Recent Advances of Halloysite Nanotubes in Biomedical Applications.

Halloysite nanotubes (HNTs) have emerged as a highly regarded choice in biomedical research due to their exceptional attributes, including superior loading capacity, customizable surface characteristics, and excellent biocompatibility. HNTs feature tubular structures comprising alumina and silica layers, endowing them with a large surface area and versatile surface chemistries that facilitate selective modifications. Moreover, their substantial pore volume and wide range of pore sizes enable efficient entrapment of diverse functional molecules. This comprehensive review highlights the broad biomedical application spectrum of HNTs, shedding light on their potential as innovative and effective therapeutic agents across various diseases. It emphasizes the necessity of optimizing drug delivery techniques, developing targeted delivery systems, rigorously evaluating biocompatibility and safety through preclinical and clinical investigations, exploring combination therapies, and advancing scientific understanding. With further advancements, HNTs hold the promise to revolutionize the pharmaceutical industry, opening new avenues for the development of transformative treatments.

Spherical Assembly of Halloysite Clay Nanotubes as a General Reservoir of Hydrophobic Pesticides for pH-Responsive Management of Pests and Weeds.

The development of smart systems for pesticidal delivery presents a significant advancement in enhancing the utilization efficiency of pesticides and mitigating environmental risks. Here an acid-responsive pesticidal delivery system using microspheres formed by the self-assembly of halloysite clay nanotubes (HNTs) is proposed. Insecticide avermectin (AVM) and herbicide prometryn (PMT) are used as two models of hydrophobic pesticide and encapsulated within the porous microspheres, followed by a coating of tannic acid/iron (TA/FeIII) complex films to generate two controlled-release pesticides, named as HCEAT and HCEPT, resulting in the loading capacity of AVM and PMT being 113.3 and 120.3 mg g-1, respectively. Both HCEAT and HCEPT exhibit responsiveness to weak acid, achieving 24 h-release ratios of 85.8% and 80.5% at a pH of 5.5. The experiment and simulation results indicate that the coordination interaction between EDTA2- and Ca2+ facilitates the spherical aggregation of HNTs. Furthermore, these novel pesticide formulations demonstrate better resistance against ultraviolet (UV) irradiation, higher foliar affinity, and less leaching effect, with negligible impact of the carrier material on plants and terrestrial organisms. This work presents a promising approach toward the development of efficient and eco-friendly pesticide formulations, greatly contributing to the sustainable advancement of agriculture.

Augmentin loaded functionalized halloysite nanotubes: A sustainable emerging nanocarriers for biomedical applications.

Clay minerals such as Halloysite nanotubes (HNTs), abundantly available green nanomaterial, exhibit a significant advantage in biomedical applications such as drug delivery, antibacterial and antimicrobials, tissue engineering or regeneration, etc. Because of the mesoporous structure and high absorbability, HNTs exhibit great potential as a nanocarrier in drug delivery applications. The sulfuric acid treatment enhances the surface area of the HNTs and thereby improves their drug-loading capacity by enlarging their lumen space/inner diameter. In the present investigation, based on the literature that supports the efficacy of drug loading after acid treatment, a dual treatment was performed to functionalize the HNTs surface. First, the HNTs were etched and functionalized using sulfuric acid. The acid-functionalized HNTs underwent another treatment using (3-aminopropyl) triethoxysilane (APTES) to better interact the drug molecules with the HNTs surfaces for efficient drug loading. Augmentin, a potential drug molecule of the penicillin group, was used for HNTs loading, and their antibacterial properties, cytotoxicity, and cumulative drug release (%) were evaluated. Different characterization techniques, such as X-ray diffractometer (XRD) and Fourier Transform Infra-Red (FT-IR), confirm the loading of Augmentin to the APTES@Acid HNTs. TEM images confirm the effective loading of the drug molecule with the HNTs. The drug encapsulation efficiency shows 40.89%, as confirmed by the Thermogravimetric Analysis (TGA). Also, the Augmentin-loaded APTES@Acid HNTs exhibited good antibacterial properties against E. coli and S. aureus and low cytotoxicity, as confirmed by the MTT assay. The drug release studies confirmed the sustainable release of Augmentin from the APTES@Acid HNTs. Hence, the treated HNTs can be considered as a potential nanocarrier for effectively delivering Augmentin and promoting enhanced therapeutic benefits.

