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Nanomaterials · 2020 ·Vol. 11 ·期 1 ·60 · IF 4.324

Highly Flowable Nano TiO2/Porous Organic Polymer (POP) Supports for Efficient Metallocene Catalysts

Xiong Wang,Wenqian Kang,Lin Gao,Guangquan Li,Xuerong Chen,Yi Guo

Porous organic polymers (POPs) have proven to be an efficient support in the olefin polymerization catalyst field. In this paper, nano TiO2beads were used to modulate the pore structure, bulk density, and surface morphology and flowability of the prepared POPs. With the incorporation of the hydrophilic nano TiO2beads, the prepared TiO2/POP supports obtained reasonable specific surface area (100–300 m2/g) and higher bulk density (0.26–0.35 g/mL) and flowability than the pure POP supports. The results show that bulk density of the prepared TiO2/POP particles increased when adding an increased amount of TiO2, and when 37.5% TiO2(weight percent to the total comonomers divinylbenzene (DVB) and 2-hydroxyethyl methacrylate (HEMA)) and 3:1 DVB/HEMA (molar ratio) were added, highly flowable TiO2/POP composites (POP-6 and POP-7) were obtained. With the modulation of the nano TiO2template during the support synthesis, the prepared POP-7 particles successfully achieved a normal distribution with a narrow particle size distribution (PSD) of 0.717 and average particle size of 24.1 μm, a specific surface area (SSA) of 279 m2/g, and relatively high bulk density of 0.30 g/mL. Furthermore, all the prepared TiO2/POP supports obtained higher ethylene polymerization activity than silica gel-supported commercial metallocene catalyst. The immobilized (n-BuCp)2ZrCl2/MAO@POP-7 catalyst exhibited the highest ethylene polymerization activity of 4794 kg PE/mol Zr.bar.h and productivity of 389 g PE/g cat, more than twice that of the commercial counterpart. Even higher catalyst productivity (3197 g PE/g cat) and bulk density of the produced PE (0.36 g/mL) could be obtained in higher ethylene partial pressure at 80 °C for 2 h, and the prepared TiO2/POP catalyst shows no obvious Zr+active sites decay during the ethylene polymerization.

研究领域: 材料科学 · 催化化学
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Journal of CO2 Utilization · 2021 · IF 7.132

MOF@POP core–shell architecture as synergetic catalyst for high-efficient CO2 fixation without cocatalyst under mild conditions

Yue Zhang,Lin Liu,Wei-Guo Xu,Zheng-Bo Han

A bifunctional MOF@POP core-shell catalyst (NH 2 -UiO-66(Hf)@CoTPy-CAP) constructed by amino functionalized NH 2 -UiO-66(Hf) and ionic porphyrin-based CoTPy-CAP was first reported to be applied in the cycloaddition of CO 2 . Because NH 2 -UiO-66(Hf)@CoTPy-CAP both possess abundant Lewis acidic sites and nucleophilic centers in one system, the catalyst can efficiently catalyze CO 2 fixation with epoxides without homogeneous cocalyst under mild conditions, achieving propylene oxide (PO) conversion of 98 % at 80 °C and 0.5 MPa. Furthermore, the bifunctional synergetic catalyst was easy to be recovered and recycled for five runs, and the reduction of activity was not obvious. This present work provides a viable direction for the fabrication of bifunctional synergetic catalysts for high-efficient CO 2 fixation without cocatalyst under mild conditions.

研究领域: 材料科学 · 催化化学
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LAB ON A CHIP · 2016 ·Vol. 17 ·期 1 ·120-127 · IF 5.586

