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In the context of industrial effluent management, the application of electrodialysis (ED) for the recovery of sulfuric acid has attracted significant interest. Despite the technological promise, the employment of traditional anion exchange membranes (AEMs) is frequently marred by substantial proton leakage, a pervasive issue that markedly degrades the effectiveness of acid recovery. To address this challenge, we embarked on a novel approach utilizing a polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) substrate. This innovative method harnessed the inherent properties of fluorine-containing groups within PVDF-HFP to provide robust acid stability, while incorporating tertiary amine groups to minimize water uptake resulted in the creation of a proton-blocking AEM. A distinguishing feature of this AEM is its thermally cross-linked diene structure, which not only preserves acid concentration properties but also considerably reduces water migration. Moreover, our investigation undertakes an exhaustive examination of the recycling concentration and water transport within the acid recovery framework, alongside the intricate interplay with energy expenditure. This investigation could facilitate the adoption of industrial acid recovery methods utilizing AEMs designed for minimal water uptake and enhanced acid-blocking capabilities.

Membrane fouling is a challenging problem that negatively affects the membrane performance. To suppress the fouling, in this work, a series of bipyridine-containing crosslinked anion exchange membranes (AEMs) (denoted as PVA-Bpy-CHO-X) have been prepared, where poly(vinyl alcohol) (PVA) is the membrane substrate and Bpy-CHO with a rigid structure is the crosslinker. The optimized PVA-Bpy-CHO-0.40 possesses an appropriate swelling ratio (11.3%), low surface area resistance (3.21 Ω·cm2), and enhanced hydrophilicity (water contact angle: 76.4°). Especially, PVA-Bpy-CHO-0.40 also exhibits a superior NaCl removal ratio of 85.16 ± 0.9% within 210 min, which is higher than that of commercial AEM-Type-II (84.46 ± 0.8%). As for the antifouling performance of AEMs, the electrodialysis (ED) stack was fed with a solution containing 0.05 M NaCl (aq.) and contaminant model of 0.8 g·L–1SDBS. The antifouling potential is evaluated by transition time, which is defined as the time that passes when voltage across the membrane (ΔE) presents a sharp rise for the increased surface area resistance when the fouling occurs. As a result, PVA-Bpy-CHO-0.40 shows a longer transition time of 750 min relative to AEM-Type-II (620 min), suggesting its superior antifouling performance and the potential to be a good candidate for ED in organic foulant systems.

Intrahepatic cholangiocarcinoma (ICC) is a deadly cancer with rapid tumor progression. While hyperactive mRNA translation caused by mis-regulated mRNA or tRNA modifications promotes ICC development, the role of rRNA modifications remains elusive. Here, we found that 18S rRNA m6A modification and its methyltransferase METTL5 were aberrantly upregulated in ICC and associated with poorer survival (log rank test, p < 0.05). We further revealed the critical role of METTL5-mediated 18S rRNA m6A modification in regulation of ICC cell growth and metastasis using loss- and gain-of function assays in vitroand in vivo. The oncogenic function of METTL5 is corroborated using liver-specific knockout and overexpression ICC mouse models. Mechanistically, METTL5 depletion impairs 18S rRNA m6A modification that hampers ribosome synthesis and inhibits translation of G-quadruplex-containing mRNAs that are enriched in the transforming growth factor (TGF)-β pathway. Our study uncovers the important role of METTL5-mediated 18S rRNA m6A modification in ICC and unravels the mechanism of rRNA m6A modification-mediated oncogenic mRNA translation control.

