Asymmetric Assembly in Microdroplets: Efficient Construction of MOF Micromotors for Anti-Gravity Diffusion.

Janus-micromotors, as efficient self-propelled materials, have garnered considerable attention for their potential applications in non-agitated liquids. However, the design of micromotors is still challenging and with limited approaches, especially concerning speed and mobility in complex environments. Herein, a two-step spray-drying approach encompassing symmetrical assembly and asymmetrical assembly is introduced to fabricate the metal-organic framework (MOF) Janus-micromotors with hierarchical pores. Using a spray-dryer, a symmetrical assembly is first employed to prepare macro-meso-microporous UiO-66 with intrinsic micropores (<0.5 nm) alongside mesopores (≈24 nm) and macropores (≈400 nm). Subsequent asymmetrical assembly yielded the UiO-66-Janus loaded with the reducible nanoparticles, which underwent oxidation by KMnO4 to form MnO2 micromotors. The micromotors efficiently generated O2 for self-propulsion in H2O2, exhibiting ultrahigh speeds (1135 µm s-1, in a 5% H2O2 solution) and unique anti-gravity diffusion effects. In a specially designed simulated sand-water system, the micromotors traversed from the lower water to the upper water through the sand layer. In particular, the as-prepared micromotors demonstrated optimal efficiency in pollutant removal, with an adsorption kinetic coefficient exceeding five times that of the micromotors only possessing micropores and mesopores. This novel strategy fabricating Janus-micromotors shows great potential for efficient treatment in complex environments.

Accelerated Wound Healing by Electrospun Multifunctional Fibers with Self-Powered Performance.

Wound healing has been a persistent clinical challenge for a long time. Electrical stimulation is an effective therapy with the potential to accelerate wound healing. In this work, the self-powered electrospun nanofiber membranes (triples) were constructed as multifunctional wound dressings with electrical stimulation and biochemical capabilities. Triple was composed of a hydrolyzable inner layer with antiseptic and hemostatic chitosan, a hydrophilic core layer loaded with conductive AgNWs, and a hydrophobic outer layer fabricated by self-powered PVDF. Triple exhibited presentable wettability and acceptable moisture permeability. Electrical performance tests indicated that triple can transmit electrical signals formed by the piezoelectric effect to the wound. High antibacterial activities were observed for triple against Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa, with inhibition rates of 96.52, 98.63, and 97.26%, respectively. In vitro cell assays demonstrated that triple cells showed satisfactory proliferation and mobility. A whole blood clotting test showed that triple can enhance hemostasis. The innovative self-powered multifunctional fibers presented in this work offer a promising approach to addressing complications and expediting the promotion of chronic wound healing.

ZIF-8@CsPbBr3 Nanocrystals Formed by Conversion of Pb to CsPbBr3 in Bimetallic MOFs for Enhanced Photocatalytic CO2 Reduction.

Perovskite nanocrystals are embedded into metal-organic frameworks (MOFs) to create composites with high light absorption coefficients, tunable electronic properties, high specific surface area, and metal atom tunability for enhanced photocatalytic carban dioxide (CO2 ) reduction. However, existing perovskite-MOF structures with a large particle size are achieved based on Pb source adsorption into the pores of MOFs, which can significantly break down the porous structure, thereby resulting in a decreased specific surface area and impacting CO2 adsorption. Herein, a novel perovskite-MOF structure based on the synthesis of bimetallic Pb-containing MOFs and post-processing to convert Pb to CsPbBr3 nanocrystals (NCs) is proposed. It is discovered that the additional Pb is not introduced by adsorption, but instead engages in coordination and generates Pb-N. The produced ZIF-8@CsPbBr3 NCs are ≈40 nm and have an ultra-high specific surface area of 1325.08 m2 g-1 , and excellent photovoltaic characteristics, which are beneficial for photocatalytic CO2 reduction. The electronic conversion rate of composites is 450 mol g-1 h-1 , which is more than three times that of pure perovskites. Additionally, the superior reduction capacity is sustained after undergoing four cycles. Density Functional Thoery (DFT) simulations are used to explore the 3D charge density at the ZIF-8@CsPbBr3 NCs interface to better understand the electrical structure.

The controllable and efficient synthesis of two-dimensional metal-organic framework nanosheets for heterogeneous catalysis.

