N-phosphonomethyl Iminodiacetic Acid Research Articles

Sequential photocatalytic degradation of organophosphorus pesticides and recovery of orthophosphate by biochar/α-Fe2O3/MgO composite: A new enhanced strategy for reducing the impacts of organophosphorus from wastewater

Photocatalysis is regarded as one of the most promising techniques for degrading organophosphorus pesticides (OPs) from wastewater given its low-cost and environmental benignity. Yet, photocatalytic degradation of OPs is an incomplete process, since PO43− is produced after photocatalysis. Here, biochar-supported α-Fe2O3/MgO composite (BC-α-Fe2O3/MgO) is developed for sequential photocatalytic degradation of OPs and recovery of the produced PO43−. The degradation efficiency of N-phosphonomethyl iminodiacetic acid (NPA) by BC-α-Fe2O3/MgO based photocatalysis reaches 90.1% within 80 min, and the recovery ratio of the produced PO43− by BC-α-Fe2O3/MgO is as high as 82.3%. Besides, the as-prepared BC-α-Fe2O3/MgO used in this integrated photocatalysis and adsorption process maintain a high stability towards NPA degradation and PO43− recovery during five cycling experiments. The mechanistic study reveals that holes, •OH, and •O2– radicals generated in the photocatalytic process are responsible for NPA degradation. UV light can activate persistent free radicals on BC-α-Fe2O3/MgO surface, which provide O2 withelectrons for the generation of •O2– and subsequent yield of •OH. Moreover, the presence of α-Fe2O3 and MgO on the surface of biochar leads to the excellent P adsorption performance of BC-α-Fe2O3/MgO. This study opens new possibilities for the recovery of P resource from organophosphorus polluted wastewater.

Kinetics of N-Phosphonomethyl Iminodiacetic Acid Catalytic Oxidation with Hydrogen Peroxide Under the Phase-Transfer Conditions

Kinetics of N-Phosphonomethyl Iminodiacetic Acid Catalytic Oxidation with Hydrogen Peroxide Under the Phase-Transfer Conditions

Multifunctional metal-chelated phosphonate/Fe3O4 magnetic nanocomposite particles for defeating antibiotic-resistant bacteria

The expression and dissemination of β-lactamase enzymes is the most frequently used antibiotic resistance mechanism in bacteria. The synthesis and characterization of a new nanocomposite particle was performed to inhibit serine β-lactamase activities. The nanostructure based on an ultra-small iron oxide (Fe3O4) nanocore, is in-situ coated with a hydrophilic and biodegradable compound of N-phosphonomethyl iminodiacetic acid (PMIDA). Through amidation reaction, a tetra-dentate molecule such as (S)-N-(5-Amino-1-carboxypentyl) iminodiacetic acid (NTA) was covalently conjugated to the acid-terminated Fe-PMIDA nanoparticles. The resulted Fe-PMIDA-NTA nanostructure was further coordinated with Co2+ ions. Once the nanoparticles loaded with the cobalt ions, the positively charged nanocomposite particles were found effective toward class C β-lactamase having 66% inhibition of enzyme activity with an IC50 of 45.68 μg/mL. A significant level of synergism was also observed by co-administration of Fe-PMIDA-NTA-Co2+ NPs and cephalexin as our model of β-lactam antibiotic against Escherichia coli bacteria.

Tungsten Peroxopolyoxo Complexes as Advanced Catalysts for the Oxidation of Organic Compounds with Hydrogen Peroxide

Selective oxidation of organic substrates by environment-friendly oxidizing agents is an important ingredient of the sustainable chemical industry. Here we report a comprehensive study in the field of metal peoroxocomplex catalysis for the selective liquid phase oxidation of various organic substrates. A number of well-defined bi-functional tungsten complex catalysts with tetra nuclear structure {PO4[WO(O2)2]4}3- in combination with a phase-transfer agents were synthesized. The structural properties were thoroughly studied using of IR, Raman and EXAFS spectroscopy. By combining different spectroscopy techniques were able to elucidate the effect of quaternary ammonium cations on the structural properties of the resulting peroxo complexes. The catalytic properties of these well-defined material were then evaluated in bi-phasic selective oxidation of cyclooctene, methyl oleate and N-phosphonomethyliminodiacetic acid with hydrogen peroxide under mild conditions. For every substrate we were able to achieve high conversion at the selectivity towards a target product close to 100%.

