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A FUN SURVEY OF THE MYSTERY OF APATITES 对磷灰石之谜的有趣调查
Pub Date : 2012-01-01 DOI: 10.3363/PRB.26.16
M. Okazaki
I had a chance to visit Kohama Island in Okinawa this March, where a beautiful coral reef expanded continuously near the sea shore. It is well known that coral is composed of inorganic calcium carbonate (Aragonite). We can find red and blue coral in addition to a popular white coral. I don’t know how they are colored. We admire the surprising colorful nature. Shells are also composed with calcium carbonate and keep a number of shapes and colors as well.
今年3月,我有幸去了冲绳县的小滨岛,那里美丽的珊瑚礁在海岸附近不断扩大。众所周知,珊瑚是由无机碳酸钙(文石)组成的。除了常见的白珊瑚外,我们还能找到红珊瑚和蓝珊瑚。我不知道它们是什么颜色的。我们欣赏令人惊讶的丰富多彩的大自然。贝壳也由碳酸钙组成,并保持许多形状和颜色。
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引用次数: 0
EFFECT OF THE ADDITION OF VARIOUS POLYSACCHARIDES ON THE MATERIAL PROPERTIES AND CYTOTOXICITY OF CHELATE-SETTING β-TRICALCIUM PHOSPHATE CEMENT 不同多糖的加入对螯合固化β-磷酸三钙水泥材料性能和细胞毒性的影响
Pub Date : 2012-01-01 DOI: 10.3363/PRB.26.59
Toshiisa Konishi, Shuhei Takahashi, Minori Mizumoto, M. Honda, K. Oribe, M. Aizawa
In order to enhance the handling ability and mechanical properties of chelate-setting β-tricalcium phosphate (β-TCP) cement, various polysaccharides, such as sodium alginate, sodium dextran sulfate, sodium chondroitin sulfate, and chitosan (Chito GL and W10), were added to mixing solutions for cement preparation. When mixing solutions containing the above additives were used, the handling ability of all the cement pastes was improved compared with the case of pure water without polysaccharide. Among the examined cement specimens, the cement with the highest compressive strength (17.4 MPa) was obtained using Chito W10. Although the viability of cells co-cultured with cements fabricated using additives was less than that of the control and water on the first day, the number of cells increased until the fifth day. The addition of chitosan (Chito W10) into the mixing solution is promising in the fabrication of chelate-setting β-TCP cement with enhanced handling ability and mechanical properties. (Received January 28, 2012; Accepted February 9, 2012)
为了提高螯合型β-磷酸三钙(β-TCP)水泥的处理能力和力学性能,在水泥配制中加入海藻酸钠、葡聚糖硫酸钠、硫酸软骨素钠、壳聚糖(Chito GL和W10)等多种多糖。当使用含有上述添加剂的混合溶液时,与不含多糖的纯水相比,所有水泥浆体的处理能力都有所提高。在所检测的水泥试样中,使用Chito W10获得的水泥抗压强度最高(17.4 MPa)。虽然第1天与添加添加剂的水泥共培养的细胞活力低于对照和水,但细胞数量一直增加到第5天。壳聚糖(Chito W10)的掺入有望制备出具有较强处理能力和力学性能的螯合固着型β-TCP水泥。(2012年1月28日收稿;2012年2月9日接受)
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引用次数: 3
Erratum: PHOTO-FENTON REACTION OF DYES WITH Fe(III)-TREATED HYDROXYAPATITES AS HETEROGENEOUS CATALYSTS IN WATER 勘误:染料与铁(III)处理的羟基磷灰石作为非均相催化剂在水中的光fenton反应
Pub Date : 2012-01-01 DOI: 10.3363/PRB.26.117
T. Moriguchi, S. Nakagawa
