Mesoporous Organosilica Hollow Nanoparticles: Synthesis and Applications

Hollow periodic mesoporous organosilicas (PMOs) with molecularly homogeneous organic functional groups in the inorganic pore walls are attracting more and more attention due to the high surface areas, tunable pore sizes, low densities, large cavities in the center, permeable thin shells, and versatile organic–inorganic hybrid frameworks, which make them promising in a variety of applications including adsorption, catalysis, drug delivery, and nanotheranostics. Herein, recent advances in the synthesis of hollow PMO nanoparticles with various organic moieties are summarized, and the mechanism and new insights of synthesis approaches, including hard‐core templating methods, liquid‐interface assembly methods, and the interfacial reassembly and transformation strategy are discussed in‐depth. Meanwhile, the design principles, properties, and synthetic strategies for some smart hollow architectures such as multishelled hollow PMOs, yolk–shell structured PMOs, and nonspherical hollow PMOs are discussed. Moreover, the typical applications of hollow PMO nanomaterials as nanoreactors for chemical transformations and nanoplatforms for biomedicine are summarized. Finally, the challenges and prospects for the future development of hollow PMOs are described.     

后接枝法合成氨丙基修饰的周期性介孔氧化硅材料

以三氯甲烷为溶剂, 氨丙基三甲氧基硅烷(APTMS)为修饰剂通过后接枝法对周期性介孔氧化硅材料(PMOs)进行修饰. 通过固态NMR、氮气吸附、元素分析和UV-vis吸光度测试等手段来表征材料. 结果表明, 氨丙基基团通过共价连接的方式成功修饰到PMOs材料. 尽管随着APTMS修饰量的增加, 比表面积、孔容和孔径都呈下降趋势, 但经25%APTMS修饰的PMOs材料依然具有良好的介孔结构, 其表面积为604m²·g^-1, 孔容为0.62cm³·^-1, 孔径狭窄分布在4.5～5.0nm之间. 修饰后的PMOs对氯金酸有明显的吸附作用.     

PEG交联有机硅/陶瓷杂化膜的制备及反渗透脱盐性能

采用聚乙二醇(PEG)和1,2-双(三乙氧基硅基)乙烷(BTESE)进行交联共聚, 以多孔α-Al₂O₃陶瓷膜为支撑体制备了一系列PEG交联的有机硅杂化膜。通过原子力显微镜(AFM)、场发射扫描电镜(FE-SEM)、傅里叶红外光谱(FT-IR)、热重分析(TGA)和水接触角测试(CA)对膜结构和物化性质进行了表征。将制备的BTESE/PEG杂化膜应用于反渗透脱盐, 考察了PEG含量、操作压力、进料浓度和操作温度等因素对改性杂化膜分离性能的影响。实验结果表明, 相比于未改性的BTESE膜, 10wt% PEG交联的有机硅杂化膜BTESE/PEG-10的水渗透率和盐离子表观截留率均有所提高。随着操作压力的升高和进料盐含量的下降, NaCl截留率上升而水渗透率基本恒定。在高达70℃的温度循环实验中, BTESE/PEG-10杂化膜表现出优异的水热稳定性, NaCl表观截留率始终保持在97%以上, 水渗透率高达1.2×10^-12 m³/(m²·s·Pa)。     

Chemistry of Mesoporous Organosilica in Nanotechnology: Molecularly Organic–Inorganic Hybridization into Frameworks

Organic–inorganic hybrid materials aiming to combine the individual advantages of organic and inorganic components while overcoming their intrinsic drawbacks have shown great potential for future applications in broad fields. In particular, the integration of functional organic fragments into the framework of mesoporous silica to fabricate mesoporous organosilica materials has attracted great attention in the scientific community for decades. The development of such mesoporous organosilica materials has shifted from bulk materials to nanosized mesoporous organosilica nanoparticles (designated as MONs, in comparison with traditional mesoporous silica nanoparticles (MSNs)) and corresponding applications in nanoscience and nanotechnology. In this comprehensive review, the state‐of‐art progress of this important hybrid nanomaterial family is summarized, focusing on the structure/composition–performance relationship of MONs of well‐defined morphology, nanostructure, and nanoparticulate dimension. The synthetic strategies and the corresponding mechanisms for the design and construction of MONs with varied morphologies, compositions, nanostructures, and functionalities are overviewed initially. Then, the following part specifically concentrates on their broad spectrum of applications in nanotechnology, mainly in nanomedicine, nanocatalysis, and nanofabrication. Finally, some critical issues, presenting challenges and the future development of MONs regarding the rational synthesis and applications in nanotechnology are summarized and discussed. It is highly expected that such a unique molecularly organic–inorganic nanohybrid family will find practical applications in nanotechnology, and promote the advances of this discipline regarding hybrid chemistry and materials.     

