Fe3O4/ 生物可降解复合材料研究

磁性氧化铁纳米粒子因具有尺寸小、低毒性和超顺磁性等特点,已经引起了生物化工、医药工业领域的广泛关注。生物可降解高分子材料是生物医用高分子研究中最活跃的领域之一,已广泛用于外科手术缝合线,植入体材料及药物释放载体等。将Fe3O4和生物可降解高分子材料进行复合,可以扩大两者的应用范围,达到理想的治疗效果,并有望开创临床治疗的新时代。本文介绍了磁性四氧化三铁粒子的化学制备方法,包括共沉淀法、溶胶-凝胶法、微乳液法,并对各种方法的优缺点进行了比较;重点阐述了磁性壳聚糖,磁性聚乳酸,磁性PEG,磁性PCL复合材料的制备,及它们在酶的固定化、磁靶向药物及基因载体等医学领域的应用,显示了Fe3O4/生物可降解复合材料在医学领域的广阔应用前景;最后对复合材料走向临床应用所面临的问题及发展前景进行了讨论。     

Fe3+络合萃取法从野葛根中分离葛根素

利用Fe3 + 能够和葛根素生成可溶性络合物的性质建立了一种从中药野葛根中萃取葛根素的新型分离方法。以甲醇冷浸从野葛根中提取葛根总黄酮 ,将其进行水解、中和 ,再给水解葛根总黄酮中加入FeCl3 使葛根素与Fe3 + 络合溶解 ,过滤除去其它不溶性物质 ,用盐酸解聚Fe3 + 葛根素络合物 ,则得葛根素粗品 ,将其重结晶可得葛根素。同时 ,利用分光光度法确定了Fe3 + 葛根素络合物解聚的最佳酸度。利用TLC标准品对照、IR和分光光度法对产品进行了定性和定量分析。该方法从葛根中提取葛根素收率为 1 2 % ,纯度为 96 5 % ,具有操作简便、工艺流程简单 ,容易实现工业化的优点。     

Proton magnetic resonance studies of 7 Fe ferredoxins: Lower potential of the [4 Fe–4 S] redox center than the [3 Fe–3 S] cluster

Two types of iron-sulfur clusters, [3 Fe–3 S] and [4 Fe–4 S], were identified by ¹H-NMR in ferredoxins from Thermus thermophilus, Mycobacterium smegmatis and Pseudomonas ovalis. The [4 Fe–4 S] clusters always showed the redox couples which had potentials lower than that of the [3 Fe–3 S] clusters.     

Fe3O4磁性纳米粒子在生物医学领域的应用

Fe_3O_4磁性纳米粒子由于其良好的磁学性能,被广泛应用到了化学、生物、物理、环境保护等各个领域。尤其是在生物医学领域中的应用越来越受到研究者的关注。由于其所具有的优秀的超顺磁性性质,Fe_3O_4磁性纳米粒子可以作为造影剂,增强核磁共振成像的对比度和成像效果;也可以结合到纳米载药系统内用于药物的靶向输送;也可以包埋到蛋白内部用于蛋白的磁性分离;也可以用于基因治疗,提高靶细胞的转染效率;由于其在近红外光的作用下具有很好的光热转换效果,使温度升高,展现出的良好热疗效果,Fe_3O_4磁性纳米粒子又可以用于癌细胞的热疗。本文针对其在该领域中作为药物的靶向传递,蛋白的磁分离,核磁共振成像,热疗,以及基因治疗的载体等方面的研究应用进行了系统性的总结,阐述了Fe_3O_4磁性纳米粒子在生物医学领域中各种应用进展和优势。     

硅烷化试剂修饰Fe3O4磁性微粒的研究进展

磁性微粒作为一种新型的功能材料,已经在生物分离、生物医学和环境工程等领域得到了广泛的应用.作者对硅烷化试剂修饰的Fe3O4磁性微粒的制备方法以及硅烷化试剂修饰的Fe3O4磁性微粒在各个领域的最新应用进展进行了评述,引用文献62篇.     