Effects of multi-walled carbon nanotubes and halloysite nanotubes on plasma lipid profiles and autophagic lipolysis pathways in mouse aortas and hearts.

Multi-walled carbon nanotubes (MWCNTs) and halloysite nanotubes (HNTs) are widely used tubular-structured nanomaterials (NMs), but their cardiovascular effects are not clear. This study compared the effects of MWCNTs and HNTs on lipid profiles in mouse plasma and gene expression profiles in aortas and hearts. Mice were intravenously injected with 50 µg NMs, once a day, for 5 days. Then, the plasma was collected for lipidomics analysis, and aortas and hearts were collected for RNA-sequencing analysis. While MWCNTs or HNTs did not induce obvious pathological changes in aortas or hearts, the lipid profiles in mouse plasma were altered. Further analysis revealed that MWCNTs more effectively upregulated sphingolipids and sterol lipids, whereas HNTs more effectively upregulated glycerophospholipids and fatty acyls. Consistently, RNA-sequencing data indicated that MWCNTs and HNTs altered signaling pathways related with lipid synthesis and metabolism, as well as those related with endoplasmic reticulum, lysosomes and autophagy, more significantly in aortas than in hearts. We further verified the changes of proteins involved in autophagic lipolysis, that MWCNTs were more effectively to suppress the autophagic biomarker LC3, whereas HNTs were more effectively to affect lipid metabolism proteins. These results may provide novel understanding about the influences of MWCNTs and HNTs on lipid profiles and lipid signaling pathways in cardiovascular systems. Importantly, previous studies considered HNTs as biocompatible materials, but the results from this study suggested that both MWCNTs and HNTs were capable to affect lipid profiles and autophagic lipolysis pathways in cardiovascular systems, although their exact influences were different.

Enhanced antimicrobial efficacy of chlorhexidine-encapsulated halloysite nanotubes incorporated in presurgical orthopedic appliances: an in vitro, controlled study.

AIMS AND OBJECTIVE: Presurgical infant's orthopedic appliances (PSIOs) play an increasingly crucial role in the interdisciplinary management of neonatal CLP, aiming to improve and maintain adequate nasolabial aesthetics, followed by primary lip/nasal surgery in both unilateral and bilateral CLP cases. The use of PSIOs in cleft lip and palate patients can lead to contamination with oral microflora, acting as a potential reservoir for infectious microorganisms. Acrylic surfaces might provide retention niches for microorganisms to adhere, and inhabit, which is difficult to control in immunocompromised patients, thus predisposing them to increased infection risks. The objective of this multi-assay in vitro study was to investigate the effects of incorporating chlorhexidine-loaded halloysite nanotubes (CHX-HNTs) fillers on the morphological, cytotoxic, release, and antimicrobial characteristics of self-cured acrylic polymethyl methacrylate (PMMA) material used in pre-surgical orthopedic appliances. METHODS: Disk-shaped PMMA specimens were prepared with varying proportions of CHX-HNTs. A control group without any addition served as a reference, and four experimental samples contained a range of different concentrations of CHX-HNTs (1.0, 1.5, 3, and 4.5 wt%). The antimicrobial efficacy was assessed using an agar diffusion test against common reference microorganisms: Candida albicans, Staphylococcus aureus, Streptococcus pneumoniae, and Streptococcus agalactiae. Cytotoxicity was examined using the L929 cell line (mouse fibroblasts) through a (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide, MTT) cell viability assay. The release kinetics of CHX were monitored using UV-spectral measurements. The statistical analysis used a one-way ANOVA followed by Tukey's post hoc test. RESULTS: The integration of CHX-HNTs in PMMA exhibited a substantial dose-dependent antifungal and antibacterial effect against microorganisms at tested mass fractions (1.0 to 4.5 wt%). CHX release was sustained for up to 60 days, supporting prolonged antimicrobial activity. Furthermore, no significant cytotoxicity was determined in the L929 fibroblast cell line (control), indicating the biocompatibility of the CHX-HNTs-enhanced PMMA. CONCLUSION: Incorporating CHX-HNTs in PMMA successfully enhanced its antimicrobial properties, providing sustained CHX release and superior antimicrobial efficacy. These findings demonstrate the potential of antimicrobial nanoparticles in dental therapies to improve therapeutic outcomes. However, rigorous further clinical trials and observational studies are warranted to validate the practical application, safety, and efficacy. CLINICAL RELEVANCE: This study has the potential to make a major impact on the health of infants born with cleft lip and palate by helping to reduce the prevalence of infectious illnesses. The incorporation of CHX-HNTs into PMMA-based appliances is a novel promising preventive approach to reduce microbial infections.