Two-dimensional (2D) MOFs exhibit unique periodicity in surface structures and thus have attracted much interest in the fields of catalysis, energy, and sensors. However, the expanded production scale of 2D MOFs had remained a great challenge in most previous studies. Herein, a controllable and efficient crystallization method for synthesizing 2D MOF nanosheets using high-gravity reactive precipitation is proposed, significantly improving heterogeneous catalysis efficiency. The two-dimensional ZIF-L nanosheets prepared in a rotating packed bed (RPB) reactor show a smaller lateral and lamellar thickness and a higher BET surface area compared to ZIF-L nanosheets prepared in a conventional stirred tank reactor (STR), with a greatly shortened reaction time. Applying the ZIF-L-RPB nanosheets as a catalyst, the catalytic Knoevenagel condensation as a probe reaction displays a high conversion rate of benzaldehyde (99.3%) within 2 h at room temperature, greatly exceeding that displayed by ZIF-L-STR and other reported catalysts. Furthermore, ZIL-L-RPB nanosheets of only 0.2 wt% enhanced the catalytic activity for the glycolysis of poly(ethylene terephthalate) (PET) with a PET conversion and a monomer yield of 90% in a short period of 15 min at 195 °C and almost completely depolymerized PET with a monomer yield of 94% in 30 min, which was far above that achieved by ZIL-L-STR. These results indicate the promising prospects of a high-gravity reactive precipitation strategy with precise size control in an economical way to prepare high-activity 2D MOF nanosheets for a wide range of heterogeneous catalysis.

A Universal Approach for Controllable Synthesis of Homogeneously Alloyed PtM Nanoflowers toward Enhanced Methanol Oxidation.

Platinum (Pt)-based alloys have received considerable attention due to their compositional variability and unique electrochemical properties. However, homogeneous element distribution at the nanoscale, which is beneficial to various electrocatalytic reactions, is still a great challenge. Herein, a universal approach is proposed to synthesize homogeneously alloyed and size-tunable Pt-based nanoflowers utilizing high gravity technology. Owing to the significant intensification of micro-mixing and mass transfer in unique high gravity shearing surroundings, five typical binary/ternary Pt-based nanoflowers are instantaneously achieved at room temperature. As a proof-of-concept, as-synthesized Platinum-Silver nanoflowers (PtAg NFs) demonstrate excellent catalytic performance and anti-CO poisoning ability for anodic methanol oxidation reaction with high mass activity of 1830 mA mgPt -1, 3.5 and 3.2 times higher than those of conventional beaker products and commercial Pt/C, respectively. The experiment in combination with theory calculations suggest that the enhanced performance is due to additional electronic transmission and optimized d-band center of Pt caused by high alloying degree.

Redox/Near-Infrared Dual-Responsive Hollow Mesoporous Organosilica Nanoparticles for Pesticide Smart Delivery.

Extremely inefficient utilization of pesticides has prompted a study of low-cost, sustainable, and smart application systems. Herein, as a promising pesticide nanocarrier, hollow mesoporous organosilica nanoparticles (HMONs) were first synthesized by using inexpensive CaCO3 nanoparticles as the hollow templates. A redox/near-infrared light dual-triggered pesticide release system was further achieved via loading avermectin (AVM) into the HMONs and coating a layer of polydopamine (PDA). The as-prepared AVM@HMONs@PDA displays a favorable pesticide load capability (24.8 wt %), outstanding photothermal performance, and high adhesion to leaves. In addition, with glutathione (GSH), the AVM cumulative release from AVM@HMONs@PDA was 3.5 times higher than that without GSH. Under ultraviolet light irradiation, the half-life of AVM@HMONs@PDA was prolonged by 17.0-fold compared to that of the AVM technical. At day 21 after treatment in the insecticidal activity, the median lethal concentrations (LC50) values displayed that the toxicity of AVM@HMONs@PDA for Panonychus citri (McGregor) was enhanced 4.0-fold compared with the commercial emulsifiable concentrate. In the field trial, at day 28 after spraying, AVM@HMONs@PDA was significantly more control effective than AVM-EC in controlling the P. citri (McGregor), even at a 50% reduced dosage. Moreover, HMONs@PDA was safe for crops. This research presents a novel preparation approach for HMONs, and it also offers a promising nanoplatform for the precise release of pesticides.

