含10mol%氧化硅的钙磷酸盐玻璃陶瓷的合成及其体外生物活性

采用高分子网络凝胶法合成出SiO2-CaO-P2O5生物玻璃陶瓷,该材料具有较低含硅量和高钙磷比(nCa/nP=1.57)的特点,更接近人体硬组织的成分。将材料在SBF溶液浸泡研究材料的体外生物活性,通过TG/DTA,XRD,FTIR和SEM等方法对粉体和浸泡后的样品表面进行表征,ICP-AES对SBF溶液中钙、磷、硅离子的浓度进行检测。结果表明,氧化硅的添加有利于玻璃陶瓷表面磷灰石晶相的形成;随着浸泡时间的延长,沉积在样品表面的碳酸羟基磷灰石层逐渐由球型突起变为叶片状,溶液中钙、磷离子浓度降低,而硅离子浓度增加,说明材料具有良好的生物活性,适宜作为牙齿和骨骼的替代或修复材料。     

CaO-P2O5-SiO2系统溶胶-凝胶生物活性多孔材料在SBF中的性能研究

利用溶胶-凝胶生物活性材料粉末二次烧结工艺,制备了CaO-P2O5-SiO2系统溶胶-凝胶生物活性多孔材料,并利用体外实验(in vitro)方法和XRD,SEM及FTIR技术研究了此烧结材料的显微形貌、晶相、生物活性和可降解性能.结果表明,经800℃烧结5 min后,有少量硅磷酸钙[Ca5(PO4)2SiO4,5CPS]析出,在模拟体液(SBF)中浸泡,随着时间的增长,材料表面最初形成的无定形钙磷化合物矿化成碳酸羟基磷灰石(HCA)纳米团簇,并逐渐相互融合形成HCA覆盖层;HCA只在烧结体的玻璃相(SG相)表面生成,在5CPS微晶相表面未发现HCA,该材料在37℃恒温的SBF溶液中具有较高的生物活性和可降解性能.     

不同模拟体液中水化硅酸三钙固化体的体外生物活性行为(英文)

研究水了化硅酸三钙(Ca3SiO5,C3S)固化体的体外生物活性行为。结果表明,干C3S固化体中含有23.97wt%的Ca(OH)2,Ca(OH)2的溶解导致模拟体液(Simulated Body Fluids,SBF)的pH值上升;磷灰石颗粒优先诱导沉积于C3S固化体表面,随后碳酸钙和磷灰石颗粒共同沉积于C3S固化体表面;HCO3-是SBF模拟体液内主要的缓冲离子;Ca(OH)2碳化和CaCO3沉积主要导致SBF的pH值下降。由于离子交换作用的减弱,C3S固化体表面最终被磷灰石完全覆盖,磷灰石的沉积促使SBF的pH值进一步降低。因此,对于C3S和其衍生材料的体外生物活性和生物相容性必须考虑到HCO3-在体内的实际含量和行为。     

新型芳磺酰基色氨酸酯以及芳磺酰基谷氨酸二酯类化合物的合成与生物活性研究

在乙酰羟酸合成酶(AHAS)与磺酰脲类化合物复合物晶体结构的基础上, 利用分子对接法进行MDL/ACD三维数据库虚拟筛选, 得到了部分结合能较低的小分子化合物结构. 对其中的芳磺酰基色氨酸酯以及芳磺酰基谷氨酸二酯类化合物进行了合成, 共合成22个具有潜在活性的新衍生化合物, 其结构通过核磁、质谱、红外及元素分析验证, 并对所有新化合物进行了体内、体外活性测试. 初步的体外生物活性测试结果表明, 两类化合物对AHAS具有较低的抑制性; 体内生物活性测试结果表明, 化合物4d, 4g和4k具有一定的除草活性, 在100 μg/mL的浓度下, 它们对油菜根长的抑制率分别为70.8%, 52.4%和50.2%.     