Fabrication of 2D/1D Bi2WO6/halloysite nanotubes photocatalyst towards water purification: a support effect onin situconstruction and electron-hole separation.

In this research work, a reusable and efficient 2D/1D heterogeneous structured photocatalyst based on amine-functionalized halloysite nanotubes (MHNTs) and Bi2WO6nanosheet (BWO) was prepared using a facile hydrothermal method for decomposing PPCPs under simulated sunlight. On the degradation of tetracycline hydrochloride (TCH), the effects of composite catalysts prepared under various conditions were discussed. The results showed that over BWO/MHNTs with a mass ratio was 3:1, the synthesizing temperature was 120 °C and the precursor pH value was 1, the TCH (10 mg l-1) degradation efficiency reached 100% after 1 h irradiation of simulated sunlight. Moreover, BWO/MHNTs composites kept good recovery and stable photocatalytic activity after 5 cycles. The excellent dispersion of Bi2WO6on the surface of clay minerals and the oxygen vacancy enhanced electron-hole separation may be responsible for the its high activity and stability. Futhermore, the radical capture test demonstrated that ·O-2was primarily responsible for the photodegradation of TCH. Thus, BWO/MHNTs composites exhibit a good application prospect in the field of sunlight-driven photocatalytic degradation towards PPCPs pollutants in water.

Synthesis and Characterization of Carvedilol-Etched Halloysite Nanotubes Composites with Enhanced Drug Solubility and Dissolution Rate.

Carvedilol is a poorly water-soluble drug employed to treat chronic heart failure. In this study, we synthesize new carvedilol-etched halloysite nanotubes (HNTs) composites to enhance solubility and dissolution rate. The simple and feasible impregnation method is used for carvedilol loading (30-37% weight). Both the etched HNTs (acidic HCl and H2SO4 and alkaline NaOH treatments) and the carvedilol-loaded samples are characterized by various techniques (XRPD, FT-IR, solid-state NMR, SEM, TEM, DSC, and specific surface area). The etching and loading processes do not induce structural changes. The drug and carrier particles are in intimate contact and their morphology is preserved, as demonstrated by TEM images. The 27Al and 13C solid-state NMR and FT-IR findings show that carvedilol interactions involve the external siloxane surface, especially the aliphatic carbons, the functional groups, and, by inductive effect, the adjacent aromatic carbons. All the carvedilol-halloysite composites display enhanced dissolution rate, wettability, and solubility, as compared to carvedilol. The best performances are obtained for the carvedilol-halloysite system based on HNTs etched with HCl 8M, which exhibits the highest value of specific surface area (91 m2 g-1). The composites make the drug dissolution independent of the environmental conditions of the gastrointestinal tract and its absorption less variable, more predictable, and independent from the pH of the medium.

New Biocide Based on Tributyltin(IV) Ferulate-Loaded Halloysite Nanotubes for Preserving Historical Paper Artworks.

