Aminomethyl Phosphonate Research Articles

β-Cyclodextrin-derived diallylamine salt: Synthesis and its copolymerizations

A diallyl amine salt monomer bearing a β-CD substituent was cyclopolymerized for the first time. The reaction of 6-O-toluenesulfonyl-β-cyclodextrin [(C6H10O5)6-(C5H7)]-CH2OTs with diallylamine followed by protonation afforded the diallylamine salt monomer [(C6H10O5)6-(C5H7)]-CH2NH+(CH2CH=CH2)2 Cl−] (I). The cyclopolymerization of monomer I and its copolymerization with monomer [Me2N+(CH2CH=CH2)2 Cl−] (II), [−O2CCH2NH+(CH2CH=CH2)2] (III), [H2O3PCH2NH+(CH2CH=CH2)2 Cl−] (IV) or [HO2CCH2CH(CO2H)NH+(CH2CH=CH2)2 Cl−] (V) yielded a series of copolymers having residues of β-CD and glycine or methyl phosphonate or aspartic acid. Terpolymerization in the presence of SO2 afforded polymers with alternating placements of the SO2 units. The solution properties of the pH-responsive polyzwitterions, including their viscosity, were examined. The water-insoluble terpolymer I/V/SO2 with 20 mol% β-CD residues removed the organic micropollutant 2-naphthol from an aqueous system via host/guest complexation. This work paves the way for the possible synthesis of cross-linked polymers that can simultaneously remove organic micropollutants and toxic metal ions (by complexation with the chelating glycine, aspartic acid, and aminomethyl phosphonate ligands) from contaminated aqueous systems.

Synthesis and application of flame retardant self‐matting aqueous polyurethane dispersion

AbstractTo address the issues of insufficient film smoothness, and flammability of aqueous polyurethane dispersions (PUD) prepared by adding matting agents, two hydrophilic chain extenders, dimethylolpropionic acid (DMPA) and sodium 2‐[(2‐aminoethyl)amino] ethanesulphonate (A95), were used to regulate the particle size of the emulsion while using FRC‐6 flame retardant as a small molecule chain extender to prepare a self‐matting and flame retardant PUD. Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscope, and atomic force microscopy were used to structurally characterize the latex films. The results showed that as theR‐value (NCO/OH molar ratio) and soft segment content decreased, the prepolymer viscosity increased, making it difficult to emulsify and reducing the glossiness of the film. Moreover, an initial increase in DMPA content led to a decrease in film glossiness, followed by an increase. Increasing the molar ratio of A95 sulfonic acid salt‐based chain extender to EDA affected the glossiness of the film, with a 2:8 molar ratio of A95: ethylenediamine (EDA) resulting in a glossiness of the film of 6.5%. The addition of reactive flame retardant diethyl bis (2‐hydroxyethyl) aminomethyl phosphonate (FRC‐6) increased the branching content in the prepolymer, improved the flame retardancy of the film, and reduced its glossiness. As a result, the self‐prepared PUD had a flat film with a glossiness as low as 6.0% and a flame retardancy rating of level 4.

Transformation of Iminodi(methylene phosphonate) on Manganese Dioxides - Passivation of the Mineral Surface by (Formed) Mn2.

