Partial Fluxes of Phosphoric Acid Anions through Anion-Exchange Membranes in the Course of NaH2PO4 Solution Electrodialysis.

Electrodialysis (ED) with ion-exchange membranes is a promising method for the extraction of phosphates from municipal and other wastewater in order to obtain cheap mineral fertilizers. Phosphorus is transported through an anion-exchange membrane (AEM) by anions of phosphoric acid. However, which phosphoric acid anions carry the phosphorus in the membrane and the boundary solution, that is, the mechanism of phosphorus transport, is not yet clear. Some authors report an unexpectedly low current efficiency of this process and high energy consumption. In this paper, we report the partial currents of H2PO4-, HPO42-, and PO43- through Neosepta AMX and Fujifilm AEM Type X membranes, as well as the partial currents of H2PO4- and H+ ions through a depleted diffusion layer of a 0.02 M NaH2PO4 feed solution measured as functions of the applied potential difference across the membrane under study. It was shown that the fraction of the current transported by anions through AEMs depend on the total current density/potential difference. This was due to the fact that the pH of the internal solution in the membrane increases with the growing current due to the increasing concentration polarization (a lower electrolyte concentration at the membrane surface leads to higher pH shift in the membrane). The HPO42- ions contributed to the charge transfer even when a low current passed through the membrane; with an increasing current, the contribution of the HPO42- ions grew, and when the current was about 2.5 ilimLev (ilimLev was the theoretical limiting current density), the PO43- ions started to carry the charge through the membrane. However, in the feed solution, the pH was 4.6 and only H2PO4- ions were present. When H2PO4- ions entered the membrane, a part of them transformed into doubly and triply charged anions; the H+ ions were released in this transformation and returned to the depleted diffusion layer. Thus, the phosphorus total flux, jP (equal to the sum of the fluxes of all phosphorus-bearing species) was limited by the H2PO4- transport from the bulk of feed solution to the membrane surface. The value of jP was close to ilimLev/F (F is the Faraday constant). A slight excess of jP over ilimLev/F was observed, which is due to the electroconvection and exaltation effects. The visualization showed that electroconvection in the studied systems was essentially weaker than in systems with strong electrolytes, such as NaCl.

An Improved Strategy for the Chemical Synthesis of 3',5'-Cyclic Diguanylic Acid.

The physiological functions of c-di-GMP and its involvement in many key processes led to its recognition as a major and ubiquitous bacterial second messenger. Aside from being a bacterial signaling molecule, c-di-GMP is also an immunostimulatory molecule capable of inducing innate and adaptive immune responses through maturation of immune mammalian cells. Given the broad biological functions of c-di-GMP and its potential applications as a nucleic-acid-based drug, the chemical synthesis of c-di-GMP has drawn considerable interest. An improved phosphoramidite approach to the synthesis of c-di-GMP is reported herein. The synthetic approach is based on the use of a 5'-O-formyl protecting group, which can be rapidly and chemoselectively cleaved from a key dinucleotide phosphoramidite intermediate to enable a cyclocondensation reaction leading to a fully protected c-di-GMP product in a yield ∼80%. The native c-di-GMP is isolated, after complete deprotection, in an overall yield of 36% based on the commercial ribonucleoside used as starting material. © 2019 by John Wiley & Sons, Inc.

The Use of a Molybdenum Polyoxometalated Compound to Increase the Amount of Extractives from Wood Wastes.

The treatment of wood wastes of Castanea sativa L., Quercus frainetto, Larix decidua, and Paulownia tomentosa S. in autoclave in the presence of micrometric crystals of H3PMo12O40 showed an impressive increase of the amount of extractives. The extractives were mainly constituted of insoluble compounds that were analyzed by using gas chromatography-mass spectrometry (GC-MS) after acetylation. The GC-MS analysis of the chloroform soluble fraction of the extractives obtained from sativa showed the presence of methyl hexadecanoate and octadecanoic acid, that of the extractives of frainetto showed the presence of octadecanal and some long chain hydrocarbons. decidua extracts showed the presence of large amounts of sesamin, while the extractives of P tomentosa revealed the presence of 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxy-3,5-dimethoxycimmanaldehyde, and relevant amounts of long chain hydrocarbons. The insoluble fraction showed the presence of relevant amounts of several carbohydrates and, in the case of C. sativa, of inositol.

Cation-enhanced capillary electrophoresis separation of atropoisomer anions.

