Interfacially crosslinked ß-cyclodextrin polymer composite porous membranes for fast removal of organic micropollutants from water by flow-through adsorption.

Persistent organic micropollutants have seriously damaged aquatic ecological equilibrium and affected human health. Conventional adsorbents are limited due to slow adsorption rate. Therefore, it's significant to integrate adsorbent into porous membrane to develop a highly efficient continuous filtration method for water purification. Herein, ß-cyclodextrin polymer (ß-CDP) composite porous membranes were prepared via convenient interfacial cross-linking. The membranes combined the adsorption ability of ß-CDP and the convective mass transport process of filtration membrane to quickly remove contaminants from water by flow-through adsorption. In optimized preparation conditions, the composite membrane exhibited a 100% of removal efficiency towards bisphenol A and a high treating capacity up to 440 mg m-2. The treating capacity kept nearly unchanged in acidic and neutral pH condition, while increased greatly with the addition of salts due to the salting-out effect. Also, the membrane could completely remove pollutants with ultrahigh flux up to 2500 L·m-2 h-1. In addition, the used membranes were fully regenerated by mild ethanol cleaning.

Macroporous membranes doped with micro-mesoporous ß-cyclodextrin polymers for ultrafast removal of organic micropollutants from water.

Herein, we report novel macroporous membranes doped with micro-mesoporous ß-cyclodextrin polymers (ß-CDP), named ß-CDP membranes, for water decontamination by the flow-through process. These membranes combine excellent adsorption behavior of ß-CDP and the advantages of membranes filtration including low energy consumption and easy scale-up. Filtration adsorption results demonstrated that the optimal ß-CDP membrane removed > 99.9% of bisphenol A with ultrahigh water flux (3000 L m-2 h-1) or high concentration (50 mg L-1). The dynamic adsorption capacity of the membrane was close to the static maximum adsorption capacity of membrane, suggesting the effective accessibility of adsorption sites. The outstanding adsorption performance was attributed to the synergistic effect of the fast adsorption of ß-CDP, abundant ß-CDP nanoparticles and large contact area offered by spongy pores. Furthermore, not only single other organic micropollutants but also mixture was completely removed by the ß-CDP membranes. In addition, the membranes were easily regenerated by simple ethanol filtration.

Hierarchically micro-mesoporous ß-cyclodextrin polymers used for ultrafast removal of micropollutants from water.

Persistent organic pollutants, including plasticizers, pesticides, pharmaceuticals and endocrine disrupters, have posed a serious threat to water safety and human health. Addressing this problem calls out new materials of purifying water with high efficiency. Here, a series of cross-linked ß-cyclodextrin polymers (ß-CDPs) with hierarchically micro-mesoporous structure and high surface area were first synthesized by introducing polymer of intrinsic microporosity (PIM) and used for adsorptive removal of organic micropollutants from water. The chemical compositions and porous structures of the obtained ß-CDPs were characterized in detail. Adsorption data showed that the quasi-second-order adsorption rate constant and maximal adsorption capacity of ß-CDPs towards bisphenol A was up to 3.88 g mg-1 min-1 and 502 mg g-1, almost 2.6 and 5.7 times as large as those of the state-of-the-art porous ß-CD polymer, respectively. Further, hierarchically porous ß-CDPs also demonstrated ultrafast adsorption rates and high adsorption capacities towards various organic pollutants under the synergistic effect of micropores and mesopores. In addition, ß-CDPs were easily regenerated by simple ethanol cleaning and kept high removal ability over 5 cycles. The virtues of extraordinary adsorption ability and convenient regeneration offer ß-CDPs potential applications in water purification.

Poly (N-vinyl imidazole) gel-filled membrane adsorbers for highly efficient removal of dyes from water.