Microfluidic PDMS on paper (POP) devices

Jin-Wen Shangguan,Yu Liu,Jian-Bin Pan,Bi-Yi Xu,Jing-Juan Xu,Hong-Yuan Chen

In this paper, we propose a generalized concept of microfluidic polydimethylsiloxane (PDMS) on paper (POP) devices, which combines well the merits of paper chips and PDMS chips. First, we optimized the conditions for accurate PDMS spatial patterning on paper, based on screen printing and a high temperature enabled superfast curing technique, which enables PDMS patterning to an accuracy of tens of microns in less than ten seconds. This, in turn, makes it available for seamless, reversible and reliable integration of the resulting paper layer with other PDMS channel structures. The integrated POP devices allow for both porous paper and smooth channels to be spatially defined on the devices, greatly extending the flexibility for designers to be able to construct powerful functional structures. To demonstrate the versatility of this design, a prototype POP device for the colorimetric analysis of liver function markers, serum protein, alkaline phosphatase (ALP) and aspartate aminotransferase (AST), was constructed. On this POP device, quantitative sample loading, mixing and multiplex analysis have all been realized.

CAS / MDL: 328-50-7
研究领域: 微流控技术 · 生物医学工程 · 分析化学
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APPLIED SURFACE SCIENCE · 2017 · IF 3.387

Highly tunable porous organic polymer (POP) supports for metallocene-based ethylene polymerization

Xiong Wang,Zhenyou Li,Xiaoyu Han,Zhengang Han,Yongxiao Bai

Porous organic Polymers (POPs) can not only exhibit high specific surface area and pore volume, but also tunable pore size distribution. Herein, copolymers of 2-hydroxyethylmethylacrylate (HEMA) and divinylbenzene (DVB) with specific pore structure were synthesized via a dispersion polymerization strategy, and then immobilized metallocene catalysts with well-defined pore structure were obtained on the produced POP supports. The nitrogen sorption and Gel permeation chromatography (GPC) results demonstrate that the pore structure of the immobilized metallocene catalyst is highly dependent on the pore structure of the POPs , and the pore structure of metallocene catalysts or the POPs has a significant influence on the molecular chain growth of the produced polyethylene. By tuning the distribution of the active species scattered in the micro- and the narrow meso-pore range (roughly ≤4   nm), the chain growth of the polyolefin can be tailored effectively during the polymerization process, although differential scanning calorimetry (DSC) and temperature rising elution fractionation (TREF) results show that the chemical composition distributions (CCDs) of produced PE from the POPs-supported metallocene catalysts are not determined by polymerization activity or molecule chain length, but mainly by the active site species scattered in the supported catalysts. Scanning electron micrograph (SEM) shows that the produced polyethylene has highly porous fabric which consists of nanofiber and spherical beads of micron dimension.

研究领域: 高分子化学 · 催化化学 · 材料科学 · 纳米材料 · 聚合物科学 · 石油化工
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Water · 2025 ·Vol. 17 ·期 6 ·885 · IF 3

Preparation of CS/PVA/POP Nanofiber Membranes and Adsorption Behavior for Hg(II) Ions

Qunhua Zhou,Yu Sun,Ziye Li,Siqin Sun,Jianshe Hu,Zhangpei Chen,Aikebaier Reheman

Chitosan (CS) and polyvinyl alcohol (PVA) nanofiber membranes were synthesized via electrospinning and used as supporting materials for powdered porous organic polymer (POP). These membranes were then crosslinked with glutaraldehyde, resulting in nanofiber membranes (CS/PVA/POP) as an efficient adsorbent for Hg(II) ions. Characterization using Fourier transform infrared spectroscopy, X-ray diffraction, and scanning electron microscopy showed that the membranes effectively removed up to 92.9% of mercury ions at optimal conditions, with an adsorption capacity of 116.1 mg/g. The adsorption data fit well with the Langmuir isotherm and pseudo-second-order kinetic models. The efficient uptake of mercury ions was attributed to chemisorption involving active groups (C=S, -NH2, -OH), facilitated by mechanisms such as chelation, complexation, or electron exchange. TheCS/PVA/POPnanofiber membranes demonstrated significant advantages in adsorption capacity, economic viability, and recyclability, providing an effective solution to mercury pollution in water.

