Tensile modulus of polymer halloysite nanotubes nanocomposites assuming stress transferring through an imperfect interphase.

In this work, Hui-Shia model is developed to reveal the efficiency of a deficient interphase on the tensile modulus of polymer halloysite nanotube (HNT) nanocomposites. "Lc" as essential HNT length providing full stress transferring is defined and effective HNT size, effective HNT concentration, and efficiency of stress transferring (Q) are expressed by "Lc". Furthermore, the influences of all terms on the "Q" and nanocomposite's modulus are clarified, and also the calculations of the model are linked to the tested data of some nanocomposites. Original Hui-Shia model overpredicts the moduli, but the innovative model's predictions appropriately fit the measured data. Lc = 200 nm maximizes the sample's modulus to 2.6 GPa, but the modulus reduces to 2.11 GPa at Lc = 700 nm. Therefore, there is a reverse relation between the sample's modulus and "Lc". Q = 0.5 produces the system's modulus of 2.1 GPa, while the modulus of 2.35 GPa is achieved at Q = 1 providing a direct relation between the nanocomposite's modulus and "Q". Generally, narrow and big HNTs, along with a low "Lc", enhance the "Q", because a lower "Lc", reveals a tougher interphase improving the stress transferring.

Flame-Resistant Inorganic Films by Self-Assembly of Clay Nanotubes and their Conversion to Geopolymer for CO2 Capture.

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 CO2 capture. As compared to the corresponding inorganic film, the CO2 adsorption efficiency is doubled for the halloysite geopolymeric materials highlighting their potential use as a sorbent.

Development of Halloysite Nanohybrids-Based Films: Enhancing Mechanical and Hydrophilic Properties for Wound Healing.

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.

Dispersion of halloysite nanotube/lipase nanohybrids as nanofillers into polyvinyl alcohol-sodium alginate cryogel: Characterization and bio-catalytic activity analysis.

The purpose of this study is to formulate and characterize the cryogels containing halloysite nanotube (HNT)/lipase nanohybrid (NH-cryogel) in comparison to pure cryogels as well as cryogels containing lipase (lipase-cryogel). The cryogels were synthesized using polyvinyl alcohol (PVA) and sodium alginate (SA). The products are tested to explore the influence of the HNT/lipase nanohybride (NH) as nanofillers on the cryogel properties using methods such as swelling degree, water uptake measurement, TGA, XRD, FESEM and FTIR. Additionally, the effects of cryogels on the stability and biocatalytic activities of lipase and NH, were studied and compared to the free lipase to evaluate their potential applications as enzyme carriers. The addition of nanofillers into the cryogel improved is thermal stability. The results implied that NH-cryogel had better enzyme activity than lipase-cryogel and free lipase at different temperatures and pH values. The NH-cryogel residual activity was 85.5 % after ten cycles of reuse while lipase-cryogel showed lower residual activity (60.3 %). Furthermore, the NH-cryogel retained 81.1 % of its residual activity while this was 51.0 % for lipase-cryogel after thirty days of storage. Therefore, the presented results in this study provide a pathway to show that produced nano-composite cryogels could be useful substances for food and pharmaceutical industries applications.

A novel technique including two steps for modulus prediction in polymer halloysite nanotube composites.

A two-step methodology has been developed utilizing the models of Paul and Takayanagi to determine the modulus of polymer halloysite nanotube (HNT) products. Initially, HNTs and the adjacent interphase are considered as pseudoparticles, and their modulus is evaluated using the Paul model. Subsequently, the modulus of a nanocomposite, consisting of a polymer medium and pseudoparticles, is predicted by Takayanagi equation. The impacts of various factors on the modulus of the products are analyzed, and the results from the two-step method are compared with experimental data from different samples. It has been observed that the modulus of samples progressively increases with an increase in interphase depth. Also, a higher interphase modulus contributes to an enhanced modulus of samples. Nevertheless, excessively high interphase moduli (Ei > 60 GPa) result in only a marginal improvement in the modulus of nanocomposites. Additionally, narrower HNTs are advantageous for producing stronger samples, though the modulus of the nanocomposites slightly diminishes at very high HNT radii (R > 55 nm). The outputs of two-step method agree with the experimental moduli of various HNT-filled systems.

Effect of Different Porous Size of Porous Inorganic Fillers on the Encapsulation of Rosemary Essential Oil for PLA-Based Active Packaging.

