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ION RELEASE BEHAVIOR OF SILICOPHOSPHATE GLASSES CONTAINING SIX-FOLD COORDINATED SILICON STRUCTURE 含六重配位硅结构的磷酸硅玻璃的离子释放行为
Pub Date : 2022-01-01 DOI: 10.3363/prb.38.1
Atsuhiro Miura, A. Obata, T. Kasuga
: To facilitate the efficient use of phosphate-based glasses in various biomedical applications, it is essential to understand the effects of ion-releasing in the living body. In this work, the ion-releasing behavior of silicophosphate glass, designed as a supply source of silicate and phosphate ions that are effective for bone formation, was investigated. Two types of P 2 O 5 -SiO 2 -CaO-Na 2 O glasses containing 45–50 mol% of P 2 O 5 with both four- and six-fold coordinated silicon structures were prepared. The glass with ~50 mol% of P 2 O 5 content had a higher proportion of six-fold coordinated silicon structure, and it showed a lower ionic release to a simulated body fluid than that with ~45 mol% P 2 O 5 content. The release of the therapeutic ions from the silicophosphate glass can be effectively controlled by choosing their composition.
为了促进磷酸盐基玻璃在各种生物医学应用中的有效使用,有必要了解离子释放在活体中的影响。在这项工作中,研究了硅磷玻璃的离子释放行为,硅磷玻璃被设计为有效的骨形成的硅酸盐和磷酸盐离子的供应来源。制备了两种p2o5 - sio2 - cao - na 2o玻璃,p2o5的质量分数为45-50摩尔%,具有四层和六层硅配位结构。p2o含量为~50 mol%的玻璃具有更高比例的六重配硅结构,其对模拟体液的离子释放量低于p2o含量为~45 mol%的玻璃。通过选择治疗离子的组成,可以有效地控制治疗离子从硅磷酸盐玻璃中的释放。
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引用次数: 1
REVISITING WET-CHEMICALLY SYNTHESIZED β-TRICALCIUM PHOSPHATE: SOLID-STATE NMR STUDY OF LOCAL STRUCTURE 重述湿法合成β-磷酸三钙:局部结构的固态核磁共振研究
Pub Date : 2022-01-01 DOI: 10.3363/prb.38.5
Toshiisa Konishi
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引用次数: 0
EFFECT OF ORGANOPHOSPHATES ON THE FORMATION OF MAGNESIUM-FREE WHITLOCKITE 有机磷对无镁白钨矿形成的影响
Pub Date : 2021-01-01 DOI: 10.3363/prb.37.26
Toshiisa Konishi, Sadayuki Watanabe
Objective of the present study was to synthesize Mg-free whitlockite (WH) particles using organophosphates with different alkyl chain lengths via a solvothermal reaction. The effects of the organophosphates and their Ca/P molar ratio on the formation of WH were investigated. With increasing alkyl chain length of the organophosphate and increasing Ca/P molar ratio, the dominant phase changed from WH to hydroxyapatite (HA). This result suggests that the organophosphates exhibited different hydrolysis rates. With all of the organophosphates, WHs were obtained only at a Ca/P molar ratio of 0.25. In addition, an analysis of the local structure using H and P nuclear magnetic resonance spectroscopy indicated that the WH contained protonated phosphate (HPO4 ) and trace amount of HA subphase. (Received Jul 12, 2021; Accepted Sept 15, 2021)
以不同烷基链长度的有机磷酸盐为原料,通过溶剂热反应合成了无镁白脱石(WH)颗粒。研究了有机磷酸盐及其Ca/P摩尔比对WH生成的影响。随着有机磷酸盐烷基链长度的增加和Ca/P摩尔比的增加,优势相由WH变为羟基磷灰石(HA)。这一结果表明,有机磷酸盐具有不同的水解速率。对于所有的有机磷酸盐,只有在Ca/P摩尔比为0.25时才能得到WHs。此外,利用H和P核磁共振波谱分析了WH的局部结构,发现WH含有质子化磷酸(HPO4)和微量HA亚相。(2021年7月12日收稿;2021年9月15日录用)
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引用次数: 0
FABRICATION OF POROUS β-TRICALCIUM PHOSPHATE SCAFFOLDS USING FOAM REPLICA WITH 3D TECHNOLOGY 泡沫3d打印技术制备多孔β-磷酸三钙支架
