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Di-tert-butyl oxymethyl phosphonates were investigated regarding their suitability for preparing the active pharmaceutical ingredient tenofovir (PMPA). First, an efficient and simple access to the crystalline di-tert-butyl(hydroxymethyl)phosphonate was developed. O-Mesylation gave high yields of the active phosphonomethylation reagent. For the synthesis of tenofovir, a two-step sequence was developed using Mg(OtBu)2 as the base for the alkylation of (R)-9-(2-hydroxypropyl)adenine. Subsequent deprotection could be achieved with aqueous acids. (Di-tert-butoxyphosphoryl)methyl methanesulfonate showed to be the most efficient electrophile tested, affording PMPA in 72% yield on a 5 g scale. The developed protocol could also be applied for the preparation of the hepatitis B drug adefovir (64% yield/1 g scale).

Currently available fungicides against potato late blight are effective but there are concerns about the sustainability of frequent applications and the risks of fungicide resistance. Therefore, we investigated how potassium phosphite can be integrated into late blight control programs with reduced fungicides in field trials. Phosphite was somewhat less effective than the conventional fungicides at suppressing late blight in the foliage, and the tubers contained less starch. However, when we reduced the amount of phosphite and combined it with reduced amounts of conventional fungicides, we observed no differences in disease suppression, total yields, and tuber starch contents compared with the full treatments with conventional fungicides. The amount of phosphite detected in the harvested tubers was linearly associated with the amount of phosphite applied to the foliage. Our analyses indicate that phosphite could replace some fungicides without exceeding the current European Union standards for the maximum residue levels in potato tubers. No phosphite was detected in the starch from the tubers. In 1 of 2 years, early blight (caused by Alternaria solani) was less severe in the phosphite treatments than in the treatments without phosphite. The integration of phosphite into current treatment strategies would reduce the dependence on conventional fungicides.

The inhibiting effect of the secondary phosphite antioxidant degradation product bis(2,4-di-tert-butylphenyl)phosphate (bDtBPP) on cell growth is well-known. The present study describes structurally related compounds which are likely to be formed from similar widely used phosphite antioxidants used in materials for the manufacturing of single-use (SU) equipment. Two potential candidates of such compounds-3,3',5,5'-tetra-tert-butyl-2,2'-dihydroxybiphenylphosphate (TtBBP) and bis(p-nonylphenyl)phosphate (bNPP)-were identified by chromatography and mass spectrometry followed by synthesis and X-ray structure elucidation. Additionally, the formation of TtBBP was confirmed in an analytical degradation study and its migration from SU bioprocessing material was estimated. The cytotoxicity evaluation by means of cell culture spiking experiments and flow cytometry analysis revealed that' even if cell growth was inhibited by all the compounds to some extent, bDtBPP showed the most severe effect and stoods out from the other two degradants investigated. Graphical abstract.

In situ synthesis of a deep eutectic solvent and homogeneous liquid-liquid microextraction performed in a narrow bore tube was developed for efficient extraction of irgaphos 168 and irganox 1010 in doogh and water samples packed in polypropylene packages. First, pH of the aqueous sample solutions containing the analytes is adjusted at 9. Then a hydrogen bond acceptor (choline chloride) and a hydrogen bond donor (oleic acid) are dissolved in the solution and vortexed to obtain a homogeneous solution. The solution is filled into a narrow bore tube, in which its bottom was clogged by a septum. Then hydrochloric acid solution is injected into the solution by a syringe. The tube is placed in an ultrasonic bath. During this step, the droplets of choline chloride:oleic acid deep eutectic solvent are produced. The method indicated high enrichment factor (435 for irgaphos 168 and 488 for irganox 1010), low limits of detection (0.03 and 0.09 ng/mL for irgaphos 168 and irganox 1010, respectively) and quantification (0.13 and 0.29 ng/mL for irgaphos 168 and irganox 1010), good recovery (74 and 83% for irgaphos 168 and irganox 1010, respectively), and satisfactory repeatabilities (relative standard deviations ≤12%) can be obtained using the developed method.

The role of a global, substrate-driven, enzyme conformational change in enabling the extraordinarily large rate acceleration for orotidine 5’-monophosphate decarboxylase (OMPDC)-catalyzed decarboxylation of orotidine 5’-monophosphate (OMP) is examined in experiments that focus on the interactions between OMPDC and the ribosyl hydroxyl groups of OMP. The D37 and T100’ side chains of OMPDC interact, respectively, with the C-3’ and C-2’ hydroxyl groups of enzyme-bound OMP. D37G and T100’A substitutions result in 1.4 kcal/mol increases in the activation barrier ΔG(‡) for catalysis of decarboxylation of the phosphodianion truncated substrate 1-(β-D-erythrofuranosyl)orotic acid (EO), but in larger 2.1–2.9 kcal/mole increases in ΔG(‡) for decarboxylation of OMP, and for phosphite dianion-activated decarboxylation of EO. This shows that these substitutions reduce transition state stabilization by the Q215, Y217 and R235 side chain at the dianion binding site. The D37G and T100’A substitutions result in

Substituted cyclohexylamines are becoming increasingly important in drug discovery. Asymmetric Heck insertion/amination of nonconjugated cyclodienes proceeds to give 5-aryl cyclohexenylamines with good enantioselectivity and exclusive trans configurations. Primary and secondary anilines, indoline, and benzylamines are suitable amines. The weakly donating diphosphite Kelliphite forms a deep unsymmetrical pocket, which is essential for stereoselective anti attack of amines. Agency for Science, Technology and Research (A*STAR) Economic Development Board (EDB) Accepted version We acknowledge financial support from Peking UniversityShenzhen Graduate School, Shenzhen Bay Laboratory(21230011-Scripps), Nanyang Technological University,GSK-EDB Trust Fund (2017 GSK-EDB Green and Sustain-able Manufacturing Award) and A*STAR Science andEngineering Research Council (AME IRG A1783c0010).

The projected decline of available phosphorus necessitates alternative methods to derive usable phosphate for fertilizer and other applications. Phosphite dehydrogenase oxidizes phosphite to phosphate with the cofactor NAD+ serving as the hydride acceptor. In addition to producing phosphate, this enzyme plays an important role in NADH cofactor regeneration processes. Mixed quantum mechanical/molecular mechanical free energy simulations were performed to elucidate the mechanism of this enzyme and to identify the protonation states of the substrate and product. Specifically, the finite temperature string method with umbrella sampling was used to generate the free energy surfaces and determine the minimum free energy paths for six different initial conditions that varied in the protonation state of the substrate and the position of the nucleophilic water molecule. In contrast to previous studies, the mechanism predicted by all six independent strings is a concerted but asynchronous dissociative mechanism in which hydride transfer from the phosphite substrate to NAD+ occurs prior to attack by the nucleophilic water molecule. His292 is identified as the most likely general base that deprotonates the attacking water molecule. However, Arg237 could also serve as this base if it were deprotonated and His292 were protonated prior to the main chemical transformation, although this scenario is less probable. The simulations indicate that the phosphite substrate is monoanionic in its active form and that the most likely product is dihydrogen phosphate. These mechanistic insights may be helpful for designing mutant enzymes or artificial constructs that convert phosphite to phosphate and NAD+ to NADH more effectively.

