Pyrophosphate Salts Research Articles

A novel mechanochemical synthesis of LiMnPO4 with manganese violet and ammonium manganese phosphate as precursors

Olivine lithium manganese phosphate was synthesized by a mechanochemical method. Inorganic cathode materials can be divided into three kinds of lithium metal oxide layered, spinel oxide and olivine metal phosphate. One important of the cathode materials used in Li-ion cells is LiMnPO4. In this paper two different precursors, manganese violet and ammonium manganese phosphate proposed as reactant in the synthesis of LiMnPO4 nanostructures. Reaction between NH4MnP2O7 and Li2CO3 takes placed in solid state at room temperature. In this mechanochemical process, a solid acid and base reaction occurred between ammonium and carbonate ions. In addition, MnIII is unstable oxidation state and convert to crystalline β-MnO2, Li2MnP2O7 and NH4H2PO4 in the disproportionation reaction. Results showed that mechanochemical reaction between NH4MnP2O7 with Li2CO3 as precursors lead to concurrent redox and acid-base reaction. As a result, we observed there is a tendency for manganese violet to disproportionation into MnO2 and manganese pyrophosphate salt in a solid-state reaction. Finally, a redox reaction between β-MnO2 and Li2MnP2O7 in pyrolysis reaction under inert atmosphere give LiMnPO4. In the other hand in the mechanochemical reaction between NH4MnPO4 and Li2CO3, only acid and base reaction occurred and the NH4+ ions were replaced with Li+ ions and amorphous LiMnPO4 was prepared. The amorphous LiMnPO4 convert to crystalline LiMnPO4 by annealing the powder under inert atmosphere. The chemical changes in formation of LiMnPO4 compound was characterized by X-Ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and energy dispersion x-ray analyses (EDX). FTIR spectra showed that the NH4+ ions were replaced with Li+ ions. X-ray diffraction show that by variation of precursor from manganese violet to ammonium manganese phosphate in the mechanochemical reaction the crystalline pattern changes to amorphous and also the reaction pathway was changed. The SEM images of LiMnPO4 nanoparticles that obtained by two precursors exhibit squamous morphologies with well-defined grain boundaries and nonuniform particle size distributions. The particle size distributions of crystalline LiMnPO4 obtained by NH4MnP2O7 and NH4MnPO4 were found in the region 60–260 and 20–130 nm respectively.

Reactivity of Fe(III)-containing pyrophosphate salts with phenolics: complexation, oxidation, and surface interaction

Mixed pyrophosphate salts with the general formula Ca2(1-x)Fe4x(P2O7)(1+2x) potentially possess less iron-phenolic reactivity compared to ferric pyrophosphate (FePP), due to decreased soluble Fe in the food-relevant pH range 3–7. We investigated reactivity (i.e., complexation, oxidation, and surface interaction) of FePP and mixed salts (with x = 0.14, 0.15, 0.18, and 0.35) in presence of structurally diverse phenolics. At pH 5–7, increased soluble iron from all salts was observed in presence of water-soluble phenolics. XPS confirmed that water-soluble phenolics solubilize iron after coordination at the salt surface, resulting in increased discoloration. However, color changes for mixed salts with x ≤ 0.18 remained acceptable for slightly water-soluble and insoluble phenolics. Furthermore, phenolic oxidation in presence of mixed salts was significantly reduced compared to FePP at pH 6. In conclusion, these mixed Ca-Fe(III) pyrophosphate salts with x ≤ 0.18 can potentially be used in designing iron-fortified foods containing slightly water-soluble and/or insoluble phenolics.

Intestinal Absorption Study of a Granular Form of Ferric Pyrophosphate.