CE was used to study the separation of the atropoisomers of four phosphoric acids and two sulfonic acids and the enantiomers of two phosphoric acids. All solutes are in their anionic forms in aqueous electrolytes. The chiral additives were two hydroxypropyl cyclodextrins (CDs) and cyclofructan 6 (CF6). The CDs were able to separate four solutes and the CF6 additive could separate only one: 1,1'-binaphthyl-2,2'-diyl hydrogenphosphate (BHP). Since CF6 is able to bind with cations, nitrate of alkaline metals, Ba(2+) , and Pb(2+) were added, greatly improving the BHP separation at the expense of longer migration times. There seems to be a link between CF6-cation-binding constants and BHP resolution factors. Cation additions were also performed with CD selectors that are less prone to form complexes with cations. Significant improvements of enantiomer or atropoisomer separations were observed also associated with longer migration times. It is speculated that the anionic solutes associate with the added cations forming larger entities better differentiated by CDs.

Adsorption of orthophosphoric, pyrophosphoric, and tripolyphosphoric acids from aqueous solutions by calcined gibbsite.

In this research, gibbsite (GB) samples calcined at 200-1000°C (GB200-GB1000) were produced. These GBs were used to adsorb orthophosphoric, pyrophosphoric, and tripolyphosphoric acids from aqueous solutions. The properties (amounts of hydroxyl groups, specific surface areas, mean pore diameters, and solution pHs) of the GBs were investigated, and their adsorption capacities for phosphoric acids evaluated. The amount of hydroxyl groups (0.46 mmol/g) and specific surface area (295.3 m(2)/g) of GB400 were greater than those of the other GBs. The mechanism of phosphoric acid adsorption on the GBs was related to the amount of hydroxyl groups and specific surface area. The optimal pH for phosphoric acid adsorption by GBs was 2.0-3.0. Equilibrium adsorption was reached within 24 h. The adsorption processes followed a pseudo-second-order kinetic model (correlation coefficient, 0.998-0.999). The adsorption capacity increased with increasing temperature. The adsorption isotherm data fitted the Langmuir (correlation coefficient: 0.921-0.992) and Freundlich (correlation coefficient: 0.948-0.997) equations well. Our results will be useful when developing methods for the adsorption of phosphoric acids from aqueous solutions.

Purification of wet process phosphoric acid by decreasing iron and uranium using white silica sand.

Natural white silica sand as an adsorbent has been developed to reduce the concentration of iron and uranium ions as inorganic impurities in crude Egyptian phosphoric acid. Several parameters such as adsorbate concentration, adsorbent dose, volume to weight ratio and temperature, were investigated. Equilibrium isotherm studies were used to evaluate the maximum sorption capacity of adsorbent. Thermodynamic parameters showed the exothermic nature of the process and the negative entropy reflects the affinity of the adsorbent material towards each metal ion.

Fast separation of antiviral nucleoside phosphoramidate and H-phosphonate diastereoisomers by reversed-phase liquid chromatography.

The nucleoside-based antiviral phosphoramidates and H-phosphonates were synthesized and separated using reversed-phase liquid chromatography on bridged ethane hybrid (BEH) C18 column packed with 1.7 µm particles of non-chiral stationary phase. The influences of the composition of mobile phase and column temperature have been investigated to optimize the diastereoisomeric separation. Complete separations of the phosphoramidate and H-phosphonate prodrugs with good resolution (R(S)=1.99-2.77) were achieved within a short time (5-9 min). The validation study of the optimized method including linearity, accuracy, repeatability and detection limit has revealed it is better performance versus conventional HPLC method. In addition, HPLC was combined with high resolution electrospray ionization time-of-flight mass spectrometry (ESI-TOF MS), which enabled the exact mass measurement and high sensitivity. Using MS as detection, the limits of detection and limits of quantification of the studied pronucleotide diastereoisomers were determined in the range of several nmol L⁻¹ level.

Decommissioning a phosphoric acid production plant: a radiological protection case study.

During a preliminary survey at the area of an abandoned fertilizer plant, increased levels of radioactivity were measured at places, buildings, constructions and materials. The extent of the contamination was determined and the affected areas were characterized as controlled areas. After the quantitative and qualitative determination of the contaminated materials, the decontamination was planned and performed step by step: the contaminated materials were categorized according to their physical characteristics (scrap metals, plastic pipes, scales and residues, building materials, etc) and according to their level of radioactivity. Depending on the material type, different decontamination and disposal options were proposed; the most appropriate technique was chosen taking into account apart from technical issues, the legal framework, radiation protection issues, the opinion of the local authorities involved as well as the owner's wish. After taking away the biggest amount of the contaminated materials, an iterative process consisting of surveys and decontamination actions was performed in order to remove the residual traces of contamination from the area. During the final survey, no residual surface contamination was detected; some sparsely distributed low level contaminated materials deeply immersed into the soil were found and removed.

