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The phytotoxicity of halloysite nanotubes (HNTs) to rice (Oryza sativa L.) was evaluated at several stages from germination, seedling growth to spike setting, and the seedling stage was selected to study the effect of HNTs on the growth of rice. Rice was cultured using different concentrations of HNTs dispersions and a blank control group was cultured with deionized water. It was found that HNTs did not affect the germination of rice seeds, and at the seedling stage, the low concentration of HNTs dispersion (0.1 mg mL -1 ) promoted the growth of rice. This significantly increased the biomass and root system of rice seedlings and also promoted the development of stems and leaves of rice seedlings. However, high concentration of HNTs dispersion (100 mg mL -1 ) had an inhibitory effect on rice growth, resulting in a significant decrease in rice biomass, causing oxidative damage (increase in H 2 O 2 content and malondialdehyde content, and disruption of cell membrane permeability), and causing a decrease in chlorophyll content in rice. The rice seedlings treated with HNTs were transplanted into the soil, and it was found that all the rice could grow healthily. The growth trend was consistent with the seedling stage, and all groups of rice were able to produce spikes, which indicated that the effect of HNTs on rice was slight. In total, this work displayed the toxicity of HNTs to rice, which lays the foundation for the application of HNTs in agricultural field., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

In this work, it is reported a scalable and systematic protocol for the preparation of xerogels based on the use of green, highly available, and low-cost materials, i.e. halloysite nanoclay and chitosan, without the need for any expensive equipment or operational/energetic demands. Starting from colloidal dispersions, rheological studies demonstrate the formation of hydrogels with zero-shear viscosities enhanced by ≈9 orders of magnitude and higher storage moduli. Hence, the corresponding self-standing xerogels are prepared by a simple solvent casting method and their properties depend on the concentration of halloysite, possessing enhanced thermal stability and outstanding mechanical performances (elastic modulus and ultimate elongation of 165 MPa and 43%, respectively). The resulting biohybrid materials can be exploited for environmental remediation. High removal efficiencies are reached for the capture of organic molecules from aqueous media and the CO 2 capture from the atmosphere is also investigated. Most importantly, the presence of an inorganic skeleton within the xerogels prevents the structure from collapsing upon drying and it allows for the control over their morphology and shape. Therefore, taking advantage of the overall features, the designed xerogels offer an attractive strategy for sustainably tackling pollution and for environmental remediation in a plethora of different domains., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Halloysite nanotubes (HNTs) are naturally occurring aluminosilicate minerals, known for their unique tubular structure, which have garnered significant interest for a wide range of applications. This study explores the morphological changes of HNTs when subjected to thermal treatment ranging from 25 °C to 1100 °C using a combination of experimental characterization techniques and molecular dynamics simulations. Techniques such as solid-state NMR (SSNMR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET) surface area measurements, and Fourier Transform Infrared Spectroscopy (FT-IR) were employed to analyse the structural evolution. The results reveal two major transitions: the first occurring between 400 and 500 °C, corresponding to the release of intercalated water and partial distortion of the HNT structure, and the second occurring between 900 and 1000 °C, marked by the collapse of the tubular structure and the exposure of alumina on the surface. These findings provide significant insights into the thermal stability of HNTs, informing future applications, especially in high-temperature environments., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors. Published by Elsevier Ltd.)

Self-assembling of very long natural clay nanotubes represents a powerful strategy to fabricate thermo-stable inorganic thin films suitable for environmental applications. In this work, self-standing films with variable thicknesses (from 60 to 300 µm) are prepared by the entanglement of 20-30 µm length Patch halloysite clay nanotubes (PT_Hal), which interconnect into fibrosus structures. The thickness of the films is crucial to confer specific properties like transparency, mechanical resistance, and water uptake. Despite its completely inorganic composition, the thickest nanoclay film possesses elasticity comparable with polymeric materials as evidenced by its Young's modulus (ca. 1710 MPa). All PT_Hal-based films are fire resistant and stable under high temperature conditions preventing flame propagation. After their direct flame exposure, produced films do not show neither deterioration effects nor macroscopic alterations. PT_Hal films are employed as precursors for the development of functional materials by alkaline activation and thermal treatment, which generate highly porous geopolymers or ceramics with a compact morphology. Due to its high porosity, geopolymer can be promising for CO 2 capture. As compared to the corresponding inorganic film, the CO 2 adsorption efficiency is doubled for the halloysite geopolymeric materials highlighting their potential use as a sorbent., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Developing high-temperature-resistant adsorbents with superior porous properties is crucial for safely disposing of heavy metal-containing solid waste via pyrolysis. We synthesized aluminosilicates hydrothermally and observed that acidic conditions, especially HCl (pH=2.6), favored sponge-like mineral (NC2.6) formation with a specific surface area of 500.31 m²/g and pore volume of 0.986 cm³ /g, while alkaline conditions (pH=12.0) promoted spherical particle growth. NC2.6 exhibited higher adsorption capacity compared to kaolinite and halloysite in the PbCl 2 vapor adsorption, reaching a maximum of 137.68 mg/g at 700 ℃ (75.91 % stable). We examined the effect of CO 2 and H 2 O on adsorption efficiency and explored the mechanisms using DFT and GCMC simulations. From GCMC results, CO 2 negatively impacted PbCl 2 adsorption due to competitive adsorption, while H 2 O increased adsorption content (144.24 mg/g at 700 ℃) by converting PbCl 2 into oxides. DFT revealed the presence of CO 2 enhanced the adsorption stability of PbCl 2 via the formation of covalent bonds between O in CO 2 and Pb, and active O on the aluminosilicate surface. H 2 O increased PbCl 2 adsorption energy, as O in H 2 O occupied an active Al that originally formed a covalent bond with Cl, while the H formed a weak hydrogen bond with this Cl., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Most of the therapeutic systems developed for managing chronic skin wounds lack adequate mechanical and hydration properties, primarily because they rely on a single component. This study addresses this issue by combining organic and inorganic materials to obtain hybrid films with enhanced mechanical behavior, adhesion, and fluid absorption properties. To that aim, chitosan/hydrolyzed collagen blends were mixed with halloysite/antimicrobial nanohybrids at 10% and 20% ( w / w ) using glycerin or glycerin/polyethylene glycol-1500 as plasticizers. The films were characterized through the use of Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and electron microscopy. The mechanical properties were evaluated macroscopically using tensile tests, and at a nanoscale through atomic force microscopy (AFM) and nanoindentation. Thermodynamic studies were conducted to assess their hydrophilic or hydrophobic character. Additionally, in vitro cytocompatibility tests were performed on human keratinocytes. Results from FTIR, TGA, AFM and electron microscopy confirmed the hybrid nature of the films. Both tensile tests and nanomechanical measurements postulated that the nanohybrids improved the films' toughness and adhesion and optimized the nanoindentation properties. All nanohybrid-loaded films were hydrophilic and non-cytotoxic, showcasing their potential for skin wound applications given their enhanced performance at the macro- and nanoscale.

Using halloysite clay and vitamin B1 hydrochloride, a novel acidic halloysite-dendrimer catalytic composite has been developed for conversion of fructose to 5-hydroxymthylfurfural. To grow the dendritic moiety on halloysite, it was first functionalized and then reacted with melamine, epichlorohydrin and vitamin B1 hydrochloride respectively. Then, the resulting composite was treated with ZnCl 2 to furnish Lewis acid sites. Use of vitamin B1 as the cationic moiety of ionic liquid obviated use of toxic chemicals and resulted in more environmentally friendly composite. Similarly, dendritic moiety of generation 2 was also grafted on halloysite and the activity of both catalysts for conversion of fructose to 5-hydroxymthylfurfural was investigated to disclose the role of dendrimer generation. For the best catalytic composite, the reaction variables were optimized via RSM and it was revealed that use of 0.035 g catalyst per 0.1 g fructose at 95 °C furnished HMF in 96% yield in 105 min. Turnover numbers (TONs) and frequencies (TOFs) were estimated to be 10,130 and 5788 h -1 , respectively. Kinetic studies also underlined that Ea was 22.85 kJ/mol. The thermodynamic parameters of Δ H ≠ , Δ S ≠ and Δ G ≠ , were calculated to be 23 kJ/mol, - 129.2 J/mol and 72.14 kJ/mol, respectively. Notably, the catalyst exhibited good recyclability and hot filtration approved heterogeneous nature of catalysis., (© 2024. The Author(s).)

