Mitigation of Biofilm Development on Thin-Film Composite Membranes Functionalized with Zwitterionic Polymers and Silver Nanoparticles.

We demonstrate the functionalization of thin-film composite membranes with zwitterionic polymers and silver nanoparticles (AgNPs) for combating biofouling. Combining hydrophilic zwitterionic polymer brushes and biocidal AgNPs endows the membrane with dual functionality: antiadhesion and bacterial inactivation. An atom transfer radical polymerization (ATRP) reaction is used to graft zwitterionic poly(sulfobetaine methacrylate) (PSBMA) brushes to the membrane surface, while AgNPs are synthesized in situ through chemical reduction of silver. Two different membrane architectures (Ag-PSBMA and PSBMA-Ag TFC) are developed according to the sequence AgNPs, and PSBMA brushes are grafted on the membrane surface. A static adhesion assay shows that both modified membranes significantly reduced the adsorption of proteins, which served as a model organic foulant. However, improved antimicrobial activity is observed for PSBMA-Ag TFC (i.e., AgNPs on top of the polymer brush) in comparison to the Ag-PSBMA TFC membrane (i.e., polymer brush on top of AgNPs), indicating that architecture of the antifouling layer is an important factor in the design of zwitterion-silver membranes. Confocal laser scanning microscopy (CLSM) imaging indicated that PSBMA-Ag TFC membranes effectively inhibit biofilm formation under dynamic cross-flow membrane biofouling tests. Finally, we demonstrate the regeneration of AgNPs on the membrane after depletion of silver from the surface of the PSBMA-Ag TFC membrane.

Antifouling Thin-Film Composite Membranes by Controlled Architecture of Zwitterionic Polymer Brush Layer.

In this study, we demonstrate a highly antifouling thin-film composite (TFC) membrane by grafting a zwitterionic polymer brush via atom-transfer radical-polymerization (ATRP), a controlled, environmentally benign chemical process. Initiator molecules for polymerization were immobilized on the membrane surface by bioinspired catechol chemistry, leading to the grafting of a dense zwitterionic polymer brush layer. Surface characterization revealed that the modified membrane exhibits reduced surface roughness, enhanced hydrophilicity, and lower surface charge. Chemical force microscopy demonstrated that the modified membrane displayed foulant-membrane interaction forces that were 1 order of magnitude smaller than those of the pristine TFC membrane. The excellent fouling resistance imparted by the zwitterionic brush layer was further demonstrated by significantly reduced adsorption of proteins and bacteria. In addition, forward osmosis fouling experiments with a feed solution containing a mixture of organic foulants (bovine-serum albumin, alginate, and natural organic matter) indicated that the modified membrane exhibited significantly lower water flux decline compared to the pristine TFC membrane. The controlled architecture of the zwitterionic polymer brush via ATRP has the potential for a facile antifouling modification of a wide range of water treatment membranes without compromising intrinsic transport properties.

Insights into solid phase denitrification in wastewater tertiary treatment: the role of solid carbon source in carbon biodegradation and heterotrophic denitrification.

The practical application of solid phase denitrification (SPD) was hindered by either poor water quality from natural plant-like materials or high cost of pure synthetic biodegradable polymers. In this study, by combining polycaprolactone (PCL) with new natural materials (peanut shell, sugarcane bagasse), two novel economical solid carbon sources (SCSs) named as PCL/PS and PCL/SB were developed. Pure PCL and PCL/TPS (PCL with thermal plastic starch) were supplied as controls. During the 162-day operation, especially in the shortest HRT (2 h), higher NO3--N removal was achieved by PCL/PS (87.60%±0.06%) and PCL/SB (87.93%±0.05%) compared to PCL (83.28%±0.07%) and PCL/TPS (81.83%±0.05%). The predicted abundance of functional enzymes revealed the potential metabolism pathways of major components of SCSs. The natural components entered the glycolytic cycle by enzymatical generation of intermediates, while biopolymers being converted into small molecule products under specific enzyme activities (i.e., carboxylesterase, aldehyde dehydrogenase), together providing electrons and energy for denitrification.

