Adsorption-enhanced catalytic oxidation for long-lasting dynamic degradation of organic dyes by porous manganese-based biopolymeric catalyst.

Improving the adsorption kinetics of metal-oxide catalysts is critical for the enhancement of catalytic performance in heterogeneous catalytic oxidation reactions. Herein, based on the biopolymer pomelo peels (PP) and metal-oxide catalyst manganese oxide (MnOx), an adsorption-enhanced catalyst (MnOx-PP) was constructed for catalytic organic dyes oxidative-degradation. MnOx-PP shows excellent methylene blue (MB) and total carbon content (TOC) removal efficiency of 99.5 % and 66.31 % respectively, and keeps the long-lasting stable dynamic degradation efficiency during 72 h based on the self-built continuous single-pass MB purification device. The chemical structure similarity and negative-charge polarity sites of the biopolymer PP improve the adsorption kinetics of organic macromolecule MB, and construct the adsorption-enhanced catalytic oxidation microenvironment. Meanwhile, the adsorption-enhanced catalyst MnOx-PP obtains lower ionization potential and O2 adsorption energy to promote the continuous generation of active substance (O2*, OH*) for the further catalytic oxidation of adsorbed MB molecules. This work explored the adsorption-enhanced catalytic oxidation mechanism for the degradation of organic pollutants, and provided a feasible technical idea for designing adsorption-enhanced catalysts for the long-lasting efficient removal of organic dyes.

A window-space-directed assembly strategy for the construction of supertetrahedron-based zeolitic mesoporous metal-organic frameworks with ultramicroporous apertures for selective gas adsorption.

Despite their scarcity due to synthetic challenges, supertetrahedron-based metal-organic frameworks (MOFs) possess intriguing architectures, diverse functionalities, and superb properties that make them in-demand materials. Employing a new window-space-directed assembly strategy, a family of mesoporous zeolitic MOFs have been constructed herein from corner-shared supertetrahedra based on homometallic or heterometallic trimers [M3(OH/O)(COO)6] (M3 = Co3, Ni3 or Co2Ti). These MOFs consisted of close-packed truncated octahedral cages possessing a sodalite topology and large ß-cavity mesoporous cages (∼22 Å diameter) connected by ultramicroporous apertures (∼5.6 Å diameter). Notably, the supertetrahedron-based sodalite topology MOF combined with the Co2Ti trimer exhibited high thermal and chemical stability as well as the ability to efficiently separate acetylene (C2H2) from carbon dioxide (CO2).

Highly Efficient Removal of Methylene Blue Dye from an Aqueous Solution Using Cellulose Acetate Nanofibrous Membranes Modified by Polydopamine.

A new type of deacetylated cellulose acetate (DA)@polydopamine (PDA) composite nanofiber membrane was fabricated by electrospinning and surface modification. The membrane was applied as a highly efficient adsorbent for removing methylene blue (MB) from an aqueous solution. The morphology, surface chemistry, surface wettability, and effects of operating conditions on MB adsorption ability, as well as the equilibrium, kinetics, thermodynamics, and mechanism of adsorption, were systematically studied. The results demonstrated that a uniform PDA coating layer was successfully developed on the surface of DA nanofibers. The adsorption capacity of the DA@PDA nanofiber membrane reached up to 88.2 mg/g at a temperature of 25 °C and a pH of 6.5 after adsorption for 30 h, which is about 8.6 times higher than that of DA nanofibers. The experimental results showed that the adsorption behavior of DA@PDA composite nanofibers followed the Weber's intraparticle diffusion model, pseudo-second-order model, and Langmuir isothermal model. A thermodynamic analysis indicated that endothermic, spontaneous, and physisorption processes occurred. Based on the experimental results, the adsorption mechanism of DA@PDA composite nanofibers was also demonstrated.

Biomimetic composite scaffolds based on surface modification of polydopamine on ultrasonication induced cellulose nanofibrils (CNF) adsorbing onto electrospun thermoplastic polyurethane (TPU) nanofibers.