紫外光辐射山茱萸水提液制备纳米银及生物活性

利用254 nm紫外光照射山茱萸水提液在室温下制备了纳米银, 并通过UV-Vis光谱检测其在410 nm附近的等离子体共振峰; 研究了溶液pH值、 料液比以及反应时间对还原反应的影响, 确定了纳米银的最优合成条件: pH=7.0, 料液比1∶1, 反应时间1 h. 通过X射线晶体衍射、 透射电子显微镜和激光粒度仪对纳米银的晶体结构、 粒径、 表面性质和形貌等进行表征发现, 在最优反应条件下制得的纳米银为面心立方结构, 呈近球形, 平均粒径(55.4±0.9) nm, 分散均匀, 表面带负电(-10.2 mV), 具有较高的稳定性. 生物活性研究结果表明, 制得的纳米银具有良好的抗氧化、 抗菌及抗癌活性. 当纳米银浓度为62.5 μg/mL时, 对DPPH自由基的清除率为70.0%; 对S. aureus和E. coli最低抑菌浓度分别为3.9和7.8 μg/mL; 对结直肠癌细胞HCT116和SW620的IC₅₀值分别为23.1和35.1 μg/mL.     

羟基磷灰石/氧化铁复合涂层的制备及其诱导骨生长的生物活性

用电泳沉积法制得羟基磷灰石/壳聚糖/氧化铁(HA/CS/Fe2O3)复合涂层,经700 ℃烧结处理得到HA/Fe2O3复合涂层。 通过SEM、EDS、XRD、FT-IR、电化学和万能材料试验机等对复合涂层的表面形貌、物相组成、抗腐蚀性和结合强度进行了表征和测试,最后采用1.5SBF浸泡法对复合涂层的生物活性进行了评价。 结果表明,当悬浮液中的HA、CS与Fe2O3质量比为100∶100∶1时,所制得的HA/Fe2O3复合涂层表面粗糙,抗腐蚀性强,具有良好的诱导骨生长生物活性,基体与复合涂层结合强度可达27.5 MPa。     

CaO-P2O5-SiO2系统溶胶-凝胶生物活性多孔材料在SBF中的性能研究

利用溶胶-凝胶生物活性材料粉末二次烧结工艺,制备了CaO-P2O5-SiO2系统溶胶-凝胶生物活性多孔材料,并利用体外实验（in vitro）方法和XRD,SEM及FTIR技术研究了此烧结材料的显微形貌、晶相、生物活性和可降解性能.结果表明,经800℃烧结5 min后,有少量硅磷酸钙[Ca5（PO4）2SiO4,5CPS]析出,在模拟体液（SBF）中浸泡,随着时间的增长,材料表面最初形成的无定形钙磷化合物矿化成碳酸羟基磷灰石（HCA）纳米团簇,并逐渐相互融合形成HCA覆盖层;HCA只在烧结体的玻璃相（SG相）表面生成,在5CPS微晶相表面未发现HCA,该材料在37℃恒温的SBF溶液中具有较高的生物活性和可降解性能.     

酰胺类KARI酶抑制剂的设计、合成和生物活性

以分子对接法进行MDL/ACD三维数据库搜寻所得到的大量结构信息为指导, 从中选取部分酰胺类小分子进行化学合成和结构表征. 生物活性测试结果表明, 设计合成的8个酰胺类化合物在200 μg/mL浓度下对水稻KARI酶具有不同程度的抑制活性, 化合物1和6的抑制率可达到57.4%和48.1%. 部分化合物在100 μg/mL浓度下对双子叶植物油菜的胚根和单子叶植物稗草的茎叶的抑制活性较为显著, 化合物1和6对油菜胚根生长抑制率分别为52.0%和72.6%, 其与KARI酶体外(in vitro)抑制活性具有一定的相关性. 这些酰胺类化合物可作为KARI酶抑制剂为后续分子设计提供借鉴.     

以大蓟髓芯为模板制备复合孔生物活性玻璃及其体外成骨性能

以天然植物大蓟髓芯为大孔模板, 以嵌段共聚物为介孔软模板, 制备了孔径为60~100 μm、孔壁为介孔相的高度有序多级复合孔生物活性玻璃. 用扫描电子显微镜(SEM)、粉末X射线衍射仪(XRD)、高分辨率透射电镜(HRTEM)及N2吸附-脱附等测试手段对合成的样品进行了表征. 结果表明, 合成的材料精确地复制了植物模板的形貌, 同时具有较高的比表面积和较大的孔容. 通过体外模拟生理体液测试表明, 这种复合孔生物活性玻璃可诱导羟基磷灰石晶体在其表面形成, 具有良好的体外成骨性能, 因而在骨组织修复方面具有潜在应用前景.     

