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CLAYS AND CLAY MINERALS · 2024 ·Vol. 69 ·期 1 ·94-104 · IF 2

Preparation and Characterization of Halloysite-Based Carriers for Quercetin Loading and Release

Shu-Ting Liu,Xue-Gang Chen,Shi-Long Zhang,Xue-Min Liu,Jun-Ji Zhang

Halloysite nanotubes (HNTs) have attracted much attention as delivery carriers for various drugs, but the loading of one such drug, quercetin, on HNTs has been investigated only rarely and usually involved cyclic vacuum pumping. The main objective of the present study was to develop a novel carrier system based on HNTs for quercetin delivery without a vacuum process and to investigate the effect of chemical modification of HNTs on the loading and release of quercetin. For this purpose, comparative studies of five chemical modification reagents (sodium lauroamphoacetate, cocoamidopropyl betaine, 1-hydroxyethyl 2-nonyl imidazoline betaine, triethanolamine, and dipicolinic acid) functionalized on HNTs were investigated for quercetin loading and in vitro release. Characterization of raw halloysite, modified halloysite, and quercetin-loaded halloysite were done by X-ray diffraction (XRD), Fourier-transform infrared spectrometry (FTIR), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). The results indicated that chemical modification could improve the interactions between HNTs and quercetin. After chemical modification, quercetin was anchored to both the inner and outer surfaces of HNTs by electrostatic attraction, hydrogen bonding, and van der Waals forces. Sodium lauroamphoacetate-modified HNTs were given the highest loading of 1.96 wt.% among the five reagents. Cocamidopropyl betaine-modified HNTs exhibited the best sustained-release profile with only 29.07% for initial burst release and 480 h of consecutive release. Carboxyl groups of the modification reagent improved the loading capacity of quercetin. Amide groups prolonged drug release due to the strong affinity between amine and phenolic hydroxyl groups of quercetin. The release of quercetin from the cocamidopropyl betaine-modified HNTs fitted a first-order kinetics model well. The present study suggested that cocamidopropyl betaine-modified HNTs offer promise as vehicles for delivery of quercetin and for extending the application of quercetin.

CAS / MDL: 499-83-2
研究领域: 药剂学 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Carbon-intercalated halloysite-based aerogel efficiently encapsulating phase change materials with excellent photothermal conversion and energy storage

Zongrui Zhang,Shiyu Huang,Pengxiao Wei,Shuangqing Li,Yafei Zhao,Yinze Yang,Bing Zhang

Latent heat storage systems based on organic phase change materials (PCMs) are considered to be an efficient solar energy utilization strategy, but leakage vulnerability and insensitivity to sunlight of PCMs limit their further application in energy storage. In this work, a new hierarchical porous aerogel was constructed with the carbon intercalated halloysite nanotubes (CHNTs) as the assembly units for PCMs encapsulation to improve the load weight, stability and sunlight absorption. The CHNTs were first successfully synthesized through intercalation and carbonization, with the aim of increasing their specific surface area and sunlight absorption.   Subsequently, the CHNTs/polyvinyl alcohol (PVA) aerogels with 3D honeycomb structure were prepared by self-assembly using a freeze-drying method, which can significantly promote the encapsulation ratio of lauric acid (LA) in the pores of both aerogels and CHNTs. The CHNTs can not only improve compressive strength of the aerogels and shape stability of the composite PCMs, but also enhance light absorption ability of the composites compared to pristine HNTs. As a support material, CHNTs aerogel (CHNP) loaded more than 92 wt% PCM (LA@CHNP) and exhibited an extremely high latent heat capacity (170.9 J/g). The LA@CHNP had good structural and thermal stability in 300 cycles without visible leakage. Besides, solar energy absorption increased from 43 % to 98 %, and the solar-to-thermal energy conversion efficiency increased to 95.88 %, which could be attributed to 3D porousness and carbon nanolayers of the CHNTs. We have successfully synthesized an eco-friendly and facile composite LA@CHNP, which will contribute to the design of advanced composites with excellent solar energy storage properties, and provide a new direction for the application of carbonized materials.