Elimination of phosphite from water is more difficult than elimination of phosphate owing to its higher solubility and resistance to biotransformation. Herein, we report an efficient, facile, electrochemical method integrating electrooxdiation (EO) and electrocoagulation (EC) to treat phosphite-laden wastewater. The mechanistic studies demonstrate that in-situ-generated Fe2+ at an Fe anode can react with in-situ-generated O2 at a mixed metal oxide (MMO) anode, leading to formation of •O2-, a reactive species predominantly responsible for oxidation of phosphite to phosphate. The phosphate is immediately coagulated by Fe hydroxides that are formed due to the production of OH- at a stainless-steel cathode. The integrated EO/EC system enables a phosphite removal efficiency of 74.25% (MMO anode, 100 mA; Fe anode, 100 mA; reaction time, 60 min), a significantly higher efficiency rate than the rate obtained in the control experiments in the absence of an MMO anode (

Kanosamine is an antibiotic and antifungal compound synthesized from glucose 6-phosphate (G6P) in Bacillus subtilis by the action of three enzymes: NtdC, which catalyzes NAD-dependent oxidation of the C3-hydroxyl; NtdA, a PLP-dependent aminotransferase; and NtdB, a phosphatase. We previously demonstrated that NtdC can also oxidize substrates such as glucose and xylose, though at much lower rates, suggesting that the phosphoryloxymethylene moiety of the substrate is critical for effective catalysis. To probe this, we synthesized two phosphonate analogues of G6P in which the bridging oxygen is replaced by methylene and difluoromethylene groups. These analogues are substrates for NtdC, with second-order rate constants an order of magnitude lower than those for G6P. NtdA converts the resulting 3-keto products to the corresponding kanosamine 6-phosphonate analogues. We compared the rates to the rate of NtdC oxidation of glucose and xylose and showed that the low reactivity of xylose could be rescued 4-fold by the presence of phosphite, mimicking G6P in two pieces. These results allow the evaluation of the individual energetic contributions to catalysis of the bridging oxygen, the bridging C6 methylene, the phosphodianion, and the entropic gain of one substrate versus two substrate pieces. Phosphite also rescued the reversible formation 3-amino-3-deoxy-d-xylose by NtdA, demonstrating that truncated and nonhydrolyzable analogues of kanosamine 6-phosphate can be generated enzymatically.

Chiral bridged [2,2,1] bicyclic lactones are privileged structural units in pharmaceutics and bioactive nature products. However, the synthetic methods for these compounds are rare. Here we report an efficient method for enantioselective construction of bridged [2,2,1] bicyclic lactones bearing a quaternary stereocenter via Rh-catalyzed asymmetric hydroformylation/intramolecular cyclization/pyridium chlorochromate (PCC) oxidation. By employing a hybrid phosphine-phosphite chiral ligand, a series of cyclopent-3-en-1-ols are transformed into corresponding γ-hydroxyl aldehydes with specific syn-selectivity. Then, hemiacetals form in situ and oxidation with PCC in one-pot affords bridged [2,2,1] bicyclic lactones in high yields and excellent enantiomeric excess. Replacing the hydroxyl group by an ester group, cyclopentanecarbaldehydes with a chiral all-carbon quaternary stereocenter in the γ-position can be generated efficiently., Enantiomeric bridged [2,2,1] bicyclic lactone skeletons and their ring-opening products are important scaffolds widely occurring in both pharmaceutics and biology active compounds. Here the authors show an efficient method for enantioselective construction of these compounds bearing a quaternary stereocenter via Rh-catalyzed asymmetric hydroformylation/intramolecular cyclization/ pyridinium chlorochromate oxidation.

The Phosphorus (III) derivatives, named Phosphonates, include congeners with properties as fungicides that are effective in controlling Oomycetes. Examples are organic compounds like Fosetyl-Al [Aluminium tris-(ethylphosphonate)] and salts formed with the anion of phosphonic acid [(OH)2HPO] and Potassium, Sodium and Ammonium cations. According to IUPAC, the correct nomenclature for these compounds is “phosphonates”, but in common language and scientific literature they are often named “phosphites”, creating ambiguity. The European legislation restricts the use of phosphonates, with the ban for application in organic agriculture. However, phosphonate residues were detected in some organic products due to their addition to fertilizers allowed in organic agriculture. The legitimacy of this addition is controversial, as it is not evident if phosphonates have also a nutritional role in addition to their fungicidal properties. The new European Directive EU 1009/2019 resolves the problem by banning the phosphonates addition to fertilizers and placing a limit of 0.5% by mass for unintentional addition. However, an official method is not available for phosphonates determination in fertilizers and approval by the European Committee for Standardization (CEN) is necessary in a short time. This review presents an overview about the chemical, biological, analytical and legislative aspects of phosphonates and aims at providing: clarity on the correct nomenclature to avoid misunderstandings; the evaluation of phosphonates properties with the absence of a nutritional role, justifying the ban on adding to fertilizers; a summary of analytical techniques that could be considered by CEN to complete the analytical background for the agricultural use of phosphonates.

Although phosphite (Phi)-based fertilizers are used in large quantities in agriculture, the use of Phi-based fungicides against soybean root rot caused by Phytophthora sojae are limited. While, their low toxicity are of high ecological and economic focus. Limited attention has been paid to Phi translocation efficiency in soybeans and the efficacy of Phi as a fungicide against P. sojae. In this study, we evaluated the efficiency of Phi translocation in the Williams soybean cultivar by determining the Phi concentrations in roots, stems, and leaves using high-performance ion chromatography after the application of Phi to the roots. Phi was translocated from roots to leaves within 1 h and its concentration increased significantly in leaves within 36 h after Phi application. Results of an in vitro growth inhibition assay and an in vivo infection assay showed that Phi inhibited P. sojae. Additionally, we examined the activation of the salicylic acid (SA) and ethylene (ET) defense pathways by Phi. The expression of SA and ET pathway-related genes was upregulated in most soybean tissues after Phi application. Our results provide evidence that Phi translocation suppresses root rot caused by P. sojae in soybean.

In this study, phosphite (HPO32−) was used as a novel activator to activate peroxymonosulfate (PMS) for acid orange 7 (AO7) removal. Under the optimized conditions, the decolorization efficiency of AO7 was 82.1% within 60 min with rate constant values (kobs) of 0.0301 min−1. Besides, effects of the solution pH and the co-existing inorganic anions including Cl−, HCO3−, HPO42− and SO42− on AO7 removal were also investigated. Except for SO42−, other examined co-existing inorganic anions displayed favorable effects on the removal of AO7. Furthermore, the mechanism for PMS activation by the HPO32− was deeply elucidated by radical scavenger including ethanol (EtOH), tert-butanol (TBA), l -histidine and tiron, and electron spin resonance (ESR) studies. It was proposed that singlet oxygen (1O2) would be the dominant reactive oxygen species (ROS) in the HPO32−/PMS system for contamination degradation at neutral pH condition. The findings of this study provided useful information for the application of the substances in industrial wastewaters to activate PMS for organic contaminants degradation and in particular for HPO32--rich electroplating wastewater treatment.

