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MOLECULES · 2024 ·Vol. 29 ·期 16 ·3868 · IF 4.2

Polyvinylidene Fluoride-Based Nanowire-Imprinted Membranes with High Flux for Efficient and Selective Separation of Artemisinin/Artemether

Minjia Meng,Jiajia Ren,Chuanxun Zhang,Wanqi Du,Jixiang Wang

A traditional phase transformation method is commonly used to prepare molecular imprinting membranes for selective separation. However, traditional molecularly imprinted polymers are mostly micron-sized particles, and the imprinting sites in their membrane are easily embedded, leading to a reduced adsorption capacity and decreased selectivity. In this study, an ultra-long nanowire with a diameter of about 15 nm was synthesized for the separation of artemisinin (ART), and its adsorption capacity was as high as 198.29 mg g−1after imprinting polymerization. Molecular imprinting membranes were prepared, using polyvinylidene fluoride (PVDF), polyethersulfone (PES), and polysulfone (PSF) as the membrane matrix, for comparison. The average membrane pore size of PVDF-MIM was about 480 nm, and PVDF-MIM had the highest adsorption capacity (69 mg g−1) for ART. The optimal flow rate for PVDF-MIM’s dynamic adsorption of ART was 7 mL min−1. Under this optimal flow rate, selectivity experiments were carried out to obtain the separation factor of PVDF-MIM (α = 8.37), which was much higher than the corresponding values of PES-MIM and PSF-MIM. In addition, the hydrophobicity and low flux of PES-MIM and PSF-MIM lead to higher non-specific adsorption. The hydrophobicity of PVDF-MIM is lower than that of PES-MIM and PSF-MIM, which greatly reduces the non-specific adsorption of the membrane, thus increasing the selectivity of the membranes. Therefore, the effective density of the imprinting sites in the pores and the membrane structure are the main factors determining the efficient separation of molecularly imprinted membranes.

研究领域: 材料科学 · 药物化学
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INORGANIC CHEMISTRY · 2024 · IF 4.3

Thiol–Amino Bifunctional Metal–Organic-Framework-Based Membrane Regulating Hydrophobic Sites for Selective Separation of Artesunate

Chuanxun Zhang,Bo Hu,Jiajia Ren,Wanqi Du,Minjia Meng

The selective separation and purification of artesunate (ARU) and artemisinin (ART) using zirconium-based metal–organic frameworks (MOF), especially UiO-66 MOF, are receiving increasing attention. In this study, tunable “hydrophobic” sites of thiol (–SH) were introduced to amino-functionalized MOFs (UiO-66-NH2) to fabricate a thiol-amino bifunctional UiO-66/polyvinylidene fluoride (PVDF)-blended membrane (S1-UiO/PVDF-DPIM) via the delayed-phase-inversion method for selective separation of ARU/ART. The adsorption results indicated that the modification of UiO-66-NH2 with thiol can indeed increase the ARU adsorption. The thiol-functional MOF (S1-UiO-66-NH2) was chosen as the optimal thiol-amino bifunctional MOF, as it possessed the maximum ARU adsorption capacity (111.14 mg g–1) and the highest selective-separation factor (α = 51.84). The ATR FT-IR dynamic spectrum disclosed the recognition mechanism, indicating that incorporating thiol groups into a hydrophilic MOF as hydrophobic sites can boost adsorption efficiency. Moreover, the static-selective permeation results showed that the S1-UiO/PVDF-DPIM preferentially transfers ARU when mixed with ART, even achieving complete ARU/ART separation. The most crucial aspect was the introduction of a hydrophobic core of –SH and new spontaneously formed disulfide bonds to S1-UiO/PVDF-DPIM, creating alternated hydrogen bonds and hydrophobic interactions. This work provides an alternative strategy to prepare hydrophobic–hydrophilic MOF-based membranes for the highly efficient and selective separation of complex analogue systems.