研究领域: 材料科学 · 能源工程
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Journal of Materials Chemistry B · 2016 ·Vol. 4 ·期 13 ·2253-2263 · IF 4.872

Functionalized halloysite nanotube by chitosan grafting for drug delivery of curcumin to achieve enhanced anticancer efficacy

Mingxian Liu,Yanzhou Chang,Jing Yang,Yuanyuan You,Rui He,Tianfeng Chen,Changren Zhou

Halloysite nanotubes (HNTs) have a unique tubular structure in nanoscale, and have shown potential as novel carriers for various drugs. Coating the nanotubes with a hydrophilic polymer shell can significantly decrease the toxicity and provide colloidal stability during blood circulation. Here, we synthesized chitosan grafted HNTs (HNTs-g-CS) and investigated their potential as a nano-formulation for the anticancer drug curcumin. The structure and properties of HNTs-g-CS were characterized using water contact angle, zeta-potential, Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and transmission electron microscopy (TEM) techniques. HNTs-g-CS exhibit a maximum 90.8% entrapment efficiency and 3.4% loading capacity of curcumin, which are higher than those of raw HNTs. HNTs-g-CS also show no obvious hemolytic phenomenon and good stability in serum. The cumulative release ratio of curcumin from HNTs-g-CS/curcumin at cell lysate after 48 hours is 84.2%. The curcumin loaded HNTs-g-CS show specific toxicity to various cancer cell lines, including HepG2, MCF-7, SV-HUC-1, EJ, Caski and HeLa, and demonstrate an inhibition concentration of IC50 at 5.3–192 μM as assessed by cytotoxicity studies. The anticancer activity of this nanoformulation is extremely high in EJ cells compared with the other cancer cell lines. The cell uptake of HNTs-g-CS is confirmed by fluorescence microscopy. Flow cytometric analysis of curcumin loaded HNTs-g-CS shows that curcumin loaded HNTs-g-CS increase apoptosis on EJ cells. The content of ROS created by HNTs-g-CS/curcumin is more than that of free curcumin. All these results suggest that HNTs-g-CS are potential nanovehicles for anticancer drug delivery in cancer therapy.

研究领域: 生物材料学 · 药理学 · 肿瘤学
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ACS Agricultural Science & Technology · 2024 · IF 2.3

Eco-friendly TiO2–Halloysite Supported Fluopyram Nanopesticide Formulation for Aquatic Safety without Compromising Efficacy

Li Man,Huayao Chen,Xiang Liao,Jinhao Zhao,Hongjun Zhou,Li Hao,Xinhua Zhou

The low utilization rate of pesticide leads to the pollution of soil and environment, which ultimately endangers human health. In this study, TiO2 nanoparticles were synthesized and loaded with fluopyram (Flu) on halloysite (Ha) via sol–gel methods which was named Flu@THa. Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to characterize the structure of all samples, and then the performances of zeta potential, fungistatic ability, antileaching behavior, and biosafety were tested. The results showed that anatase-phase TiO2 was synthesized on halloysite with a particle size of ∼10 nm. Under neutral conditions (pH 7), the cumulative rate of pesticide release from Flu@THa was three times higher than that under acidic and alkaline conditions in 24 h. Flu@THa was evenly distributed in the soil and slowed the loss of pesticides. In addition, Flu@THa can promote germination and growth of peanut seeds and had good biocompatibility with low toxicity to zebrafish. This study is expected to be able to provide implications for environmentally friendly nanopesticides.

CAS / MDL: 57-09-0
研究领域: 环境科学 · 农业科学 · 材料科学
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JOURNAL OF ELECTROANALYTICAL CHEMISTRY · 2022 · IF 4.598

Enhanced electrochemical removal of dye wastewater by PbO2 anodes using halloysite nanotubes with different surface charge properties

Jiali Yuan,Zhen Chen,Qiang Yu,Wei Zhu,Shuting Li,Lei Han,Xia Lu,Shutong Li,Yize Wu,Ze Lv,Hongjun You,Bangyao Chen

