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1.
    
A new type of monodispersed mesoporous silica nanoparticles with a core–cone structure (MSN‐CC) has been synthesized. The large cone‐shaped pores are formed by silica lamellae closely packed encircling a spherical core, showing a structure similar to the flower dahlia. MSN‐CC has a large pore size of 45 nm and a high pore volume of 2.59 cm3 g−1. MSN‐CC demonstrates a high loading capacity of large proteins and successfully delivers active β‐galactosidase into cells, showing their potential as efficient nanocarriers for the cellular delivery of proteins with large molecular weights.  相似文献   

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Nanocomposite materials have been thoroughly exploited in additive manufacturing, as a means to alter physical, chemical, and optical properties of resulting structures. Herein, nanocomposite materials suitable for direct laser writing (DLW) by two-photon polymerization are presented. These materials, comprising silica nanoparticles, bring significant added value to the technology through physical reinforcement and controllable photonic properties. Incorporation into acrylate photoresists, via a one-step fabrication process, enables the formation of complex structures with large overhangs. The inclusion of 150 nm silica nanoparticles in DLW photoresists at high concentrations, allows for the fabrication of composite microstructures that show reflected color, a product of the relative contributions from the quasi-ordering and random scattering. Using common DLW design parameters, such as slicing distance and structure dimension, a wide gamut of structural color, in solution, using a set concentration of nanoparticles is demonstrated. Numerical modeling is employed to predict the reflected wavelength of the pixel arrays, across the visible spectrum, and this information is used to encode reflected colors into different pixel arrays.  相似文献   

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Incorporation of lipid assemblies on the surface and within pores of mesoporous silica particles provides for biomimetic approaches to analyte sensing and separations using high surface area platforms. This work investigates the effect of pore confinement on the location and the diffusivity of lipid assemblies in mesoporous silica spherical particles (SBAS) as a function of nanopore diameters (nonporous, 3.0, 5.4, and 9.1 nm), which span the range of the thickness of the 1,2‐dipalmitoyl‐sn ‐glycero‐3‐phosphocholine lipid bilayer (≈4 nm). Large‐diameter SBAS are imaged with sufficient spatial resolution to distinguish lipids at the exterior surface and in the center of the particles. Lipids incorporated on the silica by evaporation deposition exist as exterior lipid bilayers on all particles and lipid assemblies in the pores of 5.4 and 9.1 nm pore diameter materials. Lipid diffusivity increases with pore size and decreases in the presence of bilayer tethering functional groups. Lipid diffusivity in the core of the particles is similar to the surface diffusivity, consistent with long‐range mobility in accessible, ordered (but randomly oriented) mesopores of SBAS materials. This work presents a framework for interpreting high density loading of lipid bilayers and their function within mesoporous materials.  相似文献   

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利用水热法合成介孔分子筛(SBA-15),选择KH560对其表面进行修饰后采用原位聚合的方法制备了介孔分子筛/线性酚醛树脂(SBA-15/PF)有机无机杂化材料。通过傅立叶红外光谱(FT-IR)、X射线衍射(XRD)、N2吸附和热失重分析(TGA)等表征手段对杂化材料的制备过程进行跟踪研究。结果表明,KH-560已嫁接到SBA-15的内外表面,线性酚醛树脂分布于介孔分子筛孔道内外,并与SBA-15存在键接作用,形成有机无机互穿网络结构;表面修饰过程对SBA-15有序结构影响较小,而原位聚合会破坏介孔分子筛部分有序结构。  相似文献   

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Direct laser writing (DLW) of mesoporous porous silicon (PS) films is shown to selectively create spatially separated nitridized and carbonized features on a single film. Nitridized or carbonized features are formed during DLW at 405 nm in an ambient of nitrogen and propane gas, respectively. The range of laser fluence required to create varying feature sizes while avoiding damage to the PS film is identified. At high enough fluence, nitridation using DLW has been shown as an effective method for laterally isolating regions on the PS films. The efficacy in preventing oxidation once passivated is investigated via energy dispersive X-ray spectroscopy. Changes in composition and optical properties of the DL written films are investigated using spectroscopic analysis. Results show carbonized DLW regions have a much higher absorption than as-fabricated PS, attributed to pyrolytic carbon or transpolyacetylene deposits in the pores. Nitridized regions exhibit optical loss similar to previously published thermally nitridized PS films. This work presents methods to engineer PS films for a variety of potential device applications, including the application of carbonized PS to selectively engineer thermal conductivity and electrical resistivity and of nitridized PS to micromachining and selective modification of refractive index for optical applications.  相似文献   

