制备工艺对羟基磷灰石包覆碳纳米管的影响

利用原位合成法获得羟基磷灰石包覆的碳纳米管复合粉体,对制备过程中可能影响羟基磷灰石包覆层效果的因素进行了探索.结果表明:羟基磷灰石可以在阴离子修饰后的多壁碳纳米管上形核结晶;在实验过程中,pH值影响最终产物的组成,而陈化温度和陈化时间对包覆层中羟基磷灰石晶粒的尺寸和厚度有明显影响.     

烧结工艺对碳纳米管/羟基磷灰石复合材料力学性能与微观结构的影响

本文主要研究了不同烧结工艺对碳纳米管/羟基磷灰石复合材料力学性能与微观结构的影响.力学性能测试结果显示,在真空气氛下烧结的复合材料力学性能在总体上要高于Ar或N2气氛保护下烧结所得复合材料,断裂韧性的提高幅度最大,其最高值达到了2.2 MPa·m1/2,远高于纯羟基磷灰石.XRD及IR研究发现,所制备复合材料纯度高,无其它杂质.SEM观察发现,1100℃,真空下所得复合材料的致密性高,晶粒细,但碳纳米管管径增大;而Ar或N2气氛保护下所得复合材料中碳纳米管容易以原始形态保存,但孔隙率高,晶粒粗.     

羟基磷灰石的合成及应用研究进展

羟基磷灰石不仅具有较好的稳定性、生物活性和生物相容性,还具有良好的骨传导作用、生物可分解及诱导骨形成的能力,是人体骨损伤时性能优良且近于理想的骨修复及替代材料.但由于其强度低、韧性差、不易成型等自身力学性能的制约,目前尚未得到广泛应用.制备综合性能优越的羟基磷灰石及其更加理想的复合材料已成为近年来研究的重心和热点.笔者根据羟基磷灰石的研究现状,综述了羟基磷灰石的起源与发展、制备方法、应用及发展前景.重点剖析了由水热法到仿生法发展过程中多种制备方法的优缺点,并进一步探讨了由致密到多孔、由单一到复合、甚至多相复合的应用发展历程和精确控制其复合材料的微观结构与骨材料结构的相似度,研究合成新型仿生骨来达到临床使用要求的发展前景.     

溶解-析晶法制备结构可控的氟羟基磷灰石微球

以羟基磷灰石(HAP)粉体为原料,用简便方法制备氟羟基磷灰石(FAP)微球.将HAP粉体在不同pH值的NaOAc缓冲液中充分搅拌,加入NaF并水浴加热,制得氟羟基磷灰石(FAP)微球, 并利用TEM、SEM、XRD、FT-IR对微球的结构、成分进行表征, 研究与探讨了微球形成的机制.研究结果表明可以通过改变缓冲液的pH值来控制FAP微球结构.     

二氧化硅@羟基磷灰石颗粒的制备及其药物装载与体外释放行为研究

以改性的St(o)ber方法制备二氧化硅核心颗粒,并用改性的Pechini方法在其表面沉积羟基磷灰石壳层,制备得到具有核壳结构的二氧化硅@羟基磷灰石颗粒.通过扫描电子显微镜、X射线衍射分析和红外光谱分析手段表征颗粒的物相和结构,确定颗粒的形成机制为羟基磷灰石壳层在聚乙二醇-柠檬酸作用下均匀地沉积在非晶态二氧化硅表面.含亚甲基蓝的二氧化硅@羟基磷灰石药物颗粒在磷缓冲液(pH =7.2 ～7.4)和lysosome-like缓冲液(pH=4.7)中的释放行为表明药物释放对颗粒结构和溶液的pH值非常敏感.     

纳微米复合HAp-ZrO2生物复合材料的制备与微观结构研究

本文主要对纳米氧化锆与羟基磷灰石(HAp)复合制备纳微米复合HAp-ZrO2复合材料的制备工艺及微观结构进行了初步研究.用XRD分析了原料及复合材料的相组成,用IR研究了HAp粉体的结构,发现所制备HAp纯度高,羟基稳定存在.用TEM观察了HAp粉体以及HAp与ZrO2复合粉体的形貌与颗粒大小,发现HAp粉体呈颗粒状,粒径在60～70nm,这表明用化学沉淀法可制备出纳米级的HAp粒子,但在后续过程中往往发生团聚而达到微米级;纳米ZrO2粒子加入后在HAp基体中分散均匀.SEM观察发现,纳米ZrO2粒子的加入可以起到抑制羟基磷灰石晶粒长大、改善材料微观结构的作用.     

