Zhi-Kang Xu

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Name: 徐志康; ZhiKang Xu
Organization: Zhejiang University , China
Department: Department of Polymer Science and Engineering
Title: Professor(PhD)

TOPICS

Co-reporter:Chao Zhang, Lu Gong, Li Xiang, Yong Du, Wenjihao Hu, Hongbo Zeng, and Zhi-Kang Xu
ACS Applied Materials & Interfaces September 13, 2017 Volume 9(Issue 36) pp:30943-30943
Publication Date(Web):August 23, 2017
DOI:10.1021/acsami.7b09774
Mussel-inspired chemistry, particularly the versatile coating capability of polydopamine (PDA), has received much research interest as a promising strategy for fabricating functional coatings in numerous fields. However, the understanding of deposition mechanisms and adhesion behaviors of PDA on different substrates still remains incomplete, significantly limiting the related fundamental research and its practical applications. In this work, a colloidal probe atomic force spectroscopy technique was employed to quantify the interaction forces and adhesion between the PDA coatings and the substrate surfaces with different wettabilities. The surface force measurements and thermodynamic analysis of interaction energy indicate that the surface wettability has a significant influence on the adhesion, deposition behaviors, and morphologies of PDA coatings. Compared with the hydrophilic surfaces, the hydrophobic surfaces exhibit stronger adhesion with the PDA coatings. Furthermore, for the first time, this work demonstrates that ethanol has the capability of effectively displacing the trapped air/vapor layer or the so-called “hydrophobic depletion layer” on the hydrophobic substrate to allow the intimate contact between PDA and the substrate, thus enhancing the adhesion and facilitating the PDA deposition. This work provides new insights into the fundamental PDA deposition mechanism as well as the design and development of versatile mussel-inspired coatings on the substrates of varying hydrophobicity.Keywords: colloidal probe AFM technique; deposition mechanism; polydopamine coatings; surface forces; surface wettability;
Co-reporter:Xi Zhang, Yan Lv, Hao-Cheng Yang, Yong Du, and Zhi-Kang Xu
ACS Applied Materials & Interfaces November 30, 2016 Volume 8(Issue 47) pp:
Publication Date(Web):November 10, 2016
DOI:10.1021/acsami.6b10693
Thin-film composite (TFC) nanofiltration membranes are prepared via interfacial polymerization with a polyphenol coating as an interlayer for the thin and smooth polyamide selective layer. The polyphenol interlayer is simply fabricated by the codeposition of tannic acid and diethylenetriamine without changing the surface morphology of the polysulfone ultrafiltration substrate. An interfacial polymerization is conducted from piperazidine and trimesoyl chloride on the polyphenol interlayer to construct the polyamide selective layer. The as-prepared TFC nanofiltration membranes show nearly tripled fold of water permeation flux as compared with those prepared at the same condition without an interlayer. They also exhibit a high rejection to Na2SO4 (>98%) because the thin and defect-free polyamide selective layer is formed on the polyphenol interlayer. These nanofiltration properties have high reproducibility, which means the TFC nanofiltration membranes are suitable for scale-up industrial applications.Keywords: interfacial polymerization; interlayer; nanofiltration; polyphenol coating; thin-film composite membrane;
Co-reporter:Peng-Fei Ren;Hao-Cheng Yang;Ling-Shu Wan;Xiao-Ling Xu;Hong-Qing Liang
Langmuir June 2, 2015 Volume 31(Issue 21) pp:5851-5858
Publication Date(Web):2017-2-22
DOI:10.1021/acs.langmuir.5b00920
Zwitterionic materials have received great attention because of the non-fouling property. As a result of the electric neutrality of zwitterionic polymers, their layer-by-layer (LBL) assembly is generally conducted under specific conditions, such as very low pH values or ionic strength. The formed multilayers are unstable at high pH or in a high ionic strength environment. Therefore, the formation of highly stable multilayers of zwitterionic polymers via the LBL assembly process is still challenging. Here, we report the LBL assembly of poly(sulfobetaine methacrylate) (PSBMA) with a polyphenol, tannic acid (TA), for protein-resistant surfaces. The assembly process was monitored by a quartz crystal microbalance (QCM) and variable-angle spectroscopic ellipsometry (VASE), which confirms the formation of thin multilayer films. We found that the (TA/PSBMA)n multilayers are stable over a wide pH range of 4–10 and in saline, such as 1 M NaCl or urea solution. The surface morphology and chemical composition were characterized by specular reflectance Fourier transform infrared spectroscopy (FTIR/SR), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Furthermore, (TA/PSBMA)n multilayers show high hydrophilicity, with a water contact angle lower than 15°. A QCM was used to record the dynamic protein adsorption process. Adsorption amounts of bovine serum albumin (BSA), lysozyme (Lys), and hemoglobin (Hgb) on (TA/PSBMA)20 multilayers decreased to 0.42, 52.9, and 37.9 ng/cm2 from 328, 357, and 509 ng/cm2 on a bare gold chip surface, respectively. In addition, the protein-resistance property depends upon the outmost layer. This work provides new insights into the LBL assembly of zwitterionic polymers.
Co-reporter:Jun-Ke Pi, Guang-Peng Wu, Hao-Cheng Yang, Christopher G. Arges, and Zhi-Kang Xu
ACS Applied Materials & Interfaces July 5, 2017 Volume 9(Issue 26) pp:21971-21971
Publication Date(Web):June 14, 2017
DOI:10.1021/acsami.7b04505
Porous separators are key components for lithium-ion batteries (LIBs) and they have drawn considerable attention because of their vital role in governing battery cost and performance (e.g., power density, safety, and longevity). Here, zirconia-coated separators were fabricated via a facile biomineralization process with the aim to improve the performance of commercialized polypropylene separators. The as-prepared organic–inorganic composite separators show excellent thermal stability, even at the melting temperature (160 °C) of polypropylene. This is due to the well-distributed zirconia coatings on the separator surfaces. Furthermore, the interfacial impedance of the composite separators is only 343.8 Ω, which is four times lower than the pristine polypropylene ones. The results demonstrate an attractive method to prepare organic–inorganic composite separators with outstanding properties, which makes them promising candidates for high-performance LIBs.Keywords: lithium-ion battery; polydopamine; polyolefin separators; thermal stability; zirconia coating;
Co-reporter:Hao-Cheng Yang, Wenwei Zhong, Jingwei Hou, Vicki Chen, Zhi-Kang Xu
Journal of Membrane Science 2017 Volume 523() pp:1-7
Publication Date(Web):1 February 2017
DOI:10.1016/j.memsci.2016.09.044
•Janus membranes are fabricated by single-sided PDA/PEI deposition on PP hollow fibers.•Thickness of the hydrophilic layer can be facilely adjusted by the deposition time.•The Janus membranes exhibit up to 120% improvement in the water flux for DCMD.•Good operational stability and high salt rejection are obtained with Janus membranes.Membrane distillation is a thermally driven separation process that is widely applied in desalination and wastewater treatment. Hydrophobic membranes with high mass transfer and low heat transfer are desirable in conventional direct contact membrane distillation (DCMD). In this work, we reported a facile method to fabricate Janus hollow fiber membranes with asymmetric wettability for DCMD. The hydrophilic polydopamine/polyethyleneimine coating was deposited onto the lumen surface of hydrophobic polypropylene hollow fiber membrane, and the hydrophilic layer thickness could be easily adjusted by the deposition time. During the DCMD test, the Janus membrane showed an improved permeate flux with the increasing deposition time and operation temperature, and the flux improvement was up to 120% for the Janus membrane deposited for 6 h with 80 °C feed. On the other hand, the Janus membrane also exhibited a high salt rejection and good long-term stability in saline feed desalination with a deposition time of 2 or 4 h. Moreover, this research provides us a facile method to fabricate Janus membranes for other applications.
Co-reporter:Jing-Jing Wang;Hao-Cheng Yang;Ming-Bang Wu;Xi Zhang
Journal of Materials Chemistry A 2017 vol. 5(Issue 31) pp:16289-16295
Publication Date(Web):2017/08/08
DOI:10.1039/C7TA00501F
Nanofiltration membranes are of great interest in brackish water desalination and drinking water purification. Improving the permeation and separation performance remains a big challenge in advanced nanofiltration membranes. Herein, we report triple-layered composite nanofiltration membranes constructed by the interfacial polymerization of diamine and acyl chloride on a cellulose nanocrystal interlayer supported by a microporous substrate. The cellulose nano-crystal interlayer plays a crucial role in the polyamide skin layer formation and the following nanofiltration process. It can store aqueous diamine monomers and slow down the interfacial polymerization for a relatively low cross-linking degree of the skin layer. This hydrophilic interlayer also facilitates water permeation through a “dragging effect”. The constructed membranes exhibit an ultra-high permeation flux up to 204 L m−2 h−1 under 0.6 MPa with a Na2SO4 rejection above 97%, which is the highest reported result to our knowledge. The ultra-high water permeation flux enables nanofiltration at low operating pressure, making it an energy-saving process. Moreover, the low cross-linking degree of the skin layer results in a high monovalent/divalent ion separation ratio.
Co-reporter:Hong-Qing Liang, Wei-Song Hung, Hao-Hao Yu, Chien-Chieh Hu, Kueir-Rarn Lee, Juin-Yih Lai, Zhi-Kang Xu
Journal of Membrane Science 2017 Volume 529(Volume 529) pp:
Publication Date(Web):1 May 2017
DOI:10.1016/j.memsci.2017.01.056
•Forward osmosis (FO) membranes with ultrahigh water flux have been fabricated.•Substrates with vertical pores are used as supports for fabricating FO membranes.•The vertical pores greatly reduce the internal concentration polarization effect.The internal concentration polarization is recognized as a major obstacle for forward osmosis (FO) membranes to achieve high water flux. Herein, porous substrates with vertical pores are first proposed to be used as supports for fabricating FO membranes in thin film composite structure. The addition of acetone in the aqueous phase facilitates the successful interfacial polymerization on the substrates with vertical pores. Positron annihilation lifetime analyses indicate that the fabricated FO membranes possess thicker and denser selective layer than traditional FO membranes with asymmetric substrates. These novel FO membranes have a low structure parameter, indicating a greatly reduced internal concentration polarization effect. They exhibit an unprecedented water flux up to 93.6 L m−2 h−1 when the selective layer is oriented towards the deionized water feed solution with 2 mol L−1 sodium chloride solution as draw stream. This performance outstands from those FO membranes reported in literatures and available commercially. The results demonstrate that substrates with vertically oriented porous structure are ideal supports for developing FO membranes with minimized or even eliminated internal concentration polarization and ultrahigh water flux.Download high-res image (269KB)Download full-size image
Co-reporter:Hong-qing Liang;Hao-nan Li;Hao-hao Yu
Chinese Journal of Polymer Science 2017 Volume 35( Issue 7) pp:846-856
Publication Date(Web):26 May 2017
DOI:10.1007/s10118-017-1943-4
Polysulfone (PSF) membranes have gained great attention in the fields of ultrafiltration, microfiltration, and thin film composite membranes for nanofiltration or reverse osmosis. For the first time, it is proposed to fabricate PSF membranes via thermally induced phase separation (TIPS) process using diphenyl sulfone (DPSO2) and polyethylene glycol (PEG) as mixed diluent. DPSO2 is chosen as a crystallizable diluent, while PEG is considered in terms of molecular weight (Mw) and dosage. We systematically investigate the interactions between PSF, DPSO2 and PEG based on the simulation calculations and solubility parameter theory. It is inferred that DPSO2 has an excellent compatibility with PSF, and the addition of PEG results in the ternary system thermodynamically less stable and then facilitates its liquid-liquid (L-L) phase separation. SEM images indicate that cellular-like pores are obvious throughout the membrane when the PEG content in the mixed diluent is 25 wt%−35 wt%. We can facilely manipulate the pore size, water flux and mechanical properties of PSF membranes with the dosage of PEG-200, the Mw of PEG or the cooling rate. The successful application of TIPS can provide a new approach for structure manipulation and performance enhancement of PSF membranes.
Co-reporter:Ming-Bang Wu, Hao-Cheng Yang, Jing-Jing Wang, Guang-Peng WuZhi-Kang Xu
ACS Applied Materials & Interfaces 2017 Volume 9(Issue 6) pp:
Publication Date(Web):January 31, 2017
DOI:10.1021/acsami.7b00017
A Janus membrane with opposing wettability was first reported with both function of water-to-oil and oil-to-water emulsification. This membrane is conveniently fabricated by single-surface deposition of polydopamine/polyethylenimine (PDA/PEI). The asymmetric wettability can also reduce the transmembrane resistance during the process, indicating an economical and promising strategy to prepare various emulsions. This research opens a novel avenue for exploring and understanding the Janus membrane, and provides a perspective to design the asymmetric membrane structures with promoted performance in conventional membrane processes.Keywords: Janus membrane; membrane emulsification; surface modification; surface wettability; transmembrane pressure;
Co-reporter:Yan Lv, Yong Du, Wen-Ze Qiu, and Zhi-Kang Xu
ACS Applied Materials & Interfaces 2017 Volume 9(Issue 3) pp:
Publication Date(Web):December 21, 2016
DOI:10.1021/acsami.6b13761
A defect-free and stable selective layer is of critical significance for thin film composite membrane with excellent separation performance and service durability. We report a facial strategy for fabricating thin film nanocomposite (TFN) nanofltration membranes (NFMs) based on the codeposition of polydopamine, polyetheylenimine, and silica nanoparticles. Tripled water flux can be obtained from the TFN NFMs as compared with those NFMs without silica nanoparticles. This is ascribed to the improved wettability of the membrane surfaces and the enlarged pore sizes of the selective layer. The interfacial compatibility of the inorganic fillers and the polymer matrices can be enhanced by the electrostatic interactions of silica nanoparticles with polyethylenimine and the adhesive characteristics of polydopamine, resulting in a defect-free selective layer and then good rejection for both bivalent cations and neutral solutes. The rigid silica nanoparticles also improve the surface mechanical strength of the TFN NFMs effectively and lead to structural stability and compaction resistance during the long-term filtration process.Keywords: mussel-inspired chemistry; nanocomposite; nanofiltration membrane; polydopamine; silica nanoparticles;
Co-reporter:Guan-Wen Yang, Guang-Peng WuXuanxuan Chen, Shisheng Xiong, Christopher G. Arges, Shengxiang Ji, Paul F. Nealey, Xiao-Bing LuDonald J. Darensbourg, Zhi-Kang Xu
Nano Letters 2017 Volume 17(Issue 2) pp:
Publication Date(Web):January 9, 2017
DOI:10.1021/acs.nanolett.6b05059
Directed self-assembly (DSA) of block copolymers (BCPs) combines advantages of conventional photolithography and polymeric materials and shows competence in semiconductors and data storage applications. Driven by the more integrated, much smaller and higher performance of the electronics, however, the industry standard polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) in DSA strategy cannot meet the rapid development of lithography technology because its intrinsic limited Flory–Huggins interaction parameter (χ). Despite hundreds of block copolymers have been developed, these BCPs systems are usually subject to a trade-off between high χ and thermal treatment, resulting in incompatibility with the current nanomanufacturing fab processes. Here we discover that polystyrene-b-poly(propylene carbonate) (PS-b-PPC) is well qualified to fill key positions on DSA strategy for the next-generation lithography. The estimated χ-value for PS-b-PPC is 0.079, that is, two times greater than PS-b-PMMA (χ = 0.029 at 150 °C), while processing the ability to form perpendicular sub-10 nm morphologies (cylinder and lamellae) via the industry preferred thermal-treatment. DSA of lamellae forming PS-b-PPC on chemoepitaxial density multiplication demonstrates successful sub-10 nm long-range order features on large-area patterning for nanofabrication. Pattern transfer to the silicon substrate through industrial sequential infiltration synthesis is also implemented successfully. Compared with the previously reported methods to orientation control BCPs with high χ-value (including solvent annealing, neutral top-coats, and chemical modification), the easy preparation, high χ value, and etch selectivity while enduring thermal treatment demonstrates PS-b-PPC as a rare and valuable candidate for advancing the field of nanolithography.Keywords: block copolymer; chemical pattern; Directed self-assembly; lithography; sub-10 nm; thermal annealing;
Co-reporter:Xi Yang, Yong Du, Xi Zhang, Ai He, and Zhi-Kang Xu
Langmuir 2017 Volume 33(Issue 9) pp:
Publication Date(Web):February 10, 2017
DOI:10.1021/acs.langmuir.6b04465
A mussel-inspired interlayer of polydopamine (PDA)/polyethylenimine (PEI) is codeposited on the ultrafiltration substrate to tune the interfacial polymerization of piperazine and trimesoyl chloride for the preparation of thin-film composite (TFC) nanofiltration membranes (NFMs). This hydrophilic interlayer results in an efficient adsorption of piperazine solution in the substrate pores. The solution height increases with the PDA/PEI codeposition time from 45 to 135 min due to the capillary effect of the substrate pores. The prepared TFC NFMs are characterized with thin and smooth polyamide selective layers by ATR/IR, XPS, FESEM, AFM, zeta potential, and water contact angle measurements. Their water permeation flux measured in a cross-flow process increases to two times as compared with those TFC NFMs without the mussel-inspired interlayer. These TFC NFMs also show a high rejection of 97% to Na2SO4 and an salt rejection order of Na2SO4 ≈ MgSO4 > MgCl2 > NaCl.
Co-reporter:Chao Zhang, Hao-Nan Li, Yong Du, Meng-Qi Ma, and Zhi-Kang Xu
Langmuir 2017 Volume 33(Issue 5) pp:
Publication Date(Web):January 16, 2017
DOI:10.1021/acs.langmuir.6b03948
Mussel-inspired polydopamine (PDA) coatings have been broadly exploited for constructing functional membrane surfaces. One-step codeposition of PDA with antifouling polymers, especially zwitterionic polymers, has been regarded as a promising strategy for fabricating antifouling membrane surfaces. However, one challenge is that the codeposition is usually a slow process over 10 h or even several days. Herein, we report that CuSO4/H2O2 is able to notably accelerate the codeposition process of PDA with poly(sulfobetaine methacrylate) (PSBMA). In our case, PSBMA is facilely anchored to the polypropylene microporous membrane (PPMM) surfaces within 1 h with the assistance of PDA because of its strong interfacial adhesion. The PDA/PSBMA-coated PPMMs show excellent surface hydrophilicity, high water permeation flux (7506 ± 528 L/m2·h at 0.1 MPa), and an outstanding antifouling property. Moreover, the antifouling property is maintained after the membranes are treated with acid and alkali solutions as well as organic solvents. To recap, it provides a facile, universal, and time-saving strategy for exploiting high-efficiency and durable antifouling membrane surfaces.
Co-reporter:Chao Zhang;Bai-Heng Wu;Yong Du;Meng-Qi Ma
Journal of Materials Chemistry C 2017 vol. 5(Issue 16) pp:3898-3902
Publication Date(Web):2017/04/20
DOI:10.1039/C7TC00530J
Structural colors are in increasing demand in many fields such as color displays, sensor devices, and anti-counterfeiting labels. Herein, large-scale and angle-independent structural colors were constructed from polydopamine (PDA) coatings with a high refractive index and uniformity. This strategy can be utilized to facilely fabricate various color patterns. These structural colors also display high solvent resistance and excellent universality to a series of substrates. Moreover, stimuli-responsive structural colors can be easily synthesized via the co-deposition of PDA with poly(N-isopropylacryl-amide). To the best of our knowledge, this is the first time that structural colors from PDA-based coatings have been reported.
Co-reporter:Yuan Yu;Qing-Yun Wu;Hong-Qing Liang;Lin Gu
Journal of Applied Polymer Science 2017 Volume 134(Issue 6) pp:
Publication Date(Web):2017/02/10
DOI:10.1002/app.44454
ABSTRACTA series of cellulose triacetate (CTA) membranes were prepared via thermally induced phase separation (TIPS) process with dimethyl sulfone (DMSO2) and polyethylene glycol (PEG400) as a crystallizable diluent and an additive, respectively. The phase separation behavior of CTA/DMSO2/PEG400 ternary system was investigated in detail by optical microscopy, differential scanning calorimetry and wide angle X-ray diffraction. This ternary system dynamically undergoes solid-solid phase separation and thus the CTA membranes possess cellular, lacy, plate-, or even ellipse-shaped pores. However, we can modulate the pore structure, porosity, water flux, and mechanical properties of the membranes by varying polymer concentration, composition of the mixed diluent, and cooling condition. Due to the intrinsic hydrophilicity, the prepared CTA membranes have better antifouling property than polysulfone membranes. These porous membranes were used as supports to fabricate thin-film composite forward osmosis (FO) membranes, which show good water permeability and selectivity. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44454.
Co-reporter:Hao-Cheng Yang, Jingwei Hou, Vicki Chen and Zhi-Kang Xu  
Journal of Materials Chemistry A 2016 vol. 4(Issue 25) pp:9716-9729
Publication Date(Web):16 May 2016
DOI:10.1039/C6TA02844F
Organic–inorganic composite (OIC) membranes have received great attention over the past decades due to their enhanced performances in many applications. It is well known that surfaces and interfaces play crucial roles in the fabrication and application of the OIC membranes. In this review, we summarize the typical processes used to fabricate the OIC membranes and categorize these membranes as either mixed matrix OIC membranes or interfacial composite OIC membranes, and primarily focus on how the organic–inorganic interfaces influence the membrane formation process and its final structure. Then we reveal how the membrane surfaces and organic–inorganic interfaces in the membrane affect the final performance in certain applications. Through this review, we wish to provide a comprehensive guide to membrane fabrication and regulation, as well as a better understanding of the structure–performance relationships in OIC membranes.
Co-reporter:Xiao-Ling Xu, Fu-Wen Lin, Yong Du, Xi Zhang, Jian Wu, and Zhi-Kang Xu
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 20) pp:12588-12593
Publication Date(Web):May 9, 2016
DOI:10.1021/acsami.6b03693
Swelling has great influences on the structure stability and separation performance of graphene oxide laminate membranes (GOLMs) for water desalination and purification. Herein, we report cross-linked GOLMs from GO assembled with cationic tetrakis(1-methyl-pyridinium-4-yl)porphyrin (TMPyP) by a vacuum-assisted strategy. The concave nonoxide regions (G regions) of GO are used as cross-linking sites for the first time to precisely control the channel size for water permeation and salt ion retention. Channels around 1 nm are constructed by modulating the assembly ratio of TMPyP/GO, and these cross-linked GOLMs show high salt rejection.
Co-reporter:Yong Du, Wen-Ze Qiu, Yan Lv, Jian Wu, and Zhi-Kang Xu
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 43) pp:29696
Publication Date(Web):October 11, 2016
DOI:10.1021/acsami.6b10367
Nanofiltration membranes (NFMs) are widely used in saline water desalination, wastewater treatment, and chemical product purification. However, conventional NFMs suffer from broad pore size distribution, which limits their applications for fine separation, especially in complete separation of molecules with slight differences in molecular size. Herein, defect-free composite NFMs with narrow pore size distribution are fabricated using a contra-diffusion method, with dopamine/polyethylenimine solution on the skin side and ammonium persulfate solution on the other side of the ultrafiltration substrate. Persulfate ions can diffuse through the ultrafiltration substrate into the other side and in situ trigger dopamine to form a codeposited coating with polyethylenimine. The codeposition is hindered on those sites completely covered by the polydopamine/polyethylenimine coating, although it is promoted at the defects or highly permeable regions because it is induced by the diffused persulfate ions. Such a “self-completion” process results in NFMs with highly uniform structures and narrow pore size distribution, as determined by their rejection of neutral solutes. These near electrically neutral NFMs show a high rejection of divalent ions with a low rejection of monovalent ions (MgCl2 rejection = 96%, NaCl rejection = 23%), majorly based on a steric hindrance effect. The as-prepared NFMs can be applied in molecular separation such as isolating cellulose hydrogenation products.Keywords: contra-diffusion; mussel-inspired chemistry; nanofiltration membrane; polydopamine; pore size distribution
Co-reporter:Yong Du, Yan Lv, Wen-Ze Qiu, Jian Wu and Zhi-Kang Xu  
Chemical Communications 2016 vol. 52(Issue 55) pp:8589-8592
Publication Date(Web):13 Jun 2016
DOI:10.1039/C6CC03842E
We propose a novel strategy for narrowing down the pore size distribution of ready-made nanofiltration membranes (NFMs) via pore wall modification. NFMs were subjected to the filtration of a highly reactive molecule solution, during which large pores were selectively reduced in size. The as-treated NFMs have high monovalent ion/divalent ion selectivity.
Co-reporter:Hong-Qing Liang, Ke-Jia Ji, Li-Yun Zha, Wen-Bing Hu, Yang Ou, and Zhi-Kang Xu
ACS Applied Materials & Interfaces 2016 Volume 8(Issue 22) pp:14174-14181
Publication Date(Web):May 17, 2016
DOI:10.1021/acsami.6b03071
Polymer membranes with well-controlled and vertically oriented pores are of great importance in the applications for water treatment and tissue engineering. On the basis of two-dimensional solvent freezing, we report environmentally friendly facile fabrication of such membranes from a broad spectrum of polymer resources including poly(vinylidene fluoride), poly(l-lactic acid), polyacrylonitrile, polystyrene, polysulfone and polypropylene. Dimethyl sulfone, diphenyl sulfone, and arachidic acid are selected as green solvents crystallized in the polymer matrices under two-dimensional temperature gradients induced by water at ambient temperature. Parallel Monte Carlo simulations of the lattice polymers demonstrate that the directional process is feasible for each polymer holding suitable interaction with a corresponding solvent. As a typical example of this approach, poly(vinylidene fluoride) membranes exhibit excellent tensile strength, high optical transparence, and outstanding separation performance for the mixtures of yeasts and lactobacilli.
Co-reporter:Zheng Xia, Wenze Qiu, Han Bao, Bin Yang, Lecheng Lei, Zhikang Xu, Zhongjian Li
Electrochemistry Communications 2016 Volume 71() pp:1-4
Publication Date(Web):October 2016
DOI:10.1016/j.elecom.2016.07.009
•A polypropylene membrane based solid electrolyte was developed for CO2 reduction.•The membrane was developed by deposition of bio-inspired polyphenolic coatings.•High CO production rate and the Faradaic efficiency were achieved.•The novel composite SPE may have great potential in industrial application.A novel solid polymer electrolyte was developed by co-deposition of catechol (CCh) and polyethyleneimine (PEI) on a polypropylene membrane for electrochemical reduction of CO2 (ERC) in gas phase. ERC performance was both investigated in a gas-gas mode and a gas-liquid mode. The maximum CO production rate was 121 μmol/h and the faradaic efficiency was 51% in the gas-liquid mode, which were much higher than those obtained with AM-7001 under the same condition. The high loading rate of quaternary ammonium ions on the membrane and the large surface area provided by the porous nano-structure of the membrane contribute to the high ERC efficiency. Furthermore, the cost of the CCh/PEI-Q membrane was much lower than commercial Nafion membranes, endowing this novel composite SPE with great potential in industrial application.
Co-reporter:Xi Zhang, Peng-Fei Ren, Hao-Cheng Yang, Ling-Shu Wan, Zhi-Kang Xu
Applied Surface Science 2016 Volume 360(Part A) pp:291-297
Publication Date(Web):1 January 2016
DOI:10.1016/j.apsusc.2015.11.015

