超顺磁单分散性Fe3O4磁纳米粒的制备及性能表征

具有超顺磁单分散性的Fe₃O₄磁纳米粒在生物医学材料领域有着广泛的用途. 本研究在水、乙醇和甲苯混合体系74℃回流的条件下制备了具有超顺磁性的表面含油酸的Fe₃O₄磁纳米粒,研究了制备过程中OH^-浓度的变化对磁纳米粒的表面性能、粒径、分散性及磁性能的影响, 并对其机理进行了初步探讨. 采用XRD、FTIR、DLS、TEM和VSM等手段对制备的磁纳米粒进行表征. 结果表明, 当NaOH/Fe(Ⅱ)摩尔比＜8时, Fe₃O₄磁纳米粒表面含油酸可良好地分散于非极性溶剂中, NaOH的加入对磁纳米粒的粒径和饱和磁化强度等性能无明显影响;而当NaOH/Fe(Ⅱ)摩尔比≥8时, Fe₃O₄磁纳米粒仅能分散于水等极性溶剂中, 饱和磁化强度虽可增至40A·m²/kg, 但为多分散且易团聚.     

低温液相化学法在合成单分散纳米微粒中的应用

单分散纳米微粒的获得,为进一步研究某一特定尺寸的纳米微粒的各种性质提供了方便.单分散纳米微粒比多分散纳米微粒具有更显著的性能,更适合于应用.国内外在这方面开展了大量的研究工作,主要报道了低温液相化学法在合成单分散金属纳米颗粒、单分散半导体纳米颗粒、单分散复合氧化物纳米颗粒、单分散聚合物纳米微球、单分散核壳结构复合纳米微粒等方面的应用情况.     

超顺磁单分散性Fe3O4磁纳米粒的制备及性能表征

具有超顺磁单分散性的Fe₃O₄磁纳米粒在生物医学材料领域有着广泛的用途. 本研究在水、乙醇和甲苯混合体系74℃回流的条件下制备了具有超顺磁性的表面含油酸的Fe₃O₄磁纳米粒,研究了制备过程中OH^-浓度的变化对磁纳米粒的表面性能、粒径、分散性及磁性能的影响, 并对其机理进行了初步探讨. 采用XRD、FTIR、DLS、TEM和VSM等手段对制备的磁纳米粒进行表征. 结果表明, 当NaOH/Fe(Ⅱ)摩尔比＜8时, Fe₃O₄磁纳米粒表面含油酸可良好地分散于非极性溶剂中, NaOH的加入对磁纳米粒的粒径和饱和磁化强度等性能无明显影响;而当NaOH/Fe(Ⅱ)摩尔比≥8时, Fe₃O₄磁纳米粒仅能分散于水等极性溶剂中, 饱和磁化强度虽可增至40A·m²/kg, 但为多分散且易团聚.     

Surface Engineering of Spherical Metal Nanoparticles with Polymers toward Selective Asymmetric Synthesis of Nanobowls and Janus‐Type Dimers

New synthetic methods capable of controlling structural and compositional complexities of asymmetric nanoparticles (NPs) are very challenging but highly desired. A simple and general synthetic approach to designing sophisticated asymmetric NPs by anisotropically patterning the surface of isotropic metallic NPs with amphiphilic block copolymers (BCPs) is reported. The selective galvanic replacement and seed‐mediated growth of a second metal can be achieved on the exposed surface of metal NPs, resulting in the formation of nanobowls and Janus‐type metal–metal dimers, respectively. Using Ag and Au NPs tethered with amphiphilic block copolymers of poly(ethylene oxide)‐block‐polystyrene (PEO‐b‐PS), anisotropic surface patterning of metallic NPs (e.g., Ag and Au) is shown to be driven by thermodynamical phase segregation of BCP ligands on isotropic metal NPs. Two proof‐of‐concept experiments are given on, i) synthesis of Au nanobowls by a selective galvanic replacement reaction on Janus‐type patched Ag/polymer NPs; and ii) preparation of Au–Pd heterodimers and Au–Au homodimers by a seed‐mediated growth on Janus‐type patched Au/polymer NPs. The method shows remarkable versatility; and it can be easily handled in aqueous solution. This synthetic strategy stands out as the new methodology to design and synthesis asymmetric metal NPs with sophisticated topologies.     