: Fe(III)-treated hydroxyapatites, HAP-300-Fe and HAP-400-Fe, were prepared from hydroxyapatites, HAP-300 (stoichiometric type) and HAP-400 (Ca-deficient type), respectively, and applied to photo-Fenton reaction of dyes as heterogeneous catalysts in comparison with other Fe catalysts such as Fe 2 O 3 , FePO 4 •2H 2 O, and FeOOH. Among the Fe catalysts, HAP-400-Fe revealed the highest consumption and mineralization in photo-Fenton reaction of alizarin red S (ARS), and also indicated good catalytic activity to other dyes, alizarin, neutral red, methyl red, methyl orange (MO), Congo red, and indigo carmine. Generation of hydroxyl radical •OH as an oxidation species from H 2 O 2 was observed in the all Fe catalysts by an indirect method using N, N-dimethylamino-4-nitrosoaniline, which is exclusively sensitive to •OH. In order to elucidate catalysis mechanism of Fe catalysts, kinetic investigation based on Michaelis-Menten theory was conducted in the reaction of ARS and MO. As a result, HAP-400-Fe indicated high ability of bearing many dye molecules but low degradative catalysis ability to H 2 O 2 , compared with Fe 2 O 3 . However, judging from high mineralization ability as well as repeating availability (5 times), HAP-400-Fe is considered as an excellent heterogeneous catalyst for photo-Fenton reaction.
以羟基磷灰石、HAP-300(化学量型)和HAP-400(缺钙型)为原料,分别制备了经Fe(III)处理的HAP-300-Fe和HAP-400-Fe,并与fe2o3、fepo4•2h2o和FeOOH等其他Fe催化剂作为非均相催化剂应用于染料的光fenton反应。Fe催化剂中,HAP-400-Fe在茜素红S (ARS)光fenton反应中消耗和矿化最高,对茜素、中性红、甲基红、甲基橙、刚果红、靛胭脂红等染料也有较好的催化活性。采用对•OH敏感的N, N-二甲胺-4-亚硝基苯胺间接法,在所有Fe催化剂中观察到羟基自由基•OH作为h2o2的氧化产物生成。为了阐明Fe催化剂的催化机理,基于Michaelis-Menten理论对ARS与MO的反应进行了动力学研究。结果表明,HAP-400-Fe与fe2o3相比,具有较高的承载多种染料分子的能力,但对h2o2的降解催化能力较低。然而,从高矿化能力和重复利用率(5次)来看,HAP-400-Fe被认为是一种优秀的光- fenton反应非均相催化剂。
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引用次数: 4
PROLIFERATION AND DIFFERENTIATION OF OSTEOBLAST-LIKE CELLS ON β-TRICALCIUM PHOSPHATE DOPED WITH MANGANESE (II) IONS 掺杂锰离子的β-磷酸三钙对成骨细胞样细胞增殖和分化的影响
Pub Date : 2012-01-01 DOI: 10.3363/PRB.26.87
Rikako Miyamoto, Asuka Ozawa, Takeshi Yamada, H. Shibata, Katsumi Yoshida, Osamu Yamanuro, K. Hashimoto
Manganese (II) ions were substituted for Ca ions at the Ca(4) and Ca(5) sites located in the A column of the β-tricalcium phosphate (β-TCP) crystal structure, and effects of additions of Mn ions on proliferation and differentiation of osteoblasts were examined using mouse MC3T3-E1 osteoblast-like cells. The X-ray diffraction patterns of β-TCP doped with manganese (II) ions (Mn-β-TCP) indicated the formation of β-TCP solid solution to 13.64 mol%. MC3T3-E1 cells attached on Mn-β-TCP well proliferated compare to those on β-TCP. In particular, Mn-β-TCP doped with 3 mol% showed the most excellent cell proliferation and the highest ALP activity level. We consider that the new bone formation may be promoted by dissolution of calcium ions and manganese ions from Mn--TCP. The present Mn-β-TCP is expected as an implant biomaterial with enhanced bioactivity. (Received May 31, 2012; Accepted June 12, 2012)