Iron deficiency is one of the most prevalent nutritional disorders worldwide. The standard treatment involves iron supplementation, but this task is challenging because of poor solubility and organoleptic issues. Moreover, the need to increase iron bioavailability represents a challenge for treating iron-related disorders. In this study, gastroresistance and iron intestinal absorption of an innovative granular formulation composed of ferric pyrophosphate, modified starch and phospholipids branded as Ferro Fosfosoma® was investigated. Gastroresistant properties were studied using standard protocols, and a bioaccessible fraction was obtained by exposing a food supplement to in vitro digestion. This fraction was used for investigating iron absorption in Caco-2 and human follicle-associated intestinal epithelium (FAE) models. Ferro Fosfosoma® showed an improved resistance to gastric digestion and higher intestinal absorption than ferric pyrophosphate salt used as a control in both models. In the FAE model, Ferro Fosfosoma® induces larger iron absorption than in the Caco-2 monolayer, most likely due to the transcytosis ability of M cells. The larger iron absorption in the Ferro Fosfosoma®-treated FAE model corresponds to higher ferritin level, proving physiological iron handling that was once delivered by granular formulation. Finally, the formulation did not induce any alterations in viability and barrier integrity. To conclude, Ferro Fosfosoma® favors iron absorption and ferritin expression, while preserving any adverse effects.

Design and characterization of Ca-Fe(III) pyrophosphate salts with tunable pH-dependent solubility for dual-fortification of foods

• Characterization of designed mixed salts: Ca 2(1-x) Fe 4x (P 2 O 7 ) (1+2x) (0 < x < 1). • Homogeneous distribution of Ca and Fe in salts was observed for 0.14 ≤ x ≤ 0.35. • Mixed pyrophosphate salts showed enhanced iron solubility in the gastric pH range. • Ca-Fe(III) pyrophosphate salt is a potential delivery system for dual-fortification. Food-fortification using poorly water-soluble mineral-containing compounds is a common approach to deliver iron. However, it comes with the challenge of ensuring iron bio-accessibility and limiting iron-phenolic interactions that can change organoleptic properties. Mixed Ca-Fe(III) pyrophosphate salts with the general formula Ca 2(1-x) Fe 4x (P 2 O 7 ) (1+2x) were designed as a system for simultaneous delivery of iron and calcium. The salts were synthesized via a co-precipitation method and characterized by TEM-EDX, XRD, and FT-IR. All mixed salts with 0.14 ≤ x ≤ 0.35 yielded homogenous amorphous particles. The iron dissolution from these mixed salts showed a fourfold increase at gastric pH compared to Fe(III) pyrophosphate. In the food-relevant pH range, the salts with x ≤ 0.15 showed up to an eight-fold decrease in iron solubility. Despite this, reactivity of the mixed salts in tea was similar to that of FePP. Our results indicate that these mixed salts are potential dual-fortificants with tunable iron content and solubility.

The ability of dual whitening anti-caries mouthrinses to remove extrinsic staining and enhance caries lesion remineralization – An in vitro study

ObjectivesThis laboratory study investigated the ability of dual whitening anti-caries mouthrinses to remove extrinsic staining from artificially stained caries lesions and to enhance their remineralization and fluoridation. Materials and MethodsEarly caries lesions were created in bovine enamel specimens. The lesions were artificially stained and pH cycled for 10 days with the daily cycling regimen consisting of twice daily 60s-treatments with one of 11 mouthrinses, a 4-h demineralization period and artificial saliva treatments in between. Mouthrinses were eight commercially available products, all containing 100ppm fluoride but utilizing hydrogen peroxide, pyro-, tri- or hexametaphosphate salts and/or sodium bicarbonate. The three control mouthrinses were 100ppm fluoride, 30 % hydrogen peroxide and deionized water. Enamel color changes (ΔE) were determined spectrophotometrically. Vickers surface microhardness (VHN) was used to determine lesion remineralization. Enamel fluoride content (EFC) was determined using the microbiopsy technique. Data were analyzed using ANOVA. ResultsΔE was significantly different among groups (p=0.0045). Thirty percent hydrogen peroxide was superior to all other mouthrinses, while there were no differences between commercial mouthrinses and deionized water. There were small, directional but non-significant differences between commercial mouthrinses with those containing hydrogen peroxide providing better whitening. There were no significant differences between mouthrinses in their ability to remineralize caries lesions (p=0.2898). EFC differed among groups (p<0.0001), with the two mouthrinses containing pyrophosphate salts having lower EFC than all but the deionized water group. ConclusionsArtificially stained caries lesions show reduced susceptibility to fluoride remineralization and whitening effects of commercial whitening and anti-caries mouthrinses. Clinical RelevanceArtificially stained caries lesions appear to require stronger than over-the-counter interventions to successfully whiten and remineralizing them.