Pub Date : 2021-01-01 DOI: 10.3363/prb.37.32
Kakeru Tsuchiya, Shohei Nakata, M. Ohno, Shigetaka Tamagawa, H. Shibata, K. Hashimoto
: The present work is based on prior research into the synthesis of porous β-tricalcium phosphate (β-TCP) with continuous pores by applying a β-TCP suspension onto a porous polyurethane foam by spray coating followed by pyrolysis of the foam. In the work reported herein, the three-dimensional (3D) pore structure of a polyurethane foam specimen was scanned using X-ray computerized tomography after which a porous acrylic foam with an optimized pore structure was fabricated using a 3D printer based on this scan. The pore size and pillar diameter of the porous printed material could be modified simply by changing the brightness value of the image data in the processing software. Specifically, the pillar diameter was increased while the pore size became smaller as the brightness was increased. β-TCP with interconnecting pores could be easily fabricated by spray coating these printed molds. The physical properties and porous structure of the product could also be tuned by modifying the pore structure of the foam and the amount of spray coating. The porous β-TCP obtained in this study had sufficient physical properties to be used as a scaffold material, suggesting the possibility of applying this scanning process to other porous materials, including living bones.
本工作是在前人研究的基础上,通过在多孔聚氨酯泡沫材料上涂覆β-磷酸三钙(β-TCP)悬浮液,然后对泡沫进行热解,合成具有连续孔隙的多孔β-磷酸三钙(β-TCP)。在本文报道的工作中,使用x射线计算机断层扫描聚氨酯泡沫试样的三维(3D)孔隙结构,然后在此扫描的基础上使用3D打印机制造具有优化孔隙结构的多孔丙烯酸泡沫。通过在处理软件中改变图像数据的亮度值,可以简单地修改多孔印刷材料的孔径和柱径。随着亮度的增加,柱直径增大,孔径变小。通过对这些打印模具进行喷涂,可以很容易地制备出具有互连孔的β-TCP。还可以通过改变泡沫的孔隙结构和喷涂量来调节产品的物理性能和多孔结构。本研究获得的多孔β-TCP具有足够的物理性能,可以用作支架材料,这表明该扫描过程可以应用于其他多孔材料,包括活骨。
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引用次数: 0
AMORPHOUS-PRECURSOR MEDIATED FORMATION OF MAGNESIUM-FREE WHITLOCKITE 非晶前体介导的无镁白钨矿的形成
Pub Date : 2021-01-01 DOI: 10.3363/PRB.37.1
Toshiisa Konishi, Sadayuki Watanabe
Calcium phosphates (CPs) were widely used as synthetic bone graft substitutes. However, the control of particle size and morphology of CP materials have not been achieved substantially, even though these factors would influence the physicochemical properties. Recent studies revealed that a uniform nanostructured Mg-free whitlockite (WH), which was structurally similar to a high temperature polymorph of β-tricalcium phosphate, was synthesized by precipitation in organic solvents of N,N-dimethylformamide (DMF) and ethylene glycol (EG). The present study therefore aims to synthesize WH particles in the DMF-EG binary solvents by a solvothermal reaction to investigate the formation mechanism of the WH particles. The nucleation of the amorphous precursor, which occurred at 3 h, was dominated by the slow hydrolysis of organophosphate, which retarded reaching critical supersaturation and hindered the fast nucleation. The investigation on the effect of reaction time on WH formation revealed that the amorphous-precursor mediated WH formation via a solid-solid phase transformation occurred between 4 and 9 h of reaction time. (Received Mar 19, 2021; Accepted Apr 13, 2021)
