Materials Science & Engineering C-Materials for Biological Applications
·
2020
·
IF 5.88
Junyu Chen,Yi Cui,Meiying Liu,Hongye Huang,Fengjie Deng,Liucheng Mao,Yuanqing Wen,Jianwen Tian,Xiaoyong Zhang,Yen Wei
Halloysite nanotubes (HNTs) are a kind of aluminosilicate clay with a unique hollow tubular structure that has been intensively explored for various applications especially in biomedical fields owing to their excellent biocompatibility, biodegrading potential and low cost. Surface modification of HNTs with functional polymers will greatly improve their properties and endow new functions for biomedical applications. In this work, a light-induced reversible addition-fragmentation chain transfer (RAFT) polymerization was introduced to successfully prepare HNTs based fluorescent HNTs/poly(PEGMA-Fl) composites in the presence of oxygen using diacrylate-fluorescein and poly (ethylene glycol) methyl ether methacrylate (PEGMA) as the monomers. Without other catalysts, heating, and deoxygenation procedure, the polymerization process can take place under mild conditions. Besides, owing to the introduction of fluorescein and PEGMA on the surface of HNTs, the resultant HNTs/poly(PEGMA-Fl) composites display high water dispersibility and stable fluorescence. The results from cell viability examination and confocal laser scanning microscopy also demonstrated that HNTs/poly(PEGMA-Fl) composites could be internalized by L929 cells with bright fluorescence and low cytotoxicity. Taken together, we developed a novel photo-initiated RAFT polymerization method for the fabrication of HNTs based fluorescent polymeric composites with great potential for biomedical applications. More importantly, many other multifunctional HNTs based polymer composites could also be fabricated through a similar strategy owing to good designability of RAFT polymerization.
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APPLIED CLAY SCIENCE
·
2022
·
IF 5.907
Yuanmeng Lou,Haiyun Ma,Yanyue Su,Yiheng Ma,Le Yang,Hong Zhang,Jianzhong Xu
Halloysite (Hal) nanotubes have become a good nano-carrier of flame retardant systems. In the present work, cavity expansion of Hal was achieved by etching with sulfuric acid to improve its loading capacity. Then, copper phytate was synthesized and encapsulated in the Hal to obtain Phyt-Cu@Hal. Finally, a sulfonyldiphenol-containing polyphosphazene derivative (PZS) was polymerized and wrapped on Phyt-Cu@Hal external surface to form a hierarchical nanohybrid structure (Phyt-Cu@Hal@PZS). Herein, Phyt-Cu encapsulated in Hal acts as catalyzing and char-forming agents while the wrapped PZS acts as an interfacial compatibilizer which can improve the dispersion and flame retardancy of Phyt-Cu@Hal@PZS in the EP matrix. The flame retardancy and smoke suppression of the corresponding EP nanocomposites were significantly enhanced due to the synergistic effect of Phyt-Cu@Hal@PZS. After adding 5 wt% Phyt-Cu@Hal@PZS, the peak heat release rate and smoke release rate were reduced maximally by 34.3% and 42.1%, respectively. Moreover, the char residue was also greatly enhanced which is 97.3 times higher than that of neat EP. The flame retardant mechanism of Phyt-Cu@Hal@PZS was assumed that the Phyt-Cu immobilized within the Hal could distinctly inhibit the flammable pyrolysis products; the external PZS layer promotes the char formation of EP matrix; the nanoscale combination of Phyt-Cu, Hal and PZS could further enhance the catalyzing carbonization to produce a physical barrier effect.
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EUROPEAN POLYMER JOURNAL
·
2023
·
IF 6
Jia Chen,Li Rong,Xueqing Liu,Jiyan Liu,Sha Peng,Xueliang Jiang
The practical application of polyurethane acrylate solid electrolytes is restricted by their flammability and inadequate of ion transportation performance. Herein, a novel flame retardant solid polymer electrolyte membrane was successfully designed through UV light curing phosphorus-containing polyurethane acrylate prepolymer, modified halloysite nanotubes and lithium salt. The FR-SPE1 electrolyte mainly composed of flame retardant polyurethane acrylate (FR-PUA) prepolymer, 20 wt% lithium bis-(trifluoromethanesulfonyl)imide) (LiTFSI) along with 5 wt% acid modified halloysite nanotubes(A-HNTs), which possesses excellent P-Al-Si synergistic flame retardancy with the limiting oxygen index (LOI) value of 39.2%, and the vertical burning test can reach the V-0 level of UL 94 standard. Meanwhile, FR-SPE1 electrolyte exhibits strong mechanical strength and electrochemical stability, which extends the electrochemical window to 4.88 V (vs. Li + /Li). Interestingly, A-HNTs can also effectively enhance the dissociation degree of lithium salts in polymers, which is conducive to improve the lithium ion transport performance. Moreover, the cell fabricated by lithium iron phosphate (LiFePO 4 ), FR-SPE1 and Li anodes evinces benign cycling performance (156.6 mAhg −1 , 0.2C) and coulombic efficiency (99.06%) after 160 cycles at 70 °C. Thus, FR-SPE1 is argued to provide an effective approach for more broadly enhancing lithium battery safety and performance.