研究领域: 材料科学 · 药物化学 · 分离技术
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2024 · IF 7.7

Hierarchical porous MOF-199 mediated cellulosic paper for selective CO2 capture

Dandan Hao,Ping Wang,Ju Liu,Huanhui Zhan,Tiantian Zhou,Bo Fu

MOF-199 is considered to be an excellent CO 2 adsorbent owing to its substantial specific surface area, suitable pore structure and abundant sorption sites. However, powdered MOF-199 is prone to agglomeration and has poor recyclability. Herein, we proposed a MOF-199-based adsorbent by combining the MOF synthesis process with traditional papermaking process. Through such a design, MOF-199 particles are adhered on the surface of wood pulp fiber. The sufficient hydroxyl groups and electrostatic forces of cellulose facilitates the homogeneous and tight adhesion of MOF crystals. The optimal MP-4 sample demonstrated a high CO 2 adsorption capacity (1.80 mmol·g ‐−1 at 25 °C) and good CO 2 /N 2 selectivity (30.06). Moreover, the composite sorbent can be easily regenerated. The adsorption mechanism was analyzed by the density functional theory approach. The simulation results showed that the carboxyl functional groups with a large number of oxygen atoms and active metal sites are the key to boost the CO 2 adsorption performance.

CAS / MDL: 554-95-0
研究领域: 材料科学 · 环境科学 · 化学工程
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AICHE JOURNAL · 2022 ·Vol. 68 ·期 8 ·e17711 · IF 4.167

Novel process for selective separation of trace artemisitene from artemisinin by ammonium functional ionic liquids

Yingying Cao,Xin Tan,Guoxiong Zhan,Qiongguang Li,Hui Wang,Zengxi Li

One of the challenges to obtain high-quality natural active substances is the selective separation of the target compound from its analogues. In this study, ionic liquids (ILs), with design flexibility, were proposed to separate artemisitene and artemisinin, typical examples of natural analogues. Based on COSMO-RS calculation, several ILs were selected to separate artemisitene/artemisinin by experiment. It was demonstrated that the aqueous solution of N -allyl- N,N,N -trimethylammonium chloride ([AA][Cl]) exhibited excellent capability for selective separation of the two compounds. Under the optimal conditions (40°C, 1 h), the separation selectivity of artemisitene/artemisinin could reach 12.23 when the initial impurity content was only 0.8 wt%. Spectroscopic analysis and molecular dynamics indicated that π – π complexation between artemisitene and [AA][Cl] plays a major role in this separation process. Moreover, the process of multistage cross-flow extraction was compared with counter-flow extraction, and the latter one exhibited advantages in energy consumption and product yield.

研究领域: 化学工程 · 天然产物化学 · 药物化学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2021 · IF 3.764

Zeolitic Imidazolate Framework Membranes with a High H2 Permeance Fabricated on a Macroporous Support with Novel Spherical Porous Hybrid Materials

Yu Qin,Li Xu,Liying Liu,Zhongwei Ding

An original synthesis strategy for tubular zeolitic imidazolate framework (ZIF) membranes was developed by the deposition of a novel porous amorphous hybrid material prepared by 3-isocyanatopropyltrimethoxysilane (IPTMS) and ZIF-8 crystals onto a coarse macroporous α-Al2O3 tubular support. This porous amorphous hybrid material (ZIF-8-IPTMS) not only strongly adhered to the support but also repaired the defects to make the support surface smooth due to the abundant hydroxyl groups and the appropriate particle size. Using this synthesis strategy, we successfully prepared a high-quality ZIF-8 membrane on an inorganic α-Al2O3 tubular support via the sufficient heterogeneous nucleation sites provided by the amino groups of ZIF-8-IPTMS. This ZIF-8 membrane with an ultrathin thickness of approximately 0.9 μm was prepared, and its ideal H2/CO2 selectivity increased as the temperature increased. The membrane exhibited a competitive selectivity of 13.8 with a remarkably high H2 permeance of 1.46 × 10–5 mol·m–2·s–1·Pa–1 at 90 °C and 0.1 MPa. H2/CO2 binary gas permeation measurements indicated a separation factor of 9.2, and the H2 permeance was maintained at 0.83 × 10–5 mol·m–2·s–1·Pa–1 at 90 °C and 0.1 MPa. This synthesis strategy was also suitable to fabricate ZIF-67 membranes. The ZIF-67 membrane with a thickness of approximately 1.2 μm exhibited a H2/CO2 ideal selectivity of 5.3 and maintained a high H2 permeance of 1.06 × 10–5 mol·m–2·s–1·Pa–1 at 35 °C and 0.1 MPa.

