Spatially Asymmetric Nanoparticles for Boosting Ferroptosis in Tumor Therapy.

Despite its effectiveness in eliminating cancer cells, ferroptosis is hindered by the high natural antioxidant glutathione (GSH) levels in the tumor microenvironment. Herein, we developed a spatially asymmetric nanoparticle, Fe3O4@DMS&PDA@MnO2-SRF, for enhanced ferroptosis. It consists of two subunits: Fe3O4 nanoparticles coated with dendritic mesoporous silica (DMS) and PDA@MnO2 (PDA: polydopamine) loaded with sorafenib (SRF). The spatial isolation of the Fe3O4@DMS and PDA@MnO2-SRF subunits enhances the synergistic effect between the GSH-scavengers and ferroptosis-related components. First, the increased exposure of the Fe3O4 subunit enhances the Fenton reaction, leading to increased production of reactive oxygen species. Furthermore, the PDA@MnO2-SRF subunit effectively depletes GSH, thereby inducing ferroptosis by the inactivation of glutathione-dependent peroxidases 4. Moreover, the SRF blocks Xc- transport in tumor cells, augmenting GSH depletion capabilities. The dual GSH depletion of the Fe3O4@DMS&PDA@MnO2-SRF significantly weakens the antioxidative system, boosting the chemodynamic performance and leading to increased ferroptosis of tumor cells.

Unipolar Ionic Diode Nanofluidic Membranes Enabled by Stepped Mesochannels for Enhanced Salinity Gradient Energy Harvesting.

Developing ionic diode membranes featuring asymmetric structures is in high demand for salinity gradient energy harvesting. These membranes offer benefits in mitigating ion concentration polarization, thereby promoting ion permeability. However, most reported works focus on the role of heterogeneous charge-based bipolar ionic diode membranes for ion concentration polarization suppression, with comparatively less attention given to maintaining ion selectivity. Herein, unipolar ionic diode nanofluidic mesoporous silica membranes featuring stepped mesochannels were developed via a micellar sequential oriented interfacial self-assembly strategy as a salinity gradient energy harvester. Due to the asymmetric mesochannels and unipolar structure (both sides carry negative charge), the ionic diode membranes exhibit a strong rectification ratio of ∼15.91 to facilitate unidirectional ion transport while maintaining excellent cation selectivity (cation transfer number of ∼0.85). Besides, the vertically aligned mesochannels significantly reduce ion transport resistance, generating a high ionic flux. Consequently, the unipolar ionic diode nanofluidic membranes demonstrate a power output of 5.88 W/m2 between artificial sea and river water. The unipolar feature gives notable enhancements of 296% and 144% in power output compared to the symmetric membrane and bipolar ionic diode membrane, respectively. This work opens up new routes for designing ionic diode membranes for salinity gradient energy harvesting.

Synthesis of Mesoporous Catechin Nanoparticles as Biocompatible Drug-Free Antibacterial Mesoformulation.

While polyphenolic substances stand as excellent antibacterial agents, their antimicrobial properties rely on the auxiliary support of micro-/nanostructures. Despite offering a novel avenue for enhancing polymer performance, controllable fabrication of mesoporous polymeric nanomaterials encounters significant challenges due to intricate intermolecular forces. In this article, mesoporous catechin nanoparticles have been successfully fabricated using a balanced multivariate interaction approach. The harmonization of the water-ethanol ratio and ionic strength effectively balances the forces of hydrogen bonding and π-π stacking, facilitating the controlled assembly of mesostructures. The mesoporous catechin nanoparticles exhibit a uniform spherical structure (∼100 nm), open mesopores with a diameter of ∼15 nm, and a high surface area of ∼106 m2 g-1. While exhibiting a good biocompatibility and negative surface charge, the mesoporous catechins possess outstanding antibacterial ability and function as an antibiotic mesoformulation without the necessity of loading any drugs. This mesoformulation inhibits 50% in vitro Staphylococcus aureus growth with a low concentration of ∼10 µg mL-1 and achieves complete inhibition at ∼25 µg mL-1. In a mouse wound model, accelerated wound healing and complete closure within 6-8 days are achieved. Proteomics of bacteria reveals that the excellent antibacterial property is attributed to the synergetic effect of mesoformulation's mesostructure and the catechin molecule intervening in bacterial metabolism. Overall, this work may pave a novel way for the future exploration of polymer nanomaterials and antibiotic formulations.