α-Glycosides are highly relevant synthetic targets due to their abundance in natural oligosaccharides involved in many biological processes. Nevertheless their preparation is hampered by several issues, due to both the strictly anhydrous conditions typically required in glycosylation procedures and the non-trivial achievement of high α-stereoselectivity, one of the major challenges in oligosaccharide synthesis. In this paper we report a novel and efficient approach for the highly stereoselective synthesis of α-glycosides. This is based on the unprecedented solvent-free combination of triethylphosphite, tetrabutylammonium bromide and N,N-diisopropylethylamine for the activation of glycosyl chlorides under air. Despite the relative stability of glycosyl chlorides with respect to more reactive halide donors, the solvent-free procedure allowed a wide set of α-glycosides, including biorelevant fragments, to be obtained in much shorter times compared with similar glycosylation approaches in solution. The presented method features a wide target scope and functional group compatibility, also serving with partially disarmed substrates, and it does not require a high stoichiometric excess of reagents nor the preparation of expensive precursors. The solvent-free glycosylation can be even directly performed from 1-hydroxy sugars without purification of the in situ generated chloride, providing an especially useful opportunity in the case of highly reactive and labile glycosyl donors.

Phosphorus absorbed in the form of phosphate (H2 PO4 - ) is an essential but limiting macronutrient for plant growth and agricultural productivity. A comprehensive understanding of how plants respond to phosphate starvation is essential for the development of more phosphate-efficient crops. Here we employed label-free proteomics and phosphoproteomics to quantify protein-level responses to 48 h of phosphate versus phosphite (H2 PO3 - ) resupply to phosphate-deprived Arabidopsis thaliana suspension cells. Phosphite is similarly sensed, taken up and transported by plant cells as phosphate, but cannot be metabolized or used as a nutrient. Phosphite is thus a useful tool for differentiating between non-specific processes related to phosphate sensing and transport and specific responses to phosphorus nutrition. We found that responses to phosphate versus phosphite resupply occurred mainly at the level of protein phosphorylation, complemented by limited changes in protein abundance, primarily in protein translation, phosphate transport and scavenging, and central metabolism proteins. Altered phosphorylation of proteins involved in core processes such as translation, RNA splicing and kinase signaling was especially important. We also found differential phosphorylation in response to phosphate and phosphite in 69 proteins, including splicing factors, translation factors, the PHT1;4 phosphate transporter and the HAT1 histone acetyltransferase - potential phospho-switches signaling changes in phosphorus nutrition. Our study illuminates several new aspects of the phosphate starvation response and identifies important targets for further investigation and potential crop improvement.

Acetoacetyl-CoA reductase (PhaB), involved in poly(3-hydroxybutyrate) [P(3HB)] biosynthesis, requires the coenzyme NADPH as a reducing agent. In this study, the effect of NADPH supply on P(3HB) production was investigated in vitro and in vivo using a phosphite dehydrogenase double mutant (PtxDEAAR), which catalyzes oxidation of phosphite to phosphate with the generation of NADH and NADPH. In an in vitro assay using purified enzymes, P(3HB) polymerization was observed only when phosphite and PtxDEAAR were present, confirming that NADPH was supplied to PhaB. In an in vivo assay using Escherichia coli as a production host for P(3HB), the presence of phosphite and PtxDEAAR did not influence the yield of P(3HB) under normal growth conditions. However, P(3HB) yield increased 3.2-fold in non-growing E. coli cells compared to the control, suggesting that PtxDEAAR-mediated NADPH generation is coupled with P(3HB) biosynthesis. This study confirmed the use of PtxDEAAR for supplying NADPH during P(3HB) synthesis in vitro and in vivo.

Phosphite (Phi)-based fungicides, such as the commercial product Phostrol™, are widely used in potato late blight control. However, the Phi translocation efficiency and the efficacy against pathogen are less discussed. In this study, the Phi concentration were quantified by high performance ion chromatography (HPIC) and the Phi translocation efficiency in potato tissues was evaluated using potato cultivar Russet Burbank with foliar application of the Phostrol solution both under greenhouse and field conditions. In the greenhouse trials, it was found that Phi was translocated from leaves to roots within 3 h and its concentration was significantly increased in the roots 24 h after the Phostrol application. In the field trials, the application rate of Phostrol affected the Phi translocation in potato tubers. To assess the efficacy of Phi against P. infestans, both the inhibition and infection tests were carried out. In the inhibition tests, three most common strains of P. infestans in Canada (US-8, US-23 and US-24) were inoculated on pea agar containing different levels of Phi. In the infection tests, both of detached leaves and whole tubers that received Phi were infected by the three strains of P. infestans. The in vitro tests indicated that the US-8 strain is the most tolerant whereas the US-23 strain is the most sensitive to Phi. Also, the in vivo tests demonstrated the dose-dependent translocation of Phi in potato leaves and tubers decreased the severity of infection by P. infestans. Moreover, potential defense mechanisms related to salicylic acid (SA) and jasmonic acid (JA) pathways that might be activated by Phi were also explored. Overall, the results of the study provided evidences that high Phi translocation efficiency encouraged late blight suppression in potato production.

A high-throughput assay was developed to screen Phytophthora species for fungicide sensitivity using optical density measurements for unbiased, automated measurement of mycelial growth. The efficacy of the optical density assay (OD) to measure phosphite sensitivity in Phytophthora species was compared to two widely used methods, radial growth (RG) and dry weight (DW) assays. Three isolates of each of Phytophthora cinnamomi, P. multivora and P. pluvialis, with known phosphite exposure and three isolates of each species with no prior phosphite exposure, were screened for phosphite sensitivity using the three assays. Mycelial growth measurements were taken after culturing for 6, 14 and 15 days for the OD, DW and RG assays respectively. Mycelial growth inhibition at 15, 80, 200 and 500 μg/mL phosphite relative to growth on control media was used to determine effective concentration values for 50% growth reduction (EC50). The species varied in their tolerance to phosphite with P. cinnamomi being the least sensitive followed by P. multivora and P. pluvialis. No significant differences in tolerance were found between isolates within the same species using any method. The OD assay produced comparable EC50 values to the RG and DW assays. The growth of the three species was more sensitive to phosphite in the DW than the RG and OD assays, however limited sample throughput and greater variation in measuring small amounts of mycelia in the dry weight assessment increase variability and limits throughput. The OD assay offers a fast method to enable an inventory of chemical resistance and is particularly advantageous for slow growing species as it requires less time and offers greater throughput than existing RG and DW methods.