Electrode materials are the core of electrocatalytic oxidation technology. Herein, chitosan (CTS)-modified halloysite nanotubes (HNTs) were used for the first time in the doping modification of PbO 2 electrodes by electrodeposition technique, and novel HNTs-CTS-PbO 2 anodes were prepared and used for the electrochemical removal of the thiazine dye methylene blue (MB). The surface structure information, electrochemical properties and oxidation activity of the materials were systematically investigated, and possible degradation pathways of methylene blue were proposed. The results showed that after doping modification, the coating became flatter and denser, and the crystalline shape and crystalline phase of the PbO 2 electrode did not change, but the grain size was significantly reduced; moreover, the modified electrode had higher oxygen precipitation overpotential, larger reactive surface area and lower charge transfer resistance. Additionally, the decolorization degradation of MB by HNTs-CTS-PbO 2 electrode mainly adopts an indirect degradation mechanism and follows the pseudo-first-order kinetic model, which exhibits higher decolorization degradation rate. Analyzing the mechanism of the electrochemical removal of MB from the modified anode, which mainly involves the breakage of C N bonds under the action of ·OH, followed by demethylation and aromatic ring cleavage to obtain monoaromatic amines, sulfonic acids and phenolic compounds, and finally mineralized into inorganic small molecules such as CO 2 and H 2 O. The above results show that HNTs-CTS-PbO 2 anode is a promising candidate in the field of dye wastewater degradation and provide new insights for the application of HNTs .

研究领域: 环境科学 · 材料科学 · 电化学工程
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JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY · 2019 ·Vol. 19 ·期 11 ·7178-7184 · IF 1.093

Influence of Acid Treatment on the Loading and Release Behavior of Halloysite with 2-Mercaptobenzothiazole

Xing Xuteng,Wang Jihui,Li Qiushi,Hu Wenbin

Halloysite nanotubes (HNTs) are natural clay minerals with a tubular structure. They have attracted considerable attention as a potential nanocontainer due to their abundance, biocompatibility and nontoxicity. In this study, HNTs were handled with H2SO4 at 70 °C. The morphology and structure of these acid-treated and original HNTs were investigated by scanning electron microscopy (SEM), energy dispersion spectrum (EDS), transmission electron microscope (TEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR), and their specific surface area was determined by automatic gas adsorption analyzer. The loading efficiency and release behavior of acid-treated HNTs for 2-Mercaptobenzothiazole (MBT) were investigated by UV-vis spectrophotometer. Results show that acid-treated HNTs retained their tubular structure, but their internal diameter expanded by 35–37 nm after 32 h of acid treatment. After 72 h of acid treatment, HNTs can be transferred into amorphous silica nanotubes. Moreover, the specific surface area of these HNTs samples initially increased with the increase in acid treatment time but then started to decrease after 32 h. The specific surface area of acid-treated HNTs at 32 h can reach 251.6 m2/g, which was much higher than that for untreated HNTs (55.3 m2/g). In addition, the loading capacity of acid-treated HNTs can reach 32.1% for HNTs-32, which is about three times higher than that of original HNTs. The acid treatment has slight effect on the release behavior.

CAS / MDL: 149-30-4
研究领域: 材料科学 · 化学工程
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2020 · IF 3.573

Site-Oriented Design of High-Performance Halloysite-Supported Palladium Catalysts for Methane Combustion

Yong Zheng,Lufeng Wang,Fulan Zhong,Guohui Cai,Yihong Xiao,Lilong Jiang

As a class of natural clay minerals, the special surface characteristic of the negatively charged outer surface and the positively charged inner lumen enables halloysite to be of potential interest for catalytic applications. In this work, thermal treatment and modification with cetyltrimethylammonium bromide made the outer surface of halloysite hydrophobic, which resulted in the selective loading of palladium on the hydrophilic inner surface of halloysite. The designed site-oriented loading endowed catalysts with the desired structure and favorable properties for methane combustion. Because of the uniformly dispersed palladium particles (ca. 2 nm), a suitable ratio of Pd2+/Pd4+, better reducibility, and appropriate surface acidity, the tailored catalyst exhibited a remarkably higher activity with the T99 decreasing from 620 °C (unmodified catalysts) to 425 °C. More importantly, the stabilized palladium species could resist sintering and the diminishing of hydroxyl groups on the surface weakened the interaction with water, invoking an excellent long-term/cyclic stability and water resistance for methane combustion.

