosphatase(PGP), also commonly referred to as phosphoglycolate hydrolase, 2-phosphoglycolate phosphatase, P-glycolate phosphatase, and phosphoglycollate phosphatase, is an enzyme responsible for catalyzing the conversion of 2-phosphoglycolate into glycolate and phosphate. First studied and purified within plants, phosphoglycolate phosphatase plays a major role in photorespiratory 2-phosphoglycolate metabolism, an essential pathway for photosynthesis in plants. The occurrence of photorespiration in plants, due to the lack of substrate specificity of rubisco, leads to the formation of 2-phosphoglycolate and 3-phosphogylcerate(PGA). PGA is the normal product of carboxylation and will enter the Calvin cycle. Phosphoglycolate, which is a potent inhibitor of phosphofructokinase and triosephosphate isomerase, must be quickly metabolized and transformed into a useful substrate, and phosphoglycolate phosphatase catalyzes the first step in the regeneration of 3-phosphoglycerate from 2-phosphoglycolate at the expense of energy in the form of ATP.

[Fructose-bisphosphate aldolase]-lysine N-methyltransferase (EC 2.1.1.259) is an enzyme that catalyses the following chemical reaction

The evolution of photosynthesis refers to the origin and subsequent evolution of photosynthesis, the process by which light energy is used to assemble sugars from carbon dioxide and a hydrogen and electron source such as water. The process of photosynthesis was discovered by Jan Ingenhousz, a Dutch-born British physician and scientist, first publishing about it in 1779.

Fractionation of carbon isotopes in oxygenic photosynthesis

Photosynthesis converts carbon dioxide to carbohydrates via several metabolic pathways that provide energy to an organism and preferentially react with certain stable isotopes of carbon. The selective enrichment of one stable isotope over another creates distinct isotopic fractionations that can be measured and correlated among oxygenic phototrophs. The degree of carbon isotope fractionation is influenced by several factors, including the metabolism, anatomy, growth rate, and environmental conditions of the organism. Understanding these variations in carbon fractionation across species is useful for biogeochemical studies, including the reconstruction of paleoecology, plant evolution, and the characterization of food chains.

Kinetic Isotope Effects of RuBisCO

The kinetic isotope effect (KIE) of ribulose-1,5-bisphosphate carboxylase oxygenase (RuBisCO) is the isotopic fractionation associated solely with the step in the Calvin-Benson Cycle where a molecule of carbon dioxide is attached to the 5-carbon sugar ribulose-1,5-bisphosphate (RuBP) to produce two 3-carbon sugars called 3-phosphoglycerate. This chemical reaction is catalyzed by the enzyme RuBisCO, and this enzyme-catalyzed reaction creates the primary kinetic isotope effect of photosynthesis. It is also largely responsible for the isotopic compositions of photosynthetic organisms and the heterotrophs that eat them. Understanding the intrinsic KIE of RuBisCO is of interest to earth scientists, botanists, and ecologists because this isotopic biosignature can be used to reconstruct the evolution of photosynthesis and the rise of oxygen in the geologic record, reconstruct past evolutionary relationships and environmental conditions, and infer plant relationships and productivity in modern environments.

References

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  2. Zelitch, Israel; Schultes, Neil P.; Peterson, Richard B.; Brown, Patrick; Brutnell, Thomas P. (January 2009). "High Glycolate Oxidase Activity Is Required for Survival of Maize in Normal Air". Plant Physiology. 149 (1): 195–204. doi:10.1104/pp.108.128439. ISSN   0032-0889. PMC   2613714 . PMID   18805949.
  3. 1 2 Flügel, Franziska; Timm, Stefan; Arrivault, Stéphanie; Florian, Alexandra; Stitt, Mark; Fernie, Alisdair R.; Bauwe, Hermann (October 2017). "The Photorespiratory Metabolite 2-Phosphoglycolate Regulates Photosynthesis and Starch Accumulation in Arabidopsis". The Plant Cell. 29 (10): 2537–2551. doi:10.1105/tpc.17.00256. ISSN   1040-4651. PMC   5774572 . PMID   28947491.
  4. 1 2 Timm, Stefan; Woitschach, Franziska; Heise, Carolin; Hagemann, Martin; Bauwe, Hermann (2019-12-02). "Faster Removal of 2-Phosphoglycolate through Photorespiration Improves Abiotic Stress Tolerance of Arabidopsis". Plants. 8 (12): 563. doi:10.3390/plants8120563. ISSN   2223-7747. PMC   6963629 . PMID   31810232.
  5. Eisenhut, M; Kahlon, S; Hasse, D; Ewald, R; Lieman-Hurwitz, J; Ogawa, T; Ruth, W; Bauwe, H; Kaplan, A; Hagemann, M (September 2006). "The plant-like C2 glycolate cycle and the bacterial-like glycerate pathway cooperate in phosphoglycolate metabolism in cyanobacteria". Plant physiology. 142 (1): 333–42. doi:10.1104/pp.106.082982. PMC   1557606 . PMID   16877700.
  6. South PF, Cavanagh AP, Liu HW, Ort DR (January 2019). "Synthetic glycolate metabolism pathways stimulate crop growth and productivity in the field". Science. 363 (6422): eaat9077. doi: 10.1126/science.aat9077 . PMC   7745124 . PMID   30606819.
  7. Greene, Dina N.; Whitney, Spencer M.; Matsumura, Ichiro (2007-06-15). "Artificially evolved Synechococcus PCC6301 Rubisco variants exhibit improvements in folding and catalytic efficiency". The Biochemical Journal. 404 (Pt 3): 517–524. doi:10.1042/BJ20070071. ISSN   0264-6021. PMC   1896282 . PMID   17391103.