Efficient Construction of pH-Stimuli-Responsive Colloidosomes with High Encapsulation Efficiency.

Intelligent responsive colloidosomes have attracted increasing attention for their potential to enhance the efficacy and decrease the side effects of drugs in biomedical applications. However, a low encapsulation efficiency and complicated preparation method greatly limit their development. Herein, we report an efficient approach for the construction of pH-stimuli-responsive colloidosomes with high encapsulation efficiency by a high-gravity technology. The conditions under which latex particles with different methacrylic acid contents can successfully self-assemble into colloidosomes are explored. During the preparation process, emulsions emulsified for only 10 min at 2500 rpm in a unique high-gravity shearing surroundings are clarified owing to the greatly enhanced micromixing, while the emulsions emulsified for 30 min by a traditional high-speed shear machine at 4000 rpm are still yellow-white. More importantly, regular spherical colloidosomes encapsulating an anticancer drug doxorubicin not only achieve a small mean diameter of 2.82 µm but also realize a high encapsulation efficiency of 76.5%. The release performance of doxorubicin has an obvious pH-stimuli-responsive regularity and follows the first-order model of sustained release. The construction of intelligent responsive colloidosomes as drug carriers provides a route for controlled drug release and biomedical applications.

Degradable PDA@PNIPAM-TA Nanocomposites for Temperature- and NIR light-Controlled Pesticide Release.

Controlled pesticide delivery systems offer many distinctive advantages over conventional pesticide formulations. In this work, degradable poly(N-isopropylacrylamide) (PNIPAM)-tannic acid (TA) microgels and multifunctional PDA@PNIPAM-TA nanocomposites were prepared in a high-gravity rotating packed bed reactor (RPB) for smart pesticide delivery and release. The as-prepared microgels and nanocomposites showed reversible temperature-dependent swelling/deswelling behavior and irreversible pH-induced degradation. A dynamic contact angle test suggested that the introduction of TA and PDA into the PNIPAM matrix could enhance foliar adhesion and deposition efficiency. The nanocomposites were further used for the encapsulation and delivery of imidacloprid (IMI) to protect it from rapid photolysis and improve its pest-control efficiency. Their thermoresponsive behavior as well as pesticide loading capacity could be tuned by tailoring the PNIPAM-TA shell thickness, which could be varied by the NIPAM amount. The release rate of IMI from the core/shell nanocomposites was positively correlated with environmental temperature and near-infrared (NIR) light, which was adaptive to the positive temperature-dependent toxicity correlation of IMI and the increasing trend of pests under high temperature. The cumulative release of IMI was 23.5% at 25 °C, while it was 81.2% at 40 °C after 24 h of incubation, and the release rate was greatly enhanced under NIR irradiation. The results indicated that the facile control of pesticide release could be realized by regulating environmental conditions. This work also provides an idea for using high-gravity technology to conveniently construct a smart, effective, and environmentally friendly pesticide delivery system for sustainable crop protection.

Greatly Intensified Guest Exchange Strategy for Highly-Efficient Activation of Metal-Organic Frameworks.

The preservation and accessibility of pores are prerequisites to the application of metal-organic frameworks (MOFs). Activation is a key step to eliciting rich features of pores, but it needs a repeated solvent-exchange process which is tedious and time/cost-consuming. Herein, a facile strategy for highly-efficient activation of MOFs utilizing rotating packed bed is proposed. With the tremendous enhancement of molecular mixing and mass transfer in high-gravity and strong-shearing surrounding, nine representative MOFs are completely activated within 2 h without structural change. Compared with conventional process, this activation displays surprising efficiency by accelerating the diffusion of solvents and redissolution of residual reactants in the pores. The complete activation time can be significantly shortened by over 90%. As a proof-of-concept, the methane storage of as-activated UiO-66 is five times that of as-synthesized UiO-66. This strategy provides a potential platform with industrial worth for the activation of MOF materials with ultra-high efficiency and versatility.

Real-Time Imaging and Quantitative Evolution for Pyrolysis of Carbon Dots-Encapsulated Metal-Organic Frameworks at the Nanoscale by In Situ Environmental Transmission Electron Microscopy.

