磁性Fe3O4纳米晶制备及应用

磁性Fe₃O₄纳米晶由于其独特的磁性能,已在许多领域得到了广泛的应用,并且在不同的应用领域其制备方法也不尽相同。本文综述了近年来磁性Fe₃O₄纳米晶的液相制备方法,如沉淀法、溶剂热法、溶胶-凝胶法、微乳液法、微波超声法等研究进展,对这些制备方法的特点进行了归纳概括,并详细分析了制备工艺中不同影响因素对Fe₃O₄纳米晶结构与性能的影响。同时,对磁性Fe₃O₄纳米晶在磁流体、微波吸收、污水处理、催化、药物载体、生物酶固定、生物传感器等方面的应用及发展趋势进行了评述,以期对Fe₃O₄纳米晶的制备及应用有较全面的认识。     

介孔二氧化硅纳米粒子应用于可控药物传输系统的若干新进展

通过对介孔二氧化硅纳米粒子(MSN)载药机理、药物控释机理和靶向方法的介绍,对MSN在可控药物传输系统中的应用加以综述.     

PVP-b-PLA 修饰 Fe3O4 磁性纳米粒子的制备与表征

通过硅烷偶联剂与Fe3O4磁性纳米粒子偶合在其表面引入C C端基,进一步与N-乙烯基吡咯烷酮(NVP)加成聚合制备含端羟基PVP包裹的磁体,再引发丙交酯(LA)开环聚合制得PVP-b-PLA修饰的Fe3O4纳米粒子.通过XRD、GPC、FTIR、SEM、TG、DSC和激光粒度仪等,对产物进行分析和表征,结果表明,纳米Fe3O4与PVP以及PVP与PLA之间均为化学键联,PVP和PLA是以嵌段共聚物的形式存在且两者之间存在明显的微相分离,纳米Fe3O4表面聚合物包覆率为35%,厚度约13 nm.此外,该PVP-b-PLA包覆的磁性纳米粒子比饱和磁化强度为53 emu/g,与未包覆相比下降约25%.     

聚丙烯酰胺修饰Fe_3O_4磁性纳米粒子的制备与表征

首先通过化学处理在Fe3O4磁性纳米粒子表面引入Si—H键,然后通过选择性的硅氢加成反应制备了一个端基带溴的磁性引发剂,并利用原子转移自由基聚合(ATRP)技术,在该磁性引发剂表面接枝了聚丙烯酰胺高分子,该聚丙烯酰胺高分子展现出分子量高度可控性和窄的分子量分布.经聚丙烯酰胺修饰后Fe3O4磁性纳米粒子的比饱和磁化强度为58.5 emu.g-1,与未修饰纳米Fe3O4相比下降约20%.     

新型磁性Fe3O4/EDTA复合纳米粒子的制备及性能研究

采用氨羧络合剂EDTA对纳米磁性Fe3O4粒子进行表面改性,制备出能够螯合金属离子和放射性核素离子的磁性Fe3O4/EDTA复合纳米粒子.用X射线衍射、红外光谱、透射电子显微镜、光电子能谱、振动样品磁强计和原子吸收光谱对复合粒子进行了表观形貌、结构、磁学及螯合性能表征.结果表明,纳米磁性Fe3O4和EDTA之间能够有效地以化学键合方式进行复合.改性后,Fe3O4/EDTA纳米复合粒子可以对包括放射性金属离子在内的多种金属离子具有良好的络合效果.     

Fe3O4磁性纳米粒子-氧化石墨烯复合材料的可控制备及结构与性能表征

首先利用高温分解法制备了粒径为18 nm的Fe₃O₄磁性纳米粒子, 并进行羧基化修饰, 然后与聚乙烯亚胺(PEI)化学修饰的氧化石墨烯进行交联反应, 得到磁功能化的氧化石墨烯(MGO)复合材料. 研究了氧化石墨烯片上的磁性纳米粒子的可控负载及其对复合材料磁性能的影响. 利用透射电子显微镜(TEM), 原子力显微镜(AFM), X射线衍射(XRD), 傅里叶变换红外(FT-IR)光谱, 热重分析(TGA), 振荡样品磁强计(VSM)等手段对MGO复合材料的形貌, 结构和磁性能进行了表征. 结果表明, 我们发展的MGO复合材料的制备方法具有简单、可控的优点, 所制备的MGO复合材料具有较高的超顺磁性. 该类磁性氧化石墨烯复合材料有望在磁靶向药物、基因输运、磁共振造影以及磁介导的生物分离和去除环境污染物等领域获得广泛的应用.     