Tetracycline (TC), a commonly utilized broad-spectrum antibiotic, is frequently detected in water and soil, posing a significant risk to the natural environment and human health. In the present study, the composite hydrogel beads based on chitosan (CS) and halloysite-supported molecularly imprinted polymers, synthesized by two procedures with significantly different solvent volumes (Hal@MIP a(b) ), were obtained and used to adsorb the antibiotic. The presence of Hal improved the thermal stability of the hydrogel beads. The system with a thinner polymer layer (CS_Hal@MIP b ), containing polymers produced under conditions of significantly higher reagent dilution, was more resistant to higher temperatures than CS_Hal@MIP a . The adsorptive properties were compared with pure CS beads, those containing incorporated Hal, and free polymers obtained by different protocols (MIP a(b) ). In the optimized pH 5.0, the maximum adsorption capacities were 175.24 and 178.05 mg g -1 for CS_Hal@MIP a and CS_Hal@MIP b, respectively. The values were slightly lower compared to the systems with free polymers, but the materials achieved equilibrium more rapidly (12 h). The adsorption process was spontaneous and exothermic. Freundlich isotherm and pseudo-second-order kinetic models most accurately described the experimental data. The hydrogel beads retained high selectivity in the presence of other antibiotics, and their high efficiency in the TC removal from real water samples was maintained. Their addition to soil enhanced adsorption capacities, surpassing that of chitosan-based beads containing free polymers. Significantly, the quantity of TC desorption diminished due to the halloysite's presence, which limited its penetration into groundwater. The primary mechanism of tetracycline adsorption on the hydrogel beads studied is pore filling, but other interactions (hydrogen bonding, π-π stacking, electrostatic attraction) are also involved., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Ceglowski Michal reports financial support was provided by National Science Centre Poland., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Background: Polymethylmethacrylate (PMMA) bone cement is used in orthopedics and dentistry to get primary fixation to bone but doesn't provide a mechanically and biologically stable bone interface. Therefore, there was a great demand to improve the properties of the PMMA bone cement to reduce its clinical usage limitations and enhance its success rate. Recent studies demonstrated that the addition of halloysite nanotubes (HNTs) to a polymeric-based material can improve its mechanical and thermal characteristics., Objectives: The purpose of the study is to assess the compressive strength, flexural strength, maximum temperature, and setting time of traditional PMMA bone cements that have been manually blended with 7 wt% HNT fillers., Methods: PMMA powder and monomer liquid were combined to create the control group, the reinforced group was made by mixing the PMMA powder with 7 wt% HNT fillers before liquid mixing. Chemical characterization of the HNT fillers was employed by X-ray fluorescence (XRF). The morphological examination of the cements was done using a scanning electron microscope (SEM). Analytical measurements were made for the compressive strength, flexural strength, maximum temperature, and setting time. Utilizing independent sample t-tests, the data was statistically assessed to compare mean values (p < 0.05)., Results: The findings demonstrated that the novel reinforced PMMA-based bone cement with 7 wt% HNT fillers showed higher mean compressive strength values (93 MPa) and higher flexural strength (72 MPa). and lower maximum temperature values (34.8 °C) than the conventional PMMA bone cement control group, which was (76 MPa), (51 MPa), and (40 °C), respectively (P < 0.05). While there was no significant difference in the setting time between the control and the modified groups., Conclusion: The novel PMMA-based bone cement with the addition of 7 wt% HNTs can effectively be used in orthopedic and dental applications, as they have the potential to enhance the compressive and flexural strength and reduce the maximum temperatures., (© 2024. The Author(s).)

One solution to comply with the strict regulations of the European Commission and reduce the environmental footprint of composites is the use of composite materials based on bio-polymers and fillers from natural resources. The aim of our work was to obtain and analyze the properties of bio-polymer nanocomposites based on bio-PA (PA) and feather keratin-halloysite nanohybrid. Keratin (KC) was mixed with halloysite (H) as such or with the treated surface under dynamic conditions, resulting in two nanohybrids: KCHM and KCHE. The homogenization of PA with the two nanohybrids was conducted using the extrusion processing process. Two types of nanocomposites, PA-KCHM and PA-KCHE, with 5 wt.% KC and 1 wt.% H were obtained. The properties were analyzed using SEM, XRD, FTIR, RAMAN, TGA, DSC, tensile/impact tests, DMA, and nanomechanical tests. The best results were obtained for PA-KCHE due to the stronger interaction between the components and the uniform dispersion of the nanohybrid in the PA matrix. Improvements in the modulus of elasticity and of the surface hardness by approx. 75% and 30%, respectively, and the resistance to scratch were obtained. These results are promising and constitute a possible alternative to synthetic polymer composites for the automotive industry.

Chemical modification of the surface of halloysite nanotubes (HNT) by alkalization (with sodium hydroxide (NaOH)) and grafting with silanes (bis(trimethylsilyl)amine (HMDS)) was carried out. The efficiency of the alkalization and grafting process was evaluated by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and the nitrogen adsorption method were used. XRD and FTIR analysis confirmed the formation of bonds of trimethylsilyl groups to the HNT surface which changed the nature of the surface from hydrophilic to hydrophobic. In addition, it was noted that grafting with silanes decreases by 7.2% the specific surface area of the halloysite compared to the alkalized material. High-density polyethylene (HDPE) composites with halloysite (HNT), alkalized halloysite (alk-HNT), and HMDS-modified halloysite (m-HNT) were processed in the molten state in a Brabender mixer chamber. On SEM/EDS micrographs of HDPE composites with silanized HNT, a change in surface characteristics from smooth to ductile was observed. Higher melting point values based on differential scanning calorimetry (DSC) analysis of HDPE composites with 5%wt silanized halloysite in comparison with HNT and alk-HNT of, respectively, 2.2% and 1.4% were found, which indicates a slight beneficial influence of the filler on the quality of ordering of the crystalline phase of the matrix.

The adsorption of copper ions and Reactive Red 120 azo dye (RR-120) as models of water pollutants on unmodified halloysite (H-NM), as well as halloysites modified with sulfuric acid (H-SA) and (3-aminopropyl)triethoxysilane (H-APTES), was investigated. The results showed that adsorption of both the adsorbates was pH-dependent and increased with the increase in halloysite dosage. The adsorption kinetics were evaluated and the results demonstrated that the adsorption followed the pseudo-second-order model. The adsorption isotherms of Cu(II) ions and RR-120 dye on the halloysites were described satisfactorily by the Langmuir model. The maximum adsorption capacities for the Cu(II) ions were 0.169, 0.236, and 0.507 mmol/g, respectively, for H-NM, H-SA, and H-APTES indicating that the NH 2 -functionalization rather than the surface area of the adsorbents was responsible for the enhanced adsorption. The adsorption capacities for RR-120 dye were found to be 9.64 μmol/g for H-NM, 75.76 μmol/g for H-SA, and 29.33 μmol/g for H-APTES. The results demonstrated that APTES-functionalization and sulfuric acid activation are promising modifications, and both modified halloysites have good application potential for heavy metals as well as for azo dye removal.

