Soft Mesoporous Organosilica Nanoplatforms Improve Blood Circulation,Tumor Accumulation/Penetration,and Photodynamic Efficacy

To date,the ability of nanoplatforms to achieve excellent therapeutic responses is hindered by short blood circulation and limited tumor accumulation/penetration.Herein,a soft mesoporous organosilica nanoplatform modified with hyaluronic acid and cyanine 5.5 are prepared,denoted SMONs-HA-Cy5.5,and comparative studies between SMONs-HA-Cy5.5(24.2 MPa)and stiff counterparts(79.2 MPa)are conducted.Results indicate that,apart from exhibiting a twofold increase in tumor cellular uptake,the soft nanoplatforms also display a remarkable pharmacokinetic advantage,resulting in considerably improved tumor accumulation.Moreover,SMONs-HA-Cy5.5 exhibits a significantly higher tumor penetration,achieving 30-μm deeper tissue permeability in multicellular spheroids relative to the stiff counterparts.Results further reveal that the soft nanoplatforms have an easier extravasation from the tumor vessels,diffuse farther in the dense extracellular matrix,and reach deeper tumor tissues compared to the stiff ones.Specifically,the soft nanoplatforms generate a 16-fold improvement(43 vs.2.72μm)in diffusion distance in tumor parenchyma.Based on the significantly improved blood circulation and tumor accumulation/penetration,a soft therapeutic nanoplatform is constructed by loading photosensitizer chlorin e6 in SMONs-HA-Cy5.5.The resulting nanoplatform exhibits considerably higher therapeutic efficacy on tumors compared to the stiff ones.

Growth of CeCo-MOF in dendritic mesoporous organosilica as highly efficient antioxidant for enhanced thermal stability of silicone rubber

High-efficient rubber antioxidants for enhanced heat resistance without compromising mechanical properties remain an enormous and long-term challenge for the rubber industry.Herein,we employed the in-situ growth of Ce-doped Co-metal-organic framework(Ce Co-MOF)in dendritic mesoporous organosilica nanoparticles(DMONs@Ce Co-MOF,denoted as DCCM)to prepare a novel antioxidant that exhibit outstanding thermal stability.Dendritic mesoporous organosilica nanoparticles(DMONs)effectively alleviated the incompatibility of Ce Co-MOF in the polymer matrix,and the effective scavenging of free radicals was attributed to the various oxidation states of metal ions in Ce Co-MOF.Surprising,by adding only0.5 phr(parts per hundred of rubber)of DMONs@Ce Co-MOF to silicone rubber,(SR),the retention rate of tensile strength increased from 37.3%to 61.6%after aging 72 h at 250℃,and the retention rate of elongation at break of DCCM/SR1 composites reached 68%,which was 5.43 times of SR.The strategy of anchoring MOFs on the surface of silica also provides a viable method for preparing effective compound functionalized rubber antioxidant.

Generic synthesis and versatile applications of molecularly organic-inorganic hybrid mesoporous organosilica nanoparticles with asymmetric Janus topologies and structures

Precise control over the morphology,nanostructure,composition,and particle size of molecularly organic-inorganic hybrid mesoporous organosilica nanoparticles （MONs） still remains a major challenge,which severely restricts their broad applications.In this work an efficient bridged organic group-determined growth strategy has been proposed for the facile synthesis of highly dispersed and uniform MONs with multifarious Janus morphologies,nanostructures,organic-inorganic hybrid compositions,and particle sizes,which can be easily controlled simply by varying the bridged organic groups and the concentration of bis-silylated organosilica precursors used in the synthesis.In addition,the formation mechanism of Janus MONs determined by the bridged organic group has been discussed.Based on the specific structures,compositions,and asymmetric morphologies,all the synthesized Janus MONs with hollow structures （JHMONs） demonstrate excellent performances in nanomedicine as desirable drug carriers with high drug-loading efficiencies/capacities,pH-responsive drug releasing,and enhanced therapeutic efficiencies,as attractive contrastenhanced contrast agents for ultrasound imaging,and as excellent bilirubin adsorbents with noticeably high adsorption capacities and high blood compatibilities.The developed versatile synthetic strategy and the obtained JHMONs are extremely important in the development and applications of MONs,particularly in the areas of nanoscience and nanotechnology.

