To endow hydrophobic poly(vinylidene fluoride) (PVDF) membranes with reliable hydrophilicity and protein resistance, an amphiphilic hyperbranched-star polymer (HPE-g-MPEG) with about 12 hydrophilic arms in each molecule was synthesized by grafting methoxy poly(ethylene glycol) (MPEG) to the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent and blended with PVDF to fabricate porous membranes via phase inversion process. The chemical composition changes of the membrane surface were confirmed by X-ray photoelectron spectroscopy (XPS), and the membrane morphologies were measured by scanning electron microscopy (SEM). Water contact angle, static protein adsorption, and filtration experiments were used to evaluate the hydrophilicity and anti-fouling properties of the membranes. It was found that MPEG segments of HPE-g-MPEG enriched at the membrane surface substantially, while the water contact angle decreased as low as 49 degrees for the membrane with a HPE-g-MPEG/PVDF ratio of 3/10. More importantly, the water contact angle of the blend membrane changed little after being leached continuously in water at 60 degrees C for 30 days, indicating a quite stable presence of HPE-g-MPEG in the blend membranes. Furthermore, the blend membranes showed lower static protein adsorption, higher water and protein solution fluxes, and better water flux recovery after cleaning than the pure PVDF membrane.

A major problem in membrane technology for applications such as wastewater treatment or desalination is often the loss of membrane permeability due to biofouling initiated from protein adsorption and biofilm formation on the membrane surface. In this study, we developed a relatively simple and yet versatile approach to prepare polypropylene (PP) membrane with highly effective non-biofouling performance. Copolymer brushes were grafted to the surface of PP membrane through UV-induced polymerization of two oppositely charged monomers, i.e., [2-(methacryloyloxy)ethyl]trimethylammonium chloride (TM) and 3-sulfopropyl methacrylate potassium salt (SA), with varying TM:SA molar ratios. Surface analysis with scanning electron microscope (SEM) clearly showed the grafted copolymer brushes on the membrane surfaces and that with X-ray photoelectron spectroscope (XPS) revealed a similar TM:SA ratio of the grafted copolymer brushes to that of the monomer solution used for the polymerization. Water contact angle measurements indicated that the hydrophilicity of the membrane surfaces was remarkably improved by the grafting of the TM/SA copolymer brushes, with the lowest water contact angle of 27 degrees being achieved at the TM:SA ratio of around 1:1. Experiments for antiprotein adsorption with bovine serum album (BSA) and lysozyme (LYZ) and antibiofilm formation with Escherichia coli (E. coli) demonstrated a great dependence of the membrane performance on the TM:SA ratios of the grafted copolymer brushes. It was found that the characteristics of the surface charges of the membrane surfaces played a very important role in the non-biofouling performance, and the membrane surface with balanced positive and negative charges showed the best non-biofouling performance for the proteins and bacteria tested in this study.

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A novel electrolyte-responsive membrane, RC-g-PSBMA, was successfully prepared from regenerated cellulose (RC) membrane through surface-initiated atom transfer radical polymerization (ATRP) of a zwitterionic monomer, sulfobetaine methacrylate (SBMA). Different degrees of polymerization for the grafted SBMA polymers (i.e., PSBMA) on the RC membrane were easily obtained by adjusting the ATRP reaction conditions. The electrolyte-responsive behavior of RC-g-PSBMA was first evaluated through the permeation experiments with sodium chloride (NaCl) solutions of different concentrations. It was found that the permeability of RC-g-PSBMA showed a clear dependence on NaCl concentration in the solutions. To further examine the potential of RC-g-PSBMA for protein purification, bovine serum album (BSA) was chosen as a model protein and polystyrene nanoparticles (NPs) of different sizes were used as representative impurities in the solutions. The rejection rates of BSA and NPs by RC-g-PSBMA were examined with the solutions containing BSA and NPs at different NaCl concentrations. The results showed that the rejection rates of BSA were at a very low level regardless of the concentration of NaCl in the solutions, indicating that the membrane allowed BSA to permeate. However, the rejection rates of NPs of different sizes by RC-g-PSBMA changed remarkably with the concentration of NaCl in the solutions. The study has demonstrated the possibility to separate BSA from NPs of different sizes by using the same membrane but simply altering the concentration of NaCl in the solutions. Membranes with such properties will have a great potential for protein purification as well as for many other separation applications.

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Inhibition of the programmed cell death-1 (PD-1)/programmed cell death-ligand 1 (PD-L1) interaction using small-molecule inhibitors is an emerging immunotherapeutic approach. A novel series of [1,2,4]­triazolo­[4,3-a]­pyridines were designed and found to be potent inhibitors of the PD-1/PD-L1 interaction. Among them, compound A22 exhibited the most potent activity, as assessed by homogenous time-resolved fluorescence assay, with an IC50 of 92.3 nM. Furthermore, A22 dose-dependent elevated interferon-γ production in a co-culture model of Hep3B/OS-8/hPD-L1 and CD3 T cells. We concluded that A22 is a promising lead compound for the development of inhibitors of the PD-1/PD-L1 interaction. In addition, we explored the structure–activity relationships of the newly synthesized [1,2,4]­triazolo­[4,3-a]­pyridines and demonstrated that a ring fusion strategy can be employed for designing analogues of the Bristol-Myers Squibb chemical series. These studies pave the way for future drug design.