Nanoceria is considered as a potent antioxidant (free radical scavenger) and its enzymatic activity is reported to be a function of the oxidation state of surface cerium ions. Here we demonstrate phosphine ligand-dependent enzymatic activity of nanoceria irrespective of its as-synthesized oxidation state.

We report the general and rapid synthesis of short DNA fragments of controllable sequence and length using multi-step, one-pot mechanochemical reactions, without bulk solvent or the need to isolate intermediates. We demonstrate, for the first time, the multi-step ball milling synthesis of DNA dimers and trimers via phosphoramidite and H-phosphonate chemistries. The use of mechanochemistry allowed for coupling of phosphoramidite monomers to the 5'-hydroxyl group of nucleosides, iodine/water oxidation of the resulting phosphite triester linkage, and removal of the 5'-dimethoxy (DMTr) protecting group in situ and in good yields (up to 60% over three steps) to produce DNA dimers in one-pot manner. Sulphurization of phosphite triester linkages was possible using elemental sulfur yielding the corresponding phosphorothioate DNA dimers in good yield (up to 80% over two steps). By using H-phosphonate chemistry under milling conditions, it was possible to couple, protect the H-phosphonate linkage, and remove the 5'-DMTr protecting group in situ, enabling an one-pot process with good yields comparable to existing solvent-based procedures (up to 65% over three steps, or ca. 87% per step). This work opens the door to creation of solvent-free methodologies for the assembly of complex DNA and RNA therapeutics.

The use of phosphite (Phi)-containing products as foliar fertilizers is a common practice in food production systems, yet their actual contribution as a source of phosphorus (P) for plant nutrition has been object of debate. In this study, we aim to determine, not only the potential impact of foliar Phi applications on tomato plants nutritional status and biomass production, but also their effect on the expression of genes related to plant phosphate (Pi)-starvation and defense responses. The effect of Phi was evaluated on hydroponic tomato plants growing under low (0.1 mM) and optimal (1.0 mM) Pi conditions. Phi-treatments consisted of foliar sprayings of KPhi, CaPhi, AlPhi or H3PO3. Gene expression analysis was carried out 24 h, 48 h and 7 days after the last Phi application, while biomass production and nutrient concentration in the plant tissues were determined seven days after the last Phi application. Regardless the Pi concentration in the hydroponic solution, foliar application of Phi influenced neither net biomass production and partitioning nor photosynthesis-related parameters nor nutrient concentration in plant tissues. Phi applications activated the plant-defense mechanisms but suppressed the Pi-starvation response of tomato plants. Foliar applications of Phi on tomato plants can be used to activate plant-defense responses, but they would not contribute to improve growth and nutritional status of tomato plants, indicating that Phi is not a relevant source of nutrients. Phi-containing products might suppress the response mechanism to Pi-starvation in plants growing under low Pi conditions. UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Agroalimentarias::Centro para Investigaciones en Granos y Semillas (CIGRAS) UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Agroalimentarias::Centro de Investigaciones Agronómicas (CIA) UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Agroalimentarias::Instituto de Investigaciones Agrícolas (IIA)

Polymer semiconductors show unique combinations of mechanical and optoelectronic properties that strongly depend on their microstructure and morphology. Here, we have used a model p-conjugated bithiophene repeat unit to incorporate optoelectronic functionality into an aliphatic polyamide backbone by solution-phase polycondensation. Intermolecular hydrogen bonding between the amide groups ensured stable short-range order in the form of lamellar crystalline domains in the resulting semiaromatic polyamides, which could be processed from the melt and exhibited structural and thermomechanical characteristics comparable with those of existing engineering polyamides. At the same time, however, pulse-radiolysis time-resolved microwave conductivity measurements indicated charge carrier mobilities that were an order of magnitude greater than previously observed in bithiophene-based materials. Our results hence provide a convincing demonstration of the potential of amide hydrogen bonding interactions for obtaining unique combinations of mechanical and optoelectronic properties in thermoplastic polymers.

Sialic acids constitute a family of negatively charged structurally diverse monosaccharides that are commonly presented on the termini of glycans in higher animals and some microorganisms. In addition to N-acetylneuraminic acid (Neu5Ac), N-glycolyl neuraminic acid (Neu5Gc) is among the most common sialic acid forms in nature. Nevertheless, unlike most animals, human cells loss the ability to synthesize Neu5Gc although Neu5Gc-containing glycoconjugates have been found on human cancer cells and in various human tissues due to dietary incorporation of Neu5Gc. Some pathogenic bacteria also produce Neu5Ac and the corresponding glycoconjugates but Neu5Gc-producing bacteria have yet to be found. In addition to Neu5Gc, more than 20 Neu5Gc derivatives have been found in non-human vertebrates. To explore the biological roles of Neu5Gc and its naturally occurring derivatives as well as the corresponding glycans and glycoconjugates, various chemical and enzymatic synthetic methods have been developed to obtain a vast array of glycosides containing Neu5Gc and/or its derivatives. Here we provide an overview on various synthetic methods that have been developed. Among these, the application of highly efficient one-pot multienzyme (OPME) sialylation systems in synthesizing compounds containing Neu5Gc and derivatives has been proven as a powerful strategy.

Phosphite (Phi), an analog of phosphate (Pi) anion, is emerging as a potential biostimulator, fungicide and insecticide. Here, we reported that Phi also significantly enhanced thermotolerance in potatoes under heat stress. Potato plants with and without Phi pretreatment were exposed to heat stress and their heat tolerance was examined by assessing the morphological characteristics, photosynthetic pigment content, photosystem II (PS II) efficiency, levels of oxidative stress, and level of DNA damage. In addition, RNA-sequencing (RNA-Seq) was adopted to investigate the roles of Phi signals and the underlying heat resistance mechanism. RNA-Seq revealed that Phi orchestrated plant immune responses against heat stress by reprograming global gene expressions. Results from physiological data combined with RNA-Seq suggested that the supply of Phi not only was essential for the better plant performance, but also improved thermotolerance of the plants by alleviating oxidative stress and DNA damage, and improved biosynthesis of osmolytes and defense metabolites when exposed to unfavorable thermal conditions. This is the first study to explore the role of Phi in thermotolerance in plants, and the work can be applied to other crops under the challenging environment.

Phosphorus acquisition is critical for life. In low phosphate conditions, some species of bacteria have evolved mechanisms to import reduced phosphorus compounds, such as phosphite and hypophosphite, as alternative phosphorus sources. Uptake is facilitated by high-affinity periplasmic binding proteins (PBPs) that bind cargo in the periplasm and shuttle it to an ATP-binding cassette (ABC)-transporter in the bacterial inner membrane. PtxB and HtxB are the PBPs responsible for binding phosphite and hypophosphite, respectively. They recognize the P-H bond of phosphite/hypophosphite via a conserved P-H...π interaction, which confers nanomolar dissociation constants for their respective ligands. PtxB also has a low-level binding affinity for phosphate and hypophosphite, whilst HtxB can facilitate phosphite uptake in vivo. However, HtxB does not bind phosphate, thus the HtxBCDE transporter has recently been successfully exploited for biocontainment of genetically modified organisms by phosphite-dependent growth. Here we use a combination of X-ray crystallography, NMR and Microscale Thermophoresis to show that phosphite binding to HtxB depends on the protonation state of the ligand, suggesting that pH may effect the efficiency of phosphite uptake by HtxB in biotechnology applications.