Biomimetic Diselenide-Bridged Mesoporous Organosilica Nanoparticles as an X-ray-Responsive Biodegradable Carrier for Chemo-Immunotherapy

Chemotherapy causes off-target toxicity and is often ineffective against solid tumors. Targeted and on-demand release of chemotherapeutics remains a challenge. Here, cancer-cell-membrane-coated mesoporous organosilica nanoparticles (MONs) containing X-ray- and reactive oxygen species (ROS)-responsive diselenide bonds for controlled release of doxorubicin (DOX) at tumor sites are developed. DOX-loaded MONs coated with 4T1 breast cancer cell membranes (CM@MON@DOX) show greater accumulation at tumor sites and prolonged blood circulation time versus an uncoated control in mice bearing 4T1 orthotopic mammary tumors. Under low-dose X-ray radiation, the DOX-loaded MONs exhibit carrier degradation-controlled release via cleavage of diselenide bonds, resulting in DOX-mediated immunogenic cell death at the tumor site. Combination with a PD-L1 checkpoint blockade further enhances inhibition of tumor growth and metastasis with low systemic toxicity. Together, the findings show the promise of these biomimetic, radiation-responsive diselenide-bond-bridged MONs in chemo-immunotherapy.     

ZIF-8-NH2/有机硅杂化膜的制备及渗透汽化脱盐性能研究

石油和天然气开采、电厂脱硫及海水淡化等工业活动会产生大量的高含盐废水, 有效处理这些高盐废水是实现液体零排放的关键。本研究以多孔α-Al₂O₃陶瓷膜为支撑体, 将氨基功能化的沸石咪唑酯骨架结构材料(ZIF-8-NH₂)填充到1,2-二(三乙氧基硅基)乙烷(BTESE)中, 制得ZIF-8-NH₂/有机硅杂化膜, 将其应用于高浓度盐水渗透汽化脱盐, 并系统考察了ZIF-8-NH₂含量、进料温度与浓度等因素对其脱盐性能的影响。实验结果表明, 与BTESE膜及ZIF-8/BTESE杂化膜相比, 氨基功能化的ZIF-8-NH₂/BTESE杂化膜的水渗透率和盐截留率均有所提高。在连续50 h渗透汽化脱盐测试中, ZIF-8-NH₂/BTESE杂化膜表现出优异的结构稳定性, NaCl表观截留率始终保持在99.95%以上, 水渗透率保持在6.3×10^-11 m³/(m²×s×Pa)以上。此外, NaCl截留率几乎不受进料温度和进料浓度的影响, 在高盐废水处理领域表现出良好的应用前景。     

超疏水有机-无机杂化凝胶的制备和表征

采用1,2-双-(三甲氧基硅基)-乙烷(BTME)和聚甲基含氢硅氧烷(PMHS)作为反应组分,在无需模板剂的溶胶-凝胶体系中制备了孔壁镶嵌乙基和孔道表面挂载甲基的有机-无机杂化多孔凝胶材料.用固体硅核磁共振、傅里叶红外光谱、低温氮气吸附/脱附、高分辨透射电镜、接触角测定和热重分析等手段研究了材料的结构和性能.结果表明,...     

A Cost-Effective,Aqueous-Solution-Processed Cathode Interlayer Based on Organosilica Nanodots for Highly Efficient and Stable Organic Solar Cells

The performance and industrial viability of organic photovoltaics are strongly influenced by the functionality and stability of interface layers. Many of the interface materials most commonly used in the lab are limited in their operational stability or their materials cost and are frequently not transferred toward large-scale production and industrial applications. In this work, an advanced aqueous-solution-processed cathode interface layer is demonstrated based on cost-effective organosilica nanodots (OSiNDs) synthesized via a simple one-step hydrothermal reaction. Compared to the interface layers optimized for inverted organic solar cells (i-OSCs), the OSiNDs cathode interlayer shows improved charge carrier extraction and excellent operational stability for various model photoactive systems, achieving a remarkably high power conversion efficiency up to 17.15%. More importantly, the OSiNDs’ interlayer is extremely stable under thermal stress or photoillumination (UV and AM 1.5G) and undergoes no photochemical reaction with the photoactive materials used. As a result, the operational stability of inverted OSCs under continuous 1 sun illumination (AM 1.5G, 100 mW cm⁻²) is significantly improved by replacing the commonly used ZnO interlayer with OSiND-based interfaces.