Enhancing ion selectivity by tuning solvation abilities of covalent-organic-framework membranes.

Understanding the molecular-level mechanisms involved in transmembrane ion selectivity is essential for optimizing membrane separation performance. In this study, we reveal our observations regarding the transmembrane behavior of Li+ and Mg2+ ions as a response to the changing pore solvation abilities of the covalent-organic-framework (COF) membranes. These abilities were manipulated by adjusting the lengths of the oligoether segments attached to the pore channels. Through comparative experiments, we were able to unravel the relationships between pore solvation ability and various ion transport properties, such as partitioning, conduction, and selectivity. We also emphasize the significance of the competition between Li+ and Mg2+ with the solvating segments in modulating selectivity. We found that increasing the length of the oligoether chain facilitated ion transport; however, it was the COF membrane with oligoether chains containing two ethylene oxide units that exhibited the most pronounced discrepancy in transmembrane energy barrier between Li+ and Mg2+, resulting in the highest separation factor among all the evaluated membranes. Remarkably, under electro-driven binary-salt conditions, this specific COF membrane achieved an exceptional Li+/Mg2+ selectivity of up to 1352, making it one of the most effective membranes available for Li+/Mg2+ separation. The insights gained from this study significantly contribute to advancing our understanding of selective ion transport within confined nanospaces and provide valuable design principles for developing highly selective COF membranes.

Enhancing Sustainable Energy Conversion Efficiency by Incorporating Photoelectric Responsiveness into Multiporous Ionic Membrane.

The evolution of porous membranes has revitalized their potential application in sustainable osmotic-energy conversion. However, the performance of multiporous membranes deviates significantly from the linear extrapolation of single-pore membranes, primarily due to the occurrence of ion-concentration polarization (ICP). This study proposes a robust strategy to overcome this challenge by incorporating photoelectric responsiveness into permselective membranes. By introducing light-induced electric fields within the membrane, the transport of ions is accelerated, leading to a reduction in the diffusion boundary layer and effectively mitigating the detrimental effects of ICP. The developed photoelectric-responsive covalent-organic-framework membranes exhibit an impressive output power density of 69.6 W m-2 under illumination, surpassing the commercial viability threshold by ≈14-fold. This research uncovers a previously unexplored benefit of integrating optical electric conversion with reverse electrodialysis, thereby enhancing energy conversion efficiency.

Catalysis of Synergistic Reactions by Host-Guest Assemblies: Reductive Carbonylation of Nitrobenzenes.

Numerous chemical transformations require two or more catalytically active sites that act in a concerted manner; nevertheless, designing heterogeneous catalysts with such multiple functionalities remains an overwhelming challenge. Herein, it is shown that by the integration of acidic flexible polymers and Pd-metallated covalent organic framework (COF) hosts, the merits of both catalytically active sites can be utilized to realize heterogeneous synergistic catalysis that are active in the conversion of nitrobenzenes to carbamates via reductive carbonylation. The concentrated catalytically active species in the nanospace force two catalytic components into proximity, thereby enhancing the cooperativity between the acidic species and Pd species to facilitate synergistic catalysis. The resulting host-guest assemblies constitute more efficient systems than the corresponding physical mixtures and the homogeneous counterparts. Furthermore, this system enables easy access to a family of important derivatives such as herbicides and polyurethane monomers and can be integrated with other COFs, showing promising results. This study utilizes host-guest assembly as a versatile tool for the fabrication of multifunctional catalysts with enhanced cooperativity between different catalytic species.

Function-Led Design of Covalent-Organic-Framework Membranes for Precise Ion Separation.

