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Halloysite
COLLOIDS AND SURFACES B-BIOINTERFACES · 2019 · IF 3.973

β-Cyclodextrin coated and folic acid conjugated magnetic halloysite nanotubes for targeting and isolating of cancer cells

Xiufang Li,Jian Chen,Hui Liu,Zhiwei Deng,Jianbing Li,Tao Ren,Ling Huang,Wenqing Chen,Yanjing Yang,Shian Zhong

The study developed a simple, effective and inexpensive strategy for capturing, enriching and detecting circulating tumor cells (CTCs) by using folic acid (FA) as the targeting molecule instead of antibodies. This work constructed magnetic halloysite nanotubes (MHNTs) coated with biocompatible β-cyclodextrin (CD), and conjugated to FA via a PEG-Ad linker, to specifically capture the FA receptor (FR)-overexpressing cancer cells. The capture efficiencies of [email protected] β [email protected] for the Skov3, Hela and A549 cancer cells were 96.3%, 97.0% and 95.6% respectively. In addition, the nanoparticles were able to capture very low numbers of the cancer cells (25–500 cells/mL) from PBS and whole blood, as well as selectively capture the cancer cells over normal HEK 293 T cells. Furthermore, the captured cells were viable and grew normally in vitro , indicating the future potential of downstream analyses. This approach can be adapted for different CTCs, once the tumor-specific surface markers are identified and the efficacy of targeting ligands is established. Taken together, FA-conjugated MHNTs nanoparticles are a highly promising tool for isolating CTCs for the diagnosis and treatment of cancer.

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RSC Advances · 2016 ·Vol. 6 ·期 59 ·54463-54470 · IF 3.289

The combination of adsorption by functionalized halloysite nanotubes and encapsulation by polyelectrolyte coatings for sustained drug delivery

Hui Li,Xiaohong Zhu,Jiangfeng Xu,Wei Peng,Shian Zhong,Yan Wang

A novel organic–inorganic hybrid nanocomposite was established for the sustained release of an analgesic. Adsorption by functionalized halloysite nanotubes (HNTs) and encapsulation by polyelectrolyte coatings (PECs) via the layer-by-layer (LBL) self-assembly of chitosan (CHI) and sodium alginate (ALG) were combined for the proposed drug delivery. In order to increase loading capacity, HNT lumen enlargement and γ-aminopropyltriethoxysilane (APTES) modification were introduced to manufacture nanocontainers denoted as AHNTs. Ibuprofen (C13H18O2, IBU) is an active analgesic that was selected as a model drug to evaluate the pharmaceutical properties. Fourier transform infrared spectroscopy, transmission electron microscopy, thermal gravimetric analysis, zeta potential, and high-performance liquid chromatography were performed to characterize the structure and properties of ALG/CHI PECs on AHNTs loaded with IBU (IBU-AHNTs@PECs). The release behavior was investigated by changing the PEC and pH conditions. An enhanced capacity for adsorption (32%) and a sustained-release performance (115 h) of IBU-AHNTs@PECs toward IBU were demonstrated, which followed the power law kinetic model. The proposed combination is expected to provide an important strategy to regulate drug delivery and extend pharmaceutical applications.

CAS / MDL: 919-30-2
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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.

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Materials · 2024 ·Vol. 17 ·期 3 ·761 · IF 3.1

Flame-Retardant and Transparent Unsaturated Polyester Based on P/N Liquid Flame Retardants and Modified Halloysite Nanotubes

Yanli Dou,Aixun Ju,Zheng Zhong,Yutong Huo,Weiguo Yao

Unsaturated polyester resin (UPR) with excellent flame retardant is mainly obtained by adding large amounts of flame retardants, usually at the expense of mechanical properties. In this work, a reactive flame retardant containing phosphorus and nitrogen (DOPO-N) was successfully synthesized and incorporated in UPR as a crosslinker. The mechanical and flame-retardant properties of UPR composites were enhanced. UPR/30DOPO-N passed a UL-94 V-1 rating with a limiting oxygen index (LOI) of 30.8%. The tensile strength of UPR/30DOPO-N increased by 24.4%. On this basis, a small amount of modified HNTs (VHNTs) was added to further improve the flame-retardant properties of the composite. With the introduction of 3 wt% VHNTs, the composite passed the UL-94 V-0 rating. The peak of heat release rate (PHRR) and total heat release (THR) of it decreased by 60.7% and 48.3%, respectively. Moreover, the detailed flame-retarding mechanism of DOPO-N and VHNTs was investigated by thermogravimetric infrared spectroscopy (TG-IR), Raman spectra, and X-ray photoelectron spectroscopy (XPS). It was found that DOPO-N played a role in quenching the flame in the gas phase and cooperated with VHNTs to enhance the barrier effect in the condensed phase.