Fe3+对浮游颤藻生长和光合作用的影响

考察了浓度为0—30mmol/L的范围内,Fe3 对浮游颤藻(Oscillatoria planctonicaWoloszynska)的生长、生化组成和光合作用的影响。结果表明,当Fe3 浓度小于10nmol/L时,浮游颤藻的生长以及叶绿素和蛋白质的合成均受到明显的抑制,对其补铁后这种抑制能够得到一定程度的缓解。当Fe3 浓度达到10mmol/L时,最大生物量与比生长速率分别是不加铁时的3倍和4倍。富铁条件下藻细胞光饱和的光合作用速率(Pm)、暗呼吸速率(Rd)和表观光合作用效率(α)显著大于缺铁条件,而光补偿点Ic及饱和光强Ik则低于缺铁条件。结果显示,铁是浮游颤藻生长的重要限制因子。     

Mössbauer and susceptibility experiments on different compounds of Fe3+-myoglobin

The static magnetic susceptibilities of different ferric high spin and low spin compounds of myoglobin (Mb(H₂O), Mb(H₂O) frozen under high pressure, MbF, MbCN) were measured in the temperature region between 4.2 K and 130 K. Mössbauer absorption experiments on Mb(H₂O) and MbF were perormed at different temperatures between 4.2 K and 180 K and in small magnetizing fields H1 kOe. The evaluation of our experimental data was performed with a Hamiltonian describing the 3d ⁵-configuration of the ferric iron by taking into account the Coulomb repulsion of the five electrons within the 3d-shell, the crystal electric field of -symmetry, and the spin-orbit coupling. The Hamiltonian contains the splitting energies of the five antibonding d-orbitals (d _xy , d _xz , d _yz , d _x 2_–y 2, d _z 2) as parameters. The values of these energies were obtained by a least squares fitting procedure using our magnetic susceptibility data together with the g-factors taken from the literature. In the case of MbF the energy difference between the two lowest Kramers doublets was also determined from present Mössbauer data. The results of the susceptibility and the Mössbauer data are in good agreement.The splitting energies of the 3d-orbitals can be correlated to the distances between the iron and its nearest neighbours. The different positions of the iron in the compounds investigated are discussed.     

Fe3O4对施氏假单胞菌反硝化过程的影响

生物反硝化是目前废水深度处理中应用最为广泛的硝酸盐氮处理技术,但该方法一般停留时间较长,在冬季因低温处理效果欠佳,因此有必要开发反硝化强化技术。以施氏假单胞菌Pseudomonas stutzeri为研究对象,考察了不同投加量下Fe3O4对P. stutzeri反硝化过程的影响。结果显示当Fe3O4投加量由0 mg/L增至4 000 mg/L时,硝酸盐氮最大比降解速率由18.0 h–1增加至23.7 h–1,体系中的总蛋白含量以及细菌体内的铁含量显著增加。RT-qPCR和非标记 (Label-free) 定量蛋白组学分析表明,投加4 000 mg/L Fe3O4体系中的P. stutzeri,其反硝化功能基因napA、narJ、nirB、norR、nosZ表达量分别提高了55.7%、24.9%、24.5%、36.5%、120%,对应反硝化还原酶Nap、Nar、Nir、Nor、Nos表达量提高了85.0%、147%、16.5%、47.1%、95.9%。对比体系中“游离细菌”和“Fe3O4粘附细菌”,发现二者的反硝化功能基因以及反硝化相关酶没有显著差别;而Fe3O4粘附细菌电子传递相关蛋白表达量有所提高,说明了Fe3O4通过与细菌直接接触促进其生长代谢,导致体系中细菌总量的增加,从而提高反硝化速率。该结果可为反硝化强化技术的开发提供理论支撑。     

磁性Fe3O4微粒对葵花籽壳酶水解的影响研究

将磁化后的Fe3O4微粒添加于葵花籽壳酶水解过程中, 分析在不同的Fe3O4添加量和不同的添加方法下, 葵花籽壳酶水解过程中纤维素酶酶活﹑纤维素转化率及还原糖浓度的变化特征, 研究磁性Fe3O4微粒对纤维素酶水解葵花籽壳的影响。并通过考察酶水解反应前后水解液的表面张力值和pH值的变化, 探讨和分析磁性Fe3O4微粒作用下纤维素酶的磁效应机制。结果表明, 磁性Fe3O4添加量为0.5 g/L~2.0 g/L时, 对纤维素酶酶活的提高﹑还原糖浓度的增加和纤维素的转化在48 h后表现出较明显的促进作用。磁性Fe     

