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Reactivation of organophosphate (OP)-inhibited acetylcholinesterase (AChE) is a key objective in the treatment of OP poisoning. This study with native, wild-type, and mutant recombinant DNA-expressed AChEs, each inhibited by representative OP compounds, establishes a relationship between edrophonium acceleration of oxime-induced reactivation of OP-AChE conjugates and phosphoryl oxime inhibition of the reactivated enzyme that occurs during reactivation by pyridinium oximes LüH6 and TMB4. No such recurring inhibition could be observed with HI-6 as the reactivator due to the extreme lability of the phosphoryl oximes formed by this oxime. Phosphoryl oximes formed during reactivation of the ethoxy methylphosphonyl-AChE conjugate by LüH6 and TMB4 were isolated for the first time and their structures confirmed by (31)P NMR. However, phosphoryl oximes formed during the reactivation of the diethylphosphoryl-AChE conjugate were not sufficiently stable to be detected by (31)P NMR. The purified ethoxy methylphosphonyl oximes formed during the reactivation of ethoxy methylphosphonyl-AChE conjugate with LüH6 and TMB4 are 10- to 22-fold more potent than MEPQ as inhibitors of AChE and stable for several hours at pH 7.2 in HEPES buffer. Reactivation of both ethoxy methylphosphonyl- and diethylphosphoryl-AChE by these two oximes was accelerated in the presence of rabbit serum paraoxonase, suggesting that organophosphorus hydrolase can hydrolyze phosphoryl oxime formed during the reactivation. Our results emphasize that certain oximes, such as LüH6 and TMB4, if used in the treatment of OP pesticide poisoning may cause prolonged inhibition of AChE due to formation of phosphoryl oximes.
Although lipid phosphoric acid mediators such as lysophosphatidic acid (LPA) are now recognized widely as intercellular signaling molecules, the medicinal chemistry of these mediators is poorly developed. With the goal of achieving a better understanding of the structure activity relationships in LPA, we have synthesized and tested a series of LPA analogs that lack the 2-hydroxyl moiety. Our series consisted of compounds with 2, 3, or 4 carbon diol or amino alcohol backbones and oleoyl or palmitoleoyl acyl groups. These molecules cannot be acylated further to form phosphatidic acids, nor do they have chiral centers. The rank order potency of these compounds in mobilization of calcium in MDA MB-231 cells suggested a maximum optimal chain length of 24-25 atoms. However, high potency for the inhibition of adenylyl cyclase in these cells was achieved only by one compound that also contained a dissociable proton five bond lengths from the phosphorus atom. That compound, N-oleoyl-2-hydroxyethyl-1-phosphate, was nearly equipotent to 1-oleoyl LPA in both assays. The striking mimicry of LPA by the ethanolamine-based compound and the presence of fatty acid amides in tissue prompts us to propose that phosphorylated N-acyl ethanolamides occur naturally.
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Analysis of element composition (sodium, potassium, magnesium, calcium, zinc, copper, iron, total sulfur and its compounds, chloride, and inorganic phosphorus) in 40 normal subjects (22 women and 18 men aged 17-30 years) showed that the composition is specific for each of the analyzed media (blood, plasma, erythrocytes, urine, saliva, exhaled air condensate). Element composition of exhaled air condensate is described for the first time. Analysis of element composition in 102 patients with asthma demonstrated characteristic shifts in the concentrations of some macro- and trace elements, which confirms the clinical significance of analysis and correction of deviations in the element composition of biological media.
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The duckweed Spirodela oligorrhiza was grown in sterile nutrient solutions that contained 1 mm phosphate-(32)P at various specific activities. In solutions with activities higher than 2 muc per mumole per ml, plant growth was inhibited after a time, and the physical appearance of the plants was affected. The critical level of radiation, at which growth was first affected, corresponded to 5 kilorads.Plants were grown for 9 days (5 generations) in a culture solution containing phosphate at 0.5 muc per mumole per ml (radiation load approx 0.5 kilorads) so that all phosphorus-containing materials in the tissue became uniformly labeled. The various radioactive compounds were extracted, chromatographed, identified, and their radioactivity was measured. From this radioactivity plus the specific activity of the supplied phosphate, the amount of each compound was calculated. The data constitute a complete balance-sheet for phosphorus in a plant tissue. The identity of 98% of the phosphorus in the tissue was determined. Inorganic phosphate (32,700 mmumoles/g fr wt) was the predominant phosphorus-containing compound; RNA (5100 mmumoles P/g fr wt) was the main organic phosphate; phosphatidyl choline (1600 mmumoles/g fr wt) was the main phospholipid, and glucose-6-phosphate (500 mmumoles/g fr wt) the main acid-soluble phosphate ester. Amounts of other phosphorus compounds are given.
A strain of Agromyces fucosus, designated Vs2, metabolized a range of organophosphonate compounds as sole phosphorus sources for growth and metabolized phosphonoacetate as a sole carbon, energy and phosphorus source for growth. With phosphonoacetate as the sole phosphorus source and a pyruvate carbon source, transient phosphate release to the medium was observed, in contrast to cultures grown with glucose and phosphonoacetate, where no phosphate release to the medium was observed. Carbon catabolite repression, specifically by means of inducer exclusion of phosphonoacetate, was proposed as the mechanism responsible, and phosphonoacetate hydrolase enzyme assays carried out on cell extracts confirmed that induced phosphonoacetate hydrolase activities were indeed higher in cells grown on pyruvate with phosphonoacetate as sole phosphorus source. This phenomenon has not previously been demonstrated in vivo, and must represent a significant metabolic control of organophosphonate metabolism. The catabolite repression phenomenon was also evident when A. fucosus grew on 2-aminoethylphosphonate as sole phosphorus source, allowing demonstration of a third mode of control for biodegradation of this compound. Excision of stained zymogram gel pieces, followed by tryptic digestion and mass spectrometric analysis, allowed the identification of phosphonoacetate hydrolase-derived peptides.
