Beneficial Effects of Phosphite in Arabidopsis thaliana Mediated by Activation of ABA, SA, and JA Biosynthesis and Signaling Pathways.

Phosphite (Phi) has gained attention in agriculture due to its biostimulant effect on crops. This molecule has been found to benefit plant performance by providing protection against pathogens, improving yield and fruit quality as well as nutrient and water use efficiency. It is still unclear how Phi enhances plant growth and protects against multiple stresses. It has been hypothesized that Phi acts by directly affecting the pathogens and interacting with the plant cellular components and molecular machinery to elicit defense responses. This study elucidates the mechanisms underlying Phi's beneficial effects on plants, revealing their complex interplay with fundamental signaling pathways. An RNA-seq study of Arabidopsis seedlings under optimal and limiting phosphate conditions helped us unveil Phi's role in promoting plant growth by activating the expression of the genes involved in the biosynthesis and signaling pathways associated with abscisic acid (ABA), salicylic acid (SA), and jasmonic acid (JA). The expression of ABA-related genes, known for their involvement in stress response and development regulation, is triggered by Phi treatment, contributing to enhanced resilience and growth. Simultaneously, the activation of the SA pathway, associated with defense responses, suggests Phi's potential in bolstering plant immunity. Moreover, Phi influences JA biosynthesis and signaling, which are crucial for defense against herbivores and pathogens, thereby strengthening plants' defenses. Our findings reveal a multifaceted mechanism through which Phi benefits Arabidopsis development. Understanding its intricate interplay with key signaling pathways opens avenues for leveraging Phi as a strategic tool to enhance plant resilience, immunity, and growth in agricultural and ecological contexts.

Computational studies on a selection of phosphite esters as antioxidants for polymeric materials.

CONTEXT: Phosphite esters, a class of organo-phosphorus compounds, are widely used as non-discolouring antioxidants in many polymeric products. Apart from normal radical scavenging, they prevent the splitting of hydroperoxides (ROOH), one of the initial products of autoxidation, from forming extremely reactive free radicals such as alkoxy (RO.) and hydroxy (.OH) radicals. The inherent molecular properties of antioxidants and the chemistry of their action are essential for researchers working in this field of science. Four organo-phosphorous compounds well-known for their antioxidant activity are selected here for theoretical analysis: Tri(m-methylphenyl) phosphite (m-TMPP), Tri(4-methyl-2,6-di-tert-butylphenyl) phosphite (TMdtBPP), Tri(allylphenyl) phosphite (TAPP) and Tri(mercaptobenzothiazoyl) thiophosphate (TMBTTP). The antioxidant activity exhibited by these compounds is theoretically verified, and the results are consistent with the available experimental data. Such theoretical predictions offer advantages in scientific research, particularly when researchers need to select certain molecules as antioxidants for experiments from a pool of molecular systems. METHODS: The chemical computations presented in this report are done in Gaussian 16 program package. The procedure of density functional theory (DFT) with the model chemistry B3LYP/6-31G(d,p) is used to generate computational data. Global reactivity indices, thermochemical data, Fukui functions, molecular electrostatic potential and NMR spectra are computed for the chosen molecular systems from their optimized geometries.

A Modified Arbuzov-Michalis Reaction for Selective Alkylation of Nucleophiles.

The alkylation of nucleophiles is among the most fundamental and well-developed transformations in chemistry. However, to achieve selective alkylation of complex substrates remains a nontrivial task. We report herein a general and selective alkylation method without using strong acids, bases, or metals. In this method, the readily available phosphinites/phosphites, in combination with ethyl acrylate, function as effective alkylating agents. Various nucleophilic groups, including alcohols, phenols, carboxylic acids, imides, and thiols can be alkylated. This method can be applied in the late-stage alkylation of natural products and pharmaceutical agents, achieving chemo- and site-selective modification of complex substrates. Experimental studies indicate the relative reactivity of a nucleophile depends on its acidity and its steric environment. Mechanistic studies suggest the reaction pathway resembles that of the Arbuzov-Michalis reaction.

Bis(2,2,2 trifluoroethyl) Phosphonate as a Convenient Precursor for the Synthesis of H-Phosphonates.