Aminopolyphosphonates (APPs) are strong chelating agents with growing use in industrial and household applications. In this study, we investigated the oxidation of the bisphosphonate iminodi(methylene phosphonate) (IDMP) - a major transformation product (TP) of numerous commercially used APPs and a potential precursor for aminomethylphosphonate (AMPA) - on manganese dioxide (MnO2). Transformation batch experiments at pH 6 revealed AMPA and phosphate as main TPs, with a phosphorus mass balance of 80 to 92% throughout all experiments. Our results suggest initial cleavage of the C-P bond and formation of the stable intermediate N-formyl-AMPA. Next, C-N bond cleavage leads to the formation of AMPA, which exhibits lower reactivity than IDMP. Reaction rates together with IDMP and Mn2+ sorption data indicate formation of IDMP-Mn2+ surface bridging complexes with progressing MnO2 reduction, leading to the passivation of the mineral surface regarding IDMP oxidation. Compound-specific stable carbon isotope analysis of IDMP in both sorbed and aqueous fractions further supported this hypothesis. Depending on the extent of Mn2+ surface concentration, the isotope data indicated either sorption of IDMP to the mineral surface or electron transfer from IDMP to MnIV to be the rate-limiting step of the overall reaction. Our study sheds further light on the complex surface processes during MnO2 redox reactions and reveals abiotic oxidative transformation of APPs by MnO2 as a potential process contributing to widespread elevated AMPA concentrations in the environment.

Hyperbranched Polyurethanes with Flammability Resistance for Leather Retanning

In this study, diethyl bis(2-hydroxyethyl) aminomethyl phosphonate was modified by hexamethylene diisocyanate, and then was utilized to partly replace the isocyanates to prepare hyperbranched polyurethanes (HPU-DPAs). The hyperbranched polyurethanes were then employed in the retanning process of wet blue. The shrinkage temperature, average thickness as well as mechanical properties of leather before and after retanning were acquired. The flammability of retanned leather was measured by cone calorimeter test. The morphologies of wet blue and leather after retanning by HPU-DAP were obtained using a scanning electron microscope. Results showed that the average thickness, tensile strength and elongation at break of leather were all improved after retanning. Retanning by HPU-DAPs can effectively increase flame retardancy of final leather.

Biosynthesis of Argolaphos Illuminates the Unusual Biochemical Origins of Aminomethylphosphonate and Nε-Hydroxyarginine Containing Natural Products.

Phosphonate natural products have a history of successful application in medicine and biotechnology due to their ability to inhibit essential cellular pathways. This has inspired efforts to discover phosphonate natural products by prioritizing microbial strains whose genomes encode uncharacterized biosynthetic gene clusters (BGCs). Thus, success in genome mining is dependent on establishing the fundamental principles underlying the biosynthesis of inhibitory chemical moieties to facilitate accurate prediction of BGCs and the bioactivities of their products. Here, we report the complete biosynthetic pathway for the argolaphos phosphonopeptides. We uncovered the biochemical origins of aminomethylphosphonate (AMPn) and Nε-hydroxyarginine, two noncanonical amino acids integral to the antimicrobial function of argolaphos. Critical to this pathway were dehydrogenase and transaminase enzymes dedicated to the conversion of hydroxymethylphosphonate to AMPn. The interconnected activities of both enzymes provided a solution to overcome unfavorable energetics, empower cofactor regeneration, and mediate intermediate toxicity during these transformations. Sequential ligation of l-arginine and l-valine was afforded by two GCN5-related N-acetyltransferases in a tRNA-dependent manner. AglA was revealed to be an unusual heme-dependent monooxygenase that hydroxylated the Nε position of AMPn-Arg. As the first biochemically characterized member of the YqcI/YcgG protein family, AglA enlightens the potential functions of this elusive group, which remains biochemically distinct from the well-established P450 monooxygenases. The widespread distribution of AMPn and YqcI/YcgG genes among actinobacterial genomes suggests their involvement in diverse metabolic pathways and cellular functions. Our findings illuminate new paradigms in natural product biosynthesis and realize a significant trove of AmPn and Nε-hydroxyarginine natural products that await discovery.