The development of antifouling ion exchange membranes (IEMs) is of great significance to the application of electrodialysis (ED). Membrane fouling is a ticklish question affecting the membrane performance, which results in an increase in energy consumption in ED and unnecessary economic loss. In this work, we report poly(vinyl alcohol) (PVA) as an IEM substrate; a large number of hydroxyl groups on the aliphatic chain react with a small rigid molecule of 4-(bromomethyl)benzaldehyde (QBMB) prepared by us and then adjust the time of quaternization by trimethylamine to design a series of antifouling anion exchange membranes (AEMs) named PVA-QBMB-X(X= 2, 4, 6, and 12). The as-prepared AEMs with a cross-linking structure within the matrix exhibit low surface area resistance and reduced swelling ratios of <16.2%. The optimized PVA-QBMB-12 AEM shows better antifouling performance in terms of a much longer transition time (1150 min) than commercial membrane AEM-Type-II (620 min) by possessing excellent hydrophilicity and superior ED performance compared with the commercial membrane. The optimized AEM shows a superior NaCl removal rate of 99.80 ± 1.5%, a current efficiency of 82.64 ± 0.8%, and an energy consumption of 2.98 ± 0.3 kWh kg–1NaCl, which are better than those of AEM-Type-II (97.51 ± 1.5, 76.26 ± 0.7%, and 4.54 ± 0.6 kWh kg–1NaCl, respectively). Thus, the investigation demonstrates the potential application of the as-prepared AEMs for ED in organic pollutant systems.

Ion-conductive polymers having a well-defined phase-separated structure show the potential application of separating mono- and bivalent ion separation. In this work, three side-chain-type poly(arylene ether sulfone)-based anion exchange membranes (AEMs) have been fabricated to investigate the effect of the stiffness of the polymer backbone within AEMs on the Cl–/NO3–and Cl–/SO42–separation performance. Our investigations via small-angle X-ray scattering (SAXS), positron annihilation, and differential scanning calorimetry (DSC) demonstrate that the as-prepared AEM with a rigid benzimidazole structure in the backbone bears subnanometer ion channels resulting from the arrangement of the rigid polymer backbone. In particular, SAXS results demonstrate that the rigid benzimidazole-containing AEM in the wet state has an ion cluster size of 0.548 nm, which is smaller than that of an AEM with alkyl segments in the backbone (0.760 nm). Thus, in the electrodialysis (ED) process, the former exhibits a superior capacity of separating Cl–/SO42–ions relative to latter. Nevertheless, the benzimidazole-containing AEM shows an inability to separate the Cl–/NO3–ions, which is possibly due to the similar ion size of the two. The higher rotational energy barrier (4.3 × 10–3Hartree) of benzimidazole units and the smaller polymer matrix free-volume (0.636%) in the AEM significantly contribute to the construction of smaller ion channels. As a result, it is believed that the rigid benzimidazole structure of this kind is a benefit to the construction of stable subnanometer ion channels in the AEM that can selectively separate ions with different sizes.

With the continuous advancement of electrodialysis (ED) technology, there arises a demand for improved monovalent cation exchange membranes (CEMs). However, limitations in membrane materials and structures have resulted in the low selectivity of monovalent CEMs, posing challenges in the separation of Li+and Mg2+. In this investigation, a designed CEM with a swelling-embedded structure was created by integrating a polyelectrolyte containing N-oxide Zwitterion into a sulfonated poly(ether ether ketone) (SPEEK) membrane, leveraging the notable solubility characteristic of SPEEK. The membranes were prepared by using N-oxide zwitterionic polyethylenimine (ZPEI) and 1,3,5-benzenetrlcarbonyl trichloride (TMC). The as-prepared membranes underwent systematic characterization and testing, evaluating their structural, physicochemical, electrochemical, and selective ED properties. During ED, the modified membranes demonstrated notable permeability selectivity for Li+ions in binary (Li+/Mg2+) systems. Notably, at a constant current density of 2.5 mA cm–2, the modified membrane PEI-TMC/SPEEK exhibited significant permeability selectivity (PMg2+Li+=5.63)in the Li+/Mg2+system, while ZPEI-TMC/SPEEK outperformed, displaying remarkable permeability selectivity (PMg2+Li+=12.43)in the Li+/Mg2+system, surpassing commercial monovalent cation-selective membrane commercial monovalent cation-selective membrane (CIMS). Furthermore, in the Li+/Mg2+binary system, Li+flux reached 9.78 × 10–9mol cm–2s–1for ZPEI-TMC/SPEEK, while its Mg2+flux only reached 2.7 × 10–9mol cm–2s–1, showing potential for lithium–magnesium separation. In addition, ZPEI-TMC/SPEEK was tested for performance and stability at high current densities. This work offers a straightforward preparation process and an innovative structural approach, presenting methodological insights for the advancement of lithium and magnesium separation techniques.