Highlights

A facile and green protocol has been developed to hydrophilize membrane surfaces.

The co-deposited coatings of tannic acid and diethlyenetriamine are almost colorless.

The protocol is suitable for various hydrophobic membranes.

Co-reporter:Wen-Ze Qiu, Yan Lv, Yong Du, Hao-Cheng Yang and Zhi-Kang Xu  
RSC Advances 2016 vol. 6(Issue 41) pp:34096-34102
Publication Date(Web):29 Mar 2016
DOI:10.1039/C6RA04074H
High performance nanofiltration (NF) membranes are facilely fabricated via the co-deposition of catechol (CCh) and polyethylenimine (PEI) on the surface of a polysulfone (PSf) ultrafiltration membrane, with subsequent cross-linking by glutaraldehyde (GA). The surface properties of the studied membranes have been investigated in detail by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning election microscopy, atomic force microscopy, zeta potential, and water contact angle. The NF performance of the membranes are dependent on the CCh/PEI ratio, co-deposition time and cross-linking condition. Results reveal that the optimum membrane yields a rejection of 88% and a permeation flux of 25 L m−2 h−1 when filtrating the 1000 mg L−1 MgCl2 solution at 0.6 MPa. And the negatively charged membrane surface is related to the following salt rejection sequence: MgSO4 > Na2SO4 > MgCl2 > CaCl2 > NaCl. Meanwhile, the membranes show excellent operation stability during a 240 h consistent filtration test.
Co-reporter:Hao-Cheng Yang;Jingwei Hou;Ling-Shu Wan;Vicki Chen
Advanced Materials Interfaces 2016 Volume 3( Issue 9) pp:
Publication Date(Web):
DOI:10.1002/admi.201500774
Co-reporter:Yong Du;Wen-Ze Qiu;Zi Liang Wu;Peng-Fei Ren;Qiang Zheng
Advanced Materials Interfaces 2016 Volume 3( Issue 15) pp:
Publication Date(Web):
DOI:10.1002/admi.201600167

Recent years have witnessed the rapid developments of self-healing coatings because they can protect materials from diverse risks and are able to autonomously heal after being physically damaged. Here, a universal yet facile method is reported with high time and cost efficiency to fabricate transparent water-enabled self-healing coatings on various substrates by precipitating hydrogen-bonded tannic acid (TA)-polyethylene glycol (PEG) complexes in aqueous solution. The precipitated complexes coalesce to form uniform and transparent coatings on the substrates; after drying, mechanically robust coatings are obtained. TA endows such coatings with strong adhesion to a wide range of substrates and admirable antioxidant properties. Repeatable self-healing of the coatings is realized by simply exposing them to water or humid environment. Furthermore, these coatings can be readily erased by soaking them in basic solution, if needed.

Co-reporter:Hao-Cheng Yang;Ming-Bang Wu;Yong-Jiu Li;Yi-Fu Chen;Ling-Shu Wan
Journal of Applied Polymer Science 2016 Volume 133( Issue 32) pp:
Publication Date(Web):
DOI:10.1002/app.43792

ABSTRACT

Mussel-inspired chemistry has attracted widespread interest in the surface modification of polymer membranes. We have previously demonstrated a dopamine (DA) assisted codeposition process of polyethyleneimine onto polypropylene microfiltration membranes (PPMMs) for surface hydrophilization. In this work, we further investigate the effects of PEI molecular weight and DA/PEI mass ratio on the codeposition process and membrane performance. The results indicate that only low-molecular-weight PEI bring a distinct promotion in both surface wettability and water permeation flux for PPMMs. On the other hand, either excess DA or PEI is detrimental to the surface hydrophilicity of the studied membranes. The optimized PEI molecular weight is 600 Da and the corresponding mass ratio is 1:1 for the surface hydrophilization of PPMMs. These results are beneficial to understand those codeposition processes of dopamine with other polymers. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43792.

Co-reporter:Chao Zhang;Yang Ou;Wen-Xi Lei;Dr. Ling-Shu Wan;Dr. Jian Ji ;Dr. Zhi-Kang Xu
Angewandte Chemie International Edition 2016 Volume 55( Issue 9) pp:3054-3057
Publication Date(Web):
DOI:10.1002/anie.201510724

Abstract

Mussel-inspired polydopamine (PDA) deposition offers a promising route to fabricate multifunctional coatings for various materials. However, PDA deposition is generally a time-consuming process, and PDA coatings are unstable in acidic and alkaline media, as well as in polar organic solvents. We report a strategy to realize the rapid deposition of PDA by using CuSO4/H2O2 as a trigger. Compared to the conventional processes, our strategy shows the fastest deposition rate reported to date, and the PDA coatings exhibit high uniformity and enhanced stability. Furthermore, the PDA-coated porous membranes have excellent hydrophilicity, anti-oxidant properties, and antibacterial performance. This work demonstrates a useful method for the environmentally friendly, cost-effective, and time-saving fabrication of PDA coatings.

Co-reporter:Chao Zhang;Yang Ou;Wen-Xi Lei;Dr. Ling-Shu Wan;Dr. Jian Ji ;Dr. Zhi-Kang Xu
Angewandte Chemie 2016 Volume 128( Issue 9) pp:3106-3109
Publication Date(Web):
DOI:10.1002/ange.201510724

Abstract

Mussel-inspired polydopamine (PDA) deposition offers a promising route to fabricate multifunctional coatings for various materials. However, PDA deposition is generally a time-consuming process, and PDA coatings are unstable in acidic and alkaline media, as well as in polar organic solvents. We report a strategy to realize the rapid deposition of PDA by using CuSO4/H2O2 as a trigger. Compared to the conventional processes, our strategy shows the fastest deposition rate reported to date, and the PDA coatings exhibit high uniformity and enhanced stability. Furthermore, the PDA-coated porous membranes have excellent hydrophilicity, anti-oxidant properties, and antibacterial performance. This work demonstrates a useful method for the environmentally friendly, cost-effective, and time-saving fabrication of PDA coatings.

