A Hollow‐Core,Magnetic, and Mesoporous Double‐Shell Nanostructure: In Situ Decomposition/Reduction Synthesis,Bioimaging, and Drug‐Delivery Properties

A novel in situ decomposition/reduction approach is developed to manu­facture hollow core, magnetic, and mesoporous double‐shell nanostructures (HMMNSs) via in situ decomposition and reduction of a β‐FeOOH nanorod core and organosilicate‐incorporated silica‐shell precursor. The formed HMMNSs are then aminated by silanization for further covalent conjugation to rhodamine B isothiocyanate (RBITC) and poly(ethylene glycol) (PEG) chains. The resultant RBITC‐grafted and PEGylated nanocomposites (HMMNS–R/Ps) have excellent blood compatibility and very low cytotoxicity towards HeLa and MCF‐7 cells, and can be taken up by cancer cells effectively in a dose‐dependent manner, as confirmed by in vitro flow cytometry, confocal luminescence imaging, and magnetic resonance imaging (MRI) studies. In vivo MRI studies coupled with Prussian blue staining of slides from different organs show that the nanocomposites preferentially accumulate in liver and spleen after intravenous injection, which suggests a potential application of the nanocomposites as MRI contrast agents. Importantly, the HMMNS–R/P nanocomposites show high loading capacity for water‐insoluble anticancer drugs (docetaxel or camptothecin) owing to the presence of a large inner cavity and enhanced surface area and pore volume. Furthermore, the drug‐loaded nanocomposites exhibit greater cytotoxicity than the corresponding free drugs. These results confirm that the HMMNS–R/P nanocomposites are promising candidates for simultaneous bioimaging and drug delivery.     

单模石英光纤和塑料光纤自动耦合系统

作为短距离通信网络的理想传输介质,塑料光纤(POF)具有广阔的应用前景.然而单模塑料光纤和其他光纤之间连接的连接器目前还没有产品.研制了一种可实现单模塑料光纤和单模石英光纤之间的自动连接(耦合)系统.该系统通过上位机控制部分对于光功率计和采集图像的反馈数据进行分析处理,进而驱动高精度位移步进电机,使两光纤达到精确耦合,从而为单模塑料光纤和塑料光纤光栅的进一步研究打下了坚实的基础.     

“Ship‐in‐a‐Bottle” Growth of Noble Metal Nanostructures

Noble metal nanostructures are grown inside hollow mesoporous silica microspheres using “ship‐in‐a‐bottle” growth. Small Au seeds are first introduced into the interior of the hollow microspheres. Au nanorods with synthetically tunable longitudinal plasmon wavelengths and Au nanospheres are obtained through seed‐mediated growth within the microspheres. The encapsulated Au nanocrystals are further coated with Pd or Pt shells. The microsphere‐encapsulated bimetallic core/shell nanostructures can function as catalysts. They exhibit high catalytic performance and their stability is superior to that of the corresponding unencapsulated core/shell nanostructures in the catalytic oxidation of o‐phenylenediamine with hydrogen peroxide. Therefore, these hollow microsphere‐encapsulated metal nanostructures are promising as recoverable and efficient catalysts for various liquid‐phase catalytic reactions.     

Revamping SiO2 Spheres by Core–Shell Porosity Endowment to Construct a Mazelike Nanoreactor for Enhanced Catalysis in CO2 Hydrogenation to Methanol

Beyond the catalytic activity of nanocatalysts, the support with architectural design and explicit boundary could also promote the overall performance through improving the diffusion process, highlighting additional support for the morphology-dependent activity. To delineate this, herein, a novel mazelike-reactor framework, namely multi-voids mesoporous silica sphere (MVmSiO₂), is carved through a top-down approach by endowing core-shell porosity premade Stöber SiO₂ spheres. The precisely-engineered MVmSiO₂ with peripheral one-dimensional pores in the shell and interconnecting compartmented voids in the core region is simulated to prove combined hierarchical and structural superiority over its analogous counterparts. Supported with CuZn-based alloys, mazelike MVmSiO₂ nanoreactor experimentally demonstrated its expected workability in model gas-phase CO₂ hydrogenation reaction where enhanced CO₂ activity, good methanol yield, and more importantly, a prolonged stable performance are realized. While tuning the nanoreactor composition besides morphology optimization could further increase the catalytic performance, it is accentuated that the morphological architecture of support further boosts the reaction performance apart from comprehensive compositional optimization. In addition to the found morphological restraints and size-confinement effects imposed by MVmSiO₂, active sites of catalysts are also investigated by exploring the size difference of the confined CuZn alloy nanoparticles in CO₂ hydrogenation employing both in-situ experimental characterizations and density functional theory calculations.     