研究领域: 材料科学 · 化学工程
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Frontiers in Chemistry · 2020 · IF 3.693

Design and Preparation of Molecularly Imprinted Membranes for Selective Separation of Acteoside

Zhao Xiaobin,Cheng Yun,Xu Helin,Hao Yanyan,Lv Yin,Li Xueqin

Acteoside (ACT) belongs to a type of phenylethanoid glycosides (PhGs), and it is worthy of obtaining high-purity due to its significant medicinal functions. In this study, a novel class of MIMs was designed and synthesized with PVDF membranes as the base membrane for high selective separation and enrichment of ACT. The effects of the different functional monomers, the amounts of functional monomers, crosslinking agents, and initiators on the separation properties of MIMs were investigated. Furthermore, adsorption ability, permeation capacity, and reusability of MIMs were discussed for ACT. It indicated that MIM7 was the optimal performance of MIMs. The adsorption ability of MIM7 for ACT was 62.83 mg/g, and the selectivity factor (α) of MIM7 was up to 2.74 and its permeability factor (β) was greater than 2.66. Moreover, the adsorption amount of MIM7 was still more than 88.57% of the initial value after five cycles. As an ACT imprinted layer of MIMs only had recognition sites for ACT molecules, which recombined with the recognition sites in the membrane permeation experiment, ACT molecules penetration was hindered. However, the analogs of ECH successfully passed MIMs. It indicated that the selective MIMs for ACT followed the mechanism of delayed permeation. This work provides an important reference for the high permselective separation of natural products.

研究领域: 药学 · 分离科学与技术
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JOURNAL OF PHARMACEUTICAL AND BIOMEDICAL ANALYSIS · 2020 · IF 3.209

Selective separation and inexpensive purification of paclitaxel based on molecularly imprinted polymers modified with ternary deep eutectic solvents

Ling Tan,Lian-Di Zhou,Zhuang-Fei Jiang,Rong-Rong Ma,Jia-Yuan He,Zhi-Ning Xia,Qi-Hui Zhang,Chong-Zhi Wang,Chun-Su Yuan

Paclitaxel (PTX) is a powerful anticancer natural product, with its separation and purification having been widely studied. In this work, new molecular imprinted polymers (MIPs) using deep eutectic solvents (DESs) with different molar ratios were prepared as functional monomers. These were then used as adsorbents in solid phase extraction (SPE) for the separation of PTX from its structural analogs. The polymers were characterized by energy disperive X-rays (EDX), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and fourier transform infrared spectroscopy (FT-IR). The results suggested that the formative regular DES-MIPs had an even pore-size distribution and a large specific surface area. The dynamic adsorption and static adsorption showed that the DES-MIPs had excellent adsorption performance, with a maximum adsorption capacity and optimum adsorption time of 87.08 mg/g and 180 min, respectively. The selective adsorption experiments showed that the material had outstanding selectivity, and the maximum selectivity factor was 6.20. For stability, after six consecutive adsorption and desorption cycles, the DES-MIPs maintained the perfect stability and reusability. Furthermore, the fabricated SPE column was successfully utilized for extracting and eluting PTX. This study provides a reliable protocol for the separation and purification PTX from its structural analogs and the DES-MIPs materials have excellent potential application value in pharmaceutical industry.