Unravelling the interface of Co–Pi/Ag/Fe2O3 and Ni–Pi/Ag/Fe2O3 heterostructures for enhanced solar water splitting

Recently, a new type of haematite-based (a-Fe₂O₃) photoanode has achieved a considerable catalytic performance through simply depositing Ag and cobalt phosphate (Co–Pi) nanoparticles (NPs) onto haematite nanosheets. However, there is no detailed mechanism study on the reason for high-performance catalysis. In view of this, we conduct first-principles calculations and our results indicate that there is a further accumulation of positive charge on Ag NPs on the heterogeneous interfaces with the addition of Co–Pi NPs than that of haematite modified only by Ag NPs. Also, there is a slight increase of the adsorption energy of water molecules.     

表面改性的纳米Fe3O4颗粒用于抗血清快速分离纯化

采用硅烷化试剂Si(OC2H5)3C3H6NH2(APTES)对纳米Fe3O4颗粒表面进行氨基化改性后, 考察了不同浓度偶联剂戊二醛对于颗粒表面固定牛血清白蛋白(BSA)量的影响。此超顺磁性免疫铁颗粒(SPIO)加入兔抗BSA血清中特异性结合BSA抗体后, 用Gly-HCl缓冲液洗脱得到IgG。结果表明当戊二醛浓度大于10%时, 单位颗粒固定蛋白的量达到最大值约140 mg/mg, 10 min, 15 mg的SPIO即可将1 mL抗血清完全分离, 经过两次快速洗脱, 颗粒表面吸附的抗体即可得到纯化; 琼脂扩散实验表明分离后的抗体仍保持较高活性, SDS-PAGE电泳结果表明用此方法纯化后的兔抗BSA IgG纯度大于99%, 比传统的(NH4)2SO4法有了较大提高, 但纯化量并没有减少; SPIO在经过五次重复利用后仍能保持78%以上的分离效果。     

红条毛肤石鳖齿舌牙齿内Fe3O4的研究

目的:探讨红条毛肤石鳖齿舌牙齿内磁性纳米物质(Fe3O4)的晶体结构、磁畴及磁晶各向异性等磁学性质.方法:从红条毛肤石鳖齿舌主要横向牙齿中提取出磁性纳米磁性矿物质(Fe3O4),用高分辨透射电子显微镜,扫描电子显微镜研究其外貌及晶体结构,用磁力显微镜观察其磁畴结构,然后利用超导量子干涉磁强计(SQUID)和磁转矩测量仪测量其磁化曲线,探讨它的磁各向异性.结果:①红条毛肤石鳖齿舌中的磁铁矿为长约几微米、宽约100纳米的长条片壮物质,由尺度约为50纳米的磁铁矿小晶粒及有机物质构成.②小晶粒的[111]方向沿着长条片状物质的长度方向,具有沿着厚度方向的单磁畴结构.③SQUID和磁转矩测量均证明长条片状纳米磁性矿物质的长度方向为易磁化方向.红条毛肤石鳖齿舌中的磁性矿物质与自然界中的磁铁矿具有相同的结构.结论:红条毛肤石鳖齿舌中的磁性物质为具有单畴结构、易磁化方向为[111]方向的Fe3O4晶体.     