Freely Tailorable Yolk-Shell Encapsulation: Versatile Applications in Ultralow-k Dielectric,Drug Delivery Systems,and Catalysts

Herein, a facile, controllable, and versatile method is reported to prepare monodisperse yolk-shell and yolk-multishell silica nanoparticles (NPs) with mesoporous shells by a novel selective etching strategy. The mechanism of selective etching based on fluoride-silica chemistry is investigated in detail and thus provides a fundamentally novel principle for the fabrication of yolk-shell NPs. Specifically, this unprecedented and versatile synthesis strategy can be used to encapsulate essentially any silica-based, carbon-based, metal, metal oxide, or other possible NPs. Noteworthy is that most of the yolk-shell mesoporous silica (mSiO₂) NPs are prepared for the first time. To demonstrate the major structural and compositional advantages of the designed yolk-shell NPs, their applications in the fields of ultralow-dielectric constant (k) materials, drug delivery systems, and catalysts were explored. In detail, the lowest k value of the prepared yolk-shellordered mesoporous silica@mSiO₂/fluorinated polybenzoxazole composite films is 2.02; The obtained yolk-shell mSiO₂/C@mSiO₂/C NPs possess high hydrophilicity and pH-responsive sensitivity; The conversion of the catalytic reaction of the designed magnetic yolk-shell hollow Fe₃O₄@SiO₂/Au@mSiO₂ NPs at 20 min is 97% with a high conversion rate (92%) and recyclability even after 10 reuses. This innovative work lays a solid foundation for freely tailorable yolk-shell encapsulation and will greatly stimulate more efforts devoted to relevant research and development.     

Optical Design of Silica Aerogels for On-Demand Thermal Management

Silica aerogels, a type of porous material featuring extra low density and thermal conductivity, have drawn increasing interest from both academia and industry owing to their excellent thermal insulation performance. However, thermal insulation is always the single consideration when silica aerogels are used for thermal management. In this study, the on-demand thermal management (ODTM) of silica aerogel with either passive thermal insulation, passive heating, or passive cooling in different environments is revealed. The ODTM behavior of silica aerogels can be simply fulfilled through their optical property variations such as solar light transparency and infrared emissivity, which are controllable via the microstructures of the building blocks and surface composition design. Robust solar heating of 25 °C higher than the ambient in the daytime and sub-ambient cooling of 7 °C at night is achieved with the traditional transparent silica aerogel. Interestingly, sub-ambient cooling of 5 °C in the daytime and a warmer state on cold nights is achieved by modifying its solar transmittance and infrared emissivity. This study guides a comprehensive understanding of the thermal management behavior of silica aerogels and leads to ODTM applications of silica aerogels by tailoring their optical and thermal conductivity properties.     

Confinement of gold quantum dot arrays inside ordered mesoporous silica thin film

Periodic disposed quantum dot arrays are very useful for the large scale integration of single electron devices. Gold quantum dot arrays were self-assembled inside pore channels of ordered amino-functionalized mesoporous silica thin films, employing the neutralization reaction between chloroauric acid and amino groups. The diameters of quantum dots are controlled via changing the aperture of pore channels from 2.3 to 8.3 nm, which are characterized by HRTEM, SEM and FT-IR. UV-vis absorption spectra of gold nanoparticle/mesoporous silica composite thin films exhibit a blue shift and intensity drop of the absorption peak as the aperture of mesopores decreases,which represents the energy level change of quantum dot arrays due to the quantum size effect.     

掺入有机硅提高溶胶-凝胶二氧化硅减反膜的稳定性研究

膜层稳定性对于激光器能否长期稳定使用极为重要。多孔SiO2减反膜经热处理后,结构中还存在许多Si-OH亲水基团,透过率稳定性受环境相对湿度的影响较大。向膜层中掺入有机硅,添加疏水基团,提高了膜层的疏水性,增强了膜层的透过率稳定性。膜层中加了Si-CH3疏水基团,膜层的疏水性大大提高;当Si-CH3与二氧化硅悬胶体中的Si的摩尔比为1/5.7时,即Si-CH3质量分数为0.35%时的二氧化硅膜层,其减反效果好,疏水性也高,从而大幅度提高了膜层的透过率稳定性,延长了膜层的寿命,对二氧化硅膜层具有高激光损伤阈值的性能没有影响。