Co-reporter:Qing-Yun Wu, Hong-Qing Liang, Lin Gu, Yuan Yu, Yuan-Qi Huang, Zhi-Kang Xu
Polymer 2016 Volume 107() pp:54-60
Publication Date(Web):19 December 2016
DOI:10.1016/j.polymer.2016.11.008
•PVDF/PAN blend separators are prepared via thermally induced phase separation method.•PVDF/PAN blend separators show enhanced tensile strength and thermal stability with the introduction of PAN.•The lithium ion batteries with PVDF/PAN blend separators exhibit high C-rate performance.•The lithium ion batteries with PVDF/PAN blend separators present good reversible charge/discharge cycle stability.PVDF/PAN blend porous membranes were prepared via thermally induced phase separation (TIPS) and used as separators for lithium ion batteries. TIPS behavior was investigated in detail to control the morphology, pore size, porosity, and mechanical properties of the blend separators as a function of PAN content. Rod-like pores are the typical structure resulted from solid−solid phase separation, while the pore size and porosity decrease with an increase of PAN in the blend. The introduction of PAN enhances the tensile strength and the thermal stability of the blend separator. The electrolyte uptake and the ionic conductivity reduce correspondingly with the decrease of the pore size and the porosity. However, the graphite/polymer electrolyte/LiFePO4 batteries with the blend separators exhibit higher C-rate performance, and better reversible charge/discharge cycle stability than those with PVDF separators and the commercial Celgard 2400.
Co-reporter:Qing-yun Wu 吴青芸;Hong-qing Liang;Meng Li
Chinese Journal of Polymer Science 2016 Volume 34( Issue 1) pp:23-33
Publication Date(Web):2016 January
DOI:10.1007/s10118-016-1723-6
Porous carbon membranes were favorably fabricated through the pyrolysis of polyacrylonitrile (PAN) precursors, which were prepared with a template-free technique-thermally induced phase separation. These carbon membranes possess hierarchical pores, including cellular macropores across the whole membranes and much small pores in the matrix as well as on the pore walls. Nitrogen adsorption indicates micropores (1.47 and 1.84 nm) and mesopores (2.21 nm) exist inside the carbon membranes, resulting in their specific surface area as large as 1062 m2/g. The carbon membranes were used to adsorb organic dyes (methyl orange, Congo red, and rhodamine B) from aqueous solutions based on their advantages of hierarchical pore structures and large specific surface area. It is particularly noteworthy that the membranes present a selective adsorption towards methyl orange, whose molecular size (1.2 nm) is smaller than those of Congo red (2.3 nm) and rhodamine B (1.8 nm). This attractive result can be attributed to the steric structure matching between the molecular size and the pore size, rather than electrostatic attraction. Furthermore, the used carbon membranes can be easily regenerated by hydrochloric acid, and their recovery adsorption ratio maintains above 90% even in the third cycle. This work may provide a new route for carbon-based adsorbents with hierarchical pores via a template-free approach, which could be promisingly applied to selectively remove dye contaminants in aqueous effluents.
Co-reporter:Hong-qing Liang;Ling-shu Wan 徐志康
Chinese Journal of Polymer Science 2016 Volume 34( Issue 12) pp:1423-1435
Publication Date(Web):2016 December
DOI:10.1007/s10118-016-1860-y
Dual-asymmetric poly(vinylidene fluoride) (PVDF) separators have been fabricated by thermally induced phase separation with dimethyl sulfone (DMSO2) and glycerol as mixed diluents. The separators have a porous bulk with large interconnected pores (~1.0 μm) and two surfaces with small pores (~30 nm). This dual-asymmetric porous structure endows the separators with higher electrolyte uptake amount and rapider uptake rate, as well as better electrolyte retention ability than the commercialized Celgard 2400. The separators even maintain their dimensional stability up to 160 °C, at which temperature the surface pores close up, leading to a dramatic decrease of air permeability. The electrolyte filled separators also show high ion conductivity (1.72 mS∙cm―1) at room temperature. Lithium iron phosphate (LiFePO4)/lithium (Li) cells using these separators display superior discharge capacity and better rate performance as compared with those from the commercialized ones. The results provide new insight into the design and development of separators for high-performance lithium ion batteries with enhanced safety.
Co-reporter:Wen-Ze Qiu, Hao-Cheng Yang, Ling-Shu Wan and Zhi-Kang Xu  
Journal of Materials Chemistry A 2015 vol. 3(Issue 27) pp:14438-14444
Publication Date(Web):05 Jun 2015
DOI:10.1039/C5TA02590G
Mussel-inspired chemistry has been broadly exploited for multifunctional coatings in the surface modification of applied materials. Polyphenols are ubiquitous in plant tissues and far less expensive than polydopamine for mussel-inspired chemistry. Herein, we report a facile and effective method to modify porous membranes via the co-deposition of catechol (CCh) and polyethyleneimine (PEI). The membrane structures and properties were investigated by ATR/FTIR, XPS, FESEM, zeta potential, water contact angle and pure water flux measurements. The results reveal that the membranes deposited with a CCh–PEI mass ratio of 1:0.25 show excellent hydrophilicity, ultrahigh water permeation flux and distinguished surface charges. These membranes were used to decolorize anionic dye solutions during filtration with superior removal efficiencies of over 99%. Moreover, they have good reusability over repeated operations with a simple regeneration process.
Co-reporter:Yan Fang, Jian Wu and Zhi-Kang Xu  
Chemical Communications 2015 vol. 51(Issue 1) pp:129-132
Publication Date(Web):03 Nov 2014
DOI:10.1039/C4CC06137C
A quartz crystal microbalance (QCM) was used to monitor dextransucrase (DSase)-catalyzed polysaccharide elongation on the glucose-/maltose-ended self-assembly monolayer (SAM) surfaces. Kinetic parameters of the enzymatic elongation indicate that maltose is a promising substrate acceptor for DSase.
Co-reporter:Hao-Cheng Yang, Yi-Fu Chen, Chen Ye, Yi-Ning Jin, Hanying Li and Zhi-Kang Xu  
Chemical Communications 2015 vol. 51(Issue 64) pp:12779-12782
Publication Date(Web):01 Jul 2015
DOI:10.1039/C5CC03216D
Zirconia-wrapped membranes were fabricated via a mineralization process on polydopamine/polyethyleneimine-deposited surfaces. The rigid and hydrophilic mineral coating simultaneously endows the membranes with enhanced curling resistance and surface wettability, enabling the membranes to separate oil-in-water emulsions.
Co-reporter:Chao Zhang, Hao-Cheng Yang, Ling-Shu Wan, Hong-Qing Liang, Hanying Li, and Zhi-Kang Xu
ACS Applied Materials & Interfaces 2015 Volume 7(Issue 21) pp:11567
Publication Date(Web):May 13, 2015
DOI:10.1021/acsami.5b02530
Immobilization of photo-Fenton catalysts on porous materials is crucial to the efficiency and stability for water purification. Here we report polydopamine (PDA)-coated porous substrates as a platform for in situ mineralizing β-FeOOH nanorods with enhanced photocatalytic performance under sunlight. The PDA coating plays multiple roles as an adhesive interface, a medium inducing mineral generation, and an electron transfer layer. The mineralized β-FeOOH nanorods perfectly wrap various porous substrates and are stable on the substrates that have a PDA coating. The immobilized β-FeOOH nanorods have been shown to be efficient for degrading dyes in water via a photo-Fenton reaction. The degradation efficiency reaches approximately 100% in 60 min when the reaction was carried out with H2O2 under visible light, and it remains higher than 90% after five cycles. We demonstrate that the PDA coating promotes electron transfer to reduce the electron–hole recombination rate. As a result, the β-FeOOH nanorods wrapped on the PDA-coated substrates show enhanced photocatalytic performance under direct sunlight in the presence of H2O2. Moreover, this versatile platform using porous materials as the substrate is useful in fabricating β-FeOOH nanorods-based membrane reactor for wastewater treatment.Keywords: mineralization; photo-Fenton; polydopamine; porous materials; β-FeOOH nanorods;
Co-reporter:Hao-Cheng Yang, Jianquan Luo, Yan Lv, Ping Shen, Zhi-Kang Xu
Journal of Membrane Science 2015 Volume 483() pp:42-59
Publication Date(Web):1 June 2015
DOI:10.1016/j.memsci.2015.02.027
•Critical review of mussel-inspired chemistry in membrane surface engineering.•Illustration of adhesion mechanisms and properties of polydopamine.•Outline of applications both in membrane fabrication and surface modification.•Great potentials in separation membranes with high-performance and multi-function.Over the past decades, polymer membranes are becoming more and more compelling due to their growing demand in environment, energy and health fields. Many efforts have been devoted to improve the membrane performance and extend their application via the methodology of surface engineering. One of the most promising strategies is mussel-inspired chemistry, which has become a powerful tool in membrane fabrication and modification because of its universality and versatility. Considering the increasing interest and advances in this field, we present this review regarding mussel-inspired chemistry in the surface engineering of polymer membranes. The adhesion mechanism and properties of polydopamine (as a representative) are briefly outlined at the beginning. Then detailed elaboration is followed on the applications of mussel-inspired chemistry in the surface science and technology of membranes. Catecholamines can be directly deposited on the membrane surface, act as an interface layer for post-modification, serve as a surface component of membrane and pre-decorate polymers for membrane modification or fabrication. Finally, we summarize recent research progress and give a further perspective of the mussel-inspired catecholamine in membrane science and technology.
Co-reporter:Yan Lv, Hao-Cheng Yang, Hong-Qing Liang, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2015 Volume 476() pp:50-58
Publication Date(Web):15 February 2015
DOI:10.1016/j.memsci.2014.11.024
•A facile process is proposed to fabricate composite nanofiltration membranes (NFMs).•Co-deposition of PDA/PEI makes the selective layer smooth and defect-free.•Adhesive PDA/PEI layer significantly enhances the structural stability of NFMs.•The composite NFMs exhibit high rejection performance against multivalent cations.Novel composite nanofiltration membranes (NFMs) were simply fabricated via co-deposition of mussel-inspired polydopamine (PDA) and polyetheylenimine (PEI) followed by glutaraldehyde (GA) crosslinking. A uniform, robust and defect-free selective layer was generated on the hydrolyzed polyacrylonitrile (HPAN) ultrafiltration membrane substrate, endowing the composite NFMs with high separation performance for multivalent ions. Zeta potential measurements indicate these NFMs are slightly positively charged, resulting in a salts rejection sequence of MgCl2>CaCl2>MgSO4>Na2SO4>NaCl at pH 5.5. The nanofiltration performance can be tuned by changing the co-deposition time and the mass ratio of dopamine/PEI. A mass ratio of 2/2 with 4 h co-deposition is the optimum protocol for the membrane performances including surface hydrophilicity, water flux and salt rejection. Moreover, the composite NFMs show a good structural stability for immersing in ethanol or for long-term nanofiltration process.
Co-reporter:Lian-Wei Wu;Ling-Shu Wan;Yang Ou;Liang-Wei Zhu
Advanced Materials Interfaces 2015 Volume 2( Issue 16) pp:
Publication Date(Web):
DOI:10.1002/admi.201500285

Isoporous separation membranes have received considerable attention because of the high-resolution performance and energy-saving characteristics. Isoporous membranes prepared by the breath figure method rely on special substrates such as water and ice because solid substrates such as polyethylene terephthalate films, which are widely used in commercial processes, often lead to nonthrough pores. In this work, it is found that highly ordered through-pore membranes can be fabricated on hydrophilic glass surface when using polymers that are able to form ordered membranes at low concentrations. On the basis of this finding, a facile strategy is proposed to fabricate isoporous membranes on various solid substrates by introducing a water-soluble polymer interlayer. The multifunctional interlayer promotes the spreading of membrane-forming solutions, enables the formation of through pores, and simplifies the transfer to macroporous supports to form composite membranes. The versatility of the proposed strategy is verified by using different substrates including highly hydrophobic polytetrafluoroethylene film and using different water-soluble polymers as the interlayer. Furthermore, the high-resolution separation performance of the isoporous composite membranes has been demonstrated by the filtration of yeasts under gravitational pressure.

Co-reporter:Peng-Fei Ren, Hao-Cheng Yang, Yi-Ning Jin, Hong-Qing Liang, Ling-Shu Wan and Zhi-Kang Xu  
RSC Advances 2015 vol. 5(Issue 59) pp:47592-47598
Publication Date(Web):12 May 2015
DOI:10.1039/C5RA05937B
Porous meshes with superhydrophilicity and underwater superoleophobicity have attracted much attention for oil/water separation. In this work, poly(sulfobetaine methacrylate) (PSBMA), was co-deposited with polydopamine (PDA) to cover steel meshes and to endow them with characteristics for oil/water separation. Compared with PDA-modified meshes, the oil contact angle increases to 158.6 ± 8.0° and the sliding angle decreases to 3.9° for the PSBMA/PDA-modified ones, indicating superoleophobic behaviour underwater and ultra-low adhesive properties towards oil. These results are mainly attributed to the superhydrophilicity of PSBMA and the highly rough surface morphology in micro-nanoscale introduced during the co-deposition process. The PSBMA/PDA-modified meshes show excellent performance in gravity-driven oil/water separation. They are stable towards organic solvent treatment, and retain the wettability in sea water for a long time. This one-step PSBMA/PDA co-deposition method provides a convenient and effective approach to modify porous materials with underwater superoleophobicity for oil/water separation.
Co-reporter:Yi-Ning Jin, Hao-Cheng Yang, He Huang and Zhi-Kang Xu  
RSC Advances 2015 vol. 5(Issue 21) pp:16112-16115
Publication Date(Web):29 Jan 2015
DOI:10.1039/C4RA16074F
Multi-walled carbon nanotubes (MWCNTs) were facilely decorated with tannic acid (TA) and the MWCNTs/TA dispersion was vacuum-filtered to fabricate carbonaceous coatings with superoleophobicity and ultra-low oil adhesion underwater (OCA = 164.8°, SA = 2.7°). The super-oil-repellent property can be well maintained for long-term use, even in strong acidic, alkaline or saline environments.
Co-reporter:Fu-Wen Lin, Xiao-Ling Xu, Jian Wu, Ling-Shu Wan and Zhi-Kang Xu  
RSC Advances 2015 vol. 5(Issue 120) pp:99361-99363
Publication Date(Web):13 Nov 2015
DOI:10.1039/C5RA19024J
Filter paper has been sequentially enchased with titania (TiO2) nanoparticles and coated by a cobalt-porphyrin/dansyl piperazine complex. A series of “turn on” fluorescence sensors are demonstrated to show high sensitivity and fast response for ammonia gas.
Co-reporter:Fu-Wen Lin, Xiao-Ling Xu, Ling-Shu Wan, Jian Wu and Zhi-Kang Xu  
RSC Advances 2015 vol. 5(Issue 39) pp:30472-30477
Publication Date(Web):24 Mar 2015
DOI:10.1039/C5RA01605C
We report thermally stable films with ordered pores from porphyrinated polyimides (PPIs) for HCl gas sensing. PPIs were synthesized by copolymerizing porphyrin units into the polyimide backbone. Thermal analyses reveal that the glass transition temperature and the thermal stability of PPIs are similar to that of the homopolyimide (HPI) without porphyrin units. The PPIs also show typical fluorescence emission behavior of the porphyrin units. Honeycomb films were prepared from PPIs and HPI via the breath figure method. The porous films show decreased pore diameters and change from monolayer to multilayer structures with the incorporation of porphyrin units. These are due to the interaction of porphyrin units with water molecules, as demonstrated by theoretical calculations based on density functional theory (DFT). The well-ordered porous PPI films have outstanding thermal stability. Furthermore, the films treated at different temperatures show remarkable fluorescence quenching behavior toward HCl gas with quenching ratios higher than 72%, whereas it is only about 50% for the corresponding dense film. Moreover, recovery experiments using ammonia gas demonstrate excellent reusability of the films. The PPI honeycomb films provide new opportunities in chemical sensing at high temperature.
Co-reporter:Jing-Wei Xu, Yao Wang, Yun-Feng Yang, Xiang-Yu Ye, Ke Yao, Jian Ji, Zhi-Kang Xu
Colloids and Surfaces B: Biointerfaces 2015 Volume 133() pp:148-155
Publication Date(Web):1 September 2015
DOI:10.1016/j.colsurfb.2015.06.002
•Quaternization endows the nanofibers with stable morphology and antibacterial activity.•Antibacterial nanofibers can be facilely prepared from simply synthesized polymers.•Mobility of the quaternized N+ is the necessary prerequisite for antibacterial activity.Electrospun nanofibers with antibacterial activity are greatly promising for medical treatment and water purification. Herein we report antibacterial nanofibers electrospun from a series of poly(dimethylamino ethyl methacrylate-co-alkyl methacrylates) (poly(DMAEMA-co-AMA)) and to distinguish the effects of free and cross-linked cations derived from quanternization on the antibacterial activity. Poly(DMAEMA-co-AMA)s are simply synthesized by free radical polymerization from commercial monomers. DSC analysis indicates that they have Tg lower than room temperature and thus the electrospun nanofibers adhere to each other and evenly tend to form films, instead of keeping cylinderic shape. Benzyl chloride (BC) and p-xylylene dichloride (XDC) can quaternize DMAEMA units and to generate cations on the nanofiber surface. XPS analysis and colorimetric assay determine the quaternization degree and the surface accessible quaternary amines (N+), respectively. It is very promising that this quaternization endows the electrospun nanofibers with both stable morphology and antibacterial activity. The BC-quaternized fibers show better antibacterial behavior against Escherichia coli and Staphylococcus aureus than those of the XDC-quaternized/cross-linked ones, because cross-linking suppresses the chain mobility of cations. Our results confirm that antibacterial nanofibers can be facilely prepared and chain mobility of the formed cations is the necessary prerequisite for their antibacterial activity.
Co-reporter:Suo-Hong Zhi, Ran Deng, Jun Xu, Ling-Shu Wan, Zhi-Kang Xu
Reactive and Functional Polymers 2015 Volume 86() pp:184-190
Publication Date(Web):January 2015
DOI:10.1016/j.reactfunctpolym.2014.09.004
Polyacrylonitrile (PAN)-based composite membranes were prepared by immersion precipitation method by using poly(N,N-dimethylaminoethyl methacrylate)-grafted silica (PDMAEMA@SiO2) nanoparticles as hydrophilic additives. The molecular weight of PDMAEMA were controlled by the surface initiated atom transfer radical polymerization of N,N-dimethylaminoethyl methacrylate on SiO2 nanoparticles. The synthesized nanoparticles have a typical core–shell structure as characterized in detail by FT-IR, TEM, DLS and GPC. The prepared PAN-based composite membranes have higher porosity and water permeation flux than those of the pure PAN membranes. They also show high rejection (⩾90%) to bovine serum albumin and high flux recovery ratio (⩾90%) to water permeation. These improved performances are attributed to the good hydrophilicity of PDMAEMA@SiO2 nanoparticles. The results suggest that PDMAEMA@SiO2 nanoparticles are suitable for the property optimization of PAN-based composite membranes.
Co-reporter:Yong Du;Hao-Cheng Yang;Xiao-Ling Xu;Dr. Jian Wu;Dr. Zhi-Kang Xu
ChemCatChem 2015 Volume 7( Issue 23) pp:3822-3825
Publication Date(Web):
DOI:10.1002/cctc.201500643

Abstract

In biological systems, disulfide bonds are formed efficiently under mild conditions without the release of harmful byproducts. Inspired by nature, we report a biomimetic polydopamine (PDA) catalyst for oxidative thiol coupling. This reaction was accelerated with only a small amount of PDA particles in neutral, weakly alkaline, and even weakly acidic aqueous media at room temperature under an air atmosphere. The catalytic particles were facilely separated and were reused without a decrease in activity. The entire process is totally biofriendly, including the synthesis of the PDA particles. This route is especially useful for the synthesis of pharmaceutical molecules.

Co-reporter:Xiao-Ling Xu;Fu-Wen Lin;Wei Xu;Dr. Jian Wu;Dr. Zhi-Kang Xu
Chemistry - A European Journal 2015 Volume 21( Issue 3) pp:984-987
Publication Date(Web):
DOI:10.1002/chem.201405675

Abstract

Fluorescence-switch-based logic devices are very sensitive compared with most of the reported devices based on UV/Vis absorption systems. Herein, we demonstrate that a simple molecule, 5,10,15,20-tetra-(4-aminophenyl)porphyrin (TAPP), shows protonation-induced multiple emission switches through intramolecular charge transfer and/or aggregation-caused quenching. Highly sensitive INHIBIT and XOR logic gates can be achieved by combining the intermolecular assembly with the intramolecular photoswitching of diprotonated TAPP (TAPPH22+). In addition, molecular simulations have been performed by DFT for a better understanding of the emission-switching processes.

Co-reporter:Hao-Cheng Yang, Kun-Jian Liao, He Huang, Qing-Yun Wu, Ling-Shu Wan and Zhi-Kang Xu  
Journal of Materials Chemistry A 2014 vol. 2(Issue 26) pp:10225-10230
Publication Date(Web):02 Apr 2014
DOI:10.1039/C4TA00143E
The surface structures and properties of a membrane largely determine its in-service performance during a filtration process. Here we report a facile hydrophilization method via co-deposition of mussel-inspired polydopamine (PDA) and polyethyleneimine (PEI) on a polypropylene microfiltration membrane. The deposition time is greatly shortened and the surface hydrophilicity is significantly improved compared to those membranes decorated only by PDA. The dopamine/PEI deposition solution can be reused several times with negligible effect on the surface hydrophilicity of membranes. Moreover, the PDA/PEI coating endows the membranes with ultra-high water permeability, allowing microfiltration separation of oil-in-water emulsions under atmospheric pressure.
Co-reporter:Hao-Cheng Yang, Jun-Ke Pi, Kun-Jian Liao, He Huang, Qing-Yun Wu, Xiao-Jun Huang, and Zhi-Kang Xu
ACS Applied Materials & Interfaces 2014 Volume 6(Issue 15) pp:12566
Publication Date(Web):July 5, 2014
DOI:10.1021/am502490j
Silica-decorated polypropylene microfiltration membranes were fabricated via a facile biomimetic silicification process on the polydopamine/polyethylenimine-modified surfaces. The membranes exhibit superhydrophilicity and underwater superoleophobicity derived from the inherent hydrophilicity and the well-defined micronanocomposite structures of the silica-decorated surfaces. They can be applied in varieties of oil-in-water emulsions separation with high permeate flux (above 1200 L/m2h under 0.04 MPa) and oil rejection (above 99%). The membranes also have relatively high oil breakthrough pressure reaching 0.16 MPa due to the microporous structure, showing great potential for practical applications. Furthermore, such mussel-inspired intermediate layer provides us a convenient and powerful tool to fabricate organic–inorganic hybrid membranes for advanced applications.Keywords: microfiltration; oil-in-water emulsion separation; silicification; superhydrophilicity; underwater superoleophobicity
Co-reporter:Hao-Cheng Yang, Wei Xu, Yong Du, Jian Wu and Zhi-Kang Xu  
RSC Advances 2014 vol. 4(Issue 85) pp:45415-45418
Publication Date(Web):16 Sep 2014
DOI:10.1039/C4RA04549A
Mussel-inspired free-standing composite films were formed by polymerization of dopamine in the presence of polyethyleneimine at the air/water interface. These films have controllable thickness and asymmetric structure. They can be potentially developed as templates for the fabrication of silver, hydroxyapatite, titania and silica hybrid films.
Co-reporter:Meng-Xin Hu;Yan Fang
Journal of Applied Polymer Science 2014 Volume 131( Issue 2) pp:
Publication Date(Web):
DOI:10.1002/app.39658

ABSTRACT

Development in the area of glycosylated membranes has been actively pursued in the past few years. This kind of promising biomimetic material is inspired by cell membranes. The recent surge of interest in these glycosylated membranes stems from their widespread number of applications to many areas in science and technology. With the glycosylation strategy, membrane separation properties, such as flux and antifouling, are greatly improved. Moreover, the ability to modulate biocompatibility, protein recognition, separation of biomolecules, enzyme immobilization, cell culture, and microorganisms capture are important in a variety of biological and medical applications. This review focuses on the recent progress in the preparation of these glycosylated membranes and highlights their applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39658.