Miscible-Solvent-Assisted Two-Phase Synthesis of Monolayer-Ligand-Protected Metal Nanoclusters with Various Sizes

Effective yet versatile synthetic strategies for size-tunable metal nanoclusters (NCs) are scarce. This has hampered the development of this unique class of nanomaterials. Here, a general protocol is reported for the synthesis of high-quality metal NCs protected by a variety of organic ligands (e.g., selenolate, thiolate, and phosphine) based on a miscible-solvent-assisted phase transfer between water and organic solution. This method is demonstrated to be facile, rapid (≤3 h), scalable (gram-scale), and versatile. The size of the selenolated and thiolated Au NCs can be tuned from Au₁₀ to Au₆₁ by simply varying the miscible solvent in proportions and types. The advantages of this method, such as quick phase separation and no need for purification treatment, enable real-time monitoring of metal NC growth within the NaBH₄ reduction system. The results show that the size of Au NCs gradually increases with increasing valence electron count by a stepwise 2x e^- hopping mechanism (x = 0–5), i.e., 0 e^- → 2 e^- → 4 e^- → 8 e^- → 18 e^- → 22 e^- → 32 e^-.     

Integration of Metal Nanoparticles into Metal–Organic Frameworks for Composite Catalysts: Design and Synthetic Strategy

Metal–organic frameworks (MOFs) are constructed by periodically alternate metal ions with organic ligands, which offer structural diversity and a wide range of interesting properties as an attractive classification of crystalline porous materials. Integration of MOFs with other size‐limited functional centers can supply new multifunctional composites, which exhibit both the properties of the components and new characteristics due to the combination of MOFs with the selected loadings. In recent years, integration of metal/metal oxide nanoparticles (MNPs) into MOFs to form the composite catalysts has attracted considerable attention due to the superior performance. In this review, the latest studies and up‐to‐date developments on the design and synthetic strategy of new MNP@MOF composite catalysts are specifically highlighted. Both the achievements and problems are evaluated and proposed, and the opportunities and challenges of MNP@MOF composite catalysts are discussed.     

纳米银/聚合物复合材料的原位法制备技术综述

纳米银/聚合物复合材料结合了纳米银优异的物理化学性能和聚合物的易加工和成膜性的特点,被广泛应用于抗菌、催化和光电等领域。原位法具有工艺简单、成本低、可形成单分散的纳米粒子等优点,被广泛用于制备纳米银/聚合物复合材料。主要综述了纳米银/聚合物复合材料的原位制备方法,主要包括原位生成法、原位聚合法、双原位合成法,并提出了纳米银/聚合物复合材料的发展方向。     

Ultrasmall Metal Nanoparticles Confined within Crystalline Nanoporous Materials: A Fascinating Class of Nanocatalysts

Crystalline nanoporous materials with uniform porous structures, such as zeolites and metal–organic frameworks (MOFs), have proven to be ideal supports to encapsulate ultrasmall metal nanoparticles (MNPs) inside their void nanospaces to generate high‐efficiency nanocatalysts. The nanopore‐encaged metal catalysts exhibit superior catalytic performance as well as high stability and catalytic shape selectivity endowed by the nanoporous matrix. In addition, the synergistic effect of confined MNPs and nanoporous frameworks with active sites can further promote the catalytic activities of the composite catalysts. Herein, recent progress in nanopore‐encaged metal nanocatalysts is reviewed, with a special focus on advances in synthetic strategies for ultrasmall MNPs (<5 nm), clusters, and even single atoms confined within zeolites and MOFs for various heterogeneous catalytic reactions. In addition, some advanced characterization methods to elucidate the atomic‐scale structures of the nanocatalysts are presented, and the current limitations of and future opportunities for these fantastic nanocatalysts are also highlighted and discussed. The aim is to provide some guidance for the rational synthesis of nanopore‐encaged metal catalysts and to inspire their further applications to meet the emerging demands in catalytic fields.     

锌锰掺杂Fe3O4纳米颗粒的尺寸可控合成

锌锰掺杂的Fe₃O₄纳米颗粒具有优异的磁性能, 在生物医药领域有广泛的应用前景。磁性纳米颗粒的尺寸与其磁学性质以及生物磁性应用密切相关。因此, 为了适应不同生物应用对尺寸的需求, 研究其尺寸调控具有重要的意义。在本研究中, 我们采用高温热分解法, 通过加入还原剂1,2-十六烷二醇, 改变金属前躯体和回流时间成功制备了尺寸在5~20 nm的锌锰掺杂Fe₃O₄纳米颗粒。研究发现:强还原剂1,2-十六烷二醇的加入有利于合成小尺寸的纳米颗粒, 而以金属氯化物作为金属前躯体和延长回流时间可以进一步合成更大尺寸的纳米颗粒; 纳米颗粒的饱和磁化强度随着尺寸的增大而增大。     