磷酸钙(CPs)作为人工骨移植替代物被广泛应用。然而,尽管这些因素会影响CP材料的物理化学性质,但对CP材料的粒度和形态的控制尚未得到实质性的实现。最近的研究表明,在N,N-二甲基甲酰胺(DMF)和乙二醇(EG)的有机溶剂中,采用沉淀法合成了一种结构类似于β-磷酸三钙高温多晶的纳米结构均匀的无mg whitlockite (WH)。因此,本研究旨在通过溶剂热反应在DMF-EG二元溶剂中合成WH颗粒,研究WH颗粒的形成机理。非晶态前驱体在3 h发生成核,主要受有机磷酸盐的缓慢水解影响,延迟了达到临界过饱和度,阻碍了快速成核。对反应时间对氢质酸生成影响的研究表明,在反应时间4 ~ 9 h之间,非晶前驱体通过固-固相变介导氢质酸生成。(2021年3月19日收稿;2021年4月13日录用)
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引用次数: 0
HYDROTHERMAL TRANSFORMATION OF CALCIUM HYDROGEN PHOSPHATE DIHYDRATE INTO MAGNESIUM WHITLOCKITE 二水合磷酸氢钙的水热转化成镁的研究
Pub Date : 2021-01-01 DOI: 10.3363/prb.37.21
Toshiisa Konishi, Sadayuki Watanabe
We here report a single-step, rapid synthesis method for magnesium whitlockite (MgWH). The hydrothermal synthesis of MgWH by transformation of calcium hydrogen phosphate dihydrate (DCPD) in formic acid solution was investigated. The fraction of MgWH increased with increasing Mg ion concentration. Single-phase MgWH with monodisperse, hexahedral-shaped particles was obtained when the reaction was conducted in the presence of 15 mmol/L Mg ions and at 220 °C for more than 3 h. The results also indicated that the hydrothermal transformation into MgWH in the presence of Mg ions was not pH-dependent precipitation but thermodynamically stable precipitation. Local structure analysis by H and P nuclear magnetic resonance confirmed the presence of protonated phosphate (HPO4 ) and showed three distinct phosphate peaks corresponding to the MgWH structure, which were consistent with the crystal structure of conventional MgWH. (Received Jul 12, 2021; Accepted Sept 15, 2021)
本文报道了一种单步快速合成镁白钻(MgWH)的方法。研究了二水合磷酸氢钙(DCPD)在甲酸溶液中转化水热合成MgWH的工艺。MgWH的比例随着Mg离子浓度的增加而增加。在15 mmol/L Mg离子存在条件下,在220℃条件下反应3 h以上,得到了单分散的单相六面体MgWH。结果还表明,在Mg离子存在下,水热转化为MgWH不是ph依赖性沉淀,而是热力学稳定的沉淀。H和P核磁共振局部结构分析证实了质子化磷酸(HPO4)的存在,并显示出与MgWH结构相对应的三个明显的磷酸峰,与常规MgWH的晶体结构一致。(2021年7月12日收稿;2021年9月15日录用)
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引用次数: 1
LOW-TEMPERATURE SYNTHESIS OF TRICALCIUM PHOSPHATE AND RELATED MATERIALS 低温合成磷酸三钙及相关材料
Pub Date : 2021-01-01 DOI: 10.3363/PRB.37.11
Toshiisa Konishi
: Calcium phosphate-based ceramics, in particular, biodegradable β- and α-tricalcium phosphate (TCP), have re-ceived much attention as synthetic bone substitutes. Although there is a consensus that β- and α-TCP are both high temperature polymorphs, in which the β phase transforms to the α phase at above ~1125 °C, recent extensive studies reported novel synthetic methods for TCP and related materials such as magnesium- or magnesium-free whitlockite at temperatures below 800 °C. While several synthesis methods for TCP and related materials have been reported, few have focused on the low-temperature synthesis of TCP and related materials, but rather on conventional methods. Therefore, the focus of this short review is upon the low-temperature synthesis of TCP and related materials. In addition, future strategies to synthesize three-dimensional shapes of TCP and related materials at low temperature are discussed.