Insufficient access to clean water and resources has emerged as one of the most pressing issues affecting people globally. Membrane-based ion separation has become a focal point of research for the generation of fresh water and the extraction of energy elements. This Review encapsulates recent advancements in the selective ion transport of covalent organic framework (COF) membranes, accomplished by strategically pairing diverse monomers to create membranes with various pore sizes and environments for specific purposes. We first discuss the merits of using COF materials as a basis for fabricating membranes for ion separation. We then explore the development of COF membranes in areas such as desalination, acid recovery, and energy element extraction, with a particular emphasis on the fundamental principles of membrane design. Lastly, we address both theoretical and practical challenges, as well as potential opportunities in the targeted design of ion-selective membranes. The goal of this Review is to stimulate future investigative efforts in this field, which is of significant scientific and strategic importance.

Preoperative small airway dysfunction is associated with skeletal muscle loss in early-stage non-small cell lung cancer.

BACKGROUND: Postoperative skeletal muscle loss (SM loss) was reported to be associated with a poor prognosis in early-stage non-small cell lung cancer (NSCLC). Small airway dysfunction (SAD) is a common but neglected respiratory abnormality. Little information is known about the association between preoperative SAD and postoperative SM loss in early-stage NSCLC. Therefore, this study aimed to investigate the correlation between preoperative SAD and SM loss after surgery in early-stage NSCLC patients. METHODS: There were 348 NSCLC patients with stages I-IIIA in this study from January 2017 to December 2020. All CT images were contrast-enhanced scans, and the skeletal muscle index (SMI) was measured using CT images. A 10.0% decrease in SMI over 12 months was determined as the cut-off value to define excessive SM loss. Logistic regression analyses were used to examine the relationship between SAD and SM loss. RESULTS: This study included 348 subjects who underwent pulmonary operation (159 males and 189 females; mean age: 57.5 ± 8.8 years). 152 (43.7%) patients were identified as having SAD before surgery, and 179 patients (51.4%) were identified as having SM loss after 1 year. Moreover, a higher incidence of SAD was found in the SM loss group compared with that in the non-SM loss group (52.0% vs. 34.9%, p = 0.001). The patients with SAD were older, had larger tumor size, and had lower albumin levels. Furthermore, there were significant correlations between the lung function parameters manifesting SAD and the percentage change in SMI (for the forced expiratory flow when 75% of forced vital capacity has been exhaled (FEF75%), Pearson r=-0.107, p = 0.046; for FEF50%, r = -0.142, p = 0.008; and for FEF25-75%, r=-0.124, p = 0.021; respectively). However, no significant correlations were found between SMI and the lung function parameters reflecting proximal airway obstruction (p > 0.05). Logistic regression analysis revealed that preoperative SAD (HR, 2.465; 95% CI, 1.256-4.838; p = 0.009) was independent risk factor for postoperative SM loss in early-stage NSCLC. In addition, multivariable analysis revealed that SAD (HR, 1.816; 95% CI, 1.025-3.216, P = 0.041) were associated with postoperative complications. CONCLUSION: Preoperative SAD is significantly associated with postoperative complications and SM loss in early NSCLC patients. Our results suggest that preoperative assessment of SAD may be useful for risk stratification of surgical candidates with potential for targeted interventions.

Guanidinium-based covalent organic framework membrane for single-acid recovery.

Acids are extensively used in contemporary industries. However, time-consuming and environmentally unfriendly processes hinder single-acid recovery from wastes containing various ionic species. Although membrane technology can overcome these challenges by efficiently extracting analytes of interest, the associated processes typically exhibit inadequate ion-specific selectivity. In this regard, we rationally designed a membrane with uniform angstrom-sized pore channels and built-in charge-assisted hydrogen bond donors that preferentially conducted HCl while exhibiting negligible conductance for other compounds. The selectivity originates from the size-screening ability of angstrom-sized channels between protons and other hydrated cations. The built-in charge-assisted hydrogen bond donor enables the screening of acids by exerting host-guest interactions to varying extents, thus acting as an anion filter. The resulting membrane exhibited exceptional permeation for protons over other cations and for Cl- over SO42- and HnPO4(3-n)- with selectivities up to 4334 and 183, respectively, demonstrating prospects for HCl extraction from waste streams. These findings will aid in designing advanced multifunctional membranes for sophisticated separation.