离子掺杂介孔生物活性玻璃的合成及应用研究

骨填充和骨替代生物材料的研究与开发是骨修复领域重要的研究方向之一。介孔生物活性玻璃（MBG）因其具有良好的生物活性以及可调节的孔径和有序的介孔结构,将在骨修复再生中发挥重要作用。通过不同的制备加工方法能得到纤维、支架、中空结构或纳米颗粒结构的MBG;大量研究表明,在MBG中掺杂少量的治疗性无机离子,能赋予它们更多的生物学特性,包括成骨、抗菌、抗炎、止血或抗癌特性;而且无机离子掺杂的MBG作为支架或纳米颗粒加工后,仍然具有出色的生物活性反应。此外,通过在介孔结构内负载生物活性分子、治疗药物和干细胞可进一步改善MBG的性能。本文介绍了近年来MBG的合成、金属离子掺杂MBG的抗菌性能以及MBG在其他方面的应用进展。     

<Emphasis Type="Italic">In vitro</Emphasis> bioactivity of 70 wt.% SiO<Subscript>2</Subscript> — 30 wt.% CaO sol-gel glass,doped with 1, 3 and 5 wt.% NbF<Subscript>5</Subscript>

The 70SiO₂-30CaO (wt.%) sol-gel glasses doped with 1, 3 and 5 NbF₅ (wt.%) were prepared via polystep sol-gel route. The synthesized glasses were characterized by XRD, FTIR and SEM. Changes in 1.5 SBF solutions were measured by ICP-AES. XRD of the glasses stabilized at 700°C for 6 hours proved the presence of niocalite. FTIR was consistent with XRD data. The in vitro bioactivity study of all glasses prepared were carried out by soaking in 1.5 simulated body fluid (1.5 SBF) at 37°C for 6 and 12 days in static conditions. The FTIR reveals the formation of A-type and B-type carbonate containing hydroxyapatite (CO₃HA) layer. Changes in 1.5 SBF solutions, after 6 days of soaking, show that the Ca concentration increased significantly, compared to the initial Ca content in the 1.5 SBF solution before in vitro test. After 12 days of immersion, the Ca concentration decreased, i.e., the formation of HA phase consumed Ca from 1.5 SBF solution. For all soaking times, the concentration of P is much lower than that the used 1.5 SBF. Based on these results we suggest that Ca and P play an active role in the future of the glasses. SEM depicts that the different morphology of hydroxyapatite can be formed as a function of soaking time.     

Organic/Inorganic bioactive materials Part III: in vitro bioactivity of gelatin/silicocarnotite hybrids

In this work we present our experimental results on synthesis, structure evolution and in vitro bioactivity assessment of new gelatin/silicocarnotite hybrid materials. The hybrids were obtained by diluting gelatin (G) and silicocarnotite (S) ceramic powder with G:S ratios of 75:25 and 25:75 wt.% in hot (40°C) water. The hybrids were characterized using XRD, FTIR, SEM/EDS and XPS. FTIR depicts that the “red shift” of amide I and COO⁻ could be attributed to the fact that the gelatin prefers to chelate Ca²⁺ from S. The growth of calcium phosphates on the surface of the hybrids synthesized and then immersed in 1.5 SBF for 3 days was studied by using of FTIR, XRD and SEM/EDS. According to FTIR results, after an immersion of 3 days, A and B-type CO₃HA can be observed on the surface. XRD results indicate the presence of hydroxyapatite with well defined crystallinity. SEM/EDS of the precipitated layers show the presence of CO₃HA and amorphous calcium phosphate on the surface of samples with different G/S content when immersed in 1.5 SBF. XPS of the G/S hybrid with 25:75 wt.% proved the presence of Ca-deficient hydroxyapatite after an in vitro test for 3 days.     

