Construction of Successive Proton Conduction Channels to Accelerate the Proton Conduction Process in Flexible Proton Exchange Membranes.

Successive proton conduction channels are constructed with the spin coating method in flexible proton exchange membranes (PEMs). In this research, phosphoric acid (PA) molecules are immobilized in the multilayered microstructure of Kevlar nanofibers and polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) polymer molecular chains. As a result, successive proton conduction channels can accelerate the proton conduction process in the prepared membrane with the multilayered microstructure. Additionally, the microstructure fractures of the composite membranes from the external force of folding and stretching operations are modified by the inner PA molecules. Notably, numerous PA molecules are further combined through formed intermolecular hydrogen bonding. The stretched membrane absorbs more PA molecules owing to the arrangement of PA molecules, Kevlar nanofibers, and SEBS molecular chains. The stretched membrane thus exhibits the enhanced proton conduction ability, such as the through-plane proton conductivity of 1.81 × 10-1 S cm-1 at 160 °C and that of 4.53 × 10-2 S cm-1 at 120 °C lasting for 600 h. Furthermore, the tensile stress of PA-doped stretched membranes reaches (3.91 ± 0.40)-(6.15 ± 0.43) MPa. A single proton exchange membrane fuel cell exhibits a peak power density of 483.3 mW cm-2 at 120 °C.

Constructing anhydrous proton exchange membranes based on cadmium telluride nanocrystal-doped sulfonated poly(ether ether ketone)/polyurethane composites.

Cadmium telluride (CdTe) nanocrystals with thiol stabilizers have been applied widely in the fields of energy storage and transformation. The aim of this work is to develop anhydrous proton exchange membranes (PEMs) by introducing CdTe nanocrystals bearing thioglycolic acid (tga) or mercaptopropionic acid (mpa) stabilizers into sulfonated poly(ether ether ketone) (SPEEK) and polyurethane (PU) systems. In the prepared SPEEK/PU/CdTe membranes, CdTe nanocrystals could provide desirable properties such as improving mechanical strength and enhancing proton conductivity by combining with phosphoric acid (PA) molecules. Successful preparation of SPEEK/PU/CdTe/PA membranes was demonstrated by the identification of high and stable proton conductivity and satisfactory thermal/chemical stability and mechanical properties. The fine appearance of membranes revealed uniform dispersion of components. Measurements of properties showed that the SPEEK(74%)/PU/CdTe-mpa(20/60/20)/100%PA membrane as a candidate anhydrous PEM is promising for use in high-temperature proton exchange membrane fuel cells. Specifically, the recommended membrane showed a proton conductivity of 1.18 × 10-1 S cm-1 at 160 °C and 3.96 × 10-2 S cm-1 at 100 °C, lasting for 600 h, and a tensile stress of 14.6 MPa at room temperature. Mixing inorganic CdTe nanocrystals with polymers to form inorganic/organic composite membranes is effective for producing anhydrous PEMs with cheaper polymers without functional groups to conduct protons.

Fabrication of layered membrane electrolytes with spin coating technique as anhydrous proton exchange membranes.

Spin coating technique is a simple and effective method to fabricate layered membranes and it has been widely used in the field of energy storage and transformation, biomaterials and electronics. The aim of this work is to develop anhydrous proton exchange membranes (PEMs) based on cheap polymers bearing the simple structure with spin coating technique. Successful fabrication of anhydrous PEMs based on polyvinylidene fluoride (PVDF) polymer, cadmium telluride (CdTe) nanocrystals and phosphoric acid (PA) molecules has been demonstrated by identification of high and stable proton conductivity. Specifically, (PVDF-CdTe-PA)5/85%PA membranes present the maximum proton conductivity of 7.70 × 10-2 S/cm at 160 °C and 1.42 × 10-2 S/cm at 140 °C lasting 620 h. The decreased proton conduction resistance is revealed from the drastic reduction of activation energy (Ea) owing to the layered structure and the adsorption of PA molecules. The introduction of CdTe nanocrystals to form the organic/inorganic composite membranes that is substantially more effective at improving proton conductivity and stiffness, showing great promise in solving the dilemma of proton conductivity and mechanical property. This study provides the support to exploit anhydrous PEMs with more cheap polymers using spin coating technique.

Anomalously Fast Diffusion of Targeted Carbon Nanotubes in Cellular Spheroids.

Understanding transport of carbon nanotubes (CNTs) and other nanocarriers within tissues is essential for biomedical imaging and drug delivery using these carriers. Compared to traditional cell cultures in animal studies, three-dimensional tissue replicas approach the complexity of the actual organs and enable high temporal and spatial resolution of the carrier permeation. We investigated diffusional transport of CNTs in highly uniform spheroids of hepatocellular carcinoma and found that apparent diffusion coefficients of CNTs in these tissue replicas are anomalously high and comparable to diffusion rates of similarly charged molecules with molecular weights 10000× lower. Moreover, diffusivity of CNTs in tissues is enhanced after functionalization with transforming growth factor ß1. This unexpected trend contradicts predictions of the Stokes-Einstein equation and previously obtained empirical dependences of diffusivity on molecular mass for permeants in gas, liquid, solid or gel. It is attributed to the planar diffusion (gliding) of CNTs along cellular membranes reducing effective dimensionality of diffusional space. These findings indicate that nanotubes and potentially similar nanostructures are capable of fast and deep permeation into the tissue, which is often difficult to realize with anticancer agents.

Anion exchange membranes based on semi-interpenetrating polymer network of quaternized chitosan and polystyrene.

Anion exchange membranes with semi-interpenetrating polymer network (semi-IPN) were prepared based on quaternized chitosan (QCS) and polystyrene (PS). The PS was synthesized by polymerization of styrene monomers in the emulsion of the QCS in an acetic acid aqueous solution under nitrogen atmosphere at elevated temperatures. The semi-IPN system was formed by post-cross-linking of the QCS. A hydroxyl ionic conductivity of 2.80×10(-2) S cm(-1) at 80°C and a tensile stress at break of 20.0 MPa at room temperature were reached, respectively, by the semi-IPN membrane containing 21 wt.% of the PS. The durability of the semi-IPN membrane in alkaline solutions was tested by monitoring the variation of the conductivity and the mechanical strength. The degradation of the conductivity at 80°C was about 5% by immersing the membrane in a 1 mol L(-1) KOH solution at room temperature for 72 h and at 60°C for 50 h, respectively. The tensile stress at break at room temperature could maintain about 20.0 MPa for the membrane soaking in a 10 mol L(-1) KOH solution at ambient temperature for more than 70 h. The water swelling of the semi-IPN membranes was discussed based on the stress relaxation model of polymer chains, and it obeyed the Schott's second-order swelling kinetics.