Submitted Successfully!
To reward your contribution, here is a gift for you: A free trial for our video production service.
Thank you for your contribution! You can also upload a video entry or images related to this topic.
Version Summary Created by Modification Content Size Created at Operation
1
Serena Riela
 -- 3196 2023-01-05 16:13:31 |
2 layout
Sirius Huang
 Meta information modification 3196 2023-01-08 17:25:21 |

Video Upload Options

We provide professional Video Production Services to translate complex research into visually appealing presentations. Would you like to try it?
No, upload directly Yes

Confirm

Are you sure to Delete?
Yes No
Cite
If you have any further questions, please contact Encyclopedia Editorial Office.
Massaro, M.;  Ciani, R.;  Cinà, G.;  Colletti, C.G.;  Leone, F.;  Riela, S. Antimicrobial Nanomaterials Based on Halloysite Clay Mineral. Encyclopedia. Available online: https://encyclopedia.pub/entry/39806 (accessed on 16 November 2024).
Massaro M,  Ciani R,  Cinà G,  Colletti CG,  Leone F,  Riela S. Antimicrobial Nanomaterials Based on Halloysite Clay Mineral. Encyclopedia. Available at: https://encyclopedia.pub/entry/39806. Accessed November 16, 2024.
Massaro, Marina, Rebecca Ciani, Giuseppe Cinà, Carmelo Giuseppe Colletti, Federica Leone, Serena Riela. "Antimicrobial Nanomaterials Based on Halloysite Clay Mineral" Encyclopedia, https://encyclopedia.pub/entry/39806 (accessed November 16, 2024).
Massaro, M.,  Ciani, R.,  Cinà, G.,  Colletti, C.G.,  Leone, F., & Riela, S. (2023, January 05). Antimicrobial Nanomaterials Based on Halloysite Clay Mineral. In Encyclopedia. https://encyclopedia.pub/entry/39806
Massaro, Marina, et al. "Antimicrobial Nanomaterials Based on Halloysite Clay Mineral." Encyclopedia. Web. 05 January, 2023.
Antimicrobial Nanomaterials Based on Halloysite Clay Mineral
Edit
This entry is adapted from the peer-reviewed paper 10.3390/antibiotics11121761

Bacterial infections represent one of the major causes of mortality worldwide. Over the years, several nanomaterials with antibacterial properties have been developed. In this context, clay minerals, because of their intrinsic properties, have been efficiently used as antimicrobial agents since ancient times. Halloysite nanotubes are one of the emerging nanomaterials that have found application as antimicrobial agents in several fields. 

clay minerals halloysite nanotubes antibacterial wound healing orthopedic implants food packaging pest control