研究领域: 催化化学 · 材料科学 · 环境科学
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INTERNATIONAL JOURNAL OF BIOLOGICAL MACROMOLECULES · 2025 · IF 8.5

Quaternized chitosan/sodium alginate functionalized halloysite for melamine formaldehyde resin impregnated paper: synergistic toughening and antibacterial properties development

Yun Feng,Jinrong He,Jinzhen Cao,Wei Qu,Limin Peng

Melamine formaldehyde (MF) resin is a widely used decorated material, but its inherent brittleness limits broader applications. In this study, a novel bio-based nanomaterial (AQ@HNTs) was fabricated via a layer-by-layer self-assembly of quaternized chitosan and sodium alginate onto halloysite nanotubes (HNTs), providing a green and efficient strategy for natural nanotube surface modification. The resulting AQ@HNTs were incorporated into MF resin to synergistically enhance its toughness and antibacterial properties without affecting its curing behavior at 120 °C. Comprehensive characterization of AQ@HNTs was performed using Fourier transform infrared spectroscopy (FTIR), Zeta potential analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). The mechanical and antibacterial performance of the resulting MF-AQH resin-impregnated paper was evaluated for mechanical properties, antibacterial performance, and crack resistance through dynamic mechanical analysis (DMA), mechanical testing, antibacterial assays, and crack resistance tests. The paper impregnated with 5 wt% AQ@HNTs exhibited significantly improved mechanical properties, with tensile strength, elongation at break, and elastic modulus increasing by 78.11 %, 39.66 %, and 27.61 %, respectively. Additionally, it demonstrated strong antibacterial activity against Escherichia coli and Staphylococcus aureus , with inhibition zones of 21.97 ± 0.57 mm and 32.19 ± 0.37 mm, and bacterial survival rates reduced to 17.99 % and 11.52 %, respectively. This work highlights a dual-functional approach combining structural reinforcement and antimicrobial activity through an innovative bio-based modification strategy, offering a promising solution for high-performance MF resin in interior decoration applications.

CAS / MDL: 108-78-1
研究领域: 材料科学 · 生物医学工程
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Journal of the Taiwan Institute of Chemical Engineers · 2017 · IF 4.217

Preparation of hierarchical porous carbons from sodium carboxymethyl cellulose via halloysite template strategy coupled with KOH-activation for efficient removal of chloramphenicol

Ruilong Zhang,Zhiping Zhou,Atian Xie,Jiangdong Dai,Jiuyun Cui,Jihui Lang,Maobin Wei,Xiaohui Dai,Chunxiang Li,Yongsheng Yan

The wide applications of antibiotics in human and veterinary medicines have attracted ever-increasing attention due to their potential adverse effects for ecological environment, therefore, it is urgent and important to efficiently remove antibiotics from water. In this paper, we prepared hierarchical porous carbons from sodium carboxymethyl cellulose (CMCHPCs) via halloysite template and KOH-activation method for efficient removal of chloramphenicol. The physicochemical properties of CMCHPCs are analyzed by means of different characterizations. The adsorption properties of CMCHPCs are evaluated by equilibrium, kinetic, and thermodynamic adsorption experiments. In addition, the effects of ionic strength, solution pH, and humic acid on adsorption are studied. The results indicated CMCHPCs exhibit higher maximum monolayer adsorption capacity up to 769.95 mg/g and shows good regenerability and adaptability. Importantly, the adsorption mechanisms of chloramphenicol adsorbed onto the CMCHPCs are also discussed.