Solubility, acid-base properties and thermodynamics of interaction between three NTA-phosphonate derivatives and the main cationic components (H+, Na+, Mg2+ and Ca2+) of natural fluids

Abstract Solution thermodynamics of three aminophosphonic acids are studied in this work. In particular, the protonation constants [ log ( K i H /mol kg−1)] of N-phosphonomethyliminodiacetic acid (NTAP), N,N-Bis(phosphonomethyl)glycine (NTAP2) and Nitrilotris(methylenephosphonic acid) (NTAP3) and the solubility of NTAP were determined by potentiometric measurements (ISE-[H+] glass electrode) in three different ionic media, namely NaCl(aq), (CH3)4NCl(aq) and (C2H5)4NI(aq) at different ionic strengths (in the range 0 log K i H on ionic strength and temperature was studied by Debye-Huckel type equation and by Specific ion Interaction Theory (SIT). At infinite dilution, the refined values of the first protonation constants are: log ( K i H /mol kg−1) = 11.4 ± 0.1, 12.4 ± 0.1 and 13.3 ± 0.1 for NTAP, NTAP2 and NTAP3, respectively and the enthalpy changes relative to the first protonation step are: −15.7 ± 0.3, −20.5 ± 0.4 and –33.5 ± 0.2 kJ mol−1 (same order). The basicity trend: NTAP3 > NTAP2 > NTAP is observed in all the ionic media. The differences in the values of the protonation constants obtained in the three ionic media were also interpreted in terms of formation of weak complex and eleven Na+/L species are obtained using the so called ΔpK method. Solubility investigations performed on NTAP allowed us to determine the Setschenow and the activity coefficients of the neutral species. The values of the total and specific solubility in pure water are: log ( S 0 T /mol kg−1) = −1.431 ± 0.003 and log ( S 0 0 /mol kg−1) = −2.293 ± 0.006, respectively. The formation constants of the three ligands with Ca2+ and Mg2+ cations were determined at T = 298.15 K in NaCl(aq) at I = 0.151 mol kg−1, finding the presence of the ML and MHL species. The stability of the Ca2+/L is slightly higher than that of the Mg2+/L ones.

Immobilization of PMIDA on Fe3O4 magnetic nanoparticles surface: Mechanism of bonding

The mechanism of N-phosphonomethyl iminodiacetic acid (PMIDA) binding with the Fe3O4 magnetic nanoparticle (MNPs) surface by Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetry was comprehensive studied. To study of microstructure, size and core structure of synthesized nanoparticles the scanning electron microscopy, X-ray diffraction analysis and Raman spectroscopy were carried out. A new scheme for the tridentate bonding of the phosphonomethyl derivative with surface Fe atoms involving unequal POFe bonds was proposed. The mechanism of thermal decomposition of PMIDA molecules on the MNP surface was studied using a thermogravimetric analyzer combined with infrared spectrometer. It was shown for the first time that during the thermal treatment of phosphonomethyl-modified MNPs, PMIDA molecules are not desorbed from the surface of MNPs but gradually decompose. We believe that obtained in this work data will be useful for a deeper understanding of the mechanisms of phosphonic acid derivatives interaction with MNPs, as well as in the design of new biomedical materials, in which the conjugation of biomolecules with carboxyl groups of PMIDA-modified MNPs is assumed.

Metal based nanoparticles as cancer antigen delivery vehicles for macrophage based antitumor vaccine

In the present study, we would like to evaluate the efficacy of modified metal oxide nanoparticles (NPs) as cancer antigen delivery vehicles for macrophage (MФs) based antitumor vaccine. The cobalt oxide nanoparticles (CoO NPs) were promising tools for delivery of antigens to antigen presenting cells and have induced an antitumor immune response. Synthesized CoO NPs were modified by N-phosphonomethyliminodiacetic acid (PMIDA), facilitated the conjugation of lysate antigen, i.e. cancer antigen derived from lysis of cancer cells. The cancer cell lysate antigen conjugated PMIDA-CoO NPs (Ag-PMIDA-CoO NPs) successfully activated macrophage (MФ) evident by the increasing the serum IFN-γ and TNF-α level. Immunization of mice with the Ag-PMIDA-CoO NPs constructed an efficient immunological adjuvant induced anticancer IgG responses, and increased the antibody dependent cellular cytotoxicity (ADCC) response than only lysate antigen treated group to combat the cancer cell. The nanocomplexes enhanced the anticancer CD4+T cell response in mice. The result showed that Ag-PMIDA-CoO NPs can stimulate the immune responses over only lysate antigens, which are the most important findings in this study. These NP-mediated Ag deliveries may significantly improve the anticancer immune response by activating MФs and may act as adjuvant and will balance the pro-inflammatory and anti-inflammatory immunoresponse. The crosstalk between the activated MФ with other immune competent cells will be monitored by measuring the cytokines which illustrate the total immunological network setups.