Despite the mechanical and physical properties of polyurethane foams (PUF), their application is still hindered by high inflammability. The elaboration of effective, low-cost, and environmentally friendly fire retardants remains a pressing issue that must be addressed. This work aims to show the feasibility of the successful application of natural nanomaterials, such as halloysite nanotubes and nanocellulose, as promising additives to the commercial halogen-free, fire-retardant triphenyl phosphate (TPP) to enhance the flame retardance of open-cell polyurethane foams. The nanocomposite foams were synthesized by in situ polymerization. Investigation of the mechanical properties of the nanocomposite PUF revealed that the nanoscale additives led to a notable decrease in the foam's compressibility. The obtained results of the flammability tests clearly indicate that there is a prominent synergetic effect between the fire-retardant and the natural nanoscale additives. The nanocomposite foams containing a mixture of TPP (10 and 20 parts per hundred polyol by weight) and either 10 wt.% of nanocellulose or 20 wt.% of halloysite demonstrated the lowest burning rate without dripping and were rated as HB materials according to UL 94 classification.

Peptide nucleic acid (PNA) is a DNA mimic that shows good stability against nucleases and proteases, forming strongly recognized complementary strands of DNA and RNA. However, due to its feeble ability to cross the cellular membrane, PNA activity and its targeting gene action is limited. Halloysite nanotubes (HNTs) are a natural and low-cost aluminosilicate clay. Because of their peculiar ability to cross cellular membrane, HNTs represent a valuable candidate for delivering genetic materials into cells. Herein, two differently charged 12-mer PNAs capable of recognizing as molecular target a 12-mer DNA molecule mimicking a purine-rich tract of neuroglobin were synthetized and loaded onto HNTs by electrostatic attraction interactions. After characterization, the kinetic release was also assessed in media mimicking physiological conditions. Resonance light scattering measurements assessed their ability to bind complementary single-stranded DNA. Furthermore, their intracellular delivery was assessed by confocal laser scanning microscopy on living MCF-7 cells incubated with fluorescence isothiocyanate (FITC)-PNA and HNTs labeled with a probe. The nanomaterials were found to cross cellular membrane and cell nuclei efficiently. Finally, it is worth mentioning that the HNTs/PNA can reduce the level of neuroglobin gene expression, as shown by reverse transcription-quantitative polymerase chain reaction and western blotting analysis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

Recently, fluorescent sensors have gained considerable attention due to their high sensitivity, low cost and noninvasiveness. Among the different materials that can be used for this purpose, carbon dots (CDs) represent valuable candidates for applications in sensing. These, indeed, are easily synthesized, show high quantum yield and are highly biocompatible. However, it was pointed out that the photoluminescence properties of these nanomaterials are strictly dependent on the synthetic and purification methods adopted. The presence of halloysite nanotubes (HNTs), a natural, low cost and biocompatible clay mineral, has been found to be efficient in obtaining small and highly monodispersed CDs without long and tedious purification techniques. Herein, we report the comparison of synthetic pathways for obtaining halloysite-N-doped CDs (HNTs-NCDs) that could be used in biological sensing. One was based on the synthesis of N-doped CDs by a bottom-up approach on HNTs' surface by a MW pyrolysis process; the other one was based on the post-modification of pristine N-doped CDs with halloysite derivatives. The evaluation of the best synthetic route was performed by different physico-chemical techniques. It was found that the bottom-up approach led to the formation of N-doped CDs with different functional groups onto the HNTs' surface. This evidence was also translated in the different fluorescence quantum yields and the existence of several functional groups in the obtained materials was investigated by potentiometric titrations. Furthermore, the ability of the synthesized nanomaterials as sensors for Fe 3+ ions detection was assessed by spectroscopic measurements, and the cellular uptake was verified by confocal/fluorescence microscopies as well.

Volatile organic compounds (VOCs), recognized as hazardous air contaminants, prompt the exploration of sustainable air purification methods. Solar photocatalytic oxidation emerges as a promising solution, utilizing semiconductor photocatalysts like titanium dioxide (TiO 2 ). However, the raw material crisis necessitates reduced TiO 2 usage, leading to investigations into TiO 2 modification techniques. The study introduces a novel approach by employing natural fibers, specifically loofah sponge, as a TiO 2 support. This method aims to maintain photocatalytic activity while minimizing TiO 2 content. The article explores using halloysite, a natural clay mineral, as a supportive material, enhancing mechanical strength and adsorption properties. The resulting TiO 2 /loofah-halloysite composites are evaluated for their efficacy in gas-phase photocatalytic oxidation of toluene and ethanol, chosen as representative VOCs. The conversion of toluene and ethanol on the composite was 88 % and 39 %, respectively, with high selectivity toward CO 2 . In addition to its high performance, the bio-composite was stable for several conversion cycles, keeping the conversion activity unchanged. The study contributes to developing green hybrid materials for VOC removal, showcasing potential applications across industries., (© 2024 Wiley‐VCH GmbH.)

The aim of this research is to synthesize a new sulfonic acid catalyst based on halloysite nanotubes (Hal-Py-SO 3 H) and characterize it as a solid acid nanocatalyst by various analytical techniques such as Fourier-Transformed Infrared spectroscopy (FTIR), Thermal gravimetric Analysis (TGA), X-ray Diffraction (XRD) analysis, Scanning Electron Microscopy (SEM), Vibrating Energy-Dispersive X-ray analysis (EDX), Transmission electron microscopy (TEM) and X-ray atomic mapping. Furthermore, this new catalyst was evaluated in synthesizing spiropyran derivatives via multicomponent reactions (MCRs) and Xanthen derivatives under environmentally sustainable conditions. The main advantages of this approach include green conditions, excellent yields, quick reaction rates, and ease of preparation. Additionally it was observed that the catalyst exhibited robust stability even after multiple recycling processes, indicating its potential for practical applications in sustainable chemical transformations., (© 2024. The Author(s).)

Iron-based catalysts are environmentally friendly, and iron minerals are abundant in the earth's crust, with great potential advantages for PMS-based advanced oxidation process applications. However, homogeneous Fe 2+ /PMS systems suffer from side reactions and are challenging to reuse. Therefore, developing catalysts with improved stability and activity is a long-term goal for practical Fe-based catalyst applications. In this study, we prepared Fe-HNTs nanoreactors by encapsulating a nitrogen-doped carbon layer with one-dimensional halloysite nanotubes (HNTs) using the molten salt-assisted method. Subsequently, Fe (Co, Ni) nanoclusters were anchored onto the nitrogen-doped carbon layer at a relatively low temperature (550℃), resulting in stable and uniform distribution of metal nanoclusters on the surface of HNTs carriers in the form of Fe-N x coordination. The results showed that the dissolution of the molten salt and leaching of post-treated metal oxides generated numerous mesopores within the Fe-HNTs nanoreactor, leading to a specific surface area more than 10 times that of HNTs. This enhanced mass transfer capability facilitates rapid pollutant removal while exposing more active sites. Remarkably, Fe-HNTs adsorbed up to 97% of tetracycline within 60 min. In the Fe-HNTs/PMS system, the predominant reactive oxygen species has been shown to be 1 O 2 , and the added tetracycline was degraded by more than 98% within 5 min. The removal of tetracycline was maintained above 96% in the presence of interfering factors such as wide pH (3-11) and inorganic anions (5 mM Cl - , HCO 3 - , NO 3 - , and SO 4 2- ). The investigated mechanism suggests that efficient degradation and interference resistance of the Fe-HNTs/PMS system is attributed to the synergistic effect between the rapid adsorption of porous structure and the non-radical ( 1 O 2 )-dominated degradation pathway., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Modern society pays further and further attention to environmental protection and the promotion of sustainable energy solutions. Heterogeneous photocatalysis is widely recognized as one of the most economically viable and ecologically sound technologies to combat environmental pollution and the global energy crisis. One challenge is finding a suitable photocatalytic material for an efficient process. Inorganic nanotubes have garnered attention as potential candidates due to their optoelectronic properties, which differ from their bulk equivalents. Among them, clay nanotubes (halloysite, imogolite, and chrysotile) are attracting renewed interest for photocatalysis applications thanks to their low production costs, their unique physical and chemical properties, and the possibility to functionalize or dope their structure to enhance charge-carriers separation into their structure. In this review, we provide new insights into the potential of these inorganic nanotubes in photocatalysis. We first discuss the structural and morphological features of clay nanotubes. Applications of photocatalysts based on clay nanotubes across a range of photocatalytic reactions, including the decomposition of organic pollutants, elimination of NOx, production of hydrogen, and disinfection of bacteria, are discussed. Finally, we highlight the obstacles and outline potential avenues for advancing the current photocatalytic system based on clay nanotubes. Our aim is that this review can offer researchers new opportunities to advance further research in the field of clay nanotubes-based photocatalysis with other vital applications in the future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