To improve the interaction between cells and scaffolds, the appropriate surface chemical property is very important for tissue engineering scaffolds. In this study, the thermoplastic polyurethane (TPU) nanofibers was firstly fabricated by electrospinning technique, and then its surface was modified with cellulose nanofibrils (CNF) particles by ultrasonic-assisted to obtain TPU/CNF nanofibers. Subsequently, the TPU/CNF-polydopamine (PDA) composite nanofibers with core/shell structure were fabricated by PDA coating method. In comparison with TPU nanofibers, the uniformization of PDA coating layer on the surface of TPU/CNF composite nanofibers significantly increased due to the addition of CNF, which used as the active sites to guide the PDA particles accumulated along with the fiber direction. The water absorption and hydrophilicity of TPU/CNF-PDA composite nanofibers were significantly increased in comparison with those of TPU and TPU/CNF nanofibers. The mechanical properties of the TPU/CNF-PDA composite nanofibers were higher than those of the TPU and TPU/CNF nanofibers due to the formation of strong hydrogen bonds between PDA and TPU/CNF, making TPU, CNF and PDA strongly adhere to each other. The attachment and viability of mouse embryonic osteoblasts cells (MC3T3-E1) cultured on TPU/CNF-PDA composite nanofibers were obviously enhanced compared with TPU and TPU/CNF nanofibers. Those results suggested that the modified TPU/CNF-PDA composite nanofibers have excellent mechanical and biological properties, which promoting them potentially useful for tissue engineering scaffolds. The presented strategy represents a general route to modify the surface of scaffolds, which are promising for tissue engineering applications.

Dual super-amphiphilic modified cellulose acetate nanofiber membranes with highly efficient oil/water separation and excellent antifouling properties.

Along with increasing oily, industrial wastewater and seawater pollution, oil spills-and their clean-up via the separation of oil and water-are still a worldwide challenge. Aiming to fabricate an oil/water separation membrane with excellent comprehensive performance, we report here a new type of multifunctional deacetylated cellulose acetate (d-CA) membrane. The cellulose acetate (CA) nanofiber membranes are fabricated by electrospinning and then deacetylated to obtain the d-CA nanofiber membranes, which are super-amphiphilic in air, oleophobic in water, and super-hydrophilic in oil. The multifunctional d-CA nanofiber membranes can be used as water-removal substances for oil/water mixtures, as well as emulsified oil/water and oil/corrosive aqueous systems, with gravity as the only needed driving force. The d-CA nanofiber membranes possess the highest separation flux, reaching up to 38,000 L/m2·h, and the highest separation efficiency, reaching up to 99.97 % for chloroform/water mixtures under the force of gravity. In fact, the separation flux was several times higher than that of commercial CA (c-CA) membranes. The excellent anti-pollution and self-cleaning abilities endow the membranes with powerful cyclic stability and reusability. The d-CA nanofiber membranes show great application prospects in chemical plants, textile mills, and the food industry, as well as offshore oil spills, to separate oil from water.

Biomimetic composite scaffolds based on surface modification of polydopamine on electrospun poly(lactic acid)/cellulose nanofibrils.

An appropriate surface chemical property is crucial in tissue engineering scaffolds, which promotes cell attachment and proliferation. A biomimetic composite scaffold with a polydopamine (PDA) coating layer on electrospun poly(lactic acid) (PLA)/cellulose nanofibrils (CNF) composite nanofiber was developed in this study. PLA/CNF composite nanofibers were fabricated and then coated via treatment with a dopamine solution. The PDA coating layer was successfully formed on the surface of the PLA/CNF composite nanofiber by using a simple, environment-friendly, and effective procedure. Results indicated that the addition of CNF into the PLA matrix can effectively improve the deposition rate of the PDA coating layer on the surface of the composite nanofiber during the initial stage of coating because of hydrogen bonding between the CNF and PDA molecular chains. The hydrophilicity and mechanical properties of the PLA/CNF-PDA scaffold were higher than those of the PLA/CNF scaffold. In addition, the cell culture test showed that the adhesion, proliferation, and growth of human mesenchymal stem cells (hMSCs) cultured on the PLA/CNF-PDA scaffold were significantly enhanced relative to those cultured on the PLA/CNF scaffold because of the introduction of the PDA coating. This finding suggested that surface biofunctionalization via the PDA coating layer could simply and effectively enhance cell biocompatibility for polymer-based scaffolds.