Hierarchical assembly of multifunctional oxide-based composite nanostructures for energy and environmental applications.

Composite nanoarchitectures represent a class of nanostructured entities that integrates various dissimilar nanoscale building blocks including nanoparticles, nanowires, and nanofilms toward realizing multifunctional characteristics. A broad array of composite nanoarchitectures can be designed and fabricated, involving generic materials such as metal, ceramics, and polymers in nanoscale form. In this review, we will highlight the latest progress on composite nanostructures in our research group, particularly on various metal oxides including binary semiconductors, ABO(3)-type perovskites, A(2)BO(4) spinels and quaternary dielectric hydroxyl metal oxides (AB(OH)(6)) with diverse application potential. Through a generic template strategy in conjunction with various synthetic approaches- such as hydrothermal decomposition, colloidal deposition, physical sputtering, thermal decomposition and thermal oxidation, semiconductor oxide alloy nanowires, metal oxide/perovskite (spinel) composite nanowires, stannate based nanocompostes, as well as semiconductor heterojunction-arrays and networks have been self-assembled in large scale and are being developed as promising classes of composite nanoarchitectures, which may open a new array of advanced nanotechnologies in solid state lighting, solar absorption, photocatalysis and battery, auto-emission control, and chemical sensing.

Electroless deposition of copper nanoparticles integrates polydopamine coating on reverse osmosis membranes for efficient biofouling mitigation.

In this study, highly antimicrobial CuNPs were integrated into a hydrophilic polydopamine (PDA) coating and immobilized on a RO TFC membrane via a mild and facile reduction approach to form a stable and durable dual-functional layer. Based on the XDLVO analysis, the introduction of PDA increased the membrane-foulant total interaction energy (ΔGmwf) to 14.13 mJ/m2, resulting in improved anti-adhesive properties as demonstrated by a 37% decrease in BSA adsorption for the modified membranes. The well dispersed and high loadings of CuNPs induced by PDA conferred strong bacterial toxicity to the modified membranes, reducing the viability of E. coli by 76%. Furthermore, the presence of catechol groups on PDA favors the formation of covalent bond with CuNPs, thus prolonging the durability of the copper-based anti-biofouling membranes. The combination of PDA coating and CuNPs functionalization imparts the membrane with simultaneous anti-adhesive and anti-microbial properties, leading to a substantial reduction in biofouling propensity in dynamic biofouling experiments. Specifically, the flux decline due to biofouling observed for the modified membranes significantly decreased from 65% to 39%, and biofilm thickness and TOC biomass were 58%, and 55% lower, respectively. This study provides a facile and versatile strategy to construct high performance RO membranes with excellent anti-biofouling functionality.

Constructing zwitterionic polymer brush layer to enhance gravity-driven membrane performance by governing biofilm formation.

In this study, zwitterionic polymer brushes with controlled architecture were grafted on the surface of gravity-driven membrane (GDM) via surface-initiated reaction to impart antifouling property. A variety of membrane characterization techniques were conducted to demonstrate the successful functionalization of zwitterionic polymers on PVDF hollow fiber membrane. The membrane underwent 90 min of reaction time possessing strong hydrophilicity and high permeability was determined as the optimal modified membrane. Long-term GDM dynamic fouling experiments operated for 30 days using sewage wastewater as feed solution indicated zwitterionic polymer modified membrane exhibit excellent membrane fouling resistance thus enhanced stable flux. Confocal laser scanning microscopy (CLSM) imaging implied that zwitterionic polymer modification significantly inhibit the adsorption of extracellular polymeric substances (EPS) which dominates fouling propensity, resulting in the formation of a thin biofilm with high porosity under synthetic functions of foulants deposition and microbial activities. Interfacial free energy prediction affirmed the presence of zwitterionic functional layer on membrane surface could substantially decrease the interactions (e.g., electrostatic attractions and hydrophobic effects) between membrane and foulants, thereby reduced flux decline and high stable flux. Our study suggests surface hydrophilic functionalization shows promising potential for improving the performance of ultra-low pressure filtration.