In this study, composite adsorbents consisting of a mixture of chitosan (CTS), boron nitride (h-BN) and halloysite (HNT) were used for the adsorption of Acid Violet 90 (AV90) dye in a batch system. Adsorbents CTS, CTS/HNT, CTS/h-BN and CTS/h-BN/HNT beads were prepared by simple dropping method and dried in a freeze dryer. The beads were characterized by FT-IR, SEM and zeta potential analysis. The effects of pH (2-8) and dye concentration (50-250 mg/L) on AV90 adsorption properties of beads were investigated. In addition, Langmuir, Freunlich, Temkin and Henry adsorption isotherm models were used to examine the dye adsorption mechanism. It was observed that the Langmuir and Freundlich adsorption isotherm models were in good agreement with the experimental data. In the dye concentration range studied, the qm values of CTS, CTS/h-BN1, CTS/h-BN3, CTS/HNT/h-BN1, CTS/HNT/h-BN3, CTS/HNT obtained from the Langmuir isotherm model was 27.62, 17.80, 10.11, 8.71, 32.57, 19.96 mg/g, respectively. Pseudo-first order, pseudo-second order and intra-particle diffusion kinetic models were used to examine the adsorption kinetics of adsorbents. As a result, it is thought that the use of this study in the field of dye adsorption can be an innovative and important study., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Lipase B from Candida antarctica (CALB) plays a prominent role as a biocatalyst in several industries, especially for biphasic conversion of functional lipids. Herein, an amphiphilic Janus halloysite nanosheet (JHNS) was fabricated and employed simultaneously as a solid surfactant for stabilizing Pickering emulsion and as a carrier for immobilizing CALB, with the aim to realize highly efficient biphasic bioconversion. The obtained JHNS could stabilize Pickering emulsion for at least 7 days. Immobilization of CALB on JHNS improved the substrate affinity, catalytic efficiency, thermal stability, and alkaline tolerance of the enzyme. Moreover, JHNS-based immobilized CALB was exploited as a biocatalytic platform for the conversion of retinyl acetate, with almost twice increase in conversion efficiency. Taken together, the JHNS-based immobilized CALB paves the way for the design of efficient biphasic conversion system for the production of added-value lipids., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Halloysite nanotubes (HNTs) are one-dimensional clay nanomaterials featuring distinct tubular structures and unique surface charges. HNTs can readily form ordered assembly structures under specific conditions, which shows significant potential applications in optical and biological fields. In this study, sodium hexametaphosphate (SHMP) was employed as a stabilizer to prepare polymer spherulite-like patterns via the evaporation-induced self-assembly (EISA) technique. The incorporation of SHMP enhanced the repulsion force among the nanotubes and the surface potential, which facilitated the orderly deposition of HNTs. The influence of HNT concentration, SHMP concentration, drying temperature, and substrate on the polymer spherulites-like pattern has been investigated in detail. The optimal conditions were 10 wt % HNT dispersion, 0.6 wt % SHMP concentration, 30 °C as drying temperature, and glass substrates. In addition, by changing the droplet volume and shape of the three-phase contact line, patterns of different sizes and shapes can be achieved. Bovine serum albumin or metal salt compounds were incorporated into the dispersion of SHMP-modified HNTs, which altered the charge and the self-assembled patterns with different area ratios. Thus, this technology can be utilized for the analysis and comparison of protein and metal ion concentration accurately. This study creates the correlation between the structural parameters and the preparation process involved in creating polymer spherulite-like patterns of modified HNTs and offers fresh insights into potential applications for the self-assembly of HNT droplets in the realms of anticounterfeiting and solution concentration analysis.

Micropatterning of biological surfaces performed via assembly of nano-blocks is an efficient design method for functional materials with complex organic-inorganic architecture. Halloysite clay nanotubes with high aspect ratios and empty lumens have attracted widespread interest for aligned biocompatible composite production. Here, we give our vision of advances in interfacial self-assembly techniques for these natural nanotubes. Highly ordered micropatterns of halloysite, such as coffee rings, regular strips, and concentric circles, can be obtained through high-temperature evaporation-induced self-assembly in a confined space and shear-force brush-induced orientation. Assembly of these clay nanotubes on biological surfaces, including the coating of human or animal hair, wool, and cotton, was generalized with the indication of common features. Halloysite-coated microfibers promise new approaches in cotton and hair dyeing, medical hemostasis, and flame-retardant tissue applications. An interfacial halloysite assembly on oil microdroplets (Pickering emulsion) and its core-shell structure (functionalization with quantum dots) was described in comparison with microfiber nanoclay coatings. In addition to being abundantly available in nature, halloysite is also biosafe, which makes its spontaneous surface micropatterning prospective for high-performance materials, and it is a promising technique with potential for an industrial scale-up., Competing Interests: No potential conflict of interest was reported by the author(s)., (© 2024 The Author(s). Published by National Institute for Materials Science in partnership with Taylor & Francis Group.)

A hyperbranched ion-imprinted polymer (IIP) material containing multiple selective adsorption sites was synthesized using halloysite nanotubes, methyl acrylate, and ethylenediamine in the presence of a template ion [i.e. Cd (II) heavy metal]. The successful preparation of the Cd-IIP composition was confirmed by FT-IR, XRD, TEM, TGA, and elemental analysis. The polymers exhibited good adsorption of Cd (II) with a maximum adsorption capacity of 64.37 mg·g -1 . The imprinting factor (α) for Cd (II) was 2.62 and the selection factor (β) was 1.78, indicating a specific adsorption of Cd (II) ion. The selection coefficients of Cd-IIP for Cd (II)/Pb (II), Cd (II)/Cu (II), Cd (II)/Ni (II), Cd (II)/Cr (III), and Cd (II)/Na (I) also indicated an excellent selectivity of the hyperbranched polymers for Cd (II) in the presence of competitive ions. The removal efficiency remained more than 75% after five cycles of desorption/adsorption. We envision that the HNTs based Cd-IIP has promising applications in the removal of Cd (II) from wastewater., (© TÜBİTAK.)