磷酸钙基陶瓷,特别是可生物降解的β-和α-三磷酸钙(TCP),作为合成骨替代物受到了广泛的关注。虽然人们普遍认为β-和α-TCP都是高温多晶,β相在~1125℃以上转变为α相,但最近大量研究报道了在800℃以下合成TCP和相关材料(如镁或无镁whitlockite)的新方法。虽然已有几种TCP及其相关材料的合成方法的报道,但很少有人关注TCP及其相关材料的低温合成,而是采用常规方法。因此,本文将重点介绍TCP的低温合成及其相关材料。此外,还讨论了低温合成三维形状TCP及相关材料的未来策略。
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引用次数: 0
PHOSPHONYLATION OF 5’-DEOXY-5-FLUOROURIDINE AND 1-?-D-ARABINOFURANOSYLCYTOSINE WITH DISODIUM DIPHOSPHONATE 5 ' -脱氧-5-氟吡啶与1-?- d -阿拉伯糖脲基胞嘧啶与二磷酸二钠
Pub Date : 2020-01-01 DOI: 10.3363/prb.36.29
Hideko Maeda, Tadashi Matsushima, Takeshi Nagai, H. Nakayama
Phosphonylations of 5’-deoxy-5-fluorouridine (5’-DFUR) and 1--D-arabinofuranosylcytosine (Ara C) in aqueous solution were successfully performed using disodium diphosphonate (DP, Na2P2O5H2). The former reaction resulted in the synthesis of both 3’-phosphonyl-5’-DFUR and 2’-phosphonyl-5’-DFUR, with an overall yield of 100%. The reaction of 1--D-arabinofuranosylcytosine (Ara C) with DP gave 5’-phosphonyl-Ara C, 3’-phosphonyl-Ara C and 2’-phosphonyl-Ara C in a total yield of more than 35%. The optimal condition for the phosphonylation of either 5’-DFUR or Ara C with DP was determined to be a 1:10 ratio of 5’-DFUR or Ara C to DP and a solution pH of 11. The phosphonylated products of 5’-DFUR and Ara C were stable at 10 oC and 25 oC, respectively, over the pH range of 7 to 9. A proposed mechanism for the reactions of 5’-DFUR and Ara C with DP was developed. (Received Nov 10, 2020; Accepted Nov 30, 2020)
用二磷酸二钠(DP, Na2P2O5H2)在水溶液中成功地进行了5 ' -脱氧-5-氟吡啶(5 ' - dfur)和1-- d -阿拉伯糖醛酸胞嘧啶(Ara C)的磷酸化。前一反应合成了3′-膦基-5′-DFUR和2′-膦基-5′-DFUR,总收率为100%。1-- d -阿拉伯糖醛酸胞嘧啶(Ara C)与DP反应得到5′-膦基Ara C、3′-膦基Ara C和2′-膦基Ara C,总收率大于35%。5′-DFUR或Ara C与DP磷酸化的最佳条件为5′-DFUR或Ara C与DP的比例为1:10,溶液pH为11。在7 ~ 9的pH范围内,5′-DFUR和Ara C的磷酸化产物分别在10℃和25℃下稳定。提出了5′-DFUR和Ara C与DP反应的机理。(2020年11月10日收稿;2020年11月30日录用)
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引用次数: 0
A COMPARITIVE IN VITRO BIOACTIVY EVALUATION OF POLYVINYLIDENE FLUORIDE AND POLYCAPROLACTONE INCORPORATED WITH AMORPHOUS CALCIUM PHOSPHATE PARTICLES 聚偏氟乙烯和聚己内酯掺入无定形磷酸钙颗粒的体外生物活性比较评价
Pub Date : 2020-01-01 DOI: 10.3363/prb.36.15
Hasnat Zamin, Takeshi Yabutsuka, S. Takai, H. Sakaguchi
A comparative study of polyvinylidene fluoride (PVDF) and polycaprolactone (PCL) incorporated with particles of amorphous calcium phosphate on the induction of apatite formation ability in simulated body fluid (SBF)-biomimetic environment has been investigated. PVDF and PCL films containing amorphous calcium phosphate particles were fabricated using the solvent casting method. These amorphous calcium phosphate particles were