Simple and Rapid High‐Yield Synthesis and Size Sorting of Multibranched Hollow Gold Nanoparticles with Highly Tunable NIR Plasmon Resonances

Branched gold nanoparticles with sharp tips are considered excellent candidates for sensing and field enhancement applications. Here, a rapid and simple synthesis strategy is presented that generates highly branched gold nanoparticles with hollow cores and a ca.100% yield through a simple one‐pot seedless reaction at room temperature in the presence of Triton X‐100. It is shown that multibranched hollow gold nanoparticles of tunable dimensions, branch density and branch length can be obtained by adjusting the concentrations of the reactants. Insights into the formation mechanism point toward an aggregative type of growth involving hollow core formation first, and branching thereafter. The pronounced near‐infrared (NIR) plasmon band of the nanoparticles is due to the combined contribution from hollowness and branching, and can be tuned over a wide range (≈700–2000 nm). It is also demonstrated that the high environmental sensitivity of colloidal dispersions based on multibranched hollow gold nanoparticles can be boosted even further by separating the nanoparticles into fractions of given sizes and improved monodispersity by means of a glycerol density gradient. The possibility to obtain highly monodisperse multibranched hollow gold nanoparticles with predictable dimensions (50–300 nm) and branching and, therefore, tailored NIR plasmonic properties, highlights their potential for theranostic applications.     

固载磷钨酸的大孔道功能化MOFs合成及催化性能

获得可固载PTA的大孔道载体,对于大分子物质的催化转化具有重要意义。本研究采用扩孔剂CTAB对MOFs载体进行扩孔并同步实现PTA的化学固载,同时在MOFs的骨架中接枝-Cl和-NH2实现其功能化。研究发现加入CTAB后虽然获得的样品均为MIL-101结构,且随CTAB加入量的增加,样品的晶面生长逐渐变差,但仍具有良好的热稳定性。MOFs的比表面积和孔径随CTAB加入量的增加而逐渐增大,经CTAB扩孔后,MOFs由微孔结构转化为微孔与介孔共存结构,在CTAB加入量为5.4mmol时,样品的介孔结构占比最大,达到87%,孔径以3.9nm和46.1nm为主。CTAB的加入不会影响-NH2与PTA的静电作用,但PTA的固载量随CTAB加入量的增加先增大后减小,当CTAB加入量为3.6mmol时PTA的固载量最大,所获得的催化剂样品催化水解微晶纤维素的葡萄糖产率也达到最大,获得葡萄糖产率可达到等量未固载PTA催化效能的76.35%。样品连续三次催化水解微晶纤维素后,葡萄糖产率仅下降了5%左右,说明接枝-NH2发挥了其通过静电作用固载PTA的功能,从而降低了PTA在反应过程中的流失。     

Tunable Luminescent Carbon Nanospheres with Well‐Defined Nanoscale Chemistry for Synchronized Imaging and Therapy

In this work, we demonstrate the significance of defined surface chemistry in synthesizing luminescent carbon nanomaterials (LCN) with the capability to perform dual functions (i.e., diagnostic imaging and therapy). The surface chemistry of LCN has been tailored to achieve two different varieties: one that has a thermoresponsive polymer and aids in the controlled delivery of drugs, and the other that has fluorescence emission both in the visible and near‐infrared (NIR) region and can be explored for advanced diagnostic modes. Although these particles are synthesized using simple, yet scalable hydrothermal methods, they exhibit remarkable stability, photoluminescence and biocompatibility. The photoluminescence properties of these materials are tunable through careful choice of surface‐passivating agents and can be exploited for both visible and NIR imaging. Here the synthetic strategy demonstrates the possibility to incorporate a potent antimetastatic agent for inhibiting melanomas in vitro. Since both particles are Raman active, their dispersion on skin surface is reported with Raman imaging and utilizing photoluminescence, their depth penetration is analysed using fluorescence 3D imaging. Our results indicate a new generation of tunable carbon‐based probes for diagnosis, therapy or both.     