Combining biologically active compounds with nanocarriers is an emerging and promising strategy for enhancing the activities of molecules while reducing their levels of toxicity. Green nanomaterials have recently gained momentum in developing protocols for treating and preserving artifacts. In this study, we designed a functional biohybrid material by incorporating tributyltin(IV) ferulate (TBT-F) into halloysite nanotubes (HNTs), generating a new formulation called HNT/TBT-F. The primary objective was to develop a formulation with robust antimicrobial properties and reinforcing features for treating paper with artistic and historical value. To characterize HNT/TBT-F, assess the HNT's loading capacity, and investigate the TBT-F release kinetics from the nanotubes, various analytical techniques, including UV-Vis and infrared spectroscopies, thermogravimetry, and microscopy analysis, were employed. Furthermore, we evaluated the antimicrobial potential of TBT-F and HNT/TBT-F against Kocuria rhizophila, a bacterial strain known for its opportunistic behavior and a cause of artifact biodeterioration. HNT/TBT-F exhibited a significantly stronger bactericidal effect than TBT-F alone against K. rhizophila cells growing planktonically or those forming a biofilm. This enhanced performance could relate to the confinement of TBT-F within the nanotubes, which likely improved its physical-chemical stability and increased the local concentration of TBT-F upon contact with the bacterial cells. Additionally, we evaluated the mechanical properties of a paper treated with HNT/TBT-F, assessing any potential alterations in its color. The findings of this study highlight the favorable attributes of the HNT/TBT-F formulation and its potential for developing protocols aimed at consolidating and preserving culturally significant paper objects.

Electrospun PAN-HNTs composite nanofiber membranes for efficient electrostatic capture of particulate matters.

The fine particulate matter (PM) pollution has become a serious concern to public health. As the core part of PM air filters, high-performance electrostatic nanofiber membranes are urgently needed. However, the existing air filters remain challenging to further decrease the pressure drop to improve the wearer comfort. On the other hand, the rapidly disappearing static electricity of the existing electrostatic nanofiber inevitably gives rise to a relatively short service life. Here, we demonstrate a novel and enhanced electrostatic nanofiber membrane by introducing the halloysite nanotubes (HNTs) to the traditional electrospun PAN nanofiber membrane. The optimal PAN-HNTs nanofiber membrane shows a high removal efficiency of 99.54%, a low pressure drop of 39 Pa, and a high quality factor of 0.89 Pa-1. This greatly improved filtration performance can be attributed to the increased surface area and diameter of nanofiber after introducing the HNTs as additives with suitable doping concentrations. More importantly, compared with the pure PAN nanofiber membrane, the electrostatic capacity of the PAN-HNTs nanofiber membrane is significantly enhanced, which is confirmed by the leaf electroscope. After introducing the HNTs as additives, the surface of the PAN-HNTs nanofiber membrane becomes hydrophilic, which benefits for preventing foulants from attaching to the surface. We anticipate that the PAN-HNTs nanofibers as high-performance membrane air filters will bring great benefits to public health.

Gaseous Arsenic Capture in Flue Gas by CuCl2-Modified Halloysite Nanotube Composites with High-Temperature NOx and SOx Resistance.

Gaseous arsenic emitted from coal combustion flue gas (CCFG) causes not only severe contamination of the environment but also the failure of selective catalytic reduction (SCR) catalysts in power plants. Development of inexpensive and effective adsorbents or techniques for the removal of arsenic from high-temperature CCFG is crucial. In this study, halloysite nanotubes (HNTs) at low price were modified with CuCl2 (CuCl2-HNTs) through ultrasound assistance and applied for capturing As2O3(g) in simulated flue gas (SFG). Experiments on arsenic adsorption performance, adsorption mechanism, and adsorption energy based on density functional theory were performed. Modification with CuCl2 clearly enhanced the arsenic uptake capacity (approximately 12.3 mg/g) at 600 °C for SFG. The adsorbent exhibited favorable tolerance to high concentrations of NOx and SOx. The As2O3(III) was oxidized and transformed into As2O5(V) on the CuCl2-HNTs. The Al-O bridge had the highest adsorption energy for the O end of the As-O group (-2.986 eV), and the combination formed between arsenic-containing groups and aluminum was stable. In addition, the captured arsenic could be stabilized in the sorbent at high temperature, making it possible to use the sorbent before the SCR system. This demonstrates that CuCl2-HNTs is a promising sorbent for arsenic oxidation and removal from CCFG.