Co-reporter:Ke Liao;Xiang-Yu Ye;Peng-Cheng Chen
Journal of Applied Polymer Science 2014 Volume 131( Issue 4) pp:
Publication Date(Web):
DOI:10.1002/app.39897

ABSTRACT

Polypropylene/calcium carbonate (CaCO3) composite nonwoven meshes were prepared on the basic principle of biomineralization by using a facile alternate soaking process (ASP) within 20 min. Negatively charged poly(acrylic acid) brushes, which can induce CaCO3 nucleation, were first tethered onto the fiber surface of polypropylene nonwoven meshes via UV-induced graft polymerization. ASP procedure was followed to mineralize CaCO3 particles on the fiber surface and to form the composite nonwoven meshes. Fourier transform infrared spectroscopy/attenuated total reflectance, field emission scanning electron microscope, equipped X-ray spectroscope, and X-ray diffraction were used to characterize the prepared composite meshes. The mineral cover density increased with the ASP cycles, and it progressively increased for the relative content of calcite in the crystalline part of the mineral layer as well. Contact angle measurements indicate that the as-prepared composite nonwoven meshes were endowed with superhydrophilicity and underwater superoleophobicity, thus they showed prominent application prospects in wastewater treatment and oil/water separation. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39897.

Co-reporter:Xiang-Yu Ye, Xiao-Jun Huang, Zhi-Kang Xu
Colloids and Surfaces B: Biointerfaces 2014 Volume 115() pp:340-348
Publication Date(Web):1 March 2014
DOI:10.1016/j.colsurfb.2013.12.025
•Conformal grafts by a modified plasma pretreatment and BP entrapment UV process.•The glycosylated non-woven meshes showed affinity adsorption to Con A lectin.•High binding capacity and fast adsorption kinetics were accomplished.•Increasing the side chain length had positive effect on lectin binding capacity.•Model studies suggest a multilayer adsorption behavior of Con A lectin.The unique characteristics of polypropylene non-woven meshes (PPNWMs), like random network of overlapped fibers, multiple connected pores and overall high porosity, make them high potentials for use as separation or adsorption media. Meanwhile, carbohydrates can specifically recognize certain lectin through multivalent interactions. Therefore glycosylated PPNWMs, combing the merits of both, can be regarded as superior affinity membranes for lectin adsorption and purification. Here, we describe a versatile strategy for the glycosylation of PPNWMs. Two hydrophilic polymers with different side chain length, poly(2-hydroxyethyl methacrylate) (PHEMA) and poly(oligo(ethylene glycol) methacrylate) (POEGMA), were first conformally tethered on the polypropylene fiber surface by a modified plasma pretreatment and benzophenone (BP) entrapment UV irradiation process. Then glucose ligands were bound through the reaction between the hydroxyl group and acetyl glucose. Chemical changes of the PPNWMs surface were monitored by FT-IR/ATR. SEM pictures show that conformal glucose ligands can be achieved through the modified process. After deprotection, the glycosylated PPNWMs became superhydrophilic and had high specific recognition capability toward Concanavalin A (Con A). Static Con A adsorption experiments were further performed and the results indicate that fast adsorption kinetics and high binding capacity can be accomplished at the same time. We also found that increasing the side chain length of polymer brushes had positive effect on protein binding capacity due to improved chain mobility. Model studies suggest a multilayer adsorption behavior of Con A.
Co-reporter:Suo-Hong Zhi, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2014 454() pp: 144-154
Publication Date(Web):
DOI:10.1016/j.memsci.2013.12.011
Co-reporter:Hong-Qing Liang, Qing-Yun Wu, Ling-Shu Wan, Xiao-Jun Huang, Zhi-Kang Xu
Journal of Membrane Science 2014 465() pp: 56-67
Publication Date(Web):
DOI:10.1016/j.memsci.2014.03.068
Co-reporter:Rong Zhou, Peng-Fei Ren, Hao-Cheng Yang, Zhi-Kang Xu
Journal of Membrane Science 2014 466() pp: 18-25
Publication Date(Web):
DOI:10.1016/j.memsci.2014.04.032
Co-reporter:Suo-Hong Zhi, Jun Xu, Ran Deng, Ling-Shu Wan, Zhi-Kang Xu
Polymer 2014 Volume 55(Issue 6) pp:1333-1340
Publication Date(Web):24 March 2014
DOI:10.1016/j.polymer.2013.12.035
Poly(vinylidene fluoride) (PVDF) ultrafiltration membranes were prepared by immersion precipitation method using poly(hydroxyethyl methacrylate)-block-poly(methyl methacrylate) grafted silica (PHEMA-b-PMMA@SiO2) nanoparticles as additives. The hybrid nanoparticles were synthesized by the surface initiated atom transfer radical polymerization (SI-ATRP), and they were characterized in detail by FT-IR, TEM, DLS and GPC. Results confirm that core–shell structure is formed after grafting PHEMA-b-PMMA brushes on the silica nanoparticles. Their average hydrodynamic diameter also increases with the prolongation of grafting time. After blending PVDF with the hybrid silica nanoparticles, the composite PVDF membranes exhibit high porosity and improved water permeation. Especially, when the molecular weight is 1.73 × 105 g/mol for PHEMA-b-PMMA on the hybrid nanoparticles, the water flux of the PVDF composite membrane is 2.5 times than that of the control PVDF membrane, while the rejection to bovine serum albumin (BSA) remains at a high level (>90%). In addition, all the composite PVDF membranes show lower BSA adsorption and larger water flux recovery ratio than the control PVDF membrane. The improvement of membrane performance is attributed to the good hydrophilicity of PHEMA-b-PMMA@SiO2 nanoparticles. Our results suggest that PHEMA-b-PMMA@SiO2 nanoparticles with moderate molecular weight of PHEMA-b-PMMA are suitable for the property optimization of PVDF-based composite membranes.
Co-reporter:Hao-Cheng Yang, Qing-Yun Wu, Ling-Shu Wan and Zhi-Kang Xu  
Chemical Communications 2013 vol. 49(Issue 89) pp:10522-10524
Publication Date(Web):19 Sep 2013
DOI:10.1039/C3CC46127K
We report a simple and facile protocol to fabricate mussel-inspired polydopamine (PDA) gradients on different surfaces. An oxygen diffusion phenomenon was used for dopamine autoxidation to form thickness gradients of PDA on different substrates. These PDA gradients showed gradual changes in thickness, roughness, wettability and light transmittance.
Co-reporter:Qing-Yun Wu, Bo-Tong Liu, Meng Li, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2013 Volume 437() pp:227-236
Publication Date(Web):15 June 2013
DOI:10.1016/j.memsci.2013.03.018
•PEG is used as a polymeric additive to suppress the crystallization of diluent.•PAN membranes are fabricated with adjustable pores by liquid–liquid TIPS.•PEG can be completely washed away from the membrane matrices by water.We report the effects of polyethylene glycol (PEG) as a polymeric additive on the phase behavior of polyacrylonitrile (PAN)/dimethyl sulfone (DMSO2) mixtures and the structure formation of PAN membranes via thermally induced phase separation (TIPS). DMSO2 was chosen as a crystallizable diluent, while PEG was considered in terms of molecular weight (Mw) and dosage. Their effects on the phase behavior and the droplet growth kinetics of PAN/DMSO2/PEG ternary system were systematically derived from optical microscopy and differential scanning calorimetry as well as the solubility parameter theory. We found that the addition of PEG brings about the ternary system thermodynamically less stable, facilitates liquid–liquid (L–L) phase separation and suppresses the crystallization of DMSO2. The L–L phase separation can be promoted by raising the Mw or the dosage of PEG, and is accompanied by an increase in the growth rate of droplets. These results match with the pore size of the obtained PAN membranes. SEM images indicate that needle-like pores are obvious in the membrane when 10 wt% PEG-200 is added, whereas lacy pores gradually appear as the Mw of PEG increases from 200 to 1000. In addition, cellular pores can be created by raising the dosage of PEG-200 or reducing the cooling rate. Correspondingly, the membrane presents relatively high water flux (1528 L/m2 h) and porosity (83.6%) when the ternary system contains 10 wt% PEG-1000 and cools in air bath at 30 °C. Besides, the presence of PEG in membrane matrix was examined by FTIR spectroscopy. PEG with different Mw almost completely leaches out and the pore structure keeps well after immersing the membrane in water for 144 h.
Co-reporter:Zheng-Dong Fei, Ling-Shu Wan, Wu-Min Wang, Ming-Qiang Zhong, Zhi-Kang Xu
Journal of Membrane Science 2013 Volume 432() pp:42-49
Publication Date(Web):1 April 2013
DOI:10.1016/j.memsci.2013.01.008
Thermo-responsive polyacrylonitrile (PAN) membranes were prepared by the immersion precipitation phase inversion process using poly(acrylonitrile-graft-isopropylacrylamide) [P(AN-g-NIPAAm)] as an additive. This additive was synthesized by a facile approach based on the combination of reversible addition–fragmentation chain transfer and thiol-ene click chemistry followed by radical copolymerization. The graft copolymer was characterized by Fourier transform infrared spectroscopy and proton nuclear magnetic resonance. Its side chains thermo-responsibility was determined by ultraviolet analysis and water contact angle measurement. Effects of P(AN-g-NIPAAm) addition on the morphologies of PAN membranes were investigated by scanning electron microscope. X-ray photoelectron spectroscopy was conducted at different take-off angles to elucidate the surface segregation of the amphiphilic graft copolymer in the prepared membranes. Results show that the hydrophilic PNIPAAm chains greatly segregate at the membrane surface, which endows these PAN membranes with obvious thermo-responsibility for water permeation.Highlights► A facile method is described for the preparation of thermo-responsive membranes. ► Poly(acrylonitrile-graft-isopropylacrylamide) was synthesized by a one-pot approach. ► Hydrophilic PNIPAAm side chains are greatly enriched at the membrane surfaces.
Co-reporter:Qing-Yun Wu, Ling-Shu Wan and Zhi-Kang Xu  
RSC Advances 2013 vol. 3(Issue 38) pp:17105-17112
Publication Date(Web):16 Jul 2013
DOI:10.1039/C3RA41034J
A series of giant spherulites at centimetre scale were effectively constructed from the mixtures of polyacrylonitrile (PAN)/dimethyl sulfone (DMSO2), although neither PAN nor DMSO2 itself forms spherical morphology during crystallization. A detailed investigation was carried out on the morphology, microstructure, and formation mechanism by polarized optical microscopy, scanning electron microscopy, wide-angle X-ray diffraction, polarized FTIR spectroscopy, and differential scanning calorimetry. These giant spherulites constituted of PAN phase and DMSO2 crystals alternately distributed in divergent patterns. The fast crystallization of DMSO2 dominates the large growth rate and the macroscopic size, while PAN composes the skeleton of the giant spherulites. The cooperative deposition of PAN beside DMSO2 crystals originates from dipole–dipole interaction between the nitrile groups of PAN and the sulfone groups of DMSO2, accounting for the branching and splaying in the giant spherulites. These macroscopic morphologies were universally observed in other mixtures of PAN/dimethyl sulfoxide, PAN/maleic anhydride, poly(vinylidene fluoride)/DMSO2, and cellulose acetate/DMSO2. We propose that the giant spherulites can be formed by introducing suitable diluent crystallization and appropriate polymer–diluent interaction. Furthermore, this spherulitic pattern has been used as a template to direct the oriented growth of calcium carbonate based on the molecular orientation in the giant spherulite.
Co-reporter:Xiang-Yu Ye, Fu-Wen Lin, Xiao-Jun Huang, Hong-Qing Liang and Zhi-Kang Xu  
RSC Advances 2013 vol. 3(Issue 33) pp:13851-13858
Publication Date(Web):27 Jun 2013
DOI:10.1039/C3RA41315B
Isotactic polypropylene (iPP) fibers with hierarchically porous structure were successfully prepared by electrospinning at 200 °C combined with thermally induced phase separation (TIPS). Dioctyl phthalate (DOP) and dibutyl phthalate (DBP) are typical diluents for iPP in TIPS and are used as solvents for electrospinning. An ionic liquid was added to increase the solution conductivity, facilitate the electrospinning process, and maintain a stable cone-jet electrospinning mode. Theoretical calculation demonstrates that the jet cools rapidly, and phase separation takes place in the jet during its travelling path, as the system traverses across the phase diagram from the single phase region to the metastable region. For the iPP/DOP system, the surface morphology of fibers changes from aligned microvoids bridged by fibrils to a wrinkled structure with the addition of ionic liquid, as the ionic liquid inhibits iPP crystallization. The pore morphology can also be modulated by varying co-diluent composition. Open pores appear on the fiber surface and the cross-section varies from closed cellular pores to a bi-continuous structure with the increase of DBP content in the co-diluent, which clearly demonstrates the phase separation mechanism changes from solid–liquid to liquid–liquid phase separation. The as-spun porous fibers show more than a 100-fold increase in specific surface area compared with the non-porous ones. The main advantages of this method are the pore formation process has a precise mechanism and the pore morphology is well correlated with the phase diagram. Furthermore, it is readily extended to other polymers with TIPS. Highly porous poly(vinylidene fluoride) (PVDF) fibers can be easily prepared from PVDF/DBP solution with a 157-fold increase in specific surface area.
Co-reporter:Yuan-Yuan Lv, Wei Xu, Fu-Wen Lin, Jian Wu, Zhi-Kang Xu
Sensors and Actuators B: Chemical 2013 Volume 184() pp:205-211
Publication Date(Web):31 July 2013
DOI:10.1016/j.snb.2013.04.094
Nanofibers with distinct luminescent property were facilely fabricated by electrospinning from porphyrinated polyimide and demonstrated as a kind of novel sensory material for trace detection of TNT vapor (10 ppb). Covalently bonding of porphyrin fluorophores into the polyimide main chains reduces the aggregation-caused fluorescence self-quenching of porphyrin and improves the physicochemical stability of the polyimide nanofibers. The large surface area-to-volume ratio and hence good gas accessibility endow the porphyrinated nanofibers with much more remarkable fluorescent quenching behavior toward trace TNT vapor than its spin-coating dense film counterparter. Besides TNT, 2,4-dinitrotoluene (DNT), 2,4,6-trinitrophenol (PA) and nitrobenzene (NB) could also quench the fluorescence of the porphyrinated nanofibers, but the quenching efficiency is much lower than that of TNT. An apparent binding affinity constant of (2.37 ± 0.19) × 107 L/mol was calculated from SPR analysis, confirming that the porphyrinated nanofibers is a promising alternative for TNT detection.
Co-reporter:Xiang-yu Ye;Yi-ning Jin;Xiao-jun Huang;Lei Luo
Chinese Journal of Polymer Science 2013 Volume 31( Issue 3) pp:514-520
Publication Date(Web):2013/03/01
DOI:10.1007/s10118-013-1238-3
In our previous work, it was found that large Bird’s Nest patterned nanofibrous membranes can be simply electrospun from chlorinated polypropylene solution doped with an ionic liquid, and a plausible formation mechanism of Bird’s Nest patterned architectures was proposed. Here, we use Ansoft Maxwell version 12 software (3D, electrostatic solver) to simulate the electrical field distribution of the electrospinning setup, and to clarify the rationality of proposed formation mechanism. Calculation results clearly show that the introduction of charged nanofibrous bundles would produce a similar patterned electrical field distribution, which definitely confirms the important role of surface residual charges. The proposed mechanism can be well extended to other polymer systems including polystyrene, poly(acrylonitrile-co-acrylic acid) and chitosan/poly(ethylene oxide).
Co-reporter:Xiao-Na Chen, Ling-Shu Wan, Qing-Yun Wu, Suo-Hong Zhi, Zhi-Kang Xu
Journal of Membrane Science 2013 441() pp: 112-119
Publication Date(Web):
DOI:10.1016/j.memsci.2013.02.054
Co-reporter:Hong-Qing Liang, Qing-Yun Wu, Ling-Shu Wan, Xiao-Jun Huang, Zhi-Kang Xu
Journal of Membrane Science 2013 446() pp: 482-491
Publication Date(Web):
DOI:10.1016/j.memsci.2013.07.008
Co-reporter:Qing-Yun Wu, Ling-Shu Wan, Zhi-Kang Xu
Polymer 2013 Volume 54(Issue 1) pp:284-291
Publication Date(Web):8 January 2013
DOI:10.1016/j.polymer.2012.11.025
Polyacrylonitrile (PAN) foams with different pore structures were prepared for the fabrication of macroporous carbon monoliths. The foams were prepared through thermally induced phase separation (TIPS) method using dimethyl sulfone (DMSO2) as a crystallizable diluent. Honeycomb-like porous foam is obtained from PAN/DMSO2 mixture containing about 5 wt.% PAN, and those with channel-like pores are resulted from the mixtures with 10–40 wt.% PAN. However, they only have few mesopores and the porosity is as low as 30–47% for the foams prepared from those mixtures containing 50–60 wt.% PAN. Real-time observation with polarized optical microscopy reveals that the channel-like structure stems from the spherulitic orientation of DMSO2 crystals in the polymer matrix. Taking into account this morphology, DMSO2 crystals are capable of acting as in situ formed templates, which subsequently enable to shape the final pore structure of PAN foams. Macroporous carbon monoliths with honeycomb- or channel-like pores were constructed from PAN foams by oxidative stabilization and carbonization. Their graphitic structure and specific surface areas were analyzed by wide-angle X-ray diffraction and Brunauer–Emmett–Teller measurement. This TIPS method using crystallizable diluent provides a new route to control the porous structure of PAN foams for carbon materials.
Co-reporter:Hao-Cheng Yang;Qing-Yun Wu;Hong-Qin Liang;Ling-Shu Wan
Journal of Polymer Science Part B: Polymer Physics 2013 Volume 51( Issue 19) pp:1438-1447
Publication Date(Web):
DOI:10.1002/polb.23347

ABSTRACT

Thermally induced phase separation (TIPS) has been developed to prepare porous membranes. The porous structures are mainly dependent on diluents adopted in the TIPS process. We obtained two typical morphologies of poly(vinylidene fluoride) (PVDF) membranes using cyclohexanone (CO) and propylene carbonate (PC) as diluents, respectively. SEM observation displays that porous spherulites are formed from PVDF/CO system, whereas smooth particles result from PVDF/PC system. The TIPS processes of these two systems have been investigated in detail by optical microscope observation and temperature-dependent FTIR combined with two-dimensional infrared correlation analysis. Rapid crystallization of PVDF can be seen around 110 °C in the PVDF/CO system, which is consistent with the results of temperature-dependent FTIR spectra. The spectral evolution indicates a transform of PVDF from amorphous to α-phase after 110 °C. The νs(CO) band at 1712 cm−1 narrows and the νs(CF) band at 1188 cm−1 shifts to 1192 cm−1 before crystallization, which implies the destruction of interaction between PVDF and CO. In contrast, the PVDF/PC system shows slow crystallization with all-trans conformation assigned to β-phase and γ-phase below 60 °C but no obvious change of polymer−diluent interaction. We propose two mechanisms for the different phase behaviors of PVDF/CO and PVDF/PC systems: a solid−liquid phase separation after destruction of polymer−diluent interaction in the former, and a liquid−liquid phase separation process coupled with rich-phase crystallization in the later. This work may provide new insight into the relationship among morphologies, crystal forms, and phase separation processes, which will be helpful to adjust membrane structure. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013, 51, 1438–1447