6.
采用模板法可制备孔径分布窄、中孔率和比表面积高的中孔碳。本文采用纳米氧化硅静电吸附十六烷基三甲基溴化铵(CTAB)及乳液聚合制备不同纳米氧化硅含量的聚丙烯腈/纳米氧化硅复合粒子,进一步通过高温碳化和氢氟酸刻蚀得到高纯度的中孔碳。发现当纳米氧化硅添加量不超过单体质量的50%时,纳米氧化硅主要以被聚合物包覆的形式存在,所制备的中孔碳的比表面积均大于800m2/g,孔径在5~10nm之间;随着纳米氧化硅/单体质量比从30%增加到60%,所制得的中孔碳的总孔容从1.111cm3/g增加至1.949cm3/g,中孔率从66.0%增至82.4%。结合中孔碳的形貌分析,认为纳米氧化硅的模板作用是形成中孔的主要因素。  相似文献   

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Functionalized ordered mesoporous materials are relevant in technologies, such as drug release, sensing, and separation. To design functionality, the silica framework can be functionalized with responsive molecules or polymers. Often, the pH value in those hybrid materials determines performance. Even though pH/pKa differences between polymers in bulk solutions and nanoscale confinement have been observed, the influence of confinement on pH‐ and pore filling dependent polyelectrolyte oligomer chain charge has yet not been investigated systematically. Here, mesoporous silica films are functionalized with (2‐dimethylamino)ethyl methacrylate) (DMAEMA) and 2‐(methacryloyloxy)ethyl phosphate (MEP) oligomers using photoiniferter initiated polymerization. This approach allows a controlled and environmentally friendly mesopore functionalization in water. The obtained oligomer functionalized pores are tunable with respect to pore filling. For both, poly(2‐(dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(2‐(methacryloxy)ethyl phosphate) (PMEP), the charge generation inside mesopore confinement is significantly delayed toward harsher pH conditions resulting in pKa shifts of 1–2 pH units. Polymer amount and ionic strength show to further influence the pKa of PDMAEMA in mesopores. The technological importance of the pH value in confinement and its effect on enzyme stabilization is demonstrated. Lipase from Aspergillus oryzae loses its activity upon encapsulation in silica nanoparticles at pH values where the enzyme is stable in bulk solution.  相似文献   

8.
利用硅烷偶联剂KH-550处理纳米二氧化硅(SiO_2)表面,得到氨基化的SiO_2,再通过溴异丁酸缩水甘油酯与氨基的开环反应,在SiO_2表面同时键接了开环聚合(ROP)的引发剂-OH和原子转移自由基聚合(ATRP)的引发剂-Br(SNPs-fOH/Br)。以SNPs-f-OH/Br为引发剂,分别进行ROP和ATRP,在纳米SiO_2表面接枝了聚己内酯(PCL)和聚苯乙烯(PS)混合聚合物刷(Mixed brush)。采用红外光谱、透射电镜、热失重、凝胶渗透色谱等方法对所得到的复合粒子进行了表征和测试。研究结果表明,混合聚合物刷成功接枝到了纳米SiO_2表面,通过控制聚合时间可以控制2种接枝聚合物的相对分子质量。本方法为纳米粒子表面接枝混合聚合物刷提供了一种简便的方法。  相似文献   

9.
光致变色聚合物的光学性能与应用   总被引:6,自引:0,他引:6  
综述了光致变色聚合物的光学性能及应用的近期研究进展,首先,介绍了光诱导双折射及双色现象形成机理及实验方法,并讨论了分子结构与外部条件对上述现象的影响。其次,介绍了光致变色聚合开关线性光学性能和应用。如由光助极化和全光极化形成的光开关现象将有可能引起数字存储或光-光开关等新装置的出现,最后,简单说明了光诱导表面光栅在近几年的研究情况,并分析了它们在全息图像存贮,光学过滤器及共振电偶中的潜在应用。  相似文献   