Nanomaterials: A Review about Halloysite Nanotubes, Properties, and Application in the Biological Field.

The use of synthetic materials and the attention towards environmental hazards and toxicity impose the development of green composites with natural origins. Clay is one of the candidates for this approach. Halloysite is a natural clay mineral, a member of the Kaolin group, with characteristic tubular morphology, usually named halloysite nanotubes (HNTs). The different surface chemistry of halloysite allows the selective modification of both the external surface and the inner lumen by supramolecular or covalent interactions. An interesting aspect of HNTs is related to the possibility of introducing different species that can be released more slowly compared to the pristine compound. Due to their unique hollow morphology and large cavity, HNTs can be employed as an optimal natural nanocarrier. This review discusses the structure, properties, and application of HNTs in the biological field, highlighting their high biocompatibility, and analyse the opportunity to use new HNT hybrids as drug carriers and delivery systems.

PEO Coatings Modified with Halloysite Nanotubes: Composition, Properties, and Release Performance.

In this work, the properties of the coatings formed on the Mg-Mn-Ce alloy by plasma electrolytic oxidation (PEO) in electrolytes containing halloysite nanotubes (HNTs) were investigated. The incorporation of halloysite nanotubes into the PEO coatings improved their mechanical characteristics, increased thickness, and corrosion resistance. The studied layers reduced corrosion current density by more than two times in comparison with the base PEO layer without HNTs (from 1.1 × 10-7 A/cm2 to 4.9 × 10-8 A/cm2). The presence of halloysite nanotubes and products of their dihydroxylation that were formed under the PEO conditions had a positive impact on the microhardness of the obtained layers (this parameter increased from 4.5 ± 0.4 GPa to 7.3 ± 0.5 GPa). In comparison with the base PEO layer, coatings containing halloysite nanotubes exhibited sustained release and higher adsorption capacity regarding caffeine.

Enhancement of photocatalytic activities of ZnFe2O4 composite by incorporating halloysite nanotubes for effective elimination of aqueous organic pollutants.

ZnFe2O4 is a highly desirable catalyst due to its exceptional photo-response in the visible light region, but various drawbacks, such as rapid recombination of photo-generated electron-hole pairs and severe particle agglomeration, make it difficult to use. In this study, a co-precipitation approach was used to create ZnFe2O4/HNT (ZF/HNTs) composites. XRD, SEM, TEM, FTIR, BET, and DRS were used to characterize the ZF/HNT composites. Furthermore, the effectiveness of removing crystal violet under simulated visible light irradiation was used to assess photocatalytic activity. The results showed that ZnFe2O4 with typical diameters of around 20 nm was significantly distributed on halloysite nanotubes. Because of the synergistic impact of the improved agglomeration phenomena of ZnFe2O4 and the decreased recombination rate of photo-generated electrons and holes, all of the composites had superior photocatalytic performance than pure ZnFe2O4. The ZF/HNTs-11 composite exhibited the highest removal performance, removing 96.7% of the sample in less than 150 min. In addition, the composite was very stable and reusable. Consequently, ZF/HNTs-11 composite is an effective catalyst for treating pollutants found in wastewater.

Understanding the Effects of Crosslinking and Reinforcement Agents on the Performance and Durability of Biopolymer Films for Cultural Heritage Protection.

In the last two decades, the naturally occurring polysaccharides, such as chitosan and pectin, have gained great attention having potential applications in different sectors, from biomedical to new generation packaging. Currently, the chitosan and pectic have been proposed as suitable materials also for the formulation of films and coatings for cultural heritage protection, as well as packaging films. Therefore, the formulation of biopolymer films, considering only naturally occurring polymers and additives, is a current challenging trend. This work reports on the formulation of chitosan (CS), pectin (PC), and chitosan:pectin (CS:PC) films, also containing natural crosslinking and reinforcement agents, such as citric acid (CA) and halloysite nanotubes (HNT), through the solvent casting technique. The produced films are characterized through water contact angle measurements, infrared and UV-visible spectroscopy and tensile test, while the durability of the CS:PC films is evaluated subjecting the film to accelerated UVB exposure and monitoring the photo-oxidation degradation in time though infrared spectroscopy. All obtained results suggest that both crosslinking and reinforcement agents have beneficial effects on the wettability, rigidity, and photo-oxidation resistance of biopolymer films. Therefore, these biopolymer films, also containing naturally occurring additives, have good properties and performance and they are suitable as coverage films for cultural heritage protection.