N-phosphonomethyl iminodiacetic acid N-oxide synthesis in the presence of bifunctional catalysts based on tungsten complexes

N-phosphonomethyl iminodiacetic acid (PMIDAA) was oxidized in a two phase liquid system by 32% hydrogen peroxide at 70°С. Reaction was performed in the presence of tungsten oxo- and peroxo- complexes, containing N-hexadecylpyridinium or quaternary ammonium cation. Substrate conversion and N-oxide PMIDAA selectivity were found to depend on anions structure and quaternary nitrogen containing cation properties. The best results were obtained when PMIDAA was oxidized in the presence of N-hexadecylpyridinium tetra(oxodiperoxotungsto)phosphate, substrate conversion being 99%, and target product selectivity being 97%.

Preparation of Glyphosate from Catalytic Oxidation N-Phosphonomethyl Iminodiacetic Acid

The activated carbon-containing catalysts (Pd/C and Pt/C) have been prepared by surface modification of the activated carbon with palladium chloride and chloroplatinic acid solution, respectively. The Pt/C catalyst is characterized by XRD pattern. The glyphosate is prepared from catalytic oxidation N-phosphonomethyl iminodiacetic acid. Effect of different catalysts and amount of the catalyst in catalytic oxidation are investigated. Compared with Pt/C catalyst, Pd/C catalyst is more active. Optimum amount of Pd/C catalyst is 45 mol/m3 PMIDA.

Determination of glyphosate in the oxidation products of N-phoshonomethyl iminodiacetic acid by IR spectrometry

A method is developed for determining N-phosphonomethyl glycine (glyphosate) in the oxidation products of N-phosphonomethyl iminodiacetic acid (PMIDA) by IR spectrometry. In the IR spectra of glyphosate and PMIDA characteristic bands at 1562 and 721 cm−1, respectively, are revealed; based on absorbance at these wavelength, quantitative determination of glyphosate in the presence of PMIDA is possible. For model mixtures a correlation is revealed between the actual glyphosate concentration and the one derived from absorbance at characteristic bands. As shown, NMR (1H, 31P) and IR spectrometry yield comparable results. The method is verified by an analysis of the final product prepared by liquid-phase oxidation of PMIDA to glyphosate using hydrogen peroxide and may be utilized in quality control in its manufacture.

Catalytic Oxidation of N-Phosphonomethyliminodiacetic Acid to Synthesize N-Phosphonomethylylycine

Catalytic Oxidation of N-Phosphonomethyliminodiacetic Acid to Synthesize N-Phosphonomethylylycine

Macro Kinetics of N-Phosphonomethyliminodiacetic Acid Catalytic Oxidation

The oxidation of N-phosphonomethyliminodiacetic acid (PMIDA) to prepare glyphosate (PMG) over active carbon was investigated. Experiments were carried out with O2 as the oxidizing agent in a 150-mL autoclave made in stainless steel, with reaction temperature ranging from 323.15 to 353.25K and the pressure from 0.12 to 0.40 MPa. The macro kinetic model of the reactions in series was developed, and the pre-exponential factor and activation energy were estimated from the measured data in experiments. The influence of dissolved oxygen concentration was also considered in this macro kinetic model. The results indicated that the two step reactions are all one-order to reactant (PMIDA or PMG) and 0.3 or 0.07 to O2 respectively. The active energy was 12.98kJ/mol for the first step reaction and 10.87kJ/mol for the second step reaction.

Macro Kinetics of N-Phosphonomethyliminodiacetic Acid Catalytic Oxidation

The oxidation of N-phosphonomethyliminodiacetic acid (PMIDA) to prepare glyphosate (PMG) over active carbon was investigated. Experiments were carried out with O2 as the oxidizing agent in a 150-mL autoclave made in stainless steel, with reaction temperature ranging from 323.15 to 353.25K and the pressure from 0.12 to 0.40 MPa. The macro kinetic model of the reactions in series was developed, and the pre-exponential factor and activation energy were estimated from the measured data in experiments. The influence of dissolved oxygen concentration was also considered in this macro kinetic model. The results indicated that the two step reactions are all one-order to reactant (PMIDA or PMG) and 0.3 or 0.07 to O2 respectively. The active energy was 12.98kJ/mol for the first step reaction and 10.87kJ/mol for the second step reaction.