TiO2/蛭石纳米复合物的制备及产物结构变化研究

以TiOSO4为钛源,采用阳离子交换、原位水解、原位脱羟技术制备了TiO2/蛭石纳米复合物.采用XRD、FTIR、FSEM等对TiO2/蛭石纳米复合物制备过程产物包括聚合羟基钛离子-蛭石、水合氧化钛/蛭石复合物以及TiO2/蛭石纳米复合物的结构、微观形貌等进行了表征和研究.结果表明:在pH值较低时,TiOSO4溶液中的聚合羟基钛离子通过阳离子交换作用进入蛭石层间域中,随着pH值逐渐升高,进入层间域中的聚合羟基钛离子水解聚合形成水合氧化钛,蛭石的层间域被撑大,有序性结构被破坏;经900℃热处理后水合氧化钛脱水形成TiO2/蛭石纳米复合物;样品中TiO2含量随结束pH值的升高而增加,并均匀地插入蛭石的层间域中或分布在蛭石片层的表面;与纯TiO2纳米粉体相比较,TiO2/蛭石纳米复合物结构中TiO2在900℃焙烧后仍未出现金红石相,表明蛭石结构层对TiO2的晶相转变具有明显的阻滞作用.     

改性羟基磷灰石制备及除氟特性研究

为了提高羟基磷灰石(HAP)的除氟容量,利用羟基铝(Al-OH)改性HAP制备羟基铝-羟基磷灰石复合材料(Al-OH-HAP),通过红外光谱(FTIR)、扫描电镜(SEM)、X-射线粉末衍射(XRD)和N2吸附-脱附曲线等方法对样品进行表征分析,结合吸附热力学和动力学模型拟合,探讨Al-OH-HAP对水溶液氟离子的吸附特性.实验结果表明:Al-OH改性后Al3+和OH-进入HAP晶格中,且改性后HAP的衍射峰更尖锐,结晶度增大.Al-OH改性后HAP的比表面积分别从106.75 m2/g增加到220.45 m2/g,且大部分孔为介孔结构.吸附拟合模型表明Al-OH-HAP对氟离子的吸附更加遵循Langmuir模型,说明Al-OH-HAP对F-的吸附更趋近于单层吸附,吸附过程中化学吸附占主导地位.热力学参数吸附吉布斯自由能(ΔGo)小于0、焓变(ΔHo)和熵变(ΔSo)大于0,说明Al-OH-HAP对F-的吸附是一个自发吸热的熵增过程,Al-OH-HAP对F-的吸附更符合拟二级反应动力学过程.Al-OH-HAP可以成为一种有潜力的饮用水除氟剂.     

基于正交实验优化沉淀法制备针状羟基磷灰石

羟基磷灰石(HAP)已在临床得到运用,但其强度低、韧性差、不易成型等缺点依旧制约着其的广泛应用.为制备出理想且能满足临床应用的纳米针状羟基磷灰石,本文在不添加任何分散剂和表面活性剂的条件下以磷酸钠与硝酸钙为原料,氢氧化钠调节pH,使用正交实验设计对沉淀法中针状HAP的制备工艺进行优化.结果表明,反应条件对HAP晶体形貌的影响程度为:温度>滴加速度>pH;当反应pH=9、反应温度为90 ℃和滴加速度为2 mL/min时为其优方案,可制备出性状规则、粒度均匀、结晶度高、趋向于针状的纳米羟基磷灰石粉体.反应温度升高可提高HAP的结晶速度,可增大HAP晶体的大小,使晶形更趋于针状,但温度过高时对长轴的促进作用开始逐渐降低,长径比的增加趋势有所减缓;降低滴加速度,可提高产物结晶程度,有利于针状羟基磷灰石的形成;此外,反应pH值升高虽可加速晶核形成,提高产物的结晶率和产物纯度,但是不利于晶粒长大,且pH过高会减缓形成针状的趋势.     