Copper-based Fenton-like agents have the ability to convert weakly oxidizing H 2 O 2 into highly oxidizing hydroxyl radicals (·OH) at tumor sites during chemodynamic therapy (CDT). In this study, the interfacial attraction properties between the negatively charged OCP - in sodium phosphathynolate (NaOCP) and the positively charged environment inside the lumen of halloysite nanotubes (HNTs) were utilized to synthesize Cu 3-x P nanoparticles in situ within the HNTs. The study investigated the chemical composition, morphology, and structure of Cu 3-x P@HNTs. The results indicated uniform distribution of Cu 3-x P particles measuring 3-5 nm within HNTs' lumen. Experiments conducted internally and externally to cells confirmed the catalytic capability of Cu 3-x P@HNTs to oxidize H 2 O 2 to ·OH. Furthermore, CP@H-CM was synthesized by enclosing Cu 3-x P@HNTs in a cancer cell membrane, which selectively targets cancer cells. The experiments revealed the cytotoxicity of CP@H-CM on 4T1 cells. Additionally, the antitumor efficacy of CP@H-CM was evaluated in vivo through tumor recurrence experiments in mice. Moreover, the efficacy of CP@H-CM in repressing tumor growth was enhanced by incorporating infrared laser, indicating a synergistic photodynamic treatment for breast cancer. This study presents an efficacious and viable therapeutic approach to inhibit postoperative tumor reappearance. The implications of this approach are promising, particularly in the domain of tumor treatment and metastasis., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

The paper presents the colloidal and thermal stability of the three-component hybrid materials containing halloysite, polysaccharides (alginic acid, cationic cellulose and hydroxyethyl cellulose) and Tritons. TX-100, TX-165 and TX-405 were used as non-ionic surfactants. Stability and other properties of the hybrid materials were tested by the following methods: UV-Vis, TGA (thermogravimetric analysis) and DSC (differential scanning calorimetry), CHN (elemental analysis), SEM-EDX (scanning electron microscopy with energy dispersive X-ray spectroscopy) and tensiometry. According to the results with the increasing polymer concentration the colloidal stability of the tested systems also increases. Moreover, the addition of the surfactants causes the increase of polysaccharide adsorption but the colloidal stability of the tested systems decreases due to large weights of formed aggregates. As follows from the thermal analysis, the comparison of the TG/DTG-DSC curves obtained for the investigated polymers confirms that their thermal decomposition courses have some common features. The obtained results have the application potential in the formation of the materials for the pollutants removal from water and sewages., (© 2023 Wiley-VCH GmbH.)

The present paper describes the preparation and characterization of novel microbeads from alginate filled with nanoclay such as halloysite nanotubes (HNTs). HNTs were used as support for the growth of layered double hydroxide (LDH) crystals producing a flower-like structure (HNT@LDH). Such nanofiller was loaded with grapefruit seed oil (GO), an active compound with antimicrobial activity, up to 50% wt. For comparison, the beads were also loaded with HNT and LDH separately, and filled with the same amount of GO. The characterization of the filler was performed using XRD and ATR spectroscopy. The beads were analyzed through XRD, TGA, ATR and SEM. The functional properties of the beads, as nanocarriers of the active compound, were investigated using UV-vis spectroscopy. The release kinetics were recorded and modelled as a function of the structural characteristics of the nanofiller.

The removal of impurity Al(III) from rare earth ion solution by selective adsorption method was one of the challenging tasks. Herein, calcination and acid dissolution treatment were used to construct the pore structure for the halloysite substrate (Hal-650-H) and provide conditions for the formation of the chitosan mesoporous membrane to prepare composite (Hal-H-2CS). The selective adsorption properties and mechanism of the Hal-H-2CS for Al(III) in the rare earth ion solution were studied. The results showed that the formation of mesoporous structures for chitosan provided abundant sites for the adsorption of Al(III). Hal-H-2CS showed remarkable selective adsorption properties for Al(III) in a wide pH range and the binary mixtures with high content of Al(III) or La(III). The maximum adsorption capacity of Al(III) was 106 mg/g, while the adsorption capacity of La(III) was only 1.41 mg/g at pH 4.0. In addition, the Hal-H-2CS exhibited excellent regeneration and structural stability. The remarkable selective properties of Hal-H-2CS was achieved by the synergistic effect between chitosan mesoporous membrane and Hal-650-H, the main adsorption sites were the OH, NH 2 , CONH 2 of chitosan and the oxygen sites of the Hal-650-H. This work provides a new strategy for the design and preparation of outstanding selective adsorbent for Al(III)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Hydrogels are characterized by their property of absorbing and releasing a high content of water and water-based liquids; thus, they can be applied in agriculture as controlled-release water and fertilizer products. The focus of this research was efficient and low-cost natural polymer-based hydrogels obtained by crosslinking gellan gum (GGLA) and starch (ST) with acetic acid (CA) and loading them with either bentonite (BET) and/or halloysite (HAL). The hydrogels were obtained by mixing 100, 75, 50, 25, and 0 wt.% of GGLA with 0, 25, 50, 75, and 100 wt.% ST water solutions. To obtain the networks, they were crosslinked with 10, 5, and 2 wt.% of CA and loaded with 2, 5, and 10 wt.% of BET and/or HAL. The samples were analyzed by infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), their swelling in water, and the state of bound water properties. The results of these analyses point to the formation of a polymeric network with a decomposition temperature of >250 °C, and tailorable swelling properties that vary between 3 and 77, depending on the hydrogel composition. In summary, GGLA-ST-BET/HAL hydrogels are a good option for eco-friendly agriculture materials., Competing Interests: The authors declare no conflicts of interest.

Chickpea flour is an affordable natural blend of starch, proteins, and lipids, which can create films with suitable properties as an eco-friendly packaging material. Nanoclays' incorporation into natural biopolymers enhances the barrier properties of the resulting nanocomposites, so they could improve the properties of flour films. The objective of this work was to assess the influence of three types of nanoclays (halloysite, bentonite, and Cloisite 20A) at two concentrations on the characteristics of chickpea flour films. In general terms, when the lowest dose (5%) was added, no or very slight significant differences with the control were observed in most parameters, except for thermal stability and opacity, which increased, and solubility, which decreased. At the highest concentration (10%), films containing any of the nanoclays demonstrated greater thermal stability, opacity, and rigidity while being less soluble than those without nanofillers. Bentonite exhibited superior film structure distribution compared to other nanoclays. At the highest concentration, it had the most significant impact on modifying the properties of chickpea flour films, increasing their tensile and puncture strengths while decreasing elasticity and water vapor permeability. The incorporation of nanoclays into chickpea flour films could be a useful technique to enhance their properties.

Urea is a common milk adulterant that falsely increases its protein content. Excessive consumption of urea is harmful to the kidney, liver, and gastrointestinal system. The conventional methods for urea detection in milk are time-consuming, costly, and require highly skilled operators. So, there is an increasing demand for the development of rapid, convenient, and cost-efficient methods for the detection of urea adulteration in milk. Herein, we report a novel colorimetric paper-based urea biosensor, consisting of a novel environment-friendly nanocomposite of halloysite nanotubes (HNT), that urease enzyme and an anthocyanin-rich extract, as a natural pH indicator are simultaneously immobilized into its internal and external surfaces. The biosensing mechanism of this biosensor is based on anthocyanin color change, which occurs due to urease-mediated hydrolysis of urea and pH increment of the environment. The colorimetric signal of this biosensor is measured through smartphone-assisted analysis of the mean RGB (Red-Green-Blue) intensity of samples and is capable of detecting urea with a detection limit of 0.2 mM, and a linear range from 0.5 to 100 mM. This biosensor has demonstrated promising results for the detection of urea in milk samples, in the presence of other milk adulterants and interferents., Competing Interests: Declaration of competing interest The authors declare that they do not have any competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

In recent years, the coagulation properties of inorganic minerals such as kaolin and zeolite have been demonstrated. This study aimed to assess the hemostatic properties of three local clays from China: natural kaolin from Hainan, natural halloysite from Yunnan, and zeolite synthesized by our group. The physical and chemical properties, blood coagulation performance, and cell biocompatibility of the three materials were tested. The studied materials were characterized by using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). All three clays showed different morphologies and particle size, and exhibited negative potentials between pH 6 and 8. The TGA and DSC curves for kaolin and halloysite were highly similar. Kaolin showed the highest water absorption capacity (approximately 93.8% ± 0.8%). All three clays were noncytotoxic toward L929 mouse fibroblasts. Kaolin and halloysite showed blood coagulation effects similar to that exhibited by zeolite, indicating that kaolin and halloysite are promising alternative hemostatic materials.