A microwave-assisted synthesis of dialkyl and cyclic H-phosphonates via bis(2,2,2 trifluoroethyl) phosphonate (BTFEP) is described. This method enables the synthesis of various cyclic H-phosphonates and hetero-substituted dialkyl H-phosphonates by simple alcoholysis under non-inert and additive-free conditions. Short reaction times and the requirement for only stoichiometric amounts of alcohol render this method attractive for synthetic applications.

Enhanced UV Nonlinear Optical Properties in Layered Germanous Phosphites through Functional Group Sequential Construction.

This study pioneers a novel strategy for synthesizing solar-blind ultraviolet (UV) nonlinear optical (NLO) crystals through functional groups sequential construction, effectively addressing the inherent trade-offs among broad transmittance, enhanced second-harmonic generation (SHG), and optimal birefringence. We have developed two innovative van der Waals layered germanous phosphites: GeHPO3, the first Ge(II)-based oxide NLO crystal which exhibits a black phosphorus-like structure, and K(GeHPO3)2Br, distinguished by its exceptional birefringence and graphene-like structure. Significantly, GeHPO3 exhibits a remarkable array of NLO properties, including the highest SHG coefficient recorded among all NLO crystals for phase-matching and generating 266 nm coherent light via quadruple frequency conversion. It delivers a potent SHG intensity, surpassing KH2PO4 (KDP) by 10.3 times at 1064 nm and ß-BaB2O4 by 1.3 times at 532 nm, complemented by a distinct UV absorption edge at 211 nm and moderate birefringence of 0.062 at 546 nm. Comprehensive theoretical analysis links these exceptional characteristics to the unique NLO-active GeO3 4- units and the distinctive, highly ordered layered structures. Our findings deliver essential experimental insights into the development of Ge(II)-based optoelectronic materials and present a strategic blueprint for engineering structure-driven functional materials with customized properties.

Proteomic analysis revealed that the oomyceticide phosphite exhibits multi-modal action in an oomycete pathosystem.

Phytopathogenic oomycetes constitute some of the most devastating plant pathogens and cause significant crop and horticultural yield and economic losses. The phytopathogen Phytophthora cinnamomi causes dieback disease in native vegetation and several crops. The most commonly used chemical to control P. cinnamomi is the oomyceticide phosphite. Despite its widespread use, the mode of action of phosphite is not well understood and it is unclear whether it targets the pathogen, the host, or both. Resistance to phosphite is emerging in P. cinnamomi isolates and other oomycete phytopathogens. The mode of action of phosphite on phosphite-sensitive and resistant isolates of the pathogen and through a model host was investigated using label-free quantitative proteomics. In vitro treatment of sensitive P. cinnamomi isolates with phosphite hinders growth by interfering with metabolism, signalling and gene expression; traits that are not observed in the resistant isolate. When the model host Lupinus angustifolius was treated with phosphite, proteins associated with photosynthesis, carbon fixation and lipid metabolism in the host were enriched. Increased production of defence-related proteins was also observed in the plant. We hypothesise the multi-modal action of phosphite and present two models constructed using comparative proteomics that demonstrate mechanisms of pathogen and host responses to phosphite. SIGNIFICANCE: Phytophthora cinnamomi is a significant phytopathogenic oomycete that causes root rot (dieback) in a number of horticultural crops and a vast range of native vegetation. Historically, areas infected with phosphite have been treated with the oomyceticide phosphite despite its unknown mode of action. Additionally, overuse of phosphite has driven the emergence of phosphite-resistant isolates of the pathogen. We conducted a comparative proteomic study of a sensitive and resistant isolate of P. cinnamomi in response to treatment with phosphite, and the response of a model host, Lupinus angustifolius, to phosphite and its implications on infection. The present study has allowed for a deeper understanding of the bimodal action of phosphite, suggested potential biochemical factors contributing to chemical resistance in P. cinnamomi, and unveiled possible drivers of phosphite-induced host plant immunity to the pathogen.

Contamination of dairy products with tris(2,4-di-tert-butylphenyl) phosphite and implications for human exposure.