Essential oils are interesting active additives for packaging manufacturing as they can provide the final material with active functionalities. However, they are frequently volatile compounds and can be degraded during plastic processing. In this work Rosmarinus officinalis (RO) essential oil was encapsulated into Diatomaceous earth (DE) microparticles and into Halloysite nanotubes (HNTs) and further used to produce eco-friendly active packaging based on polylactic acid (PLA). PLA-based composites and nanocoposites films based on PLA reinforced with DE + RO and HNTs + RO, respectively, were developed by melt extrusion followed by cast-film, simulating the industrial processing conditions. As these materials are intended as active food packaging films, the obtained materials were fully characterized in terms of their mechanical, thermal and structural properties, while migration of antioxidant RO was also assessed as well as the compostability at laboratory scale level. Both DE and HNTs were able to protect the Rosmarinus officinalis (RO) from thermal degradation during processing, allowing to obtain films with antioxidant properties as demonstrated by the antioxidant assays after the materials were exposed for 10 days to a fatty food simulant. The results showed that incorporating Rosmarinus officinalis encapsulated in either DE or HNTs and the good dispersion of such particles into the PLA matrix strengthened its mechanical performance and sped up the disintegration under composting conditions of PLA, while allowing to obtain films with antioxidant properties of interest as antioxidant active food packaging materials.

Ion-Sieving Separator Functionalized by Natural Mineral Coating toward Ultrastable Zn Metal Anodes.

Aqueous zinc-ion batteries (AZIBs) exhibit promising prospects in becoming large-scale energy storage systems due to environmental friendliness, high security, and low cost. However, the growth of Zn dendrites and side reactions remain heady obstacles for the practical application of AZIBs. To solve these challenges, a functionalized Janus separator is successfully constructed by coating halloysite nanotubes (HNTs) on glass fiber (GF). Impressively, the different electronegativity on the inner and outer surfaces of HNTs endows the HNT-GF separator with ion-sieving property, leading to a significantly high transference number of Zn2+ (tZn2+ = 0.71). Meanwhile, the HNT-GF separator works as an interfacial ion comb to regular Zn2+ flux and realizes multisite progressive nucleation, bringing decreased nucleation overpotential and uniform Zn2+ deposition. Consequently, the HNT-GF separator enables the Zn anode to display an ultralong plating/stripping life of 3000 h and high rate tolerance with a stable long cycle life even under a density of 50 mA cm-2. Moreover, the Zn∥HNT-GF∥MnO2 full cell represents an ultrastable cycling stability with a high capacity retention of 93.4% even after 1000 cycles at a current density of 2 A g-1. This work provides a convenient method for the separator modification of AZIBs.

​Statistical-based optimization and mechanism assessments of Arsenic (III)​ adsorption by ZnO-Halloysite nanocomposite​.

Arsenic contamination in aqueous media is a serious environmental problem, especially in developing countries. In this research, the Box-Behnken response surface methodology was used to optimize the most relevant variables affecting arsenic adsorption on the ZnO-halloysite surface, including temperature, adsorbent dosage, pH, contact time, and As (III) initial concentration. The regression analysis indicated that the experimental data were appropriately fitted to a quadratic model with the adjusted R-squared value (R2) of 0.982 for As(III) adsorption capacity and a linear model with R2 of 0.931 for As(III) removal. The p-values for both adsorption capacity and removal efficiency were below 0.05, with F-values of 116.91 and 115.58, respectively, supporting the model's validity. The optimum conditions for maximum removal of As(III) were determined through numerical and graphical optimization using the desirability function. It was found that the optimum conditions for adsorption were pH = 7.99, contact time of 3.99 h, As(III) initial concentration of 49.96 mg/L, and adsorbent dosage of 0.135 g/40 ml. The accuracy of the optimization procedure was confirmed by a confirmatory experiment, which showed a maximum arsenic removal of 91.31% and an adsorption capacity of 12.63 mg/g under optimized conditions. Moreover, XPS analysis was performed at different pH levels to investigate the As (III) adsorption mechanism. The results demonstrated that As(III) adsorption occurs at acidic and neutral pH levels. On the other hand, when pH is increased to 8, As (III) oxidizes to As (V), and then adsorption occurs.

Halloysite functionalized with dendritic moiety containing vitamin B1 hydrochloride as a bio-based catalyst for the synthesis of 5-hydroxymthylfurfural.

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 ZnCl2 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.

