An Electroacoustic Investigation of Concentrated Aqueous Suspensions of Calcium Pyrophosphate

The zeta potential of concentrated suspensions of calcium pyrophosphate were investigated using electroacoustics. The particles were negatively charged over the entire pH range studied. It proved impossible to reduce the pH of the suspension below 1.8, but the iso electric point could be estimated to occur at approximately pH 1. Two commercially available dispersants (one cationic and one anionic) were then added in small increments to the suspension in order to follow the change in zeta potential as the dispersants adsorbed onto the particles. From the shape of the curve it was possible to estimate the optimum adsorbed amount of dispersant required to fully coat the particles. The cationic dispersant adsorbed strongly and the optimum dosage was estimated at 2.5 ml of active polymer/kg of powder. Anionic dispersants are known to adsorb onto negatively charged ceramic oxide particles, but the anionic dispersant used in this study did not adsorb onto the negatively charged calcium pyrophosphate particles.     

2D层状焦磷酸锰(Ⅱ)[NH4]2[Mn3(P2O7)2(H2O)2]的结构和磁性研究

A two-dimensional layered manganese(Ⅱ) pyrophosphate, [NH₄]₂[Mn₃(P₂O₇)₂(H₂O)₂] (1), has been synthesized hydrothermally. Its structure is determined by single-crystal X-ray diffraction analysis. Its structure is built up by MnO₆ octahedra and P₂O₇ units, with ammonium NH₄⁺ cations residing in the interlayer regions. The manganese pyrophosphate layer consists of infinite chains of cis and trans edge sharing MnO₆ octahedra linked by P₂O₇ units. Magnetic susceptibility measurements show that this compound exhibits ferrimagnetic-like ordering below 3.2 K. Further study shows that there are two possible superexchange pathways via the oxygen anions in Mn²⁺ ions. Owing to the different bridging modes of O^2-, the competition between ferromagnetic interactions and antiferromagnetic interactions in Mn²⁺ ions results in the ferrimagnetic behavior of 1.     

Aluminum Lon Removal from Monoaluminum Ovotransferrin by Pyrophosphate

The rates at which aluminum was removed from the N- and C-terminal monoaluminum ovotransferrins by pyrophosphate were evaluated by UV difference spectra in 0.01 mol/L Hepes, pH=7.4 and at 37℃. Pesudo first-order rate constants as a function of pyrophosphate concentration were measured. The results indicate that the pathways of aluminum removal are different. For the N-terminal binding site, aluminum removal follows simple saturation kinetics, while the removal of aluminum from the C-terminal binding site reverts to the combination of saturation and first-order kinetics. The saturation component is consistent with a rate-limiting conformational change in the protein as has been reported. We propose that the first-order kinetics mechanism is attributed to a pre-equilibrium process. The rate constants of saturation kinetics are accelerated from both terminals with the addition of 0.1 mol/L chloride to the monoaluminum ovotransferrin solutions, whereas the rates of the first-order kinetics are decreased for the C-terminal binding site. The effect of chloride ionic strength causes a continuing increase on kobs for the N- and C-terminal binding sites. Moreover, the kinetics behavior of the N-terminal is more easily affected by chloride than that of the C-terminal. In the experiment presumably the N-terminal site is apparently kinetically more labile than the C-terminal site.     

[Mn(H_2P_2O_7)_3]~(3-)引发淀粉与丙烯腈接枝聚合反应的动力学研究

以[Mn(H_2P_2O_7)_3]~(3-)为引发剂,研究了丙烯腈与玉米淀粉的接枝共聚反应。由实验结果求出了反应速率与引发剂浓度、单体浓度、淀粉浓度和反应温度的关系,推导并验证了接枝反应动力学模型,探讨了反应机理,求得了接枝反应活化能。     

Structure and Phase Transitions of SnP2O7

SnP₂O₇ is a member of the ZrP₂O₇ family of materials, several of which show unusual thermal expansion behavior over certain temperature ranges and which show a number of displacive phase transitions on cooling from high temperature. Here we describe the structural properties of SnP₂O₇ from 100 to 1243 K as determined by X-ray and neutron powder diffraction. These studies reveal that SnP₂O₇ shows two phase transitions in this temperature range. At room temperature the material has a pseudo-cubic 3×3×3× superstructure. Electron diffraction studies show that the symmetry of this structure is P2₁3 or lower. On warming to ∼560 K it undergoes a phase transition to a structure in which the subcell reflections show a triclinic distortion; above 830 K the subcell reflections show a rhombohedral distortion. Significant hysteresis in cell parameters is observed between heating and cooling. The structure of SnP₂O₇ is discussed with references to other members of the AM₂O₇ family of materials.     