Tris(2,4-di-tert-butylphenyl) phosphite (AO168), an organophosphite antioxidant, can be oxidized to tris(2,4-di-tert-butylphenyl) phosphate (AO168 = O) during the production, processing, and application of plastics. AO168 = O can be further transformed to bis(2,4-di-tert-butylphenyl) phosphate and 2,4-di-tert-butylphenol. Here, we discovered the contamination of AO168 and its transformation products in dairy products for the first time. More samples contained AO168 (mean concentration: 8.78 ng/g wet weight [ww]), bis(2,4-di-tert-butylphenyl) phosphate (mean:11.1 ng/g ww) and 2,4-di-tert-butylphenol (mean: 46.8 ng/g ww) than AO168 = O (mean: 40.2 ng/g ww). The concentrations of AO168 and its transformation products were significantly correlated, and differed with the packaging material and storage conditions of the product. Estimated daily intakes (EDIs) of AO168 and its transformation products were calculated. Although the overall dietary risks were below one, transformation products accounted for 96.7% of the total hazard quotients. The high-exposure EDIs of total AO168 were above the threshold of toxicological concern (300 ng/kg bw/day), and deserve continual monitoring.

Fungicide Sensitivity of Phytophthora Isolates from the Washington Red Raspberry Industry.

Phytophthora rubi is an important pathogen causing Phytophthora root rot of red raspberries worldwide. Management of this disease is partially achieved with fungicides, but efficacy has been low, and growers are concerned about fungicide resistance. To determine whether fungicide resistance is developing, Phytophthora species were isolated from 26 raspberry fields with root rot, identified, and evaluated for sensitivity to four fungicides: mefenoxam, phosphorous acid, oxathiapiprolin, and dimethomorph. The majority of the recovered 152 Phytophthora isolates were P. rubi (143 isolates, 25 fields), with P. megasperma (8 isolates, 2 fields) and P. gonapodyides (1isolate, 1field) being found much less frequently. These results confirm P. rubi as the dominant species affecting the Washington red raspberry industry. Almost all tested isolates were sensitive to all four fungicide chemistries, although three isolates were less sensitive to mefenoxam, with effective concentration for 50% growth inhibition (EC50) values ranging from 3.53 to 100 µg active ingredient/ml. No resistance was detected against current fungicide label rates. However, other reasons were identified for why fungicides have been ineffective. Label rates vary widely by brand, and most fungicides are applied in the fall when P. rubi is inactive. In addition, some phosphorous acid products are only labeled for foliar applications, which have been shown to be less effective than soil applications in other agricultural systems. Efficacy trials are needed to compare foliar and soil fungicide applications at different times of the year for their ability to control Phytophthora root rot in red raspberry production fields.

An efficient synthesis of functionalized ß-amino- and ß-hydrazinoalkylphosphonates by three-component reaction between trialkyl phosphites, dialkyl acetylenedicarboxylates and aromatic amines or hydrazines.

Three-component reaction between trialkyl phosphites, dialkyl acetylenedicarboxylates and aromatic amines afforded ß-aminoalkylphosphonate derivatives. Similar reaction between trialkyl phosphites, dialkyl acetylenedicarboxylates and dinitrophenylhydrazine afforded ß-hydrazinooalkylphosphonate derivatives. This method includes both the C-N and C-P bond formation in a one pot and single synthetic step in neutral and simple reaction conditions. All reactions were conducted in CH2Cl2 as solvent at room temperature without using any catalyst, and the stable products were obtained in high yields. The structures of all products were proved by 1H, 13C and 31P NMR and IR spectral and elemental analysis data.

An efficient synthesis of phosphonated cyclopentenones by NaN3-catalyzed three-component reaction between trialkyl phosphites, ethyl arylmethylidenecyanoacetates and dialkyl acetylenedicarboxylates.

NaN3-catalysed three-component reaction between trialkyl phosphites, dialkyl acetylenedicarboxylates and ethyl arylmethylidenecyanoacetates afforded phosphonated cyclopentenone derivatives. The process involves one C-P and two C-C bond formations in one synthetic step. All reactions were conducted in acetone as solvent at room temperature and the products were obtained in high yields as stable solids. The products were isolated and purified by simple washing with water and diethyl ether without need to tedious chromatography methods. The structures of products were proved by 1H, 13C and 31P NMR and IR spectral and elemental analysis data.

Expression of bacterial phosphite dehydrogenase confers phosphite availability in a unicellular red alga Cyanidioschyzon merolae.

