磁性Fe3O4纳米颗粒的制备和磁性研究

讨论了一种制备磁性Fe3O4纳米颗粒的新方法，利用自行设计的反应容器，引入磁场和电场的相互作用，制得颗粒大小比较均一、分散性较好的Fe3O4纳米颗粒。通过改变反应时间、磁铁高度，得到了平均粒径为5～10nm的Fe3O4纳米颗粒，并对其进行磁特性测量。     

强磁性Ni掺杂Fe3O4纳米磁粉的研制

用化学共沉淀法制备了强磁性的Ni掺杂Fe3O4纳米磁粉。采用X射线衍射仪、电感耦合等离子发射光谱仪、傅立叶红外-拉曼光谱仪、透射电子显微镜、振动样品磁强计对掺杂Fe3O4纳米粒子进行了物相结构和磁性能表征。结果表明，掺杂Fe3O4磁粉的粒径在20nm左右，其比饱和磁化强度（σs）可达114emu／g，大大超过了一般Fe3O4纳米磁粉的比饱和磁化强度（σs），并进一步分析了掺杂Fe3O4纳米粒子的磁性能有较大提高的原因。     

Fe3O4／羧甲基化壳聚糖纳米粒子的制备与表征

磁性壳聚糖纳米粒子可用于药物载体及废水处理吸附剂。以化学共沉淀法制备Fe3O4纳米粒子，壳聚糖先进行羧甲基化改性，再经碳二亚胺活化，包履在Fe3O4颗粒表面,透射电镜（TEM）表明，Fe3O4纳米粒子被CMC包履，粒径约10nm；X射线衍射（XRD）分析表明复合纳米粒子中磁性物质为Fe3O4；傅立叶红外光谱（FTIR）表明壳聚糖发生羧甲基反应；磁性测试表明，Fe3O4／CMC具有超顺磁性，饱和磁化强度25.73emu／g，且有良好的磁稳定性。     

磁性羧甲基化壳聚糖纳米粒子的制备与表征

以化学共沉淀法制备了Fe3O4纳米粒子,壳聚糖经羧甲基化改性后接枝在Fe3O4颗粒表面,得到了磁性羧甲基化壳聚糖(Fe3O4/CMC)纳米粒子.利用透射电镜(TEM)、X射线衍射(XRD)、傅立叶红外光谱(FT-IR)及磁性测试对产物进行了表征.TEM表明Fe3O4纳米粒子被CMC包覆,粒径约10 nm;XRD分析表明复合纳米粒子中磁性物质为Fe3O4;FT-IR表明壳聚糖发生羧甲基反应以及在Fe3O4表面的接枝反应.Fe3O4/CMC纳米粒子具有超顺磁性,比饱和磁化强度25.73 emu/g,有良好的磁稳定性.     

Tumor Microenvironment‐Triggered Aggregation of Antiphagocytosis 99mTc‐Labeled Fe3O4 Nanoprobes for Enhanced Tumor Imaging In Vivo

A tumor microenvironment responsive nanoprobe is developed for enhanced tumor imaging through in situ crosslinking of the Fe₃O₄ nanoparticles modified with a responsive peptide sequence in which a tumor‐specific Arg‐Gly‐Asp peptide for tumor targeting and a self‐peptide as a “mark of self” are linked through a disulfide bond. Positioning the self‐peptide at the outmost layer is aimed at delaying the clearance of the nanoparticles from the bloodstream. After the self‐peptide is cleaved by glutathione within tumor microenvironment, the exposed thiol groups react with the remaining maleimide moieties from adjacent particles to crosslink the particles in situ. Both in vitro and in vivo experiments demonstrate that the aggregation substantially improves the magnetic resonance imaging (MRI) contrast enhancement performance of Fe₃O₄ particles. By labeling the responsive particle probe with ^99mTc, single‐photon emission computed tomography is enabled not only for verifying the enhanced imaging capacity of the crosslinked Fe₃O₄ particles, but also for achieving sensitive dual modality imaging of tumors in vivo. The novelty of the current probe lies in the combination of tumor microenvironment‐triggered aggregation of Fe₃O₄ nanoparticles for boosting the T₂ MRI effect, with antiphagocytosis surface coating, active targeting, and dual‐modality imaging, which is never reported before.     