Co-reporter:Peng-Cheng Chen, Ling-Shu Wan and Zhi-Kang Xu  
Journal of Materials Chemistry A 2012 vol. 22(Issue 42) pp:22727-22733
Publication Date(Web):12 Sep 2012
DOI:10.1039/C2JM34203K
Surface hydrophilicity is a prerequisite of polymer membranes used for clean water regeneration, although commercial membranes are generally manufactured from hydrophobic polymers. Here, we report a promising approach to hydrophilize hydrophobic membranes using a CaCO3-based mineral coating inspired by biomineralization. Poly(acrylic acid) (PAA) brushes, which are negatively charged and can induce nucleation of CaCO3, were tethered on the pore surface of microporous polypropylene membranes (MPPMs) via photoinitiated graft polymerization. The CaCO3-based coating was then fabricated on the pore surface by an alternate soaking process. The resulting mineral coating is composed of CaCO3 nanoparticles which are much smaller than the pore diameter and distributed evenly on the pore surface throughout the membrane, ensuring the separation performance of membranes. Due to the intrinsic superhydrophilicity of CaCO3, the hybrid membranes are superhydrophilic, and show excellent water permeability with high water flux and ultralow operational pressure. As such, this work provides a generally applicable and cost-effective chemical route to improve the surface hydrophilicity of membranes or other porous materials which have potential in chemical separation, microfluidics, catalysis and other applications.
Co-reporter:Yan Fang, Wei Xu, Jian Wu and Zhi-Kang Xu  
Chemical Communications 2012 vol. 48(Issue 91) pp:11208-11210
Publication Date(Web):28 Sep 2012
DOI:10.1039/C2CC35369E
Enzymatic transglycosylation has been successfully implemented by β-galactosidase (β-Gal) on PEG brushes. Kinetic parameters validate this kind of chemoenzymatic strategy which is promising for construction of biomimetic surfaces with glycocalyx-like structures.
Co-reporter:Qing-Yun Wu, Xiao-Na Chen, Ling-Shu Wan, and Zhi-Kang Xu
The Journal of Physical Chemistry B 2012 Volume 116(Issue 28) pp:8321-8330
Publication Date(Web):June 18, 2012
DOI:10.1021/jp304167f
Polyacrylonitrile (PAN) is a semicrystalline polymer with high polarity and is usually processed from solutions. Selected solvents for processing influence both the structure and properties of PAN products. We describe the interactions between PAN and various solvents by theoretical calculation based on density functional theories (DFT), and by experimental methods of Fourier transform infrared (FTIR) spectra and two-dimensional infrared (2D-IR) correlation analysis. The selected solvents include dimethyl sulfone (DMSO2), dimethyl sulfoxide (DMSO), ethylene carbonate (EC), propylene carbonate (PC), N,N-dimethyl formamide (DMF), and N,N-dimethyl acetamide (DMAc). Calculation results show that the PAN model monomer (PAN′) interacts with each solvent through dipole–dipole interaction and formed PAN′–solvent complexes. Each complex displays an antiparallel alignment of interacting pair between the C≡N group of PAN′ and the polar group of solvent molecule (S═O or C═O group). The calculated binding energies (ΔE) reveal that PAN′ preferentially interacts with solvent in the order of DMSO2 > DMSO > EC > PC > DMF > DMAc. Red shifts of vibration frequencies are observed for C≡N, S═O, and C═O stretching bands. The C≡N stretching band shifts from 2245 cm–1 in PAN to 2240, 2242, and 2241 cm–1 in PAN–DMSO, PAN–EC, and PAN–DMF mixtures, respectively, indicating the existence of PAN–solvent interactions. Moreover, 2D-IR correlation analysis shows that as the PAN content increases, DMSO molecules vary prior to PAN–DMSO complexes, and change earlier than PAN bulk. However, PAN–EC and PAN–DMF mixtures follow the order of PAN bulk > PAN–solvent complexes > solvent molecules. This combination of theoretical simulation and experimental characterization is useful in selection of solvents for PAN or even other polar polymers and can provide an insight into the physical behavior of PAN–solvent complexes.
Co-reporter:Xiang-Lin Meng, Yan Fang, Ling-Shu Wan, Xiao-Jun Huang, and Zhi-Kang Xu
Langmuir 2012 Volume 28(Issue 38) pp:13616-13623
Publication Date(Web):September 5, 2012
DOI:10.1021/la302389e
The interactions between glycopolymer brushes and lectin are very important for the development of affinity membrane chromatography in protein separation. Here, we report the combination of surface-initiated atom transfer radical polymerization (SI-ATRP) and surface plasmon resonance (SPR) to investigate the relationship between the structure of glycopolymer brushes and the affinity adsorption of lectin. The glycopolymer brushes were fabricated from self-assembly of 11-mercapto-1-undecanol (MUD)/1-undecanethiol (UDT) mixture, immobilization of ATRP initiators, and then SI-ATRP of 2-lactobionamidoethyl methacrylate (LAMA). Brush thickness and grafting density were adjusted by controlling polymerization time and thiol ratio in MUD/UDT mixture, respectively. Sugar epitope density was also controlled through copolymerization of 2-hydroxylethyl methacrylate (HEMA) with LAMA. Ricinus communis agglutinin (RCA120), one kind of lectin that can bind galactose specifically, was chosen to study the effects of brush architectures on lectin adsorption. SPR results indicate not only the thickness but also the grafting density and the epitope density of glycopolymer brushes can achieve the best performance of sugar cluster effect in affinity adsorption of lectin. In addition, the mass transport effect is crucial in the adsorption process. We propose that it is important to keep the balance between the sugar cluster effect and the mass transport effect in the preparation of high-performance affinity membrane chromatography.
Co-reporter:Xiang-yu Ye;Xiao-jun Huang 徐志康
Chinese Journal of Polymer Science 2012 Volume 30( Issue 1) pp:130-137
Publication Date(Web):2012 January
DOI:10.1007/s10118-012-1096-4
Electrospun material with bio-inspired ordered architectures and patterns is very interesting, yet remains a challenge. We report here that nanofibrous mats with bird’s nest patterned structures can be directly electrospun from chlorinated polypropylene solutions doped with an ionic liquid. The solution viscosity and the ionic liquid content are two dominant factors to influence the topological morphology of the nanofibrous mats. The patterned structures can be further modulated by the collection time of electrospinning, the humidity of environment and the design of collector. We suggest the electrostatic repulsion between the residual charges of the mat surface and the upcoming nanofibers plays a key role in the formation of the bird’s nest patterns.
Co-reporter:Qing-Yun Wu, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2012 s 409–410() pp: 355-364
Publication Date(Web):
DOI:10.1016/j.memsci.2012.04.006
Co-reporter:Yan Fang, Wei Xu, Xiang-Lin Meng, Xiang-Yu Ye, Jian Wu, and Zhi-Kang Xu
Langmuir 2012 Volume 28(Issue 37) pp:13318-13324
Publication Date(Web):August 24, 2012
DOI:10.1021/la302738s
We present a detailed picture to screen general ligands from simple chemicals for fabricating affinity surface to glycosidase enzymes. The surface was constructed by grafting poly(2-hydroxyethyl methacrylate) (PHEMA) brush on SPR gold chip via surface-initiated atom-transfer radical polymerization, after which poly(methoxyethyl methacrylate) (PMEMA) and poly(oligo(ethylene glycol) methacrylate) (POEGMA) brushes were also prepared for comparison. SPR measurements were adopted to monitor the early-stage adsorption of two glycosidases and three other typical proteins. PHEMA resists the adsorption of lysozyme, bovine serum albumin, and fibrinogen, while it is capable of specifically adsorbing β-glucosidase (GLU) and β-galactosidase (GAL). These are quite different from the nonspecific adsorption of PMEMA and the anti-nonspecific adsorption of POEGMA to the studied proteins, because PHEMA is the acceptor substrate of the glycosidases. About 69.6 and 93.7 ng/cm2 of GAL and GLU are adsorbed on the PHEMA brush surface, of which more than 49.6 ng/cm2 is remained after washing with PBS. The specific adsorption process is appropriately described by Freundlich isothermal model rather than Langmuir one, and is also indicated to be spontaneous, endothermic, and entropy driven through thermodynamic studies. Taking into account all stated results above, we propose that molecular recognition takes place between the hydroxyl groups of PHEMA and the active sites of glycosidases, which subsequently enables the oriented adsorption of glycosidases on the brush surface. The adsorbed enzyme can be effectively eluted with 1.0 M aqueous solution of ethanol. Our findings open the door to the further development in the design of novel acceptor substrate–ligand affinity chromatography for enzyme purification.
Co-reporter:Ai-Fu Che, Xiao-Jun Huang, Zhi-Kang Xu
Journal of Membrane Science 2011 Volume 366(1–2) pp:272-277
Publication Date(Web):1 January 2011
DOI:10.1016/j.memsci.2010.10.012
Affinity membrane chromatography is of great importance for the separation and purification of proteins. Electrospun nanofibrous mats decorated with the glycosylated surfaces, combining the merits of large surface area and high porosity as well as good specificity with lectin, are regarded as superior affinity membranes. We report a simple and effective approach to acquire a new kind of glycosylated nanofibrous membrane (GNM). Poly(acrylonitrile-co-hydroxyethyl methacrylate) (PAHM) was electrospun into nanofibrous mat with an average fiber diameter of 200 nm and glucose ligands were bound on the nanofiber surface through a reaction between glucose pentaacetate and the hydroxyl groups of PAHM. Interactions between the GNM surfaces and proteins were studied by confocal laser scanning microscopy. Static and dynamic protein adsorptions were also evaluated. Results indicates that the GNM selectively recognizes lectin concanavalin A (Con A) while shows almost no affinity binding with another lectin peanut agglutinin (PNA). It also shows strong multivalent and reversible binding capability as well as high adsorption capacity to Con A. We suggest that the GNM is promising in affinity chromatography for the separation and purification of lectins.Research highlights▶ Novel affinity membrane for lectin separation has been prepared by the surface glycosylation of polyacrylonitrile-based nanofibrous membrane. ▶ This affinity membrane recognizes lectin Con A selectively but shows almost no binding with lectin PNA, due to the specific glucose–Con A interactions. ▶ This affinity membrane adsorbs Con A in a wide range of concentration and the adsorption behavior can be described by Langmuir adsorption model.
Co-reporter:Lin-Jun Shao;Jian Wu;Zhen-Mei Liu
Journal of Applied Polymer Science 2011 Volume 120( Issue 3) pp:1679-1684
Publication Date(Web):
DOI:10.1002/app.33321