The pyrolysis of metal-organic frameworks (MOF) has been widely used approach to generate hierarchical structures with the corresponding metal, metal carbide, or metal oxide nanoparticles embedded in a porous carbon matrix with a high specific surface area for industrial catalysis, energy storage and transfer, etc. MOF-derived heterogeneous catalysts can be constructed by the encapsulation of carbon dots (CDs) with plenty of hydroxyl and amine groups to enhance the performance of the final product. Controlled formation of metallic carbon structures at the nanoscale, especially matter cycling and transformation on the nanoscale interface, is important for the production of industrial catalysts as well as the research of materials science and engineering progress. However, the mass transfer at the nanoscale during the processing of MOF pyrolysis remains less understood due to the lack of direct observation. Herein, by using in situ environmental transmission electron microscopy, real-time imaging and quantitative evolution of porous carbon decorated with metal species by the pyrolysis of CDs-encapsulated zeolitic imidazolate framework-67 are achieved. The migration of Co, the flow of aggregates, and the growth of carbon nanotubes observed in the nanoscale pyrolysis laboratory working at 600 °C with an air atmosphere are present. Experimental studies based on reduction and oxidation reaction models reveal that the synergistic effect between doped graphite nitrogen and confined Co nanoparticles is beneficial for boosting catalytic performance.

Three-Fluid Nozzle Spray Drying Strategy for Efficient Fabrication of Functional Colloidosomes.

Colloidosomes as Pickering emulsion microcapsules are expected to serve various applications, including encapsulation of drugs and loading of functional materials. Normally, when using colloidosomes for drug encapsulation, the latex particles as shell materials need to be mixed with drugs before the assembly process. However, this procedure may cause aggregation of latex particles, thereby resulting in disordered assembled shells or a low loading efficiency. Herein, we propose a three-fluid nozzle spray drying process to efficiently assemble latex particles of P(styrene (St)-co-butyl acrylate (BA)) into colloidosomes. The three-fluid nozzle spray drying equipment allows for the preparation for drug encapsulation without advance mixing of drug and shell materials. This strategy enables the construction of colloidosomes with uniform and controllable pores and the loading of functional materials. The effects of the compressed air flow rate, inlet temperature, feed rate, and solid content were explored, revealing the formation mechanism of colloidosomes during the spray drying process. Doxycycline hydrochloride (DH) was encapsulated in colloidosomes for controllable release, and the sustained release time is up to 100 h. The release rate can be adjusted by varying the glass transition temperature (Tg) and size of latex particles. Furthermore, Fe3O4 nanoparticle (NP)-loaded colloidosomes were constructed by this strategy. The magnetic response intensity of colloidosomes can be modulated by varying the amount of Fe3O4 NPs. The anticancer drug encapsulation and loading of other functional particles were also explored to expand applications.

A new skin flap from the zygomaticotemporal region: Anatomical study and clinical application to eyelid reconstruction.

BACKGROUND: Eyelid reconstruction is a demanding task faced by plastic surgeons. Island flaps from the zygomaticotemporal region, where the zygomatico-orbital artery predominates in vascularization, represent the recent local approaches to this problem. Questions exist as to where and on what element the flap should be based, and whether or not they should be adapted in relation to the behavior of the zygomatico-orbital artery. METHODS AND MATERIALS: A total of 22 fresh-frozen adult cadaver heads were employed. The fasciocutaneous perforators of the zygomatico-orbital artery and their anastomoses with the surrounding arteries, especially those in the upper palpebra, were investigated. On this basis, a distally based perforator flap was created and executed for eyelid reconstruction in 7 patients. RESULT: The zygomatico-orbital artery was interconnected through its perforators with the subdermal plexus over the zygomaticotemporal region and with the arteries in the surroundings. The transverse facial artery took the place of zygomatico-orbital artery where it was absent. Both the arteries anastomosed consistently with the superficial orbital arcade at a predictable site. All 7 flaps survived completely. CONCLUSION: A new distally based perforator flap from the zygomaticotemporal region is described regarding its anatomical basis and clinical applications to eyelid reconstruction. With a vascular axis consistently present and a pivot adjacent to the defects, the flap is more reliable in vascularization, and less harm to its donor site than orbicularis oculi myocutaneous flaps, and poses no concern about whether the zygomatico-orbital artery is present or not.