In recent decades cryogels as monolithic materials have gained interest as stationary phase in chromatography for purification of biomolecules. In this study, polyacrylamide-alginate (PAAm-Alg) monolithic cryogels were prepared by cryo-copolymerization of acrylamide and alginate monomers and methylene-bisacrylamide as crosslinker to be used as a matrix in affinity chromatography for purification of proteins. Ortho-phospho-L-tyrosine (P-Tyr) was covalently attached onto PAAm-Alg cryogels via bisoxirane-activation (PAAm-Alg-Bix-P-Tyr) and both derivatized and non-derivatized cryogels were utilized for the purification of immunoglobulin G (IgG) from human serum. Cryogels were characterized by scanning electron microscopy, swelling tests, elemental analysis, FTIR, and flow dynamics. The effects of buffer systems, conductivity, and pH on IgG adsorption were studied. Through breakthrough curve analysis a dynamic capacity of 9.2 mg IgG/mL with an IgG purity of 94% was obtained (based on ELISA analysis of IgG and albumin) for PAAm-Alg-Bix-P-Tyr cryogel when human serum was diluted in 10 mmol/L NaP buffer at pH 6.0. The adsorption isotherm data were well described by the Langmuir model with value of maximum adsorption capacity of 36.12 ± 3.63 mg of IgG/g for PAAm-Alg-Bix-P-Tyr. The PAAm-Alg-Bix-P-Tyr cryogel provides an attractive alternative for adsorption of IgG from human serum.

Catalysts applied in cobalt-catalyzed cyclotrimerizations reactions in general rely on the use of Co(I) precatalysts or the in situ generation of Co(I) catalysts from Co(II) sources by reduction in the presence of steering ligands, often by addition of less noble metals. In this paper, we report the synthesis and properties of novel stable CpCo(III) complexes as precatalysts and their exemplary evaluation for application in catalytic [2+2+2] cycloadditions. The role of phosphite neutral ligands, as well as iodide and cyanide as anionic ligands, on the reactivity of the complexes was evaluated. A modified one-pot approach to the synthesis of Cp ring-functionalized Cp’Co(III) complexes was developed. The investigations demonstrated that CpCo(III) complexes can be directly applied as catalysts in catalytic cyclotrimerizations of triynes without reducing agents as additives. © 2021 by the authors. Licensee MDPI, Basel, Switzerland.

Resumo: O objetivo deste trabalho foi avaliar o efeito de indutores de resistência abióticos no controle da fusariose (Fusarium guttiforme) do abacaxizeiro na fase pré-colheita, em área de ocorrência natural da doença, e verificar se promoveram alterações físico-químicas e bioquímicas nos frutos. Os produtos testados foram fosfito de potássio, fosfito de cálcio, fosfito de cobre, Agro-Mos, silicato de cálcio, Biopirol e Bion pulverizados em campo, nas dosagens recomendadas pelos fabricantes. Fosfito de potássio, Biopirol e fosfito de cobre foram os mais eficientes na redução da incidência da fusariose do abacaxizeiro em campo, com 91,67, 70,01 e 67,68% de controle, respectivamente. As análises físico-químicas mostraram que os tratamentos não promoveram alteração no pH, nos sólidos solúveis totais e na acidez total dos frutos, enquanto, nas análises bioquímicas, apenas a β-1,3-glucanase apresentou menor atividade em relação à testemunha (água destilada esterilizada), com exceção do tratamento com fosfito de potássio. Assim, a adubação foliar com fosfito de potássio e fosfito de cobre, assim como o tratamento com o Biopirol, podem auxiliar no controle da fusariose do abacaxi. Abstract: The objective of this work was to evaluate the effect of abiotic resistance inducers on the control of pineapple fusariosis (Fusarium guttiforme) in the pre-harvest period, in an area with natural occurrence of the disease in the field, and to check for any physicochemical and biochemical changes in the fruits. The products tested were potassium phosphite, calcium phosphite, copper phosphite, Agro-Mos, calcium silicate, Biopirol, and Bion sprayed on the field, at the dosages recommended by the manufacturers. Potassium phosphite, Biopirol, and copper phosphite were the most effective in reducing the incidence of pineapple fusariosis in the field, with 91.67%, 70.01%, and 67.68% of control, respectively. The physicochemical analyses showed that the treatments did not promote change in pH, total soluble solids, and total acidity of fruits, while, in biochemical analyses, only β-1,3-glucanase showed lower expression compared with the control (sterilized distilled water), except for the treatment with potassium phosphite. Therefore, foliar fertilization with potassium phosphite and copper phosphite, as well as the treatment with Biopirol, may aid in the control of pineapple fusariosis.

Synthesis of α-aminophosphonates by a three-component condensation of an aldehyde, amines and dialkyl phosphites in the presence of a non-ionic surfactant Triton X-100 catalyst at 70 °C in aqueous medium is accomplished. The advantages are high yield, mild reaction conditions, simple work-up and eco-friendliness. All the newly-synthesized compounds (4a–j) exhibited moderate in vitro antibacterial and antifungal activities.

An advanced oxidative process relying on the interaction of peroxymonosulphate and cobalt(II) was implemented for generating the sulphate radicals in flow analysis, in order to accomplish in-line sample preparation thus improving the spectrophotometric determination of phosphate and phosphite in liquid foliar fertilizers. To this end, a flow-batch system with a heated chamber was designed. The sample was handled twice, with and without the step of phosphite oxidation to phosphate, and the formed orthophosphate was quantified after interaction with the vanadate-molybdate reagent. Phosphite was determined as the difference in analytical signals corresponding to sample handling with and without the oxidation step. Influence of Co(II) on the peroxymonosulphate activation, reagent concentrations and added volumes, acidity, temperature and heating time were investigated like aiming at to improve analytical recovery and measurement repeatability, as well as the and system ruggedness. The 6.6–20.0 mg L −1 P 2 O 5 standards were in-line prepared from a single stock solution. Detection limits were estimated as 0.8 and 0.1 mg L −1 for P 2 O 5 and P-PO 4 . Twenty-four samples are were run per hour, and results are were in agreement with those obtained by the official procedure.