The Effect and Counter-Effect of Impurities on Crystallization of an Agrochemical Active Ingredient: Stereochemical Rationalization and Nanoscale Crystal Growth Visualization

The molecular mechanisms underpinning the effects of impurities (reaction byproduct) on the crystallization of N-phosphonomethyl glycine (PMG), a common herbicide, are presented. The impurities, iminobismethylene phosphonic acid (IMPA) and amino methyl phosphonic acid (AMPA), were incorporated into PMG crystals by selectively adsorbing onto the (100) face, and subsequently, caused major reduction in the growth rate of this face of the crystal. In contrast, the impurity N-phosphonomethyl imino diacetic acid (PIDA), with a lower binding affinity to PMG crystals, did not affect the crystal habit significantly. These experimental results are rationalized based on stereospecific interaction of the impurities with the PMG crystal and binding energy calculations. Interestingly, when PIDA is present along with IMPA or AMPA in the crystallizing solution, it produced a beneficial effect by counteracting the habit-modifying effects of the other two impurities. In situ monitoring of crystal growth from pure and impur...

Single step surface modification of highly stable magnetic nanoparticles for purification of His-tag proteins

The aim of this study was to develop a simple, cheap, and rapid method for purification of His-tag recombinant proteins with high yields. The new immobilized metal ion affinity adsorbent containing superparamagnetic nanoparticles and hydrophilic resins are proposed here to improve the purification of His-tagged recombinant proteins. In this report, we have described the preparation of nanosized superparamagnetic nanoparticles (Fe3O4) which were prepared by chemical precipitation method followed by surface modification using phosphonomethyl iminodiacetic acid. The stable surface functionalized nanoparticles were further linked with Ni2+ for purification of 6× His-tagged proteins. The phosphonate group of the N-phosphonomethyl iminodiacetic acid ligand acts as a surface anchoring agent on magnetite nanoparticles and the remaining free –COOH groups outside for binding with Ni2+ ions. The nanoparticles were approximately 6–8 nm in size and were stable and had negligible non-specific binding for protein. The proteins were purified within 1 h and observed on sodium dodecyl sulfate-polyacrylamide electrophoresis gel.

Biofunctionalized, Phosphonate‐Grafted, Ultrasmall Iron Oxide Nanoparticles for Combined Targeted Cancer Therapy and Multimodal Imaging

A novel, inexpensive biofunctionalization approach is adopted to develop a multimodal and theranostic nanoagent, which combines cancer-targeted magnetic resonance/optical imaging and pH-sensitive drug release into one system. This multifunctional nanosystem, based on an ultrasmall superparamagnetic iron oxide (USPIO) nanocore, is modified with a hydrophilic, biocompatible, and biodegradable coating of N-phosphonomethyl iminodiacetic acid (PMIDA). Using appropriate spacers, functional molecules, such as rhodamine B isothiocyanate, folic acid, and methotrexate, are coupled to the amine-derivatized USPIO-PMIDA support with the aim of endowing simultaneous targeting, imaging, and intracellular drug-delivering capability. For the first time, phosphonic acid chemistry is successfully exploited to develop a stealth, multifunctional nanoprobe that can selectively target, detect, and kill cancer cells overexpressing the folate receptor, while allowing real-time monitoring of tumor response to drug treatment through dual-modal fluorescence and magnetic resonance imaging.

Active carbons as catalysts for liquid phase reactions

This paper gives three examples of applications of activated carbons, including synthetic carbons obtained from polymers, in selective liquid phase organic reactions. It is shown that ruthenium supported on activated carbon cloths (ACC) obtained by carbonisation of woven rayon fabric are very selective in the hydrogenation of glucose to sorbitol. This is attributed to an easy mass transfer from the micropores to the liquid phase which favours the fast desorption of sorbitol avoiding epimerisation to mannitol. Synthetic carbons obtained by carbonisation of cross-linked phenolic resins are active in the oxidation with air of cyclic ketones (cyclohexanone, cyclododecanone, 3,3,5-trimethylcyclohexanone) to the corresponding dicarboxylic acids. The activity and selectivity depend upon treatments favouring the presence of surface functional groups, particularly quinone/carbonyl groups. This paper also shows that activated carbons obtained from natural sources can be modified by thermal treatments favouring the presence of basic sites which improve the rate of the oxidative decarboxylation of N-phosphonomethyl iminodiacetic acid to glyphosate. The nitrogen-containing basic functions generated by high temperatures thermal treatment of the activated carbon in NH 3 are particularly active.