highly active in inducing apatite formation. Results showed that both PCL and PVDF successfully resulted in apatite formation in SBF. However, it was found that the amount of amorphous calcium phosphate particles and the induction period of the apatite formation in SBF significantly varied for PVDF and PCL. These types of bioactive polymeric composite materials are attractive candidates as bone restorative materials with flexibility as well as high apatite forming ability. (Received Aug 28, 2020; Accepted Sep 11, 2020)
比较研究了聚偏氟乙烯(PVDF)和聚己内酯(PCL)掺入无定形磷酸钙颗粒对模拟体液(SBF)仿生环境中磷灰石形成能力的诱导作用。采用溶剂浇铸法制备了含无定形磷酸钙颗粒的PVDF和PCL薄膜。这些无定形磷酸钙颗粒在诱导磷灰石形成方面非常活跃。结果表明PCL和PVDF均能成功地在SBF中形成磷灰石。然而,我们发现PVDF和PCL在SBF中无定形磷酸钙颗粒的数量和磷灰石形成的诱导期有显著差异。这些类型的生物活性高分子复合材料是有吸引力的候选骨修复材料,具有灵活性和高磷灰石形成能力。(2020年8月28日收稿;接受2020年9月11日)
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引用次数: 1
DISSOLUTION BEHAVIOR OF MgO-CaO-P2O5-TiO2 INVERT GLASSES MgO-CaO-P2O5-TiO2反晶玻璃的溶解行为
Pub Date : 2020-01-01 DOI: 10.3363/prb.36.10
Sungho Lee, F. Nagata, Katsuya Kato, T. Kasuga
Magnesium is an essential element to the human body, and Mg ion can work to enhance cell adhesion, proliferation, differentiation, and mineralization. From the viewpoint of inorganic glass formation, MgO can be classified as an intermediate, that improves the glass-forming and ion-releasing abilities. The present work reports fundamental data for designing MgO-containing bioactive phosphate glasses with manipulated ion-releasability. MgO-CaO-P2O5-TiO2 invert glasses were prepared, in which TiO2 was substituted by MgO, and their structure and dissolution behavior were examined. Magnesium in the glasses was preferentially bonded to orthophosphate groups. The glass-forming ability and chemical durability of the glasses decreased with increasing MgO content, since P-O-Mg bonds are weaker than P-O-Ti bonds. In contrast, the ion-releasing ability of the glasses improved with increasing MgO content, and the released amount of Mg ion was expected to be within the range suitable to stimulate cell adhesion and proliferation. (Received Jul 10, 2020; Accepted Aug 13, 2020)
镁是人体必需的元素,镁离子可以增强细胞的粘附、增殖、分化和矿化。从无机玻璃形成的角度来看,MgO可归类为中间体,提高了玻璃形成和离子释放能力。本工作报告了设计具有可控离子释放性的含氧化镁生物活性磷酸盐玻璃的基础数据。用MgO取代TiO2制备了MgO- cao - p2o5 -TiO2反晶玻璃,并对其结构和溶解行为进行了研究。玻璃中的镁优先与正磷酸盐基团结合。随着MgO含量的增加,玻璃的形成能力和化学耐久性下降,因为P-O-Mg键比P-O-Ti键弱。相反,玻璃的离子释放能力随着MgO含量的增加而提高,Mg离子的释放量有望在适宜刺激细胞粘附和增殖的范围内。(2020年7月10日收稿;接受2020年8月13日)
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引用次数: 2
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Phosphorus Research Bulletin
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