With the process of industrialization, many production fields produce high-salt organic wastewater. In this work, we have employed an electrodialysis (ED)-resin-bipolar membrane electrodialysis (BMED) mixed process to address sodium acrylate wastewater, achieving resource recovery. The influences of the initial volume ratio and applied voltage were investigated. In the ED-resin, the separation of organic compounds and pigments such as sodium acrylate and phenol was realized. The desalting rate could reach 93.1%, the energy consumption is 0.6 kWh/kg C3H3O2Na, and the chroma removal rate can reach 99%. In the subsequent BMED phase, we attain notable acrylic acid and base concentrations, reaching levels of 1.59mol/L and 3.12mol/L, with a current efficiency of 58.14% and an energy consumption of 3.28 kWh/kg NaOH. In addition, economic and environmental evaluations verify the feasibility of this process, which is indicative of its prospect of industrial application.

Metal–organic frameworks (MOFs) have a good separation potential due to their uniform pore size, easy functionalization, and adjustable structure. Therefore, we make use of this feature of MOFs for the separation of Cl–/SO42–systems with different charges and sizes. In this work, two kinds of UiO-66 membranes with different functional groups were synthesized and applied to the monovalent perm-selective separation of the Cl–/SO42–system in electrodialysis (ED). UiO-66-NH2membranes were used to investigate the influence of current density and initial solution concentration on perm selectivity. A layer of UiO-66-NH2was first grown on the anodic alumina oxide (AAO) disks. After that, short chains containing sulfonic acid groups were grafted onto the amino groups by the ring-opening reaction of 1,3-propanesulfonate. The structural stability of the MOF layer was confirmed by XRD analysis of the membrane surface after the ED test. Ion exchange capacity (IEC) and elemental mapping were used to confirm the comparison changes in the degree of sulfonation. It was found that UiO-66-NH2membranes exhibited a higher monovalent anion perm selectivity with a peak value of 36.23 (initial mixture solution of 0.05 M NaCl and 0.05 M Na2SO4) at lower current density (2.5 mA·cm–2). The perm selectivity of UiO-66-SO3H membranes increased with running time under 24 h of sulfonation time. In particular, with low IEC value of 0.10–0.16, it still showed a good performance on perm selectivity. Compared with published polymer ion exchange membranes (perm selectivity < 5) for ED, it has higher perm selectivity, more convenient functionalization, and resistance to organic solvents.

Radiofrequency ablation (RFA) is a widely used therapy for hepatocellular carcinoma (HCC). However, in cases of insufficient RFA (iRFA), nonlethal temperatures in the transition zone increase the risk of postoperative relapse. The pathological analysis of HCC tissues shows that iRFA‐induced upregulation of myeloid‐derived suppressor cells (MDSCs) in residual tumors is critical for postoperative recurrence. Furthermore, this study demonstrates, for the first time, that combining MDSCs suppression strategy during iRFA can unexpectedly lead to a compensatory increase in PD‐L1 expression on the residual MDSCs, attributed to relapse due to immune evasion. To address this issue, a novel size‐tunable hybrid nano‐microliposome is designed to co‐deliver MDSCs inhibitors (IPI549) and αPDL1 antibodies (LPIP) for multipathway activation of immune responses. The LPIP is triggered to release immune regulators by the mild heat in the transition zone of iRFA, selectively inhibiting MDSCs and blocking the compensatory upregulation of PD‐L1 on surviving MDSCs. The combined strategy of LPIP + iRFA effectively ablates the primary tumor by activating immune responses in the transition zone while suppressing the compensatory immune evasion of surviving MDSCs. This approach avoids the relapse of the residual tumor in a post‐iRFA incomplete ablation model and appears to be a promising strategy in RFA for the eradication of HCC. The study proposes a novel nano‐micro‐tunable hybrid liposome to co‐deliver myeloid‐derived suppressor cells (MDSCs) inhibitor and anti‐PD‐L1 antibody in response to the temperature of insufficient radiofrequency ablation (iRFA) for multipathway activation of immune responses. This approach effectively ablates the tumor while suppressing compensatory immune evasion of MDSCs, avoiding the relapse and progression of incompletely ablated hepatocellular carcinoma.