聚乙醇-Fe3O4粒子的制备

金属离子在高分子基体中趋于成簇并形成所谓的纳米级相结构[1] 。利用金属离子在高分子相中的这一独特结构 ,可用共沉淀法制备以四氧化三铁为核 ,高分子为壳的具有核壳结构的粒子 ,该粒子既具有超顺磁性同时又具有强的吸附蛋白质的能力。Ｆｅ3+与高分子基体并不是简单的混合[2 ] ,而是通过配位键结合的。Ｆｅ3+在高分子基体中存在离子簇 ,但由于它们的结构相对疏松且颗粒太小 ,所以未观察到任何分散相结构。聚乙二醇 (ＰＥＧ)是一种无毒、非抗原、物理化学性质稳定的水溶性非离子型高聚物并具有与药物配伍不发生任何反应的优良性能[3- 5] 。…     

水溶性Fe3O4磁性纳米催化剂的合成及应用

利用对氨基苯磺酸氟硼酸重氮盐与Fe₃O₄磁性纳米粒子(MNPs)的偶联反应,非常方便地制备出表面含有磺酸基的Fe₃O₄磁性纳米粒子。 透射电子显微镜(TEM) 测试结果表明,粒子的平均粒径在 20 nm左右。 溶解性实验表明,该纳米粒子具有较好的水溶性,但不溶于常用的有机溶剂,因此可利用其磁性回收并循环使用。 将该纳米粒子用于催化羧酸与醇的酯化反应,产物酯的收率为71%~86%。 催化剂在酯化反应中的最优使用量为1.5%(质量分数)。 同时,该催化剂可催化果糖合成5-羟甲基糠醛(HMF),收率为32%。     

单分散双相可溶四氧化三铁纳米微粒的多醇法制备及磁性

以具有生物相容性的三嵌段共聚物聚氧乙烯-聚氧丙烯-聚氧乙烯为表面活性剂,利用多醇合成法制备了Fe3O4纳米微粒;采用X射线粉末衍射仪、傅立叶变换红外光谱仪及透射电子显微镜分析了Fe3O4纳米微粒的晶体结构、化学结构及显微结构,采用振动样品磁强计测定了其磁性能.结果表明,所制得的Fe3O4磁性纳米微粒结晶度高,在室温下显示近似超顺磁性.采用Langevin方程对Fe3O4纳米微粒的磁滞回线进行拟合,结果显示其为磁性单畴.此外,Fe3O4磁性纳米微粒在无机和有机溶剂中均具有很好的分散性,显示出广阔的应用前景.     

磁性纳米多酶催化剂的制备及其用于葡萄糖浓度的检测

制备了一种用戊二醛交联壳聚糖包裹Fe_3O_4与葡萄糖氧化酶(GOX)的多酶催化剂(Chit-Fe_3O_4-GOX),并对其进行了表征与性能研究。待测溶液中的葡萄糖在GOX作用下产生H_2O_2,进而在具有模拟辣根过氧化物酶催化特性的Fe_3O_4的催化下产生羟基自由基,再与TMB反应显蓝色。从而通过在特定波长下吸光度与H_2O_2浓度间的关系间接得出底物葡萄糖浓度,建立了可视化检测葡萄糖含量的方法。所制得的多酶催化剂具有良好的超顺磁性,可以方便实现磁分离和回收,具有较高的催化效率。多酶催化剂的最佳使用条件是:反应温度30℃、反应时间6 h、多酶催化剂用量2 mg/mL、TMB用量3 mg/mL。吸光度与葡萄糖含量的线性关系为y=0. 0026+0. 10432x。方法可快速检测血液或者尿液中葡萄糖含量。     

Bioresponsive Hyaluronic Acid‐Capped Mesoporous Silica Nanoparticles for Targeted Drug Delivery

In this paper, we present a facile strategy to synthesize hyaluronic acid (HA) conjugated mesoporous silica nanoparticles (MSP) for targeted enzyme responsive drug delivery, in which the anchored HA polysaccharides not only act as capping agents but also as targeting ligands without the need of additional modification. The nanoconjugates possess many attractive features including chemical simplicity, high colloidal stability, good biocompatibility, cell‐targeting ability, and precise cargo release, making them promising agents for biomedical applications. As a proof‐of‐concept demonstration, the nanoconjugates are shown to release cargoes from the interior pores of MSPs upon HA degradation in response to hyaluronidase‐1 (Hyal‐1). Moreover, after receptor‐mediated endocytosis into cancer cells, the anchored HA was degraded into small fragments, facilitating the release of drugs to kill the cancer cells. Overall, we envision that this system might open the door to a new generation of carrier system for site‐selective, controlled‐release delivery of anticancer drugs.     