The effect of solvent in evaporation-induced self-assembly:A case study of benzene periodic mesoporous organosilica

Volatile organic solvents were considered to have little influence on the synthesis of mesostructured materials through evaporation-induced self-assembly(EISA),because upon evaporation they leave the sol and hence do not interfere with the self-assembly process.We show here that the choice of solvent is crucial in the synthesis of thin films of phenylene-bridged periodic mesoporous organosilica(benzene PMO).Methanol is found to be a better solvent for the synthesis of thin films,whereas ethanol favors the formation of(HO)3Si-C6H4-Si(OH)3 crystals,the identity and structure of which is established by X-ray diffraction.A ternary reactant composition diagram is designed to visualize the relationship among multiple synthesis experiments and to guide the interpretation of experimental results and optimization of the quality of the periodic mesoporous organosilica film.Our study highlights the importance of solvent choice,a factor often neglected in EISA.We expect it to inspire researchers to explore the effect of solvent in designing the synthesis of mesoporous materials.

Functionalized periodic mesoporous organosilicas: Hierarchical and chiral materials

The integration of organic and inorganic fragments within the pore walls of the periodic mesoporous organosilicas (PMOs) represents one of the recent breakthroughs in material science. The resulting PMOs are promising materials for applications in such areas as catalysis, adsorption, separation and drug-delivery. We summarize here the recent progress made in the synthesis of PMOs with hierarchical structures and large functional groups, with special emphasis on the chiral mesoporous organosilicas and their potential applications as novel chiral solids in heterogeneous asymmetric catalysis.

A smart dual-responsive nanoplatform for delivery of prochloraz for the control of rice blast disease

Nano-controlled release formulations present a promising strategy to mitigate pesticide losses and enhance efficiency.In this study,a pH and GSH-responsive nanoplatform using mesoporous organosilica nanoparticles(MONs)as a carrier and poly(tannic acid)(PTA)as capping agent was established for controlling prochloraz(Pro)release.The obtained Pro@MON@PTA was characterized by transmission electron microscopy(TEM),scanning electron microscopy(SEM),Fourier transform infrared spectroscopy(FTIR),thermogravimetric analysis(TGA).The results indicate the successful preparation of Pro@MON@PTA nanoparticles,featuring uniform particle size(190 nm),excellent dispersibility,and a prochloraz loading efficiency of 17.2%.Evaluation of contact angle and adhesion work demonstrated superior adhesion of MON@PTA to rice leaves compared to MON.Controlled release studies revealed dual-responsive release properties of Pro@MON@PTA to acid and GSH.Additionally,photostability testing indicated effective ultraviolet light shielding by the carrier,reducing prochloraz degradation under irradiation.Bioassay results indicated equivalent fungicidal activity against Magnaporthe oryzae between Pro@MON@PTA and prochloraz technical and prochloraz EW after a 7-day treatment.However,in vivo experiments demonstrated that Pro@MON@PTA exhibited superior control efficacy compared to prochloraz EW.These findings suggested that MON@PTA holds significant potential for plant disease management.

Amphipathicity mediated endocytosis of mesoporous silica nanoparticles with tunable frameworks

Due to the amphiphilic nature of phospholipids in the cell membrane,the amphipathicity of the nanomedicine plays a crucial role in the endocytosis.However,limited biological characterization methods restrict the study of the state of nanoparticles with different amphiphilicities on cell membranes.The understanding of interaction of amphiphilic particle with cell membrane is still lacking.Herein,by combining the dissipative particle dynamics(DPD)with the framework construction of mesoporous silica nanoparticles(MSNs),we demonstrate the enhanced endocytosis induced by the hydrophobicity.DPD results confirm that the presence of hydrophobic groups on the surface of nanoparticles can disturb the integrity of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine(POPC)membrane and induce activation of phospholipids to a higher energy level,thereby facilitating the wrapping of nanoparticles.To validate the simulation findings,uniform MSNs with hydrophilic pure silica framework and two types of amphiphilic MSNs with varying hydrophilic organic groups in the framework are rationally synthesized by using different silane precursors.The obtained three kinds of MSNs show similar diameter(~100 nm)and mesopores(~2 nm),but distinct hydrophobicity/hydrophilicity ratio.The phenyl-bridged MSN with a carbon content of 27.1%exhibits enhanced cellular uptake,consistent with the theoretical simulation results.This work sheds light on how the surface amphipathicity influences endocytosis through the interaction with cell membrane.