Chitosan-based hydrogel beads with molecularly imprinted receptors on halloysite nanotubes for tetracycline separation in water and soil.

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@MIPa(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@MIPb), containing polymers produced under conditions of significantly higher reagent dilution, was more resistant to higher temperatures than CS_Hal@MIPa. The adsorptive properties were compared with pure CS beads, those containing incorporated Hal, and free polymers obtained by different protocols (MIPa(b)). In the optimized pH 5.0, the maximum adsorption capacities were 175.24 and 178.05 mg g-1 for CS_Hal@MIPa and CS_Hal@MIPb, 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.

Hydrothermal synthesized kaolin group lamellar/spongy aluminosilicates for enhanced lead vapor capture.

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 PbCl2 vapor adsorption, reaching a maximum of 137.68 mg/g at 700 â„ƒ (75.91 % stable). We examined the effect of CO2 and H2O on adsorption efficiency and explored the mechanisms using DFT and GCMC simulations. From GCMC results, CO2 negatively impacted PbCl2 adsorption due to competitive adsorption, while H2O increased adsorption content (144.24 mg/g at 700 â„ƒ) by converting PbCl2 into oxides. DFT revealed the presence of CO2 enhanced the adsorption stability of PbCl2 via the formation of covalent bonds between O in CO2 and Pb, and active O on the aluminosilicate surface. H2O increased PbCl2 adsorption energy, as O in H2O occupied an active Al that originally formed a covalent bond with Cl, while the H formed a weak hydrogen bond with this Cl.

Modification of polymethylmethacrylate bone cement with halloysite clay nanotubes.

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.

Development of alginate film filled with halloysite-carbon dots for active food packaging.

The development of functional bionanocomposites for active food packaging is of current interest to replace non-biodegradable plastic coatings. In the present work, we report the synthesis of an alginate-based nanocomposite filled with modified halloysite nanotubes (HNTs) to develop coatings with improved barrier properties for food packaging. Firstly, HNTs were chemically modified by the introduction of carbon dots units (CDs) onto their external surface (HNTs-CDs) obtaining a nanomaterial where CDs are uniformly present onto the tubes as verified by morphological investigations, with good UV absorption and antioxidant properties. Afterwards, these were dispersed in the alginate matrix to obtain the alginate/HNTs-CDs nanocomposite (Alg/HNTs-CDs) whose morphology was imaged by AFM measurements. The UV and water barrier properties (in terms of moisture content and water vapor permeability) were investigated, and the antioxidant properties were evaluated as well. To confer some antimicrobial properties to the final nanocomposite, the synthetized filler was loaded with a natural extract (E) from M. cisplatensis. Finally, the extract kinetic release both from the filler and from the nanocomposite was studied in a medium mimicking a food simulant and preliminary studies on the effect of Alg/HNTs-CDs/E on coated and uncoated fruits, specifically apples and bananas were also carried out.

All-natural aerogel of nanoclay/cellulose nanofibers with hierarchical porous structure for rapid hemostasis.

Developing an effective and user-friendly hemostatic agent is highly desired in the treatment of hemorrhage. Inspired by the natural nanostructure and abundant hydroxyl groups of cellulose and clay minerals, we designed an aerogel (HNTs/TOCNs) composed of halloysite nanotubes (HNTs) and TEMPO-oxidized cellulose nanofibers (TOCNs) with a hierarchical porous structure for the treatment of bleeding, using a simple and environmentally friendly self-assembly method. TOCNs formed a three-dimensional porous scaffold with excellent water-holding capacity. The incorporation of HNTs enhanced the hemostatic efficiency and mechanical properties of the 3D framework. The large interlayer spaces and wide channels within the HNTs/TOCNs aerogel provided rapid passage for blood, facilitating blood concentration and offering ample room for interactions between the HNTs/TOCNs aerogel and platelets, erythrocytes, and coagulation factors, thereby promoting hemostasis. Benefiting from the natural hemostatic properties and well-designed structure, the HNTs/TOCNs aerogel displayed excellent hemostatic performance both in vitro and in vivo. Notably, the hemostatic time of HNTs/TOCNs-2 was only 74 ± 8 s, which is approximately 50 % shorter than the blank control (151 ± 20 s) in liver femoral artery injury model. This design of an HNTs/TOCNs aerogel presents a unique opportunity to enhance hemostatic efficacy by synergizing the advantages of natural materials.