CAS / MDL: 78-67-1
研究领域: 药物化学 · 分析化学
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ELECTROCHIMICA ACTA · 2015 · IF 4.504

Surface Modification of Anion Exchange Membrane by Covalent Grafting for Imparting Permselectivity between Specific Anions

Xun-liang Wang,Meng Wang,Yu-xiang Jia,Bei-bei Wang

An anion exchange membrane (AEM) embracing stable permselectivity for the specific anions is badly needed in the relevant electrodialysis process. Accordingly, a covalent modification scheme for a conventional AEM was put forward in this work, including the introduction of carboxyl groups by chemical reduction of aryl diazonium salts, the PEI immobilization by amidation reaction and then glutaraldehyde-induced PEI multilayers deposition. Firstly, the changes in the surface morphology and its chemical composition after membrane modification were investigated by scanning probe microscope and attenuated total reflection-Fourier transform infrared spectroscopy. Then, the ion exchange capacity, water content, membrane conductivity, limiting current density as well as salt permeability coefficient corresponding to different modified stages were discussed in detail. Especially, in order to simulate the possible applications in the comprehensive seawater utilization and water purification , series of electrodialysis experiments for SO 4 2− /Cl − system were conducted for evaluating the selective separation property of the membranes after modification in terms of the permselectivity coefficient of sulfate ion against chlorine ion and the leakage rate of sulfate ion. In addition, the surface homogeneity after modification was also explored by chronopotentiometric curves and current–voltage curves. The experiment results indicated that the covalent modification scheme proposed in this study can effectively adjust the surface hydrophilicity of heterogeneous AEMs for imparting the permselectivity between the specific anions with different hydration energy and improve its surface homogeneity for ameliorating concentration polarization at the same time.

研究领域: 材料科学 · 环境工程 · 化学工程
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2015 · IF 3.368

Selective adsorption and separation of organic dyes from aqueous solution on polydopamine microspheres

Jianwei Fu,Qianqian Xin,Xuechen Wu,Zhonghui Chen,Ya Yan,Shujun Liu,Minghuan Wang,Qun Xu

Polydopamine (PDA) microspheres, synthesized by a facile oxidation polymerization route, were evaluated as a potential adsorbent for selective adsorption and separation of organic dyes. The adsorption processes towards nine water-soluble dyes (anionic dyes: methyl orange (MO), eosin-Y (EY), eosin-B (EB), acid chrome blue K (ACBK), neutral dye: neutral red (NR), and cationic dyes: rhodamine B (RhB), malachite green (MG), methylene blue (MB), safranine T (ST)) were thoroughly investigated. The adsorption selectivity of organic dyes onto PDA microspheres was successfully applied for the separation of dyes mixtures. Various influential factors such as solution pH, temperature, and contact time were employed to ascertain the optimal condition for adsorption of representative organic dyes including MB, MG and NR. The pseudo-first-order and pseudo-second-order kinetics models were used to fit the adsorption kinetics process. Five isothermal adsorption models (Langmuir, Dubnin–Radushkevich, Temkin, Freundlich and Harkins–Jura) were used to investigate the adsorption thermodynamics properties. The results showed that the PDA microspheres owned good selective adsorption ability towards cationic dyes. The adsorption kinetics process conformed to the pseudo-second-order kinetics model and the Langmuir isotherm model was more appropriate for tracing the adsorption behavior than other isotherm models. Thus, we can conclude PDA microspheres may be a high-efficiency selective adsorbent towards some cationic dyes.

