Anion exchange membrane fuel cells (AEMFCs) have been developed as promising energy conversion devices for stationary and mobile applications due to their potentially low cost. To realize high-performance AEMFCs, new polymeric membranes are needed that are highly conductive and chemically stable. Here we report a systematic study of anion exchange membranes (AEMs) with multiple cations per side chain site to demonstrate how this motif can boost both the conductivity and stability of poly(2,6-dimethyl-1,4-phenylene oxide)-based AEMs. The highest conductivity, up to 99 mS/cm at room temperature, was observed for a triple-cation side chain AEM with 5 or 6 methylene groups between cations. This conductivity was considerably higher than AEM samples based on benzyltrimethylammonium or benzyldimethylhexylammonium groups with only one cation per side chain site. In addition to high conductivity, the multication side chain AEMs showed good alkaline and dimensional stabilities. High retention of ion exchange capacity (IEC) (93% retention) and ionic conductivity (90% retention) were observed for the triple-cation side chain AEMs in degradation testing under 1 M NaOH at 80 °C for 500 h. Based on the high-performance triple-cation side chain AEM, a Pt-catalyzed fuel cell with a peak power density of 364 mW/cm2 was achieved at 60 °C under 100% related humidity.
Bipolar membranes maintain a steady pH in electrolytic cells through water autodissociation at the interface between their cation- and anion-exchange layers. We analyze the balance of electric field and catalysis in accelerating this reaction.
Currently, a serious problem obstructing the large-scale clinical applications of fluorescence technique is the shallow penetration depth. Two-photon fluorescence microscopic imaging with excitation in the longer-wavelength near-infrared (NIR) region (>1100 nm) and emission in the NIR-I region (650-950 nm) is a good choice to realize deep-tissue and high-resolution imaging. Here, we report ultradeep two-photon fluorescence bioimaging with 1300 nm NIR-II excitation and NIR-I emission (peak ∼810 nm) based on a NIR aggregation-induced emission luminogen (AIEgen). The crab-shaped AIEgen possesses a planar core structure and several twisting phenyl/naphthyl rotators, affording both high fluorescence quantum yield and efficient two-photon activity. The organic AIE dots show high stability, good biocompatibility, and a large two-photon absorption cross section of 1.22 × 10 GM. Under 1300 nm NIR-II excitation, in vivo two-photon fluorescence microscopic imaging helps to reconstruct the 3D vasculature with a high spatial resolution of sub-3.5 μm beyond the white matter (>840 μm) and even to the hippocampus (>960 μm) and visualize small vessels of ∼5 μm as deep as 1065 μm in mouse brain, which is among the largest penetration depths and best spatial resolution of in vivo two-photon imaging. Rational comparison with the AIE dots manifests that two-photon imaging outperforms the one-photon mode for high-resolution deep imaging. This work will inspire more sight and insight into the development of efficient NIR fluorophores for deep-tissue biomedical imaging.
Rationale: Cerebrovascular diseases, together with malignancies, still pose a huge threat to human health nowadays. With the advantages of its high spatial resolution and large penetration depth, fluorescence bioimaging in the second near-infrared spectral region (NIR-II, 900-1700 nm) and its related imaging-guided therapy based on biocompatible fluorescence dyes have become a promising theranostics method.Methods: The biocompatibility of IR-820 we used in NIR-II fluorescence bioimaging was verified by long-term observation. The model of the mouse with a cranial window, the mouse model of middle cerebral artery occlusion (MCAO) and a subcutaneous xenograft mouse model of bladder tumor were established. NIR-II fluorescence cerebrovascular functional imaging was carried out by IR-820 assisted NIR-II fluorescence microscopy. Bladder tumor was treated by NIR-II fluorescence imaging-guided photothermal therapy.Results: We have found that IR-820 has considerable NIR-II fluorescence intensity, and shows increased brightness in serum than in water. Herein, we achieved real time and in vivo cerebrovascular functional imaging of mice with high spatial resolution and large penetration depth, based on IR-820 assisted NIR-II fluorescence microscopy. In addition, IR-820 was successfully employed for NIR-II fluorescence imaging and photothermal therapy of tumor in vivo, and the subcutaneous tumors were inhibited obviously or eradicated completely.Conclusion: Due to the considerable fluorescence intensity in NIR-II spectral region and the good photothermal effect, biocompatible and excretable IR-820 holds great potentials for functional angiography and cancer theranostics in clinical practice.
A series of tough and chemically stable semi-interpenetrating network anion exchange membranes (SIPN AEMs) composed of a rigid and ion-conductive component, quaternized poly(2,6-dimethyl phenylene oxide) (QAPPO), and a hydrophilic, cross-linked, flexible poly(ethylene glycol)-co-poly(allyl glycidyl ether) (xPEG–PAGE) component were synthesized. The SIPN AEMs containing both rigid and flexible polymer constituents exhibited outstanding mechanical strength and flexibility and were much tougher than conventional QAPPO membranes. The introduction of the hydrophilic network ensured SIPN AEMs with high hydration numbers, which contributed to the high ion conductivity of these materials. The physical properties of the SIPN AEMs could be varied by the mass fractions of the QAPPO and xPEG–PAGE components, and a trade-off was observed between the samples’ conductive and swelling properties. Among the compositions studied, SIPN-60-2 (MassQAPPO‑60/MassPEG–PAGE = 2:1) with an IEC of 1.43 mmol/g was found to have balanced ionic conductivity (67.7 mS/cm at 80 °C) and swelling ratio (26% at 80 °C). The alkaline stabilities of the SIPN AEMs were evaluated in 1 M NaOH at 80 °C for 30 days. Good mechanical (72% and 74% retention in tensile strength and elongation at break, respectively) and dimensional (11% increase in water uptake) stability was retained by the SIPN AEM due to the presence of the alkali-resistant xPEG–PAGE network. The quaternary ammonium groups in SIPN-60-2 were found to be relatively stable (24% and 26% decrease in IEC and OH– conductivity in 1 M NaOH at 80 °C for 30 days, respectively), and the low initial IEC and the high dimensional stability of the membrane protected the cation from severe degradation during the extended aging test.
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