Phospha-Michael addition, which is the addition reaction of a phosphorus-based nucleophile to an acceptor-substituted unsaturated bond, certainly represents one of the most versatile and powerful tools for the formation of P-C bonds, since many different electrophiles and P nucleophiles can be combined with each other. This offers the possibility to access many diversely functionalized products. In this work, two kinds of basic pyridine-based organo-catalysts were used to efficiently catalyze phospha-Michael addition reactions, the 4-N,N-dimethylaminopyridinium saccharinate (DMAP·Hsac) salt and a fluorous long-chained pyridine (4-Rf-CH2OCH2-py, where Rf = C11F23). These catalysts have been synthesized and characterized by Lu’s group. The phospha-Michael addition of diisopropyl, dimethyl or triethyl phosphites to α, β-unsaturated malonates in the presence of those catalysts showed very good reactivity with high yield at 80–100 °C in 1–4.5 h with high catalytic recovery and reusability. With regard to significant catalytic recovery, sometimes more than eight cycles were observed for DMAP·Hsac adduct by using non-polar solvents (e.g., ether) to precipitate out the catalyst. In the case of the fluorous long-chained pyridine, the thermomorphic method was used to efficiently recover the catalyst for eight cycles in all the reactions. Thus, the easy separation of the catalysts from the products revealed the outstanding efficacy of our systems. To our knowledge, these are good examples of the application of recoverable organo-catalysts to the DMAP·Hsac adduct by using non-polar solvent and a fluorous long-chained pyridine under the thermomorphic mode in phospha-Michael addition reactions.

Uranium phosphites have recently emerged as promising materials to remediate radioactive contamination. In this study, the redox mechanisms of uranyl phosphites at mineral surfaces have been addressed by periodic DFT calculations with dispersion corrections. Different from other ligands, the phosphite anions (H2PO3−, HPO32−) are efficient reducing agents for uranyl reduction, and the redox reactions are divided into three steps, as isomerization between two phosphite anion isomers (Step 1), conformational transition (Step 2) and dissociation of the water molecule (Step 3). A second water molecule is critical to lower the activation barriers of Step 1, and all activation barriers are moderate so that the redox reactions occur favorably under normal conditions, which are further dramatically accelerated by the highly exergonic Step 3. Accordingly, formation of uranyl phosphites becomes an effective approach to manage uranium pollution. Moreover, the lower activation barriers for H2PO3− rather than HPO32− rationalize the superior reduction activities of uranyl phosphites and the enhanced stability of U(IV) products at lower pH conditions. Owing to the cooperative proton/electron transfer, the U(VI) reduction to U(IV) and P(III) oxidation to P(V) are completed within one step, with transition states being featured by the U(V) and P(IV) species.

Recent progress in genetic engineering and synthetic biology have greatly expanded the production capabilities of cyanobacteria, but concerns regarding biosafety issues and the risk of contamination of cultures in outdoor culture conditions remain to be resolved. With this dual goal in mind, we applied the recently established biological containment strategy based on phosphite (H3PO3, Pt) dependency to the model cyanobacterium Synechococcus elongatus PCC 7942 ( Syn 7942). Pt assimilation capability was conferred on Syn 7942 by the introduction of Pt dehydrogenase (PtxD) and hypophosphite transporter (HtxBCDE) genes that allow the uptake of Pt, but not phosphate (H3PO4, Pi). We then identified and disrupted the two indigenous Pi transporters, pst (Synpcc7942_2441 to 2445) and pit (Synpcc7942_0184). The resultant strain failed to grow on any media containing various types of P compounds other than Pt. The strain did not yield any escape mutants for at least 28 days with a detection limit of 3.6 × 10-11 per colony forming unit, and rapidly lost viability in the absence of Pt. Moreover, growth competition of the Pt-dependent strain with wild-type cyanobacteria revealed that the Pt-dependent strain could dominate in cultures containing Pt as the sole P source. Because Pt is rarely available in aquatic environments this strategy can contribute to both biosafety and contamination management of genetically engineered cyanobacteria.

In the pharmaceutical industry the sulfurisation of nucleotide-phosphites to produce more biologically stable thiophosphates is often achieved using ‘aged’ solutions of phenylacetyl disulfide (PADS) which consist of a mixture of polysulfides that are more efficient sulfur transfer reagents. However, both ‘fresh’ and ‘aged’ solutions of PADS are capable of the sulfurisation of phosphites. The rates of both processes in acetonitrile are first order in sulfurising agent, phosphite and a pyridine base, although with ‘aged’ PADS the rate becomes independent of base at high concentrations. The Brönsted β values for sulfurisation using ‘fresh’ and ‘aged’ PADS with substituted pyridines are 0.43 and 0.26, respectively. With ‘fresh’ PADS the Brönsted βnuc = 0.51 for substituted trialkyl phosphites is consistent with a mechanism involving nucleophilic attack of the phosphite on the PADS disulfide bond to reversibly generate a phosphonium intermediate, the rate-limiting breakdown of which occurs by a base catalysed elimination process, confirmed by replacing the ionisable hydrogens in PADS with methyl groups. The comparable polysulfide phosphonium ion intermediate seen with ‘aged’ PADS presents a more facile pathway for product formation involving S–S bond fission as opposed to C–S bond fission.

Direct reactions of the MRI contrast agent K2[Gd(DTPA)(H2O)]·5H2O (1) (H5DTPA = diethylenetriaminepentaacetic acid) with dipotassium hydrogen phosphate (K2HPO4) or phosphite (K2HPO3) result in the isolation of well-defined Gd-DTPA phosphite K6[Gd2(DTPA)2(HPO3)]·7H2O (2) or phosphate K6[Gd2(DTPA)2(HPO4)]·10H2O (3), respectively. Their lanthanum analogs K4[La2(DTPA)2(H2O)]·8H2O (4), K6[La2(DTPA)2(HPO3)]·7H2O (5) and K6[La2(DTPA)2(HPO4)]·10H2O (6) are used for comparison. The phosphate and phosphite groups are able to substitute the coordinated water molecules in 1 and 4 in a close physiological aqueous solution, and act as bridging ligands to link adjacent Ln(DTPA)(2-) (Ln = Gd and La) into dimeric structures. Solid state and solution (13)C NMR spectra of dimer 4 show complete dissociation into its monomeric species in solution, while no dissociation is observed for lanthanum phosphite 5 and phosphate 6 in solution, which show only one set of (13)C spectra with the largest downfield shifts at 182.0 and 182.3 ppm respectively. Comparisons of the bond distances and spectral data indicate that the interaction between DTPA and central Ln(3+) cations are weakened after the substitutions, which support phosphate substituted Gd-DTPA as an initial intermediate in nephrogenic systemic fibrosis.

A one-pot synthesis of glycosyl phosphates and their P-modified analogs from glycosyl boranophosphates under mild basic conditions has been conducted. 31P NMR monitoring of the reaction mixture revealed that the key intermediates of these reactions were acyl phosphites, which could not be formed from the corresponding H-phosphonate diesters.