Nucleation-Inhibited Emulsion Interfacial Assembled Polydopamine Microvesicles as Artificial Antigen-Presenting Cells.

Albeit microemulsion systems have emerged as efficient platforms for fabricating tunable nano/microstructures, lack of understanding on the emulsion-interfacial assembly hindered the control of fabrication. Herein, a nucleation-inhibited microemulsion interfacial assembly method is proposed, which deviates from conventional interfacial nucleation approaches, for the synthesis of polydopamine microvesicles (PDA MVs). These PDA MVs exhibit an approximate diameter of 1 µm, showcasing a pliable structure reminiscent of cellular morphology. Through modifications of antibodies on the surface of PDA MVs, their capacity as artificial antigen presentation cells is evaluated. In comparison to solid nanoparticles, PDA MVs with cell-like structures show enhanced T-cell activation, resulting in a 1.5-fold increase in CD25 expression after 1 day and a threefold surge in PD-1 positivity after 7 days. In summary, the research elucidates the influence of nucleation and interfacial assembly in microemulsion polymerization systems, providing a direct synthesis method for MVs and substantiating their effectiveness as artificial antigen-presenting cells.

Boosted Oxygen Kinetics of Hierarchically Mesoporous Mo2C/C for High-current-density Zn-air Battery.

The high-current-density Zn-air battery shows big prospects in next-generation energy technologies, while sluggish O2 reaction and diffusion kinetics barricade the applications. Herein, the sequential assembly is innovatively demonstrated for hierarchically mesoporous molybdenum carbides/carbon microspheres with a tunable thickness of mesoporous carbon layers (Meso-Mo2C/C-x, where x represents the thickness). The optimum Meso-Mo2C/C-14 composites (≈2 µm in diameter) are composed of mesoporous nanosheets (≈38 nm in thickness), which possess bilateral mesoporous carbon layers (≈14 nm in thickness), inner Mo2C/C layers (≈8 nm in thickness) with orthorhombic Mo2C nanoparticles (≈2 nm in diameter), a high surface area of ≈426 m2 g-1, and open mesopores (≈6.9 nm in size). Experiments and calculations corroborate the hierarchically mesoporous Mo2C/C can enhance hydrophilicity for supplying sufficient O2, accelerate oxygen reduction kinetics by highly-active Mo2C and N-doped carbon sites, and facilitate O2 diffusion kinetics over hierarchically mesopores. Therefore, Meso-Mo2C/C-14 outputs a high half-wave potential (0.88 V vs RHE) with a low Tafel slope (51 mV dec-1) for oxygen reduction. More significantly, the Zn-air battery delivers an ultrahigh power density (272 mW cm-2), and an unprecedented 100 h stability at a high-current-density condition (100 mA cm-2), which is one of the best performances.

A Mesostructure Multivariant-Assembly Reinforced Ultratough Biomimicking Superglue.

The imitation of mussels and oysters to create high-performance adhesives is a cutting-edge field. The introduction of inorganic fillers is shown to significantly alter the adhesive's properties, yet the potential of mesoporous materials as fillers in adhesives is overlooked. In this study, the first report on the utilization of mesoporous materials in a biomimetic adhesive system is presented. Incorporating mesoporous silica nanoparticles (MSN) profoundly enhances the adhesion of pyrogallol (PG)-polyethylene imine (PEI) adhesive. As the MSN concentration increases, the adhesion strength to glass substrates undergoes an impressive fivefold improvement, reaching an outstanding 2.5 mPa. The adhesive forms an exceptionally strong bond, to the extent that the glass substrate fractures before joint failure. The comprehensive tests involving various polyphenols, polymers, and fillers reveal an intriguing phenomenon-the molecular structure of polyphenols significantly influences adhesive strength. Steric hindrance emerges as a crucial factor, regulating the balance between π-cation and charge interactions, which significantly impacts the multicomponent assembly of polyphenol-PEI-MSN and, consequently, adhesive strength. This groundbreaking research opens new avenues for the development of novel biomimetic materials.