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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2025 · IF 5.4

Cationic oligomer surfactant self-assembly modified halloysite nanotubes improves the spread and retention of chlorpyrifos on leaves

Yan Qin,Zhujun Xiao,Jianning Wu,Lin Cui,Guihua Meng,Shengchao Yang,Zhiyong Liu,Xuhong Guo

At present, it is very important to develop a nanoparticle drug delivery system that can spread and retain the leaf surface of plants at the same time, which can improve the loss of pesticide carriers on the leaf surface and improve the bioavailability of pesticides. The photosensitive pesticide chlorpyrifos was loaded with halloysite nanotubes. The coating of polydopamine (PDA) provided the interface adhesion ability for the pesticide carrier, and the assembly of cationic oligomeric surfactant provided the wetting and spreading ability for the pesticide carrier. The wettability and spreadability of pesticide carrier can be adjusted by changing the length of hydrophobic chain segment, and the contact angle of cotton leaf surface can reach 36.87°. The retention rate after simulated rain erosion can reach 83.65 %. The maximum release rate was 60.76 % after 60 hours of cumulative release, which showed sustained release performance. After 24 h of simulated solar illumination, the degradation rate of chlorpyrifos (CPF) was 62.76 %. Improving the adhesion and wetting spreading ability of inorganic nanopesticide carriers on leaf surface and reducing the loss and degradation of CPF of photosensitive pesticides play a positive role in improving the bioavailability of pesticides, so it has a wide range of significance in agricultural applications and environmental protection.

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JOURNAL OF MATERIALS CHEMISTRY · 2012 ·Vol. 22 ·期 8 ·3360-3369 · IF 5.968

Selective recognition of 2,4,5-trichlorophenol by temperature responsive and magnetic molecularly imprinted polymers based on halloysite nanotubes

Jianming Pan,Bing Wang,Jiangdong Dai,Xiaohui Dai,Hui Hang,Hongxiang Ou,Yongsheng Yan

Fe3O4/Halloysite nanotube magnetic composites (MHNTs) were firstly prepared via an effective polyol-medium solvothermal method, and then the surface of the MHNTs was endowed with reactive vinyl groups through modification with 3-(methacryloyloxy)propyl trimethoxysilane (MPS). Based on the MHNTs-MPS, temperature responsive and magnetic molecularly imprinted polymers (t-MMIPs) were further synthesized by adopting methacrylic acid (MAA) and N-isopropylacrylamide (NIPAM) as the functional monomer and temperature responsive monomer, respectively. The as-prepared t-MMIPs were characterized by FT-IR, TEM, TGA and VSM, which indicated that the t-MMIPs exhibit magnetic sensitivity (Ms = 2.026 emu g−1), magnetic stability (especially in the pH range of 4.0–8.0) and thermal stability and are composed of an imprinted layer. The molecular interaction between 2,4,5-trichlorophenol (TCP) and MAA was investigated by 1H-NMR spectroscopy and ultraviolet absorption spectroscopy, which suggest that hydrogen bonding may be largely responsible for the recognition mechanism. The t-MMIPs were then applied to selectively recognise and release TCP molecules at 60 °C and 20 °C, respectively. The maximum amount of binding at 60 °C was 197.8 mg g−1 and 122.6 mg g−1 for t-MMIPs and temperature responsive and magnetic non-imprinted polymers (t-MNIPs), respectively. At 20 °C, about 32.3%–42.7% of TCP adsorbed by t-MMIPs was released, whereas 25.3%–39.9% of TCP was released by t-MNIPs. The selective recognition experiments demonstrated the high affinity and selectivity of t-MMIPs towards TCP over competitive phenolic compounds, and the specific recognition of binding sites may be based on the distinct size, structure and functional group to the template molecules.

