基于微生物体系合成无机纳米材料的研究进展

无机纳米材料在能源、生物医学等领域应用非常广泛,过去几十年间关于无机纳米材料合成方法的研究一直受到广泛关注。自然界中普遍存在的生物矿化过程赋予了生物体合成含有特殊结构和功能的无机纳米材料的能力。微生物体系合成的无机纳米材料具有环境友好、成本低廉、生物相容性好等优点,正成为纳米材料科学的一个重要研究领域。我们主要聚焦于微生物体系合成无机纳米材料的机理、影响因素、材料分类及其应用,总结了近年来关于微生物体系合成无机纳米材料的研究历程,并对该领域面临的挑战及未来的发展方向进行了展望。     

纳米粒子的分类合成及其在生物领域的应用

纳米粒子是当今最受关注也是最常报道的一类纳米材料,尺寸处于纳米级别是纳米粒子的突出特点,这赋予其在化学、光学、电学和磁学等方面优于传统块体材料的独特性能,因而纳米粒子越来越受到人们的重视,并广泛应用于很多领域,尤其是生物医药领域。本文围绕可生物应用的纳米粒子,从组成以及结构的角度着手,将纳米粒子分为有机纳米粒子、无机纳米粒子以及有机/无机杂化纳米粒子。同时结合近三年国内外关于各类纳米粒子新颖的合成报道,分别阐述了上述不同种类纳米粒子所具有的适合生物应用的物理和化学方面的特征,并针对不同类别的新型纳米粒子,着重描述了其具体合成方法和潜在的生物应用。最后,简单介绍了纳米粒子在生命科学这一领域的具体应用实例,如刺激响应感应器、生物特异性标记及基因药物载体等,并展望了纳米粒子在该领域的长远发展。     

仿生无机纳米材料改造生物体的研究进展

在进化的过程中,生物体学会了利用材料来改造自身以适应环境的变化。自然界中的一些生物体可以通过生物矿化合成无机纳米材料为自己提供保护或其他特殊功能。但是自然界中还有部分生物体不具备生物矿化功能,受到自然界生物体利用纳米材料的启发,科学家们开始尝试通过人工赋予生物体纳米材料来对其进行改造。本文就基于生物-材料界面复合技术的纳米材料对生物体的改造,依次从调控机制、改造方法、功能应用等方面做了系统的阐述,重点介绍了通过仿生矿化对生物体进行纳米改造的研究进展,对仿生无机纳米材料改造生物体的领域现状做了分析和总结,并且对该领域的发展前景进行了展望。     

贵金属纳米颗粒的微生物合成

金属纳米颗粒在材料、催化、医学、环境等众多领域应用广泛,其中,金、银、铂、钯等贵金属的纳米颗粒作为良好的催化剂可提高反应的速率,因此,贵金属纳米颗粒的合成吸引了众多研究者的关注。传统的物理化学法虽能高效、可控地合成贵金属纳米颗粒,但是合成条件苛刻、成本昂贵、且会产生对环境有害的化学物质。因此,探索节能、环保、可持续的绿色合成方法成为纳米合成研究的热点之一。贵金属纳米颗粒的微生物合成法具备绿色合成技术的诸多要素,研究表明某些微生物能将金属盐转化成纳米材料,且微生物繁殖速度快、培养成本低、生长条件温和,从而得到了研究者们的广泛关注。本文归纳总结了目前微生物合成贵金属纳米颗粒的主要研究进展,包括贵金属纳米颗粒可能的合成机制以及尺寸与形貌控制方法,探讨了其在医学、催化、生物传感、环境方面的具体应用,并对贵金属纳米颗粒微生物合成的未来发展进行了展望。     

热液法制备磁性纳米材料

磁性纳米材料作为新兴的无机功能材料,因其具有与常规材料不同的特殊性质,如高比表面积、强磁响应性、良好的化学稳定性和生物相容性等,被广泛应用在生物合成、生物分离、生物传感器、免疫测定、有机催化、药物传输、数据存储和环境治理等方面。目前合成磁性纳米材料的方法主要有化学共沉降法、高温热分解法、溶胶-凝胶法及热液法等。由于热液法具有条件简易、成本低廉、反应活性高、产率可观和绿色环保等优势,近年来受到了广泛的关注,并已应用在工业生产中。本文根据磁性材料组成与构成方式的不同,综述了热液法合成磁性纳米材料的研究进展。     

共轭聚合物荧光纳米粒子研究进展

近年来,共轭聚合物荧光纳米粒子因其优异的光学性能,在化学、医学和环境科学等研究领域显示了极其广阔的应用前景.相比于传统无机半导体荧光纳米材料,共轭聚合物荧光纳米粒子具有结构多样性、功能可设计性、生物相容性好等显著优势.本文从共轭聚合物荧光粒子的制备方法、光学性能、表面功能化修饰出发,重点讨论了近年来共轭聚合物纳米粒子作为荧光探针在细胞成像及生物化学检测方面的研究进展,阐述了当前研究的主要发展方向和仍需解决的问题.     