在β-磷酸三钙(β-TCP)晶体结构A柱的Ca(4)和Ca(5)位点上用锰(II)离子取代钙离子,并利用小鼠MC3T3-E1成骨细胞样细胞检测锰离子的添加对成骨细胞增殖和分化的影响。掺杂锰(II)离子(Mn-β-TCP)的β-TCP的x射线衍射图表明,β-TCP形成了13.64 mol%的固溶体。MC3T3-E1细胞在Mn-β-TCP上的增殖比在β-TCP上的增殖良好。其中,Mn-β-TCP掺杂浓度为3mol %时,细胞增殖效果最佳,ALP活性最高。我们认为新骨的形成可能是由Mn-- tcp中钙离子和锰离子的溶解促进的。目前Mn-β-TCP有望成为一种具有增强生物活性的植入生物材料。(收于2012年5月31日;2012年6月12日录用)
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引用次数: 0
PREPARATION AND APATITE-FORMING ABILITY OF CaSO4-PHOSPHATE GLASS COMPOSITES 碳酸钙-磷酸玻璃复合材料的制备及其形成磷灰石的能力
Pub Date : 2012-01-01 DOI: 10.3363/PRB.26.95
Naoya Yoshida, Takayo Shirai, T. Okura
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引用次数: 0
PREPARATION AND ACIDIC PROPERTIES OF IRON PHOSPHATES WITH SODIUM DODECYL-SULFATE 十二烷基硫酸钠制备磷酸铁及其酸性性能研究
Pub Date : 2012-01-01 DOI: 10.3363/PRB.27.28
H. Onoda, T. Sakumura
: Iron phosphate was prepared from iron nitrate and phosphoric acid with sodium dodecyl-sulfate at various stirring hours. The chemical composition of the obtained samples was estimated from ICP and XRD measurements. Particle shape and size distribution were observed by SEM images and laser diffraction / scattering methods. Further, the catalytic activity was studied with the decomposition of the complex between hormaldehyde and acetylacetone. Samples heated at 600ºC indicated XRD peaks of FePO 4 . Iron phosphates heated at 200 and 400ºC works as a catalyst.
以硝酸铁和磷酸为原料,用十二烷基硫酸钠在不同搅拌时间下制备磷酸铁。所得样品的化学成分由ICP和XRD测量估计。采用扫描电镜(SEM)和激光衍射/散射方法观察颗粒的形状和尺寸分布。进一步研究了甲醛与乙酰丙酮配合物的催化活性。样品在600℃下加热,XRD峰为fepo4。在200和400℃下加热的磷酸铁可作为催化剂。
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引用次数: 3
IN VIVO BIOCOMPATIBILITY OF APATITE-FIBER SCAFFOLD WITH ENHANCED MECHANICAL PROPERTY USING PIG MODEL BY IMPLANTING INTO TIBIA 增强力学性能的磷灰石纤维支架在猪模型胫骨内的生物相容性研究
Pub Date : 2012-01-01 DOI: 10.3363/PRB.26.1
T. Ganmoto, M. Honda, Toshiisa Konishi, Minori Mizumoto, H. Matsunari, Yasuhiro Takeuchi, H. Nagashima, M. Aizawa
We have successfully synthesized single-crystal apatite fibers (AF) by a homogeneous precipitation method with urea. The AF has a higher solubility than isotropic HAp powders. Thus, using the AF, we developed apatite-fiber scaffolds (AFSs) that enables three-dimensionally cell culture and induces differentiation into osteoblasts. Recently, we have successfully enhanced mechanical properties of the AFSs using carbon beads (CB) with a diameter of 150 m and 20 m, together with uniaxial pressing of the green compacts. In this study, we fabricated the AFSs with enhanced mechanical property (AFS700(50-50)), and then implanted them into tibia of pig to evaluate a biocompatibility to a hard tissue. The porosity of the resulting and compressive strength of typical AFS700(50-50) were 93.5% and 128 