Halloysite-based inorganic-organic hybrid coatings for durable flame retardant, hydrophobic and antibacterial properties of cotton fabrics.

Developing durable protective cotton fabrics (CF) against potential environmental dangers such as fire hazards and bacterial growth remains an imperative but tough challenge. In this study, flame retardant, antibacterial and hydrophobic CF were successfully prepared via two-step coating. The inner coating entailed polyelectrolyte complexes consisting of polyethyleneimine and ammonium polyphosphate with the goal of enhancing the flame retardancy of CF. Halloysite nanotubes (HNTs), a kind of tubular silicate mineral, were creatively modified and introduced to multifunctional coatings to improve flame retardant and antibacterial properties of CF. N-halamine modified HNTs (HNTs-EA-Cl) and polydimethylsiloxane were applied as the outer coating to endow CF with antibacterial and hydrophobic properties and further improve the flame retardancy of CF. After halloysite-based inorganic-organic hybrid coatings, the limiting oxygen index of the treated samples (PAHP-CF) was over 28 %, and the release of heat and smoke was significantly inhibited. PAHP-CF could inactivate 100 % E. coli and S. aureus within 2 h. More importantly, PAHP-CF showed excellent hydrophobicity with a water contact angle of 148° and exhibited great prevention of bacterial adhesion. PAHP-CF exhibited excellent washing durability undergoing 5 washing cycles. This study promotes the development of multifunctional coatings and offers a new way to manufacture multifunctional cotton fabrics.

Mechanical and Shape Memory Properties of Additively Manufactured Polyurethane (PU)/Halloysite Nanotube (HNT) Nanocomposites.

This paper investigates the impact of halloysite nanotube (HNT) content on mechanical and shape memory properties of additively manufactured polyurethane (PU)/HNT nanocomposites. The inclusion of 8 wt% HNTs increases their tensile strength by 30.4% when compared with that of virgin PU at 44.75 MPa. Furthermore, consistently significant increases in tensile modulus, compressive strength and modulus, as well as specific energy absorption are also manifested by 47.2%, 34.0%, 125% and 72.7% relative to neat PU at 2.29 GPa, 3.88 MPa, 0.28 GPa and 0.44 kJ/kg respectively. However, increasing HNT content reduces lateral strain due to the restricted mobility of polymeric chains, leading to a decrease in negative Poisson's ratio (NPR). As such, shape recovery ratio and time of PU/HNT nanocomposites are reduced by 9 and 45% with the inclusion of 10 wt% HNTs despite an increasing shape fixity ratio up to 12% relative to those of neat PU.

Morphological, Thermal, and Mechanical Properties of Nanocomposites Based on Bio-Polyamide and Feather Keratin-Halloysite Nanohybrid.

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.

The Effect of Silanized Halloysite Nanotubes on the Structure of Polyethylene-Based Composite.

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.

Construction of hyperbranched imprinted nanomaterials for selective adsorption of cadmium (II).

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 (ß) 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.

Anti-tumor therapy through high ROS performance induced by Ag nanoenzyme from boron cluster with halloysite clay nanotubes.

The conventional silver nanoparticles (Ag NPs) are characterized with high loading rate and stacking phenomenon, leading to shedding caused biotoxicity and low catalytic efficiency. This seriously hinders their application in biomedicine. Here, we modified the highly dispersible Ag NPs and Ag single-atoms (SAs) synthesis by combining the halloysite clay nanotubes (HNTs) and dodecahydro-dodecaborate (closo-[B12H12]2-) to increase the biocompatible properties and decrease the loading rate. This novel Ag single-atom nanoenzyme alongside Ag NPs nanoenzyme avoid the elevated-temperature calcination while maintaining the exceptionally high-level efficiency of Ag utilization via the reducibility and coordination stabilization of closo-[B12H12]2- and HNTs. With theoretical calculation and electron paramagnetic resonance, we confirmed that both Ag SAzymes and Ag NPs in HNT@B12H12@Ag nanoenzyme are capable decompose the H2O2 into hydroxyl radical (·OH). For the application, we investigated the catalytic activity in the tumor cells and antitumor effects of HNT@B12H12@Ag nanoenzyme both in vitro and in vivo, and confirmed that it effectively suppressed melanoma growth through ·OH generation, with limited biotoxicity. This study provides a novel Ag nanoenzyme synthesis approach to increase the possibility of its clinical application.