Abstract

A series of poly(γ-alkyl α L-glutamate)s with different alkyl groups were synthesized by the ring opening polymerization of corresponding α-amino acid N-carboxyanhydrides. The characteristics of these polyglutamate surfaces were evaluated by attenuated total reflectance Fourier transform infrared spectroscopy spectra, water contact angle, water absorption, protein adsorption, and platelet adhesion measurements. Changing the length of the alkyl side chain provides a unique opportunity to study the influence of carbon number in the alkyl group on the surface properties of the polyglutamates. Water contact angle and water absorption data show that the hydrophilicity of these polyglutamate surfaces decreases with the increasing of methylene in the alkyl group. Protein adsorption on these polyglutamate surfaces increases with the enhancing of surface hydrophobicity. However, the changes in platelets adhesion could be attributed to the hydrophilicity/hydrophobicity of the polyglutamates and the specific effect of alkyl group. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Co-reporter:Ling DI, Cang WANG, Jian WU, Lin-Shu WAN, Zhi-Kang XU
Chinese Journal of Analytical Chemistry 2011 Volume 39(Issue 4) pp:592-598
Publication Date(Web):April 2011
DOI:10.1016/S1872-2040(10)60435-5
Because of the strong interaction with diol moieties, boric acid plays a critical role in the design of saccharide sensors. We present an overview about the development of saccharide sensors based on various mechanisms, including spectroscopies, pH indicators, and electrochemistry. The chemistry involved in the binding between boric acid and saccharides is also described. Furthermore, potential directions of future research for these boric acid based saccharide sensors are discussed.
Co-reporter:Zheng-Wei Dai ; Jun Ling ; Xiao-Jun Huang ; Ling-Shu Wan
The Journal of Physical Chemistry C 2011 Volume 115(Issue 21) pp:10702-10708
Publication Date(Web):May 5, 2011
DOI:10.1021/jp201040g
In this work, molecular dynamics (MD) simulation was employed to evaluate the influence of hydrophilization on the interaction of polypropylene surfaces with water. Constrained MD and simulated annealing were applied to construct theoretical models for the amorphous surfaces of hydrophobic polypropylene and those hydrophilized with amino, carboxyl, ammonium, and carboxylate groups. These model surfaces were studied by wetting with water droplets, and the corresponding water contact angles were calculated and compared with experimental results. We have confirmed the feasibility of the models in simulating the surfaces of realistic polypropylene. The structure and behavior of interfacial water molecules on these model surfaces can be achieved and compared with each other. Results indicate the formation of a dynamic hydration layer on the hydrophilized polypropylene surfaces. By the decomposition of the interaction potential, we found that the introduction of polar groups significantly improves the electrostatic component of the interaction potential for the surfaces with water.
Co-reporter:Zheng-Wei Dai ; Ling-Shu Wan ; Xiao-Jun Huang ; Jun Ling
The Journal of Physical Chemistry C 2011 Volume 115(Issue 45) pp:22415-22421
Publication Date(Web):October 6, 2011
DOI:10.1021/jp206733b
Surface modification for hydrophilization is a versatile approach to significantly improve the separation performance of membranes prepared from hydrophobic polymers such as polypropylene (PP). This improvement is closely related to changes in the chemical characteristics of membrane surface and alterations in the adsorption behaviors of feed components. We simulated the interaction of isopropyl alcohol aqueous solution with nascent and hydrophilized PP surfaces by molecular dynamics to understand the molecular mechanism of these variations. The results were used to evaluate the selective adsorption of isopropyl alcohol on the model surfaces. The isopropyl alcohol molecule shows surfactant-like behaviors due to one hydroxyl group as the polar end and two methyl groups as the apolar end. For nascent PP surface, dispersive force plays a key role in the interaction of isopropyl alcohol molecules with model surface. Isopropanol is therefore selectively adsorbed from the aqueous solution, and water is repelled out of the interfacial layer. For the hydrophilized surfaces, however, the electrostatic interaction between water molecules and surface polar groups exceeds the effect of dispersive force. As a result, water molecules are attracted onto the modified surface and hydration layers are observed.
Co-reporter:Meng-Xin Hu, Zhi-Kang Xu
Colloids and Surfaces B: Biointerfaces 2011 Volume 85(Issue 1) pp:19-25
Publication Date(Web):15 June 2011
DOI:10.1016/j.colsurfb.2010.10.030
Carbohydrates (saccharides) are ubiquitous on the extracellular surface of living cells and mediate a myriad of biological recognition and signaling processes. Carbohydrate decoration of polymer surfaces with covalent attachment of saccharides offers a new realm of opportunities to mimic cellular events such as protein recognition and binding. We describe the carbohydrate decoration (surface glycosylation) of poly(2-hydroxyethyl methacrylate)-grafted microporous polypropylene membranes (poly(HEMA)-g-MPPMs) with mono- and disaccharides. Galactose, lactose, glucose, and maltose were covalently attached on the surfaces of poly(HEMA)-g-MPPMs and were compared in detail. The process was verified by solid state 13C NMR spectra. Membranes with high binding degree (BD) of saccharide ligands on the surfaces were facilely prepared from poly(HEMA)-g-MPPMs with high grafting degree (GD) of poly(HEMA). For poly(HEMA)-g-MPPM with the same GD of poly(HEMA), the BD of disaccharides is lower than that of monosaccharides and the disaccharide-decorated MPPMs are more hydrophilic than the monosaccharide-decorated ones. The carbohydrate-decorated MPPMs prepared from galactose, lactose, glucose, and maltose (denoted as MPPM-Gal, MPPM-Lac, MPPM-Glc and MPPM-Mal, respectively) recognize and adsorb specifically one of the two lectins, concanavalin A (Con A) and peanut agglutinin (PNA). As the BD of saccharide increases, the “glycoside cluster effect” plays a primary role in lectin adsorption. MPPM-Lac has enhanced affinity to PNA as compared with MPPM-Gal having similar BD of saccharide., on the other hand, MPPM-Mal shows no enhanced affinity to Con A in comparison with MPPM-Glc as the BD of saccharide is above 0.9 μmol/cm2, where the “glycoside cluster effect” occurs.Graphical abstractResearch highlights▶ Mono- and disaccharides modified microporous polypropylene membranes adsorb lectin. ▶ Membranes with high binding degree of saccharides exert “glycoside cluster effect”. ▶ Lactose modified membrane adsorbs more PNA than galactose modified one dose. ▶ Maltose modified membrane shows no more affinity to Con A than glucose modified one.
Co-reporter:Xiang-Lin Meng, Ling-Shu Wan, Zhi-Kang Xu
Colloids and Surfaces A: Physicochemical and Engineering Aspects 2011 Volume 389(1–3) pp:213-221
Publication Date(Web):20 September 2011
DOI:10.1016/j.colsurfa.2011.08.024
We report the experimental and modeling results of water contact angle (CA) on anisotropic surfaces with aligned fibers fabricated by electrospinning. The aligned fibers with radius of several micrometers can effectively stop the three-phase contact line (TPCL) and lead to a very high “static” CA as well as stick–slip patterns. The maximal CA, which appears during the advancing CA measurement, is nearly the same on those surfaces with different fiber densities. A thermodynamic model was applied to describe the free energy change and the location of metastable states. It is found that the energy barrier of potential wells is precisely linear to the fiber radius. By adjusting the reference energy of the model, the calculated result can fit the experimental ones well. Results also indicate that the process for static CA measurement is similar to that for advancing CA to some extent but without much driving force. Static CA in the direction parallel to the fibers is very different from that perpendicular to the fibers since there is no obvious barrier for the TPCL to advance along the fibers. These experimental and modeling results provide some insights into the CA on rough surfaces as well as the stick–slip phenomenon. Relationship between the metastable potential wells and the external energy determines when the “slip” or “stick” happens. Furthermore, the results may be helpful for designing of microfluidic system.Graphical abstractHighlights► Contact angles on aligned fibers were studied experimentally and theoretically. ► Modification was made to a 2-D thermodynamic model to adapt sophisticated surfaces. ► The maximal CA is nearly the same on surfaces with different fiber densities. ► Calculated results can fit the experimental ones well with proper parameters.
Co-reporter:Yun-Feng Yang, Han-Qiong Hu, Yang Li, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2011 376(1–2) pp: 132-141
Publication Date(Web):
DOI:10.1016/j.memsci.2011.04.012
Co-reporter:Shi-Liang Chen;Xiao-Jun Huang
Cellulose 2011 Volume 18( Issue 5) pp:
Publication Date(Web):2011 October
DOI:10.1007/s10570-011-9572-5
A versatile method is reported for the preparation of cellulose nanofiber mats immobilized with cobalt tetraaminophthalocyanine (CoPc). This functionalized cellulose nanomaterial was used as an efficient catalyst for the decoloration of reactive dye wastewater. Cellulose acetate was electrospun into nanofiber mats (CA-NM), hydrolyzed with KOH, and then oxidized by NaIO4 to generate aldehyde groups for CoPc immobilization. The functionalization processes on the nanofiber mats were monitored by attenuated total reflection Fourier transform infrared spectroscopy (ATR/FT-IR), X-ray photoelectron spectroscopy (XPS), and field emission scanning electron microscope (FESEM). We found these CoPc-functionalized nanofiber mats (CoPc-NM) have high adsorption capacity for reactive dye from synthetic wastewater, which enhances the catalytic oxidation rate of reactive dye when H2O2 is present as oxidant. More than 90% of reactive red X-3B can be eliminated by CoPc-NM/H2O2 in 90 min. UV and GC-MS analyses indicate the catalytic oxidation not only breaking the azo linkages but also decomposing the aromatic parts of reactive red X-3B, and the main products are biodegradable aliphatic acids, such as fumaric acid, succinic acid, and maleic acid, etc. Repetitive measurements also show that this CoPc-NM is quite stable and remains efficient with no obvious decrease of catalytic activity.
Co-reporter:Zheng-Wei Dai, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2010 Volume 348(1–2) pp:245-251
Publication Date(Web):15 February 2010
DOI:10.1016/j.memsci.2009.11.007
Natural polysaccharides such as chitosan have been widely used to prepare polymer membranes for pervaporation dehydration. As their synthetic analogues, glycopolymers are also promising materials for the same purpose due to their high affinity interactions with water. In this work, glycopolymer-filled composite membranes were prepared by a pore-filling strategy from microporous polypropylene membrane using ultraviolet-initiated in situ copolymerization of acrylic acid (AA) and d-gluconamidoethyl methacrylate (GAMA). The morphologies and chemical structures of the fabricated membranes were characterized and the dense pore-filled structure was evaluated. Swelling experiments in water, isopropanol and their mixture revealed that the sorption selectivity of the GAMA units in the glycopolymer with water was higher than that of the AA units. Pervaporation on isopropanol/water mixture containing 10 wt% water was carried out and the membranes showed separation selectivity on water with high normalized flux. Investigation on sorption selectivity and diffusion selectivity indicated that the sorption selectivity of the GAMA units on water was the determining factor for the separation property of the glycopolymer-filled composite membranes. These membranes showed fine structural and performance stability during a ten-day operation.
Co-reporter:Yun-Feng Yang, Yang Li, Qing-Lian Li, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2010 Volume 362(1–2) pp:255-264
Publication Date(Web):15 October 2010
DOI:10.1016/j.memsci.2010.06.048
The anti-biofouling properties, i.e. the resistance to protein adsorption and the inhibition of bacterial adhesion (biofilm formation) are of vital importance to separation membranes. Surface hydrophilization is thought to be the most common approach to improve these performances for hydrophobic polymer membranes, such as microporous polypropylene membrane (MPPM). In this work, MPPM was highly hydrophilized by the UV-induced grafting of polysulfobetaine methacrylate (polySBMA), an outstanding representative of zwitterionic anti-/non-fouling polymers. A sequential grafting strategy was improved by combining the conventional benzophenone entrapment and covalent immobilization methods. FT-IR/ATR, XPS and FESEM were used to characterize the detailed surface structures of MPPM. The hydrophilization effect was evaluated by water contact angle (WCA) and pure water flux measurements. Besides, both protein filtration and initial adhesion of bacteria were performed to investigate the anti-biofouling properties of the modified MPPM. The surface hydrophobicity of the bacteria was also measured and correlated with the adhesion results. It is found that the improved strategy allows the grafting to take place on the external surface and the grafting density to be well controlled by modulating the SBMA concentration. The surface hydrophilicity of MPPM is significantly enhanced, characterized by a decrease of WCA from 145 to ∼15° and an increase of flux by 4 times. These hydrophilized MPPM has strong resistance to protein fouling, having a flux recovery ratio higher than 95% under optimized conditions. The initial adhesion of bacteria on the MPPM can be completely suppressed when the grafting density reaches 560 μg/cm2, regardless of the bacterial surface hydrophobicity.Research highlights▶ A zwitterionic polymer, polysulfobetaine methacrylate (polySBMA), was tethered onto microporous polypropylene membrane (MPPM) by UV-induced grafting. ▶ The grafting of polySBMA significantly enhances the surface hydrophilicity of MPPM. ▶ The hydrophilized MPPM with an appropriate grafting density not only strongly resists protein fouling but also completely suppresses the initial adhesion of bacteria.
Co-reporter:Cang Wang;Jian Wu
Macromolecular Rapid Communications 2010 Volume 31( Issue 12) pp:1078-1082
Publication Date(Web):
DOI:10.1002/marc.200900866
Co-reporter:Ai-Fu Che;Xiao-Jun Huang
Macromolecular Bioscience 2010 Volume 10( Issue 8) pp:955-962
Publication Date(Web):
DOI:10.1002/mabi.201000002
Co-reporter:Yuan-Yuan Lv, Jian Wu, Zhi-Kang Xu
Sensors and Actuators B: Chemical 2010 Volume 148(Issue 1) pp:233-239
Publication Date(Web):30 June 2010
DOI:10.1016/j.snb.2010.05.029
A novel sensor fabricated from the nanofibrous membrane of porphyrinated polyimide (PPI) for the rapid detection of trace amount of hydrogen chloride (HCl) gas is described. Covalently bonding of the porphyrin fluorophores into polyimide main chains overcomes the disadvantage of porphyrin aggregation and improves the physicochemical stability of polyimide simultaneously. The dual chromo- and fluorogenic responses of the nanofibrous membrane upon exposure to HCl gas are interpreted in terms of the out-of-plane distortion of porphyrin macrocycle, which ultimately affects its optical properties. UV–vis and fluorescence spectroscopies were used to further study the protonation of porphyrin moieties in polyimide. With large amount of available surface area and hence good gas accessibility, the nanofibrous membrane of porphyrinated polyimide shows unusually high sensitivity and fast response time in sensing application. An apparent binding affinity constant of (1.05 ± 0.23) × 104 L mol−1 was calculated from surface plasmon resonance (SPR) analysis, confirming that the porphyrinated nanofibrous membrane is an applicable material for constructing HCl-sensitive gas sensor.
Co-reporter:Yun-Feng Yang, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2009 Volume 337(1–2) pp:70-80
Publication Date(Web):15 July 2009
DOI:10.1016/j.memsci.2009.03.023
To endow microporous polypropylene membrane (MPPM) with durable surface hydrophilicity, a facile interfacial crosslinking approach was developed, combined with a pretreatment by dielectric barrier discharge (DBD) plasma at atmospheric pressure. The commercially available polyethylenimine (PEI) was coated on MPPM firstly and was sequentially crosslinked with p-xylylene dichloride and quaternized with iodomethane to form a permanently positively charged layer. The physical and chemical changes of the membrane surface were characterized by tensile test, FT-IR/ATR, XPS, and FESEM. The surface hydrophilicity of the modified MPPMs was evaluated by water contact angle and pure water flux measurements. Besides, the influence of surface charge on protein filtration involving flux decline and protein transmission was also investigated in detail. It is found that the optimal time of DBD plasma treatment is ∼30 s. Mass gain for the MPPMs during the interfacial crosslinking can be controlled conveniently by adjusting the PEI concentration from 1.0 to 15 g/L. The surface hydrophilicity can be significantly enhanced and is durable, characterized by the sharp decrease of water contact angle, the double increase of pure water flux and the stability test. The results of protein filtration suggest that the obtained highly hydrophilic and charged membrane surface is resistant to protein fouling. Furthermore, almost 100% of protein transmission indicates that the microfiltration characteristic of MPPMs is unchanged.
Co-reporter:Meng-Xin Hu, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2009 Volume 335(1–2) pp:111-117
Publication Date(Web):15 June 2009
DOI:10.1016/j.memsci.2009.03.005
Affinity membranes are fast growing for bioseparation techniques. Using membrane as the chromatography media can overcome some disadvantages of the column chromatography. The products of affinity membrane chromatography possess extremely high purity due to the highly specific binding between the ligands immobilized on the membranes and the targets in the solution. The glycosylated microporous polypropylene membranes (MPPMs) can be used as affinity membranes for proteins separation on the basis of the specific interactions between saccharide ligands and lectins. These glycosylated membranes can be facilely prepared by the immobilization of saccharide ligands on the poly(2-hydroxyethyl methacrylate) (poly(HEMA))-grafted MPPMs through the reaction between hydroxyl groups and acetylated saccharides. The tentacle-like poly(HEMA) chains on the membrane with pendent saccharide ligands not only increase the specific area of membrane but also are benefit to adsorb multilayer proteins, which can enhance the binding capacity of protein on the affinity membrane. The glucose modified MPPMs can specifically adsorb one kind of lectin, Concanavalin A (Con A). Binding degree of glucose residues on the affinity membrane plays a positive role on the binding capacity of Con A. The protein molecules adsorbed on the outer layer of flexible polymer chains can be transferred into the inner layer through the reversible binding between Con A and glucose residues. Therefore, multilayer of Con A is adsorbed on the affinity membrane. Compared with the competitive eluants, such as glucose and methyl α-mannopyranoside, 1 M HAc solution is more effective to elute the adsorbed Con A from the glucose modified MPPMs. Besides, the results of CLSM directly demonstrate the specific adsorption of proteins on the glycosylated MPPMs.
Co-reporter:Yun-Feng Yang, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2009 Volume 326(Issue 2) pp:372-381
Publication Date(Web):20 January 2009
DOI:10.1016/j.memsci.2008.10.011
A hydrophilic surface is very important for hydrophobic separation membranes such as polypropylene microporous membranes (PPMMs). In this work a facile and effective method, interfacial crosslinking combined with pretreatment by dielectric barrier discharge plasma at atmospheric pressure, was developed for endowing PPMMs with a hydrophilic and charged surface. Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and p-xylylene dichloride were selected for quaternization crosslinking to form a positively charged coating layer, which was characterized with FT-IR/ATR, XPS, and FESEM. Water contact angle and pure water flux measurements were conducted to evaluate the surface hydrophilicity. The influence of surface charges on protein filtration was also investigated. It is found that the mass gain of interfacial crosslinking increases almost linearly with increasing the PDMAEMA concentration from 0.5 to 10 g/L. The crosslinking degree is larger than 80% according to the XPS results, ensuring the stability of the crosslinking layer. The surface hydrophilicity is demonstrated by the sharp decrease of water contact angle from 145° to 20°. The pure water flux also increases 3 times under the optimized conditions. Furthermore, the results of protein filtration suggest that these highly hydrophilic and charged surfaces can effectively resist the fouling of proteins.
Co-reporter:Ling-Shu Wan, Yun-Feng Yang, Jing Tian, Meng-Xin Hu, Zhi-Kang Xu
Journal of Membrane Science 2009 Volume 327(1–2) pp:174-181
Publication Date(Web):5 February 2009
DOI:10.1016/j.memsci.2008.11.032
In this paper, we describe a thermo-responsive membrane based on microporous polypropylene membrane (MPPM). Comb-like poly(N-isopropylacrylamide) (PNIPAM) was grafted onto the MPPM surface using surface-initiated atom transfer radical polymerization (ATRP). Hydroxyl groups were firstly introduced onto the membrane surface by the ultraviolet-induced graft polymerization of 2-hydroxyethyl methacrylate. Then ATRP initiators were immobilized through the reaction between the tethered hydroxyl groups and 2-bromoisobutyryl bromide, which initiated the ATRP of NIPAM on the membrane surface. Attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and field emission scanning electron microscopy were used to characterize the chemical composition and surface morphologies of the modified membranes. The thermo-response of the modified membranes was evaluated by water contact angle and water permeation measurements. It is found that both water contact angles and water fluxes have obvious response to the environmental temperature. This type of membrane with controlled PNIPAM graft layer can be applied in many fields including smart separation.
Co-reporter:Zhen-Gang Wang, Ling-Shu Wan and Zhi-Kang Xu  
Soft Matter 2009 vol. 5(Issue 21) pp:4161-4168
Publication Date(Web):19 Aug 2009
DOI:10.1039/B902637A
The properties of immobilized enzyme preparation are governed by the properties of both the enzyme and the carrier material. The interaction between the two provides an immobilized enzyme with specific biological and chemical properties. To more clearly understand the role of the carrier surface in the activity and stability of immobilized enzyme, we modified poly(acrylonitrile-co-acrylic acid) nanofibrous membrane with bovine serum albumin (BSA), which has a heart shape, and collagen, which is a fibril. The protein coverage density was verified with UV-vis spectrophotometry and confocal laser scanning microscopy. Catalase from bovine liver was then immobilized on the protein-modified nanofibrous membranes using either glutaraldehyde or N-(3-dimethylaminopropyl)-N′-ethyl-carbodiimide hydrochloride as coupling agent. Atomic force microscopy and water contact angle measurement were used to evaluate the topographical and hydrophilic/hydrophobic properties of the protein-modified surfaces. Results indicate that the enzyme loading and the specific activity of immobilized catalase depend on the protein coverage density, kinds of proteins and coupling agents. The activity of catalase can be enhanced by surface modification with both BSA and collagen. However, they show different effects on the thermal stabilities of the immobilized catalase, which is ascribed to whether hydrophobic interaction occurs between the immobilized catalase and the protein-modified surface.
Co-reporter:Ling-Shu Wan, Zhen-Mei Liu and Zhi-Kang Xu  
Soft Matter 2009 vol. 5(Issue 9) pp:1775-1785
Publication Date(Web):25 Feb 2009
DOI:10.1039/B813600A
The surface properties of polymer membranes are crucial to their application. This Review provides concise comments on surface engineering strategies for macroporous polypropylene membranes. The applications of surface engineering concepts in membrane-based bioreactors, bioseparation, biosensing, biosynthesis, environmental analysis, water purification, energy technology, medical devices (artificial lung and liver), and some novel separation processes (intelligent membrane separation) are summarized. The prospect of surface engineered biomimetic polypropylene membrane is also looked at.
Co-reporter:Ling-Shu Wan
Journal of Biomedical Materials Research Part A 2009 Volume 89A( Issue 1) pp:168-175
Publication Date(Web):
DOI:10.1002/jbm.a.31907

Abstract

Fibrous membranes (nonwoven meshes) prepared via electrospinning technique have great potential in tissue engineering. This work is the first study on the behaviors of blood platelets at the nanostructured surface generated by electrospinning. Poly[acrylonitrile-co-(N-vinyl-2-pyrrolidone)] (PANCNVP) that shows excellent antiplatelet adhesion ability was directly electrospun onto its dense membrane surface. Polyacrylonitrile (PAN) samples were used as controls. The depth as well as the density of the nanofibers can be easily controlled. The results showed that the PANCNVP dense membrane certainly suppressed the activation and adhesion of platelets. However, whether the nanofibers and underlying membranes were composed of PAN or PANCNVP, the nanostructured surfaces promoted the activation, adhesion, and orientation of platelets. It was also found that, if the space between fibers was too large or the depth of fibers was too small, the nanostructured surface did not change the property of antiplatelet adhesion of PANCNVP. The promotion of activation and adhesion of platelets was obviously due to the presence of nanofibers, which induced the changes of surface topography and charge. © 2008 Wiley Periodicals, Inc. J Biomed Mater Res, 2009

Co-reporter:Xiang-Yu Ye, Zhen-Mei Liu, Zhen-Gang Wang, Xiao-Jun Huang, Zhi-Kang Xu
Materials Letters 2009 Volume 63(Issue 21) pp:1810-1813
Publication Date(Web):31 August 2009
DOI:10.1016/j.matlet.2009.05.054
Magnetic nanofibrous composite membranes were electrospun from the mixtures of poly(acrylonitrile-co-acrylic acid) (PANCAA) and Fe3O4 nanoparticles. Field emission scanning electron microscopy (FESEM) and thermal gravimetric analysis (TGA) were used to characterize the composite membranes. TGA results indicate that the addition of Fe3O4 nanoparticles catalyzes the carbonization of PANCAA as well as dramatically increases the carbonization temperature. The intrinsic peroxidase-like activity of Fe3O4 nanoparticles was measured by the color reaction of phenol/4-amino antipyrine in the presence of H2O2. Under optimal conditions, the electrospun composite membranes show high peroxidase-like catalytic activity and reusability. Taking into account of the potentiality for separation, these as-prepared magnetic nanofibrous composite membranes will be applied in phenolic wastewater treatment.
Co-reporter:Ai-Fu Che, Ling-Shu Wan, Jun Ling, Zhen-Mei Liu and Zhi-Kang Xu
The Journal of Physical Chemistry B 2009 Volume 113(Issue 20) pp:7053-7058
Publication Date(Web):April 29, 2009
DOI:10.1021/jp902163s
Molecular imprinting polymers (MIPs) are synthetic materials having specific cavities tailored for a target molecule. Thoroughly understanding the molecular recognition mechanism is favorable for the rational design, preparation, and application of MIPs. In this work, theophylline (THO)-imprinted poly(acrylonitrile-co-acrylic acid) (PANCAA) films with acrylic acid (AA) as the functional monomer were fabricated and a set of concentration-dependent Fourier transform infrared (FT-IR) spectra were collected. Two-dimensional (2D) correlation analysis of the spectra and density functional theory (DFT) calculation were conducted to evaluate the molecular recognition mechanism. DFT at the B3LYP/6-31+G(d,p) level is efficacious to calculate the binding energies (ΔE) and the theoretical vibration frequencies for the possible configurations of THO_AA complexes. An optimized cyclic hydrogen-bonded configuration (complex THO_AA1) has the highest binding energy (−16.63 kcal mol−1) that is more stable than others. In addition, the experimental vibrations of the carbonyl groups in the FT-IR spectra were assigned on the basis of the DFT results. Moreover, methylacrylic acid (MAA) and caffeine (CAF) as compared analogues were also investigated. The DFT-based theoretical predictions are coincident with the reported results.
Co-reporter:Ling-Shu Wan;Hao Lei;Yao Ding;Lei Fu;Jing Li
Journal of Polymer Science Part A: Polymer Chemistry 2009 Volume 47( Issue 1) pp:92-102
Publication Date(Web):
DOI:10.1002/pola.23124