Efficacy of Chinese Herbal Medicines on Pregnancy Outcomes in Patients with Endometriosis in Long-Term Management: A Multicenter Retrospective Cohort Study.

OBJECTIVE: To analyze the factors related to pregnancy of endometriosis and whether Chinese herbal medicines (CHMs) can improve pregnancy outcomes in patients with endometriosis in long-term management. METHODS: This multicenter cohort study retrospectively analyzed the clinical data of endometriosis patients with fertility needs from January 2019 to November 2019. A total of 252 patients with endometriosis from 5 level-III Grade A hospitals in Beijing were included in this study. Univariate and multivariate logistic regression analysis were performed for the relevant factors. The propensity score matching (PSM) function of SPSS software was used to match the CHMs group with the non-CHMs group. The pregnancy rate and live birth rate were analyzed. RESULTS: The results of univariate analysis showed that age, disease course, presence of infertility, presence of adenomyosis, time after surgery or use of gonadotropin-releasing hormone agonist (GnRH-a), use of CHMs and follow-up time were influencing factors of pregnancy in endometriosis patients (P<0.05). The results of multivariate analysis showed that age, presence of adenomyosis, time after surgery or use of GnRH-a, use of CHMs and follow-up time were independent factors affecting pregnancy in endometriosis patients, among which, age ⩾35 years old, presence of adenomyosis and follow-up time >6 months were independent risk factors (OR=0.445, 0.348, 0.140, respectively, P<0.05), time after surgery or use of GnRH-a ⩽6 months and use of CHMs were independent protective factors (OR=3.839, 3.842, respectively, P<0.05). After PSM, 99 pairs of two groups were matched successfully. The pregnancy rate of the CHMs group was higher than that of the non-CHMs group [55.56% (55/99) vs. 36.36% (36/99), P<0.05]. The live birth rate of the CHMs group was higher than that of the non-CHMs group [49.49% (49/99) vs. 35.35% (35/99), P<0.05]. CONCLUSION: CHMs can effectively improve clinical pregnancy rate and live birth rate of patients with endometriosis in the chronic disease management.

Construction and Chlorine Resistance of Thiophene-Poly(ethyleneimine)-Based Dual-Functional Nanofiltration Membranes.

The demand to improve the chlorine resistance of polyamide (PA) membranes is escalated with greater amounts of chlorine-containing disinfectant being used in global water treatment during the COVID-19 pandemic. In this work, we designed thiophene-functionalized poly(ethyleneimine) (TPEI) materials first and grafted them onto a conventional PA membrane to develop novel nanofiltration membranes (PEI-M, TPEI-1-M, TPEI-2-M). These membranes have dual-functionalized selective surfaces covered by hydrophilic amino groups and electron-rich thiophene moieties, which endow these membranes with superior chlorine resistance and improved separation performance. The modified membranes increase the rejection of MgCl2 from 86.5% of the nascent PA membrane (PA-M) to higher than 93.0% without sacrificing the membrane water permeability. More stable separation performance is achieved with all of the as-prepared membranes than PA-M after exposure to a 2000 ppm sodium hypochlorite solution. TPEI-2-M outperforms other membranes after being treated in a chlorination intensity of 16,000 ppm·h with the smallest flux loss and the highest MgCl2 rejection. This is mainly ascribed to the highest amount of amino and thiophene moieties on the TPEI-2-M surface. This study provides an effective protocol for developing novel PA-based nanofiltration membranes while demonstrating its superiority over current technologies with exceptional separation performance and antichlorine ability.

The Establishment of China Bronchiectasis Registry and Research Collaboration (BE-China): Protocol of a prospective multicenter observational study.