kPa, respectively. The AFS700(50-50) had a number of micro pores, macro-pores and interconnected pores. In the histological observation after 13 weeks implantation, newly-formed bone and cells were invaded into pores of the AFS700(50-50), and the scaffolds were incorporated into a cycle of bone remodeling. The AFS700(50-50) was also observed to be replaced with autologous tissue. The present scaffold may be expected as a high performance scaffold for bone regeneration. (Received May 8, 2012; Accepted May 16, 2012)
采用尿素均相沉淀法成功合成了单晶磷灰石纤维。AF具有比各向同性HAp粉末更高的溶解度。因此,利用AF,我们开发了磷灰石纤维支架(AFSs),可以进行三维细胞培养并诱导分化为成骨细胞。最近,我们成功地使用直径为150m和20m的碳珠(CB)以及绿色压坯的单轴挤压来增强afs的机械性能。在本研究中,我们制备了力学性能增强的AFS700(50-50)的afs,然后将其植入猪胫骨,以评估其与硬组织的生物相容性。典型AFS700(50-50)的孔隙率和抗压强度分别为93.5%和128 kPa。AFS700(50-50)具有微孔、大孔和连通孔。在植入13周后的组织学观察中,新形成的骨和细胞侵入AFS700的孔隙(50-50),将支架纳入骨重塑周期。AFS700(50-50)也被自体组织替代。该支架有望成为一种高性能的骨再生支架。(收于2012年5月8日;2012年5月16日录用)
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引用次数: 1
PREPARATION OF HIGH-CONCENTRATION HYDROXYAPATITE SOLUTION BY CARBON DIOXIDE BLOWING FOR MORPHOLOGICAL CONTROL OF HYDROXYAPATITE 二氧化碳吹制高浓度羟基磷灰石溶液用于羟基磷灰石的形态控制
Pub Date : 2012-01-01 DOI: 10.3363/PRB.26.91
T. Toyama, H. Nakajima, Y. Kojima, N. Nishimiya
: Morphological control of hydroxyapatite (HAp) is very difficult because this compound has very low solubility. However, CaCO 3 , a calcium salt with the same insolubility, dissolves easily in solutions containing CO 2 . Therefore, HAp was easily dissolved by CO 2 blowing into the HAp suspension. The dissolution amount was 200 times that found without CO 2 blowing. Thus, a high-concentration HAp solution could be prepared through the simple process of CO 2 blowing. Moreover, flower-like HAp particles were deposited by outgassing the dissolved CO 2 in the HAp solution under heating.
羟基磷灰石(HAp)的形态控制是非常困难的,因为这种化合物的溶解度很低。然而,碳酸钙,一种同样不溶性的钙盐,很容易溶解在含有二氧化碳的溶液中。因此,HAp很容易被吹入HAp悬浮液中的co2溶解。溶解量是不吹CO 2的200倍。因此,通过简单的co2吹制工艺可以制备出高浓度的HAp溶液。此外,在加热的条件下,将溶解在HAp溶液中的co2放气,形成了花状HAp颗粒。
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引用次数: 3
POLARIZED YTTRIA-STABILIZED ZIRCONIA IMPROVES DURABILITY FOR DEGRADATION AND APATITE FORMATION IN SIMULATED BODY FLUID 极化氧化钇稳定氧化锆提高耐久性降解和磷灰石形成在模拟体液
Pub Date : 2012-01-01 DOI: 10.3363/PRB.26.77
Miho Nakamura, Masahiro Inuzuka, K. Hashimoto, A. Nagai, K. Yamashita
Yttria-stabilized zirconia is currently used as an orthopedic and dental material, because of its excellent mechanical properties. In this study, we have improved the bioactivity of yttria-stabilized zirconia by a combination of electrical polarization and chemical treatment. The phase transformation from tetragonal to monoclinic ZrO2 after alkaline treatment was inhibited on positively charged yttria-stabilized zirconia surfaces compared with negatively charged and conventional surfaces. During polarization, some oxide