1. Introduction

Halloysite is a natural phyllosilicate clay belonging to the kaolin group that shows an Al:Si ratio of 1:1 and a general formula of Al2Si2O5(OH)4∙nH2O. Typically, it is naturally found as nanotubes and therefore is usually referred to as halloysite nanotubes (HNTs). HNTs are constituted by 10–15 aluminosilicate bilayers, with a spacing of approximately 0.72 nm. The arrangement of the sheets generates an external surface composed by siloxane (Si–O–Si) groups and a lumen constituted by a gibbsite-like array of aluminol (Al–OH) groups. Furthermore, the rolling process causes some structural defects the also be present at the HNTs’ edges in the form of some Al–OH and Si–OH groups. The different chemical composition causes the tubes to undergo ionization in aqueous media in an opposite way, generating tubes with inner and outer surfaces oppositely charged across a wide pH range. In particular, the lumen is positively charged, whereas on the external surface there is a permanent negative charge.
By exploiting the different chemical composition and the different surface charges, HNTs can be modified, resulting in different nanomaterials with tunable properties that have found applications as fillers in polymeric matrices [1][2][3], drug carriers and delivery systems [4][5], supports for metal nanoparticles for catalytic purposes [6][7][8][9], and so on [10][11]. The growing number of halloysite-related publications and patents attests to the clay’s growing popularity. It is noteworthy that the number of publications is comparable to that of patents, indicating an actual involvement of academia beyond industrial applications.
HNTs are biocompatible materials, and several in vitro and in vivo studies have assessed the non-toxic nature of this clay mineral. Halloysite, indeed, was found to be nontoxic for different cells [12][13], model organisms [14][15], and yeast cells [16]. Furthermore, it was found that by feeding HNTs to different animals, such as chickens and piglets, no toxic effects were observed [17][18].
Recently, an in vivo study was reported that allowed the researchers to estimate the maximum concentration of HNTs that could be administered without observing toxicity. It was discovered that prolonged oral administration of 50 mg of HNTs per body weight for up to 30 days caused aluminum accumulation in mice lungs, resulting in pulmonary fibrosis [19].
HNTs can interact with cells in different ways, some of them are driven by electrostatic (attraction) and/or hydrophobic interactions and/or van der Waals forces. On the contrary, the cells interact with HNTs depending on their nature. For example, while bacteria incorporate HNTs into their biofilm structure, in mammalian cells HNTs are uptaken through their membrane, whether via endocytosis or mechanisms where actin filaments are reported.
Due to its intrinsic properties, halloysite, in contrast to some other clays, cannot be considered an antibacterial nanomaterial. It, indeed, lacks interlayer cation exchange properties and does not possess the ability to release metal ions, properties that are fundamental to exerting some bactericidal effects [20], as was already discussed. However, by suitable modification of the surfaces, it is possible to obtain nanomaterials with promising antibacterial activities. Furthermore, because HNTs possess an empty lumen, they have been used as nanocontainers for different antibiotics, obtaining nanomaterials that are used to treat common pathogens for different applications (Table 1) [21][22].
Table 1. Different HNTs based antimicrobial nanomaterials and their relative applications.
Nanomaterial Biocide Pathogen Application Ref.
HNTs-NH2 Gentamicin E. coli, S. aureus and
S. epidermidis		 Antibacterial [23]
HNTs Oregano essential oil E. coli, S. aureus Food packaging [24]
HNTs Carvacrol A. hydrophila, P. putida,
L. monocytogenes and
S. aureus, A. alternata		 Antibacterial [25][26]
HNTs CdS E. coli, S. aureus Antibacterial [27]
HNTs/pectin Salicylic acid Salmonella, P. aeruginosa,
E. coli and S. aureus		 Food packaging [28]
HNTs/pectin
HNTs/alginate		 Salicylic acid E. coli, S. typhimurium,
P. aeruginosa and S. aureus		 Food packaging [29]
HNTs/low-density polyethylene Carvacrol and thymol E. coli Food packaging [30]
HNTs/polyethylene Carvacrol A. hydrophila Food packaging [31]
HNTs-poly(4-vinylpyridine) CuNPs E. coli Antibacterial [32]
HNTs- poly(4-vinylpyridine)/polyethersulfone AgNPs E. coli, S. aureus Antifouling and antibacterial [33]
HNTs/chitosan Norfloxacin E. coli, S. aureus Antibacterial [34]
HNTs/chitosan/polyvinyl alcohol nanofibers Benzocaine E. coli, S. aureus Antibacterial [35]
HNTs/sodium alginate-poly (ethylene oxide) fibrous mats Levofloxacin E. coli, S. aureus Wound dressing [36]
HNTs/chitosan/pullulan Rutin E. coli, L. monocytogenes Food packaging [37]
HNTs/alginate Cephalexin E. coli, P. aeruginosa and
S. aureus		 Antibacterial protection [38]
HNTs/polyethylene glycol ClO2 / Food packaging [39]
HNTs/poly(lactic) acid Clove essential oil / Food packaging [40]
HNTs/chitosan Clove essential oil B. mojavensis, E. coli Food packaging [41]
HNTs/LDPE Carvacrol E. coli, S. aureus Food packaging [42]
HNTs/silk fibroin microfibers Tetracycline hydrochloride E. coli, S. aureus Wound dressing [43]
HNTs/poly(lactic) acid Clove essential oil / Food packaging [40]