BACKGROUND: Bronchiectasis is a highly heterogeneous chronic airway disease with marked geographic and ethnic variations. Most influential cohort studies to date have been performed in Europe and USA, which serve as the examples for developing a cohort study in China where there is a high burden of bronchiectasis. The Establishment of China Bronchiectasis Registry and Research Collaboration (BE-China) is designed to: (1) describe the clinical characteristics and natural history of bronchiectasis in China and identify the differences of bronchiectasis between the western countries and China; (2) identify the risk factors associated with disease progression in Chinese population; (3) elucidate the phenotype and endotype of bronchiectasis by integrating the genome, microbiome, proteome, and transcriptome with detailed clinical data; (4) facilitate large randomized controlled trials in China. METHODS: The BE-China is an ongoing prospective, longitudinal, multi-center, observational cohort study aiming to recruit a minimum of 10,000 patients, which was initiated in January 2020 in China. Comprehensive data, including medical history, aetiological testing, lung function, microbiological profiles, radiological scores, comorbidities, mental status, and quality of life (QoL), will be collected at baseline. Patients will be followed up annually for up to 10 years to record longitudinal data on outcomes, treatment patterns and QoL. Biospecimens, if possible, will be collected and stored at - 80 °C for further research. Up to October 2021, the BE-China has enrolled 3758 patients, and collected 666 blood samples and 196 sputum samples from 91 medical centers. The study protocol has been approved by the Shanghai Pulmonary Hospital ethics committee, and all collaborating centers have received approvals from their local ethics committee. All patients will be required to provide written informed consent to their participation. CONCLUSIONS: Findings of the BE-China will be crucial to reveal the clinical characteristics and natural history of bronchiectasis and facilitate evidence-based clinical practice in China. Trial registration Registration Number in ClinicalTrials.gov: NCT03643653.

Anomalous thermo-osmotic conversion performance of ionic covalent-organic-framework membranes in response to charge variations.

Increasing the charge density of ionic membranes is believed to be beneficial for generating high output osmotic energy. Herein, we systematically investigated how the membrane charge populations affect permselectivity by decoupling their effects from the impact of the pore structure using a multivariate strategy for constructing covalent-organic-framework membranes. The thermo-osmotic energy conversion efficiency is improved by increasing the membrane charge density, affording 210 W m-2 with a temperature gradient of 40 K. However, this enhancement occurs only within a narrow window, and subsequently, the efficiency plateaued beyond a threshold density (0.04 C m-2). The complex interplay between pore-pore interactions in response to charge variations for ion transport across the upscaled nanoporous membranes helps explain the obtained results. This study has far-reaching implications for the rational design of ionic membranes to augment energy extraction rather than intuitively focusing on achieving high densities.

Thermo-Osmotic Energy Conversion Enabled by Covalent-Organic-Framework Membranes with Record Output Power Density.

A vast amount of energy can be extracted from the untapped low-grade heat from sources below 100 °C and the Gibbs free energy from salinity gradients. Therefore, a process for simultaneous and direct conversion of these energies into electricity using permselective membranes was developed in this study. These membranes screen charges of ion flux driven by the combined salinity and temperature gradients to achieve thermo-osmotic energy conversion. Increasing the charge density in the pore channels enhanced the permselectivity and ion conductance, leading to a larger osmotic voltage and current. A 14-fold increase in power density was achieved by adjusting the ionic site population of covalent organic framework (COF) membranes. The optimal COF membrane was operated under simulated estuary conditions at a temperature difference of 60 K, which yielded a power density of ≈231 W m-2 , placing it among the best performing upscaled membranes. The developed system can pave the way to the utilization of the enormous supply of untapped osmotic power and low-grade heat energy, indicating the tremendous potential of using COF membranes for energy conversion applications.

The value of AGR2 and KRT5 as an immunomarker combination in distinguishing lung squamous cell carcinoma from adenocarcinoma.