研究领域: 环境科学 · 材料科学
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CHEMOSPHERE · 2019 · IF 5.108

New insight into the mechanism of POP-induced obesity: Evidence from DDE-altered microbiota

Yiran Liang,Donghui Liu,Jing Zhan,Mai Luo,Jiajun Han,Peng Wang,Zhiqiang Zhou

Although epidemiological studies demonstrate that persistent organic pollutants (POPs) could lead to metabolic syndrome, the mechanism has remained unclear. The dysbiosis of gut microbiota and the lipid metabolome have been put forward in the pathophysiology of metabolic syndrome. In this study, we used dichlorodiphenyldichloroethylene (DDE) as an example to study the effects of POP-impaired microbial composition and metabolome homeostasis on metabolic syndrome. The results showed that DDE exposure increased body weight and fat content and impaired glucose homeostasis. Further investigation revealed that DDE induced gut dysbiosis as indicated by an increased Firmicutes -to- Bacteroidetes ratio, which may impact energy harvest efficiency. Meanwhile, the plasma lipid metabolome profile was significantly altered by DDE. Furthermore, phosphatidylcholine, phosphatidylserine, phosphatidylethanolamine, and triacylglycerol were identified as key metabolites affected by DDE treatment, and these altered lipid metabolites were highly correlated with changed microbiota composition. This study provides novel insight into the underlying mechanism of POP-induced obesity and diabetes, pointing to gut microbiota as one of the targets.

CAS / MDL: 72-55-9
研究领域: 环境科学 · 微生物学 · 代谢组学 · 公共卫生
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JOURNAL OF CONTROLLED RELEASE · 2018 · IF 7.877

Steric shielding protected and acidity-activated pop-up of ligand for tumor enhanced photodynamic therapy

Kai Han,Zhaoyu Ma,Xinxin Dai,Jin Zhang,Heyou Han

Tumor targeted drug delivery in vivo remains a significant challenge in tumor therapy. In this article, we fabricated a steric shielding protected/tumor acidity-activated chimeric peptide for tumor targeted photodynamic therapy . This amphiphilic chimeric peptide could form spherical nanoparticles at neutrally physiological environment with the shielding of biotin molecule (tumor target ligand). When in tumor acidic microenvironment, acidity-sensitive dimethylmaleic amide was rapidly hydrolyzed, resulting in subsequent liberation of (Lys) 8 and the recovery of intramolecular electrostatic interaction between (Lys) 8 and (Glu) 8 . Then (Glu) 8 folded (Lys) 8 and biotin molecule was popped up to the surface of nanoparticles. Both in vitro and in vivo studies indicated that this steric shielding protected/tumor acidity-activated pop-up strategy demonstrated here could remarkably enhance tumor specific accumulation/internalization of chimeric peptide, improve photodynamic therapy efficacy and minimize the side effects. This strategy should not only be used for phototherapy, but also open a window to endow nanocarriers with effective tumor target ability.

研究领域: 肿瘤学 · 药剂学 · 分子生物学
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Catalysts · 2022 ·Vol. 12 ·期 3 ·270 · IF 4.501

Ionic Liquid-Modified Porous Organic Polymers as Efficient Metallocene Catalyst Supports

Wenqian Kang,Sheng Chen,Xiong Wang,Guangquan Li,Xiaoyu Han,Minfeng Da

Porous organic polymers (POPs) are widely used in various areas such as adsorption, separation and catalysis. In the present work, ionic liquid-modified porous organic polymers (IL-POPs) synthesized by dispersion polymerization were applied to immobilize metallocene catalysts for olefin polymerization. The prepared IL-POPs were characterized by Fourier transform infrared spectrometer (FT-IR), nitrogen sorption porosimetry, X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), inductively coupled plasma atomic emission spectrometer (ICP) and scanning electron microscope (SEM) analysis. The IL-POPs obtained pores with surface specific area (SSA) ranging from 16.9 m2/g to 561.8 m2/g, and total pore volume (TPV) ranging from 0.08 cm3/g to 0.71 cm3/g. The supported catalysts Zr/MAO@IL-POPs exhibit great activity (3700 kg PE/mol·Zr·bar·h) in ethylene polymerization, and the GPC-IR results show that the polyethylene has narrow molecular weight distribution (2.2 to 2.8). The DSC results show that the melting point of prepared polyethylene was as high as 138 °C, and the TREF analysis results indicate that they have similar chemical composition distribution with elution temperature at 100.5–100.7 °C.Keywords:ionic liquid;porous organic polymer (POP);metallocene catalyst;ethylene polymerization;heterogeneous polymerization

