ROS-dependent S-palmitoylation activates cleaved and intact gasdermin D.

Gasdermin D (GSDMD) is the common effector for cytokine secretion and pyroptosis downstream of inflammasome activation and was previously shown to form large transmembrane pores after cleavage by inflammatory caspases to generate the GSDMD N-terminal domain (GSDMD-NT)1-10. Here we report that GSDMD Cys191 is S-palmitoylated and that palmitoylation is required for pore formation. S-palmitoylation, which does not affect GSDMD cleavage, is augmented by mitochondria-generated reactive oxygen species (ROS). Cleavage-deficient GSDMD (D275A) is also palmitoylated after inflammasome stimulation or treatment with ROS activators and causes pyroptosis, although less efficiently than palmitoylated GSDMD-NT. Palmitoylated, but not unpalmitoylated, full-length GSDMD induces liposome leakage and forms a pore similar in structure to GSDMD-NT pores shown by cryogenic electron microscopy. ZDHHC5 and ZDHHC9 are the major palmitoyltransferases that mediate GSDMD palmitoylation, and their expression is upregulated by inflammasome activation and ROS. The other human gasdermins are also palmitoylated at their N termini. These data challenge the concept that cleavage is the only trigger for GSDMD activation. They suggest that reversible palmitoylation is a checkpoint for pore formation by both GSDMD-NT and intact GSDMD that functions as a general switch for the activation of this pore-forming family.

Three-Dimensional Analysis of the Natural-Organic-Matter Distribution in the Cake Layer to Precisely Reveal Ultrafiltration Fouling Mechanisms.

Cake layer formation is the dominant ultrafiltration membrane fouling mechanism after long-term operation. However, precisely analyzing the cake-layer structure still remains a challenge due to its thinness (micro/nano scale). Herein, based on the excellent depth-resolution and foulant-discrimination of time-of-flight secondary ion mass spectrometry, a three-dimensional analysis of the cake-layer structure caused by natural organic matter was achieved at lower nanoscale for the first time. When humic substances or polysaccharides coexisted with proteins separately, a homogeneous cake layer was formed due to their interactions. Consequently, membrane fouling resistances induced by proteins were reduced by humic substances or polysaccharides, leading to a high flux. However, when humic substances and polysaccharides coexisted, a sandwich-like cake layer was formed owing to the asynchronous deposition based on molecular dynamics simulations. As a result, membrane fouling resistances were superimposed, and the flux was low. Furthermore, it is interesting that cake-layer structures were relatively stable under common UF operating conditions (i.e., concentration and stirring). These findings better elucidate membrane fouling mechanisms of different natural-organic-matter mixtures. Moreover, it is demonstrated that membrane fouling seems lower with a more homogeneous cake layer, and humic substances or polysaccharides play a critical role. Therefore, regulating the cake-layer structure by feed pretreatment scientifically based on proven mechanisms should be an efficient membrane-fouling-control strategy.

New insights into the humic acid fouling mechanism of ultrafiltration membranes for different Ca2+ dosage ranges: results from micro- and macro-level analyses.

To reveal the mechanisms of the influence of Ca2+ on membrane fouling with humic acid (HA), the adhesion forces of HA with both other HA molecules and the membrane, the HA fouling layer structure, HA fouling experiments, and the HA rejections at a wide range of Ca2+ dosages were investigated. The results indicated that the effect of Ca2+ on HA fouling can be divided into three stages. At lower ionic strength (IS) of CaCl2, the change in electrostatic forces is the main factor in controlling HA fouling behavior; i.e., increasing Ca2+ dosages resulted in more serious membrane fouling. When the IS of CaCl2 reached 10 mM, HA aggregates became the dominant factor in the fouling process, which could result in a porous fouling layer accompanied by less membrane fouling. Interestingly, much weaker membrane fouling was observed when the IS increased to 100 mM and the HA rejection began to decline. This was because a stronger hydration repulsion force was generated, which could weaken the compactness of the fouling layer and the adhesion forces of HA with both the membrane and HA, while enabling smaller-sized HA to pass more easily into the permeate, which led to less membrane fouling and a lower HA rejection.