With the advancement of tumor subtype-specific treatments, precise histopathologic distinction between adenocarcinoma (ADC) and squamous cell carcinoma (SCC) is of significant clinical importance. Nevertheless, the current markers are insufficiently precise in poorly differentiated tissue. This study aimed to establish a histology-specific immunomarker combination to subclassify non-small cell lung cancer (NSCLC) specimens. Based on previous work, we assessed the differential expression of anterior gradient 2 (AGR2) and keratin 5 (KRT5) in ADC and SCC by analyzing public datasets and postoperative specimens. Subsequently, we established a train set (n = 188) and a validation set (n = 42) comprised of NSCLC surgical specimens for training and verifying the subtype-identification capabilities of the two biomarkers separately and in combination, and contrasted the diagnostic utility of AGR2-KRT5 with that of the classic immunomarker combination, TTF1-P40. Differential expression of the two genes was statistically significant in ADC and SCC samples, both at the mRNA and protein levels. The specificity and sensitivity of AGR2 to detect ADC in the training set were 97.0% and 94.4%, while the sensitivity and specificity of KRT5 to determine SCC were 93.9% and 98.9%, respectively. The accuracies of AGR2-KRT5 in ADC, SCC, and across all samples were 93.3%, 92.0% and 92.6% respectively. In the validation cohort, the predictive accuracy of AGR2-KRT5 was up to 100% for ADC and 86.7% for SCC. Compared with TTF1-P40 in ADC samples, AGR2-KRT5 had 8.4% higher accuracy. In summary, the AGR2-KRT5 immunomarker combination reliably distinguished SCC from ADC, and was more accurate than TTF1-P40 in ADC.

Membrane Surface Functionalization with Imidazole Derivatives to Benefit Dye Removal and Fouling Resistance in Forward Osmosis.

Water contaminated with low concentrations of pollutants is more difficult to clean up than that with high pollutant content levels. Membrane separation provides a solution for removing low pollutant content from water. However, membranes are prone to fouling, losing separation performances over time. Here we synthesized neutral (IM-NH2) and positively charged (IL-NH2) imidazole derivatives to chemically functionalize membranes. With distinct properties, these imidazole grafts could tailor membrane physicochemical properties and structures to benefit forward osmosis (FO) processes for the removal of 20-100 ppm of Safranin O dye-a common dye employed in the textile industry. The water fluxes produced by IM-NH2- and IL-NH2-modified membranes increased by 67% and 122%, respectively, with DI water as the feed compared to that with the nascent membrane. A 39% flux increment with complete dye retention (∼100%) was achieved for the IL-NH2-modified membrane against 100 ppm of Safranin O dye. Regardless of the dye concentration, the IL-NH2-modified membrane exhibited steadily higher permeation performance than the original membrane in long-term experiments. Reproducible experimental results were obtained with the IL-NH2-modified membrane after cleaning with DI water, demonstrating the good antifouling properties and renewability of the newly developed membrane.

Enhancing Chlorine Resistance and Water Permeability during Forward Osmosis Separation Using Superhydrophilic Materials with Conjugated Systems.

Poor resistance to free chlorine severely impairs the service of conventional polyamide (PA) membrane in water treatment. Here we design a series of superhydrophilic aromatic sulfonate materials (ASMs) comprising successively increasing conjugated systems and ionizable groups (ASM-1, ASM-2, ASM-3) to develop a chlorine-resistant membrane via chemical modification. By altering the membrane physicochemical properties and surface structure, ASMs substantially improve the chlorine resistance and water permeability of membrane. With 0.5 M NaCl as the draw solution, all ASMs enhance membrane water fluxes by more than 60% relative to those of the nascent PA membrane in forward osmosis (FO) processes. After exposed to a 1000 ppm sodium hypochlorite solution for 2-8 h, the modified membranes exhibit smaller variations in FO performance than the PA membrane. Having the largest conjugated system and the most sulfonate groups, ASM-3 enables the membrane to sustain a chlorination strength of up to 8000 ppm·h with an insignificant NaCl loss during the FO process, surpassing other recently developed PA membranes in chlorine resistance. These results manifest that the combination of a large conjugated system and ionizable group is key for imbuing membrane with excellent chlorine resistance and water permeability.

Chinese Medicine Sequential Therapy Improves Pregnancy Outcomes after Surgery for Endometriosis-Associated Infertility: A Multicenter Randomized Double-blind Placebo Parallel Controlled Clinical Trial.