Production of technical grade phosphoric acid from incinerator sewage sludge ash (ISSA).

The recovery of phosphorus from sewage sludge ash samples obtained from 7 operating sludge incinerators in the UK using a sulfuric acid washing procedure to produce a technical grade phosphoric acid product has been investigated. The influences of reaction time, sulfuric acid concentration, liquid to solid ratio and source of ISSA on P recovery have been examined. The optimised conditions were the minimum stoichiometric acid requirement, a reaction time of 120 min and a liquid to solid ratio of 20. Under these conditions, average recoveries of between 72% and 91% of total phosphorus were obtained. Product filtrate was purified by passing through a cation exchange column, concentrated to 80% H(3)PO(4) and compared with technical grade H(3)PO(4) specifications. The economics of phosphate recovery by this method are briefly discussed.

Preparation of alumina-iron oxide compounds by gel evaporation method and its simultaneous uptake properties for Ni2+, NH4+ and H2PO4-.

Fe(2)O(3)/Al(2)O(3) powders with a range of Fe/Al compositions were prepared by a gel evaporation method to investigate the effect of alumina on the product phases, magnetic properties and simultaneous adsorption of Ni(2+) (a model heavy metal cation), NH(4)(+) (a model eutrophication-related cation) and H(2)PO(4)(-) (a model harmful anion). Precursor gels were prepared by dissolving Fe(NO(3))(3).9H(2)O and Al(NO(3))(3).9H(2)O in ethylene glycol, evaporating to dryness, grinding and heating at 300-1000 degrees C for 5h. The crystalline products were gamma-Fe(2)O(3) (maghemite), formed at 300-600 degrees C, or alpha-Fe(2)O(3) (hematite) and AlFeO(3), formed >600 degrees C. The temperatures of the phase change from gamma-Fe(2)O(3) to alpha-Fe(2)O(3) increased with increasing alumina additions. The resulting lattice parameters suggest that Al(3+) is incorporated into these phases up to about 15 mol.% at 300 degrees C, falling to 11 mol.% in the gamma-Fe(2)O(3) formed at 600 degrees C. The alpha-Fe(2)O(3) formed at 700 degrees C contained 6 mol.% Al, increasing to 14 mol.% at 1000 degrees C. The magnetic properties of the samples were measured using a vibrating sample magnetometer. The saturation magnetization values of the gamma-Fe(2)O(3)-containing samples increased with the addition of alumina to a maximum value of 61emu/g in the sample containing 95 mol.% Fe(2)O(3) heated at 400 degrees C. The simultaneous adsorption of Ni(2+), NH(4)(+) and H(2)PO(4)(-) from water was investigated by a batch method. The highest adsorption values were found for the sample containing 80 mol.% Fe(2)O(3) heated at 600 degrees C, which contained both gamma-Fe(2)O(3) and alpha-Fe(2)O(3). It was therefore concluded that the addition of alumina to iron oxide affects the crystalline phases and phase changes, and enhances the simultaneous cation and anion uptake ability of the materials.

Behaviour and fluxes of natural radionuclides in the production process of a phosphoric acid plant.

In recent years there has been an increasing awareness of the occupational and public hazards of the radiological impact of non-nuclear industries which process materials containing naturally occurring radionuclides. These include the industries devoted to the production of phosphoric acid by treating sedimentary phosphate rocks enriched in radionuclides from the uranium series. With the aim of evaluating the radiological impact of a phosphoric acid factory located in the south-western Spain, the distribution and levels of radionuclides in the materials involved in its production process have been analysed. In this way, it is possible to asses the flows of radionuclides at each step and to locate those points where a possible radionuclide accumulation could be produced. A set of samples collected along the whole production process were analysed to determine their radionuclide content by both alpha-particle and gamma spectrometry techniques. The radionuclide fractionation steps and enrichment sources have been located, allowing the establishment of their mass (activity) balances per year.

Separation of nucleoside phosphoramidate diastereoisomers by high performance liquid chromatography and capillary electrophoresis.

Separations of five diastereoisomers of nucleoside phosphoramidate derivatives (pronucleotides) were performed by both HPLC method using derivatized cellulose and amylose chiral stationary phases and CE method using anionic cyclodextrins added in the background electrolyte (BGE). An optimal baseline separation (Rs > 1.5) was readily obtained with all silica-based celluloses and amyloses using in a normal-phase methodology. Capillary electrophoresis was used as an alternative technique to HPLC for the separation of pronucleotides. The diastereoisomers were fully resolved with sulfated cyclodextrins at both BGE pH (2.5 and 6.2). Limits of detection and limits of quantification, calculated for both methods, are up to 200 times higher in CE separations than in HPLC separations. The analytical HPLC method was then applied in a preliminary study for the pronucleotide 1 quantification in cellular extract.