In vitro bioactivity of Polyurethane/85S Bioglass composite scaffolds

In the present work Polyurethane (PU)/Bioglass (BG) composite materials were synthesized with different content of BG (10 and 20 mol.%) as filler. The 85S Bioglass was synthesized via polystep sol-gel method. The chemical composition of BG is 85SiO₂-10CaO-5P₂O₅ (wt.%). The synthesis of PU was carried out by a two-step polyaddition reaction. The 85S BG was added in situ during the polymerization reaction. In vitro bioactivity of the prepared composites was examined in the presence of 1.5 SBF for 7 days in static conditions. The structure of synthesized PU/BG composites before and after in vitro test was determined by XRD, FTIR and SEM. XRD of the samples before in vitro test proved that the phase of γCa₂P₂O₇ in the PU/20BG is visible. FTIR revealed the presence of urethane bond between OH-(from BG) and NCO groups (from PU). Based on FTIR results after in vitro test in 1.5 SBF solutions, A/B-carbonate containing hydroxyapatite (CO₃HA) was formed. XRD proved that HA was formed on the surface of the samples, but Ca₂P₂O₇ does not undergo any changes in the 1.5 SBF solution. SEM depicted the nano-HA agglomerated in spherical particles after immersion in 1.5 SBF for 7 days.     

Superior corrosion protection and in vitro biocompatibility of Na-HAp/CS composite coating on PoPD-coated 316L SS

The synthesis and development of sodium (Na)-substituted hydroxyapatite (HAp)/chitosan (CS) composite using poly (O-phenylenediamine) (PoPD) coating on 316L SS substrate for improving bioactivity and corrosion protection was studied. The surface of Na-HAp/CS/PoPD bilayer coatings on 316L SS substrate was characterized by diverse analytical techniques. The open circuit potential (OCP) measurement, potentiodynamic polarization, and impedance test revealed that the bilayer coating provides excellent protection to the substrate against the corrosion in the simulated body fluid (SBF) solution. This interior layer of the coating acts as a barrier against the release of metal ions from the substrate, which was confirmed by inductively coupled plasma-atomic emission spectroscopy. Besides, the mechanical properties of the coatings were analyzed. From the obtained results, the bilayer coating exhibited greater mechanical strength than the individual coating. An in vitro bioactivity of the coatings was assessed by immersion in the SBF solution at 7–28 days. The apatite formation of bilayer coatings on 316L SS substrate is found to be more bioactive compared with the Na-HAp, PoPD, and Na-HAp/CS. The in vitro biocompatibility test showed no adverse effects, which was proved by the enhanced biocompatibility of the bilayer coating on 316L SS.     

Sol-gel bioactive glass-ceramics Part I: Calcium phosphate silicate/wollastonite glass-ceramics

In this work we present experimental results about synthesis, structure evolution and in vitro bioactivity of new calcium phosphate silicate/wollastonite (CPS/W) glass-ceramics. The samples obtained were synthesized via polystep sol-gel process with different Ca/P+Si molar ratio (R). The structure of the materials obtained was studied by XRD, FTIR spectroscopy and SEM. XRD showed the presence of Ca₁₅(PO₄)₂(SiO₄)₆, β-CaSiO₃ and α-CaSiO₃ for the sample with R=1.89 after thermal treatment at 1200°C/2h. The XRD results are in good agreement with FTIR analysis. SEM denotes that apatite formation can be observed after soaking in simulated body fluid (SBF).      

In vitro surface biocompatibility of high-content silicon-substituted calcium phosphate ceramics

The present work investigates surface biocompatibility of silicon-substituted calcium phosphate ceramics. Different silicon-substituted calcium phosphate ceramic bodies were prepared from co-precipitated powders by sintering at 1300°C. The in vitro bioactivity of the ceramics was assessed in simulated body fluid (SBF) at 37°C for periods up to 4 weeks. The changes in the surface morphology and composition were determined by scanning electron microscopy (SEM) coupled with electron probe microanalysis and energy dispersive spectrometer (EDX). Inductively coupled plasma optical emission spectroscopy (ICP-OES) was used to observe the change in ionic concentration of SBF after removal of the samples. The bioactivity of the ceramics increased with an increasing silicate ion substitution in a systematic way. The surface of ceramics with 2.23% silicon substitution was partially covered with apatite layer after one week, while ceramics with 8.1% silicon substitution were completely covered with apatite in the first week. The porous microstructure of high-concentration Si-substituted ceramics helps the dissolution of surface ions and the leaching process. This allows SBF to reach supersaturation in a short time and accelerate the deposition of apatite layer.      