Abstract

We describe the synthesis of three novel thermoresponsive copolymers of acrylonitrile (AN) with N-isopropylacrylamide (NIPAM) by a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and atom transfer radical polymerization (ATRP). Linear copolymer polyacrylonitrile (PAN)-b-PNIPAM was directly prepared by RAFT polymerization. Comb-like copolymers were synthesized by ATRP using brominated AN/2-hydroxyethyl methacrylate copolymers as macroinitiators, which were prepared by RAFT polymerization. FT-IR, NMR, and GPC were employed to characterize the synthesized copolymers. Results indicate that the polymerization processes can be well controlled and the resultant copolymers have well-defined structures as well as narrow polydispersity. Then dense films were fabricated from these thermoresponsive copolymers and the surface wettability was evaluated by water contact angle measurements at different temperatures. It is found that the surface wettability is temperature-dependant and both the transition temperature and decrement of water contact angle are affected by the copolymer shapes as well as the length of PNIPAM blocks. Considering the excellent fiber- and membrane-forming properties of PAN-based copolymers, the obtained thermoresponsive copolymers are latent materials for functional fibers and membranes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 92–102, 2009

Co-reporter:Zhen-Gang Wang, You Wang, Hui Xu, Guang Li and Zhi-Kang Xu
The Journal of Physical Chemistry C 2009 Volume 113(Issue 7) pp:2955-2960
Publication Date(Web):2017-2-22
DOI:10.1021/jp807047s
Due to its unique electrical properties, carbon nanotubes offer the exciting possibility for developing ultrasensitive electrochemical biosensors. In this work, nanofibrous membranes filled with multiwalled carbon nanotube (MWCNT) were electrospun from the mixture of poly(acrylonitrile-co-acrylic acid) (PANCAA) and MWCNT. These nanofibrous membranes were directly deposited on Pt electrodes for the fabrication of glucose biosensors. Glucose oxidase (GOx) was covalently immobilized on the membranes through the activation of carboxyl groups on the PANCAA nanofiber surface. The fluorescence spectra and circular dichroism were recorded from the mixtures of MWCNT and soluble GOx. Results show that MWCNT will disturb the secondary structure of soluble GOx but can get close to its active site. The morphologies of the nanofibrous membranes were visualized by scanning electron microscopy, illustrating that the membranes are composed of beads and nanofibers. The electrochemical properties of enzyme electrodes were characterized by chronoamperometric measurments. It is found that as MWCNT concentration increases, the current enhances correspondingly with a maximum of 50%, while the MWCNT filling delays the electrode response. Kinetic studies of the electrodes show that the secondary structure of the immobilized GOx is disturbed, while the embedded MWCNT enhances the maximum current of GOx electrode. Moreover, the enzyme electrodes can be used up to 6 times with a small decrease in current.
Co-reporter:LingShu Wan;BeiBei Ke;XiaoKai Li;XiangLin Meng
Science China Chemistry 2009 Volume 52( Issue 7) pp:969-974
Publication Date(Web):2009 July
DOI:10.1007/s11426-009-0007-1
Highly ordered honeycomb-patterned polystyrene (PS)/poly(ethylene glycol) (PEG) films were prepared by a water-assisted method using an improved setup, which facilitated the formation of films with higher regularity, better reproducibility, and larger area of honeycomb structures. Surface aggregation of hydrophilic PEG and adsorption of bovine serum albumin (BSA) on the honeycomb-patterned films were investigated. Field emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM) were used to observe the surface morphologies of the films before and after being rinsed with water. As confirmed by the FESEM images and the AFM phase images, PEG was enriched in the pores and could be gradually removed by water. The adsorption of fluorescence-labeled BSA on the films was studied in visual form using laser scanning confocal microscopy. Results clearly demonstrated that the protein-resistant PEG was selectively enriched in the pores. This water-assisted method may be a latent tool to prepare honeycomb-patterned biofunctional surfaces.
Co-reporter:Meng-Xin Hu, Ling-Shu Wan, Zhen-Mei Liu, Zheng-Wei Dai and Zhi-Kang Xu  
Journal of Materials Chemistry A 2008 vol. 18(Issue 39) pp:4663-4669
Publication Date(Web):03 Sep 2008
DOI:10.1039/B807181K
Synthetic membranes with glycosylated surfaces have great potential in pharmaceutics, clinically in diagnosis and protein purification. A versatile method of constructing glycosylated membrane surfaces was developed using poly(2-hydroxyethyl methacrylate) (poly(HEMA))-tethered microporous polypropylene membranes (MPPMs) as supports. Glucose moieties were bound on the membrane surfaces through the reaction between glucose pentaacetate and the hydroxyl group of poly(HEMA). The binding degree of glucose moieties on the MPPMs was controlled in a wide range by changing the grafting degree of poly(HEMA). The maximum binding degree reaches 10 µmol cm−2 when the grafting degree of poly(HEMA) on the membrane surface is 29.40 µmol cm−2. These glycosylated membrane surfaces were characterized by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. Water contact angles of the glycosylated membrane surfaces before and after removing the acetyl groups differ remarkably from each other. After deprotection, the glycosylated membrane surfaces become highly hydrophilic, which greatly inhibits the non-specific adsorption of bovine serum albumin or peanut agglutinin on these surfaces. Furthermore, the glycosylated membranes can selectively recognize concanavalin A (ConA). When the binding degree of glucose moieties is above 0.39 µmol cm−2, the “glycoside cluster effect” occurs and plays an important role in the recognition and adsorption of proteins. Due to the reversible affinity, the adsorbed ConA can be desorbed with glucose solution. The results suggest that these MPPMs with glycosylated surfaces are promising for the isolation/purification of proteins.
Co-reporter:Zheng-Wei Dai, Ling-Shu Wan, Zhi-Kang Xu
Journal of Membrane Science 2008 Volume 325(Issue 1) pp:479-485
Publication Date(Web):15 November 2008
DOI:10.1016/j.memsci.2008.08.013
Surface glycosylation is one of the most promising strategies to fabricate biomimetic surface for membrane. Previous studies confirmed that cyclic sugars provide recognition sites for specific proteins, while ring-opening sugars offer better hydrophilicity and anti-adsorption ability to proteins. To improve the anti-fouling property of polyacrylonitrile (PAN) ultrafiltration membrane, a ring-opening glycomonomer d-gluconamidoethyl methacrylate (GAMA) was grafted onto the surface of the membrane by ultraviolet (UV)-initiated grafting polymerization. Attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FT-IR) and field emission scanning electron microscopy (FESEM) were used to characterize the chemical and morphological changes of the membrane surface. Water contact angle, protein adsorption and protein filtration were employed to evaluate the anti-fouling performance of the membrane. The protein adsorption experiment was carried out with fluorescein isothiocyanate-labeled bovine serum albumin (FITC-BSA), and the adsorption quantity was measured locally by laser confocal scanning microscope (LCSM). This method supplied a simple and direct manner to evaluate the protein adsorption performance of membrane, and the interference of the support was also avoided. The results revealed that by the surface glycosylation procedure, the hydrophilicity was enhanced and the adsorption of FITC-BSA was inhibited significantly. The flux recovery ratio was also increased after modification, indicating that the anti-fouling performance of PAN membrane was improved by the glycosylation strategy.
Co-reporter:ZhengWei Dai;LingShu Wan;ZhiKang Xu
Science China Chemistry 2008 Volume 51( Issue 10) pp:901-910
Publication Date(Web):2008 October
DOI:10.1007/s11426-008-0103-7
Surface glycosylation of polymeric membranes has been inspired by the structure of natural biomembranes. It refers to that glycosyl groups are introduced onto the membrane surface by various strategies, which combine the separation function of the membrane with the biological function of the saccharides in one system. In this review, progress in the surface glycosylation of polymeric membranes is highlighted in two aspects, i.e. the glycosylation methods and the potential applications of the surface-glycosylated membranes.
Co-reporter:Yuan-Yuan Lv ; Jian Wu ; Ling-Shu Wan
The Journal of Physical Chemistry C 2008 Volume 112(Issue 29) pp:10609-10615
Publication Date(Web):June 28, 2008
DOI:10.1021/jp7105549
A series of copolymers based on diaminotetraphenylporphyrin (DATPP), oxidianiline (ODA), and pyromellitic dianhydride (PMDA) were synthesized. The resulting copoly(amic acid)s (CPAAs) were electrospun into uniform nanofibers. Subsequently, copolyimide (CPI) nanofibers were obtained from the CPAA nanofibers by thermal imidization. The morphologies and luminescence of these nanofibers were characterized by field emission scanning electron microscopy (FESEM) and confocal laser scanning microscopy (CLSM). It was found from the CLSM analyses that fluorescence quenching took place after the nanofibers were imidized. This could be attributed to the photoinduced electron transfer from excited porphyrin units to diimide acceptor groups. Thermogravimetric (TG) analyses indicated the CPI nanofibers possessed excellent thermal stability. This kind of CPI nanofibers with high temperature resistance and unique photoelectric properties could be potential materials for optical switches, catalysis, nonlinear optics, and molecular wires used in normal and especially in high temperature circumstances.
Co-reporter:Ai-Fu Che, Zhen-Mei Liu, Xiao-Jun Huang, Zhen-Gang Wang and Zhi-Kang Xu
Biomacromolecules 2008 Volume 9(Issue 12) pp:
Publication Date(Web):October 25, 2008
DOI:10.1021/bm800882z
Lectin affinity membranes have been receiving much attention for the separation and detection of various glycoconjugates. In this work, we present a simple and efficient method for the preparation of lectin affinity nanofibrous membranes. Chitosan-modified poly(acrylonitrile-co-acrylic acid) (PANCAA) nanofibrous membranes were first prepared by a coupling reaction between the primary amino groups of chitosan and the carboxyl groups of PANCAA electrospun membranes. Surface characterizations by attenuated total reflectance Fourier transform infrared spectroscopy (FT-IR/ATR), X-ray photoelectron spectroscopy (XPS) and field-emission scanning electron microscopy (FESEM) confirm the chemical and morphological changes of the studied nanofibrous membranes. Fluorescence-labeled concanavalin A (FL-Con A) was then immobilized on these membranes via noncovalent binding. Analyses by fluorescence spectrophotometer (FS) and confocal laser scanning microscopy (CLSM) reveal that the immobilization of Con A onto the modified nanofibrous membranes has been successfully achieved on the basis of the electrostatic interaction and the specific recognition between Con A and chitosan. The results show that the amount of adsorbed FL-Con A increases dramatically with the increasing coupling degree of chitosan (CDC) on the nanofibrous membrane. Moreover, Con A immobilized on the chitosan-modified nanofibrous membranes (CMNMs) can remain relatively stable at pH 5.3. Therefore, it is believed that this work may provide a new kind of material for affinity application.
Co-reporter:Ling-Shu Wan, Zhi-Kang Xu, Xiao-Jun Huang, Xiao-Dan Huang, Ke Yao
Acta Biomaterialia 2007 Volume 3(Issue 2) pp:183-190
Publication Date(Web):March 2007
DOI:10.1016/j.actbio.2006.09.007

Abstract

Polyacrylonitrile modified with N-vinyl-2-pyrrolidone (NVP) shows good hemocompatibility. This work, which aims to evaluate the cytocompatibility of membranes fabricated from poly(acrylonitrile-co-N-vinyl-2-pyrrolidone) (PANCNVP), studied the adhesion of macrophages and endothelial cell (EC) cultures. It was found that PANCNVP membranes with higher NVP content decreased the adhesion of both macrophages and ECs. Compared with polyacrylonitrile and tissue culture polystyrene control, however, these PANCNVP membranes promoted the proliferation of ECs. Furthermore, the viability of ECs cultured on the PANCNVP membrane surfaces was also relatively competitive. Both static and dynamic water contact angle measurements were conducted to explain the nature of cell adhesion to the PANCNVP membranes. On the basis of these results and the phenomena of water swelling and water states reported previously, it was presumed that the coexistence of large amounts of bound water and free water induced by NVP moieties are responsible for the lower adhesion and better function of cells adhering to the PANCNVP membranes.

Co-reporter:Meng-Xin Hu;Zhi-Sheng Fu;Ling-Shu Wan;Zhi-Qiang Fan
Macromolecular Rapid Communications 2007 Volume 28(Issue 24) pp:2325-2331
Publication Date(Web):22 OCT 2007
DOI:10.1002/marc.200700487

Surface modification of commercial PPBs with different saccharides is described. Surface-glycosylated PPBs were prepared through reaction between the hydroxyl groups of poly(HEMA) and acetylated saccharides such as α-glucose pentaacetate, β-galactose pentaacetate, and lactose octaacetate. The modified PPBs were characterized by XPS and water contact angle measurement. It was found that the grafting degree of poly(HEMA) increases with UV irradiation time, monomer concentration, and water content in solvent. The binding degree of monosaccharides is higher than that of disaccharides. The glycosylated PPBs can selectively recognize lectins, indicating potential for protein isolation.

Co-reporter:Hai-Yin Yu, Zhi-Kang Xu, Hao Lei, Meng-Xin Hu, Qian Yang
Separation and Purification Technology 2007 Volume 53(Issue 1) pp:119-125
Publication Date(Web):15 February 2007
DOI:10.1016/j.seppur.2006.07.002
Polypropylene hollow fiber microporous membranes (PPHFMMs) were surface-modified by the photoinduced graft polymerization of acrylamide (AAm). Structural and morphological changes on the membrane surface were characterized by attenuated total reflection-Fourier transform infrared spectroscopy (FT-IR/ATR) and field emission scanning electron microscopy (FE-SEM). Water contact angles of the membrane surfaces were also measured by the sessile drop method. Results of FT-IR/ATR indicated the successful graft polymerization of AAm onto the membrane surface. Water contact angle of the modified membrane decreased with the increase of the grafting degree. It showed 34.9° for the modified membrane with a grafting degree of 278.4 wt.%, nearly 94° lower than that of the nascent one. The antifouling characteristics of the PPHFMMs before and after surface modification were assessed by the filtration of activated sludge in a submerged membrane bioreactor for synthetic wastewater treatment. It demonstrated that after continuous operation for about 42 h, the flux recovery were 36.9, 63.7% and the relative flux ratio were 1.00, 1.32 for the nascent and modified PPHFMMs, respectively.
Co-reporter:Meng-Xin Hu, Qian Yang, Zhi-Kang Xu
Journal of Membrane Science 2006 Volume 285(1–2) pp:196-205
Publication Date(Web):15 November 2006
DOI:10.1016/j.memsci.2006.08.023
Membrane surfaces modified with polymers based on 2-hydroxyethyl methacrylate (HEMA) is promising for hydrophilicity, biocompatibility, and functionality. In this work, the UV-induced graft polymerization of HEMA onto polypropylene microporous membrane (PPMM) was studied using ferric chloride (FeCl3) and benzophenone (BP) as co-photoinitiators with different methods for the first time. It was found that the conventional photoinitiator, BP, could not initiate the grafting polymerization of HEMA on the PPMM. Incorporation of FeCl3 into the reaction system remarkably enhanced the grafting of HEMA onto PPMM, which could be ascribed to the “synergistic effect” between Fe3+ and BP. Results indicated that the maximum grafting degree for the soak method, which added monomer, photoinitiators and membranes in acetone/water mixture together was 2.5-fold greater than that for the adsorption method. Therefore, the grafting degree of HEMA on the membrane surface could be modulated in a wide range through the variation of UV irradiation time, monomer concentration, and BP/FeCl3 ratio. The poly(HEMA)-modified membrane surfaces were characterized by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. Static water contact angle of the membrane surface indicated a decrease from 145° to 42° with the grafting degree increasing from 0 to 35.67 wt.%. Water drop lied on the modified surface with 35.67 wt.% of grafting degree permeated completely into the membrane pores in 3 s. Furthermore, these poly(HEMA)-tethered membranes showed well protein resistance and potential hemocompatibility due to the enhancement of surface hydrophilicity.
Co-reporter:Ling-Shu Wan;Zhen-Gang Wang;Jian Wu;Christophe Innocent;Patrick Seta
Macromolecular Rapid Communications 2006 Volume 27(Issue 7) pp:516-521
Publication Date(Web):13 MAR 2006
DOI:10.1002/marc.200500885

Summary: Nanofibrous membranes that possess reactive groups are fabricated by the electrospinning process from PANCAA solutions that contain MWCNTs. Field emission scanning electron microscopy is used to evaluate the morphology and diameter of the nanofibers. Potentials for applying these nanofibrous membranes to immobilize redox enzymes by covalent bonding are explored. It is envisaged that the electrospun nanofibrous membranes could provide a large specific area and the MWCNTs could donate/accept electrons for the immobilized redox enzymes. Results indicate that, after blending with MWCNTs, the diameter of the PANCAA nanofiber increases slightly. The PANCAA/MWCNT nanofibrous membranes immobilize more enzymes than that without MWCNTs. Moreover, as the concentration of the MWCNTs increases, the activity of the immobilized catalase is enhanced by about 42%, which is mainly attributed to the promoted electron transfer through charge-transfer complexes and the π system of MWCNTs.

Co-reporter:Zhen-Gang Wang;Ling-Shu Wan;Jian Wu;Christophe Innocent;Patrick Seta
Macromolecular Rapid Communications 2006 Volume 27(Issue 7) pp:
Publication Date(Web):30 MAR 2006
DOI:10.1002/marc.200690010
Co-reporter:Qian Yang;Jun-Jie Li;Meng-Xin Hu;Jian Wu
Macromolecular Rapid Communications 2006 Volume 27(Issue 22) pp:1942-1948
Publication Date(Web):16 NOV 2006
DOI:10.1002/marc.200600470

Summary: Nanofibrous sugar sticks with linear PANCGAMA and cyclic PANCAG glucose pendants were fabricated by electrospinning from acrylonitrile-based glycopolymers. Field emission scanning electron microscope was used to characterize the morphologies of the nanofibers. Utilizing the specific carbohydrate-protein interaction, these two kinds of nanofiber mats were applied to separate the protein mixtures. Con A and BSA were used as model proteins. The Con A/BSA mixture solution was isolated successfully by selective adsorption of Con A to the cyclic glucose pendants on the PANCAG nanofibrous sugar sticks. However, PANCGAMA nanofibers showed almost no selectivity for these two proteins due to the poor specificity between linear glucose pendants and Con A.