Surface modification has been proven to be an effective approach for ion exchange membranes to achieve separation of counterions with different valences by altering interfacial construction of membranes to improve ion transfer performance. In this work, we have fabricated a series of novel cation exchange membranes (CEMs) by modifying sulfonated polysulfone (SPSF) membranes via codeposition of mussel-inspired dopamine (DA) and 4′-aminobenzo-15-crown-5 (ACE), followed by glutaraldehyde cross-linking, aiming at achieving selective separation of specific cations. The as-prepared membranes before and after modification were systematically characterized in terms of their structural, physicochemical, electrochemical, and electrodialytic properties. In the electrodialysis process, the modified membranes exhibit distinct perm selectivity to K+ions in binary (K+/Li+, K+/Na+, K+/Mg2+) and ternary (K+/Li+/Mg2+) systems. In particular, at a constant current density of 5.0 mA·cm–2, modified membrane M-co-0.50 shows significantly prominent perm selectivity (PMg2+K+=5.99)in the K+/Mg2+system and M-co-0.75 exhibits remarkable performance in the K+/Li+system (PLi+K+=2.87), superior to commercial monovalent-selective CEM (CIMS, PMg2+K+=5.36, PLi+K+=1.16). Besides, in the K+/Li+/Mg2+ternary system, K+flux reaches 30.8 nmol·cm–2·s–1for M-co-0.50, while it reaches 25.8 nmol·cm–2·s–1for CIMS. It possibly arises from the effects of pore-size sieving and the synergistic action of electric field driving and host–guest molecular recognition of ACE and K+ions. This study can provide new insights into the separation of specific alkali metal ions, especially on reducing influence of coexisting cations K+and Na+on Li+ion recovery from salt lake and seawater.

To realize the practical application of lithium–sulfur (Li–S) batteries, bifunctional binders featured with the capability of trapping soluble polysulfide species besides the strong binding property are highly desired. Herein, we demonstrate the strong potential of a commercially available, environmentally friendly, water-soluble linear polyethylenimine (PEI) as a superior bifunctional binder for high-sulfur-loading cathodes in Li–S batteries. Our investigation shows the significantly improved cathode performance with enhanced sulfur utilization (i.e., higher capacity), reduced capacity decay, and longer cycling life upon the use of PEI as the binder, relative to the traditional polyvinylidene fluoride (PVDF) binder. This arises from the significantly stronger binding strength and valuable polysulfide trapping ability of the linear PEI binder. In particular, its superior polysulfide adsorption capability has been evidenced experimentally with both ex situ and in situ studies, as well as through theoretical density functional theory (DFT) calculations. At a sulfur loading of 2.4 mg cm–2, the capacity decay rate of the cathode with the linear PEI binder is reduced to as low as 0.042% per cycle over 500 cycles at 2 C. In addition, it also enables the fabrication of high-sulfur-loading cathodes (as high as 6.5 mg cm–2) with high areal capacity (ca. 4.5 mAh cm–2) and high cycling stability. With its superior performance, linear PEI is promising for fabricating high-sulfur-loading cathodes of significantly lowered capacity decay for practical applications.