Chemical Design of Nuclear‐Targeting Mesoporous Silica Nanoparticles for Intra‐nuclear Drug Delivery

Targeted drug delivery has been widely explored for efficient tumor therapy with desired efficacy but minimized side effects. It is widely known that large numbers of DNA‐toxins, such as doxorubicin, genes, reactive oxygen species, serving as therapeutic agents, can result in maximized therapeutic effects via the interaction directly with DNA helix. So after cellular uptake, these agents should be further delivered into cell nuclei to play their essential roles in damaging the DNA helix in cancer cells. Here, we demonstrate the first paradigm established in our laboratory in developing nuclear‐targeted drug delivery systems (DDSs) based on MSNs for enhanced therapeutic efficiency in the hope of speeding their translation into the clinics. Firstly, nuclear‐targeting DDSs based on MSNs, capable of intranuclear accumulation and drug release therein, were designed and constructed for the first time, resulting in much enhanced anticancer effects both in vitro and in vivo. Such an MSNs‐based and nuclear‐targeted drug/agent delivery strategy was further applied to overcome multidrug resistance (MDR) of malignant tumors, intra‐nuclearly deliver therapeutic genes, photosensitizers, radio‐enhancement agents and photothermal agents to realize efficient gene therapy, photodynamic therapy, radiation therapy and photothermal therapy, respectively.     

Self‐Propelled Janus Mesoporous Silica Nanomotors with Sub‐100 nm Diameters for Drug Encapsulation and Delivery

The synthesis of an innovative self‐propelled Janus nanomotor with a diameter of about 75 nm that can be used as a drug carrier is described. The Janus nanomotor is based on mesoporous silica nanoparticles (MSNs) with chromium/platinum metallic caps and propelled by decomposing hydrogen peroxide to generate oxygen as a driving force with speeds up to 20.2 μm s^?1 (about 267 body lengths per second). The diffusion coefficient (D) of nanomotors with different H₂O₂ concentrations is calculated by tracking the movement of individual particles recorded by means of a self‐assembled fluorescence microscope and is significantly larger than free Brownian motion. The traction of a single Janus MSN nanomotor is estimated to be about 13.47×10^?15 N. Finally, intracellular localization and drug release in vitro shows that the amount of Janus MSN nanomotors entering the cells is more than MSNs with same culture time and particle concentrations, meanwhile anticancer drug doxorubicin hydrochloride loaded in Janus MSNs can be slowly released by biodegradation of lipid bilayers in cells.     

Effects of Co-Solvent Nature and Acid Concentration in the Size and Morphology of Wrinkled Mesoporous Silica Nanoparticles for Drug Delivery Applications

Hierarchically porous materials, such as wrinkled mesoporous silica (WMS), have gained interest in the last couple of decades, because of their wide range of applications in fields such as nanomedicine, energy, and catalysis. The mechanism of formation of these nanostructures is not fully understood, despite various groups reporting very comprehensive studies. Furthermore, achieving particle diameters of 100 nm or less has proven difficult. In this study, the effects on particle size, pore size, and particle morphology of several co-solvents were evaluated. Additionally, varying concentrations of acid during synthesis affected the particle sizes, yielding particles smaller than 100 nm. The morphology and physical properties of the nanoparticles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and dynamic light scattering (DLS). Homogeneous and spherical WMS, with the desired radial wrinkle morphology and particle sizes smaller than 100 nm, were obtained. The effect of the nature of the co-solvents and the concentration of acid are explained within the frame of previously reported mechanisms of formation, to further elucidate this intricate process.     

荧光介孔二氧化硅纳米粒子的合成及药物运输

合成了荧光介孔二氧化硅纳米粒子（MSNs-FITC）,并研究了其在持续药物释放和生物示踪成像方面的应用。首先,采用一步法合成出MSNs-FITC,结合SEM、TEM、FT-IR、XRD和氮气吸附脱附等表征技术进行表征。其次,将抗癌药物阿霉素（DOX）负载到MSNs-FITC中。载药粒子的药物释放行为具有明显的pH依赖性,酸性环境加速释放速率。同时,体外细胞毒性测试表明MSNs-FITC具有良好的生物相容性。激光共聚焦扫描显微镜（CLSM）图像表明,MSNs-FITC可以进入细胞并具有剂量依赖性,流式细胞术分析（FCM）进一步证明了这一结果。     

Bis‐clickable Mesoporous Silica Nanoparticles: Straightforward Preparation of Light‐Actuated Nanomachines for Controlled Drug Delivery with Active Targeting