　Microalgae are promising cell factories for producing value-added products. Large-scale microalgal cultivation suffers from invasion by contaminating microorganisms. Since most contaminating organisms cannot utilize phosphite as a unique phosphorus source, phosphite-utilizing ability may provide a growth advantage against contaminating organisms and solve this problem. Studies showed that microorganisms, typically unable to metabolize phosphite, can utilize phosphite by expressing exogenous phosphite dehydrogenase. Here, we constructed Cyanidioschyzon merolae strains introduced with the phosphite dehydrogenase gene, ptxD, from Ralstonia sp. 4506. The ptxD-introduced strains grew in a phosphite-dependent manner, with the phosphite-related growth rate almost matching that with phosphate as sole phosphorus source.

Prebiotic Syntheses of Organophosphorus Compounds from Reduced Source of Phosphorus in Non-Aqueous Solvents.

Reduced-oxidation-state phosphorus (reduced P, hereafter) compounds were likely available on the early Earth via meteorites or through various geologic processes. Due to their reactivity and high solubility, these compounds could have played a significant role in the origin of various organophosphorus compounds of biochemical significance. In the present work, we study the reactions between reduced P compounds and their oxidation products, with the three nucleosides (uridine, adenosine, and cytidine), with organic alcohols (glycerol and ethanolamine), and with the tertiary ammonium organic compound, choline chloride. These reactions were studied in the non-aqueous solvent formamide and in a semi-aqueous solvent comprised of urea: ammonium formate: water (UAFW, hereafter) at temperatures of 55-68 °C. The inorganic P compounds generated through Fenton chemistry readily dissolve in the non-aqueous and semi-aqueous solvents and react with organics to form organophosphites and organophosphates, including those which are identified as phosphate diesters. This dual approach (1) use of non-aqueous and semi-aqueous solvents and (2) use of a reactive inorganic P source to promote phosphorylation and phosphonylation reactions of organics readily promoted anhydrous chemistry and condensation reactions, without requiring any additive, catalyst, or other promoting agent under mild heating conditions. We also present a comparative study of the release of P from various prebiotically relevant phosphate minerals and phosphite salts (e.g., vivianite, apatite, and phosphites of iron and calcium) into formamide and UAFW. These results have direct implications for the origin of biological P compounds from non-aqueous solvents of prebiotic provenance.

Triethyl phosphine decorated cerium oxide nanoparticles exhibit selective killing of the unicellular protozoan parasite Leishmania donovani.

Globally, Leishmaniasis affects underprivileged communities of the nations and chemotherapy remains one of the preferred treatment options. However, the cytotoxicity, side effects, and cost of the present chemotherapies limit their utilization. Auranofin [an organogold compound having significant structural similarity with triethyl-phosphine (TEP)] has been reported as an effective therapy for Leishmaniasis treatment. Considering the high cost of gold and the strong affinity of cerium oxide nanoparticles (CeNPs) to phosphine ligands, we designed TEP-decorated CeNPs (CeNPs-TEP) and used them as a novel antileishmanial agent. The hydrodynamic size of synthesized CeNPs and CeNPs-TEP was observed to be 22.2 ± 3.7 nm and 92.11 ± 6.2 nm, respectively. CeNPs-TEP provided aqueous stability to TEP as TEP alone is extremely unstable in water. Exposure of CeNPs-TEP showed ~ 60 and ~ 82% cell death in Leishmania donovani Ag83 promastigotes after 24 and 48 h, respectively. The same concentration of CeNPs-TEP did not affect the cellular viability of RAW 264.7 macrophage cells significantly. The oxidative stress and depolarization of the mitochondrial membrane were also observed after the treatment of CeNPs-TEP. Exposure of CeNPs-TEP induced a ~ 2.2-fold increase in ROS generation inside Leishmania donovani Ag83 cells. Dual staining with ethidium bromide and acridine orange reveals that these processes ultimately result in cell death. The results conclude that a combination of CeNPs and TEP could open the door for developing novel antileishmanial therapeutics in the future. Supplementary Information: The online version contains supplementary material available at 10.1007/s13205-023-03813-7.

Integration of molecular and computational approaches paints a holistic portrait of obscure metabolisms.