A review on the interactions between engineered nanoparticles with extracellular and intracellular polymeric substances from wastewater treatment aggregates.

Engineered nanoparticles (ENPs) will inevitably enter wastewater treatment plants (WWTPs) due to their widespread application; thus, it is necessary to study the migration and transformation of nanoparticles in sewage treatment systems. Extracellular polymeric substances (EPSs) such as polysaccharides, proteins, nucleic acids, humic acids and other polymers are polymers released by microorganisms under certain conditions. Intracellular polymeric substances (IPSs) are microbial substances contained in the body with compositions similar to those of extracellular polymers. In this review, we summarize the characteristics of EPSs and IPSs from sewage-collecting microbial aggregates containing pure bacteria, activated sludge, granular sludge and biofilms. We also further investigate the dissolution, adsorption, aggregation, deposition, oxidation and other chemical transformation processes of nanoparticles, such as metals, metal oxides, and nonmetallic oxides. In particular, the review deeply analyzes the migration and transformation mechanisms of nanoparticles in EPS and IPS matrices, including physical, chemical, biological interactions mechanisms. Moreover, various factors, such as ionic strength, ionic valence, pH, light, oxidation-reduction potential and dissolved oxygen, influencing the interaction mechanisms are discussed. In recent years, studies on the interactions between EPSs/IPSs and nanoparticles have gradually increased, but the mechanisms of these interactions are seldom explored. Therefore, developing a systematic understanding of the migration and transformation mechanisms of ENPs is significant.

Integrated forward osmosis-membrane distillation process for human urine treatment.

This study demonstrated a forward osmosis-membrane distillation (FO-MD) hybrid system for real human urine treatment. A series of NaCl solutions at different concentrations were adopted for draw solutions in FO process, which were also the feed solutions of MD process. To establish a stable and continuous integrated FO-MD system, individual FO process with different NaCl concentrations and individual direct contact membrane distillation (DCMD) process with different feed temperatures were firstly investigated separately. Four stable equilibrium conditions were obtained from matching the water transfer rates of individual FO and MD processes. It was found that the integrated system is stable and sustainable when the water transfer rate of FO subsystem is equal to that of MD subsystem. The rejections to main contaminants in human urine were also investigated. Although individual FO process had relatively high rejection to Total Organic Carbon (TOC), Total Nitrogen (TN) and Ammonium Nitrogen (NH4(+)-N) in human urine, these contaminants could also accumulate in draw solution after long term performance. The MD process provided an effective rejection to contaminants in draw solution after FO process and the integrated system revealed nearly complete rejection to TOC, TN and NH4(+)-N. This work provided a potential treatment process for human urine in some fields such as water regeneration in space station and water or nutrient recovery from source-separated urine.

Immobilization of dehydrogenase onto epoxy-functionalized nanoparticles for synthesis of (R)-mandelic acid.

Epoxy functionalized magnetic Fe3O4@SiO2 nanoparticles were successfully prepared and characterized by Fourier-transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The prepared nanoparticles were used for immobilization of alcohol dehydrogenase (ADH) from Saccharomyces cerevisiae by covalent attachment. The optimal immobilization conditions were obtained as follows: enzyme/support 4.49mg/g, pH 8.0, buffer concentration 0.05M, time 12h and temperature 30°C. Under these conditions, a high immobilization yield and efficiency of above 92% were obtained after the optimization. Broad pH tolerance and high thermostability were achieved by the immobilization. The immobilized ADH retained about 84% initial activity after five cycles. Kinetic parameters Vmax and Km of free and immobilized ADH were determined as 56.72µM/min, 44.27µM/min and 11.54mM, 31.32mM, respectively. (R)-mandelic acid synthesis with the immobilized ADH was carried out, and the yield of (R)-mandelic acid was as high as 64%. These results indicate that the ADH immobilized onto epoxy-functionalized nanoparticles is an efficient and simple way for preparation of stable ADH, and the immobilized ADH has potential applications in the production of (R)-mandelic acid.