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ANALYTICAL AND BIOANALYTICAL CHEMISTRY
·
2018
·Vol. 410
·期 28
·7357-7371
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IF 3.307
Liu Wei,Wang Ruya,Hu Fan,Wu Pinping,Huang Tao,Fizir Meriem,He Hua
The co-adsorption of mixed nonionic surfactant and imidazolium-based ionic liquid, Triton X100 (TX100), with 1-cetyl-3-methylimidazolium bromide (C 16 mimBr) adsorbed onto the surface of magnetic halloysite nanotubes (MHNTs) was used as an efficient adsorbent for simultaneous determination of amlodipine and nimodipine in urine. The designed adsorbent was characterized by TEM, TGA, FTIR, and DLS analysis methods. All the parameters that influence the extraction efficiency are optimized with the aid of response surface methodology (RSM). The effects of nonionic surfactant TX100 with different structures of ionic-liquid-coated MHNTs were investigated. Under optimum conditions, extraction recoveries of amlodipine and nimodipine were in the range of 73.8–81.2 and 94.3–96.1%, with RSDs ( n = 3) of 2.6–5.5% in spiked urine samples, respectively. The adsorption mechanism principal of mixed hemimicelles was discussed in this study. The limit of detection obtained for analytes was < 0.002 μg·mL −1 . To our knowledge, this was the first attempt using a mixed hemimicelle solid-phase extraction (SPE) based on MHNTs and nonionic surfactant and imidazolium-based ionic liquid for the simultaneous determination of amlodipine and nimodipine in biological samples.
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Polymers
·
2018
·Vol. 10
·期 10
·1171
·
IF 2.935
Xiandong Zhang,Guangshun Wu
The quality of interphase in carbon fibers (CFs) composites makes a key contribution to overall performance of composites. Here, we achieved for the first time the chemical grafting of halloysite nanotubes (HNTs) with amino or carboxyl groups onto the CFs surface aiming to increase composites interfacial strength. HNTs were grafted using 3-aminopropyltriethoxysilane (APS) followed by succinic anhydride treatment, and HNTs with amino groups (HNT–NH2) or carboxyl groups (HNT–COOH) were separately introduced into the interphase of composites. Functional groups of HNTs and fiber surface structures were characterized, which confirmed the modification success. The wettability between the modified CFs and resin have been enhanced obviously based on the improved fiber polarity and enhanced surface roughness by the introduced two functionalized HNTs with the uniform distributions onto fiber surface. Moreover, interfacial properties and anti-hydrothermal aging behaviors of modified methylphenylsilicone resin (MPSR) composites were improved significantly, especially for HNT–COOH grafting. In addition, the interfacial reinforcement mechanisms for untreated and modified CF composites are discussed and compared.Keywords:carbon fibers;surface grafting;halloysite nanotubes;polymer composites;interface
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RSC Advances
·
2013
·Vol. 4
·期 16
·7967-7978
·
IF 2.562
Jiangdong Dai,Xiao Wei,Zhijing Cao,Zhiping Zhou,Ping Yu,Jianming Pan,Tianbian Zou,Chunxiang Li,Yongsheng Yan
Here, a general and effective method for preparing molecularly a imprinted polymer nanoshell on magnetic halloysite nanotubes (MHNTs) to make highly-controllable core–shell nanorods (MMINs) is described for the first time, and the as-obtained nanomaterials were then used for selective recognition and rapid adsorption of tetracycline (TC) from aqueous solution. Magnetic nanoparticles were uniformly loaded into the lumen of halloysite nanotubes (cheap, abundantly available and durable) using the impregnation and pyrolysis method. Vinyl groups were then anchored at the surface of MHNTs, subsequently directing the highly selective occurrence of imprinted polymerization at the surface, and the uniformly core–shell imprinted nanorods were easily produced via in situ precipitation polymerization, with tunable nanoshell thickness, by controlling the total amounts of monomers. The MMINs with a shell thickness of 35 nm exhibited the largest saturation adsorption capacity to TC, and the equilibrium data was well-described using the Langmuir isotherm model. The kinetic experiment showed the adsorption process reached equilibrium in about 10 min, and a pseudo-second-order kinetic model was used to fit the data well. The nanocomposites displayed selective recognition for TC and could be rapidly separated from solution by a magnet, with good stability and regeneration property, which provided practical applications for wastewater treatment, biological molecule purification and drug extraction.