Microorganisms are essential drivers of earth's geochemical cycles. However, the significance of elemental redox cycling mediated by microorganisms is often underestimated beyond the most well-studied nutrient cycles. Phosphite, (per)chlorate, and iodate are each considered esoteric substrates metabolized by microorganisms. However, recent investigations have indicated that these metabolisms are widespread and ubiquitous, affirming a need to continue studying the underlying microbiology to understand their biogeochemical effects and their interface with each other and our biosphere. This review focuses on combining canonical techniques of culturing microorganisms with modern omic approaches to further our understanding of obscure metabolic pathways and elucidate their importance in global biogeochemical cycles. Using these approaches, marker genes of interest have already been identified for phosphite, (per)chlorate, and iodate using traditional microbial physiology and genetics. Subsequently, their presence was queried to reveal the distribution of metabolic pathways in the environment using publicly available databases. In conjunction with each other, computational and experimental techniques provide a more comprehensive understanding of the location of these microorganisms, their underlying biochemistry and genetics, and how they tie into our planet's geochemical cycles.

A novel salt- and organic solvent-tolerant phosphite dehydrogenase from Cyanothece sp. ATCC 51142.

Phosphite dehydrogenase (PtxD) is a promising enzyme for NAD(P)H regeneration. To expand the usability of PtxD, we cloned, expressed, and analyzed PtxD from the marine cyanobacterium Cyanothece sp. ATCC 51142 (Ct-PtxD). Ct-PtxD exhibited maximum activity at pH 9.0°C and 50°C and high stability over a wide pH range of 6.0-10.0. Compared to previously reported PtxDs, Ct-PtxD showed increased resistance to salt ions such as Na+, K+, and NH4 +. It also exhibited high tolerance to organic solvents such as ethanol, dimethylformamide, and methanol when bound to its preferred cofactor, NAD+. Remarkably, these organic solvents enhanced the Ct-PtxD activity while inhibiting the PtxD activity of Ralstonia sp. 4506 (Rs-PtxD) at concentrations ranging from 10% to 30%. Molecular electrostatic potential analysis showed that the NAD+-binding site of Ct-PtxD was rich in positively charged residues, which may attract the negatively charged pyrophosphate group of NAD+ under high-salt conditions. Amino acid composition analysis revealed that Ct-PtxD contained fewer hydrophobic amino acids than other PtxD enzymes, which reduced the hydrophobicity and increased the hydration of protein surface under low water activity. We also demonstrated that the NADH regeneration system using Ct-PtxD is useful for the coupled chiral conversion of trimethylpyruvic acid into L-tert-leucine using leucine dehydrogenase under high ammonium conditions, which is less supported by the Rs-PtxD enzyme. These results imply that Ct-PtxD might be a potential candidate for NAD(P)H regeneration in industrial applications under the reaction conditions containing salt and organic solvent.

Cage-Shaped Phosphites Having C3 -Symmetric Chiral Environment: Steric Control of Lewis Basicity and Application as Chiral Ligands in Rhodium-Catalyzed Conjugate Additions.

Designing chiral ligands with an axial symmetry higher than C2 -rotational symmetry is one of the most crucial approaches to improving enantioselectivity in asymmetric synthesis. Herein, C3 -symmetric chiral cage-shaped phosphites are reported. Their Lewis basicity and chiral environment are precisely controlled by the tethered group. The cage-shaped phosphites successfully worked as chiral ligands in Rh-catalyzed asymmetric conjugate additions, realizing acceptable yields with excellent enantioselectivity, and were used to synthesize a pharmacologically important molecule.

Phototransformation of phosphite induced by zinc oxide nanoparticles (ZnO NPs) in aquatic environments.