Harnessing phosphonate antibiotics argolaphos biosynthesis enables a synthetic biology-based green synthesis of glyphosate

Glyphosate is a widely used herbicide with an annual production of more than one million tons globally. Current commercialized production processes of glyphosate are generally associated with manufacturing hazards and toxic wastes. Recently, many countries have strengthened environmental supervision and law enforcement on glyphosate manufacturing. Therefore, a green source of glyphosate is required. Here, we characterize the genes required for producing aminomethylphosphonate (AMP), one of the intermediates in the biosynthesis of the potent antibiotics argolaphos. We apply a synthetic biology strategy to improve AMP production in Streptomyces lividans, with fermentation titers of 52 mg L-1, a 500-fold improvement over the original strain. Furthermore, we develop an efficient and practical chemical process for converting AMP to glyphosate. Our findings highlight one greenness-driven alternative in the production of glyphosate.

Preparation and performance of polyether elastomer with a combination of polyurethane and polytriazole

AbstractPolyether polyurethane elastomers prepared by polyisocyanate N100 and ethylene oxide‐tetrahydrofuran copolymer (PET) were compared to that polytriazole polyethylene oxide‐tetrahydrofuran (PTPET) elastomers prepared by alkynyl‐terminated polyethylene oxide‐tetrahydrofuran (ATPET) and glycidyl azide polymer (GAP) at a comparative molecular weight. The polyether polyurethane (PET‐N100) elastomers turned out to have better mechanical properties than that of PTPET/GAP elastomer. In order to explore the effectiveness of nitrogen‐enriched structures in the field of flame‐retardancy, PET‐N100 and PTPET/GAP elastomers were tested by cone calorimetry. The PET‐N100 elastomer exhibited an inferior performance of flame‐retardancy to that of PTPET/GAP elastomer. Therefore, a modification of the terminal hydroxyl group in GAP with 4,4′‐methylene‐bisphenyl‐isocyanate (MDI) and flame‐retardant diethyl bis(2‐hydroxyethyl) amino methyl phosphonate (DBMAP) was attempted and characterized by FT‐IR, NMR, and gel permeation chromatography. It was found that the synthesized GAP‐MDI‐DBAMP could serve as a novel curing agent for ATPET, which would endow the novel PTPET elastomer a combination of the advantageous properties, that is, the outstanding mechanical properties from PET‐N100 elastomer, favorable flame‐retardancy from PTPET/GAP elastomer and DBAMP. The thermogravimetry analysis/DTG, DSC, tensile strength test, and swelling analysis proved that PTPET/GAP‐MDI‐DBAMP elastomer had excellent thermal stability and mechanical strength.

Using twin screw extrusion reaction (TSER) to produce thermoplastic polyurethane (TPU): Tunable, stoichiometric and eco‐friendly

TPU and flame‐retardant TPU (FR‐TPU) were prepared through a polyaddition reaction with polytetramethylene ether glycol (PTMEG) and 4,4′‐methylene‐bisphenyl‐isocyanate (MDI) by reactive extruding. 1,4‐Butanediol (BDO) and diethyl bis(2‐hydroxyethyl) amino methyl phosphonate (DBAMP) were used as the chain extender in different ratios, respectively, to obtain TPU and flame‐retardant TPU (FR‐TPU)with adjusted molecular weight and mechanical properties. The resulting TPU and FR‐TPU were characterized by FTIR, DSC, TGA, and NMR. A kinetic model based on the data from extrusion process was used to depict the polymerization of TPU. These reactions carried out without any solvent and the residual water showed that the polymerization with BDO could be achieved in 20 minutes, instead, that with DBAMP in 55 minutes while with a similar molecular weight. These results point out that Twin Screw Extrusion Reaction (TSER) is a suitable and convenient way to produce a variety of polymers.

Diethyl [(4-{(9H-carbazol-9-yl)methyl}-1H-1,2,3-triazol-1-yl)(benzamido)methyl]phosphonate

The title compound, diethyl [(4-{(9H-carbazol-9-yl)methyl}-1H-1,2,3-triazol-1-yl)(benzamido)methyl]phosphonate, was synthesized with excellent yield and high regioselectivity through 1,3-dipolar cycloaddition reaction between the α-azido diethyl amino methylphosphonate and the heterocyclic alkyne, 9-(prop-2-yn-1-yl)-9H-carbazole. The cyclization reaction by “click chemistry” was carried out in a water/ethanol solvent mixture (50/50), in the presence of copper sulfate pentahydrate and catalytic sodium ascorbate. The characterization of the structure of the resulting 1,4-regioisomer was performed by 1D and 2D-NMR experiments, infrared spectroscopy, and elemental analysis.