Phosphorylated derivatives that activate or inhibit mammalian adenosine kinase provide insights into the role of pentavalent ions in AK catalysis.

The enzyme adenosine kinase (AK) exhibits a nearly complete dependency on the presence of pentavalent ions (PVI) such as phosphate, arsenate, and vanadate. To understand its basis, the effect of a large number of phosphorylated compounds on AK activity was examined. Several compounds, such as phosphoribosyl pyrophosphate, phosphoenol pyruvate, creatine phosphate, phosphorous acid, phosphonoformic acid, and inorganic pyrophosphate, were found to substitute for PVI in stimulating AK activity. Similar to PVI, these compounds lowered the Km of AK for adenosine. In contrast, many other structurally related compounds (i.e., phosphonoacetic acid, 2-carboxyethyl phosphonic acid, N-phosphonomethyl glycine, N-phosphonomethyl iminodiacetic acid) inhibited AK activity. These compounds seemed to compete with the activators for binding to AK. Structural comparisons of different compounds indicate that all activating compounds contain a net positive charge on the pentavalent atom (e.g., phosphorous), which should enable it to act as an acceptor for a nucleophilic group. We suggest that a phosphate (or other activator) bound near the active site participates in AK catalysis by forming a transient pentavalent intermediate with a nonbridging oxygen of the beta-phosphate in ATP. This interaction likely facilitates the transfer of gamma-phosphate from ATP to adenosine, thus accounting for the stimulating role of PVI in AK catalysis. The insight provided by these studies concerning the structural features of activators and inhibitors should also prove helpful in the design of more potent inhibitors of AK.

Effect of the Nature of Carbon Catalysts on Glyphosate Synthesis

Aqueous solutions of PMIDA (N-phosphonomethyliminodiacetic acid) were oxidized, using air, to obtain glyphosate (N-(phosphonomethyl)glycine) an active herbicide. The oxidative decarboxylation reaction was catalyzed selectively by active carbons obtained from different precursors and modified by specific thermal treatments. The activities were highly dependent upon the functional groups present on the carbon surface. Nitrogen-containing functional groups greatly enhanced the oxidation rates; these groups were either issued from the carbon precursors or introduced by thermal treatment under NH3of active carbons. The highest rates of PMIDA oxidation were obtained using nonactivated carbons treated with NH3at 900°C. Activities were also enhanced by thermal treatments at 900°C under N2which eliminated the acidic sites from the carbon surface, and possibly created active basic sites.

Biodegradation of N-phosphonomethyliminodiacetic acid by microorganisms from industrial activated sludge

A microbial population that biodegraded N-phosphonomethyliminodiacetic acid (PIA), a key component of glyphosate (N-phosphonomethylglycine) process waste, was established. The stoichiometric conversion of PIA to aminomethylphosphonic acid (AMPA) was observed in a laboratory sequencing batch reactor (SBR) containing activated sludge from a glyphosate-manufacturing facility and PIA as sole source of carbon. PIA degradation was determined by high-performance liquid chromatography and confirmed by radiolabeled studies. Greater than 90% of the [carboxymethyl-2-14C]-label of PIA was released as 14CO2 in 7 days using samples of sludge from the SBR. The cycle time required to biodegrade up to 7.5 mM PIA in SBRs was reduced from 21 to < 3 days. PIA biodegradation was also established in an immobilized bacteria column inoculated with mixed liquor from a SBR; > 99% PIA removal was achieved at an influent concentration of 2.2 mM and a hydraulic retention time of < 10 h. A pure bacterial culture was isolated from a SBR by streaking samples of sludge on solid media with PIA as sole carbon source. The isolate was identified as Xanthomonas maltophilia. In liquid culture, X. maltophilia degraded up to 4.4 mM PIA within 10 days and produced stoichiometric amounts of AMPA. The results demonstrate the biodegradation of PIA and suggest the potential for its treatment in industrial biological treatment systems.