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JOURNAL OF DRUG DELIVERY SCIENCE AND TECHNOLOGY
·
2024
·
IF 4.5
Haigang Li,Jiaxuan Liu,Lei Zhang,Xinru Zhu,Jing Jiang,Zhaohui Ge,Yifei Zuo,Xiangzhu Chen,Chun Zhang
This study aims to achieve co-delivery of paeoniflorin (PF) and butyric acid (BA) to the colon through Eudragit S100 (EUS100)-coated halloysite nanotube/o-butyryl chitosan microspheres (EUS100-HNT-BUCHNPs). O-butyrylated chitosan (BUCH) was prepared by the acylation reaction of chitosan (CH) and butyric anhydride with methane sulfonic acid as a catalyst. PF-loaded halloysite nanotube/o-butyrylated chitosan microspheres (HNT-BUCHNPs) were prepared by emulsion crosslinking with glutaraldehyde as the crosslinking agent and then coated with EUS100 using the emulsion solvent evaporation method. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy results indicated the presence of EUS100 coating on the surface of HNT-BUCHNPs. In vitro release studies demonstrated that the EUS100 coating effectively prevented the release of PF and BA at pH 1.2, while the halloysite nanotube slowed down PF release at pH 6.8. Sequential release experiments in different pH media showed lower release of PF and BA at pH 1.2 and pH 6.8, and higher release at pH 7.4, reaching approximately 80 % and 85 %, respectively. Gastrointestinal tract retention studies in mice confirmed that EUS100-HNT-BUCHNPs reduced the release of PF and BA in the upper digestive tract, facilitating delivery to the colon. In vivo and in vitro results indicated efficient transport of PF and BA to the colon, suggesting the potential of EUS100-HNT-BUCHNPs as colon-targeted carriers for PF and BA.
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES
·
2024
·
IF 7.7
Xi Yu,Lu He,Xiaofeng Zhang,Gege Bao,Rong Zhang,Xiaobei Jin,Daochun Qin
Bamboo fibers (BF), as an important sustainable natural material, are becoming a hot alternative to synthetic fibers for the reinforcement of polypropylene (PP)-based composites. However, the weak interfacial compatibility between BF and PP as matrix and their inherent flammability limit the practical application of BF/PP composites (BPC). Here, a fire-safe BPC was fabricated by constructing flame-retardant interfacial layers containing tannic acid (TA)-Fe 3+ complex and halloysite nanotubes (HNTs) on the fiber matrix followed by a hot-pressing process. The results showed that the interfacial chelating of TA with Fe 3+ improved the dispersion of HNTs on the fibers and the interfacial interactions within the fiber matrix, resulting in the as-fabricated composite with significantly improved mechanical properties and water resistance. In addition, the flame-retardant composite exhibited higher thermal stability and enhanced residual char content. Moreover, the composite possessed significant flame-retardant performances with a reduction of 23.75 % in the total heat release and 32.44 % in the total smoke production, respectively, owing to the flame retarding in gaseous phase and condensed phase of TA-Fe 3+ @HNTs layers. This work offers a green and eco-friendly strategy to address the inherent problems of BPC material in terms of fire safety and interfacial compatibility, thus broadening their applications in the automotive interior and construction industries.
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FOOD CHEMISTRY
·
2024
·
IF 8.5
Jiaran Zhang,Jie Yu,Hao Yin,Zhixin Jia,Ce Shi,Yuntao Yue
A fluorescent hybrid film composed of nitrogen-doped graphene quantum dots (N-GQDs) loaded on halloysite nanotubes (HNTs) (N-GQDs/HNTs nanocomposite) as a sensitive element and polyvinyl alcohol (PVA) as a film-forming matrix was designed for freshness detection. The PVA-N-GQDs/HNTs hybrid film exhibited significantly enhanced fluorescence attributed to the loading of N-GQDs onto the surface of HNTs through electrostatic interactions and hydrogen bonding , effectively reducing their aggregation. The fluorescence of the hybrid film could be quenched by ammonia via photoinduced electron transfer (PET), with good linearity in the range of 20 ppm to 500 ppm ammonia and a limit of detection (LOD) of 0.63 ppm. In addition, the hybrid film was applied to monitor the freshness of seawater fish and freshwater fish stored at refrigeration and room temperature to evaluate the practicality of this approach. The developed hybrid film showed promise for nondestructive and on-site monitoring of fish spoilage.