Ex Vivo and in Vivo Study of Sucrosomial® Iron Intestinal Absorption and Bioavailability.

The present study aimed to demonstrate that Sideral® RM (SRM, Sucrosomial® Raw Material Iron) is transported across the excised intestine via a biological mechanism, and to investigate the effect that this transport route may produce on oral iron absorption, which is expected to reduce the gastrointestinal (GI) side effects caused by the bioavailability of non-absorbed iron. Excised rat intestine was exposed to fluorescein isothiocyanate (FITC)-labeled SRM in Ussing chambers followed by confocal laser scanning microscopy to look for the presence of fluorescein-tagged vesicles of the FITC-labeled SRM. To identify FITC-labeled SRM internalizing cells, an immunofluorescence analysis for macrophages and M cells was performed using specific antibodies. Microscopy analysis revealed the presence of fluorescein positive particulate structures in tissues treated with FITC-labeled SRM. These structures do not disintegrate during transit, and concentrate in macrophage cells. Iron bioavailability was assessed by determining the time-course of Fe3+ plasma levels. As references, iron contents in liver, spleen, and bone marrow were determined in healthy rats treated by gavage with SRM or ferric pyrophosphate salt (FP). SRM significantly increased both area under the curve (AUC) and clearance maxima (Cmax) compared to FP, thus increasing iron bioavailability (AUCrel = 1.8). This led to increased iron availability in the bone marrow at 5 h after single dose gavage.

H3PO4/metal halide induces a one-pot solvent-free esterification–halogenation of glycerol and diols

As part of our continued effort to achieve the synthesis of halohydrin esters from polyols by a sustainable method, here we report on a multicomponent inorganic acid-mediated solvent-free synthesis. The synthesis was designed to ensure few waste materials. Using this approach, the process shows a low E-factor and a high reaction mass efficiency. The new process involves the preparation of a reaction mixture containing either a fatty acid or fatty material, glycerol or diol, a halide salt and H3PO4. This mixture is heated at 100 °C for 48 h, yielding up to 88% of halohydrin ester. The process also allows recovery of pyrophosphate salts, compounds that have various applications in agriculture, and in the pharmaceutical, chemical and food industries.

Stabilization through precipitation in a system of colloidal iron(III) pyrophosphate salts

The ionic strength of a solution decreases during the precipitation of an insoluble salt, which can cause an initially unstable colloidal system to stabilize during its formation. We show this effect in the precipitation and aging of colloidal iron(III) pyrophosphate, where we observe two distinct stages in the aggregation process. The first stage is the formation of nanoparticles that immediately aggregate into clusters with sizes on the order of 200nm. In the second stage these clusters slowly grow in size but remain in dispersion for days, even months for dialyzed systems. Eventually these clusters become macroscopically large and sediment out of dispersion. Noting the clear instability of the nanoparticles, it is interesting to find two stages in their aggregation even without the use of additives such as surface active molecules. This is explained by accounting for the rapid decrease of ionic strength during precipitation, rendering the nanoparticles relatively stable when precipitation is complete. Calculating the interaction potentials for this scenario we find good agreement with the experimental observations. These results indicate that coupling of ionic strength to aggregation state can be significant and should be taken into account when considering colloidal stability of insoluble salts.

A Novel, Highly Sensitive, Rapid, Non-PCR Based Method for the Detection of the JAK2 V617F Mutation in Chronic Myeloproliferative Neoplasms.