Influence of Polymer Solvents on the Properties of Halloysite-Modified Polyethersulfone Membranes Prepared by Wet Phase Inversion.

Ultrafiltration polyethersulfone (PES) membranes were prepared by wet phase inversion. Commercial halloysite nanotubes (HNTs) in the quantities of 0.5 wt% vs. PES (15 wt%) were introduced into the casting solution containing the polymer and different solvents: N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), or 1-methyl-2-pyrrolidinone (NMP). The type of solvent influenced the membranes' morphology and topography, as well as permeability, separation characteristics, and antifouling and antibacterial properties. The membranes prepared using DMA exhibited the loosest cross-section structure with the thinnest skin and the roughest surface, while the densest and smoothest were the DMF-based membranes. The advanced contact angles were visibly lower in the case of the membranes prepared using DMF compared to the other solvents. The highest water permeability was observed for the DMA-based membranes, however, the most significant effect of the modification with HNTs was found for the NMP-based series. Regardless of the solvent, the introduction of HNTs resulted in an improvement of the separation properties of membranes. A noticeable enhancement of antifouling performance upon application of HNTs was found only in the case of DMF-based membranes. The study of the antibacterial properties showed that the increase in surface roughness had a positive effect on the inhibition of E. coli growth.

ENHANCEMENT OF DENTURE-BASED MATERIAL PMMA BY INCORPORATION OF SILANIZED HALLOYSITE NANOTUBES.

OBJECTIVE: The aim: This study evaluates the effect of adding silanized halloysite nanotubes to the polymethylmethacrylate (PMMA) resin on its hardness, impact strength, transverse strength. PATIENTS AND METHODS: Materials and methods: Three groups of acrylic resin were prepared, one group without HNTs, was used as a control group (A). The other two groups contained 0.3% (B), 0.6% wt of silanized halloysite nanotubes (C). For each one, hardness, impact strength and transverse strength were measured. One-way ANOVA and Tukey's test were used for comparison. RESULTS: Results: Regarding to the impact test, there was no significant difference between 0.3% concentration and the pure (control) group while 0.6% concentration had significant decrease compared to the pure group and so between the 0.3% group 0.6% group. For the hardness test, the 0.3% group had no significant difference with the pure group and a significant difference between group 0.6% group and the pure group while there was a no significant decrease between the 0.3% and 0.6% group with the higher hardness mean in the 0.3% compared to 0.6% group. For the transverse strength, both 0.3% wt concentration and 0.6% concentration showed significant difference compared to the pure group and also between each other with the lowest impact strength in 0.6% group followed by 0.3% group with the highest transverse strength in the pure group. CONCLUSION: Conclusions: The silanation of halloysite nanotubes reduces the mechanical properties of the heat-cured acrylic denture base material. The more concentration of silanazed halloysite nanotubes is added, the more weakening occurs in the acrylic material relating to the hardness, transverse strength and impact strength.

Unraveling the electrochemical properties of lanthanum cobaltite decorated halloysite nanotube nanocomposite: An advanced electrocatalyst for determination of flutamide in environmental samples.

