Microporous Polyethersulfone Membranes Grafted with Zwitterionic Polymer Brushes Showing Microfiltration Permeance and Ultrafiltration Bacteriophage Removal.

Virus removal from water using microfiltration (MF) membranes is of great interest but remains challenging owing to the membranes' mean pore sizes typically being significantly larger than most viruses. We present microporous membranes grafted with polyzwitterionic brushes (N-dimethylammonium betaine) that combine bacteriophage removal in the range of ultrafiltration (UF) membranes with the permeance of MF membranes. Brush structures were grafted in two steps: free-radical polymerization followed by atom transfer radical polymerization (ATRP). Attenuated total reflection Fourier transform infrared (ATR-FTIR) and X-ray photoelectron (XPS) verified that grafting occurred at both sides of the membranes and that the grafting increased with increasing the zwitterion monomer concentration. The log reduction values (LRVs) of the pristine membrane increased from less than 0.5 LRV for T4 (∼100 nm) and NT1 (∼50 nm) bacteriophages to up to 4.5 LRV for the T4 and 3.1 LRV for the NT1 for the brush-grafted membranes with a permeance of about 1000 LMH/bar. The high permeance was attributed to a high-water fraction in the ultra-hydrophilic brush structure. The high measured LRVs of the brush-grafted membranes were attributed to enhanced bacteriophages exclusion from the membrane surface and entrapment of the ones that penetrated the pores due to the membranes' smaller mean pore-size and cross-section porosity than those of the pristine membrane, as seen by scanning electron microscopy (SEM) and measured using liquid-liquid porometry. Micro X-ray fluorescence (µ-XRF) spectrometry and nanoscale secondary ion mass spectrometry showed that 100 nm Si-coated gold nanospheres accumulated on the surface of the pristine membrane but not on the brush-coated membrane and that the nanospheres that penetrated the membranes were entrapped in the brush-grafted membrane but passed the pristine one. These results corroborate the LRVs obtained during filtration experiments and support the inference that the increased removal was due to a combined exclusion mechanism and entrapment. Overall, these microporous brush-grafted membranes show potential for use in advanced water treatment.

Semi-wrapped gold nanoparticles for surface-enhanced Raman scattering detection.

Researchers have struggled to develop highly reliable and sensitive surface-enhanced Raman scattering (SERS) substrates for detecting compounds in complicated systems. In this work, a strategy by constructing Au cores with incompletely wrapped Prussian blue (PB) for highly reliable and sensitive SERS substrate is proposed. The wrapped PB layers can provide the internal standard (IS) to calibrate the SERS signal floatation, whereas the exposed surface of Au cores offers the enhancement effect. The balance between the signal self-calibration and enhancement (hence the trade-off between SERS reliability and sensitivity) is obtained by the approximate semi-wrapping configuration of PB layers on Au cores (i.e., SW-Au@PB). The proposed SW-Au@PB nanoparticles (NPs) exhibit the similar enhancement factor as the pristine Au NPs and contribute to the ultralow RSD (8.55%) of calibrated SERS signals using R6G as probe molecules. The simultaneously realized reliability and sensitivity of SW-Au@PB NPs also enables the detection of hazardous pesticide residues such as paraquat and thiram in herbal plants, with the average detection accuracy up to 92%. Overall, this work mainly provides a controllable synthetic strategy for incompletely wrapped NPs, and most importantly, explores the potential with a proof-of-concept practical application in accurate and sensitive Raman detection of hazardous substances with varying solubility.

Mechanism of Permselectivity Enhancement in Polyelectrolyte-Dense Nanofiltration Membranes via Surfactant-Assembly Intercalation.