Abstract 3892Poster Board III-828 BackgroundThe point mutation G1849T (V617F) of the JAK2 gene occurs at high frequency in several Ph-negative chronic myeloproliferative neoplasms (Ph-neg-CMNs), such as Polycythemia Vera (PV), Essential Thrombocythemia (ET) and Myelofibrosis (MF). The molecular analysis of this mutation is mandatory in the diagnostic work up of these diseases. Several molecular diagnostic techniques are currently used but each of them present some important limitations such as a low sensitivity and the requirement of labor intensive procedures performed with expensive specialized equipment that may not always be readily available in clinical laboratories. MethodWe have developed a non-PCR method for the identification of the JAK2V617F mutation called Allele Specific (AS)-LAMP, based on the Loop mediated isothermal AMPlification (LAMP) principle (Notomi et al. NAR 2000). LAMP reaction efficiently produces, within one hour, a large amount of amplified DNA and does not require gel separation of the amplified product which is indirectly detected by measuring the loss of intensity of a light beam through the reaction solution in which suspended particles of magnesium pyrophosphate are generated as a result of the DNA amplification process. Pyrophosphate salts produce turbidity which is both visible to the naked-eye and monitorable in Real-Time turbidimetry. AS-LAMP consists of 4 primers suitable for LAMP and a self-annealed primer highly specific for the mutated target sequence. To ensure efficiency and sensitivity a Peptide Nucleic Acid (PNA) probe specific for the wild-type allele was added thus resulting in absence of normal allele amplification within the reaction time. The AS-LAMP assay was optimized on plasmid controls and on human genomic DNA extracted from the HEL and K562 cell lines, respectively carrying or not the JAK2V617F mutation. The level of sensitivity was determined by testing serial dilutions of mutant HEL DNA in K562 DNA at concentrations of 100, 10, 1, 0.5, 0.1, 0.05, 0.01 and 0%. ResultsThis simple, easy to perform and rapid AS-LAMP assay selectively detects the JAK2V617F mutated DNA down to 0.05%. Moreover, when mutant DNA is present in the range of 1%-100% in wild type DNA, we observed a linear relationship between the mutant allele burden and the amplification time. We have validated this AS-LAMP assay on DNA obtained from 87 patient samples previously analyzed by conventional Allele Specific PCR (ASO-PCR): 19 PV, 58 TE, 3 IMF, 1 post ET Acute Myeloid Leukemia (AML), 1 post PV and 1 post ET Myelofibrosis, 2 Idiopathic Erythrocytosis (IE) and 2 unclassified CMNs. All samples which proved positive by ASO-PCR resulted positive with our AS-LAMP assay (100% concordance). In addition, 6 ET and 1 IE previously found negative by ASO-PCR were found to be low-positive (<1%) with AS-LAMP. Interestingly, the molecular monitoring in one patient with post-PV MF achieving complete remission after allogenic transplantation, proved repeatedly negative by ASO-PCR but positive by AS-LAMP. Sequencing analysis after PCR amplification with PNA confirmed the presence of the JAK2V617F mutation in all these LAMP-low-positive samples. None of the negative controls, (1 AML, 2 Acute Lymphoblastic Leukemia, 2 Follicular Non Hodgkin's Lymphoma, 2 Chronic Lymphocytic Leukemia, and 1 healthy donor) gave false positive results. ConclusionsThis novel, non-PCR based allele-specific LAMP assay is rapid and reduces the risk of contamination related to post amplification manipulations. Most importantly, it is highly specific and sensitive and significantly increases our ability to detect a low JAK2V617F tumor allele burden. For all these reasons, the AS-LAMP assay can be a valid and powerful tool in the routine diagnostic work up and the molecular monitoring of these diseases. Disclosures:Minnucci:Diasorin S.p.A.: Employment. Amicarelli:Diasorin S.p.A: Employment. Salmoiraghi:Diasorin S.p.A.: Consultancy, Honoraria. Spinelli:Diasorin S.p.A: Consultancy, Honoraria. Adlerstein:Diasorin S.p.A.: Employment. Rambaldi:Diasorin S.p.A.: Consultancy, Honoraria.

Stabilized–Solubilized Ferric Pyrophosphate as a New Iron Source for Food Fortification. Bioavailability Studies by Means of the Prophylactic–Preventive Method in Rats

The purpose of the present work was to evaluate the iron bioavailability of a new ferric pyrophosphate salt stabilized and solubilized with glycine. The prophylactic-preventive test in rats, using ferrous sulfate as the reference standard, was applied as the evaluating methodology both using water and yogurt as vehicles. Fifty female Sprague-Dawley rats weaned were randomized into five different groups (group 1: FeSO(4); group 2: pyr; group 3: FeSO(4) + yogurt; group 4: pyr + yogurt and group 5: control). The iron bioavailability (BioFe) of each compound was calculated using the formula proposed by Dutra-de-Oliveira et al. where BioFe % = (HbFef - HbFei) x 100/ToFeIn. Finally, the iron bioavailability results of each iron source were also given as relative biological value (RBV) using ferrous sulfate as the reference standard. The results showed that both BioFe % and RBV % of the new iron source tested is similar to that of the reference standard independently of the vehicle employed for the fortification procedure (FeSO(4) 49.46 +/- 12.0% and 100%; Pyr 52.66 +/- 15.02% and 106%; FeSO(4) + yogurth 54.39 +/- 13.92% and 110%; Pyr + yogurt 61.97 +/- 13.54% and 125%; Control 25.30 +/- 6.60, p < 0.05). Therefore, the stabilized and soluble ferric pyrophosphate may be considered as an optimal iron source for food fortification.