Prostate cancer is one of the primary causes of death around the world. As an important drug, flutamide has been used in the clinical diagnosis of prostate cancer. However, the over dosage and improper discharge of flutamide could affect the living organism. Thus, it necessary to develop the sensor for detection of flutamide with highly sensitivity. In this paper, we report the synthesis of lanthanum cobaltite decorated halloysite nanotube (LCO/HNT) nanocomposite prepared by a facile method and evaluated for selective reduction of flutamide. The as-prepared LCO/HNT nanocomposite shows the best catalytic performance towards detection of flutamide, when compared to other bare and modified electrodes. The good electrochemical performance of the LCO/HNT nanocomposite modified electrode is ascribed to abundant active sites, large specific surface area and their synergetic effects. Furthermore, the LCO/HNT modified electrode exhibits low detection limit (0.002 µM), wide working range (0.009-145 µM) and excellent selectivity with remarkable stability. Meaningfully, the developed electrochemical sensor was applied in real environmental samples with an acceptable recovery range.

Past, Present and Future Perspectives on Halloysite Clay Minerals.

Halloysite nanotubes (HNTs), clay minerals belonging to the kaolin groups, are emerging nanomaterials which have attracted the attention of the scientific community due to their interesting features, such as low-cost, availability and biocompatibility. In addition, their large surface area and tubular structure have led to HNTs' application in different industrial purposes. This review reports a comprehensive overview of the historical background of HNT utilization in the last 20 years. In particular it will focus on the functionalization of the surfaces, both supramolecular and covalent, following applications in several fields, including biomedicine, environmental science and catalysis.

Fabrication of High-Performance Bamboo-Plastic Composites Reinforced by Natural Halloysite Nanotubes.

Bamboo-plastic composites (BPCs) as new biomass-plastic composites have recently attracted much attention. However, weak mechanical performance and high moisture absorption as well as low thermal stability greatly limit their industrial applications. In this context, different amounts of halloysite nanotubes (HNTs) were used as a natural reinforcing filler for BPCs. It was found that the thermal stability of BPCs increased with increasing HNT contents. The mechanical strength of BPCs was improved with the increase in HNT loading up to 4 wt% and then worsened, while the impact strengths were slightly reduced. Low HNT content (below 4 wt%) also improved the dynamic thermomechanical properties and reduced the water absorption of the BPCs. Morphological studies confirmed the improved interfacial compatibility of the BPC matrix with 4 wt% HNT loading, and high-concentration HNT loading (above 6 wt%) resulted in easy agglomeration. The results highlight that HNTs could be a feasible candidate as nanoreinforcements for the development of high-performance BPCs.

Facile Fabrication of Natural Polyelectrolyte-Nanoclay Composites: Halloysite Nanotubes, Nucleotides and DNA Study.

Complexation of biopolymers with halloysite nanotubes (HNTs) can greatly affect their applicability as materials building blocks. Here we have performed a systematic investigation of fabrication of halloysite nanotubes complexes with nucleotides and genomic DNA. The binding of DNA and various nucleotide species (polyAU, UMP Na2, ADP Na3, dATP Na, AMP, uridine, ATP Mg) by halloysite nanotubes was tested using UV-spectroscopy. The study revealed that binding of different nucleotides to the nanoclay varied but was low both in the presence and absence of MgCl2, while MgCl2 facilitated significantly the binding of longer molecules such as DNA and polyAU. Modification of the nanotubes with DNA and nucleotide species was further confirmed by measurements of ζ-potentials. DNA-Mg-modified nanotubes were characterized using transmission electron (TEM), atomic force (AFM) and hyperspectral microscopies. Thermogravimetric analysis corroborated the sorption of DNA by the nanotubes, and the presence of DNA on the nanotube surface was indicated by changes in the surface adhesion force measured by AFM. DNA bound by halloysite in the presence of MgCl2 could be partially released after addition of phosphate buffered saline. DNA binding and release from halloysite nanotubes was tested in the range of MgCl2 concentrations (10-100 mM). Even low MgCl2 concentrations significantly increased DNA sorption to halloysite, and the binding was leveled off at about 60 mM. DNA-Mg-modified halloysite nanotubes were used for obtaining a regular pattern on a glass surface by evaporation induced self-assembly process. The obtained spiral-like pattern was highly stable and resisted dissolution after water addition. Our results encompassing modification of non-toxic clay nanotubes with a natural polyanion DNA will find applications for construction of gene delivery vehicles and for halloysite self-assembly on various surfaces (such as skin or hair).