研究领域: 材料科学 · 化学工程 · 高分子科学
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JOURNAL OF CONTROLLED RELEASE · 2025 · IF 11.5

Ice-pop making inspired photothermal ultra-swelling microneedles to facilitate loading and intradermal vaccination of tumor antigen

Zhiming Li,Xueyu Wen,Shaojie Lu,Yanting Zheng,Puxuan Zhao,Sijia Mu,Xin Wang,Yanan Shi,Fengli Qu,Hao Chang

Cancer vaccines hold great promise in the fight against cancer. Here, we report an ice-pop making inspired photothermal ultra-swelling microneedle (PUSMN) patch for facilitating and enhancing cancer vaccination. The PUSMN patch consist of an array of microneedles made from photo-crosslinked methacrylated hyaluronic acid and polydopamine, a near-infrared photothermal conversion material, connected to a customized resin handle like an ice-pop stick. Using a fabrication process similar to ice-pop making, the PUSMNs exhibit a rapid swelling ratio of over 2000 %, enabling straightforward and efficient loading of tumor antigen with just a 1-min incubation in the antigen solution, followed by 15 min of drying. The handle not only ensures convenient application but also guarantees full embedding of the PUSMNs in the skin after penetration. Under near-infrared irradiation, PUSMNs efficiently generate local heat, further promoting the activation and maturation of dendritic cells. In vivo vaccination with the model antigen ovalbumin using PUSMNs combined with near-infrared irradiation elicits robust tumor antigen-specific cellular and humoral immune responses, ultimately resulting in delayed tumor growth. Given its ease of use, efficiency, and safety features, this biocompatible PUSMN patch could greatly improve cancer vaccination.

CAS / MDL: 9006-59-1
研究领域: 癌症研究 · 生物医学工程 · 免疫学 · 药物递送系统
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CHEMICAL ENGINEERING SCIENCE · 2025 · IF 4.3

Mixed valence Fe/Mn bimetallic MOF modified carbon fiber paper cathode designed for the degradation of 2-mercaptobenzothiazole by inhomogeneous Electro-Fenton

Xiaoqiang Li,Xin Zhang,Xiaorui Zhang,Hao Lu,Jian Wang,Siyuan He,Xiaoxiao Duan,Yongsheng Ren

2-Mercaptobenzothiazole (MBT), a widely utilized metal corrosion inhibitor in industrial production processes, has become a typical persistent organic pollutant (POP) in the circulating water of coal chemical pipelines. In this study, Fe/Mn bimetallic MOF materials supported on carbon fiber paper (PC) were employed for the first time as an electro-Fenton cathode (Fe/Mn@MPC) in a heterogeneous electro-Fenton system, achieving efficient degradation of MBT. Specifically, this novel cathode enabled 96.35 % removal of MBT within 2 h. The uniformly rough fiber morphology presented by the Fe/Mn@MPC cathode results in an increased electrochemically active surface area and reduced resistance. Remarkably, it maintains a very stable catalytic activity over a wide pH range (3–11) and after 10 h of continuous operation, which confirms that the bimetallic synergistic effect enhances the stability of the system. EPR and quenching experiments identified hydroxyl radicals as the primary active species. Based on HPLC-MS results, MBT degradation pathways involving sulfur oxidation intermediate cleavage and benzothiazole ring detachment were proposed. This work presents a promising cathode design for the treatment of thiol-containing wastewater and offers new insights into the efficient remediation of coal chemical wastewater.