Ti3Al/HAP复合材料的制备与性能研究

采用化学沉淀法在模拟体液中制备了纳米羟基磷灰石(HAPs)粉体,用金属钛粉和铝粉经过机械合金法,制备了金属间化合物Ti3 Al;将制备的HAP粉体作为基体材料加入第二相Ti3Al粉体,经过球磨分散得到Ti3Al/HAP复合粉体,经过热压烧结,得到羟基磷灰石与金属间化合物Ti3Al的复合材料.通过XRD、SEM及TEM等测试方法,分析了用普通化学沉淀法制备的羟基磷灰石(HAPc)和在模拟体液中生成的羟基磷灰石(HAPs)的区别及Ti3Al对羟基磷灰石结构和性能的影响.测试结果显示:在模拟体液中生成的羟基磷灰石颗粒均匀细小,纯度较高,结晶度较低;羟基磷灰石掺入一定量的Ti3Al后,弯曲强度和断裂韧性有所降低,X射线衍射显示复合材料中只有Ti3 Al和HAP两种物质,没有新物质生成.     

Triethyl ammonium salt of O,O′-bis(p-tolyl)dithiophosphate, [Et3NH]+[(4-MeC6H4O)2PS2]−

Triethyl ammonium Salt of O,O′-bis(p-tolyl)dithiophosphate and O,O′-bis(m-tolyl)dithiophosphate have been obtained by reaction of p- and m-cresol, respectively with P₂S₅ in toluene and have been characterized by elemental analysis, IR, ¹H and ³¹P NMR spectroscopy. The molecular structure of O,O′-bis(p-tolyl)dithiophosphate has been determined. Crystal data: [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻: Monoclinic, P2₁/c, a=15.2441(9) ?, b=10.415(2) ?, c=3.9726(9) ?, β=91.709(7)°, V=2217.5(1) ?⁻³, Z=4.Supplementary materials Additional material available from the Cambridge Crystallographic Data Centre (CCDC no. 600927 for [Et₃NH]⁺[(4-MeC₆H₄O)₂PS₂]⁻ comprises the final atomic coordinates for all atoms, thermal parameters, and a complete listing of bond distances and angles. Copies of this information may be obtained free of charge on application to The Director, 12 Union Road, Cambridge CB2 2EZ, UK (fax: +44-1223-336033; email: deposit@ccdc.cam.ac.uk or www:http://www.ccdc.cam.ac.uk).     

First-principles coexistence simulations of supercooled liquid silicon

We perform first-principles coexistence simulations of the low-density and the high-density phases of supercooled liquid silicon and find a negative slope for the coexisting line in the temperature-pressure plane. Electron density maps and electron-localization function plots of the two phases of silicon show marked differences. The calculated differences suggest more localized electrons in the low-density liquid compared to the high-density liquid, coming from an increased population of covalent bonds, which further explain the calculated negative slope in the two phase coexistence regime. This is consistent with the presence of a pseudo-gap in low-density liquid silicon, absent in the high-density liquid which shows a metallic behavior.     

Crystal structures of thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane

Structures of both thecis andtrans isomers of dithiahexahydro[3.3]metacyclophane, ?C₆H₄?CH₂SCH₂?C₆H₁₀?CH₂SCH₂?, have been determined, wherecis andtrans refer to the attachments to the cyclohexane ring. Thecis form crystallizes in the monoclinic space groupP2₁/c witha=8.4299(11)Å,b=21.772(2)Å,c=8.9724(13)Å, β=116.574(11)^o, andZ=4. Thetrans isomer packs into the monoclinic space groupP2₁ witha=8.159(16)Å,b=10.185(5)Å,c=9.558(2)Å, β=112.435(18)^o, andZ=2. The cyclohexane ring of thecis isomer is in the chair conformation, while the cyclohexane of thetrans isomer is found in a twisted boat conformation.     

CTAB与SDBS对碳酸锶粒子生长形态调控及机理研究

以表面活性剂CTAB和SDBS为化学添加剂,采用化学共沉淀法对碳酸锶晶体的生长形态进行调控,成功地制备出了实心的树枝状和花瓣为空心的花状碳酸锶粉体,并用X射线衍射(XRD)、扫描电子显微镜(SEM)和傅里叶变换红外光谱(FT-IR)等分析手段对样品进行了表征;最后重点对化学添加剂可能产生的影响机理进行了初步的探讨.结果表明,CTAB和SDBS在晶体生长的过程中能起到显著的影响作用,两者对粒子分散性能的作用效果相反,而且后者对晶体(013)和(213)晶面表面能降低的贡献明显大于前者.     

Crystal structure of Zn4Na(OH)6SO4Cl·6H2O

The structure of Zn₄Na(OH)₆SO₄Cl·6H₂O, a secondary mineral from Hettstedt, Germany, was determined by single-crystal X-ray diffraction. The crystals are hexagonal,a=8.413(8),c=13.095(24) Å, space group $P\bar 3$ , Z=2. The structure was refined to R=0.0554 and R_w=0.0903 for 970 reflections with I≥3σ(I). The structure can be described as zinc hydroxide layers perpendicular toc, from which sulfates and chlorides extend. The layers are held together by a system of hydrogen bonds involving hexaaquo Na⁺ ions which occupy the interlayer space.     

