Phosphorus Research Bulletin

Editorial Board

2015 年 30 巻 p. i-
発行日: 2015年
公開日: 2015/08/05

DOIhttps://doi.org/10.3363/prb.30.i

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Structural modifications from NiNa₃P₃O₁₀•12H₂O toNiNa₃P₃O₁₀ new triphosphate during dehydration process

M. Tridane, I. Fahim, S. Benmokhtar, S. Belaaouad

2015 年 30 巻 p. 1-7
発行日: 2015年
公開日: 2015/08/05

DOIhttps://doi.org/10.3363/prb.30.1

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A nickel-sodium triphosphate NiNa₃P₃O₁₀•12H₂O already known has been prepared by the method of ion exchange resin of aqueous chemistry and studied by X-Ray diffraction, thermal analyses (TGA-DTA) and infrared spectrometry which show the characteristic bands of a triphosphate P₃O₁₀^5-. The results of the compound heated at different temperatures showed that, after dehydration, NiNa₃P₃O₁₀•12H₂O decomposes into an amorphous compound, then it crystallizes at 700°C in order to give the new triphosphate NiNa₃P₃O₁₀. NiNa₃P₃O₁₀ crystallizes in the hexagonal system, space group P-31c, Z = 2 with the following unit-cell dimensions: a = b = 13.310(5) Å, c = 9.551(8) Å, M(20) = 80, F(20) = 93 (0.0028; 77) and V = 1465.58(0) Å³. NiNa₃P₃O₁₀ is stable until its melting point at 744°C. Two different methods Ozawa and KAS have been selected in studying the kinetics of thermal behavior of the triphosphate P₃O₁₀ for the first time. The kinetic and thermodynamic characteristics of the dehydration of NiNa₃P₃O₁₀•12H₂O and the thermal phenomena accompanying this dehydration were determinated and discussed on the basis of the proposed crystalline structure.

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SYNTHESIS AND CHARACTERIZATION OF Ce(III)-SUBSTITUTED CALCIUM HYDROXYAPATITE PARTICLES BY FORCED HYDROLYSIS OF Ca(OH)₂-Na₅P₃O₁₀-CeCl₃-MIXED SOLUTION

Kazuhiko Kandori, Minori Mitsui

2015 年 30 巻 p. 8-14
発行日: 2015年
公開日: 2015/08/05

DOIhttps://doi.org/10.3363/prb.30.8

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The formation of large and morphologically uniform Ce(III)-doped calcium hydroxyapatite (CeHap) particles by a forced hydrolysis method using Ca(OH)₂-Na₅P₃O₁₀-CeCl₃-mixed solutions was investigated and the precipitated particles were characterized by various methods. The ellipsoidal secondary particles with ca. 115 nm in particle length of those were composed by aggregation of ellipsoidal primary particles with ca. 20 nm in diameter were produced at X_Ce (Ce/(Ca+Ce) atomic ratio) = 0. The morphology of the particles was changed to rod-like with ca. 50~100 nm in width and 100~300 nm in length at 0.1≦X_Ce≦0.2. Furthermore, particle shape varied to needle-like at 0.4≦X_Ce≦0.8 and finally fine spherical particles with 5~10 nm in diameter were precipitated at X_Ce=1.0. The XRD patterns of the particles indicated that highly crystallized pure CeHap particles are produced at X_Ce≦0.2. On the contrary, the needle-like and very fine spherical particles precipitated at X_Ce=0.4~1.0 were identified as CePO₄. The time resolved TEM and XRD measurements suggested that the rod-like large CeHap particles are produced by the Ostwald ripening mechanism. The diffuse reflectance UV measurement indicated that CeHap particles have a UV absorption property, especially produced at X_Ce=0.15.

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PHOSPHORYLATION OF THEANINE WITH CYCLO-TRIPHOSPHATE IN AQUEOUS SOLUTION

Hideko Maeda, Hitomi Kanazawa, Mae Komatsu, Hiroyuki Nariai, Hirokazu ...