This study reports on the development of nanocomposites utilizing a mineral inhibitor and a micronutrient filler. The objective was to produce a slow release fertilizer, with zinc sulfate as the filler and halloysite nanotubes as the inhibitor. The study seeks to chemically activate the intercalation of zinc into the macro-, meso-, and micropores of the halloysite nanotubes to enhance their performance. As a result, we obtained three nanocomposites in zinc sulfate solution with concentrations of 2%, 20%, and 40%, respectively, which we named Hly-7Å-Zn2, Hly-7Å-Zn20, and Hly-7Å-Zn40. We investigated the encapsulation of zinc sulfate in halloysite nanotubes using X-ray diffraction analysis, transmission electron spectroscopy, infrared spectroscopy (FTIR), and scanning electron microscopy with an energy-dispersive spectrometer. No significant changes were observed in the initial mineral parameters when exposed to a zinc solution with a concentration of 2 mol%. It was proven that zinc was weakly intercalated in the micropore space of the halloysite through the increase in its interlayer distance from 7.2 to 7.4. With an increase in the concentration of the reacted solution, the average diameter of the nanotubes increased from 96 nm to 129 nm, indicating that the macropore space of the nanotubes, also known as the "site", was filled. The activated nanocomposites exhibit a maximum fixed content of adsorbed zinc on the nanotube surface of 1.4 wt%. The TEM images reveal an opaque appearance in the middle section of the nanotubes. S SEM images revealed strong adhesion of halloysite nanotubes to plant tissues. This property guarantees prolonged retention of the fertilizer on the plant surface and its resistance to leaching through irrigation or rainwater. Surface spraying of halloysite nanotubes offers accurate delivery of zinc to plants and prevents soil and groundwater contamination, rendering this fertilizer ecologically sound. The suggested approach of activating halloysite with a zinc solution appears to be a possible route forward, with potential for the production of tailored fertilizers in the days ahead.

The design and development of nanomaterials capable of penetrate cancer cells is fundamental when anticancer therapy is involved. The use of collagenase (Col) is useful since this enzyme can degrade collagen, mainly present in the tumor extracellular matrix. However, its use is often limited since collagenase suffers from inactivation and short half-life. Use of recombinant ultrapure collagenase or carrier systems for their delivery are among the strategies adopted to increase the enzyme stability. Herein, based on the more stability showed by recombinant enzymes and the possibility to use them in anticancer therapy, we propose a novel strategy to further increase their stability by using halloysite nanotubes (HNTs) as carrier. ColG and ColH were supramolecularly loaded onto HNTs and used as fillers for Veegum gels. The systems could be used for potential local administration of collagenases for solid tumor treatment. All techniques adopted for characterization showed that halloysite interacts with collagenases in different ways depending with the Col considered. Furthermore, the hydrogels showed a very slow release of the collagenases within 24 h. Finally, biological assays were performed by studying the digestion of a type-I collagen matrix highlighting that once released the Col still possessed some activity. Thus we developed carrier systems that could further increase the high recombinant collagenases stability, preventing their inactivation in future in vivo applications for potential local tumor treatment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Graphitic carbon nitride (g-C 3 N 4 ) has drawn extensive attention with some features including visible-light response as non-metallic semiconductor, low cost in raw material and green pollution-free for environment, but suffers from some issues such as fast charge carriers' recombination, easy aggregation, etc. In this work, the 1D-2D HNTs&g-C 3 N 4 -X binary materials similar to meat floss pattern in a series of halloysite loading amounts are designed via a facile electrostatic self-assembly strategy with debris g-C 3 N 4 after cell pulverizing treatment and HNTs that outwardly modified by cetyltrimethylammonium bromide (CTAB) as the building blocks. The halloysite-mediated satellite-core material displays a photocatalytic of H 2 evolution performance with the highest evolution rate of 137.0 μmol g -1  h -1 in visible light condition with no co-catalysts, and is ∼3.4 times that of bulk g-C 3 N 4 , mainly benefiting from the reduced nanometer size of debris g-C 3 N 4 and enhanced interface dispersion ability by HNTs, resulting in ameliorative separation efficiency of photogenerated charge carriers. This research conclusively provides the new perspective towards the performance enhancement of water splitting of g-C 3 N 4 in raw clay mineral modification mode and broadens the applications of mineral-based composite in the renewable energy utilization field., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

In this study, we utilized low-cost halloysite (Hal) for the first time to enhance the solid-phase enrichment and stability of heavy metals (HMs) during solid waste pyrolysis through experimental and theoretical methods, and compared with kaolinite (Kao). Experimental results demonstrated that Hal was superior to Kao in improving the solid-phase enrichment of HMs. Specifically, the solid-phase enrichment of Cd increased by 32.6 % (500 °C) and 25.94 % (600 °C), while that of Pb and Zn increased by 17.37 %/16.83 % and 19.82 %/22.37 % (700/800 °C), respectively. Adding Hal reduced the proportion of HMs in the unstable fraction (F1 + F2), consequently lowering the environmental risk of biochar and the extractable state of HMs. Through Grand canonical Monte Carlo and Density Functional Theory (DFT) simulations, we analyzed the adsorption amounts, adsorption sites, and adsorption mechanisms of Cd/Pb compound on Hal/Kao surfaces, revealing that the primary factor influencing the adsorption performance of Hal and Kao was the difference in specific surface area. The adsorption amounts of HMs by Hal were significantly higher than Kao and decreased with increasing temperature, while the difference in adsorption performance caused by structural bending was negligible. The DFT results indicated that Cd and Pb monomers were stabilized by establishing covalent bonds with OH or reactive O atoms on the Al-(001) surface, whereas the covalent bonds with ionic bonding properties formed between Cl atoms and unsaturated Al atoms played a crucial role in stabilizing HM chlorides. Furthermore, the adsorption energy of Hal on HMs increased with the removal rate of OH. Our study highlights the potential of Hal in stabilizing HMs during pyrolysis without requiring any modifications, thereby avoiding the generation of modified waste solutions and unnecessary cost loss., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Corrosion is one of the major issues for sustainable manufacturing globally. The annual global cost of corrosion is US$2.5 trillion (approximately 3.4% of the world's GDP). The traditional ways of corrosion protection (such as barriers or inhibiting) are either not very effective (in the case of barrier protection) or excessively expensive (inhibiting). Here, we demonstrate a concept of nanoreactors, which are able to controllably release or adsorb protons or hydroxides directly on corrosion sites, hence, selectively regulating the corrosion reactions. A single nanoreactor comprises a nanocompartment wrapped around by a pH-sensing membrane represented, respectively, by a halloysite nanotube and a graphene oxide/polyamine envelope. A nanoreactor response is determined by the change of a signaling pH on a given corrosion site. The nanoreactors are self-assembled and suitable for mass-line production. The concept creates sustainable technology for developing smart anticorrosion coatings, which are nontoxic, selective, and inexpensive.

A novel type of PEG-modified halloysite was prepared and used as a hydrophilic interaction and cation exchange mixed-mode sorbent for solid-phase extraction of biogenic amines in fish samples. The eluates were analyzed by high-performance liquid chromatography-ultraviolet detection after the derivatization with benzoyl chloride. The developed sorbent was characterized by scanning electron microscopy, infrared spectroscopy, X-ray diffraction, zeta potential analyzer, and thermo-gravimetric analysis. After the optimization of various parameters influencing the extraction efficiency, the PEG-modified halloysite-based SPE method was evaluated. The adsorption capacities of putrescine, spermine, phenethylamine, and histamine were as high as 9.3, 8.5, 5.7, and 5.6 mg g -1 , respectively. Satisfactory reproducibility of sorbent preparation was obtained with within-batch and batch-to-batch relative standard deviations (RSDs) lower than 3.9% and 8.6%, respectively. The biogenic amine spiking recoveries in fish samples ranged from 84.3 to 105.5% with good RSDs lower than 7.8%. Intra-day and inter-day precision, expressed as RSDs, were better than 8.8%. The limits of detection of histamine, putrescine, phenethylamine, and spermine were 9.4, 1.9, 0.5, and 0.9 μg L -1 , respectively. This work provides a new hydrophilic interaction and cation exchange mixed-mode sorbent and is successfully applied to the extraction of trace biogenic amines from fish samples., (© 2022. Springer-Verlag GmbH Germany, part of Springer Nature.)