Effect of Hydration Forces on Protein Fouling of Ultrafiltration Membranes: The Role of Protein Charge, Hydrated Ion Species, and Membrane Hydrophilicity.

To investigate the influence of hydration forces on the protein fouling of membranes and the major influence factors of hydration forces during the ultrafiltration process, bovine serum albumin (BSA) was chosen as model foulant. For various pH levels and hydrated ion and membrane species, the membrane-BSA and BSA-BSA interaction forces, and fouling experiments with BSA, as a function of ionic strength, were measured. Results showed that hydration forces were a universal phenomenon during the membrane filtration process, when the levels of pH, ion species, and membrane performances were appropriate. First, for the BSA negatively charged or neutral, hydration forces caused a decrease in the membrane fouling. Conversely, for the BSA positively charged, the hydration forces were absent because the counterions were not hydrated, and membrane fouling was enhanced. For different hydrated ions, the smaller the radii of the ions were, the stronger the hydration forces that were produced, and the membrane fouling observed was less, indicating that hydration forces are closely correlated with the size of the hydrated ions. Moreover, in comparison with a hydrophobic membrane, it is more difficult to observe hydrophilic membrane-BSA hydration forces because the hydrophilic membrane surface adsorbs water molecules, which weakens its binding efficiency to hydrated ions.

Enhancement and Mitigation Mechanisms of Protein Fouling of Ultrafiltration Membranes under Different Ionic Strengths.

To determine further the enhancement and mitigation mechanisms of protein fouling, filtration experiments were carried out with polyvinylidene fluoride (PVDF) ultrafiltration (UF) membranes and bovine serum albumin (BSA) over a range of ionic strengths. The interaction forces, the adsorption behavior of BSA on the membrane surface, and the structure of the BSA adsorbed layers at corresponding ionic strengths were investigated. Results indicate that when the ionic strength increased from 0 to 1 mM, there was a decrease in the PVDF-BSA and BSA-BSA electrostatic repulsion forces, resulting in a higher deposition rate of BSA onto the membrane surface, and the formation of a denser BSA layer; consequently, membrane fouling was enhanced. However, at ionic strengths of 10 and 100 mM, membrane fouling and the BSA removal rate decreased significantly. This was mainly due to the increased hydration repulsion forces, which caused a decrease in the PVDF-BSA and BSA-BSA interaction forces accompanied by a decreased hydrodynamic radius and increased diffusion coefficient of BSA. Consequently, BSA passed more easily through the membrane and into permeate. There was less accumulation of BSA on the membrane surface. A more nonrigid and open structure BSA layer was formed on the membrane surface.

In situ acid production by organic matter induced with trace homogeneous Fenton reagent for membrane fouling control.

The homogeneous Fenton process involves both coagulation and oxidation, but it requires added acidity, so it is rarely used to control membrane fouling. This work found that the pH of neutral simulated wastewater sharply declined to 4.1 after pre-treatment with 0.1 mM Fenton reagent (Fe2+:H2O2=1:1) without added acidity. This occurred mainly because the trace homogeneous Fenton reagent induced in situ acid production by organic matter in the wastewater, which supplied the acidic conditions required for the Fenton reaction and ensured that the reaction could proceed continuously. Then, oxidation during the pre-Fenton process enhanced the electrostatic repulsion forces and effectively weakened the hydrogen bonds of organic matter at the membrane surface by altering the net charge and hydroxyl content of organic matter, while coagulation caused the foulants to gather and form large aggregates. These changes diminished the deposition of foulants onto the membrane surface and resulted in a looser fouling layer, which eventually caused the membrane fouling rate to decline from 83 % to 24 % and the flux recovery rate to increase from 44 % to 98 % during 2 h of filtration. This membrane fouling mitigation ability is much superior to that of pre-H2O2, pre-Fe2+ or pre-Fe3+ processes with equivalent doses.