Surface biofunctionalization of three-dimensional porous poly(lactic acid) scaffold using chitosan/OGP coating for bone tissue engineering.

As one of the stimulators on bone formation, osteogenic growth peptide (OGP) improves both proliferation and differentiation of the bone cells in vitro and in vivo. The aim of this work was the preparation of three dimensional porous poly(lactic acid) (PLA) scaffold with high porosity from PLA-dioxane-water ternary system with the use of vacuum-assisted solvent casting, phase separation, solvent extraction and particle leaching methods. Then, by surface coating of PLA scaffold with chitosan (CS)/OGP solution, biofunctionalization of PLA scaffold had been completed for application in bone regeneration. The effects of frozen temperature (-20, -50, -80°C) and PLA solution concentration (10, 12, 14wt%) on the microstructure, water absorption, porosity, hydrophilicity, mechanical properties, and biocompatibility of PLA and CS/OGP/PLA scaffold were investigated. Results showed that both PLA and CS/OGP/PLA scaffolds have an interconnected network structure and a porosity of up to 96.1% and 91.5%, respectively. The CS/OGP/PLA scaffold exhibited better hydrophilicity and mechanical properties than that of uncoated PLA scaffold. Moreover, the results of cell culture test showed that CS/OGP coating could stimulate the proliferation and growth of osteoblast cells on CS/OGP/PLA scaffold. These finding suggested that the surface biofunctionalization by CS/OGP coating layer could be an effective method on enhancing cell adhesion to synthetic polymer-based scaffolds in tissue engineering application and the developed porous CS/OGP/PLA scaffold should be considered as alternative biomaterials for bone regeneration.

Fabrication and characterization of chitosan/OGP coated porous poly(ε-caprolactone) scaffold for bone tissue engineering.

As one of the stimulators on bone formation, osteogenic growth peptide (OGP) improves both proliferation and differentiation of the bone cells in vitro and in vivo. The aim of this work was the preparation of three dimensional porous poly(ε-caprolactone) (PCL) scaffold with high porosity, well interpore connectivity, and then its surface was modified by using chitosan (CS)/OGP coating for application in bone regeneration. In present study, the properties of porous PCL and CS/OGP coated PCL scaffold, including the microstructure, water absorption, porosity, hydrophilicity, mechanical properties, and biocompatibility in vitro were investigated. Results showed that the PCL and CS/OGP-PCL scaffold with an interconnected network structure have a porosity of more than 91.5, 80.8%, respectively. The CS/OGP-PCL scaffold exhibited better hydrophilicity and mechanical properties than that of uncoated PCL scaffold. Moreover, the results of cell culture test showed that CS/OGP coating could stimulate the proliferation and growth of osteoblast cells on CS/OGP-PCL scaffold. These finding suggested that the surface modification could be a effective method on enhancing cell adhesion to synthetic polymer-based scaffolds in tissue engineering application and the developed porous CS/OGP-PCL scaffold should be considered as alternative biomaterials for bone regeneration.

Biomimetic composite scaffolds based on mineralization of hydroxyapatite on electrospun poly(ɛ-caprolactone)/nanocellulose fibers.

A biomimetic nanocomposite scaffold with HA formation on the electrospun poly(ɛ-caprolactone) (PCL)/nanocellulose (NC) fibrous matrix was developed in this study. The electrospun PCL/NC fiber mat was built and then biomineralized by treatment in simulated body fluid (SBF). Using such a rapid and effective procedure, a continuous biomimetic crystalline HA layer could be successfully formed without the need of any additional chemical modification of the substrate surface. The results showed that the introduction of NC into composite fibers is an effective approach to induce the deposition of HA nucleus as well as to improve their distribution and growth of a crystalline HA layer on the fibrous scaffolds. The water contact angle (WCA) of the PCL/NC/HA scaffolds decreases with increasing NC content and mineralization time, resulting in the enhancement of their hydrophilicity. These results indicated that HA-mineralized on PCL/NC fiber can be prepared directly by simply using SBF immersion.