ions move from the positively charged surface to the negatively charged surface, leading to an increase in oxygen vacancies on the positive surface and hence greater formation of Zr-OH when this surface was exposed to alkaline solution. The bioactivity was assessed by immersing the samples in simulated body fluid and evaluating the growth of apatite on the surfaces. The combination of polarization and alkaline treatment increased the bioactivity in vitro. (Received January 11, 2012; Accepted February 3, 2012) INTRODUCTION Since the late 1960s, yttria-stabilized zirconia (YSZ), especially 3 mol% Y2O3-doped zirconia, has been shown to be a biomaterial with excellent mechanical properties, and YSZ ceramics are currently used as ball heads in artificial hip joints and post-crowns in dental applications [1-2]. YSZ is however bioinert, meaning that no direct bonding of YSZ to natural bones occurs in vivo. In the present study, we have addressed this shortcoming by employing chemical treatments with the aim of increasing the bioactivity of YSZ. We have recently demonstrated that the ceramic hydroxyapatite (HA) [3] may be polarized via proton migration [4], and that the polarized surfaces of HA enhanced tissue regeneration of both hard [5] and soft [6] tissues in vivo. Additionally, the polarized HA also accelerated protein adsorption [7] and cell adhesion through improved wettability of water [8]. Thus electrical polarization can have excellent chemical, biological, and biomedical effects. Another serious problem with YSZ lies in its instability due to a tetragonal (t) to monoclinic (m) phase transformation at relatively low temperatures of (< 400C) in moist air or hot water [9]. These phenomena are usually termed low temperature degradation (LTD). Kobayashi et al. have reported that the annealing treatment of zirconia at 65-400C in water for a long time spontaneously gave rise to the transformation of tetragonal into monoclinic phase [10]. This t-m phase transformation in YSZ is reportedly accompanied by cracking on the surface due to the volume expansion of about 4-5% and degradation of mechanical strength, which can cause critical accidents in medical applications. It is crucial to inhibit the LTD of YSZ in medical and structural applications and also to understand the role of moisture in LTD. We observed that our polarization process successfully inhibited LTD in the chemical treatments of YSZ ceramics. This report details the bioa