PtCuRu Nanoflowers with Ru-Rich Edge for Efficient Fuel-Cell Electrocatalysis.

Enhancing the catalytic activity of Pt-based alloy by a rational structural design is the key to addressing the sluggish kinetics of direct alcohol fuel cells. Herein, a facile one-pot method is reported to synthesize PtCuRu nanoflowers (NFs). The synergetic effect among Pt, Cu, and Ru can lower the d-band center of Pt, regulate the morphology, generate Ru-rich edge, and allow the exposure of more high index facets. The optimized Pt0.68 Cu0.18 Ru0.14 NFs exhibit outstanding electrocatalytic performances and excellent anti-poisoning abilities. The specific activities for the methanol oxidation reaction (MOR) (7.65 mA cm-2 ) and ethanol oxidation reaction (EOR) (7.90 mA cm-2 ) are 6.0 and 7.1 times higher than commercial Pt/C, respectively. The CO stripping experiment and the chronoamperometric (5000 s) demonstrate the superior anti-poisoning property and durability performance. Density functional theory calculations confirm that high metallization degree leads to the decrease of d-band center, the promotion of oxidation of CO, and improvement of the inherent activity and anti-poisoning ability. A Ru-rich edge exposes abundant high index facets to accelerate the reaction kinetics of rate-determining steps by decreasing the energy barrier for forming *HCOOH (MOR) and CC bond breaking (EOR).

Mechanical behavior and reinforcement mechanism of nanoparticle cluster fillers in dental resin composites: Simulation and experimental study.

OBJECTIVES: In dental resin composites (DRCs), the structure of fillers has a great impact on the mechanical behavior. The purpose of this study is to gain an in-depth understanding of the reinforcement mechanism and mechanical behavior of DRCs with nanoparticle clusters (NCs) fillers, thereby providing a guidance for the optimal design of filler structures for DRCs. METHODS: This work pioneers the use of discrete element method (DEM) simulations combined with experiments to study the mechanical behavior and reinforcement mechanism of DRCs with NCs fillers. RESULTS: The uniaxial compressive strength (UCS) of NCs-reinforced DRCs have an improvement of 9.58 % and 15.02 % in comparison with nanoparticles (NPs) and microparticles (MPs), respectively, because of the ability of NCs to deflect cracks and absorb stress through gradual fracturing. By using NCs and NPs as co-fillers, the internal defects of DRCs can be reduced, resulting in a further improvement of UCS of DRCs by 6.21 %. Furthermore, the mechanical properties of DRCs can be effectively improved by increasing the strength of NCs or reducing the size of NCs. SIGNIFICANCE: This study deepens the understanding of relationship between filler structure and mechanical behavior in DRCs at the mesoscale and provides an avenue for the application of DEM simulations in composite materials.

Enhancing CH4 Capture from Coalbed Methane through Tuning van der Waals Affinity within Isoreticular Al-Based Metal-Organic Frameworks.

Efficient separation of the CH4/N2 mixture is of great significance for coalbed methane purification. It is an effective strategy to separate this mixture by tuning the van der Waals interaction due to the nonpolar properties of CH4 and N2 molecules. Herein, we prepared several isoreticular Al-based metal-organic frameworks (MOFs) with different ligand sizes and polarities because of their high structural stability and low cost/toxicity feature of Al metal. Adsorption experiments indicated that the CH4 uptake, Qst of CH4, and CH4/N2 selectivity are in the order of Al-FUM-Me (27.19 cm3(STP) g-1, 24.06 kJ mol-1 and 8.6) > Al-FUM (20.44 cm3(STP) g-1, 20.60 kJ mol-1 and 5.1) > Al-BDC (15.98 cm3(STP) g-1, 18.81 kJ mol-1 and 3.4) > Al-NDC (10.86 cm3(STP) g-1, 14.89 kJ mol-1 and 3.1) > Al-BPDC (5.90 cm3(STP) g-1, 11.75 kJ mol-1 and 2.2), confirming the synergetic effects of pore sizes and pore surface polarities. Exhilaratingly, the ideal adsorbed solution theory selectivity of Al-FUM-Me is higher than those of all zeolites, carbon materials, and most water-stable MOF materials (except Al-CDC and Co3(C4O4)2(OH)2), which is comparable to MIL-160. Breakthrough results demonstrate its excellent separation performance for the CH4/N2 mixture with good regenerability. The separation mechanism of Al-FUM-Me for the CH4/N2 mixture was elucidated by theoretical calculations, showing that the stronger affinity of CH4 can be attributed to its relatively shorter interaction distance with adsorption binding sites. Therefore, this work not only offers a promising candidate for CH4/N2 separation but also provides valuable guidance for the design of high-performance adsorbents.