纳米Fe3O4对生菜生长及土壤细菌群落结构的影响

纳米Fe₃O₄的广泛应用增加了其暴露到农田环境的可能性,因此亟待研究纳米Fe₃O₄对农业生态环境的影响.本研究采用盆栽试验方式,研究不同浓度纳米Fe₃O₄颗粒(1、10、100 mg·kg^-1)对生菜生长及土壤细菌群落的影响,并与相应浓度的普通Fe₃O₄处理进行对比.通过测定植物光合速率常数、植株Fe含量来评价植物生长;采用高通量测序技术研究土壤细菌群落结构及组成.结果表明: 不同浓度纳米Fe₃O₄的影响不同.低浓度纳米Fe₃O₄能提高植物生物量,增强植物叶片光合速率,增加土壤中黄单胞菌目的相对丰度,降低蓝细菌、鞘脂杆菌纲的相对丰度,但对群落多样性指数影响不显著.高浓度纳米Fe₃O₄抑制作物生长,提高植株中Fe积累及土壤电导率,降低细菌群落系统发育多样性,降低黄单胞菌目、鞘脂杆菌纲相对丰度,增加蓝细菌相对丰度.此外,一些土壤功能微生物对纳米Fe₃O₄及普通Fe₃O₄处理的响应也存在差异,说明不同粒径及浓度的Fe₃O₄均会对土壤微生物群落产生影响,并可能影响地上部分植物性状.因此,在评估纳米颗粒的生物学效应时需较多关注土壤微生物.     

M?ssbauer studies of aconitase. Substrate and inhibitor binding, reaction intermediates, and hyperfine interactions of reduced 3Fe and 4Fe clusters

Active beef heart aconitase contains a [4Fe-4S] cluster. One iron of the cluster, Fea, is labile and can be removed easily by oxidation in air to yield the [3Fe-4S]1+ cluster of inactive aconitase. We have previously shown that substrate binds to Fea. We have continued our M?ssbauer studies by further investigating the active and inactive forms of the enzyme. When active aconitase, [4Fe-4S]2+, is mixed with substrate, two species (substrates or intermediates bound to Fea) labeled S1 and S2 are obtained. With the nitroanalogs of citrate and isocitrate, thought to be transition state analogs, and fluorocitrate, species S2, but not S1, is observed, suggesting that S2 represents a carbanion transition state complex. We have prepared M?ssbauer samples by rapid mix/rapid freeze techniques. Using either citrate, isocitrate or cis-aconitate, the natural substrates, we have been able to detect at 0 degree C reaction intermediates in the 5-35 ms time range and, studying enzyme substrate interactions at subzero temperatures in a water/methanol/ethylene glycol solvent, we have observed new species when substrates were added at -60 degrees C. Details of these experiments are given, although in neither case can unique interpretations be offered at this time. We have also investigated reduced active aconitase ([4Fe-4S]1+; EPR at g = 1.94) in the presence of substrate with material selectively enriched with 57Fe in either Fea or the other three cluster sites. The spectra were analyzed with a spin Hamiltonian, and the results are discussed and interpreted in terms of three inequivalent Fe sites in the cluster. Finally, we have studied enzyme containing the reduced [3Fe-4S]0 cluster. There is no indication that citrate binds to the 3Fe cluster, and since no significant activity was observed, we conclude that aconitase containing a 3Fe cluster is not active in either oxidation state.     

Mechanism of Fe uptake by the leaf symplast: Is Fe inactivation in leaf a cause of Fe deficiency chlorosis?

The mechanism of iron (Fe) uptake from the leaf apoplast into leaf mesophyll cells was studied to evaluate the putative Fe inactivation as a possible cause of Fe deficiency chlorosis. For this purpose, sunflower (Helianthus annuus L.) and faba bean plants (Vicia faba L.) were precultured with varied Fe and bicarbonate (HCO ₃ ^- ) supply in nutrient solution. After 2–3 weeks preculture, Fe^III reduction and ⁵⁹Fe uptake by leaf discs were measured in solutions with Fe supplied as citrate or synthetic chelates in darkness. The data clearly indicate that Fe^III reduction is a prerequisite for Fe uptake into leaf cells and that the Fe nutritional status of plants does not affect either process. In addition, varied supply of Fe and HCO ₃ ^- to the root medium during preculture had no effect on pH of the xylem sap and leaf apoplastic fluid. A varied pH of the incubation solution had no significant effect on Fe^III reduction and Fe uptake by leaf discs in the physiologically relevant pH range of 5.0–6.0 as measured in the apoplastic leaf fluid. It is concluded that Fe inactivation in the leaf apoplast is not a primary cause of Fe deficiency chlorosis induced by bicarbonate. This revised version was published online in June 2006 with corrections to the Cover Date.     