研究领域: 材料科学 · 环境科学 · 化学工程
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2014 · IF 2.235

A Novel Surface Ion-Imprinted Cation-Exchange Membrane for Selective Separation of Copper Ion

Huining Deng,Shengjun Zhao,Qingqiang Meng,Wei Zhang,Baisong Hu

Ion-exchange membranes have been widely used in the separation of ionic mixtures or as a barrier in some types of chemical power source because of their selectivity to cations and anions. In this article, a novel single-ion selective ion-exchange membrane was fabricated to selectively separate copper ion from aqueous media. Polyethylenemine (PEI) was deposited onto a commercial cation-exchange membrane through an electric-field-enhanced procedure, and was subsequently modified with an ion imprinting technique. The effects of different parameters such as current density and feed composition on the deposition of PEI were studied. The copper ion imprinted membrane (Cu-IIM) showed lower resistance than the nonimprinted membrane (NIM) indicating the formation of a specific transportation path for the ions. The difference of binding isotherms for copper ion and zinc ion confirmed that the Cu-IIM had specificity to recognize copper ions. The permselectivity of the Cu-IIM was tested on an electrodialysis setup. The imprinting factor calculated from the separation factors of the imprinted and nonimprinted membrane was 1.99, demonstrating that the imprinting process enhanced the permselectivity of the membrane. The transport mechanism of ions in the Cu-IIM was also studied and analyzed.

研究领域: 化学工程 · 材料科学 · 环境科学
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JOURNAL OF SEPARATION SCIENCE · 2018 ·Vol. 41 ·期 10 ·2110-2118 · IF 2.415

Investigation of the chromatographic regulation properties of benzyl groups attached to bridging nitrogen atoms in a calixtriazine-bonded stationary phase

Wenjie Zhao,Xuhua Lou,Jizhao Guo,Peijian Sun,Yunzhen Jia,Limei Zheng,Lijun He,Shusheng Zhang

Two reversed-phase/anion-exchange mixed-mode stationary phases for high-performance liquid chromatography using calixtriazines as chromatographic ligands were investigated with Tanaka test solutes, monosubstituted benzenes, aromatic positional isomers, and inorganic anions. Calixtriazine as a chromatographic ligand has been reported previously, but the benzylated nitrogen-bridged calixtriazine-bonded silica gel reported in this study is new. The experimental data showed that the calixtriazine platform is a unique chromatographic selector because its multiple active sites are available for different solutes and its chromatographic selectivity could be tuned by introducing substituent on the bridging nitrogen atoms present in the calixtriazine matrix. The synergistic effects of aromatic rings, nitrogen atoms, benzyl groups, and tunable cavity in the host molecule influenced the separation selectivity by multiple retention mechanisms. Such hybrid stationary phases provide more versatility and have great potential in the analysis of complex samples. Moreover, the synthetic protocols presented herein may provide an alternative understanding on macrocyclic host–guest chemistry, leading to new and selective separation media.

CAS / MDL: 13822-56-5
研究领域: 分析化学 · 色谱技术
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SEPARATION SCIENCE AND TECHNOLOGY · 2016 · IF 1.083

Preparation of a novel chelating resin bearing amidinothiourea moieties and its removal properties for Hg(II) ions in aqueous solution

Maosheng Deng,Ying Huang,Xin Zhang,Zhijun Feng,Jinfeng Gou,Binjie Sun

A novel chelating resin bearing amidinothiourea (ADTU) moieties was prepared by chloroethyl crosslinked polystyrene (CMPS) with ADTU in the presence of a phase transfer catalyst. Fourier transform infrared spectra (FT-IR) and scanning electron microscopy (SEM) were used to characterized the resulting chelating resin. The saturated adsorption capacity of Hg(II) ions estimated from the Langmuir model was up to 1215 mg g−1at 313 K. Furthermore, the resin was able to selectively separate Hg(II) from multicomponent solutions with Cd(II), Co(II), Cu(II), Zn(II), Mg(II) and Pb(II). The desorption process showed the mercury recovery reached to 99.2% under eluting condition of 1 M HCl + 8% thiourea.

研究领域: 环境科学 · 材料科学
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