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PROGRESS IN ORGANIC COATINGS
·
2025
·
IF 7.3
Pengwei Ran,Banghao Wang,Fuping Dong,Yuzhu Xiong,Chang-Sik Ha
A superhydrophobic composite coating with exceptional durability was fabricated by integrating octadecyltrimethoxysilane (ODTMS)-modified halloysite nanotubes (HNTs) into a polyurea (PU) matrix. The hierarchical micro-nano structure, constructed through hydrogen bonding networks between PU and HNTs, synergized with the low surface energy of ODTMS to achieve a water contact angle of 157°. Fourier-transform infrared spectroscopy, X-ray powder diffractometer and X-ray photoelectron spectroscopy analyses confirmed successful ODTMS grafting and homogeneous dispersion of HNTs within the PU matrix. Remarkably, the coating retained superhydrophobicity (contact angle >150°) after 50 tape-peeling cycles and 130 cm sandpaper abrasion, attributed to the dual reinforcement mechanism of PU's elasticity and HNTs' mechanical robustness. Furthermore, the coating exhibited pH stability (pH 2–12 for 20 h) and thermal resistance up to 250 °C. This work provides a scalable strategy for designing durable superhydrophobic coatings, demonstrating potential applications in construction, ships, and electronic devices under extreme conditions.
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CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Zhuangxin Wei,Pan Wang,Jiangnan Wang,Jianming Pan
Searching for alternative porous substrates which can realize anisotropic preparation of “tailor-made” complementary binding sites is an important way to improve the identification efficiency and interfacial stability of the surface molecularly imprinted polymers (SMIPs). In this work, a functional polymer (FP) with multi-functional properties was firstly synthesized using 3-(isobutenyloxy) propyltrimethoxysilane, 1-(vinylbenzyl) thymidine and cinnamoyloxyethyl methacrylate (CEMA) as monomers, and then FP with post-crosslinking property was covalently deposited onto the outer surface of halloysite nanotubes (HNTs) using silanol chemistry to prepare 2′-deoxyadenosine (dA) imprinted sorbents (HNTs-SMIPs). More than 65 % of dA molecules was captured within the first 2.0 h. The number of high affinity site from the total binding sites of HNTs-SMIPs is estimated to be as high as 73.25 %, and the maximum adsorption amount of HNTs-SMIPs is 48.78 μmol g -1 at 25 °C. The imprinting factor ( IF ) of HNTs-SMIPs towards dA is 1.89, and 79.49 % the adsorption capacity is remained after five adsorption–desorption cycles. In addition, 70.2 % of the dA from spiked human urine samples can be selectively extracted by HNTs-SMIPs. HNTs-SMIPs have excellent interfacial stability and strong affinity for the template molecule dA, and this work provides a new strategy for the specific separation and enrichment of dA.
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Molecular Catalysis
·
2025
·
IF 4.9
Jiayi Zhou,Hongyao Zhao,Yifang Zhang,Hongyang Zhu,Yueji Cai,Yanyun Wang,Danhong Shang,Tongyi Yang,Fu Yang,Jingjing Tang
The solar-driven photothermal photocatalytic contaminant degradation and water evaporation coupled technique is promising for practical wastewater treatment. This study developed photothermal HNTs@Ag/C-5 nanocomposites by polycondensation of tannic acid with silver and following carbonization to construct plasmonic silver nanoparticle onto halloysite nanotubes (HNTs). The incorporation of Ag onto HNTs enhanced electron-hole separation, enabling efficient activation of potassium peroxymonosulfate (PMS) under sunlight. A floatable integrated device was constructed by anchoring the catalyst to a melamine sponge via calcium ion-cross-linked sodium alginate. This device achieved 84.3 % degradation of carbamazepine (CBZ) in 90 min under light, with a reaction rate constant of 0.01685 min − ¹, nearly four times higher than unmodified halloysite nanotubes. The photocatalytic PMS activation over HNTs@Ag/C-5 also show great potential for detoxifying other pharmaceutical compounds such as tetracycline (TC) and norfloxacin (NFX) in wastewater. Radical trapping and quenching experiments confirmed hydroxyl radicals (·OH) as the dominant reactive oxidative species in CBZ degradation. Additionally, the device functioned as a solar-driven photothermal evaporator, achieving an evaporation rate of 1.654 kg m − ² h − ¹. Reusability tests demonstrated consistent performance, with only a 4 % efficiency drop after multiple degradation cycles. This reported monolith evaporator affords possible opportunity for treating complex wastewater when harnessing the evaporation to obtain freshwater and synchronously degrade contaminant.
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危险品化学品经营许可证（带存储）