Fouling behavior of typical organic foulants in polyvinylidene fluoride ultrafiltration membranes: characterization from microforces.

To further unravel the organic fouling behavior of polyvinylidene fluoride (PVDF) ultrafiltration (UF) membranes, the adhesion forces of membrane-foulant and foulant-foulant were investigated by atomic force microscopy (AFM) in conjunction with self-made PVDF colloidal probe and foulant-coated colloidal probe, respectively. Fouling experiments with bovine serum albumin, sodium alginate, humic acid, and secondary wastewater effluent organic matter (EfOM) were carried out with PVDF UF membrane. Results showed a positive correlation between the membrane-foulant adhesion force and the flux decline rate and extent in the initial filtration stage, whereas the foulant-foulant interaction force was closely related to the pseudostable flux and the cake layer structure in the later filtration stage. For each type of foulant used, the membrane-foulant adhesion force was much stronger than the foulant-foulant interaction force, and membrane flux decline mainly occurred in the earlier filtration stage indicating that elimination of the membrane-foulant interaction force is important for the control of membrane fouling. Upon considering the foulant-foulant interaction force and the membrane flux recovery rate of fouled membranes, it was evident that the main contributor to physically irreversible fouling is the foulant-foulant interaction force.

Forward osmosis membrane doped with water-based zirconium fumarate MOFs to enhance dye pollutant removal and membrane antifouling performance.

Metal-organic frameworks (MOFs) can be applied to enhance the property of forward osmosis membranes. However, organic solvents can easily remain in organic synthetic metal-organic frame materials and cause membrane fouling and a decrease in membrane permeability. In this study, water-based Zr-fumarate MOFs were synthesized and doped into the membrane active layer by interfacial polymerization to provide a water-based MOF-doped thin-film composite membrane (TFC membrane). It was found that doping the water-based MOFs effectively improved membrane hydrophilicity, and nanowater passages were introduced in the active layer to improve permeability. The water flux of the water-based MOF-doped TFC membranes was increased by 21% over that of the original membrane, and the selectivity performance of the membrane was improved while keeping the salt rejection basically unchanged. Additionally, the water-based MOF-doped TFC membrane showed good removal efficiency (Rd > 94%) and strong antipollution performance in the treatment of dye pollutants.

Study of antifouling modified ultrafiltration membrane based on the secondary treated water of urban sewage.

Mixtures of polyvinylidene fluoride (PVDF) and polyvinyl alcohol (PVA) containing hydrophilic ultrafiltration membranes were prepared by adding PVA (5 to 30%) to PVDF by the phase inversion method. The hydrophilic contact angle (CA), equilibrium water content, pure water flux and bovine serum albumin retention were studied to assess the membrane performance. The anti-fouling performance of modified membrane to the secondary treated water was evaluated by flux decline, washing recovery rate and fouling resistance analysis. Scanning electron microscopy showed that the cross-section structure of the membranes had finger-like pores, which were well developed and uniformly distributed, and the sub-layer structure was looser and more porous with the increasing content of PVA. The CA gradually decreased. The steady flux was 800 L/m(2) h from P15 to P30, and the BSA retention sharply declined. The ultrafiltration tests for secondary treated water indicated that the main fouling source of the modified membrane was the concentration polarization and cake layer resistance. After physical flushing, the flux recovery ratio of the membrane could reach 100% when the PVA content was 5-15%, which shows excellent anti-pollution performance and good prospects for use in processing wastewater from urban sewage.

Roles of membrane-foulant and inter/intrafoulant species interaction forces in combined fouling of an ultrafiltration membrane.