Amino acid structure analog as a corrosion inhibitor of carbon steel in 0.5 M H2SO4: Electrochemical, synergistic effect and theoretical studies

Abstract In this study, a novel corrosion inhibitor named diethyl(4-methylphenyl)-N-(phenyl) aminomethylphosphonate (AP) has been exploited versus corrosion of carbon steel (CS) in 0.5 M H2SO4. The effect of AP inhibitor on CS corrosion was studied employing potentiodynamic polarization (PDP) curves and electrochemical impedance spectroscopy (EIS) measurements at 298 K. The results showed that AP acted as a mixed inhibitor with predominantly anodic, whose inhibition action was improved by increasing its concentration. The inhibition performance (I.E) was improved by the introduction of halide ion (KI) in the process. The synergistic effect between AP and KI was evaluated by estimating the synergism parameter. The adsorption of AP compound onto carbon steel surface obeyed to Langmuir's adsorption isotherm. Quantum calculations were conducted by employing the Density Functional Theory (DFT). The interaction between the inhibitor and the surface Fe (1 0 0) was assessed by molecular dynamics simulation (MDs).

Synthesis of aminophosphonate polyols and polyurethane foams with improved fire retardant properties

ABSTRACTAminophosphonated polyols with flame retardant properties are synthesized by ring opening polymerization using diethyl‐N,N‐bis(2‐hydroxyethyl) aminomethyl phosphonate (Fyrol‐6) as initiator. The influence of the catalyst type and its concentration on the polymerization rate are studied. The catalyst system formed by potassium methoxide (MeOK) in DMSO as a solvent presents the highest polymerization rate and allows reducing the polydispersity. The thermal resistance of the synthesized polyols is confirmed by the char residues formation. Finally, PU foams are synthesized containing up to a 50 pph of PFyCs[1:1], preserving good cellular structure up to a 25 pph content and improving the fire resistance by increasing the char residue from 7.79 to 22.13 wt % and decreasing the PHRR and the smoke production according to TGA and cone calorimeter tests, respectively. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47780.

Effect of New Thiophene-Derived Aminophosphonic Derivatives on Growth of Terrestrial Plants. Part 2. Their Ecotoxicological Impact and Phytotoxicity Test Toward Herbicidal Application in Agriculture.

Background: The aim of this work was to evaluate phytotoxicity of the thiophene derivatives against three persistent weeds of a high degree of resistance (Galinsoga parviflora Cav., Rumex acetosa L., and Chenopodium album) as well as their ecotoxicological impact on Heterocypris incongruens. In addition, Aliivibrio fischeri was measured. Two of eight described aminophosphonates, namely dimethyl N-(2-methoxyphenyl)amino(2-thienyl)methylphosphonate (2d) and dimethyl N-(tert-butyl)- (2-thienyl)methylphosphonate (2h), have never been reported before. Methods: The phytotoxicity of tested aminophosphonates toward their potential application as soil-applied herbicides was evaluated according to the OECD 208 Guideline. Ecotoxicological properties of investigated compounds were made using the OSTRACODTOXKITTM and Microtox® tests. Results: Obtained results showed that four aminophosphonates have interesting herbicidal properties and N-(2-methylphenyl)amino- (2-thienyl)methylphosphonate (2a) was found to kill efficiently the most resistant plant Chenopodium album. None of the tested compounds showed important toxicity against Aliivibrio fischeri. However, their toxic impact on Heterocypris incongruens was significantly elevated. Conclusions: The aminophosphonate 2a showed herbicidal potential and it is not toxic against tested bacteria (EC50 over 1000 mg/L). It was found to be moderately toxic against ostracods [mortality 48% at 10 mg/kg of soil dry weight (s.d.w.)] and this problem should be solved by the use of the controlled release from a polymeric carrier.

