Using Metal-Organic Framework HKUST-1 for the Preparation of High-Conductive Hybrid Membranes Based on Multiblock Copolymers for Fuel Cells.

Novel proton-conducting hybrid membranes consisting of sulfonated multiblock copolymer of polysulfone and polyphenylsulfone (SPES) reinforced with a HKUST-1 metal-organic framework (MOF) (5, 10, and 20 wt. %) were prepared and characterized for fuel cell applications. The presence of the MOF in the copolymer was confirmed by means of FE-SEM and EDS. The hybrid membranes show a lower contact angle value than the pure SPES, in agreement with the water uptake (WU%), i.e., by adding 5 wt. % of the MOF, this parameter increases by 20% and 40% at 30 °C and 60 °C, respectively. Additionally, the presence of the MOF increases the ion exchange capacity (IEC) from 1.62 to 1.93 mequivH+ g−1. Thermogravimetric analysis reveals that the hybrid membranes demonstrate high thermal stability in the fuel cell operation temperature range (<100 °C). The addition of the MOF maintains the mechanical stability of the membranes (TS > 85 MPa in the Na+ form). Proton conductivity was analyzed using EIS, achieving the highest value with a 5 wt. % load of the HKUST-1. This value is lower than that observed for the HKUST-1/Nafion system. However, polarization and power density curves show a remarkably better performance of the hybrid membranes in comparison to both the pure SPES and the pure Nafion membranes.

Cancer-Associated Dysregulation of Sumo Regulators: Proteases and Ligases.

SUMOylation is a post-translational modification that has emerged in recent decades as a mechanism involved in controlling diverse physiological processes and that is essential in vertebrates. The SUMO pathway is regulated by several enzymes, proteases and ligases being the main actors involved in the control of sumoylation of specific targets. Dysregulation of the expression, localization and function of these enzymes produces physiological changes that can lead to the appearance of different types of cancer, depending on the enzymes and target proteins involved. Among the most studied proteases and ligases, those of the SENP and PIAS families stand out, respectively. While the proteases involved in this pathway have specific SUMO activity, the ligases may have additional functions unrelated to sumoylation, which makes it more difficult to study their SUMO-associated role in cancer process. In this review we update the knowledge and advances in relation to the impact of dysregulation of SUMO proteases and ligases in cancer initiation and progression.

Characterization and Modeling of Free Volume and Ionic Conduction in Multiblock Copolymer Proton Exchange Membranes.

Free volume plays a key role on transport in proton exchange membranes (PEMs), including ionic conduction, species permeation, and diffusion. Positron annihilation lifetime spectroscopy and electrochemical impedance spectroscopy are used to characterize the pore size distribution and ionic conductivity of synthesized PEMs from polysulfone/polyphenylsulfone multiblock copolymers with different degrees of sulfonation (SPES). The experimental data are combined with a bundle-of-tubes model at the cluster-network scale to examine water uptake and proton conduction. The results show that the free pore size changes little with temperature in agreement with the good thermo-mechanical properties of SPES. However, the free volume is significantly lower than that of Nafion®, leading to lower ionic conductivity. This is explained by the reduction of the bulk space available for proton transfer where the activation free energy is lower, as well as an increase in the tortuosity of the ionic network.

On the Conductivity of Proton-Exchange Membranes Based on Multiblock Copolymers of Sulfonated Polysulfone and Polyphenylsulfone: An Experimental and Modeling Study.

The effect of relative humidity (RH) and degree of sulfonation (DS) on the ionic conductivity and water uptake of proton-exchange membranes based on sulfonated multiblock copolymers composed of polysulfone (PSU) and polyphenylsulfone (PPSU) is examined experimentally and numerically. Three membranes with a different DS and ion-exchange capacity are analyzed. The heterogeneous structure of the membranes shows a random distribution of sulfonated (hydrophilic) and non-sulfonated (hydrophobic) domains, whose proton conductivity is modeled based on percolation theory. The mesoscopic model solves simplified Nernst-Planck and charge conservation equations on a random cubic network. Good agreement is found between the measured ionic conductivity and water uptake and the model predictions. The ionic conductivity increases with RH due to both the growth of the hydrated volume available for conduction and the decrease of the tortuosity of ionic transport pathways. Moreover, the results show that the ionic conductivity increases nonlinearly with DS, experiencing a strong rise when the DS is varied from 0.45 to 0.70, even though the water uptake of the membranes remains nearly the same. In contrast, the increase of the ionic conductivity between DS=0.70 and DS=0.79 is significantly lower, but the water uptake increases sharply. This is explained by the lack of microphase separation of both copolymer blocks when the DS is exceedingly high. Encouragingly, the copolymer membranes demonstrate a similar performance to Nafion under well hydrated conditions, which can be further optimized by a combination of numerical modeling and experimental characterization to develop new-generation membranes with better properties.