树状大分子/金属（化合物）纳米复合材料*

本文综述了一类新的有机/无机杂化材料——树状大分子/金属（化合物）纳米复合材料的研究进展。该杂化纳米材料由树状大分子内或树状大分子间螯合金属离子通过还原生成相应的零价金属纳米粒子或与阴离子反应生成金属化合物的方法制备。其中树状大分子内复合物粒子体积与原树状大分子内负载的金属离子数量有关,树状大分子间复合物粒子体积与树状大分子的浓度和代数有关。     

纳米级SiO2填充PVC/CPE复合材料研究

80年代以后发展起来的纳米材料被称为"21世纪最有前途的材料",已成为材料学中跨世纪的研究热点[1].纳米级无机粒子/聚合物复合材料是纳米材料中的一种具有重要价值的新型材料,可广泛应用于橡胶、塑料、纤维三大合成材料之中[2].其中,纳米级SiO2是纳米材料中的重要一员,它被称作跨世纪的高科技材料[3].因此, 本文就纳米级SiO2填充PVC/CPE复合材料进行探讨.     

PTFE/纳米SiO2复合材料的制备及其力学性能

聚合物／纳米级无机粒子复合材料是纳米材料中的一种具有重要价值的新型材料，可广泛应用于橡胶、塑料、纤维三大合成材料之中。采用纳米级无机粒子填充聚合物基复合材料，可以在材料的补强、增韧等改性中获得良好的效果。本文以纳米SiO2为填料，将其经过有机处理后，制备了FIFE／纳米SiO2复合材料，并研究了纳米SiO2的含量对PTFE复合材料性能的影响。     

金纳米粒子在重金属离子检测方面的应用研究

近年来,贵金属纳米材料由于其具有独特的光学性质、稳定性、生物相容性和自身的结构特性等优点,被广泛用于重金属检测领域。总结了近年来金纳米粒子在重金属离子检测方面的研究现状,最后对贵金属纳米材料在重金属离子检测中的发展前景进行了展望。     

原位生成法制备高分子磁性粒子

高分子和无机磁性粒子间因其特性的差异,较难进行均匀的复合与杂化,而原位生成法可以制得磁性粒子均匀复合的结构,较好地解决这一问题.本文对近年来国内外采用原位生成法制备磁性复合粒子的方法进行了比较和综述.     

Amine-functionalized lanthanide-doped zirconia nanoparticles: optical spectroscopy, time-resolved fluorescence resonance energy transfer biodetection, and targeted imaging

Ultrasmall inorganic oxide nanoparticles doped with trivalent lanthanide ions (Ln(3+)), a new and huge family of luminescent bioprobes, remain nearly untouched. Currently it is a challenge to synthesize biocompatible ultrasmall oxide bioprobes. Herein, we report a new inorganic oxide bioprobe based on sub-5 nm amine-functionalized tetragonal ZrO(2)-Ln(3+) nanoparticles synthesized via a facile solvothermal method and ligand exchange. By utilizing the long-lived luminescence of Ln(3+), we demonstrate its application as a sensitive time-resolved fluorescence resonance energy transfer (FRET) bioprobe to detect avidin with a record-low detection limit of 3.0 nM. The oxide nanoparticles also exhibit specific recognition of cancer cells overexpressed with urokinase plasminogen activator receptor (uPAR, an important marker of tumor biology and metastasis) and thus may have great potentials in targeted bioimaging.     

Silver nanoparticles: synthesis through chemical methods in solution and biomedical applications

Chemical methods provide an easy way to synthesize silver nanoparticles (Ag NPs) in solution. These metal nanoparticles have a great potential for biomedical applications as an antibacterial, antifungal, and antiviral agent or in wound healing. The adjustment of the parameters involved in these reactions permits a precise control over the size, shape, monodispersity, and the surfaces of the nanoparticles. These nanoparticles are being used in the design of new hybrid organic-inorganic or inorganic nanomaterials for biomedical applications.      

Ionic liquid-assisted direct synthesis of PdO nanoparticles immobilized on boehmite nanoparticles

We demonstrated a simple route to simultaneously synthesize PdO and boehmite nanoparticles, and to directly immobilize the former on the latter using an ionic liquid (IL)-assisted one-pot solution method. PdO nanoparticles were directly immobilized on boehmite nanoparticles, and their amount and distribution were controlled by the stoichiometry of the mixture. In particular, γ-alumina nanofibers, which were topochemically transformed from boehmites, exhibited lengths of ca. 40-70 nm and diameters of ca. 1.5-3 nm, while PdO nanoparticles had diameters of ca. 2-4 nm. The nanocrystalline structures of the PdO nanoparticles immobilized on the boehmite nanoparticles were characterized by high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), and (27)Al nuclear magnetic resonance (NMR). The one-step synthetic method described herein allows for the design and fabrication of host-guest systems of inorganic or metallic nanomaterials with hetero-nanostructures.     