Adsorption behavior of hexafluorophosphate on selected bonded phases.

The adsorption behavior of ammonium hexafluorophosphate was studied on four HPLC columns packed with adsorbents of different ability for dispersive interactions using frontal chromatography with LC/MS detection in negative ESI mode. Hexafluorophosphate (PF(6)(-)) adsorption isotherms were measured from acetonitrile/water and methanol/water mixtures. Increased PF(6)(-) adsorption with increased acetonitrile content was found between 0 and 15% of acetonitrile in the eluent. Further increase of the acetonitrile concentration leads to an exponential decrease of PF(6)(-) adsorption. Methanol, on the other hand, causes a steady decrease of PF(6)(-) adsorption with increased organic concentration in the mobile phase.

Isolation and characterization of some hydroxy fatty and phosphoric acid esters of 10-hydroxy-2-decenoic acid from the royal jelly of honeybees (Apis mellifera).

The present work characterizes novel FA in the royal jelly of honeybees (Apis mellifera). TLC analysis showed that the chloroform/methanol extract obtained from royal jelly consists mainly of FA. The FABMS spectrum of this extract gave several ion peaks due to compounds with higher M.W. than those of the FA so far reported. The methanol extract was found to contain unknown phospholipids. By means of reversed-phase HPLC with various solvent systems, 13 compounds were obtained in pure state. Their structures including absolute configurations were determined by chemical, NMR, and MS spectral analysis. Six compounds were identified as novel mono- or di-esters of 10-hydroxy-2E-decenoic acid in which the hydroxyl group was esterified by another FA unit, and one was hydroxy-2E-decenoic acid 10-phosphate. In addition, we demonstrated that 9-hydroxy-2E-decenoic acid exists as a mixture of optical isomers.

Liquid chromatographic separation of phosphoramidate diastereomers on a polysaccharide-type chiral stationary phase.

To improve the therapeutic potential of anti-HIV nucleoside analogues (d4T, AZT, 3TC and ddl), the delivery of the corresponding monophosphate from neutral, membrane-permeable prodrugs has been realised by the synthesis of lipophilic phosphoramidate triester prodrugs, such as the simple phenyl-L-alaninephosphate derivatives. However, the present non-stereoselective synthesis results in a mixture of 1:1 diastereomers, which differ from the configuration of the phosphorus atom asymmetric center. Since each diastereomer may have different biological activity and pharmacokinetic profile, analytical methods have to be developed for their separation. This work aims at showing the ability of a polysaccharide-type chiral stationary phase to resolve such diastereomers in reversed-phase high-performance liquid chromatography. The influence of operating parameters has been studied to optimise the separation; a thermodynamic approach has also been investigated to gain an insight in the retention mechanism of the prodrugs. Preliminary validation study (linearity, accuracy, repeatability) has yielded good results; in addition, the feasibility of HPLC-electrospray-mass spectrometry (HPLC-ESI-MS) coupling has been demonstrated and it is expected that this will lead to lower detection limits.

Differential elution of sodium or potassium dihydrogen- and hydrogenphosphate ions from a sephadex G-15 column with sodium or potassium chloride solution.

When a mixed solution of sodium or potassium dihydrogenphosphate and disodium or dipotassium hydrogenphosphate was eluted from a Sephadex G-15 column with either a sodium or potassium chloride solution, the elution profiles of ions showed that the hydrogenphosphate ion was eluted more rapidly than the dihydrogenphosphate ion. When the sample solutions containing potassium dihydrogenphosphate and/or dipotassium hydrogenphosphate, all of which were supplemented with phosphorus-32-labelled potassium dihydrogenphosphate, were eluted with sodium chloride solution, the elution profiles of radioactivity showed that the dihydrogenphosphate ion changed to hydrogenphosphate ion and vice versa, depending on the pH values of the sample solution and the availability of the cation of the eluent during elution for the phosphate ion to pair with.

Synthesis and purification of oligonucleotide N3'-->P5' phosphoramidates and their phosphodiester and phosphorothioate chimeras.

This unit describes the synthesis and purification of oligonucleotide N3'-->P5' phosphoramidates, wherein each 3'-oxygen is replaced by a 3'-amine in the 2'-deoxyribose ring. The synthesis of required monomers and application of the method to preparation of phosphodiester- and phosphorothioate-containing chimera of phosphoramidate is also reported.