The blood-brain barrier (BBB) is an obstacle to the permeation of most therapeutic drugs into the brain, limiting treatments for neurological disorders. Drugs loaded within nanocarriers that pass through the BBB can overcome this limitation. Halloysite consists of naturally occurring biocompatible clay nanotubes of 50 nm diameter and 15 nm lumen, allowing the loading and sustained release of loaded drugs. These have demonstrated the ability to transport loaded molecules into cells and organs. We propose to use halloysite nanotubes as a "nano-torpedo" for drug delivery through the BBB due to their needle-like shape. To determine if they can cross the BBB using a non-invasive, clinically translatable route of administration, we loaded halloysite with either diazepam or xylazine and delivered these intranasally to mice daily over six days. The sedative effects of these drugs were observed in vestibulomotor tests conducted at two, five, and seven days after the initial administration. Behavioral tests were conducted 3.5 h after administration to show that the effects were from halloysite/delivered drugs and not from the drug alone. As expected, the treated mice performed more poorly than the sham, drug alone, and halloysite-vehicle-treated mice. These results confirm that halloysite permeates the BBB to deliver drugs when administered intranasally.

Uncontrolled massive hemorrhage is a crucial cause of death, and developing efficient hemostatic materials are of great medical importance. Herein, we prepared a halloysite-chitosan-collagen composite sponge by directional freeze-drying method and coated the sponge with hydrophobic polydimethylsiloxane coating for rapid and effective hemostasis. The aligned channel structure of the sponge with a pore size of ~30 μm was beneficial for the transport of blood. Morphology and spectrum results suggested that chitosan and collagen are capable of adsorbing on the outer surface of HNTs due to the hydrogen bonding and electrostatic attractions. The directional freeze-dried sponge absorbed the majority of the blood within 10 s, and that process essentially was completed in 30 s, which are faster than its non-directional counterpart. The composite sponges exhibited high antibacterial properties towards E. coli and S. aureus, and they are non-cytotoxic towards mouse fibroblasts and have high hemocompatibility. The hemostatic dressing avoided unnecessary blood loss because of excessive blood absorption. In vivo experiments of rats also confirmed the ability of the asymmetric sponges to rapidly clot and reduce reducing blood loss. This work developed a high-performance and hemostatic dressing by material design and processing technique, which shows a promising application in wound healing., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Constructing a system to carry medicine for more effective remedy of cancer has been a leading challenge, as the number of cancer cases continues to increase. In this present research, a curcumin-loaded chitosan/halloysite/carbon nanotube nanomixture was fabricated by means of water/oil/water emulsification method. The drug loading efficiency (DL) and entrapment efficiency (EE), as a result, reached 42 % and 88 %, respectively and FTIR and XRD analysis confirmed the bonding between the drug and nanocarrier. Morphological observation through FE-SEM and characterization through DLS analysis demonstrated that the average size of nanoparticles is 267.37 nm. Assessment of release within 96 h in pH 7.4 and 5.4 showed sustained release. For more investigation, release data was analyzed by diverse kinetic models to understand the mechanism in the release procedure. An MTT assay was also carried out, and the results illustrated apoptosis induction on MCF-7 cells and exhibited ameliorated cytotoxicity of the drug-loaded nanocomposite compared to the free curcumin. These findings suggest that the unique pH-responsive chitosan/halloysite/carbon nanotube nanocomposite might make a good option for drug delivery systems, particularly for the cancer treatment., Competing Interests: Declaration of competing interest The authors declare that there is no conflict of interest., (Copyright © 2023. Published by Elsevier B.V.)

Halloysite nanotubes (HNTs) are clay minerals with a tubular structure that can be used for many different applications in place of carbon nanotubes. Indeed, HNTs display low/non-toxicity, are biocompatible, and can be easily prepared. Moreover, the aluminum and silica groups present on HNTs' inner and outer surfaces facilitate the interaction with various functional agents, such as alkalis, organosilanes, polymers, surfactants, and nanomaterials. This allows the deposition of different materials, for instance, metal and non-metal oxides, on different substrate types. This review article first briefly presents HNTs' general structure and the various applications described in the last 20 years (e.g., drug delivery, medical implants, and energy storage). Then, it discusses in detail HNT applications for water purification (inorganic and organic pollutants). It focuses particularly on HNT-TiO 2 composites that are considered very promising photocatalysts due to their high specific surface area and adsorption capacity, large pore volume, good stability, and mechanical features.

Clay minerals are historically among the most used materials with a wide variety of applications. In pharmaceutical and biomedical fields, their healing properties have always been known and used in pelotherapy and therefore attractive for their potential. In recent decades, the research has therefore focused on the systematic investigation of these properties. This review aims to describe the most relevant and recent uses of clays in the pharmaceutical and biomedical field, especially for drug delivery and tissue engineering purposes. Clay minerals, which are biocompatible and non-toxic materials, can act as carriers for active ingredients while controlling their release and increasing their bioavailability. Moreover, the combination of clays and polymers is useful as it can improve the mechanical and thermal properties of polymers, as well as induce cell adhesion and proliferation. Different types of clays, both of natural (such as montmorillonite and halloysite) and synthetic origin (layered double hydroxides and zeolites), were considered in order to compare them and to assess their advantages and different uses.

The application of amorphous ferrihydrite (Fh) for Cd(II) removal is restricted by its unstable and easily transformable nature. Although doping with silicates stabilized ferrihydrite, its product siliceous ferrihydrite (SiFh) again suffered from the disadvantage of spontaneous agglomeration. Herein, ferrihydrite was hybridized with halloysite nanotubes (HNTs) to prepare a novel siliceous ferrihydrite - coated halloysite nanorods (SiFh@HNTs) in alkaline medium, to break through the current barriers. The characterization results showed that SiFh@HNTs could simultaneously overcome the defects of easy phase transformation of ferrihydrite and easy aggregation of SiFh nanoparticles (NPs). Meanwhile, the optimal SiFh@HNT 40 with halloysite content of 40 % formed a well-developed mesoporous structure and exhibited the desired surface properties: a high specific surface area of 303.4 m 2 /g, an isoelectric point as low as pH iep  = 4.5, and rich functional Fe - OH groups. The formation mechanism of such excellent sturcture-properties of SiFh@HNT 40 were mainly attributed to two factors: the generation of smaller (∼5 nm) SiFh NPs induced by the integration of halloysite-derived SiO 4 4- for Cd(II) was up to 137.8 mg/g at 30 °C and pH 6, which was much higher than that of aggregated ferrihydrite (11.2 mg/g), halloysite (18.8 mg/g) and goethite (49.4 mg/g). The adsorption thermodynamics study revealed the adsorption of Cd(II) on SiFh@HNT 40 for Cd(II) was up to 137.8 mg/g at 30 °C and pH 6, which was much higher than that of aggregated ferrihydrite (11.2 mg/g), halloysite (18.8 mg/g) and goethite (49.4 mg/g). The adsorption thermodynamics study revealed the adsorption of Cd(II) on SiFh@HNT 40 was clearly chemisorption with a (ΔH ads ) q of 43.3 kJ/mol. Characterization results of XPS and FTIR confirmed that the rich Fe - OH groups on SiFh@HNT 40 was the main adsorption sites, and Cd(II) was specifically adsorbed by inner-sphere surface complexation. In addition, SiFh@HNT 40 had application potential in the mixed-metal wastewaters treatment. Cyclic regeneration experiments showed that SiFh@HNT 40 had good regeneration performance and could be reused many times., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