Timely Visualization of the Collaterals Formed during Acute Ischemic Stroke with Fe3O4 Nanoparticle‐based MR Imaging Probe

Ischemic stroke is one of the major leading causes for long‐term disability and mortality. Collateral vessels provide an alternative pathway to protect the brain against ischemic injury after arterial occlusion. Aiming at visualizing the collaterals occurring during acute ischemic stroke, an integrin α_vβ₃‐specific Fe₃O₄–Arg‐Gly‐Asp (RGD) nanoprobe is prepared for magnetic resonance imaging (MRI) of the collaterals. Rat models are constructed by occluding the middle cerebral artery for imaging studies of cerebral ischemia and ischemia–reperfusion on 7.0 Tesla MRI using susceptibility‐weighted imaging sequence. To show the binding specificity to the collaterals, the imaging results acquired with the Fe₃O₄–RGD nanoprobe and the Fe₃O₄ mother nanoparticles, respectively, are carefully compared. In addition, an RGD blocking experiment is also carried out to support the excellent binding specificity of the Fe₃O₄–RGD nanoprobe. Following the above experiments, cerebral ischemia–reperfusion studies show the collateral dynamics upon reperfusion, which is very important for the prognosis of various revascularization therapies in the clinic. The current study has, for the first time, enabled the direct observation of collaterals in a quasi‐real time fashion and further disclosed that the antegrade flow upon reperfusion dominates the blood supply of primary ischemic tissue during the early stage of infarction, which is significantly meaningful for clinical treatment of stroke.     

表面活性剂对磁流体稳定性及外层包覆结构的影响

采用化学共沉淀法制备粒径分布均匀的纳米Fe3O4颗粒,用油酸钠和聚乙二醇4000(PEG4000)对纳米Fe3O4颗粒进行表面修饰,制得分散稳定的纳米Fe3O4磁流体,通过电动电位(Zeta电位)、粒径测试、离心沉淀、红外光谱分析(FT-IR)和热分析(TG)对修饰后的纳米Fe3O4颗粒进行了稳定性能评价与结构表征。结果表明,油酸钠与纳米Fe3O4颗粒存在两种不同类型的化学键作用;增大油酸钠加入量不会改变Fe3O4颗粒表面包覆结构,但是,其在纳米Fe3O4颗粒表面的吸附量呈先增加后降低的趋势;PEG4000物理吸附于油酸钠包覆的纳米Fe3O4颗粒表面,PEG4000的加入会进一步提高磁流体的稳定性。     

Photonic Reactions Leading to Fluorescence in a Polymeric System Induced by the Photothermal Effect of Magnetite Nanoparticles Using a 780 nm Multiphoton Laser

Recently, polymer‐coated magnetite (Fe₃O₄) nanoparticles (NPs) are extensively studied for applications in therapeutics or diagnostics using photothermal effect. Therefore, it is essential to understand the interactions between Fe₃O₄ NPs and polymers when optical stimuli are applied. Herein, the photonic reactions of Fe₃O₄ NPs and polymer composites upon application of a 780 nm multiphoton laser are analyzed. The photonic reactions produce unique results including fluorescence from conformationally changed polymer and low‐temperature phase transformation of Fe₃O₄ NPs. Typically, π‐conjugated chains are formed, inducing fluorescence through a series of main and side‐chain cleavage reactions of polymers with the aliphatic chain. In addition, fluorescence is detected in the cellular system by photonic reactions between Fe₃O₄ NPs and biomolecules. After multiphoton laser irradiation, light emission is detected near the intracellular Fe₃O₄ NPs, and a stronger intensity is observed in large‐sized NPs.     

超顺磁性纳米Fe3O4的热分解法制备及表征

以单甲氧基聚乙二醇、对甲苯磺酰氯、邻苯二甲酰亚胺钾等为原料,根据盖布瑞尔合成法原理,合成了一端为氨基的单甲醚聚乙二醇(mPEG-NH2)。并以其为还原剂,聚乙二醇(PEG)为溶剂,利用热分解法制备了水分散性的超顺磁性纳米Fe3O4。采用红外光谱(FT-IR)、X射线衍射(XRD)、透射电镜(TEM)、热重分析(TG)、超导量子干涉仪(SQUID)和纳米粒度与Zeta电位分析仪等测试技术对其性能进行表征,实验结果表明,所制得的纳米Fe3O4粒子结晶度高,粒度均匀,分散良好,平均粒径为(12.2±1.6)nm,具有超顺磁性,饱和磁化强度为54 emu/g,在中性水溶液中其表面带正电,Zeta电位为+33 mV。TG测试结果表明,Fe3O4纳米粒子表面有机物的含量约为28%,Fe3O4的产率为57%左右。