From tolerance to resistance: mechanisms governing the differential response to glyphosate in Chloris barbata.

Susceptibility and the mechanism (s) governing tolerance/resistance to glyphosate were characterized in two putative-glyphosate-resistant Chloris barbata populations (R1 and R2), collected in Persian lime orchards from Colima State, Mexico, comparing them with one non-treated population (referred to as S). Glyphosate doses required to reduce fresh weight or cause mortality by 50% were 4.2-6.4 times higher in resistant populations than in the S population. The S population accumulated 4.3 and 5.2 times more shikimate than the R2 and R1 populations, respectively. There were no differences in 14 C-glyphosate uptake between R and S populations, but the R plants translocated at least 12% less herbicide to the rest of plant and roots 96 h after treatment. Insignificant amounts of glyphosate were metabolized to aminomethyl phosphonate and glyoxylate in both R and S plants. The 5-enolpyruvylshikimate-3-phosphate synthase gene of the R populations contained the Pro106-Ser mutation, giving them a resistance 12 (R2) and 14.7 (R1) times greater at target-site level compared with the S population. The Pro106-Ser mutation governs the resistance to glyphosate of the R1 and R2 C barbata populations, but the impaired translocation could contribute to the resistance. These results confirm the first case of glyphosate resistance evolved in this species. © 2018 Society of Chemical Industry.

Dibenzyl amino(pyren-1-yl)methyl phosphonates—Their NMR and mass spectrometry characterizations

GRAPHICAL ABSTRACT

The formation of dimethyl amino(pyrene-1-yl)methylphosphonates in the Kabachnik-Fields reaction with dibenzyl phosphite, pyrene-1-carboxaldehyde and a non-aromatic amine in methanol

GRAPHICAL ABSTRACT

Synthesis, fluorescence properties and the promising cytotoxicity of pyrene-derived aminophosphonates.

A large series of variously substituted amino(pyren-1-yl)methylphosphonic acid derivatives was synthesized using a modified aza-Pudovik reaction in 20–97% yields. The fluorescence properties of the obtained compounds were investigated revealing that N-alkylamino(pyren-1-yl)methylphosphonic derivatives are stronger emissive compounds than the corresponding N-aryl derivatives. N-Benzylamino(pyren-1-yl)methylphosphonic acid displayed strong fluorescence (ΦF = 0.68) in phosphate-buffered saline (PBS). The influence of a series of derivatives on two colon cancer cell lines HT29 and HCT116 was also investigated. The most promising results were obtained for N-(4-methoxyphenyl)amino(pyren-1-yl)methylphosphonate, which was found to be cytotoxic for the HCT116 cancer cell line (IC50 = 20.8 μM), simultaneously showing weak toxicity towards normal lymphocytes (IC50 = 230.8 µM).

Multifunctional phosphate-based inorganic-organic hybrid nanoparticles.