Spray-drying-assisted fabrication of CaF2/SiO2 nanoclusters for dental restorative composites.

OBJECTIVE: The objective of this study is to develop novel CaF2/SiO2 nanoclusters (NCs) fillers, which can endow the dental resin composites (DRCs) with excellent mechanical properties, stable and sustained fluoride ion release, and good antibacterial activity. METHODS: The CaF2/SiO2 NCs were efficiently fabricated by assembling CaF2/SiO2 nanoparticles (NPs) as building blocks with a spray-drying technology. CaF2/SiO2 NCs with different SiO2 coating amounts (20 wt%, 50 wt% and 80 wt%) were incorporated into the DRCs at the filler content of 55 wt% for the measurement of mechanical properties including flexural strength, flexural modulus, compressive strength, and hardness. The effect of the filling amount of CaF2/50SiO2 NCs (50 represents 50 wt% SiO2 coating amount) in the DRCs was investigated, while CaF2/50SiO2 NPs were adopted as comparison group. The fluoride ion release and antibacterial activity of the DRCs with the optimal mechanical performances were evaluated. Furthermore, the statistical analyses were performed for mechanical properties. RESULTS: Spherical CaF2/50SiO2 NCs with an average size of 2.4 µm were obtained at the feed rate of 7.4 mL/min and the CaF2/50SiO2 NPs solid content of 2 wt% in the suspension. The optimum comprehensive performances of the DRCs can be achieved by filling 55 wt% CaF2/50SiO2 NCs. Compared with CaF2/50SiO2 NPs, the filling amount of CaF2/50SiO2 NCs was increased by 5 wt% (50-55 wt%), and under the same filling amount of 50 wt%, the flexural strength, flexural modulus, compressive strength, and hardness of the DRCs containing CaF2/50SiO2 NCs were improved by 9.8%, 17.7%, 7.5% and 69.8%, respectively. Furthermore, the DRCs filled with 50 wt% CaF2/50SiO2 NCs exhibited more cumulative F-release by 126% and more stable F-release rate than the counterpart filled with 50 wt% CaF2/50SiO2 NPs after immersed for 1800 h. And 55 wt% CaF2/50SiO2 NCs filled DRCs could inhibit the growth of S. mutans, reaching an antibacterial ratio of 93%. SIGNIFICANCE: The spray-dried CaF2/50SiO2 NCs are promising fillers for the development of high-performance multifunctional DRCs.

Defect-Rich, Highly Porous PtAg Nanoflowers with Superior Anti-Poisoning Ability for Efficient Methanol Oxidation Reaction.

The design of efficient and sustainable Pt-based catalysts is the key to the development of direct methanol fuel cells. However, most Pt-based catalysts still exhibit disadvantages including unsatisfied catalytic activity and serious CO poisoning in the methanol oxidation reaction (MOR). Herein, highly porous PtAg nanoflowers (NFs) with rich defects are synthesized by using liquid reduction combining chemical etching. It is demonstrated that the proportion of precursors determines the inhomogeneity of alloy elements, and the strong corrosiveness of nitric acid to silver leads to the eventual porous flower-like structure. Impressively, the optimal etched Pt1 Ag2 NFs have the mixed defects of surface steps, dislocations, and bulk holes, and their mass activity (1136 mA mgPt-1 ) is 2.6 times higher than that of commercial Pt/C catalysts, while the ratio of forward and backward peak current density (If /Ib ) can reach 3.2, exhibiting an excellent anti-poisoning ability. Density functional theory calculations further verify their high anti-poison properties from both an adsorption and an oxidation perspective of CO intermediate. The introduction of Ag makes it easier for CO to be oxidized and removed. This study provides a facile approach to prepare rich defects and porous alloy with excellent MOR performance and superior anti-poisoning ability.