研究领域: 环境科学 · 材料科学
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COMPOSITES COMMUNICATIONS · 2024 · IF 6.5

Aligning halloysite nanotubes in elastomer toward flexible film with enhanced dielectric constant

Jiamin Chen,Zongyuan Shen,Yi Zhao,Xueqing Liu,Feng Chen,Jiyan Liu

Naturally occurring halloysite nanotubes (HNTs) are considered electrically insulating counterparts of carbon nanotubes, and they are always randomly distributed in the reported polymer composites. With the recent optimization in advanced processing techniques for the production of muti-functional polymer composites, efficiently aligning micro-/nano-fillers in polymer matrix have been available. Here, we fabricate such aligned HNTs-silicon elastomer (PDMS) composites enabled by alternating current (AC) electric field driven alignment and report that at 7 wt% HNTs loading, the dielectric constant of aligned HNTs/PDMS composite film is almost 150 % (8.46 vs 5.71) higher than that of unaligned one at measurement frequency of 1 kHz. It is also observed that such high loading of nanoparticles brings negligible increase in dielectric loss and does not compromise much of the flexibility. This work provides a renewed understanding of the potential of aligning fillers in polymer matrix, allowing the proper utilization of the high polarization and extremely low dielectric loss predicted for HNTs in the fabrication of polymer composite dielectrics.

研究领域: 材料科学 · 电气工程
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2017 · IF 4.233

Polymer grafted-magnetic halloysite nanotube for controlled and sustained release of cationic drug

Meriem Fizir,Pierre Dramou,Kai Zhang,Cheng Sun,Chuong Pham-Huy,Hua He

In this research, novel polymer grafted-magnetic halloysite nanotubes with norfloxacin loaded (NOR-MHNTs) and controlled-release, was achieved by surface-initiated precipitation polymerization. The magnetic halloysite nanotubes exhibited better adsorption of NOR (72.10   mg   g −1 ) compared with the pristine HNTs (30.80   mg   g −1 ). Various parameters influencing the drug adsorption of the MHNTs for NOR were studied. Polymer grafted NOR-MHNTs has been designed using flexible docking in computer simulation to choose optimal monomers . NOR-MHNTs/poly (methacrylic acid or acrylamide- co -ethylene glycol dimethacrylate) nanocomposite were synthesized using NOR-MHNTs, methacrylic acid (MAA) or acrylamide (AM), ethylene glycol dimethacrylate (EGDMA) and AIBN as nanotemplate, monomers , cross linker and initiator, respectively. The magnetic nanocomposites were characterized by FTIR, TEM , XRD and VSM . The magnetic nanocomposites show superparamagnetic property and fast magnetic response (12.09   emu   g −1 ). The copolymerization of monomers and cross linker led to a better sustained release of norfloxacin (   >60   h) due to the strong interaction formed between monomers and this cationic drug. The cumulative release rate of NOR is closely related to the cross linker amount. In conclusion, combining the advantages of the high adsorption capacity and magnetic proprieties of this biocompatible clay nanotube and the advantages of polymer shell in the enhancement of controlled-sustained release of cationic drug, a novel formulation for the sustained-controlled release of bioactive agents is developed and may have considerable potential application in targeting drug delivery system.

研究领域: 材料科学 · 药学 · 生物医学工程
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Halloysite nanotube-based self-healing fluorescence hydrogels in fabricating 3D cube containing UV-sensitive QR code information

Bo Zhang,Shanshan Li,Yuan Wang,Yonggang Wu,Hailei Zhang

With the evolution of information technology, the development of smart materials for the information storage and encryption is in urgent need. Herein, halloysite nanotubes (HNTs)-based self-healing hydrogels were facilely prepared by using aryl arylboronic acid-bearing tetraphenylethylene (TPE) as crosslinker agent, in which the HNTs were covalently bonded into the polymeric matrix. With the addition of HNTs, the obtained hydrogel (H2) shows improved compression resistance performance and self-healing property, which can be customed in certain shapes. The TPE-crosslinked hydrogels (H1 and H2) are able to emit bright blue fluorescence centering at 457 nm when exposed to 365 nm light. By holding together with 1,4-phenylenebisboronic acid-crosslinked hydrogels (H3) with non-fluorescence property, the obtained cube is able to store UV-sensitive QR code information which is potentially to be recognized by QR code scanner or other smart tools.

研究领域: 材料科学 · 信息加密技术
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