A Pressure and Proximity Sensor Based on Laser-Induced Graphene.

Smart wearable devices are extensively utilized across diverse domains due to their inherent advantages of flexibility, portability, and real-time monitoring. Among these, flexible sensors demonstrate exceptional pliability and malleability, making them a prominent focus in wearable electronics research. However, the implementation of flexible wearable sensors often entails intricate and time-consuming processes, leading to high costs, which hinder the advancement of the entire field. Here, we report a pressure and proximity sensor based on oxidized laser-induced graphene (oxidized LIG) as a dielectric layer sandwiched by patterned LIG electrodes, which is characterized by high speed and cost-effectiveness. It is found that in the low-frequency range of fewer than 0.1 kHz, the relative dielectric constant of the oxidized LIG layer reaches an order of magnitude of 104. The pressure mode of this bimodal capacitive sensor is capable of detecting pressures within the range of 1.34 Pa to 800 Pa, with a response time of several hundred milliseconds. The proximity mode involves the application of stimulation using an acrylic probe, which demonstrates a detection range from 0.05 mm to 37.8 mm. Additionally, it has a rapid response time of approximately 100 ms, ensuring consistent signal variations throughout both the approach and withdrawal phases. The sensor fabrication method proposed in this project effectively minimizes expenses and accelerates the preparation cycle through precise control of laser processing parameters to shape the electrode-dielectric layer-electrode within a single substrate material. Based on their exceptional combined performance, our pressure and proximity sensors exhibit significant potential in practical applications such as motion monitoring and distance detection.

Implanting Colloidal Nanoparticles into Single-Crystalline Zeolites for Catalytic Dehydration.

The encapsulation of functional colloidal nanoparticles (100 nm) into single-crystalline ZSM-5 zeolites, aiming to create uniform core-shell structures, is a highly sought-after yet formidable objective due to significant lattice mismatch and distinct crystallization properties. In this study, we demonstrate the fabrication of a core-shell structured single-crystal zeolite encompassing an Fe3O4 colloidal core via a novel confinement stepwise crystallization methodology. By engineering a confined nanocavity, anchoring nucleation sites, and executing stepwise crystallization, we have successfully encapsulated colloidal nanoparticles (CN) within single-crystal zeolites. These grafted sites, alongside the controlled crystallization process, compel the zeolite seed to nucleate and expand along the Fe3O4 colloidal nanoparticle surface, within a meticulously defined volume (1.5×107≤V≤1.3×108 nm3). Our strategy exhibits versatility and adaptability to an array of zeolites, including but not restricted to ZSM-5, NaA, ZSM-11, and TS-1 with polycrystalline zeolite shell. We highlight the uniformly structured magnetic-nucleus single-crystalline zeolite, which displays pronounced superparamagnetism (14 emu/g) and robust acidity (~0.83 mmol/g). This innovative material has been effectively utilized in a magnetically stabilized bed (MSB) reactor for the dehydration of ethanol, delivering an exceptional conversion rate (98 %), supreme ethylene selectivity (98 %), and superior catalytic endurance (in excess of 100 hours).

Mesoporous Nano-Badminton with Asymmetric Mass Distribution: How Nanoscale Architecture Affects the Blood Flow Dynamics.

While the nanobio interaction is crucial in determining nanoparticles' in vivo fate, a previous work on investigating nanoparticles' interaction with biological barriers is mainly carried out in a static state. Nanoparticles' fluid dynamics that share non-negligible impacts on their frequency of encountering biological hosts, however, is seldom given attention. Herein, inspired by badmintons' unique aerodynamics, badminton architecture Fe3O4&mPDA (Fe3O4 = magnetite nanoparticle and mPDA = mesoporous polydopamine) Janus nanoparticles have successfully been synthesized based on a steric-induced anisotropic assembly strategy. Due to the "head" Fe3O4 having much larger density than the mPDA "cone", it shows an asymmetric mass distribution, analogous to real badminton. Computational simulations show that nanobadmintons have a stable fluid posture of mPDA cone facing forward, which is opposite to that for the real badminton. The force analysis demonstrates that the badminton-like morphology and mass distribution endow the nanoparticles with a balanced motion around this posture, making its movement in fluid stable. Compared to conventional spherical Fe3O4@mPDA nanoparticles, the Janus nanoparticles with an asymmetric mass distribution have straighter blood flow trails and ∼50% reduced blood vessel wall encountering frequency, thus providing doubled blood half-life and ∼15% lower organ uptakes. This work provides novel methodology for the fabrication of unique nanomaterials, and the correlations between nanoparticle architectures, biofluid dynamics, organ uptake, and blood circulation time are successfully established, providing essential guidance for designing future nanocarriers.