CAS / MDL: 149-30-4
研究领域: 环境科学 · 材料科学 · 电化学 · 水处理 · 污染控制
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ACS Applied Materials & Interfaces · 2022 · IF 10.383

Degradable Multifunctional Porphyrin-Based Porous Organic Polymer Nanosonosensitizer for Tumor-Specific Sonodynamic, Chemo- and Immunotherapy

Meiting Li,Yaqian Zhang,Xiaoge Zhang,Zhuoyin Liu,Junjie Tang,Miao Feng,Baizhu Chen,Dalin Wu,Jie Liu

Sonodynamic therapy (SDT) benefiting from its intrinsic merits, such as noninvasiveness and deep tissue penetrability, is receiving increasing considerable attention in reactive oxygen species (ROS)-based tumor treatment. However, current sonosensitizers usually suffer from low tumor lesion accumulation, insufficient ROS generation efficiency under ultrasound, and non-biodegradability, which seriously impede the therapeutic outcomes. Additionally, it is difficult that SDT alone can completely eradicate tumors because of the complex and immunosuppressive tumor microenvironment (TME). Herein, we simultaneously employ sonosensitive porphyrin building blocks and glutathione (GSH)-responsive disulfide bonds to construct a novel degradable multifunctional porphyrin-based hollow porous organic polymer (POP) nanosonosensitizer (H-Pys-HA@M/R), which combine SDT, “on-demand” chemotherapy, and immunotherapy. Taking the unique advantages of POPs with designable structures and high specific surface area, this H-Pys-HA@M/R nanosonosensitizer can achieve tumor target accumulation, GSH-triggered drug release, and low-frequency ultrasound-activating ROS generation with encouraging results. Furthermore, this multifunctional nanosonosensitizer can effectively evoke immunogenic cell death (ICD) response through the combination of SDT and chemotherapy for both primary and distal tumor growth suppression. Meanwhile, H-Pys-HA@M/R exhibits favorable biodegradation and biosafety. Therefore, this study provides a new strategy for reasonably designing and constructing POP-related sonosensitizers combining SDT/chemotherapy/immunotherapy triple treatment modalities to eradicate malignant tumors.

研究领域: 生物医学工程 · 癌症治疗 · 纳米技术 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Selective capture of uranium and zirconium from strong HNO3 solution by ethenylphosphonic acid copolymerized polymer

Muhammad Hammad ul Haq,Xu Zhang,Fengqi Zhang,Alemtsehay Tesfay Reda,Dongxiang Zhang,Muhammad Zahid,Muhammad Khurram Tufail,Muhire Constantin,Noor Hasaan,Jinying Li,Xiyan Xu

The nuclear fuel rod contains mainly uranium (U) as the fuel and zirconium (Zr) as the cladding material. Improper disposition of the dissolved solution of the exhausted fuel rod releases radioactive acidic aqueous solution, which is a waste of U and Zr resources and also poses a great threat to the environment and living beings. The present work aims to selectively capture U and Zr from a 4 mol/L HNO 3 aqueous solution in the presence of competing ions including La, Zn, Cd, Gd, Ce, Sr, Mn, Cu and Ba. Trimethylolpropane trimethacrylate (TMPTMA) copolymerized with ethenylphosphonic acid (EPA). TMPTMA improved the mesoporous character and adsorption ability of the adsorbent towards U and Zr. The synthesized polymer adsorbent was characterized by SEM, EDS, FT-IR, TGA, XRD, BET, XPS, and NMR to study the adsorption. The results indicated that the EPA-POP-2 adsorbent showed considerable adsorption capacity towards U(VI) (374.1 mg g −1 ) and Zr(IV) (217.4 mg g −1 ) in a strong HNO 3 medium. Langmuir isotherm model fitted well to the experimental data, indicating that the monolayer adsorption process was dominating. The fitted pseudo-second-order (PSO) model represents that the adsorption mechanism is chemisorption. XPS, FT-IR, and DFT calculation results revealed that this adsorption capacity towards U and Zr was because of the P = O ligands present in the adsorbent. Van’t Hoff graph for U and Zr were also drawn to calculate the enthalpy, entropy, and Gibb’s free energy of the reaction. The reusability test showed that the adsorption capacity of synthesized adsorbent was high enough towards the U and Zr even after five consecutive cycles of adsorption and desorption.

CAS / MDL: 3290-92-4
研究领域: 核工程 · 环境科学 · 材料科学 · 化学工程
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