Synthesis and Crystal Structure of 5-[2-(6-bromonaphthalenyloxymethyl)]-3-(4-morpholinomethyl)-1,3,4-oxadiazole-2(3<Emphasis Type="Italic">H</Emphasis>)-thione

Abstract  The title compound, C₁₈H₁₈BrN₃O₃S, a derivative of 1,3,4-oxadiazole, crystallizes in the triclinic space group P-1 with unit cell parameters a = 6.8731(3), b = 8.9994(4), c = 15.7099(6) ?, α = 92.779(3)°, β = 130.575(3)°, γ = 107.868(4)°, Z = 2. The dihedral angle between the mean planes of the planar naphthyl and morpholine (chair) rings with the planar oxadiazol ring is 50.1(8) and 76.8(6)°, respectively. The planar naphthyl ring is twisted 52.2(5)° with the mean plane of the morpholine ring. A group of four intermolecular close contacts are observed between a bromine atom and hydrogen atoms from the closely packed naphthyl, morpholine and oxy–methyl groups in the unit cell. These molecular interactions in concert with an additional series of π–π stacking interactions that occur between the center of gravity of the two 6-membered rings of the naphthalene group influence the twist angles of each of these three groups. A MOPAC AM1 calculation of the conformation energy of the crystal structure [226.0128(9) kcal] compared to that of the minimum energy structure after geometry optimization [29.9744(1) kcal] reveals a significantly reduced value. The twist angles of the three groups above also change after the AM1 calculation giving support to the influence of both intermolecular C–H···Br short-range interactions and Cg π–π stacking interactions on these angles which therefore play a role in stabilizing crystal packing. Graphical Abstract  Crystal structure of 5-{[(6-bromonaphthalen-2-yl)oxy]methyl}-3-(morpholin-4-ylmethyl)-1,3,4-oxadiazole-2(3H)-thione, C₁₈H₁₈BrN₃O₃S, is reported and its geometric and packing parameters described and compared to a MOPAC computational calculation. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Crystal structure of irisolidone from the flowers of Pueraia lobata

Irisolidone (5,7-dihydroxy-6,4′-dimethoxyisoflavone) was isolated from the flowers of Pueraia lobata and its crystal structure was examined by X-ray single crystal diffraction. The crystal structure of irisolidone is monoclinic, space group P2₁/c with a = 15.491(9) ?, b = 7.895(4) ?, c = 13.321(7) ?, β = 110.546(9)° and Z = 4. Hydrogen bonding and aromatic π–π stacking assemble the title compound into a three-dimensional networking structure.     

Synthesis of spinacine and spinacine derivatives: crystal and molecular structures of Nπ-hydroxymethyl spinacine and Nα-methyl spinaceamine

The natural amino acid L-Spinacine (4,5,6,7-tetrahydro-1H-imidazo[4,5-c]pyridine-6-carboxylic acid) has been synthesized following a new pathway which gives a chemically and optically pure product with an excellent yield. The crystal structures of a synthetic intermediate, N^π-hydroxymethyl-spinacine, and a spinacine derivative, N^α-methyl-spinaceamine, have been investigated through X-ray diffraction: Spi(πMeOH)·H₂O, monoclinicP2 _i,a=8.571(1),b=6.682(1),c=8.588(1) Å, and β=94.67(1)^o. Spm(αMe)·2HCl·H₂O, triclinicP l,a=7.492(4),b=10.799(3),c=7.040(2) Å, α=91.88(2), β=98.36(3) and γ=73.34(3)^o. Spi(πMeOH) crystallizes with a water molecule and displays a zwitterionic character. The carboxylate group is in equatorial position and forms a short electrostatic interaction of 2.618(2) Å between one of its oxygens and the protonated nitrogen of the tetrahydropyridine ring. The crystal packing is assured by strong O?H???O, O?H???N, N?H???N intermolecular hydrogen bonds and C?H???O close contacts. The biprotonated compounds Spm(αMe) crystallizes with two Cl^? anions and a water molecule. The positive charge on the imidazole ring is delocalized on the conjugated moiety N=C?N. The crystal is built up by clusters formed by two biprotonated Spm(αMe) molecules, four Cl^? anions and two water molecules linked together by hydrogen bonds.