Enhancing the water permeance while maintaining the solute rejection of a nanofiltration (NF) membrane can potentially result in significant cost-reduction for NF-a membrane process that excels in several unique environmental applications of growing interests. In this work, we demonstrate for the first time that intercalation of surfactant self-assemblies in the polyelectrolyte multilayer (PEM) can lead to significant performance enhancement of salt-rejecting dense NF membranes fabricated using layer-by-layer assembly of polyelectrolytes. Specifically, the intercalation of sodium dodecyl sulfate (SDS) bilayers in a PEM comprising poly(diallyldimethylammonium chloride) (PDADMAC) and poly (sodium 4-styrenesulfonate) (PSS) resulted in a decrease in PEM thickness, increase in pore size, and a smoother and more hydrophilic surface. The water permeance of the resulting PEM NF membrane increased by 100% without compromising the rejection of Na2SO4. Experiments with a quartz crystal microbalance also provide direct evidence that the intercalation of the surfactants substantially reduces the subsequent adsorption of the polyelectrolytes of a similar charge. Based on its mechanism of performance enhancement, surfactant intercalation may become a universally applicable and highly cost-effective approach for dramatically enhancing the performance of PEM NF membranes.

Polyamide nanofiltration membrane with highly uniform sub-nanometre pores for sub-1 Å precision separation.

Separating molecules or ions with sub-Angstrom scale precision is important but technically challenging. Achieving such a precise separation using membranes requires Angstrom scale pores with a high level of pore size uniformity. Herein, we demonstrate that precise solute-solute separation can be achieved using polyamide membranes formed via surfactant-assembly regulated interfacial polymerization (SARIP). The dynamic, self-assembled network of surfactants facilitates faster and more homogeneous diffusion of amine monomers across the water/hexane interface during interfacial polymerization, thereby forming a polyamide active layer with more uniform sub-nanometre pores compared to those formed via conventional interfacial polymerization. The polyamide membrane formed by SARIP exhibits highly size-dependent sieving of solutes, yielding a step-wise transition from low rejection to near-perfect rejection over a solute size range smaller than half Angstrom. SARIP represents an approach for the scalable fabrication of ultra-selective membranes with uniform nanopores for precise separation of ions and small solutes.

Enhancing Performance of Capacitive Deionization with Polyelectrolyte-Infiltrated Electrodes: Theory and Experimental Validation.

The energy efficiency of capacitive deionization (CDI) with porous carbon electrodes is limited by the high ionic resistance of the macropores in the electrodes. In this study, we demonstrate a facile approach to improve the energy efficiency by filling the macropores with ion-conductive polyelectrolytes, which is termed polyelectrolyte-infiltrated CDI (pie-CDI or πCDI). In πCDI, the filled polyelectrolyte effectively turns the macropores into a charged ion-selective layer and thus increases the conductivity of macropores. We show experimentally that πCDI can save up to half of the energy consumption compared to membrane CDI, achieving identical desalination during the charging step. The energy consumption can be even lower if the process is operated at a smaller average salt adsorption rate. Further energy breakdown analysis based on a theoretical model confirms that the improved energy efficiency is largely attributed to the increased conductivity in the macropores.

Fabrication and evaluation of electrospun PCL-gelatin micro-/nanofiber membranes for anti-infective GTR implants.

Infection is the major reason for GTR/GBR membrane failure in clinical applications. In this work, we developed GTR/GBR membranes with localized drug delivery function to prevent infection. Hierarchical membranes containing micro- and nano-fibers were fabricated. The effects of the incorporation of gelatin and loading content of metronidazole (MNA) (0, 5, 10, 20, 30, and 40 wt% polymer) on the properties of the electrospun membranes were investigated. The interaction between PCL and MNA was identified by molecular dynamics simulation. MNA was released in a controlled manner, and the antibacterial activity of the released MNA remained. The incorporation of gelatin and MNA improved the hydrophilicity, biocompatibility, and in vitro biodegradation rate of PCL nanofibers. The electrospun membranes allowed cells to adhere to and proliferate on them and showed excellent barrier function. The membrane loaded with 30% MNA had the best comprehensive properties. Subcutaneous implantation results demonstrated that MNA-loaded membranes evoked a less severe inflammatory response than pure PCL nanofibers. These results demonstrated the potential of MNA-loaded membranes as GTR/GBR membranes with antibacterial and anti-inflammatory functions for biomedical applications.