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FOOD CHEMISTRY · 2024 · IF 8.5

A novel halloysite nanotubes-based hybrid monolith for in-tube solid-phase microextraction of polar cationic pesticides

Jinhan Zhang,Yihui Chen,Meilin Ni,Chunyan Hou,Xiaoqiang Qiao,Tingting Wang

The accurate determination of polar cationic pesticides in food poses a challenge due to their high polarity and trace levels in complex matrices. This study hypothesized that the use of halloysite nanotubes (HNTs) can significantly enhance the extraction efficiency and sensitivity of these analytes because of their rich hydroxyl groups and cation exchange sites. Therefore, we chemically incorporated HNTs with organic polymer monoliths for in-tube solid-phase microextraction (SPME). This novel hybrid monolith extended service life, improved adsorption capacity, and exhibited excellent extraction performance for polar cationic pesticides. Based on these advancements, a robust and sensitive in-tube SPME-HILIC-MS/MS method was constructed to determine trace levels of polar cationic pesticides in complex food matrices. The method achieved limits of detection of 1.9, 2.1, and 0.1 μg/kg for maleic hydrazide , amitrole , and cyromazine , respectively. The spiked recoveries in five food samples ranged from 80.2 to 100.8%, with relative standard deviations below 10.7%.

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CHEMICAL ENGINEERING JOURNAL · 2017 · IF 6.216

Core@double-shell structured magnetic halloysite nanotube nano-hybrid as efficient recyclable adsorbent for methylene blue removal

Xinyi Wan,Yingqing Zhan,Zhihang Long,Guangyong Zeng,Yi He

Design and fabrication of structurally optimized absorbents are important for wastewater treatment such as dyes and heavy metals removal. Herein, we reported the core@double-shell structured magnetic halloysite nanotube nano-hybrid absorbent with target micro-structure and high efficiency removal capacity of dyestuffs. Our core@double-shell structured absorbent consisted of a halloysite nanotube as skeleton, an intermediate magnetic nanoparticles coating with more specific surface area and magnetic separation property, and poly(DA   +   KH550) derivate layer outside provided active adsorption sites. This well-defined core@double-shell configuration was quite distinct from conventional core-shell or hybrid structures. The integrated advantages of HNTs skeleton, Fe 3 O 4 nanoparticles inner shell and poly(DA   +   KH550) outside shell contributed to the high adsorption capacity of methylene blue (up to 714.29   mg   g −1 ) and excellent cycling stability. Furthermore, the novel core@double-shell structured absorbent exhibited better removal efficiency for methylene blue in solution with high pH, and the adsorption process can be described by using the pseudo-second-order model. More importantly, the recycling process of adsorbents was more energetically and economically sustainable by using a permanent magnet. The characteristic high removal capacity, cycling stability and easy separation made core@double-shell structured absorbent promising for the efficient removal of dyestuffs from the wastewater.

CAS / MDL: 62-31-7 77-86-1
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SOLAR ENERGY MATERIALS AND SOLAR CELLS · 2024 · IF 6.3

The PPy-coated halloysite nanotubes nanofluids with high stability and broad-spectrum absorption for effective photothermal conversion

Wei Xie,Xiaoke Li,Jiaying Zhou,Fei Yin,Yaogang Jiang,Liu Yang

In this study, a novel approach for the synthesis of eco-friendly and cost-effective composite nanomaterials PPy@HNTs was introduced. The proposed synthesis method offers environmental friendliness, simplicity, and cost-effectiveness. The resulting PPy@HNTs nanofluids , obtained through dispersion in a specially formulated base solution, demonstrate excellent dispersion stability , desirable thermophysical properties , and remarkable photothermal conversion performance. At a concentration of 800 ppm, the PPy@HNTs nanofluids exhibited an impressive efficiency of 79.2 %, surpassing the performance of conventional heat transfer fluids (HTFs). This research presents a promising avenue for the utilization of low-cost nanofluids in the field of photothermal applications.

CAS / MDL: 109-97-7
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JOURNAL OF SEPARATION SCIENCE · 2025 ·Vol. 48 ·期 7 ·e70226 · IF 2.8

Synthesis of Perfluorooctyl-Functionalized Halloysite Nanotubes for Dispersive Solid-Phase Extraction of Antimalarial Inhibitors in Whole Blood