Energy-efficient and time-saving process for recovery of hazardous dyes from wastewater is highly desired in dyeing industry. In this work, poly(N-vinyl imidazole) (PVI) gel-filled membrane adsorbers were developed for highly efficient recovery of dyes through adsorption filtration. The membrane adsorbers were fabricated via dip-coating of Nylon macroporous membranes in PVI solutions followed by quaternization crosslinking with p-xylylene dichloride (XDC). Physicochemical characterizations indicated that PVI gel was successfully filled and fixed inside the Nylon matrix. In optimized conditions. The treating capacity of membrane adsorbers to typical dye sunset yellow (25 ppm of the feed concentration) reached up to 197 mg/g with the removal ratio >99%. Both the treating capacity and the removal ratio were kept steady even when the permeation flux was as high as 1000 L/m2 h. The membrane adsorbers developed in this work were able to not only remove anionic dyes from water, but also separate anionic dyes from cationic ones. The zeta potential and adsorption tests showed that the electrostatic interaction between PVI gel and dye molecules was responsible for the high removal efficiencies to anionic dyes. The membrane adsorbers can be regenerated effectively with NaOH solution and demonstrated good stability in both acidic and alkaline conditions.

A crosslinked ß-cyclodextrin polymer used for rapid removal of a broad-spectrum of organic micropollutants from water.

Organic micropollutants in aquatic environment such as plasticizer, pesticide and pharmaceuticals, have posed a serious threat to human health and are emerging as a great challenge to humanity. Traditional water treatment techniques fail to achieve high removal efficiency for low concentration of organic micropollutants. Here we demonstrate a water-insoluble crosslinked ß-cyclodextrin (ß-CD) polymer able to remove a broad-spectrum of organic micropollutants from water by rapid adsorption. A family of ß-CD polymers (ß-CDPs) were synthesized by nucleophilic aromatic substitution of ß-CD hydroxyl groups and 4,4'-difluorodiphenylsulfone. The ß-CDPs were used to adsorb various organic micropollutants in water by static or dynamic adsorption process. It was found that more than 99% micropollutants in water were removed by flowing the feed water through the column of ß-CDPs. The results of static adsorption experiments indicated the adsorption process was fast and the adsorption capacity was very high (the maximal value was 113.0mg of bisphenol A per gram of ß-CDP). The adsorption process was fitted well with the quasi-second-order kinetics and the Langmuir isothermal adsorption model, suggesting that it is mainly a chemical adsorption of monolayer. The water-insoluble characteristic of the ß-CDPs is convenient for their separation from the treated solution after adsorption saturation for regeneration and reuse. The adsorption ability of ß-CDPs was kept nearly unchanged after five filtration-regeneration cycles.

[Effect of tyrosine kinase inhibitors on airway remodeling in bronchial asthma].

OBJECTIVE: To investigate the effect of tyrosine kinase inhibitors (TKIs) on asthmatic rat airway remodeling. METHODS: The inhibitive effects of three TKIs (Genistein, jin-zhuan-ting and Tyrphostin AG1478) on proliferation of primary cultures of rat tracheal epithelial cells were assessed by MTT assay. Then, jin-zhuan-ting was adopted in the asthmatic rat model; immunohistofluorescene method was used to stain phosphorylated tyrosine (P-tyr) for disclosing the activation of EGFR; Sirius Red staining of submucosal collagen I and III was performed, and an analysis was made on the correlation between EGFR activation and collagen I and III deposition. RESULTS: All the three TKIs inhibited the growth of tracheal epithelial cells in a time and dose depending manner, and the inhibition rates among them showed no statistical differences; airway subepithelial collagen I and III deposition degrees were markedly elevated in asthmatic groups and jin-zhuan-ting reduced the deposition in a certain degree; EGFR activation (P-tyr) in airways epithelium of asthmatic groups was greatly increased in comparison with that of control groups, and it was evidently decreased in jin-zhuan-ting groups. Correlation analysis demonstrated that the amount of airway subepithelial collagen I and III was positively correlated to EGFR activation. CONCLUSION: TKIs may have preventive implications for asthmatic airway remodeling.