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The photochemistry of anthracene, a new class of photoresist for direct laser writing, is used to enable visible‐light‐gated control over the mechanical properties of 3D microstructures post‐manufacturing. The mechanical and viscoelastic properties (hardness, complex elastic modulus, and loss factor) of the microstructures are measured over the course of irradiation via dynamic mechanical analysis on the nanoscale. Irradiation of the microstructures leads to a strong hardening and stiffening effect due to the generation of additional crosslinks through the photodimerization of the anthracene functionalities. A relationship between the loss of fluorescence—a consequence of the photodimerization—and changes in the mechanical properties is established. The fluorescence thus serves as a proxy read‐out for the mechanical properties. These photoresponsive microstructures can potentially be used as “mechanical blank slates”: their mechanical properties can be readily adjusted using visible light to serve the demands of different applications and read out using their fluorescence.  相似文献   

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The selective formation of either oxidized or carbonized features into 2.5 µm thick porous silicon (PS) films using laser writing at a wavelength of 405 nm is demonstrated. Oxidized features are formed in air while carbonized features are achieved during the flow of propane at 600 sccm. Voids which have been previously associated with the use of propane are not observed, largely due to the rapid heating and high flow rates achieved in the experiment. Carbonized regions with feature widths down to 1.8 µm are achieved and chemical resistance to both hydrofluoric acid and potassium hydroxide is demonstrated. Once carbonized regions are formed, the surrounding areas can be overwritten in air to convert the surrounding regions into oxidized PS allowing films to be created with as‐fabricated, oxidized and carbonized regions. Energy dispersive X‐ray and Raman analysis confirms the presence of carbon within the written structures. At high optical powers, cracking around the carbonized features is observed which is attributed to a contraction of the film. Such cracking is not observed during selective oxidation of features. This work significantly enhances the ability to engineer and pattern the composition of PS films enabling selective control of the material's properties and functionality.  相似文献   

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Tuberculosis is a major global health problem for which improved therapeutics are needed to shorten the course of treatment and combat emergence of drug resistance. Mycobacterium tuberculosis, the etiologic agent of tuberculosis, is an intracellular pathogen of mononuclear phagocytes. As such, it is an ideal pathogen for nanotherapeutics because macrophages avidly ingest nanoparticles even without specific targeting molecules. Hence, a nanoparticle drug delivery system has the potential to target and deliver high concentrations of drug directly into M. tuberculosis‐infected cells—greatly enhancing efficacy while avoiding off‐target toxicities. Stimulus‐responsive mesoporous silica nanoparticles of two different sizes, 100 and 50 nm, are developed as carriers for the major anti‐tuberculosis drug isoniazid in a prodrug configuration. The drug is captured by the aldehyde‐functionalized nanoparticle via hydrazone bond formation and coated with poly(ethylene imine)–poly(ethylene glycol) (PEI–PEG). The drug is released from the nanoparticles in response to acidic pH at levels that naturally occur within acidified endolysosomes. It is demonstrated that isoniazid‐loaded PEI–PEG‐coated nanoparticles are avidly ingested by M. tuberculosis‐infected human macrophages and kill the intracellular bacteria in a dose‐dependent manner. It is further demonstrated in a mouse model of pulmonary tuberculosis that the nanoparticles are well tolerated and much more efficacious than an equivalent amount of free drug.  相似文献   

14.
    
Additive manufacturing with two‐photon polymerization (TPP) has opened new opportunities for the rapid fabrication of 3D structures with sub‐micrometer resolution, but there are still many fabrication constraints associated with this technique. This study details a postprocessing method utilizing oxygen‐plasma etching to increase the capabilities of TPP. Underutilized precision in the typical fabrication process allows this subtractive technique to dramatically reduce the minimum achievable feature size. Moreover, since the postprocessing occurs in a dry environment, high aspect ratio features that cannot survive the typical fabrication route can also be achieved. Finally, it is shown that the technique also provides a pathway to realize structures that otherwise are too delicate to be fabricated with TPP, as it enables to introduce temporary support material that can be removed with the plasma. As such, the proposed approach grants access to a massively expanded design domain, providing new capabilities that are long sought in many fields, including optics, biology, robotics, and solid mechanics.  相似文献   

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介孔氧化硅是最为典型的介孔材料,其具有比表面积高、孔径均一、易于表面修饰等优异特性,广泛应用于吸附分离、催化、传感以及物质负载与缓释等领域。关于粉体和薄膜形态的介孔氧化硅已有大量报道,但纤维形态,特别是连续纤维形态的介孔氧化硅材料的制备仍然是一项挑战。近年来随着静电纺技术的发展,连续纤维形貌的介孔氧化硅材料的制备取得了重要进展。根据纤维介孔结构的有序度和介孔结构引入方式的不同,对静电纺介孔氧化硅基纳米纤维进行详细的介绍。  相似文献   

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