Aluminum hypophosphite (AHP) is an effective phosphorus-containing flame retardant. But AHP also has fire risk that it will decompose and release phosphine which is spontaneously flammable in air and even can form explosive mixtures with air in extreme cases. In this paper, AHP has been microencapsulated by melamine cyanurate (MCA) to prepare microencapsulated aluminum hypophosphite (MCAHP) with the aim of enhancing the fire safety in the procedure of production, storage and use. Meanwhile, MCA was a nitrogen-containing flame retardant that can work with AHP via the nitrogen-phosphorus synergistic effect to show improved flame-retardant property than other capsule materials. After microencapsulation, MCA presented as a protection layer inhibit the degradation of AHP and postpone the generation of phosphine. Furthermore, the phosphine concentration could be effectively diluted by inert decomposition products of MCA. These nonflammable decomposition products of MCA could separate phosphine from air delay the oxidizing reaction with oxygen and decrease the heat release rate, which imply that the fire safety of AHP has been improved. Furthermore, MCAHP was added into polyamide 6 to prepare flame retardant polyamide 6 composites (FR-PA6) which show good flame retardancy.

This work demonstrates the potential of zeolite Y supported nickel phosphide materials as highly active catalysts for the upgrading of bio-oil as an improved alternative to noble metal and transition metal sulphide systems. Our systematic work studied the effect of using different counterions (NH4 +, H+, K+ and Na+) and Si/Al ratios (2.56 and 15) of the zeolite Y. It demonstrates that whilst the zeolite counterion itself has little impact on the catalytic activity of the bare Y-zeolite, it has a strong influence on the activity of the resulting nickel phosphide catalysts. This effect is related to the nature of the nickel phases formed during the synthesis process Zeolites containing K+ and Na+ favour the formation of a mixed Ni12P5/Ni2P phase, H+ Y produces both Ni2P and metallic Ni, whereas NH4 + Y produces pure Ni2P, which can be attributed to the strength of the phosphorus-aluminium interaction and the metal reduction temperature. Using quinoline as a model for the nitrogen-containing compounds in bio-oils, it is shown that the hydrodenitrogenation activity increases in the order Ni2P > Ni0 > Ni12P5. While significant research has been dedicated to the development of bio-oils produced by thermal liquefaction of biomass, surprisingly little work has been conducted on the subsequent catalytic upgrading of these oils to reduce their heteroatom content and enable processing in conventional petrochemical refineries. This work provides important insights for the design and deployment of novel active transition metal catalysts to enable the incorporation of bio-oils into refineries.

Highlight Phosphate transporters AtPHT1;8 and AtPHT1;9, but not AtPHT1;1, discriminate between phosphite and phosphate. Phosphate-starvation-responsive transcript profiles show altered kinetics with phosphite, hence allowing further dissection of phosphorus signalling networks., Phosphite is a less oxidized form of phosphorus than phosphate. Phosphite is considered to be taken up by the plant through phosphate transporters. It can mimic phosphate to some extent, but it is not metabolized into organophosphates. Phosphite could therefore interfere with phosphorus signalling networks. Typical physiological and transcriptional responses to low phosphate availability were investigated and the short-term kinetics of their reversion by phosphite, compared with phosphate, were determined in both roots and shoots of Arabidopsis thaliana. Phosphite treatment resulted in a strong growth arrest. It mimicked phosphate in causing a reduction in leaf anthocyanins and in the expression of a subset of the phosphate-starvation-responsive genes. However, the kinetics of the response were slower than for phosphate, which may be due to discrimination against phosphite by phosphate transporters PHT1;8 and PHT1;9 causing delayed shoot accumulation of phosphite. Transcripts encoding PHT1;7, lipid-remodelling enzymes such as SQD2, and phosphocholine-producing NMT3 were highly responsive to phosphite, suggesting their regulation by a direct phosphate-sensing network. Genes encoding components associated with the ‘PHO regulon’ in plants, such as At4, IPS1, and PHO1;H1, generally responded more slowly to phosphite than to phosphate, except for SPX1 in roots and MIR399d in shoots. Two uncharacterized phosphate-responsive E3 ligase genes, PUB35 and C3HC4, were also highly phosphite responsive. These results show that phosphite is a valuable tool to identify network components directly responsive to phosphate.

The reaction of triarylantimony diacetates [Ar3Sb(OAc)2] with dialkyl H-phosphites [H-PO(OR)2] in the presence of a Pd(PPh3)4 (5 mol%) catalyst led to the formation of arylphosphonates in moderate to excellent yield under base-free conditions. This reaction is the first example of carbon-phosphorus bond formation by using an organoantimony compound as a pseudo-halide.

The development of a P-tether-mediated, iterative SN2′-cuprate alkylation protocol for the formation of 1,3-skipped polyol stereotetrads is reported. This two-directional synthetic strategy builds molecular complexity from simple, readily prepared C2-symmetric dienediols and unites the chemistry of both temporary phosphite–borane tethers and temporary phosphate tethers—through an oxidative “function switch” of the P-tether itself—to generate intermediates that were previously inaccessible via either method alone.

A three-component reaction between diamines (diaminobenzenes, diaminocyclohexanes, and piperazines), triethyl orthoformate, and diethyl phosphite was studied in some detail. In the case of 1,3- and 1,4-diamines and piperazines, products of the substitution of two amino moieties&mdash, the corresponding tetraphosphonic acids&mdash, were obtained. In the cases of 1,2-diaminobenzene, 1,2-diaminocyclohexanes and 1,2-diaminocyclohexenes, only one amino group reacted. This is most likely the result of the formation of hydrogen bonding between the phosphonate oxygen and a hydrogen of the adjacent amino group, which caused a decrease in the reactivity of the amino group. Most of the obtained compounds inhibited the proliferation of RAW 264.7 macrophages, PC-3 human prostate cancer cells, and MCF-7 human breast cancer cells, with 1, trans-7, and 16 showing broad nonspecific activity, which makes these compounds especially interesting in the context of anti-osteolytic treatment and the blocking of interactions and mutual activation of osteoclasts and tumor metastatic cells. These compounds exhibit similar activity to zoledronic acid and higher activity than incadronic acid, which were used as controls. However, studies of sheep with induced osteoporosis carried out with compound trans-7 did not support this assumption.

A family of complexes of the formula trans-[RuCl2(L)(R-pybox)] (R-pybox = (S,S)-iPr-pybox, (R,R)-Ph-pybox, L = monodentate phosphonite, PPh(OR)2, and phosphinite, L = PPh2(OR), ligands) were screened in the catalytic asymmetric transfer hydrogenation of acetophenone, observing a strong influence of the nature of both the R-pybox substituents and the L ligand in the process. The best results were obtained with complex trans-[RuCl2{PPh2(OEt)}{(R,R)-Ph-pybox}] (2c), which provided high conversion and enantioselectivity (up to 96% enantiomeric excess, e.e.) for the reduction of a variety of aromatic ketones, affording the (S)-benzylalcohols.