Phosphate-based inorganic-organic hybrid nanoparticles (IOH-NPs) with the general composition [M](2+)[Rfunction(O)PO3](2-) (M = ZrO, Mg2O; R = functional organic group) show multipurpose and multifunctional properties. If [Rfunction(O)PO3](2-) is a fluorescent dye anion ([RdyeOPO3](2-)), the IOH-NPs show blue, green, red, and near-infrared fluorescence. This is shown for [ZrO](2+)[PUP](2-), [ZrO](2+)[MFP](2-), [ZrO](2+)[RRP](2-), and [ZrO](2+)[DUT](2-) (PUP = phenylumbelliferon phosphate, MFP = methylfluorescein phosphate, RRP = resorufin phosphate, DUT = Dyomics-647 uridine triphosphate). With pharmaceutical agents as functional anions ([RdrugOPO3](2-)), drug transport and release of anti-inflammatory ([ZrO](2+)[BMP](2-)) and antitumor agents ([ZrO](2+)[FdUMP](2-)) with an up to 80% load of active drug is possible (BMP = betamethason phosphate, FdUMP = 5'-fluoro-2'-deoxyuridine 5'-monophosphate). A combination of fluorescent dye and drug anions is possible as well and shown for [ZrO](2+)[BMP](2-)0.996[DUT](2-)0.004. Merging of functional anions, in general, results in [ZrO](2+)([RdrugOPO3]1-x[RdyeOPO3]x)(2-) nanoparticles and is highly relevant for theranostics. Amine-based functional anions in [MgO](2+)[RaminePO3](2-) IOH-NPs, finally, show CO2 sorption (up to 180 mg g(-1)) and can be used for CO2/N2 separation (selectivity up to α = 23). This includes aminomethyl phosphonate [AMP](2-), 1-aminoethyl phosphonate [1AEP](2-), 2-aminoethyl phosphonate [2AEP](2-), aminopropyl phosphonate [APP](2-), and aminobutyl phosphonate [ABP](2-). All [M](2+)[Rfunction(O)PO3](2-) IOH-NPs are prepared via noncomplex synthesis in water, which facilitates practical handling and which is optimal for biomedical application. In sum, all IOH-NPs have very similar chemical compositions but can address a variety of different functions, including fluorescence, drug delivery, and CO2 sorption.

PAA-SIO2 Catalyzed Synthesis, Uv Absorption, and Fluorescence Emission Studies of Diethyl (Aryl/Hetero Aryl Amino)(Pyren-1-Yl)Methylphosphonates

GRAPHICAL ABSTRACT

Construction of 1H-pyrrol-2-ylphosphonates via [3+2] cycloaddition of phosphate azomethine ylides with ynones

An efficient route for the construction of 1H-pyrrol-2-ylphosphonates via the [3+2] cycloaddition of phosphonate azomethine ylides with ynones is described. This transformation proceeds with good functional group tolerance under mild conditions with good efficiency and selectivity. And the synthesis of 1H-pyrrol-2-ylphosphonates could also be achieved via the three-component reaction of benzaldehydes, aminomethyl phosphonates and ynones.

In vivo ³¹P-nuclear magnetic resonance studies of glyphosate uptake, vacuolar sequestration, and tonoplast pump activity in glyphosate-resistant horseweed.

Horseweed (Conyza canadensis) is considered a significant glyphosate-resistant (GR) weed in agriculture, spreading to 21 states in the United States and now found globally on five continents. This laboratory previously reported rapid vacuolar sequestration of glyphosate as the mechanism of resistance in GR horseweed. The observation of vacuole sequestration is consistent with the existence of a tonoplast-bound transporter. (31)P-Nuclear magnetic resonance experiments performed in vivo with GR horseweed leaf tissue show that glyphosate entry into the plant cell (cytosolic compartment) is (1) first order in extracellular glyphosate concentration, independent of pH and dependent upon ATP; (2) competitively inhibited by alternative substrates (aminomethyl phosphonate [AMPA] and N-methyl glyphosate [NMG]), which themselves enter the plant cell; and (3) blocked by vanadate, a known inhibitor/blocker of ATP-dependent transporters. Vacuole sequestration of glyphosate is (1) first order in cytosolic glyphosate concentration and dependent upon ATP; (2) competitively inhibited by alternative substrates (AMPA and NMG), which themselves enter the plant vacuole; and (3) saturable. (31)P-Nuclear magnetic resonance findings with GR horseweed are consistent with the active transport of glyphosate and alternative substrates (AMPA and NMG) across the plasma membrane and tonoplast in a manner characteristic of ATP-binding cassette transporters, similar to those that have been identified in mammalian cells.