氧化钇稳定氧化锆由于其优异的机械性能,目前被用作骨科和牙科材料。在这项研究中,我们通过电极化和化学处理相结合的方法提高了氧化钇稳定氧化锆的生物活性。与带负电荷和常规氧化锆表面相比,带正电荷的氧化钇稳定氧化锆表面经过碱性处理后,ZrO2由四方向单斜的相变受到抑制。在极化过程中,一些氧化离子从带正电的表面移动到带负电的表面,导致正电表面的氧空位增加,因此当正电表面暴露于碱性溶液中时,Zr-OH的形成更大。通过将样品浸泡在模拟体液中并评估其表面磷灰石的生长情况来评估其生物活性。极化与碱性联合处理提高了体外生物活性。(2012年1月11日收稿;自20世纪60年代末以来,钇稳定的氧化锆(YSZ),特别是3mol % y2o3掺杂的氧化锆,已被证明是一种具有优异力学性能的生物材料,YSZ陶瓷目前被用作人工髋关节和牙冠的球头[1-2]。然而,YSZ是生物惰性的,这意味着YSZ在体内不会与天然骨骼直接结合。在本研究中,我们通过化学处理来解决这一缺点,目的是提高YSZ的生物活性。我们最近已经证明陶瓷羟基磷灰石(HA)[3]可以通过质子迁移[4]而极化,并且HA的极化表面可以促进体内硬组织[5]和软组织[6]的组织再生。此外,极化后的透明质酸还通过改善水的润湿性来加速蛋白质吸附[7]和细胞粘附[8]。因此,电极化可以具有优异的化学、生物学和生物医学效果。YSZ的另一个严重问题是在湿空气或热水中相对较低的温度(< 400℃)下,由四方(t)到单斜(m)相变所导致的不稳定性[9]。这些现象通常被称为低温降解(LTD)。Kobayashi等人报道,氧化锆在65-400℃下在水中长时间退火处理,会自发地产生四方相向单斜相转变[10]。据报道,YSZ中的这种t-m相变伴随着由于体积膨胀约4-5%而导致的表面开裂和机械强度下降,这在医疗应用中可能导致严重事故。在医疗和结构应用中抑制YSZ的LTD以及了解水分在LTD中的作用是至关重要的。我们观察到我们的极化工艺成功地抑制了YSZ陶瓷化学处理中的LTD。本文详细介绍了极化YSZ陶瓷的生物活化和ltd抑制,并讨论了极化机制。材料与方法氧化钇部分稳定氧化锆粉末(TZ-3Y, Tosoh, Japan)在120 MPa下压入模具中。在1400℃空气中烧结1 h,烧结后的相对密度值约为99.20.1%。如前所述[4],用一对铂电极在20 V的直流(直流)电场中以200°C的频率进行电极化。电极化后的YSZ样品在商用玻璃管中用碱性(5 mol, 95℃,24 h)溶液处理。化学处理后,样品用去离子水洗涤,在60℃下干燥3 h。经碱性处理和未经碱性处理的未极化YSZ分别命名为O和YSZ作为对照。碱法处理后带负电荷的YSZ表面和带正电荷的YSZ表面分别表示为N和P;
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引用次数: 2
PREPARATION AND CHARACTERIZATION OF CALCIUM PHOSPHATE PARTICLES FROM FORCED HYDROLYSIS OF Ca(OH)2-TRIPHOSPHATE-K2S2O8 MIXED SOLUTION 钙(OH)2-三磷酸- k2s2o8混合溶液强制水解制备磷酸钙颗粒及表征
Pub Date : 2012-01-01 DOI: 10.3363/PRB.27.37
K. Kandori, N. Matsui
The effects of potassium peroxodisulfate (K2S2O8) on the formation of calcium phosphate particles produced by aging Ca(OH)2 and sodium triphosphate (sodium tripolyphosphate, Natpp: Na5P3O10) mixed solution at 100~160 C for 18 h were examined. Spherical and monodispersed particles were produced at low K2S2O8 concentration ([K2S2O8]) region ([K2S2O8]≤4 mM) and their size was increased by increase in [K2S2O8]. On the contrary, fine irregular particles were produced at [K2S2O8]≥6 mM. The monodispersed spherical particles produced at [K2S2O8]≤4 mM were amorphous, though small irregular particles produced at [K2S2O8]≥6 mM were poorly crystallized calcium pyrophosphates (-Ca2P2O7). The Ca/P atomic ratios of these samples were 0.79~0.90, fairly closed to the Ca/P atomic ratio of 1.0 for -Ca2P2O7. A high adsorption selectivity of H2O was observed on amorphous monodispersed spherical particles. On the other hand, the -Ca2P2O7 particles with small amounts of hydrated H2O produced at [K2S2O8]≥6 mM exhibited no selective adsorption of H2O. With increase in the aging temperature, small numbers of transparent balloon-like hollow spheres were obtained at 120~140C. However, the fraction of hollow spheres was less than 5%. Aging above 150C, no balloon-like hollow sphere was precipitated but finally calcium hydroxyapatite (Ca10(PO4)6(OH)2, Hap) particles with small rod-like shape could be precipitated. These Hap particles produced at 150 and 160 C did not exhibit selective adsorption of H2O. (Received July 9, 2012; Accepted July 30, 2012)
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引用次数: 0
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Phosphorus Research Bulletin
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