This tutorial review aims at presenting recent contributions dealing with organic chemistry of organophosphorus radicals. The first part briefly lays out the physical organic background of such intermediates. In a second part the use of organophosphorus radicals possessing a P-H bond that can undergo homolytic cleavage as alternative mediators is detailed. The third part is focused on radical additions of phosphorus-centered radicals to unsaturated compounds, an old reaction that is being rejuvenated. Lastly, radical eliminations of phosphorus-centered radical are introduced in the fourth part. Most of the latter are relatively novel reactions, and have never been reviewed previously.
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Aluminum toxicity is becoming more and more evident as a complication of maintenance dialysis treatment. The aluminum contamination of the dialysate bath solution no longer plays an important role. The main source of aluminum overloading turns out to be the ingestion of aluminum-containing antacids as phosphate binders in the impaired renal aluminum excretion. In 19 dialysis patients an antacid poor in aluminum (Magaldrate) was compared with one rich in aluminum (compound M 70). The serum concentrations of aluminum, magnesium, phosphorus and calcium were investigated over a period of 14 days. After M 70 the aluminum and magnesium levels were markedly more elevated than after Magaldrate. Calcium remained unchanged with both compounds. Phosphorus was diminished only by M 70. The results of this short term study on dialysis patients are also important for patients with normal renal function, in particular in cases of uncontrolled long term treatment with antacids rich in aluminum.
A method for the selective concentration of dissolved organic phosphorus (DOP) from complex surface water samples for the first time allows mass spectral characterization of individual DOP compounds in phosphorus-limited ecosystems. The entire dissolved organic matter (DOM) pool is first separated according to molecular weight by tangential cross-flow ultrafiltration (CFF). DOP is selectively isolated and concentrated from CFF fractions by a barium precipitation procedure. The DOP precipitate is then reconstituted in distilled water and excess barium, and other cations are removed with an ion-exchange resin. The DOP isolation/concentration step can provide up to 15-fold concentration and 300-fold concentration of high molecular weight DOP when combined with the inherent concentration provided by CFF. The procedure also removes cations and most of the background DOM, leaving DOP in a matrix suitable for electrospray ionization and mass spectral characterization. Model organic phosphate standards representative of DOP species expected in aquatic environments were used to evaluate the technique. It was then applied to a series of high molecular weight (>1000) CFF retentates isolated from sites within the Everglades Nutrient Removal (ENR) treatment wetland. The elemental compositions of several individual DOP compounds observed at different sites within the ENR were determined by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.
This paper evaluates the experiences with modelling full-scale biological phosphorus and nitrogen removing wastewater treatment plants. For the simulation, we used a metabolic phosphorus model integrated in ASM2d, further referred to as TUDP-model. It was found that the metabolic model for bio-P removal can be applied for modelling full-scale wwtp's, without extensive parameter adjustments. A stepwise modelling approach was proposed. Only three specific parameters were calibrated. Two parameters, the inert fraction in the influent and the actual anoxic sludge fraction will need calibration for all systems. Parameter sensitivity analyses showed that the sensitivity of operational data, often considered as known input data, is high. The model kinetics were found less sensitive. This will in general be the case for all low-loaded wwtp's recorded in their pseudo-steady state. Based on mass balance calculations, operational data and measurements were evaluated. Since all terms on a phosphorus balance can be measured, errors in operational data (e.g. SRT and flow rates) become very apparent in P-removal models (ASM2d, TUDP). We suggest using the P-balance in general for wwtp modelling, as a check on data consistency. This study showed that considering operational data per definition as known input data is not justified. Therefore, operational data should be evaluated, or considered in model calibration over the use of kinetic and stoichiometric parameters.
The influence of nutrients, Mycobacterium sp. strain CH1 and Mycobacterium sp. strain CH2 on the degradation of aged creosote hydrocarbon contaminants was investigated. The Mycobacterium sp. strain CH2 showed the highest positive influence on the degradation of three- and four-ring PAH compounds. The addition of Mycobacterium sp. strain CH1 had the second highest measured positive influence on the degradation of four-ring compounds. Soluble nitrogen and phosphorus also increased the degradation of aged creosote compounds in the contaminated soil. The addition of bacteria decreased the number of measured bacterial species, indicating competition for limited nutrients in the soil.
This paper describes a novel method for the detection of compounds that do not contain nitrogen or phosphorus by a thermionic nitrogen-phosphorus specific detector (NPD), which normally detects only nitrogen- or phosphorus-containing compounds. This method allows for the calibration of gas chromatographic columns with NPD detectors using n-alkanes instead of nitrogen-containing drug mixtures. This results in a more rapid and accurate calibration for the calculation of relative retention indices (RRI), such as Kováts indices, than was previously possible when employing an NPD detector. The proposed method describes the temporary conversion of the NPD detector into a detector with properties much like a flame ionization detector. After a deliberate increase in the hydrogen gas flow rate to the thermionic bead from 4 ml/min to 8 ml/min, the n-alkanes (containing no nitrogen) can be detected and used as RRI calibrators. Once the column has been calibrated, the hydrogen gas flow rate is lowered to the normal rate of 4 ml/min. The detector then behaves as a normal NPD, no longer detecting the n-alkanes.
BOP-Cl was found to be an efficient coupling reagent for the introduction of thiopeptide bonds on imino acid residues (Pro, Sar). Boc-amino monothioacids were coupled at moderate temperature (0 degree C-RT) with fair yields and with retained optical purity. The mechanism of the coupling reaction is discussed.
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