2. Orthopedic Implants

The rising age and longevity of the population have led to the implementation of primary arthroplasties worldwide. A consequence of this treatment is often represented by the occurrence of some infections, depending upon the type of bacteria involved and whether the infection is acute or chronic [44].
Over the years, to avoid bacterial infections, different biomaterials have been designed and engineered to ensure antibacterial protection. In this context, halloysite is an emerging filler that can be successfully used.
Lvov et al. (2012) investigated the possibility of using HNTs as a filler for poly-(methyl methacrylate) (PMMA), which has long been used as bone cement. To avoid bacterial infections, the researchers loaded HNTs with gentamicin, obtaining, after inclusion in the polymeric matrix, a nanocomposite with good mechanical strength and sustained release of the active ingredient [45]. Antibacterial tests highlighted that the gentamicin release inhibited the bacterial growth of E. coli and S. aureus, which were chosen as models.
A 3D-printed poly-ε-caprolactone (PCL) filled with HNTs and hydroxyapatite (HA) nanocomposite was fabricated by Riool et al. to release gentamicin sulfate (GS) when used as a coating for weight-bearing materials [46]. Specifically, the nanocomposite was obtained by mixing PCL, HNTs, HA, and GS, and the obtained mixture was subjected to fused filament fabrication (FFF) 3D printing technology to obtain a nanomaterial in the shape of a bone fixation plate. The nanocomposite obtained was intended to be applied to replace a mouse femur. The implant obtained was tested in in vitro, ex vivo, and in vivo experiments to study its antimicrobial efficacy. The experimental results highlighted the potentiality of this scaffold, which in the future can serve to produce load-bearing implantable devices with specific drug release properties.

3. Dental Implants

Nowadays, it is estimated that about 3.5 billion people worldwide suffer from oral diseases [47]. Often, to address this, it is necessary to resort to some dental implants and replacement procedures that, similarly to the orthopedic ones, are affected by bacterial infections.
In this context, Bottino et al. developed an injectable chlorhexidine (CHX)-loaded HNTs-modified GelMA hydrogel for dental infection ablation. GelMA is a photocrosslinkable gelatin methacryloyl [48], a polymer often used in regenerative engineering because of its good cell−tissue affinity and degradability in the presence of matrix metalloproteinases. The good antibacterial activity of the nanocomposite was tested on different pathogens associated with secondary endodontic infection. In addition, an in vivo test on stem cells from human-exfoliated deciduous teeth and the study of an inflammatory response using a subcutaneous rat model revealed good cytocompatibility with the hydrogel.
Similarly, chlorhexidine was loaded into HNTs, and the obtained nanomaterials were used as fillers for a dental resin [49]. The experimental findings show that the incorporation of different percentages of filler in the resin produced a nanocomposite with enhanced mechanical properties. In addition, it shows a slight decrease in curing depth and degree of conversion values, which are indicative of its durability. Biological assays showed no cytotoxicity on NIH-3T3 cell lines, and most importantly, antibacterial test on a strain of Streptococcus mutans highlighted the good antimicrobial activity of the nanocomposite.

4. Halloysite Based Nanomaterials for Wound Healing

Wound healing is a very complex process that occurs in subsequent or overlapped phases, involves a series of events, and requires the intervention of various mediators. Chronic skin wounds are lesions that fail to restore the skin’s anatomical and functional integrity, resulting in ulcers that take several years to heal. One of the most important issues that impairs the wound healing process is, of course, the occurrence of bacterial infections.
In this context, terpenoids structurally similar to carvacrol were loaded into HNTs, resulting in nanomaterials that performed well in cell-based scratch assays with a HaCaT cell monolayer on an in vitro artificial wound model for re-epithelialization and wound healing. In addition, the antimicrobial effects of the nanomaterials on the common pathogens that frequently colonize chronic wounds were also evaluated. The results of the experiments revealed promising antibacterial activity against four different Gram-positive and Gram-negative strains, namely S. aureus ATCC 43300, S. aureus ATCC 29213, S. epidermidis ATCC 35984, and P. aeruginosa ATCC 27853 [50].
Polymyxin B sulfate loaded on HNTs was used as filler for gelatin-based elastomers previously loaded with ciprofloxacin. As a result, a potentially useful biomaterial for wound dressing was obtained [2]. To validate the potentiality of the nanocomposite as antimicrobial agent, its antibacterial effects were studied on two different strains, S. aureus (Gram-positive) and P. aeruginosa (Gram-negative), commonly known to infect wounds, by evaluating the presence of inhibition zones around the bacterial discs. The experimental results showed good antimicrobial performance for at least 7 days, thanks to the slow release of both drugs from the nanocomposite.
AuNPs encapsulated in HNT lumen were used to confer both photothermal and antimicrobial properties to chitin-based hydrogels for wound healing applications [51]. The nanocomposite hydrogels possessed high cytocompatibility on mouse fibroblasts, and, by in vitro antibacterial experiments, it was demonstrated that, because of the photothermal properties, they showed high antibacterial ability towards E. coli and S. aureus. In addition, the chitin-based hydrogel showed the peculiarity of possessing high hemostatic performance in mouse liver and tail bleeding. In in vivo experiments, the researchers showed that wound infection healing results confirmed the healing-promoting effect of the hydrogel material.