OBJECTIVE: To evaluate the efficacy and safety of Chinese medicine (CM) improving pregnancy outcomes after surgery for endometriosis-associated infertility. METHODS: A multicenter, randomized, double-blind placebo parallel controlled clinical trial was designed. A total of 202 patients who had laparoscopy for endometriosis-associated infertility with qi stagnation and blood stasis syndrome were included and randomly divided into the CM treatment group and placebo control group at a ratio of 1:1 using a central block randomization from May 2014 to September 2017, 101 patients in each group. The two groups received continuous intervention at 1-5 days after surgery, for 6 menstrual cycles. Before ovulation, the CM group was treated Huoxue Xiaoyi Granule (); after ovulation, Bushen Zhuyun Granule ( was involved. The control group was treated with placebo. Transvaginal ultrasonography was performed every menstrual cycle during the treatment, and female hormone levels in the follicular and luteal phases were measured during the 1st, 3rd and 6th menstrual cycles. The analysis was continued until pregnancy. The primary outcomes were clinical pregnancy rate and pregnancy outcome, and the secondary outcomes were follicular development and endometrial receptivity. Safety evaluations were performed before and after treatment. RESULTS: (1) Clinical pregnancy and live birth rates: the clinical pregnancy and live birth rates of the CM group were significantly higher than those of the placebo group [44.6% (45/101) vs. 29.7% (30/101), 34.7% (35/101) vs. 20.8% (21/101), both P<0.05]. (2) Follicle development: the incidence of dominant follicles, rate of cumulative cycle ovulation, and rate of cumulative cycle mature follicle ovulation were significantly higher in the CM group than those in the placebo group [93.8% (350/373) vs. 89.5% (341/381), 80.4% (275/342) vs. 69.1% (253/366), 65.8% (181/275) vs 56.1% (142/253), P<0.05 or P<0.01]). The incidence of cumulative cycle luteinized unruptured follicle syndrome was significantly lower in the CM group than in the placebo group [11.7% (40/342) vs. 17.8% (65/366), P<0.05). (3) Endometrial receptivity: after treatment, both endometrial types and endometrial blood flow types in the CM group were mainly types A and B, while those in the placebo group were mainly types B and C, with a significant difference between the two groups (both P<0.05). (4) Adverse events: the incidence of adverse events between the two groups was not significantly different (P>0.05). CONCLUSION: Strategies for activating blood circulation-regulating Gan (Liver)-tonifying Shen (Kidney) sequential therapy can effectively improve the clinical pregnancy rate and live birth rate of endometriosis-associated infertility with qi stagnation and blood stasis after laparoscopy, improve follicular development, promote ovulation, improve endometrial receptivity, while being a safe treatment option. (Trial registration No. NCT02676713).

Rose bengal as photocatalyst: visible light-mediated Friedel-Crafts alkylation of indoles with nitroalkenes in water.

A novel and facile visible-light-mediated alkylation of indoles and nitroalkenes has been developed. In this protocol, rose bengal acts as a photosensitizer, and environmentally benign water was used as the green and efficient reaction medium. Indoles reacted smoothly with nitroalkenes under the irradiation of visible-light and generated corresponding 3-(2-nitroalkyl)indoles in moderate to good yields (up to 87%).

Enantioselective photooxygenation of ß-dicarbonyl compounds in batch and flow photomicroreactors.

A series of C-2' modified cinchonine-derived phase-transfer catalysts were synthesized and used in the enantioselective photo-organocatalytic aerobic oxidation of ß-dicarbonyl compounds with excellent yields (up to 97%) and high enantioselectivities (up to 90% ee). Furthermore, the reaction was carried out in a flow photomicroreactor, in which the heterogeneous gas-liquid-liquid asymmetric photocatalytic oxidation reaction was performed affording good yields (up to 97%) and enantioselectivities (up to 86% ee) within 0.89 min.