Metal-organic frameworks (MOFs) are studied for the design of advanced nanocomposite membranes, primarily due to their ultrahigh surface area, regular and highly tunable pore structures, and favorable polymer affinity. However, the development of engineered MOF-based membranes for water treatment lags behind. Here, thin-film nanocomposite (TFN) membranes containing poly(sodium 4-styrenesulfonate) (PSS) modified ZIF-8 (mZIF) in a polyamide (PA) layer were constructed via a facile interfacial polymerization (IP) method. The modified hydrophilic mZIF nanoparticles were evenly dispersed into an aqueous solution comprising piperazine (PIP) monomers, followed by polymerizing with trimesoyl chloride (TMC) to form a composite PA film. FT-IR spectroscopy and XPS analyses confirm the presence of mZIF nanoparticles on the top layer of the membranes. SEM and AFM images evince a retiform morphology of the TFN-mZIF membrane surface, which is intimately linked to the hydrophilicity and adsorption capacity of mZIF nanoparticles. Furthermore, the effect of different ZIF-8 loadings on the overall membrane performance was studied. Introducing the hydrophilizing mZIF nanoparticles not only furnishes the PA layer with a better surface hydrophilicity and more negative charge but also more than doubles the original water permeability, while maintaining a high retention of NaSO. The ultrahigh retentions of reactive dyes (e.g., reactive black 5 and reactive blue 2, >99.0%) for mZIF-functionalized PA membranes ensure their superior nanofiltration performance. This facile, cost-effective strategy will provide a useful guideline to integrate with other modified hydrophilic MOFs to design nanofiltration for water treatment.
Oxygen evolution from water poses a significant challenge in solar fuel production because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen evolution reaction (OER). Here, a new strategy was developed to synthesize nonsupported ultrasmall cobalt oxide nanocubanes through an in situ phase transformation mechanism using a layered Co(OH)(OCH3) precursor. Under sonication, the precursor was exfoliated and transformed into cobalt oxide nanocubanes in the presence of NaHCO3-Na2SiF6 buffer solution. The resulting cobalt catalyst with an average particle size less than 2 nm exhibited a turnover frequency of 0.023 per second per cobalt in photocatalytic water oxidation. X-ray absorption results suggested a unique nanocubane structure, where 13 cobalt atoms fully coordinated with oxygen in an octahedral arrangement to form 8 Co4O4 cubanes, which may be responsible for the exceptionally high OER activity.
BACKGROUND: Circulating tumor DNA (ctDNA) has emerged as a noninvasive biomarker for dynamically monitoring tumors. However, published data on perioperative ctDNA in patients with operable non-small cell lung cancer (NSCLC) are currently limited. METHODS: This prospective study recruited 123 patients with resectable stage I to IIIA NSCLC. Preoperative and postoperative plasma samples and tumor tissue samples were subjected to next-generation sequencing with a panel of 425 cancer-related genes. Peripheral blood samples were collected before surgery, postoperatively within 1 month, and every 3 to 6 months for up to 3 years. RESULTS: After 4 exclusions, 119 eligible patients were enrolled from June 2016 to February 2019. Presurgical ctDNA was detectable in 29 of 117 patients (24.8%) and was associated with inferior recurrence-free survival (RFS; hazard ratio [HR], 2.42; 95% CI, 1.11-5.27; P = .022) and inferior overall survival (OS; HR, 5.54; 95% CI, 1.01-30.35; P = .026). Similarly, ctDNA was detected in 12 of 116 first postsurgical samples (10.3%) and was associated with shorter RFS (HR, 3.04; 95% CI, 1.22-7.58; P = .012). During surveillance after surgery, longitudinal ctDNA-positive patients (37 of 119; 31.1%) had significantly shorter RFS (HR, 3.46; 95% CI, 1.59-7.55; P < .001) and significantly shorter OS (HR, 9.99; 95% CI, 1.17-85.78; P = .010) in comparison with longitudinal ctDNA-negative patients. Serial ctDNA detection preceded radiologic disease recurrence by a median lead time of 8.71 months. CONCLUSIONS: These results suggest that perioperative ctDNA analyses can predict recurrence and survival, and serial ctDNA analyses can identify disease recurrence/metastasis earlier than routine radiologic imaging in patients with resectable NSCLC.
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