The healing process of chronic wounds continues to be a current clinical challenge, worsened by the risk of microbial infections and bacterial resistance to the most frequent antibiotics. In this work, non-antibiotic nanohybrids based on chlorhexidine dihydrochloride and clay minerals have been developed in order to design advanced therapeutic systems aimed to enhance wound healing in chronic lesions. To prepare the nanohybrids, two methodologies have been compared: the intercalation solution procedure and the spray-drying technique, the latter as a one-step process able to reduce preparation times. Nanohybrids were then fully studied by solid state characterization techniques. Computational calculations were also performed to assess the interactions between the drug and the clays at the molecular level. In vitro human fibroblast biocompatibility and antimicrobial activity against Staphylococcus aureus and Pseudomonas aeruginosa were assessed to check biocompatibility and potential microbicidal effects of the obtained nanomaterials. The results demonstrated the effective organic/inorganic character of the nanohybrids with homogeneous drug distribution into the clayey structures, which had been confirmed by classical mechanics calculations. Good biocompatibility and microbicidal effects were also observed, especially for the spray-dried nanohybrids. It was suggested that it could be due to a greater contact area with target cells and bacterial suspensions.

Nanotechnology has been comprehensively applied as a new approach to managing wound healing. Particularly, nanoclays are being used to improve traditional wound healing approaches or new therapies. Nanoclays are nanoscale aluminosilicates with remarkable intrinsic properties, including the capacity to promote hemostatic response, anti-inflammatory effects, angiogenesis, and re-epithelization. The main purpose of the present review is focusing on skin lesions, post-surgical wounds, burn wounds, and chronic ulcer skin wounds that can be treated using nanoclays, not only as vehicles for therapeutic molecules' efficacy improvement but also alone due to their native beneficial features. A systematic search of the PubMed, ScienceDirect, Scopus, Web of Science, and Google Scholar databases revealed several studies satisfying the purpose of our study. In addition, the selected keywords were used to refine the information. Non-planar hydrous phyllosilicates have been compared with other nanoclays considering their acute specific surface area and loading capacity are strongly influenced by their structure. Nanocomposites in the powder form may be directly incorporated in polymers to form gels, biofilms, and scaffolds that may be adjustable to wound sites. Also, nanoclays can be directly incorporated into polymer mats. Regarding hydrogels/films and mats, nanoclays can improve their mechanical strength, thermal stability, viscosity, and cohesive strength. Additionally, nanoclays are able to control drug release, as well as their skin bioavailability, and seem to be promising candidates to overcome cytotoxicity problems; further in vivo toxicity studies are required., (© 2022. Controlled Release Society.)

In this work, a green and cost-effective method based on halloysite as natural catalyst for the synthesis of α-amino nitriles via Strecker three-component reaction is introduced. The chemical and physical structure of natural halloysite has characterized thoroughly, and then the effect of different parameters such as the amount of catalyst, solvent, and temperature was optimized in the synthesis of 2-phenyl-2-(phenylamino)acetonitrile as the model reaction. Then, various substituted benzaldehydes and anilines were converted to the desired α-amino nitriles under the optimized conditions. Electronic properties of substituents on aldehydes and aromatic amines have been affected the reaction efficiency. For all substrates, good to excellent yields of the corresponding α-amino nitriles were obtained under solvent-free conditions at room temperature. The catalyst has been recovered and reused five times in successive Strecker reaction., (© 2022. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Potato thermoplastic starch (TPS) containing 1 wt.% of pure halloysite (HNT), glycerol-modified halloysite (G-HNT) or polyester plasticizer-modified halloysite (PP-HNT) was prepared by melt-extrusion. Halloysites were characterized by FTIR, SEM, TGA, and DSC. Interactions between TPS and halloysites were studied by FTIR, SEM, and DMTA. The Vicat softening temperature, tensile, and flexural properties were also determined. FTIR proved the interactions between halloysite and the organic compound as well as between starch, plasticizers and halloysites. Pure HNT had the best thermal stability, but PP-HNT showed better thermal stability than G-HNT. The addition of HNT and G-HNT improved the TPS's thermal stability, as evidenced by significantly higher T 5% . Modified TPS showed higher a Vicat softening point, suggesting better hot water resistance. Halloysite improved TPS stiffness due to higher storage modulus. However, TPS/PP-HNT had the lowest stiffness, and TPS/HNT the highest. Halloysite increased T α and lowered T β due to its simultaneous reinforcing and plasticizing effect. TPS/HNT showed an additional β-relaxation peak, suggesting the formation of a new crystalline phase. The mechanical properties of TPS were also improved in the presence of both pure and modified halloysites.

Nanocomposite hydrogels based on tyramine conjugated gum tragacanth, poly (vinyl alcohol) (PVA), and halloysite nanotubes (HNTs) were prepared by electron beam irradiation and characterized. The FTIR, 1 H NMR, and TGA results confirmed the chemical incorporation of HNTs into gum tragacanth. Gel content and swelling of hydrogels decreased with HNTs loading up to 20 % wt. The mechanical strength of hydrogels increased by increasing HNTs content up to 10 % with 371 kPa fracture stress at 0.95 fracture strain, compared to 312 kPa stress at 0.79 strain for gum tragacanth/PVA hydrogel. Hydrogel's biocompatibility and osteogenic activity were tested by seeding rabbit bone marrow mesenchymal stem cells. The cell viability was >85 % after 7 days of culture. In vitro secretion of ALP and calcium deposition on hydrogels in alizarin red assay after 21 days of culture indicated hydrogel potential for bone tissue engineering., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Ebrahim Vasheghani-Farahani reports financial support was provided by Iran National Science Foundation (INSF) with grant number 96004459., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Halloysite particles, with their unique multilayer nanostructure, are demonstrated here as highly efficient and readily available sorbent of heavy metals that can be easily scaled up and used in large-scale water remediation facilities. The various methods of raw material purification were applied, and their effects were verified using techniques such as BET isotherm (determination of specific surface area and size of pores), XRF analysis (composition), and SEM imaging (determination of morphology). A series of adsorption experiments for aqueous solutions of metal ions (i.e., lead, cadmium) were carried out to quantify the sorption capacity of halloysite particles for selected heavy metals. The ability of adequately activated halloysite to efficiently remove heavy metal ions from water solutions was confirmed. The value of the zeta potential of raw and purified halloysite particles in water was determined. This enables us to understand its importance for the sorption of positively charged ions (metal, organics) at various pH values. The adsorption process conducted in the pH range of 6.0-6.5 showed significant improvement compared to the acidic conditions (pH value 3.0-3.5) and resulted in a high sorption capacity of lead ions-above 24.3 mg/g for the sulphuric acid-treated sample. The atomic scale ab initio calculations revealed a significant difference in adsorption energy between the external siloxane surface and cross-sectional interlayer surface, resulting in pronounced adsorption anisotropy. A low energy barrier was calculated for the interlayer migration of heavy metals into the halloysite interior, facilitating access to the active sites in these regions, thus significantly increasing the sorption capacity and kinetics. DFT (density functional theory) calculations supporting this study allowed for predicting the sorption potential of pure halloysite structure towards heavy metals. To confront it with experimental results, it was crucial to determine proper purification conditions to obtain such a developed structure from the mineral ore. The results show a massive increase in the BET area and confirm a high sorption potential of modified halloysite towards heavy metals.