Surface curvature-induced oriented assembly of sushi-like Janus therapeutic nanoplatform for combined chemodynamic therapy.

BACKGROUND: Chemodynamic therapy (CDT) based on Fenton/Fenton-like reaction has emerged as a promising cancer treatment strategy. Yet, the strong anti-oxidation property of tumor microenvironment (TME) caused by endogenous glutathione (GSH) still severely impedes the effectiveness of CDT. Traditional CDT nanoplatforms based on core@shell structure possess inherent interference of different subunits, thus hindering the overall therapeutic efficiency. Consequently, it is urgent to construct a novel structure with isolated functional units and GSH depletion capability to achieve desirable combined CDT therapeutic efficiency. RESULTS: Herein, a surface curvature-induced oriented assembly strategy is proposed to synthesize a sushi-like novel Janus therapeutic nanoplatform which is composed of two functional units, a FeOOH nanospindle serving as CDT subunit and a mSiO2 nanorod serving as drug-loading subunit. The FeOOH CDT subunit is half covered by mSiO2 nanorod along its long axis, forming sushi-like structure. The FeOOH nanospindle is about 400 nm in length and 50 nm in diameter, and the mSiO2 nanorod is about 550 nm in length and 100 nm in diameter. The length and diameter of mSiO2 subunit can be tuned in a wide range while maintaining the sushi-like Janus structure, which is attributed to a Gibbs-free-energy-dominating surface curvature-induced oriented assembly process. In this Janus therapeutic nanoplatform, Fe3+ of FeOOH is firstly reduced to Fe2+ by endogenous GSH, the as-generated Fe2+ then effectively catalyzes overexpressed H2O2 in TME into highly lethal ·OH to achieve efficient CDT. The doxorubicin (DOX) loaded in the mSiO2 subunit can be released to achieve combined chemotherapy. Taking advantage of Fe3+-related GSH depletion, Fe2+-related enhanced ·OH generation, and DOX-induced chemotherapy, the as-synthesized nanoplatform possesses excellent therapeutic efficiency, in vitro eliminating efficiency of tumor cells is as high as ~ 87%. In vivo experiments also show the efficient inhibition of tumor, verifying the synthesized sushi-like Janus nanoparticles as a promising therapeutic nanoplatform. CONCLUSIONS: In general, our work provides a successful paradigm of constructing novel therapeutic nanoplatform to achieve efficient tumor inhibition.

Gradient Hierarchically Porous Structure for Rapid Capillary-Assisted Catalysis.

Synthesis of hierarchically porous structures with uniform spatial gradient and structure reinforcement effect still remains a great challenge. Herein, we report the synthesis of zeolite@mesoporous silica core-shell nanospheres (ZeoA@MesoS) with a gradient porous structure through a micellar dynamic assembly strategy. In this case, we find that the size of composite micelles can be dynamically changed with the increase of swelling agents, which in situ act as the building blocks for the modular assembly of gradient mesostructures. The ZeoA@MesoS nanospheres are highly dispersed in solvents with uniform micropores in the inner core and a gradient tubular mesopore shell. As a nanoreactor, such hierarchically gradient porous structures enable the capillary-directed fast mass transfer from the solutions to inner active sites. As a result, the ZeoA@MesoS catalysts deliver a fabulous catalytic yield of ∼75% on the esterification of long-chain carboxylic palmitic acids and high stability even toward water interference, which can be well trapped by the ZeoA core, pushing forward the chemical equilibrium. Moreover, a very remarkable catalytic conversion on the C-H arylation reaction of large N-methylindole is achieved (∼98%) by a Pd-immobilized ZeoA@MesoS catalyst. The water tolerance feature gives a notable enhancement of 26% in catalytic yield compared to the Pd-dendritic mesoporous silica without the zeolite core.