Phosphite, an essential component in the biogeochemical phosphorus cycle, may make significant contributions to the bioavailable phosphorus pool as well as water eutrophication. However, to date, the potential impacts of coexisting photochemically active substances on the environmental fate and transformation of phosphite in aquatic environments have been sparsely elucidated. In the present study, the effect of zinc oxide nanoparticles (ZnO NPs), a widely distributed photocatalyst in aquatic environments, on phosphite phototransformation under simulated solar irradiation was systematically investigated. The physicochemical characteristics of the pristine and reacted ZnO NPs were thoroughly characterized. The results showed that the presence of ZnO NPs induced the indirect phototransformation of phosphite to phosphate, and the reaction rate increased with increasing ZnO NPs concentration. Through experiments with quenching and trapping free radicals, it was proved that photogenerated reactive oxygen species (ROS), such as hydroxyl radical (•OH), superoxide anion (O2•-), and singlet oxygen (1O2), made substantial contributions to phosphite phototransformation. In addition, the influencing factors such as initial phosphite concentration, pH, water matrixes (Cl-, F-, Br-, SO42-, NO3-, NO2-, HCO3-, humic acid (HA) and citric acid (CA)) were investigated. The component of generated precipitates after the phosphite phototransformation induced by ZnO NPs was still dominated by ZnO NPs, while the presence of amorphous Zn3(PO4)2 was identified. This work explored ZnO NPs-mediated phosphite phototransformation processes, indicating that nanophotocatalysts released into aquatic environments such as ZnO NPs may function as photosensitizers to play a beneficial role in the transformation of phosphite to phosphate, thereby potentially mitigating the toxicity of phosphite to aquatic organisms while exacerbating eutrophication. The findings of this study provide a novel insight into the comprehensive assessment of the environmental fate, potential ecological risk, and biogeochemical behaviors of phosphite in natural aquatic environments under the condition of combined pollution.

On the potential roles of phosphorus in the early evolution of energy metabolism.

Energy metabolism in extant life is centered around phosphate and the energy-dense phosphoanhydride bonds of adenosine triphosphate (ATP), a deeply conserved and ancient bioenergetic system. Yet, ATP synthesis relies on numerous complex enzymes and has an autocatalytic requirement for ATP itself. This implies the existence of evolutionarily simpler bioenergetic pathways and potentially primordial alternatives to ATP. The centrality of phosphate in modern bioenergetics, coupled with the energetic properties of phosphorylated compounds, may suggest that primordial precursors to ATP also utilized phosphate in compounds such as pyrophosphate, acetyl phosphate and polyphosphate. However, bioavailable phosphate may have been notably scarce on the early Earth, raising doubts about the roles that phosphorylated molecules might have played in the early evolution of life. A largely overlooked phosphorus redox cycle on the ancient Earth might have provided phosphorus and energy, with reduced phosphorus compounds potentially playing a key role in the early evolution of energy metabolism. Here, we speculate on the biological phosphorus compounds that may have acted as primordial energy currencies, sources of environmental energy, or sources of phosphorus for the synthesis of phosphorylated energy currencies. This review encompasses discussions on the evolutionary history of modern bioenergetics, and specifically those pathways with primordial relevance, and the geochemistry of bioavailable phosphorus on the ancient Earth. We highlight the importance of phosphorus, not only in the form of phosphate, to early biology and suggest future directions of study that may improve our understanding of the early evolution of bioenergetics.

Enriched Fe Doped on Amorphous Shell Enable Crystalline@Amorphous Core-Shell Nanorod Highly Efficient Electrochemical Water Oxidation.

The rational design of efficient and cost-effective electrocatalysts for oxygen evolution reaction (OER) with sluggish kinetics, is imperative to diverse clean energy technologies. The performance of electrocatalyst is usually governed by the number of active sites on the surface. Crystalline/amorphous heterostructure has exhibited unique properties and opens new paradigms toward designing electrocatalysts with abundant active sites for improved performance. Hence, Fe doped Ni-Co phosphite (Fe-NiCoHPi) electrocatalyst with cauliflower-like structure, comprising crystalline@amorphous core-shell nanorod, is reported. The experiments uncover that Fe is enriched in the amorphous shell due to the flexibility of the amorphous component. Further density functional theory calculations indicate that the strong electronic interaction between the enriched Fe in the amorphous shell and crystalline core host at the core-shell interface, leads to balanced binding energies of OER intermediates, which is the origin of the catalyst-activity. Eventually, the Fe-NiCoHPi exhibits remarkable activity, with low overpotentials of only 206 and 257 mV at current density of 15 and 100 mA cm-2 . Unceasing durability over 90 h is achieved, which is superior to the effective phosphate electrocatalysts. Although the applications at high current remain challenges , this work provides an approach for designing advanced OER electrocatalysts for sustainable energy devices.