Study of Electroplating Zn-Sn-Ni Alloy

When Zn-Sn-Ni ternary alloy is electroplated on electrolyte copper foil, the surface properties can be comprehensively improved by using alkaline salt pyrophosphate solution. After the bath composition and processing conditions are optimized, and an appropriate additive is chosen, the SEM images shows the electrocrystalized substance obtained is composed of nano-crystals. Besides, XRD analysis on the deposits of electroplated Zn-Sn-Ni alloy shows Zn in the deposits exist in the form of metal compound, including δ phase Ni3Zn22 as well as γ Ni5Zn21. This indicates under the pyrophosphate salt the process of nucleation of Zn-Sn-Ni ternary alloy is similar to the process of three-dimensional successive nucleation controlled by diffuseness. All these demonstrate that after the disposal of this study, the corrosion resistance, the heat resistance and the binding intensity of electrolyte copper foil are obviously improved.

Synthesis of Conjugatable Bisphosphonates for Molecular Imaging of Large Animals

Synthesis of Conjugatable Bisphosphonates for Molecular Imaging of Large Animals

Crystal structure, vibrational spectra and thermal decomposition study of a new, dicationic, acidic pyrophosphate: KHMgP2O7⋅2H2O

Colourless crystals of a new, dicationic, hydropyrophosphate dihydrate salt, KHMgP2O7⋅ 2H2O, are formed, when a mixture of aqueous equimolar solutions of MgCl2⋅4H2O and K4P2O7, at pH 2.12, are left to stand at ambient temperature for 4 days. The new pyrophosphate salt has been characterized by single-crystal X-ray diffraction, IR and Raman spectra, and DSC-TG thermal analysis. The structure consists of alternating layers of [HP2O7]3− groups and MgO6 octahedra, joined by K+ ions and bridging hydrogen bonds. The [P2O7]4− anions exhibit a bent eclipsed conformation. The absence of coincidences for the majority of the IR and Raman bands is in accord with the centrosymmetric structure of the material. The 31P chemical shift tensor components have been determined from the solid-state MAS NMR spectra. The structural changes occurring during thermal decomposition have been examined by TG-DSC, X-ray powder diffraction (XRD) and IR spectroscopy. When the new pyrophosphate salt is heated gradually, it first becomes amorphous and then condenses to chain metaphosphates.

Influence of Zinc on the Formation of Granules of Calcium Pyrophosphate

ABSTRACTAccumulation of metals in inorganic granules is very common in invertebrates. The formation of metal deposits in both intra- and extracellular sites can be seen as a process for the detoxification of heavy metals. In barnacles, such inorganic granules usually contain calcium pyrophosphate. Incorporation of metals within such granules occurs mainly via the formation of metal pyrophosphate salts. In order to assess the chemistry of some reactions occurring during granule formation, the synthesis of calcium pyrophosphate, doped with zinc(II) ions with different [Zn]:[Ca] molar ratios, has been investigated at pH 7 and 25 °C. The thermal stability of the products was studied at different temperatures. Considerable variations occur in the structure of calcium pyrophosphate when zinc ions are present in solution in small concentrations.

Synthesis of acyl pyrophosphates. Application to the synthesis of nucleotide lipophilic prodrugs

We describe the first synthesis of acyl nucleoside diphosphates and acyl nucleoside triphosphates designed to be nucleotide lipophilic prodrugs. An improved preparation of acyl pyrophosphate salts, from carboxylic acid and tristetrabutylammonium pyrophosphate, is a key step in this synthesis.