Discovery of and Insights into DNA “Codes” for Tunable Morphologies of Metal Nanoparticles

The discovery and elucidation of genetic codes has profoundly changed not only biology but also many fields of science and engineering. The fundamental building blocks of life comprises of four simple deoxyribonucleotides and yet their combinations serve as the carrier of genetic information that encodes for proteins that can carry out many biological functions due to their unique functionalities. Inspired by nature, the functionalities of DNA molecules have been used as a capping ligand for controlling morphology of nanomaterials, and such a control is sequence dependent, which translates into distinct physical and chemical properties of resulting nanoparticles. Herein, an overview on the use of DNA as engineered codes for controlling the morphology of metal nanoparticles, such as gold, silver, and Pd‐Au bimetallic nanoparticles is provided. Fundamental insights into rules governing DNA controlled growth mechanisms are also summarized, based on understanding of the affinity of the DNA nucleobases to various metals, the effect of combination of nucleobases, functional modification of DNA, the secondary structures of DNA, and the properties of the seed employed. The resulting physical and chemical properties of these DNA encoded nanomaterials are also reviewed, while perspectives into the future directions of DNA‐mediated nanoparticle synthesis are provided.     

静电组装法在纳米SiO_2表面构筑高分子刷的合成与表征(英文)

本文采用静电自组装技术在表面阳离子化的SiO2粒子（SiO2-CBAFS）上构筑了高分子刷,并采用核磁、红外、热失重、接触角和原子力显微镜分别表征了组装粉体的结构、组装量以及自组装单层膜的组装行为和表面拓扑形貌。研究结果表明,采用静电自组装技术可以成功地在SiO2-CBAFS上构筑组装量高达27％的高分子刷,远远高于国际上已见报道的采用共价键合法构筑的高分子刷的组装量（20％）。研究发现,组装量随聚合物（PS-NH—SO3Na）分子量呈非线性增长,其组装行为受到PS-NH—SO3Na的分子量和溶液浓度的影响。     

Phosphine‐Based Covalent Organic Framework for the Controlled Synthesis of Broad‐Scope Ultrafine Nanoparticles

In this work, a phosphine‐based covalent organic framework (Phos‐COF‐1) is successfully synthesized and employed as a template for the confined growth of broad‐scope nanoparticles (NPs). Ascribed to the ordered distribution of phosphine coordination sites in the well‐defined pores, various stable and well‐dispersed ultrafine metal NPs including Pd, Pt, Au, and bimetallic PdAuNPs with narrow size distributions are successfully prepared as determined by transmission electron microscopy, X‐ray photoelectron spectroscopy, inductively coupled plasma, and powder X‐ray diffraction analyses. It is also demonstrated that the as‐prepared Phos‐COF‐1‐supported ultrafine NPs exhibit excellent catalytic activities and recyclability toward the Suzuki–Miyaura coupling reaction, reduction of nitro‐phenol and 1‐bromo‐4‐nitrobenzene, and even tandem coupling and reduction of p‐nitroiodobenzene. This work will open many new possibilities for preparing COF‐supported ultrafine NPs with good dispersity and stability for a broad range of applications.     

Intracellular Uptake and Toxicity of Ag and CuO Nanoparticles: A Comparison Between Nanoparticles and their Corresponding Metal Ions

An increased understanding of nanoparticle toxicity and its impact on human health is essential to enable a safe use of nanoparticles in our society. The aim of this study is to investigate the role of a Trojan horse type mechanism for the toxicity of Ag‐nano and CuO‐nano particles and their corresponding metal ionic species (using CuCl₂ and AgNO₃), i.e., the importance of the solid particle to mediate cellular uptake and subsequent release of toxic species inside the cell. The human lung cell lines A549 and BEAS‐2B are used and cell death/membrane integrity and DNA damage are investigated by means of trypan blue staining and the comet assay, respectively. Chemical analysis of the cellular dose of copper and silver is performed using atomic absorption spectroscopy. Furthermore, transmission electron microscopy, laser scanning confocal microscopy, and confocal Raman microscopy are employed to study cellular uptake and particle‐cell interactions. The results confirm a high uptake of CuO‐nano and Ag‐nano compared to no, or low, uptake of the soluble salts. CuO‐nano induces both cell death and DNA damage whereas CuCl₂ induces no toxicity. The opposite is observed for silver, where Ag‐nano does not cause any toxicity, whereas AgNO₃ induces a high level of cell death. In conclusion: CuO‐nano toxicity is predominantly mediated by intracellular uptake and subsequent release of copper ions, whereas no toxicity is observed for Ag‐nano due to low release of silver ions within short time periods.