[Inflammatory memory of pulmonary local lymphocytes in asthmatic mice].

OBJECTIVE: To investigate if long-lived inflammatory memory exists in the airway of asthmatic mice, and whether pulmonary local lymphocytes could transfer the inflammatory memory. METHODS: 97 mice were divided into six groups by random number meter: asthma group (group A, n = 50), long term group (group B, n = 20), control group of long term (group C, n = 6), adoptive transfer group (group D, n = 12, subgroups D1, D2 and D3 divided based on the transferred cells counts), adoptive transfer control group (group E, n = 6), and naive group( group F, n = 3). There were subgroups using BSA (bovine serum album) substituting OVA (ovalbumin) for the second challenge, named subgroup B-BSA in group B and subgroup D-BSA in group D. Pathologic changes, alveolar eosinophil infiltration, total cell counts (TCC) in bronchoalveolar lavage fluid (BALF), leukocyte differentials, and BALF IL-5 level were assayed in every group. Comparisons of inflammation responses between group B and group A, also between group D and group A were made. From asthmatic mice 34 d post aerosol, bronchoalveolar lavage (BAL) cells and splenocytes free of red blood cells (NR-splenocyte in brief) were cultured in vitro and stimulated with allergens, to detect cell proliferations and IL-5 levels in the supernatant. RESULTS: (1) Vasculitis, alveolitis and bronchiolitis were observed in group A. TCC, BALF eosinophil and IL-5 reached peak on 240 h and 8 h, 24 h post aerosol respectively [ (22 +/- 5 ) x 10(4)/ml, (1.43 +/- 0.09) x 10(4)/ml and (75.1 +/- 52. 9) pg/ml, respectively]. There were scattered vasculitis and al)veolitis in group B before second OVA challenge; and more severe vasculitis and 3-fold higher alveolitis (ratio of alveolar eosinophil inflammation indexes is 21.23/7.14) were observed after second challenge. TCC and BALF eosinophils reached peak 24 h post aerosol [(121.5 +/- 19.1) x 10(4)/ml and (12.960 +/- 2.040) x 10(4)/ml respectively], BALF IL-5 reached to its highest level [(50.8 +/- 18.5) pg/ml] 48 h post aerosol. There were mild vasculitis in group B-BSA, while TCC [(5.3 +/- 2. 1) x 10(4)/ml] and eosinophil [(0.060 +/- 0. 050) x 10(4)/ml] were both significantly lower than those of group B 24 h post aerosol [(121.5 +/- 19. 1 ) x 10(4)/ml and (12.960 +/- 2.040) x 10(4)/ml respectively, P < 0.05]. BAL cells stimulated with OVA in vitro proliferated stronger [(166.8 +/- 4.81) Bq] than those with BSA stimulation [(61.0 +/- 24.1) Bq] (P < 0.05). Supernatant IL-5 levels in cell cultures with OVA or BSA stimulation were similar [(49 +/- 4) pg/ml and (46 +/- 21) pg/ml respectively] (P > 0.05). (2) There were vasculitis in group D2, with TCC [(5.0 +/- 1.0) x 10(4)/ml] and BALF IL-5 [(24.4 +/- 2.1) pg/ml] 24 h post aerosol. There were bronchiolitis in group D3, with TCC [(7.3 +/- 5.8) x 10(4)/ml] and BALF IL-5 [(45 +/- 6.2) pg/ml] 24 h post aerosol. There was significant difference between group D2 and D3 on BALF IL-5 (P < 0. 05), but not on TCC (P > 0. 05). No vasculitis was observed in group D-BSA, with TCC [(3.3 +/- 4.2) x 10(4)/ml] not statistically different from group D [(5.0 +/- 1.0) x 10(4)/ml] (P > 0. 05). CONCLUSION: It is illustrated that long-lived inflammatory memory may exist in asthmatic mice lung, and pulmonary local lymphocytes may sufficient to transfer the memory.