Beiträge zum thermischen Verhalten wasserfreier Phosphate. IX. Darstellung und Kristallstruktur von Cr6(P2O7)4. Ein gemischtvalentes Pyrophosphat mit zwei- und dreiwertigem Chrom

Contributions on the Thermal Behaviour of Anhydrous Phosphates. IX. Synthesis and Crystal Structure of Cr₆(P₂O₇)₄. A Pyrophosphate Containing Di- and Trivalent Chromium Cr₆(P₂O₇)₄ (Cr₂²⁺Cr₄³⁺(P₂O₇)₄) can be obtained reducing CrPO₄ by phosphorus (950°C, 48 h, 100 mg iodine as mineralizer). By means of chemical transport reactions (transport agent iodine; 1050 → 950°C) the compound has been separated from its neighbour phases (Cr₂P₂O₇, CrP₃O₉) and crystallized (greenish, transparent crystals; edge length up to 0.3 mm). The crystal structure of Cr₆(P₂O₇)₄ (Spcgrp.: P-1; z = 1; a = 4.7128(8) Å, b = 12.667(3) Å, c = 7.843(2) Å, α = 89.65(2)°, β = 92.02(2)°, γ = 90.37(2) has been solved and refined from single crystal data (2713 unique reflections, 194 parameter, R = 0.035). Cr²⁺ is surrounded by six oxygen atoms which occupy the corners of an elongated octahedron (4 × d^{Cr? O} ≈? 2.04 Å; 2 × d^{Cr? O} ≈? 2.62 Å). The Cr³⁺ ions are also coordinated octahedraly (1.930 Å ≤ d_{Cr? O} ≤ 2.061 Å). The crystallographically independent pyrophosphate groups show nearly eclipsed conformation. The bridging angles (P? O? P) are 136.5° and 138.9° respectively.     

The Determination of the Titre of Ascorbic Acid Standard Solutions

Abstract

A new method for the determination of the titre of ascorbic acid standard solutions employing potassium dichromate as a primary standard has been developed. In a pyrophosphate medium, the pyrophosphate complex of divalent manganese is oxidized by dichromate to the pyrophosphate complex of tervalent manganese; the latter oxidizes o-tolidine reversibly with formation of the corresponding quinonediimine, which is visually titrated by the ascorbic acid standard solution.     

Structure of the calcium pyrophosphate monohydrate phase (Ca2P2O7·H2O): towards understanding the dehydration process in calcium pyrophosphate hydrates

Calcium pyrophosphate hydrate (CPP, Ca₂P₂O₇·nH₂O) and calcium orthophosphate compounds (including apatite, octacalcium phosphate etc.) are among the most prevalent pathological calcifications in joints. Even though only two dihydrated forms of CPP (CPPD) have been detected in vivo (monoclinic and triclinic CPPD), investigations of other hydrated forms such as tetrahydrated or amorphous CPP are relevant to a further understanding of the physicochemistry of those phases of biological interest. The synthesis of single crystals of calcium pyrophosphate monohydrate (CPPM; Ca₂P₂O₇·H₂O) by diffusion in silica gel at ambient temperature and the structural analysis of this phase are reported in this paper. Complementarily, data from synchrotron X‐ray diffraction on a CPPM powder sample have been fitted to the crystal parameters. Finally, the relationship between the resolved structure for the CPPM phase and the structure of the tetrahydrated calcium pyrophosphate β phase (CPPT‐β) is discussed.     

Effect of calcination temperature on the structure of vanadium phosphorus oxide materials and their catalytic activity in the decomposition of 2-propanol

The synthesis of vanadyl phosphate by reaction of an alcoholic solution of V₂O₅ and o-H₃PO₄ has been studied. The solids obtained were investigated by various physico-chemical techniques as in situ X-ray diffraction (XRD), thermogravimetric analysis (TGA), and differential thermal analysis (DTA) under inert atmosphere. The compounds have been further characterized by infrared and UV–Visible spectroscopies. The isopropanol conversion is carried out to evaluate the catalytic activity of the samples. The isopropanol conversion increases with the reaction temperature from 433 to 503 K for vanadyl phosphorus oxides calcined at a different temperature. However, the conversion attains 100% at 503 K, and the solid calcined at 973 K exhibits high selectivity towards propene (100% at 503 K).     

Direct mono-phosphorylation of 1,3-diols. A synthesis of FTY720-phosphate

A novel method for selective and direct phosphorylation of various 1,3-diols using silver(I) oxide, tetrabenzyl pyrophosphate (TBPP), and tetrahexylammonium iodide affording mono-phosphates was developed. We applied the present method to the synthesis of FTY720-phosphate.