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1. Dissolved organic phosphorus bond-class utilization by Synechococcus

   https://doi.org/10.1093/femsec/fiae099  

   Waggoner, Emily_M; Djaoudi, Kahina; Diaz, Julia_M; Duhamel, Solange (July 2024, FEMS Microbiology Ecology)

   Abstract Dissolved organic phosphorus (DOP) contains compounds with phosphoester, phosphoanhydride, and phosphorus–carbon bonds. While DOP holds significant nutritional value for marine microorganisms, the bioavailability of each bond-class to the widespread cyanobacterium Synechococcus remains largely unknown. This study evaluates bond-class specific DOP utilization by Synechococcus strains from open and coastal oceans. Both strains exhibited comparable growth rates when provided phosphate, a phosphoanhydride [3-polyphosphate and 45-polyphosphate], or a DOP compound with both phosphoanhydride and phosphoester bonds (adenosine 5′-triphosphate). Growth rates on phosphoesters [glucose-6-phosphate, adenosine 5′-monophosphate, bis(4-methylumbelliferyl) phosphate] were variable, and neither strain grew on selected phosphorus–carbon compounds. Both strains hydrolyzed 3-polyphosphate, then adenosine 5′-triphosphate, and lastly adenosine 5′-monophosphate, exhibiting preferential enzymatic hydrolysis of phosphoanhydride bonds. The strains’ exoproteomes contained phosphorus hydrolases, which combined with enhanced cell-free hydrolysis of 3-polyphosphate and adenosine 5′-triphosphate under phosphate deficiency, suggests active mineralization of phosphoanhydride bonds by these exoproteins. Synechococcus alkaline phosphatases presented broad substrate specificities, including activity toward the phosphoanhydride 3-polyphosphate, with varying affinities between strains. Collectively, these findings underscore the potentially significant role of compounds with phosphoanhydride bonds in Synechococcus phosphorus nutrition and highlight varied growth and enzymatic responses to molecular diversity within DOP bond-classes, thereby expanding our understanding of microbially mediated DOP cycling in marine ecosystems. 

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2. P–P Coupling with and without Terminal Metal–Phosphorus Intermediates

   https://doi.org/10.1021/jacs.4c16833  

   Thompson, Richard R; Figgins, Matthew T; Wannipurage, Duleeka C; Renteria-Gomez, Angel; Gogoi, Achyut Ranjan; Telser, Joshua; Tierney, David L; Neben, Marc C; Demeshko, Serhiy; Gutierrez, Osvaldo; et al (February 2025, Journal of the American Chemical Society)
3. Metabolite shift in Medicago truncatula occurs in phosphorus deprivation

   https://doi.org/10.1093/jxb/erab559  

   Dokwal, Dhiraj; Cocuron, Jean-Christophe; Alonso, Ana Paula; Dickstein, Rebecca; Nakamura, ed., Yuki (December 2021, Journal of Experimental Botany)

   Abstract Symbiotic nitrogen (N) fixation entails successful interaction between legume hosts and rhizobia that occur in specialized organs called nodules. N-fixing legumes have a higher demand for phosphorus (P) than legumes grown on mineral N. Medicago truncatula is an important model plant for characterization of effects of P deficiency at the molecular level. Hence, a study was carried out to address the alteration in metabolite levels of M. truncatula grown aeroponically and subjected to 4 weeks of P stress. First, GC-MS-based untargeted metabolomics initially revealed changes in the metabolic profile of nodules, with increased levels of amino acids and sugars and a decline in amounts of organic acids. Subsequently, LC-MS/MS was used to quantify these compounds including phosphorylated metabolites in the whole plant. Our results showed a drastic reduction in levels of organic acids and phosphorylated compounds in –P leaves, with a moderate reduction in –P roots and nodules. Additionally, sugars and amino acids were elevated in the whole plant under P deprivation. These findings provide evidence that N fixation in M. truncatula is mediated through a N feedback mechanism that in parallel is related to carbon and P metabolism. 

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4. VPT ‐like genes modulate Rhizobium –legume symbiosis and phosphorus adaptation

   https://doi.org/10.1111/tpj.16363  

   Liu, Jinlong; Yang, Rongchen; Yan, Jun; Li, Chun; Lin, Xizhen; Lin, Lin; Cao, Yanyan; Xu, Tiandong; Li, Jianxuan; Yuan, Yangyang; et al (October 2023, The Plant Journal)

   SUMMARY Although vacuolar phosphate transporters (VPTs) are essential for plant phosphorus adaptation, their role inRhizobium–legume symbiosis is unclear. In this study, homologous genes ofVPT1(MtVPTs)were identified inMedicago truncatulato assess their roles inRhizobium–legume symbiosis and phosphorus adaptation.MtVPT2andMtVPT3mainly positively responded to low and high phosphate, respectively. However, bothmtvpt2andmtvpt3mutants displayed shoot phenotypes with high phosphate sensitivity and low phosphate tolerance. The root‐to‐shoot phosphate transfer efficiency was significantly enhanced inmtvpt3but weakened inmtvpt2, accompanied by lower and higher root cytosolic inorganic phosphate (Pi) concentration, respectively. Low phosphate inducedMtVPT2andMtVPT3expressions in nodules.MtVPT2andMtVPT3mutations markedly reduced the nodule number and nitrogenase activity under different phosphate conditions. Cytosolic Pi concentration in nodules was significantly lower inmtvpt2andmtvpt3than in the wildtype, especially in tissues near the base of nodules, probably due to inhibition of long‐distance Pi transport and cytosolic Pi supply. Also,mtvpt2andmtvpt3could not maintain a stable cytosolic Pi level in the nodule fixation zone as the wildtype under low phosphate stress. These findings show thatMtVPT2and MtVPT3modulate phosphorus adaptation and rhizobia–legume symbiosis, possibly by regulating long‐distance Pi transport. 

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5. Reaction Chemistry at Discrete Organometallic Fragments on Black Phosphorus

   https://doi.org/10.1002/anie.202311575  

   Mitra, Kendahl L. Walz; Riehs, Michael; Draguicevic, Andrei; Swann, William A.; Li, Christina W.; Velian, Alexandra (November 2023, Angewandte Chemie International Edition)

   Abstract Black phosphorus (bP) is a two‐dimensional van der Waals material unique in its potential to serve as a support for single‐site catalysts due to its similarity to molecular phosphines, ligands quintessential in homogeneous catalysis. However, there is a scarcity of synthetic methods to install single metal centers on the bP lattice. Here, we demonstrate the functionalization of bP nanosheets with molecular Re and Mo complexes. A suite of characterization techniques, including infrared, X‐ray photoelectron and X‐ray absorption spectroscopy as well as scanning transmission electron microscopy corroborate that the functionalized nanosheets contain a high density of discrete metal centers directly bound to the bP surface. Moreover, the supported metal centers are chemically accessible and can undergo ligand exchange transformations without detaching from the surface. The steric and electronic properties of bP as a ligand are estimated with respect to molecular phosphines. Sterically, bP resembles tri(tolyl)phosphine when monodentate to a metal center, and bis(diphenylphosphino)propane when bidentate, whereas electronically bP is a σ‐donor as strong as a trialkyl phosphine. This work is foundational in elucidating the nature of black phosphorus as a ligand and underscores the viability of using bP as a basis for single‐site catalysts. 

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