Development of High-Performance Iron-Based Phosphate Cathodes toward Practical Na-Ion Batteries.

Iron-based phosphate cathode of Na4Fe3(PO4)2(P2O7) has been regarded as a low-cost and structurally stable cathode material for Na-ion batteries (NIBs). However, their practical application is greatly hindered by the insufficient electrochemical performance and limited energy density. Here, we report a new iron-based phosphate cathode of Na4.5Fe3.5(PO4)2.5(P2O7) with the intergrown heterostructure of the maricite-type NaFePO4 and orthorhombic Na4Fe3(PO4)2(P2O7) phases at a mole ratio of 0.5:1. Benefited from the increased composition ratio and the spontaneous activation of the maricite-type NaFePO4 phase, the as-prepared Na4.5Fe3.5(PO4)2.5(P2O7) composites deliver a reversible capacity over 130 mA h g-1 and energy density close to 400 W h kg-1, which is far beyond that of the single-phase Na4Fe3(PO4)2(P2O7) cathode (∼120 mA h g-1 and ∼350 W h kg-1). Moreover, the kg-level products from the scale-up synthesis demonstrate a stable cycling performance over 2000 times at 3 C in pouch cells. We believe that our findings could show the way forward the practical application of the iron-based phosphate cathodes for NIBs.

Interaction between reduced glutathione and PEO-PPO-PEO copolymers in aqueous solutions: studied by 1H NMR and spin-lattice relaxation.

In order to investigate the effect of PEO-PPO-PEO copolymers on the glutathione (GSH)/glutathione-S-transferase (GST) detoxification system, interaction between the copolymers and GSH is studied by NMR measurements. Selective rotating-frame nuclear Overhauser effect (ROE) experiment confirms that glutamyl (Glu) α-H of GSH has spatial contact with EO methylene protons. Spin-lattice relaxation times of GSH Glu α-H show a decrease when PEO-PPO-PEO copolymers are added, and the decrease is greater with copolymers possessing more EO units. Other protons of GSH show little change in the presence of the copolymers. The addition of GSH promotes the dehydration of PEO-PPO-PEO copolymers. This results from the breaking of hydrogen bonds between water and the polymers and the forming of hydrogen bonds between Glu α-carboxylate protons and oxygen atoms of EO units. The dissociation constant between GSH and P85 copolymer is determined by spin-lattice relaxation measurements, which shows the binding is of low affinity and the two molecules are in fast dissociation kinetics. This study suggests that GSH transporting or utilizing systems may be affected by treatment of PEO-PPO-PEO copolymers.

Dual responsive copolymer micelles for drug controlled release.

pH- and temperature-responsive polymeric drug carriers based on Chitosan oligosaccharide (CSO)-g-Pluronic copolymers were successfully synthesized for Doxorubicin (DOX) controlled release. The critical aggregation concentration of CSO-g-Pluronic is 0.035 mg/mL at 25 degrees C. The CSO-g-Pluronic and DOX-loaded CSO-g-Pluronic micelles have an average hydrodynamic diameter of 23.3 nm and 43.6 nm respectively at 30 degrees C and pH 7.0 with narrow size distribution. The temperature or pH responsive behavior of the micelles was characterized by dynamic light scattering, fluorescence spectroscopy, and zeta Potential Analysis. The temperature-dependent micellar transformation was induced by dehydration of Pluronic segments at higher temperature. The pH responsive volume increase was traced to the electrostatic repulsion between CSO segments from protonation of amino groups under acidic conditions. Consequently, the DOX release time was prolonged by CSO-g-Pluronic micelles at body temperature of 37 degrees C, and the DOX release was accelerated at mild acidic conditions (i.e. the pH environment around tumor tissues). The temperature- and pH-responsive properties of CSO-g-Pluronic copolymer have provided promising potentials for biomedical and biotechnological applications.

Spontaneous vesicle formation of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer.

A novel method has been developed to prepare vesicles from aqueous solutions of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer, by adding anionic surfactant sodium dodecyl sulfate (SDS) and inorganic salt NaF. As determined by TEM and dynamic light scattering (DLS) measurements, the average diameter of vesicles is about 800 nm having 50 nm outer shell thickness. Identifying hydrophobic interactions between the block copolymers and the microenvironments around the vesicles using FTIR, 1H NMR, and fluorescence spectroscopy techniques revealed the vesicle formation mechanism. The spontaneously formed vesicles were further cross-linked by converting the terminal hydroxyl groups of block copolymers into aldehydes, and then chemically bridging the polymer chains by the reaction between aldehydes and diamine compounds. The cross-linked vesicles are proved much more stable than free vesicles even at higher dilutions. The obtained vesicles with good stability and biocompatibility are promising candidates for widespread applications.