2015 年 30 巻 p. 15-18
発行日: 2015年
公開日: 2015/08/05

DOIhttps://doi.org/10.3363/prb.30.15

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Phosphorylation of theanine (Thea) has been achieved using inorganic cyclo-triphosphate (P_3m) in aqueous solution. The optimum condition for the phosphorylation of Thea with P_3m is Thea : P_3m = 2.0 M : 0.5 M, pH 11 and 10 °C. N²-(Phosphono)theanine was synthesized with the yield of more than 90 % and then remained constant after 40 d without hydrolysis of the monophosphate derivative. The phosphorylated product of Thea has a N-P bond in the molecule. The reaction mechanism of Thea with P_3m was discussed.

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HYDROXYAPATITE DISPERSION BY PHOSPHONATES, POLYMERS AND PHOSPHONATE/POLYMER BLENDS

Zahid Amjad, Amannie Kweik

2015 年 30 巻 p. 19-25
発行日: 2015年
公開日: 2016/01/07

DOIhttps://doi.org/10.3363/prb.30.19

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The dispersion of hydroxyapatite, Ca₅(PO₄)₃OH, HAP, in aqueous systems in the presence of variety of polymers of different composition and ionic charge has been investigated. The dispersion data show that polymer effectiveness as HAP dispersant strongly depends upon polymer architecture. It has been found that phosphonates exhibit poor performance as HAP dispersants. Additionally, it has also been observed that phosphonates exhibit antagonistic effect on the performance of anionic polymeric dispersants.

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COBALT(III) PRETREATMENT FOR TOTAL PHOSPHORUS DETERMINATION

Hiroya Kubo, Azumi Miyazaki, Kazunori Kuritani, Masaki Takeuchi, Hidej ...

2015 年 30 巻 p. 26-29
発行日: 2015年
公開日: 2016/01/07

DOIhttps://doi.org/10.3363/prb.30.26

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Abstract: A fast and simple pretreatment method of phosphorus compounds using Co³⁺ has been studied for the spectrophotometric determination of total phosphorus in water samples. Sample was mixed with a pretreatment solution (0.05 mol dm^-3 CoSO₄ in 1 mol dm^-3 H₂SO₄) in an electrolytic cell at the volume ratio of 4:1. Highly reactive Co³⁺ was continuously generated through the electrolysis of Co²⁺ during the pretreatment. Aliquot of the solution was injected to the system of flow injection - Molybdenum Blue spectrophotometry in order to evaluate phosphate ion (PO₄^3-) produced. Organic phosphorus compounds are completely decomposed to PO₄^3- within 2 min by Co³⁺ under moderate condition (70°C). The Co³⁺ is also effective for the acid hydrolysis of polyphosphates; diphosphate and tripolyphosphate are converted to PO₄^3- within 8 min through the pretreatment. Possible mechanisms of the pretreatment are discussed based on the strong oxidizing activity and the Lewis acid nature of Co³⁺.

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THE ROLE OF NIOBIUM IONS IN CALCIUM PHOSPHATE INVERT GLASSES FOR BONE REGENERATION

Akiko Obata, Hirotaka Maeda, Kyosuke Ueda, Takayuki Narushima, Toshihi ...

2015 年 30 巻 p. 30-34
発行日: 2015年
公開日: 2016/03/02

DOIhttps://doi.org/10.3363/prb.30.30

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Abstract: Phosphate invert glasses (PIGs) containing niobium were prepared by a conventional melt-quenching method and the structures and chemical durability of the glasses and osteoblast-like cell responses to them were examined. Raman and solid state ³¹ P NMR spectra of the glasses demonstrated that two types of niobate groups, NbO₄ and NbO₆ units, were contained in the glasses and prepared to combine to pyrophosphate structure than orthophosphate one. The chemical durability in Tris-HCl solution was increased with the increase in the niobium content in the glasses, since niobium replaced to phosphorus and contributed to the formation of P-O-Nb and Nb-O-Nb bonds, which are stronger than P-O-P bond. The niobium ions released from the glasses enhanced the differentiation and mineralization of the cells, rather than the initial adhesion and proliferation. The upregulation of these cell functions by the niobium ions possessed doze-dependence; the medium containing 1 x 10^-7 M of the ions exhibited the highest levels of the cell functions.

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