Recent studies indicated that insufficient radiofrequency ablation (RFA) could endow hepatocellular carcinoma (HCC) with higher aggressive potential. Stress-induced phosphoprotein 1 (STIP1), which was found highly expressed in HCC, is a chaperone molecule mediating cell homeostasis under thermal stress. We aimed to explore the role of STIP1 on the metastasis of residual HCC after RFA. Mice model with orthotopic HCC implants or caudal vein injection were employed to assess potential of lung metastasis and/or intrahepatic metastasis (IHM) of HCC cells. Cell culture model was used to determine cell invasion, mesenchymal marker genes expression, and underlying molecular mechanisms. Clinical specimens were collected to analyze the relationship between STIP1 and clinical outcome. We found that insufficient RFA elicited more IHM of HCCLM3 tumors, which could be reduced by silencing STIP1. Knockdown of STIP1 also significantly decreased lung metastatic potential of HCCLM3 cells. In vitro, HCCLM3 and HepG2 displayed a spindle-shaped morphology with upregulation of STIP1 and mesenchymal markers after sublethal heat exposure. Mechanistically, heat exposure induced the formation of STIP1-heat shock protein 90 (HSP90) complex, which could shuttle epithelial transcription repressor Snail1 into nucleus and regulate mesenchymal gene transcription. Blocking the HSP90–STIP1 complex reduced the invasive potential of HCC cells after heat exposure. Using clinical specimen, we found that STIP1 was expressed significantly higher in metastatic tumor tissues and in sera from metastatic HCC patients (p< 0.05). The high expression of STIP1 was significantly linked to shorter recurrence-free survival (p< 0.05). To sum up, our study found that STIP1 is positively associated with the sublethal heat-induced cancer cell metastasis through mediating the mesenchymal gene transcription. Blocking STIP1 activity may suppress HCC cell metastatic potential after RFA.

Hexacyanocobalic acid (H3Co(CN)6) is an important material utilized in the cyanide complex catalyst, which can be used for ring-opening polymerization of epoxides, cyclic anhydrides, and episulfides. The current method for synthesizing H3Co(CN)6involves a chemical synthesis. However, it is impeded by the complex preparation process, extra reagent usage, and the presence of intermediate products. In this work, hexacyanocobalic acid was prepared from potassium hexacyanocobalate by a clean and efficient bipolar membrane electrodialysis (BMED) method. The effects of different feed concentrations, acid–base compartment volume ratios, and membrane stack configurations on H3Co(CN)6preparation were investigated. The experimental results show that at the operation voltage of 8 V, feed/base compartment volume ratio of 2:1, and feed concentration of 0.4 mol/L, the concentration of H3Co(CN)6approached 0.2 mol/L with a conversion rate of 35.3%. Simultaneously, the K+concentration in the acid compartment decreased to a low value of 32.1 g/L. The specific energy consumption and current efficiency for the BMED stack are 1.6 kW h/kg of H3Co(CN)6and 85.8%, respectively. Economic analysis indicated the total process cost of preparing H3Co(CN)6by BMED is 1.1 $/kg. Therefore, this facile strategy provides valuable insight for H3Co(CN)6production without the introduction of additional chemicals.

Radiotherapy causes DNA damage by direct ionization and indirect generation of reactive oxygen species (ROS) thereby destroying cancer cells. However, ionizing radiation (IR) unexpectedly elicits metastasis and invasion of cancer cells by inducing cancer stem cells’ (CSCs) properties. As BMI1 is a crucial gene that causes radioresistance and an unfavorable prognosis of hepatocellular carcinoma (HCC), BMI1 inhibitor PTC-209 has been encapsulated in a ROS-responsive liposome (LP(PTC-209)) to be temporally and spatially delivered to radioresistant HCC tissue. The ROS generated during IR was not only considered to directly cause tumor cell death but also be used as a stimulator to trigger ROS-responsive drug release from LP(PTC-209). The PTC-209 released into resistant HCC tissue under radiotherapy further led to cancer stem cell (CSC) differentiation and then recovered radiosensitivity of HCC tumor. The suppression of the radioresistant performance of LP(PTC-209) has been proved on radiosensitive and radioresistant Hepa1-6 CSC tumor models, respectively. Our study clarified the relationship between radiotherapy and cancer stemness and provided insights to achieve complete suppression of radioresistant HCC tumor by inhibiting cancer stemness.