To explore better the combined organic-inorganic fouling mechanisms of ultrafiltration (UF) membranes, SiO2 and bovine serum albumin (BSA), humic acid (HA) were chosen as model inorganic and organic foulants, respectively. Fouling experiments with single and combined foulants, corresponding fouling layer structure, and the membrane-foulant and inter/intrafoulant species interaction forces were investigated. The results showed that the addition of SiO2 particles led to opposite fouling phenomena for BSA and HA, which could be explained by the membrane-foulant and interfoulant species interaction forces. In the initial filtration stage, the combined fouling behavior was related to the relative strength of the interaction forces of membrane with both inorganic and organic foulant. Specifically, when the SiO2-membrane interaction force>organic-membrane interaction force, the combined fouling would be enhanced with the addition of SiO2 particles; otherwise, it would be mitigated. In the later filtration stage, the combined fouling was related to the inorganic-organic interaction forces. Thus, the stronger SiO2-BSA interaction force led to the formation of large SiO2-BSA aggregates, which resulted in a more porous fouling layer and higher hydraulic permeability. In contrast, the negligible SiO2-HA interaction forces caused the SiO2 particles to fill uniformly in or between the HA molecules, which resulted in a more compact fouling layer and more serious membrane fouling.

Enhanced gypsum scaling by organic fouling layer on nanofiltration membrane: Characteristics and mechanisms.

To investigate how the characteristics of pregenerated organic fouling layers on nanofiltration (NF) membranes influence the subsequent gypsum scaling behavior, filtration experiments with gypsum were carried out with organic-fouled poly(piperazineamide) NF membranes. Organic fouling layer on membrane was induced by bovine serum albumin (BSA), humic acid (HA), and sodium alginate (SA), respectively. The morphology and components of the scalants, the role of Ca(2+) adsorption on the organic fouling layer during gypsum crystallization, and the interaction forces of gypsum on the membrane surface were investigated. The results indicated that SA- and HA-fouled membranes had higher surface crystallization tendency along with more severe flux decline during gypsum scaling than BSA-fouled and virgin membranes because HA and SA macromolecules acted as nuclei for crystallization. Based on the analyses of Ca(2+) adsorption onto organic adlayers and adhesion forces, it was found that the flux decline rate and extent in the gypsum scaling experiment was positively related to the Ca(2+)-binding capacity of the organic matter. Although the dominant gypsum scaling mechanism was affected by coupling physicochemical effects, the controlling factors varied among foulants. Nevertheless, the carboxyl density of organic matter played an important role in determining surface crystallization on organic-fouled membrane.

Identifying polyvinylidene fluoride ultrafiltration membrane fouling behavior of different effluent organic matter fractions using colloidal probes.

The interaction forces between effluent organic matter (EfOM) fractions and membrane were measured by atomic force microscopy in conjunction with self-made membrane material colloidal probes. The inter-EfOM-fraction and intra-EfOM-fraction interactions were investigated using corresponding EfOM-fraction-coated colloidal probe. We combined this analysis with corresponding fouling experiments to identify the EfOM fractions responsible for polyvinylidene fluoride (PVDF) ultrafiltration membrane fouling. Results show that hydrophilic and hydrophobic fractions were the dominant fractions responsible for membrane fouling and flux decline in the initial and later filtration stages, respectively, which was mainly attributed to the stronger PVDF-hydrophilic fraction and intra-hydrophobic-fraction interaction forces. This phenomenon, in conjunction with the fact that each interaction force of PVDF-EfOM fraction was stronger than corresponding intra-EfOM-fraction force, suggests that the elimination of the PVDF-hydrophilic fraction interaction force is the best strategy for controlling EfOM fouling. Moreover, the inter-EfOM-fraction interaction force was mainly controlled by the corresponding intra-EfOM-fraction interaction forces. And, while the membrane-EfOM fraction and intra-EfOM-fraction interactions for each type of EfOM fraction are equivalent, the EfOM fractions with the molecular weight smaller than the molecular weight cutoff of the membranes used were mainly responsible for membrane fouling rather than the relatively high-molecular-weight fractions.