Potential applications of fluorhydroxyapatite as biomaterials in medicine

The present work was undertaken to investigate the bioactivity and cytotoxicity of fluorhydroxyapatite ceramics. The bioactivity was evaluated by in vitro testing in simulated body fluid (SBF), in which ion concentrations are almost identical with inorganic ion concentrations of human blood plasma. Pellets of FA, HA and FHA were immersed in SBF for 48 hours, 1 week and 4 weeks at 36.5°C. Changes of the surface microstructure of the samples were observed by scanning electron microscopy (SEM). 48 hours and one week immersion in SBF did not result in any substantial progress in bioactivity. After 4 weeks in SBF a new biologically active layer was created on the surface of the biomaterials. In addition, the embryonal mouse fibroblast cell line NIH-3T3 was used for a comparative study of basal cytotoxicity of FHA, HA and FA discs. The sensitivity of these cells for tested biomaterials was evaluated on the basis of two cytotoxic end points: cell proliferation and cell morphology. The basal cytotoxicity of FHA, FA and HA discs was measured by a direct contact method. After 24, 48 and 72 hours, the cell growth was evaluated by direct counting of non-affected cells and cells treated by biomaterials. After 72 hours of biomaterials treatment, about 25% inhibition of cell number and unchanged morphology was found.      

非离子型可聚合聚氨酯/苯乙烯的超浓乳液聚合

研究了以非离子型可聚合聚氨酯(PUAG)和苯乙烯(St)为混合单体的超浓乳液聚合, 并且考察了n(NCO)/n(OH)摩尔比、复合乳化剂体系质量浓度[E]、不同乳化剂的种类、引发剂质量浓度[I]、单体体积分数(或分散相体积分数, 也称内相比Φ)、聚合温度等因素对聚合稳定性、动力学的影响. 同时结合光相关光谱(PCS)测定了聚合物乳胶粒子大小和粒径分布, 用透射电子显微镜(TEM)观察了粒子形态, 结果表明: 当n(NCO)/n(OH)＝2∶1, T＝328 K, Φ＝80.39%, [I]＝0.8% g/g (PUAG-St), [E]＝0.22 g/mL H₂O, m(MS-1)/m(CA)＝2∶1, PVA＝0.01 g/mL H₂O时, 超浓乳液不仅有较好的聚合稳定性和较快的聚合速率, 而且粒径小分布均匀. 同时, 在此条件下的表观动力学表达式和表观活化能分别确定为R_p＝k[I]^0.50[E]^0.73[M]^0.54和 E_a＝29.7 kJ/mol. 热失重分析(TGA)进一步表明: 调节PUAG的含量可以达到对聚苯乙烯的改性, 提高聚苯乙烯的热稳定性.     

Sol-gel bioactive glass-ceramics Part II: Glass-ceramics in the CaO-SiO2-P2O5-MgO system

Ceramics, with basic composition based on the CaO-SiO₂-P₂O₅-MgO system with different Ca+ Mg/P+Si molar ratio (R), were prepared via polystep sol-gel technique. The structure of the obtained ceramic materials has been studied by XRD, FTIR spectroscopy, and SEM. X-ray diffraction showed the presence of akermanite and HA for the sample with R = 1.68 and Mg substituted β-TCP and silicocarnotite for the sample with R = 2.16, after thermal treatment at 1200°C/2 h. The obtained results are in good agreement with FTIR. In vitro test for bioactivity in static condition proved that the carbonate containing hydroxyapatite (CO₃HA) can be formed on the surface of the synthesized samples. CO₃HA consisted of both A- and B-type CO₃²⁻ ions. SEM micrographs depicted different forms of HA particles, precipitated on the surface after soaking in 1.5 simulated body fluid (SBF).