5. Food Packaging

Nowadays, food spoilage due to microbial contamination represents a significant problem, which every year causes enormous economic loss. It is estimated that, in the United States alone, the wastefulness of food accounts for ca. 30–40% of the total food supply. Therefore, to prevent bacterial contamination, biofilms with antimicrobial properties should be prepared for active food packaging applications [52]. Among the different antimicrobial agents that have been used for this purpose, essential oils are the most-employed. Most of them have indeed been classified as “Generally Recognized as Safe” (GRAS) by the US Food and Drug Administration (FDA), and, in addition, they have been long been used as flavoring agents. However, they are highly flavoring, show high volatility, and show the tendency to be oxidized, and thus it is necessary to develop efficient carrier systems for their practical utilization.
In this context, thyme essential oil was loaded into HNTs, and then the nanomaterial obtained was mixed with flexographic ink and coated on paper for applications as food packaging materials [53].
Antimicrobial experiments on E. coli, for a 25-day treatment showed that the packaging paper filled with HNTs/TO nanomaterial, possessed a strong antimicrobial effect in the first 10 days. In particular, the packaging paper resulted in very high efficiency and was especially effective in eradicating E. coli within the initial 5 days, with the bacterial count reduced to ~1.5 log CFU cm−2.
Similarly, Gorrasi et al. [54] used rosemary essential oil loaded in HNTs as a filler for pectin matrix, while peppermint essential oil was loaded on cucurbit[6]uril (CB[6])-modified HNTs [55]. In this case, the HNTs/CB[6] nanomaterial was mixed by an optimized casting process into pectin, obtaining a nanocomposite with superior antioxidant and antibacterial activities. The in vitro antimicrobial activity of the nanocomposite was evaluated on E. coli and S. aureus, isolated from beef and cow milk, respectively, at three different temperatures. It was found that the percentage of bacterial viability for both bacterial strains was reduced at 65 °C compared to those at 37 °C and 4 °C. Of note, only 15% of the E. coli survived after the treatment at 65 °C.
Following the same approach, grapefruit seed oil was encapsulated into HNTs’ lumen and then dispersed in a pectin matrix, obtaining a nanocomposite that was effective in the protection of fruits [56]. The researchers, indeed, coated fresh strawberries with the film developed and stored them for 10 days at room temperature RH = 60%. The nanocomposite films prevented mold formation, extending the storage time of such fruit, in contrast to the uncoated strawberry, which showed mold after two days with a wrinkled and damaged appearance.
One of the most-used chemical species active in food packaging is represented by ZnO nanoparticles. It is indeed registered by the US Food and Drug Administration (FDA) (FDA, 2011) on the Generally Recognized as Safe (GRAS) list. Therefore, over the years, when the utilization of HNTs as filler for active food packaging applications is concerned, several efforts have been made to develop innovative nanomaterials/nanocomposites with ZnO.
In 2015, Pasbakhsh et al. reported the deposition of ZnO on HNTs to obtain a filler for poly(lactic acid) (PLA) films [57]. The nanocomposite obtained showed enhanced mechanical properties in comparison to the neat polymer, and most importantly, it possessed exceptional antimicrobial activities against E. coli and S. aureus.
Similarly, ZnO@HNTs nanomaterials with a nominal wt% ratio of ZnO to halloysite equal to 4 as filler for chitosan/polyvinyl alcohol (CS/PVOH) matrices were obtained [58]. The films were tested for their antimicrobial efficacy against four common food pathogenic bacteria, namely E. coli, S. enterica, L. monocytogenes, and S. aureus. To prove the biological activity, two different parameters were evaluated: the inhibitory activity, by measuring the diameter of the clear inhibition zone, and the bacterial growth inhibition. Both experiments showed enhanced antibacterial activity of the nanocomposite in comparison to chitosan.