A nuclear magnetic resonance study of 1H, 23Na, and 31P relaxation and molecular dynamics in the sodium salts of some pyrophosphates

Proton second moments and spin-lattice relaxation times in the laboratory and rotating frames and 31P and 23Na spin-lattice relaxation times in the laboratory frame have been measured over the temperature region 295 &gt; T &gt; 100 K for the sodium pyrophosphate salts, Na2P2O7∙10H2O and Na2H2P2O7. Laboratory-frame 31P and 23Na spin-lattice relaxation times have also been measured over the same temperature range for Na4P2O7. In the case of Na4P2O7∙10H2O, the results show clearly that the H2O molecules execute a twofold jump motion at higher temperatures. The potential barriers to these motions range from 30 to 40 kJ/mol. The 31P and 23Na relaxations are also influenced by these motions. The [Formula: see text] ion in Na2H2P2O7 is stationary over the temperature range studied. T1(Na) is most probably dominated by acoustical lattice vibrations. The [Formula: see text] ion in Na4P2O7 is not involved in a molecular reorientation. A shallow T1(P) minimum of 55 s is associated with a limited motion of the pyrophosphate molecule.

Calcium pyrophosphate crystal deposition. An in vitro study using a gelatin matrix model.

Deposition of crystalline triclinic (t) and monoclinic (m) calcium pyrophosphate dihydrate (CPPD) in fibrocartilage and articular cartilage is the hallmark of chondrocalcinosis. Using biologic grade gelatin to model this crystal growth process, t-CPPD, m-CPPD, amorphous calcium pyrophosphate, orthorhombic calcium pyrophosphate tetrahydrate (o-CPPT), and 3 mixed calcium/sodium pyrophosphate salts were grown at physiologic pH. Amorphous and o-CPPT appeared to be kinetic precursor crystals in the formation of t-CPPD and m-CPPD. Optimal concentration ranges for the different crystals were determined.

The osmotic and activity coefficients of some pyrophosphates

Osmotic and activity coefficients are reported for three pyrophosphate salts: K 4P 2O 7, Na 4P 2O 7, and K 2H 2P 2O 7 at (298.15 ± 0.01) K. The results are discussed in terms of the pyrophosphates as models for biologically important compounds such as the sodium and potassium salts of adenosine-5′-triphosphate.

The proteins of rapeseed (Brassica napus L.) soluble in salt solutions.

The salt-soluble proteins from rapeseed (Brassica napus L.), variety Nugget, have been extracted with 0.01 M sodium pyrophosphate (pH 7.0) and with 10% sodium chloride, and subsequently separated into a number of components. There are two major proteins in the pyrophosphate salt extract, one is neutral (the 12 S protein) and the other is basic (the 1.7 S protein). They constitute 30% of the nitrogen in the extract. There are nine other minor components in this extract. The 10% sodium chloride extract contains a water-insoluble protein (the 12 S protein) which constitutes 21% of the nitrogen in the extract and appears to be similar in properties to the 12 S protein in the pyrophosphate salt extract. This protein, upon sedimentation analysis in 6 M urea solution and in 0.1 M glycine–HCl buffer (pH 2.2), appeared to be an aggregate of units of smaller molecular weight.

The Radiation Annealing of Phosphorus-32 with Cobalt-60 Gamma-rays for Several Neutron-irradiated Inorganic Phosphorus Compounds

Abstract Radiation annealings with cobalt-60 gammarays have been investigated for several neutronirradiated inorganic phosphorus compounds. The group separation technique by one-dimensional paper-partition chromatography was adopted to separate chemical species containing phosphorus-32. The reduced species in the sodium and potassium orthophosphate salts and in the sodium pyrophosphate salt decreased upon gamma irradiation, and an increase in the retention was observed. However, the polyphosphate increased initially in the several orthophosphate salts. Three processes has been observed, the rate constants for these processes have been estimated, and two other processes have been suggested. The main process is the oxidation of the reduced species to phosphorus(V) species. Radiation annealing have been studied for phosphates as a functions of the dose rate, the total dose of irradiation, and the temperature during gamma irradiation, it has been found that annealings are dependent upon the total dose and the temperature during irradiation and are independent of the dose rate. In orthophosphates and pyrophosphate, chemical species other than the parent species are easily annealed by gamma irradiation, whereas no detectable annealing has been observed in sodium orthophosphite or sodium hypophosphite. In series of sodium and potassium orthophosphates, annealing was affected by the hydrogen content of the salts.