Co-reporter:Xiao-Jun Huang, An-Guo Yu, Jun Jiang, Chao Pan, Jing-Wen Qian, Zhi-Kang Xu
Journal of Molecular Catalysis B: Enzymatic (May 2009) Volume 57(Issues 1–4) pp:250-256
Publication Date(Web):1 May 2009
DOI:10.1016/j.molcatb.2008.09.014
In this work, poly(acrylonitrile-co-acrylic acid) (PANCAA) was electrospun into nanofibers with a mean diameter of 180 nm. To create a biofriendly microenvironment for enzyme immobilization, collagen or protein hydrolysate from egg skin (ES) was respectively tethered on the prepared nanofibrous membranes in the presence of 1-ethyl-3-(dimethyl-aminopropyl) carbodiamine (EDC)/N-hydroxyl succinimide (NHS). Confocal laser scanning microscopy (CLSM) was used to verify the surface modification and protein density on the nanofibrous membranes. Lipase from Candida rugosa was then immobilized on the protein-modified nanofibrous membranes by covalent binding using glutaraldehyde (GA) as coupling agent, and on the nascent PANCAA nanofibrous membrane using EDC/NHS as coupling agent, respectively. The properties of the immobilized enzyme were assayed. It was found that different pre-tethered biomacromolecules had distinct effects on the immobilized enzyme. The activity retention of the immobilized lipase on ES hydrolysate-modified nanofibrous membrane increased from 15.0% to 20.4% compared with that on the nascent one, while it was enhanced up to more than quadrupled (activity retention of 61.7%) on the collagen-modified nanofibrous membrane. The kinetic parameter, Km and Vmax, were also determined for the free and immobilized lipases. Furthermore, the stabilities of the immobilized lipases were obviously improved compared with the free one.
Co-reporter:Xiao-Jun Huang, Peng-Cheng Chen, Fu Huang, Yang Ou, Ming-Rui Chen, Zhi-Kang Xu
Journal of Molecular Catalysis B: Enzymatic (July 2011) Volume 70(Issues 3–4) pp:95-100
Publication Date(Web):1 July 2011
DOI:10.1016/j.molcatb.2011.02.010
A biocatalyst with high activity retention of lipase was fabricated by the covalent immobilization of Candida rugosa lipase on a cellulose nanofiber membrane. This nanofiber membrane was composed of nonwoven fibers with 200 nm nominal fiber diameter. It was prepared by electrospinning of cellulose acetate (CA) and then modified with alkaline hydrolysis to convert the nanofiber surface into regenerated cellulose (RC). The nanofiber membrane was further oxidized by NaIO4. Aldehyde groups were simultaneously generated on the nanofiber surface for coupling with lipase. Response surface methodology (RSM) was applied to model and optimize the modification conditions, namely NaIO4 content (2–10 mg/mL), reaction time (2–10 h), reaction temperature (25–35 °C) and reaction pH (5.5–6.5). Well-correlating models were established for the residual activity of the immobilized enzyme (R2 = 0.9228 and 0.8950). We found an enzymatic activity of 29.6 U/g of the biocatalyst was obtained with optimum operational conditions. The immobilized lipase exhibited significantly higher thermal stability and durability than equivalent free enzyme.Graphical abstractDownload full-size imageResearch highlights► Application of cellulose as supporting material in enzyme immobilization. ► Electrospun nanofiber membrane used for covalent binding with Candida rugose lipase. ► Using response surface methodology to achieve a high performance biocatalyst.
Co-reporter:Rong ZHOU, Ling DI, Cang WANG, Yan FANG, Jian WU, Zhikang XU
Chinese Journal of Chemical Engineering (January 2014) Volume 22(Issue 1) pp:11-18
Publication Date(Web):1 January 2014
DOI:10.1016/S1004-9541(14)60012-4
Affinity membranes are fabricated for boric acid removal by the surface functionalization of microporous polypropylene membrane (MPPM) with lactose-based polyols. The affinity is based on specific complexation between boric acid and saccharide polyols. A photoinduced grafting-chemical reaction sequence was used to prepare these affinity membranes. Poly(2-aminoethyl methacrylate hydrochloride) [poly(AEMA)] was grafted on the surfaces of MPPM by UV-induced graft polymerization. Grafting in the membrane pores was visualized by dying the cross-section of poly(AEMA)-grafted MPPM with fluorescein disodium and imaging with confocal laser scanning microscopy. It is concluded that lactose ligands can be covalently immobilized on the external surface and in the pores by the subsequent coupling of poly(AEMA) with lactobionic acid (LA). Physical and chemical properties of the affinity membranes were characterized by field emission scanning electron microscopy and Fourier Transform Infrared/Attenuated Total Refraction spectroscopy (FT-IR/ATR). 3-Aminophenyl boric acid (3-APBA) was removed from aqueous solution by a single piece of lactose-functionalized MPPM in a dynamic filtration system. The results show that the 3-APBA removal reaches an optimal efficiency (39.5%) under the alkaline condition (pH 9.1), which can be improved by increasing the immobilization density of LA. Regeneration of these affinity membranes can be easily realized through acid-base washing because the complexation of boric acid and saccharide polyol is reversible.
Co-reporter:Teng Zhang, Xiao-Ling Xu, Yi-Ning Jin, Jian Wu, Zhi-Kang Xu
Journal of Molecular Catalysis B: Enzymatic (August 2014) Volume 106() pp:56-62
Publication Date(Web):1 August 2014
DOI:10.1016/j.molcatb.2014.04.015
•Polyimide/MWCNTS nanofibers are electrospun for enzyme immobilization.•The retention activity of immobilized HRP is obviously improved by MWCNTS.•Electron transfer among “HRP I”, “HRP II” and MWCNTs is facilitated.Carbon nanotubes are widely applied in electronics, which offers great potential for enhancing the activity of redox enzyme. In this work, polyimide (PI) was blended with multiwalled carbon nanotubes (MWCNTs) and then electrospun into nanofibers for the immobilization of horseradish peroxidase (HRP), a redox enzyme. SEM and TEM were used to characterize the surface morphology of the PI/MWCNTs nanofibers and to analyze the protruding parts induced by the blending of MWCNT. The results indicate that, compared to the virgin PI nanofibers, the blending of MWCNTs increases the retention activity of immobilized HRP from 2.38% to 12.50%. Circular dichroism and UV–vis molecular absorption spectrometry were used to explore the interactions between HRP and MWCNTs. It seems that MWCNTs increase the enzyme activity by the facilitation of electron transfer among the catalytic intermediates “HRP I”, “HRP II” and MWCNTs.Download full-size image
Co-reporter:Zhen-Gang Wang, Ling-Shu Wan, Zhen-Mei Liu, Xiao-Jun Huang, Zhi-Kang Xu
Journal of Molecular Catalysis B: Enzymatic (April 2009) Volume 56(Issue 4) pp:189-195
Publication Date(Web):1 April 2009
DOI:10.1016/j.molcatb.2008.05.005
Enzyme immobilization has attracted continuous attention in the fields of fine chemistry, biomedicine, and biosensor. The performance of immobilized enzyme largely depends on the structure of supports. Nanostructured supports are believed to be able to retain the catalytic activity as well as ensure the immobilization efficiency of enzyme to a high extent. Electrospinning provides a simple and versatile method to fabricate nanofibrous supports. Compared with other nanostructured supports (e.g. mesoporous silica, nanoparticles), nanofibrous supports show many advantages for their high porosity and interconnectivity. This review mainly discusses the recent advances in using nanofibers as hosts for enzyme immobilization by two different methods, surface attachment and encapsulation. Surface attachment refers to physical adsorption or covalent attachment of enzymes on pristine or modified nanofibrous supports, and encapsulation means electrospinning a mixture of enzyme and polymer. We make a detailed comparison between these two immobilization approaches and highlight their distinct characteristics. The prospective applications of enzyme immobilized electrospun nanofibers in the development of biosensors, biofuel cells and biocatalysts are also discussed.
Co-reporter:Ling-Shu Wan, Bei-Bei Ke, Zhi-Kang Xu
Enzyme and Microbial Technology (4 March 2008) Volume 42(Issue 4) pp:332-339
Publication Date(Web):4 March 2008
DOI:10.1016/j.enzmictec.2007.10.014
Catalases decompose hydrogen peroxide (H2O2) into water and oxygen in an effective and environmentally friend way. The decomposition of H2O2 by nanofibrous membrane-supported catalases is reported in this work. Poly(acrylonitrile-co-N-vinyl-2-pyrrolidone) (PANCNVP) and polyacrylonitrile (PAN) blending with or without multi-walled carbon nanotubes (MWCNTs) were electrospun into nanofibrous membranes as enzyme immobilization matrixes and were carefully characterized. To immobilize catalase covalently, the nanofibrous membranes were treated with alkali solution to generate carboxyl groups followed by activation procedure with EDC/NHS. Results indicate that the nanofibrous membranes can bind large amount of catalases due to their superior surface area to volume ratio. The decomposition behavior of H2O2 with these immobilized catalases was explored. The increment of activity retention induced by the NVP moieties and/or MWCNTs is remarkable. Stabilities of the immobilized catalases including the effects of substrate pH and reaction temperature, thermal stability, operational stability and storage stability were also carefully studied. Results elucidate the improved stabilities of the nanofibrous membrane-supported catalases. In conclusion, the nanofibrous membranes electrospun from this biocompatible polymer, especially those filled with MWCNTs, are suitable matrices for catalase immobilization.
Co-reporter:Hai-Yin Yu, Zhi-Kang Xu, Hao Lei, Meng-Xin Hu, Qian Yang
Separation and Purification Technology (15 February 2007) Volume 53(Issue 1) pp:119-125
Publication Date(Web):15 February 2007
DOI:10.1016/j.seppur.2006.07.002
Polypropylene hollow fiber microporous membranes (PPHFMMs) were surface-modified by the photoinduced graft polymerization of acrylamide (AAm). Structural and morphological changes on the membrane surface were characterized by attenuated total reflection-Fourier transform infrared spectroscopy (FT-IR/ATR) and field emission scanning electron microscopy (FE-SEM). Water contact angles of the membrane surfaces were also measured by the sessile drop method. Results of FT-IR/ATR indicated the successful graft polymerization of AAm onto the membrane surface. Water contact angle of the modified membrane decreased with the increase of the grafting degree. It showed 34.9° for the modified membrane with a grafting degree of 278.4 wt.%, nearly 94° lower than that of the nascent one. The antifouling characteristics of the PPHFMMs before and after surface modification were assessed by the filtration of activated sludge in a submerged membrane bioreactor for synthetic wastewater treatment. It demonstrated that after continuous operation for about 42 h, the flux recovery were 36.9, 63.7% and the relative flux ratio were 1.00, 1.32 for the nascent and modified PPHFMMs, respectively.
Co-reporter:Chao Zhang, Bai-Heng Wu, Yong Du, Meng-Qi Ma and Zhi-Kang Xu
Journal of Materials Chemistry A 2017 - vol. 5(Issue 16) pp:NaN3902-3902
Publication Date(Web):2017/03/06
DOI:10.1039/C7TC00530J
Structural colors are in increasing demand in many fields such as color displays, sensor devices, and anti-counterfeiting labels. Herein, large-scale and angle-independent structural colors were constructed from polydopamine (PDA) coatings with a high refractive index and uniformity. This strategy can be utilized to facilely fabricate various color patterns. These structural colors also display high solvent resistance and excellent universality to a series of substrates. Moreover, stimuli-responsive structural colors can be easily synthesized via the co-deposition of PDA with poly(N-isopropylacryl-amide). To the best of our knowledge, this is the first time that structural colors from PDA-based coatings have been reported.
Co-reporter:Hao-Cheng Yang, Kun-Jian Liao, He Huang, Qing-Yun Wu, Ling-Shu Wan and Zhi-Kang Xu
Journal of Materials Chemistry A 2014 - vol. 2(Issue 26) pp:NaN10230-10230
Publication Date(Web):2014/04/02
DOI:10.1039/C4TA00143E
The surface structures and properties of a membrane largely determine its in-service performance during a filtration process. Here we report a facile hydrophilization method via co-deposition of mussel-inspired polydopamine (PDA) and polyethyleneimine (PEI) on a polypropylene microfiltration membrane. The deposition time is greatly shortened and the surface hydrophilicity is significantly improved compared to those membranes decorated only by PDA. The dopamine/PEI deposition solution can be reused several times with negligible effect on the surface hydrophilicity of membranes. Moreover, the PDA/PEI coating endows the membranes with ultra-high water permeability, allowing microfiltration separation of oil-in-water emulsions under atmospheric pressure.
Co-reporter:Peng-Cheng Chen, Ling-Shu Wan and Zhi-Kang Xu
Journal of Materials Chemistry A 2012 - vol. 22(Issue 42) pp:NaN22733-22733
Publication Date(Web):2012/09/12
DOI:10.1039/C2JM34203K
Surface hydrophilicity is a prerequisite of polymer membranes used for clean water regeneration, although commercial membranes are generally manufactured from hydrophobic polymers. Here, we report a promising approach to hydrophilize hydrophobic membranes using a CaCO3-based mineral coating inspired by biomineralization. Poly(acrylic acid) (PAA) brushes, which are negatively charged and can induce nucleation of CaCO3, were tethered on the pore surface of microporous polypropylene membranes (MPPMs) via photoinitiated graft polymerization. The CaCO3-based coating was then fabricated on the pore surface by an alternate soaking process. The resulting mineral coating is composed of CaCO3 nanoparticles which are much smaller than the pore diameter and distributed evenly on the pore surface throughout the membrane, ensuring the separation performance of membranes. Due to the intrinsic superhydrophilicity of CaCO3, the hybrid membranes are superhydrophilic, and show excellent water permeability with high water flux and ultralow operational pressure. As such, this work provides a generally applicable and cost-effective chemical route to improve the surface hydrophilicity of membranes or other porous materials which have potential in chemical separation, microfluidics, catalysis and other applications.
Co-reporter:Yan Fang, Jian Wu and Zhi-Kang Xu
Chemical Communications 2015 - vol. 51(Issue 1) pp:NaN132-132
Publication Date(Web):2014/11/03
DOI:10.1039/C4CC06137C
A quartz crystal microbalance (QCM) was used to monitor dextransucrase (DSase)-catalyzed polysaccharide elongation on the glucose-/maltose-ended self-assembly monolayer (SAM) surfaces. Kinetic parameters of the enzymatic elongation indicate that maltose is a promising substrate acceptor for DSase.
Co-reporter:Yan Fang, Wei Xu, Jian Wu and Zhi-Kang Xu
Chemical Communications 2012 - vol. 48(Issue 91) pp:NaN11210-11210
Publication Date(Web):2012/09/28
DOI:10.1039/C2CC35369E
Enzymatic transglycosylation has been successfully implemented by β-galactosidase (β-Gal) on PEG brushes. Kinetic parameters validate this kind of chemoenzymatic strategy which is promising for construction of biomimetic surfaces with glycocalyx-like structures.
Co-reporter:Meng-Xin Hu, Ling-Shu Wan, Zhen-Mei Liu, Zheng-Wei Dai and Zhi-Kang Xu
Journal of Materials Chemistry A 2008 - vol. 18(Issue 39) pp:NaN4669-4669
Publication Date(Web):2008/09/03
DOI:10.1039/B807181K
Synthetic membranes with glycosylated surfaces have great potential in pharmaceutics, clinically in diagnosis and protein purification. A versatile method of constructing glycosylated membrane surfaces was developed using poly(2-hydroxyethyl methacrylate) (poly(HEMA))-tethered microporous polypropylene membranes (MPPMs) as supports. Glucose moieties were bound on the membrane surfaces through the reaction between glucose pentaacetate and the hydroxyl group of poly(HEMA). The binding degree of glucose moieties on the MPPMs was controlled in a wide range by changing the grafting degree of poly(HEMA). The maximum binding degree reaches 10 µmol cm−2 when the grafting degree of poly(HEMA) on the membrane surface is 29.40 µmol cm−2. These glycosylated membrane surfaces were characterized by attenuated total reflectance Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy. Water contact angles of the glycosylated membrane surfaces before and after removing the acetyl groups differ remarkably from each other. After deprotection, the glycosylated membrane surfaces become highly hydrophilic, which greatly inhibits the non-specific adsorption of bovine serum albumin or peanut agglutinin on these surfaces. Furthermore, the glycosylated membranes can selectively recognize concanavalin A (ConA). When the binding degree of glucose moieties is above 0.39 µmol cm−2, the “glycoside cluster effect” occurs and plays an important role in the recognition and adsorption of proteins. Due to the reversible affinity, the adsorbed ConA can be desorbed with glucose solution. The results suggest that these MPPMs with glycosylated surfaces are promising for the isolation/purification of proteins.
Co-reporter:Wen-Ze Qiu, Hao-Cheng Yang, Ling-Shu Wan and Zhi-Kang Xu
Journal of Materials Chemistry A 2015 - vol. 3(Issue 27) pp:NaN14444-14444
Publication Date(Web):2015/06/05
DOI:10.1039/C5TA02590G
Mussel-inspired chemistry has been broadly exploited for multifunctional coatings in the surface modification of applied materials. Polyphenols are ubiquitous in plant tissues and far less expensive than polydopamine for mussel-inspired chemistry. Herein, we report a facile and effective method to modify porous membranes via the co-deposition of catechol (CCh) and polyethyleneimine (PEI). The membrane structures and properties were investigated by ATR/FTIR, XPS, FESEM, zeta potential, water contact angle and pure water flux measurements. The results reveal that the membranes deposited with a CCh–PEI mass ratio of 1:0.25 show excellent hydrophilicity, ultrahigh water permeation flux and distinguished surface charges. These membranes were used to decolorize anionic dye solutions during filtration with superior removal efficiencies of over 99%. Moreover, they have good reusability over repeated operations with a simple regeneration process.
Co-reporter:Hao-Cheng Yang, Jingwei Hou, Vicki Chen and Zhi-Kang Xu
Journal of Materials Chemistry A 2016 - vol. 4(Issue 25) pp:NaN9729-9729
Publication Date(Web):2016/05/16
DOI:10.1039/C6TA02844F
Organic–inorganic composite (OIC) membranes have received great attention over the past decades due to their enhanced performances in many applications. It is well known that surfaces and interfaces play crucial roles in the fabrication and application of the OIC membranes. In this review, we summarize the typical processes used to fabricate the OIC membranes and categorize these membranes as either mixed matrix OIC membranes or interfacial composite OIC membranes, and primarily focus on how the organic–inorganic interfaces influence the membrane formation process and its final structure. Then we reveal how the membrane surfaces and organic–inorganic interfaces in the membrane affect the final performance in certain applications. Through this review, we wish to provide a comprehensive guide to membrane fabrication and regulation, as well as a better understanding of the structure–performance relationships in OIC membranes.
Co-reporter:Hao-Cheng Yang, Qing-Yun Wu, Ling-Shu Wan and Zhi-Kang Xu
Chemical Communications 2013 - vol. 49(Issue 89) pp:NaN10524-10524
Publication Date(Web):2013/09/19
DOI:10.1039/C3CC46127K
We report a simple and facile protocol to fabricate mussel-inspired polydopamine (PDA) gradients on different surfaces. An oxygen diffusion phenomenon was used for dopamine autoxidation to form thickness gradients of PDA on different substrates. These PDA gradients showed gradual changes in thickness, roughness, wettability and light transmittance.
Co-reporter:Yong Du, Yan Lv, Wen-Ze Qiu, Jian Wu and Zhi-Kang Xu
Chemical Communications 2016 - vol. 52(Issue 55) pp:NaN8592-8592
Publication Date(Web):2016/06/13
DOI:10.1039/C6CC03842E
We propose a novel strategy for narrowing down the pore size distribution of ready-made nanofiltration membranes (NFMs) via pore wall modification. NFMs were subjected to the filtration of a highly reactive molecule solution, during which large pores were selectively reduced in size. The as-treated NFMs have high monovalent ion/divalent ion selectivity.
Co-reporter:Hao-Cheng Yang, Yi-Fu Chen, Chen Ye, Yi-Ning Jin, Hanying Li and Zhi-Kang Xu
Chemical Communications 2015 - vol. 51(Issue 64) pp:NaN12782-12782
Publication Date(Web):2015/07/01
DOI:10.1039/C5CC03216D
Zirconia-wrapped membranes were fabricated via a mineralization process on polydopamine/polyethyleneimine-deposited surfaces. The rigid and hydrophilic mineral coating simultaneously endows the membranes with enhanced curling resistance and surface wettability, enabling the membranes to separate oil-in-water emulsions.
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