Anisotropic Self-Assembly of Asymmetric Mesoporous Hemispheres with Tunable Pore Structures at Liquid-Liquid Interfaces.

Asymmetric materials have attracted tremendous interest because of their intriguing physicochemical properties and promising applications, but endowing them with precisely controlled morphologies and porous structures remains a formidable challenge. Herein, a facile micelle anisotropic self-assembly approach on a droplet surface is demonstrated to fabricate asymmetric carbon hemispheres with a jellyfish-like shape and radial multilocular mesostructure. This facile synthesis follows an interface-energy-mediated nucleation and growth mechanism, which allows easy control of the micellar self-assembly behaviors from isotropic to anisotropic modes. Furthermore, the micelle structure can also be systematically manipulated by selecting different amphiphilic triblock copolymers as a template, resulting in diverse novel asymmetric nanostructures, including eggshell, lotus, jellyfish, and mushroom-shaped architectures. The unique jellyfish-like hemispheres possess large open mesopores (∼14 nm), a high surface area (∼684 m2 g-1), abundant nitrogen dopants (∼6.3 wt %), a core-shell mesostructure and, as a result, manifest excellent sodium-storage performance in both half and full-cell configurations. Overall, our approach provides new insights and inspirations for exploring sophisticated asymmetric nanostructures for many potential applications.

Enzyme-Based Mesoporous Nanomotors with Near-Infrared Optical Brakes.

As one of the most important parameters of the nanomotors' motion, precise speed control of enzyme-based nanomotors is highly desirable in many bioapplications. However, owing to the stable physiological environment, it is still very difficult to in situ manipulate the motion of the enzyme-based nanomotors. Herein, inspired by the brakes on vehicles, the near-infrared (NIR) "optical brakes" are introduced in the glucose-driven enzyme-based mesoporous nanomotors to realize remote speed regulation for the first time. The novel nanomotors are rationally designed and fabricated based on the Janus mesoporous nanostructure, which consists of the SiO2@Au core@shell nanospheres and the enzymes-modified periodic mesoporous organosilicas (PMOs). The nanomotor can be driven by the biofuel of glucose under the catalysis of enzymes (glucose oxidase/catalase) on the PMO domain. Meanwhile, the Au nanoshell at the SiO2@Au domain enables the generation of the local thermal gradient under the NIR light irradiation, driving the nanomotor by thermophoresis. Taking advantage of the unique Janus nanostructure, the directions of the driving force induced by enzyme catalysis and the thermophoretic force induced by NIR photothermal effect are opposite. Therefore, with the NIR optical speed regulators, the glucose-driven nanomotors can achieve remote speed manipulation from 3.46 to 6.49 µm/s (9.9-18.5 body-length/s) at the fixed glucose concentration, even after covering with a biological tissue. As a proof of concept, the cellar uptake of the such mesoporous nanomotors can be remotely regulated (57.5-109 µg/mg), which offers great potential for designing smart active drug delivery systems based on the mesoporous frameworks of this novel nanomotor.

Streamlined Mesoporous Silica Nanoparticles with Tunable Curvature from Interfacial Dynamic-Migration Strategy for Nanomotors.

Streamlined architectures with a low fluid-resistance coefficient have been receiving great attention in various fields. However, it is still a great challenge to synthesize streamlined architecture with tunable surface curvature at the nanoscale. Herein, we report a facile interfacial dynamic migration strategy for the synthesis of streamlined mesoporous nanotadpoles with varied architectures. These tadpole-like nanoparticles possess a big streamlined head and a slender tail, which exhibit large inner cavities (75-170 nm), high surface areas (424-488 m2 g-1), and uniform mesopore sizes (2.4-3.2 nm). The head curvature of the streamlined mesoporous nanoparticles can be well-tuned from ∼2.96 × 10-2 to ∼5.56 × 10-2 nm-1, and the tail length can also be regulated from ∼30 to ∼650 nm. By selectively loading the Fe3O4 catalyst in the cavity of the streamlined silica nanotadpoles, the H2O2-driven mesoporous nanomotors were designed. The mesoporous nanomotors with optimized structural parameters exhibit outstanding directionality and a diffusion coefficient of 8.15 µm2 s-1.