水溶性有机溶剂对Fe3O4磁性纳米粒子过氧化物酶样活性的影响

采用化学共沉淀法合成10nm的Fe3O4磁性纳米粒子(MNPs)。以辣根过氧化物酶(HRP)为对照,研究了四氢呋喃、1,4-二氧六环、丙酮、N,N-二甲基酰胺、甲醇和二甲亚砜等6种水溶性有机溶剂对Fe3O4MNPs过氧化物酶样活性的影响。结果表明,在有机溶剂浓度(V/V)为30%～75%时,Fe3O4MNPs相对酶活力迅速下降至近于完全失活。在15%有机溶液中,Fe3O4MNPs的最适反应温度多为50oC,最适反应pH在3.6左右。经15%有机溶液处理后的水相反应酶活显示,Fe3O4MNPs表现出对有机溶剂较强的热稳定性和pH稳定性,且对75%有机溶液也具有良好的稳定性。以上多数性质均优于相同条件下的HRP组,表明Fe3O4MNPs是一种比HRP对水溶性有机溶剂更稳定的过氧化物酶。由于Fe3O4MNPs具有易制备、成本低、易于磁分离和可循环使用的特点,因此其具有替代HRP用于有机催化的应用潜力。     

棕色石灰土和红壤碳释放对添加矿物质(Fe(OH)_3和CaCO_3)的响应

为阐明喀斯特地区土壤演变过程(脱钙镁富铁铝化作用)中土壤特有矿物对碳释放的影响,本文以喀斯特区典型的高和低有机碳含量水平的棕色石灰土和红壤为研究对象,通过80 d室内培养试验,研究土壤碳释放(有机碳和无机碳)对添加土壤中特有矿物质(Ca14CO3和Fe(OH)3)的响应。结果表明:添加Ca14CO3和Fe(OH)3均对棕色石灰土和红壤中原有碳的释放有正激发效应,以前者(培养结束时土壤原有碳累积释放量为823.8~1367.2 mg·kg-1)显著大于后者(502.5~635.7 mg·kg-1),说明喀斯特地区土壤由富钙镁的石灰土向富铁铝的红壤演变过程可能是土壤碳库逐渐稳定的过程。添加Ca14CO3和Fe(OH)3后,土壤原有碳的累积释放量的大小与土壤有机碳本身含量水平密切相关,均以高量有机碳红壤低量有机碳红壤和石灰土高量有机碳石灰土(P0.05)。培养过程中,无论是添加Ca14CO3还是Fe(OH)3,土壤可溶性有机碳(DOC)含量与碳释放激发效应的变化趋势一致,表明DOC可用于指示棕色石灰土和红壤激发效应强弱。土壤微生物生物量碳与碳释放激发效应的变化趋势不一致,说明添加Ca14CO3或Fe(OH)3对土壤原有碳的激发效应主要源于外源物添加后改变了土壤物理和化学环境,而土壤微生物的贡献相对较少。     

Synthesis of polypyrrole within the cell wall of yeast by redox-cycling of [Fe(CN)6]3−/[Fe(CN)6]4−

Yeast cells are often used as a model system in various experiments. Moreover, due to their high metabolic activity, yeast cells have a potential to be applied as elements in the design of biofuel cells and biosensors. However a wider application of yeast cells in electrochemical systems is limited due to high electric resistance of their cell wall. In order to reduce this problem we have polymerized conducting polymer polypyrrole (Ppy) directly in the cell wall and/or within periplasmic membrane. In this research the formation of Ppy was induced by [Fe(CN)₆]³⁻ions, which were generated from K₄[Fe(CN)₆], which was initially added to polymerization solution. The redox process was catalyzed by oxido-reductases, which are present in the plasma membrane of yeast cells. The formation of Ppy was confirmed by spectrophotometry and atomic force microscopy. It was confirmed that the conducting polymer polypyrrole was formed within periplasmic space and/or within the cell wall of yeast cells, which were incubated in solution containing pyrrole, glucose and [Fe(CN)₆]⁴⁻. After 24 h drying at room temperature we have observed that Ppy-modified yeast cell walls retained their initial spherical form. In contrast to Ppy-modified cells, the walls of unmodified yeast have wrinkled after 24 h drying. The viability of yeast cells in the presence of different pyrrole concentrations has been evaluated.