Spray drying-assisted construction of hierarchically porous ZIF-8 for controlled release of doxorubicin.

The intrinsic properties and structure of carrier materials, as well as the drug-loading method, are crucial to the fabrication of high-performance controlled drug release systems. Metal-organic frameworks (MOFs) have attracted great attention in drug delivery due to their rich variety and very precisely designable structures, but their inherent small pores limit their application towards large-size drug molecules. Herein, we report a facile and efficient approach for the construction of hierarchically porous ZIF-8 (HP-ZIF-8) by spray drying. The homogeneously distributed mesopores, which result from the interspaces in the closely arranged nanosized ZIF-8 (N-ZIF-8), can be tuned by adjusting the primary particle size. More importantly, a drug (doxorubicin (DOX), for example) can be simultaneously encapsulated during the fabrication process of HP-ZIF-8, achieving a high loading rate of 79% and an encapsulation efficiency of 79%. Furthermore, we demonstrate that the obtained DOX@HP-ZIF-8 is a pH-responsive system and the release can also be controlled by the mesopore size. Although HP-ZIF-8 shows obvious advantages in drug loading and release performance compared with N-ZIF-8 loaded with DOX by the same solvent adsorption approach, DOX@HP-ZIF-8 displays significantly increased loading capacity (more than 3 times) and the slowest release rate due to its drug-loading method. Their therapeutic efficacy on HeLa cells has also been proved. These findings have important implications for the construction of HP-MOFs as drug carriers and will also present a new platform for controlled drug release and biomedical applications.

Macro-Meso-Microporous Metal-Organic Frameworks: Template-Assisted Spray Drying Synthesis and Enhanced Catalysis.

Hierarchically porous metal-organic frameworks (HP-MOFs) are promising in many applications. However, most previous studies focus on HP-MOFs with two kinds of pore structures. Herein, a strategy for efficient construction of HP-MOFs possessing macro-meso-micropores using template-assisted spray drying followed by etching process is proposed. Taking ZIF-8 as an example, using polystyrene (PS) templates, the complete HP-ZIF-8 with all the three categories of pores can be easily fabricated. The close arrangement of intrinsic microporous nanosized ZIF-8 (N-ZIF-8) in the spray drying process results in the creation of mesopores, while the macropores are further generated after the removal of PS templates. The structures of macropores and mesopores can be easily adjusted by altering the size and proportion of PS and the size of N-ZIF-8, respectively. Furthermore, this method is extended to the preparation of HP-HKUST-1. As a proof-of-concept, HP-ZIF-8 displays excellent catalytic properties in Knoevenagel reaction owing to its unique pore features. Compared with conventional microsized ZIF-8 (M-ZIF-8) with similar size, HP-ZIF-8 achieves the significantly increased conversion of benzaldehyde from 55% to 100% within 3 h, and shows better recycling performance than N-ZIF-8.

N-Doped MoS2 Nanoflowers for Efficient Cr(VI) Removal.

The removal of Cr(VI) has attracted extensive attention since it causes serious harm to public health. Herein, we report a two-step method to synthesize N-doped MoS2 nanoflowers (NFs) with controllable sizes, which are first utilized for Cr(VI) removal and display outstanding removal performance. The N-MoS2 NFs with an average size of 40 nm (N-MoS2 NFs-40 nm) can rapidly remove Cr(VI) in 15 min under optimal conditions. The maximum adsorption capacity of N-MoS2 NFs-40 nm can reach 787.41 mg·g-1, which is significantly larger than that of N-MoS2 NFs-150 and -400 nm (314.46 and 229.88 mg·g-1). Meanwhile, N-MoS2 NFs-400 nm have a higher maximum adsorption capacity than pure MoS2 NFs-400 nm (172.12 mg·g-1). In this adsorption/reduction process, N-MoS2 NFs have abundant adsorption sites due to a high surface area. N doping can generate more sulfur vacancy defects in the MoS2 NF structure to accelerate electron transfer and enhance the reduction of Cr(VI) to low-toxicity Cr(III). This study provides a facile approach to fabricating N-MoS2 nanoflowers and demonstrates their superior removal ability for Cr(VI).