Synthesis of Fully Exposed Single-Atom-Layer Metal Clusters on 2D Ordered Mesoporous TiO2 Nanosheets.

A sulfhydryl monomicelles interfacial assembly strategy is presented for the synthesis of fully exposed single-atom-layer Pt clusters on 2D mesoporous TiO2 (SAL-Pt@mTiO2 ) nanosheets. This synthesis features the introduction of the sulfhydryl group in monomicelles to finely realize the controllable co-assembly process of Pt precursors within ordered mesostructures. The resultant SAL-Pt@mTiO2 shows uniform SAL Pt clusters (≈1.2 nm) anchored in ultrathin 2D nanosheets (≈7 nm) with a high surface area (139 m2 g-1 ), a large pore size (≈25 nm) and a high dispersion (≈99 %). Moreover, this strategy is universal for the synthesis of other SAL metal clusters (Pd and Au) on 2D mTiO2 with high exposure and accessibility. When used as a catalyst for hydrogenation of 4-nitrostyrene, the SAL-Pt@mTiO2 shows a high catalytic activity (TOF up to 2424 h-1 ), 100 % selectivity for 4-aminostyrene, good stability, and anti-resistance to thiourea poisoning under relatively mild conditions (25 °C, 10 bar).

Surface-Confined Winding Assembly of Mesoporous Nanorods.

Bending and folding are important stereoscopic geometry parameters of one-dimensional (1D) nanomaterials, yet the precise control of them has remained a great challenge. Herein, a surface-confined winding assembly strategy is demonstrated to regulate the stereoscopic architecture of uniform 1D mesoporous SiO2 (mSiO2) nanorods. Based on this brand-new strategy, the 1D mSiO2 nanorods can wind on the surface of 3D premade nanoparticles (sphere, cube, hexagon disk, spindle, rod, etc.) and inherit their surface topological structures. Therefore, the mSiO2 nanorods with a diameter of ∼50 nm and a variable length can be bent into arc shapes with variable radii and radians, as well as folded into 60, 90, 120, and 180° angular convex corners with controllable folding times. Additionally, in contrast to conventional core@shell structures, this winding structure induces partial exposure and accessibility of the premade nanoparticles. The functional nanoparticles can exhibit large accessible surface and efficient energy exchanges with the surroundings. As a proof of concept, winding-structured CuS&mSiO2 nanocomposites are fabricated, which are made up of a 100 nm CuS nanosphere and the 1D mSiO2 nanorods with a diameter of ∼50 nm winding the nanosphere in the perimeter. The winding structured nanocomposites are demonstrated to have fourfold photoacoustic imaging intensity compared with the conventional core@shell nanostructure with an inaccessible core because of the greatly enhanced photothermal conversion efficiency (increased by ∼30%). Overall, our work paves the way to the design and synthesis of 1D nanomaterials with controllable bending and folding, as well as the formation of high-performance complex nanocomposites.

Sequential Chemistry Toward Core-Shell Structured Metal Sulfides as Stable and Highly Efficient Visible-Light Photocatalysts.

A universal sequential synthesis strategy in aqueous solution is presented for highly uniform core-shell structured photocatalysts, which consist of a metal sulfide light absorber core and a metal sulfide co-catalyst shell. We show that the sequential chemistry can drive the formation of unique core-shell structures controlled by the constant of solubility product of metal sulfides. A variety of metal sulfide core-shell structures have been demonstrated, including CdS@CoSx , CdS@MnSx , CdS@NiSx , CdS@ZnSx , CuS@CdS, and more complexed CdS@ZnSx @CoSx . The obtained strawberry-like CdS@CoSx core-shell structures exhibit a high photocatalytic H2 production activity of 3.92 mmol h-1 and an impressive apparent quantum efficiency of 67.3 % at 420 nm, which is much better than that of pure CdS nanoballs (0.28 mmol h-1 ), CdS/CoSx composites (0.57 mmol h-1 ), and 5 %wt Pt-loaded CdS photocatalysts (1.84 mmol h-1 ).