Kejie Wang,Bingye Shi,Yihui Chen,Chunyan Hou,Xie Li,Xiaoqiang Qiao,Tingting Wang

Quinine, chloroquine, and hydroxychloroquine are effective antimalarial drugs that have shown antiviral activity against SARS-CoV-2 in initial in vitro studies. However, their excessive use can lead to adverse effects in humans. Therefore, rapid and accurate analysis of these inhibitors in whole blood samples is crucial for public health, although this presents significant challenges. In this study, perfluorooctyl-functionalized halloysite nanotubes were synthesized and used as sorbents for dispersive solid-phase extraction. The developed sorbents interacted with inhibitors through various mechanisms, including hydrophobic interactions, electrostatic interactions, F–π interactions, and hydrogen bonding. Notably, their adsorption capacity was twice that of unmodified halloysite nanotubes. By combining the perfluorooctyl-functionalized halloysite nanotubes-based dispersive solid-phase extraction method with liquid chromatography-tandem mass spectrometry, an analytical method was developed to determine concentrations of the three inhibitors in whole blood samples. Under optimized conditions, the limits of detection ranged from 1.2 to 2.1 ng/mL. The recoveries achieved 91.9%–101.5% for intra-day and 92.8%–101.2% for inter-day. The inter- and intra-day relative standard deviations were in the range of 0.6%–3.8% and 2.3%–8.1%, respectively. This study introduces a novel approach for developing sorbents to target drugs and presents an innovative analytical method for therapeutic monitoring. These advancements will facilitate the evaluation of the pharmacokinetics of these inhibitors in patients and support ongoing clinical trials.

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Journal of Environmental Chemical Engineering · 2024 · IF 7.4

Robust halloysite nanotubes modified PVDF membranes with improved wetting resistance for hypersaline wastewater treatment via membrane distillation

Shengyou Wu,Shuaifei Zhao,Zhe Zhai,Yan Huang,Shiwei Liu,Hao Yang,Yuchao Zhao

Membrane distillation (MD) is a viable technology and potential candidate for desalination of hypersaline wastewater. Nevertheless, MD membranes with high flux and superior antiwetting ability face a significant challenge for realizing high-efficient desalination. Herein, polyvinylidene fluoride (PVDF) hydrophobic porous membranes are fabricated by non-solvent induced phase separation. The structure of PVDF membranes, such as pore type, size, porosity, and surface hydrophobicity, can be well tuned over a wide range via adjusting phase separation conditions. To enhance the robustness of PVDF membrane, hydrophobized halloysite nanotubes (HNTs) are blended for membrane fabrication. The enhanced mechanical strength of membrane increases wetting resistance via inhibiting pore deformation and LEP reduction during salt crystals growth. In the treatment of hypersaline wastewater (70 g∙L −1 ) containing 3 g∙L −1 CaCl 2 and 3 g∙L −1 Na 2 SO 4 via VMD, the HNTs/PVDF membrane with 50 wt% HNTs shows a high flux of 54 L∙m −2 ∙h −1 , over 99.99 % NaCl rejection, and outstanding stability for 100 h. Our work not only offers a novel strategy to enhance wetting resistance of MD membranes for hypersaline wastewater treatment, but also demonstrates that the mechanical strength of membranes also significantly influences antiwetting ability of MD membranes.

CAS / MDL: 78-10-4
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DESALINATION · 2025 · IF 9.8

Photothermal halloysite nanotube hybrids with CoO/carbon layers for enhanced pollutant degradation and solar-powered water purification

Yifang Zhang,Hongyao Zhao,Jiayi Zhou,Yanyun Wang,Yangping Zhang,Jialing Shen,Danhong Shang,Feng Zeng,Jianming Pan,Yiyan Song,Fu Yang,Edison Huixiang Ang

Advanced environmental governance techniques using photothermal nanomaterials for pollutant removal and water recycling are highly regarded. Here, we incorporated CoO nanospecies onto halloysite nanotubes via in-situ polymerization of tannic acid coordinated with Co ions and carbonization. The resulting halloysite nanotube hybrids with CoO/carbon layer (HNTs@CoO/C) afford great exposure of CoO nanospecies onto the N-doping carbon layer modified halloysite. Compared to composites without a carbon layer, optimized Co(II)/Co(III) redox cycles are achieved. More pyridine nitrogen species on the carbon layer enhance the catalyst's surface affinity for polar contaminants. HNTs@CoO/C has nearly 8.6 fold higher catalytic degradation efficiency for norfloxacin (0.164 min −1 versus 0.019 min −1 for HNTs@CoO). Quenching experiments show that co-existing multiple active species ( SO₄ − , OH, O₂ − , and 1 O₂) play important roles in norfloxacin (NFX) degradation, among which 1 O₂ is dominant. The optimal HNTs@CoO/C also effectively removes other contaminants like sulfadiazine (SDZ), tetracycline (TC), oxytetracycline (OTC), and carbamazepine (CBZ). Moreover, anchoring HNTs@CoO/C on a used cotton towel forms a 2D evaporator. Under the simulated sunlight, it has a good photothermal conversion ability, heating from 19.9 °C to 40.3 °C in 8 min. As a floatable system, it efficiently evaporates water and degrades contaminants in the presence of PMS. These results indicate the potential of this approach for water treatment and resource utilization.

CAS / MDL: 9005-38-3
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