A simple route to ordered metal oxide nanoparticle arrays using block copolymer thin films

Oxide nanoparticles arrays are easily synthesized in a 3-steps method including (i) the deposition of poly(styrene)-b-poly(4-vinylpyridine) (PS-b-PVP) thin films, (ii) the selective deposition of inorganic precursors and (iii) the synthesis of oxide nanoparticles and the elimination of the polymer scaffold by thermal annealing. The specific staining of the PVP domains by inorganic precursors is obtained in this study thanks to a simple and fast spin coating process using an alcoholic solution of the precursors. This simple lab-procedure is used to synthesize a wide range of metallic (silicon, titanium, cerium, ruthenium, zinc and manganese) oxides, showing that this method can be extended to the synthesis of all kinds of oxides with all kinds of precursors as long as the precursor is soluble in P4VP solvent. It is shown that this strategy can be extended to the synthesis of oxide nanorods.     

大孔道介孔氧化硅/碳基纳米材料的设计合成与应用

由于具有较大的孔道尺寸、 丰富的化学组成以及广阔的应用前景, 大孔道介孔纳米材料近年来引起了科研工作者的广泛关注. 分别利用复合胶束和无机纳米晶作为结构基元进行可控自组装的软模板法和硬模板法是合成这类大孔道介孔纳米材料最有效的两类方法. 本文总结了一系列基于不同类型软模板或硬模板共组装形成大孔道介孔纳米材料的合成方法和策略, 并讨论了所获得的大孔道介孔纳米材料在催化、 能量转换与存储以及生物医学中的应用. 最后, 对利用新型嵌段聚合物或复杂结构纳米晶合成大孔道介孔纳米材料的前景和挑战进行了展望.     

How Many Phosphoric Acid Units Are Required to Ensure Uniform Occlusion of Sterically Stabilized Nanoparticles within Calcite?

Polymerization‐induced self‐assembly (PISA) mediated by reversible addition–fragmentation chain transfer (RAFT) polymerization offers a platform technology for the efficient and versatile synthesis of well‐defined sterically stabilized block copolymer nanoparticles. Herein we synthesize a series of such nanoparticles with tunable anionic charge density within the stabilizer chains, which are prepared via statistical copolymerization of anionic 2‐(phosphonooxy)ethyl methacrylate (P) with non‐ionic glycerol monomethacrylate (G). Systematic variation of the P/G molar ratio enables elucidation of the minimum number of phosphate groups per copolymer chain required to promote nanoparticle occlusion within a model inorganic crystal (calcite). Moreover, the extent of nanoparticle occlusion correlates strongly with the phosphate content of the steric stabilizer chains. This study is the first to examine the effect of systemically varying the anionic charge density of nanoparticles on their occlusion efficiency and sheds new light on maximizing the loading of guest nanoparticles within calcite host crystals.     

Decoration carbon nanotubes with Pd and Ru nanocrystals via an inorganic reaction route in supercritical carbon dioxide-methanol solution

This work describes a method to decorate carbon nanotubes (CNTs) with metallic Pd and Ru nanocrystals via inorganic reactions in supercritical (SC) CO2-methanol solutions. In this route, PdCl2 or RuCl3.3H2O dissolved in SC CO2-methanol solution acted as a metal precursor and CNTs functioned as a template to direct the deposition of produced nanoparticles. Methanol served as the reductant for the precursors as well as cosolvent to enhance the dissolution of precursors in SC CO2. Dry products were readily obtained through in situ extraction with SC CO2 after reactions. The products were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. It was demonstrated that the loading content and particle size of the nanoparticles deposited on CNTs could be tuned by changing the weight ratio of the precursor to CNTs. This simple and efficient approach may also be utilized to synthesize other high-purity materials using inorganic salt precursors in SC CO2-based solution.     

形貌各异ZnO微结构的合成与表征——一个简单有趣的化学综合实验

设计了一个操作简单的合成ZnO微结构的化学综合实验,通过一种形貌改性剂柠檬酸的辅助,可制备出形貌各异的ZnO微粒。通过实验使学生对无机纳米材料的微观结构和形貌有了科学的认识,对纳米颗粒的合成方法及常见的表征手段有了初步了解。实验方案的设计既简单又具有探究性,有利于培养学生的独立科研能力和创新能力。     

A novel method to synthesize polystyrene nanospheres immobilized with silver nanoparticles by using compressed CO2

In this work, a novel route to synthesize polymer/metal composite nanospheres has been proposed. This method combines the advantages that the polymer chains collapse and entangle in the presence of compressed CO(2), which acts as antisolvent, and the metal nanoparticles and polymers can be precipitated simultaneously from micellar solutions by the easy control of CO(2) pressure. Ag/polystyrene (PS) nanocomposites have been successfully prepared using this method. The transmission electronic micrographs (TEM) of the obtained nanocomposites show that the smaller Ag nanoparticles are immobilized by PS nanospheres of about 50 nm; the phase structure was characterized by X-ray diffraction (XRD). The Ag/PS nanocomposites show absorption properties at a wavelength of approximately 417 nm. The results of X-ray photoelectron spectra (XPS) and FT-IR spectra indicate that there is no chemical linkage or strong interaction between PS and Ag nanoparticles in the resultant products. This method has many potential advantages for applications and may easily be applied to the preparation of a range of inorganic/ polymer composite nanoparticles.