Bis(clickable) mesoporous silica nanospheres (ca. 100 nm) were obtained by the co‐condensation of TEOS with variable amounts (2–5 % each) of two clickable organosilanes in the presence of CTAB. Such nanoparticles could be easily functionalized with two independent functions using the copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) reaction to transform them into nanomachines bearing cancer cell targeting ligands with the ability to deliver drugs on‐demand. The active targeting was made possible after anchoring folic acid by CuAAC click reaction, whereas the controlled delivery was performed by clicked azobenzene fragments. Indeed, the azobenzene groups are able to obstruct the pores of the nanoparticles in the dark whereas upon irradiation in the UV or in the blue range, their trans‐to‐cis photoisomerization provokes disorder in the pores, enabling the delivery of the cargo molecules. The on‐command delivery was proven in solution by dye release experiments, and in vitro by doxorubicin delivery. The added value of the folic acid ligand was clearly evidenced by the difference of cell killing induced by doxorubicin‐loaded nanoparticles under blue irradiation, depending on whether the particles featured the clicked folic acid ligand or not.     

pH-Responsive Drug Delivery and Imaging Study of Hybrid Mesoporous Silica Nanoparticles

A system of pH-responsive and imaging nanocarriers was developed using mesoporous silica nanoparticles (MSNs), in which gadolinium (Gd) was doped through in situ doping (Gd₂O₃@MSN). Sodium alginate (SA) was attached to the surfaces of the amino groups of MSNs (NH₂-Gd₂O₃@MSN) through the electrostatic adsorption between the amino groups and the carboxyl groups with the formation of hybrid SA-Gd₂O₃@MSN nanoparticles (NPs). The SA-coated NPs were spherical or near-spherical in shape with an average size of nearly 83.2 ± 8.7 nm. The in vitro drug release experiments of a model rhodamine B (RhB) cargo were performed at different pH values. The result confirmed the pH-responsiveness of the nanocarriers. The results of the cytotoxicity studies indicated that the SA-Gd₂O₃@MSN NPs were not cytotoxic by themselves. The results of the in vivo safety evaluation and the hemolysis assay confirmed that the system is highly biocompatible. It is noteworthy that the T1 contrast of the system was significantly enhanced by the Gd, as indicated by the result of the MR imaging. This study confirms that the synthesized hybrid nanosystem is promising for pH-responsive drug delivery and MR imaging for cancer diagnosis and treatment.     

Chitosan‐Capped Mesoporous Silica Nanoparticles as pH‐Responsive Nanocarriers for Controlled Drug Release

Herein, we present a straightforward synthesis of pH‐responsive chitosan‐capped mesoporous silica nanoparticles (MSNs). These MCM‐41‐type MSNs could be used as nanocapsules to accommodate guest molecules. Subsequently, (3‐glycidyloxypropyl)trimethoxysilane was grafted onto the surface of the MSNs, which served as a bridge to link between MSNs and chitosan, which is ubiquitous in nature and commercially available. Owing to the pH‐responsive and biocompatible features of chitosan, the loading and release of an anti‐cancer drug, doxorubicin hydrochloride, were carried out in vitro, in which the composite chitosan‐capped MSNs (CS‐MSNs) showed excellent environmental response. As the pH value of the media decreased, the degree of drug release correspondingly increased. Moreover, thanks to the perfect biocompatibility of chitosan, the CS‐MSNs exhibited lower cytotoxicity than that of the naked MSNs in an MTT assay. In addition, the in vitro kill potency against MCF‐7 breast‐cancer cells was enhanced over time, as well as with increasing concentration of the drug‐loaded CS‐MSNs. These results indicate that CS‐MSNs are promising candidates for pH‐responsive drug delivery in cancer therapy.     

Redox‐ and Temperature‐Controlled Drug Release from Hollow Mesoporous Silica Nanoparticles

A controlled drug‐delivery system has been developed based on mesoporous silica nanoparticles that deliver anticancer drugs into cancer cells with minimized side effects. The copolymer of two oligo(ethylene glycol) macromonomers cross‐linked by the disulfide linker N,N′‐bis(acryloyl)cystamine is used to cap hollow mesoporous silica nanoparticles (HMSNs) to form a core/shell structure. The HMSN core is applied as a drug storage unit for its high drug loading capability, whereas the polymer shell is employed as a switch owing to its redox/temperature dual responses. The release behavior in vitro of doxorubicin demonstrated that the loaded drugs could be released rapidly at higher temperature or in the presence of glutathione (GSH). Thus, the dual‐stimulus polymer shell exhibiting a volume phase transition temperature higher than 37 °C can effectively avoid drug leakage in the bloodstream owing to the swollen state of the shell. Once internalized into cells, the carriers shed the polymer shell because of cleavage of the disulfide bonds by GSH, which results in the release of the loaded drugs in cytosol. This work may prove to be a significant development in on‐demand drug release systems for cancer therapy.