Mannitol is a six carbon sugar alcohol that finds applications in the pharmaceutical and food industries. A novel Escherichia coli strain capable of converting D-glucose to D-mannitol has been constructed, wherein native mannitol-1-phosphate dehydrogenase (MtlD) and codon-optimized Eimeria tenella mannitol-1-phosphatase (M1Pase) have been overexpressed. Codon-optimized Pseudomonas stutzeri phosphite dehydrogenase (PtxD) was overexpressed for cofactor (NADH) regeneration with the concomitant oxidation of phosphite to phosphate. Whole-cell biotransformation using resting cells in a medium containing D-glucose and equimolar sodium phosphite resulted in d-mannitol yield of 87 mol%. Thus, production of an industrially relevant biochemical without using complex media components and elaborate process control mechanisms has been demonstrated.

An effective one-pot synthesis of dialkoxyphosphoryl-2-oxo-2H-pyran derivatives by three-component reaction of alky bromides and dialkyl acetylenedicarboxylates in the presence of trialkyl phosphite is described. The reactions were performed under solvent-free conditions at 50°C and neutral conditions and provided good yields of products.

The element phosphorus (P) controls growth in many ecosystems as the limiting nutrient, where it is broadly considered to reside as pentavalent P in phosphate minerals and organic esters. Exceptions to pentavalent P include phosphine--PH3--a trace atmospheric gas, and phosphite and hypophosphite, P anions that have been detected recently in lightning strikes, eutrophic lakes, geothermal springs, and termite hindguts. Reduced oxidation state P compounds include the phosphonates, characterized by C-P bonds, which bear up to 25% of total organic dissolved phosphorus. Reduced P compounds have been considered to be rare; however, the microbial ability to use reduced P compounds as sole P sources is ubiquitous. Here we show that between 10% and 20% of dissolved P bears a redox state of less than +5 in water samples from central Florida, on average, with some samples bearing almost as much reduced P as phosphate. If the quantity of reduced P observed in the water samples from Florida studied here is broadly characteristic of similar environments on the global scale, it accounts well for the concentration of atmospheric phosphine and provides a rationale for the ubiquity of phosphite utilization genes in nature. Phosphine is generated at a quantity consistent with thermodynamic equilibrium established by the disproportionation reaction of reduced P species. Comprising 10-20% of the total dissolved P inventory in Florida environments, reduced P compounds could hence be a critical part of the phosphorus biogeochemical cycle, and in turn may impact global carbon cycling and methanogenesis.

The paper describes a convenient and efficient method for regioselective synthesis of phosphorylated α-hydroxyallenes using an atom economical [2,3]-sigmatropic rearrangement of intermediate propargyl phosphites or phosphinites. These can be readily prepared via reaction of protected alkynols with dimethyl chlorophosphite or chlorodiphenyl phosphine respectively in the presence of a base.

In neutral media, reactions of gadolinium ethylenediaminetetraacetates with phosphorous acid result in the formation of the mixed-ligand polymeric complex K3n[Gd(EDTA)(HPO3)]n·7nH2O (1) and dimeric complex Na6[Gd2(EDTA)2(HPO3)2]·2.5NaCl·21H2O (2) (H4EDTA = ethylenediaminetetraacetic acid) in warm solution. Further substitution with citric acid gives the monomeric gadolinium citrate with EDTA (NH4)2Na[Gd(EDTA)(H2cit)]·4H2O (3). The compounds were characterized by elemental analysis, single crystal X-ray diffraction, FT-IR, ESI-MS and thermogravimetric analysis. Structural analysis indicates that three coordinated water molecules in the gadolinium ethylenediaminetetraacetate trihydrates are replaced by phosphite ions (HPO32−) in the compounds 1 and 2. Gadolinium atoms are octa-coordinated by EDTA and the phosphite ion, the latter links adjacent Gd–EDTA units to generate an infinite one-dimensional chain in compound 1 and a dimeric octatomic ring in 2. In complex 3, coordinated water molecules were substituted by the α-hydroxy, α-carboxy and β-carboxy groups of citrate. Citrate is favourable for inhibiting the formation of Gd–EDTA phosphite. All the complexes are very easily soluble in water. The solution behavior of the isostructural lanthanum complexes was probed with 13C and 31P NMR spectra in D2O for comparison. ESI-MS analysis and recrystallization proved that complexes 1 and 2 dissociate to the monomeric unit of Gd–EDTA and free HPO32− in aqueous solution. Substitutions of gadolinium ethylenediaminetetraacetates to 1 and 2 are attributed to be the cause of nephrogenic systemic fibrosis in some way.

Triosephosphate isomerase (TIM) catalyzes the isomerization of dihydroxyacetone phosphate to form D-glyceraldehyde 3-phosphate. The effects of two structural mutations at TIM on the kinetic parameters for catalysis of the reaction of the truncated substrate glycolaldehyde (GA) and the activation of this reaction by phosphite dianion are reported. The P168A mutation results in similar 50-fold and 80-fold decreases, respectively, in (kcat/Km)E and (kcat/Km)E•HPi for deprotonation of GA catalyzed by free TIM and by the TIM•HPO32− complex. The mutation has little effect on the observed and intrinsic phosphite dianion binding energy, or on the magnitude of phosphite dianion activation of TIM for catalysis of deprotonation of GA. A loop 7 replacement mutant (L7RM) of TIM from chicken muscle was prepared by substitution of the archaeal sequence 208-TGAG for 208-YGGS. The L7RM exhibits a 25-fold decrease in (kcat/Km)E and a larger 170-fold decrease in (kcat/Km)E•HPi for reactions of GA. The mutation has little effect on the observed and intrinsic phosphodianion binding energy, and only a modest effect on phosphite dianion activation of TIM. The observation that both the P168A and loop 7 replacement mutations affect mainly the kinetic parameters for TIM-catalyzed deprotonation, but result in much smaller changes in the parameters for enzyme activation by phosphite dianion provide support for the conclusion that catalysis of proton transfer and dianion activation of TIM take place at separate, weakly interacting, sites in the protein catalyst.

The oxidation of hypophosphite and phosphite in an aqueous solution by an ultraviolet (UV)/H2O2 process was studied in this work. The reactions were performed in a lab-scale batch photoreactor. The effect of different parameters such as H2O2 dosage, H2O2 feeding mode and the initial pH of the solution on the oxidation efficiency of the process was investigated. The results indicated that the UV/H2O2 process could effectively oxidize hypophosphite and phosphite in both synthesized and real wastewater. However, neither H2O2 nor UV alone was able to appreciably oxidize the hypophosphite or phosphite. The best way of feeding H2O2 was found to be 'continuous feeding', which maximized the reaction rate. It was also found that the process presented a wide range of applicable initial pH (5-11). When treating real rinse-wastewater, which was obtained from the electroless nickel plating industry, both hypophosphite and phosphite were completely oxidized within 60 min, and by extending by another 30 min, over 90% of the chemical oxygen demand removal was obtained. Without any additional catalyst, the UV/H2O2 process can oxidize hypophosphite and phosphite to easily removable phosphate. It is really a powerful and environmentally friendly treatment method for the wastewater containing hypophosphite and phosphite.