Spatial Isolation of Carbon and Silica in a Single Janus Mesoporous Nanoparticle with Tunable Amphiphilicity.

Like surfactants with tunable hydrocarbon chain length, Janus nanoparticles also possess the ability to stabilize emulsions. The volume ratio between the hydrophilic and hydrophobic domains in a single Janus nanoparticle is very important for the stabilization of emulsions, which is still a great challenge. Herein, dual-mesoporous Fe3O4@mC&mSiO2 Janus nanoparticles with spatial isolation of hydrophobic carbon and hydrophilic silica at the single-particle level have successfully been synthesized for the first time by using a novel surface-charge-mediated selective encapsulation approach. The obtained dual-mesoporous Fe3O4@mC&mSiO2 Janus nanoparticles are made up of a pure one-dimensional mesoporous SiO2 nanorod with tunable length (50-400 nm), ∼100 nm wide and ∼2.7 nm mesopores and a closely connected mesoporous Fe3O4@mC magnetic nanosphere (∼150 nm diameter, ∼10 nm mesopores). As a magnetic "solid amphiphilic surfactant", the hydrophilic/hydrophobic ratio can be precisely adjusted by varying the volume ratio between silica and carbon domains, endowing the Janus nanoparticles surfactant-like emulsion stabilization ability and recyclability under a magnetic field. Owing to the total spatial separation of carbon and silica, the Janus nanoparticles with an optimized hydrophilic/hydrophobic ratio show spectacular emulsion stabilizing ability, which is crucial for improving the biphasic catalysis efficiency. By selectively anchoring catalytic active sites into different domains, the fabricated Janus nanoparticles show outstanding performances in biphasic reduction of 4-nitroanisole with 100% conversion efficiency and 700 h-1 high turnover frequency for biphasic cascade synthesis of cinnamic acid.

Near-Infrared Triggered Decomposition of Nanocapsules with High Tumor Accumulation and Stimuli Responsive Fast Elimination.

A near-infrared (NIR) induced decomposable polymer nanocapsule is demonstrated. The nanocapsules are fabricated based on layer-by-layer co-assembly of azobenzene functionalized polymers and up/downconversion nanoparticles (U/DCNPs). When the nanocapsules are exposed to 980 nm light, ultraviolet/visible photons emitted by the U/DCNPs can trigger the photoisomerization of azobenzene groups in the framework. The nanocapsules could decompose from large-sized nanocapsule to small U/DCNPs. Owing to their optimized original size (ca. 180 nm), the nanocapsules can effectively avoid biological barriers, provide a long blood circulation (ca. 5 h, half-life time) and achieve four-fold tumor accumulation. It can fast eliminate from tumor within one hour and release the loaded drugs for chemotherapy after NIR-induced dissociation from initial 180 nm capsules to small 20 nm U/DCNPs.

Filtration Shell Mediated Power Density Independent Orthogonal Excitations-Emissions Upconversion Luminescence.

Lanthanide doped core-multishell structured NaGdF4:Yb,Er@NaYF4:Yb@NaGdF4:Yb,Nd@NaYF4@NaGdF4:Yb,Tm@NaYF4 nanoparticles with power-density independent orthogonal excitations-emissions upconversion luminescence (UCL) were fabricated for the first time. The optical properties of these core-multishell structured nanoparticles were related to the absorption filtration effect of the NaGdF4:Yb,Tm layer. By tuning the thickness of the filtration layer, the nanoparticles can exhibit unique two independent groups of UCL: Tm(3+) prominent UV/blue (UV=ultraviolet) UCL under the excitation at 980 nm and Er(3+) prominent green/red UCL under the excitation at 796 nm. The filtration-shell mediated orthogonal excitations-emissions UCL are power-density independent. As a proof of concept, the core-multishell nanoparticles are used in multi-dimensional security design and imaging-guided combined photodynamic therapy and chemotherapy.