Acid-treated HNTs were used as nanocontainers for cinnamaldehyde and as filler in alginate film [59]. The use of HNTs was helpful in slowing down the release of the active ingredient from the film. Kinetic release experiments, using isooctane as the release medium, to simulate fatty foods, showed that after 72 h, the filler containing HNTs still retained about 60 wt% of the total amount of cinnamaldehyde loaded. Antimicrobial tests highlighted the usefulness of HNTs in the nanocomposite; indeed, the hybrid nanocomposite demonstrated prolonged antimicrobial action on E. coli and S. aureus for at least four and five days more, respectively, in comparison to cinnamaldehyde simply dispersed in the alginate.
Similarly, using layer-by-layer (LbL) self-assembly technology [60], HNTs loaded with cinnamaldehyde were further functionalized with positively charged poly(allylamine hydrochloride) (PAH) and negatively charged poly(styrene sulfonate) (PSS). The goal of this kind of functionalization was to cloak the tubes with end-stoppers to avoid the fast release of the active ingredients. The researchers demonstrated that cinnamaldehyde was selectively released at a low pH value; therefore, the nanomaterial could be used to develop smart packaging for food protection. To prove this hypothesis, some antimicrobial tests on S. aureus and a pilot study of packed fresh wheat noodles with the developed nanomaterial were performed. It was demonstrated that the HNT-based nanomaterial showed good fumigant antimicrobial activity, and the total plate count, study of pH and color change, and environmental SEM characterization of the treated noodles highlighted that it can be effectively used to extend the shelf-life of fresh wheat noodles.
Recently, to solve the problems arising from the low water solubility and high volatility of some antimicrobial agents, an innovative strategy was adopted based on Pickering emulsion. In this context, properly modified HNTs were used to prepare emulsions based on cassia oil, selected as the oil phase [61]. To render the external surface of halloysite hydrophobic, and therefore to obtain stable emulsions, HNTs were firstly subjected to ball milling in a polytetrafluoroethylene (PTFE) jar. During the process, PTFE was transferred from the milling jar walls to HNTs surface, changing its hydrophilicity and electrical properties. Finally, the obtained nanomaterials were used as solid particles on the oil−water interface for preparing Pickering emulsions. Antibacterial experiments showed that the use of hydrophobic HNTs as an emulsifier of cassia oil enhanced its antibacterial properties towards S. aureus and E. coli. Bacterial growth kinetics experiments and live/dead bacterial viability assays further confirmed the improved biological properties of the nanoemulsions and showed that cassia oil is slowly released from the HNTs. The results obtained in the present work open the doorway to the use of HNTs as emulsifiers for the preparation of Pickering emulsions for future applications in food protection.

6. Carrier for Pesticides

Population growth has necessitated increased food production, which has been hampered by climate change and agricultural crop pests, to name a few. Up until now, pest control has been a fundamental part of good manufacturing practice in food processing from an economic, hygienic, and regulatory viewpoint. Therefore, the development of systems capable of being carriers and gradually releasing the pesticides is crucial to reducing both their environmental impact and ensuring pest protection over time. In this context, halloysite, which has shown excellent eco-compatibility [62][63][64], represents an inexpensive carrier for several pesticides.
Acid-treated HNTs were used as carrier for chlorpyrifos (CPF), a hydrophobic pesticide, followed by the coating of the tubes with alginate gels, used to slow down the release of the CPF from the tubes. To increase the loading of the active ingredient, a three-dimensional structure involving the acid-treated HNTs was also created via a step-by-step modification of the HNTs’ surface with Ca2+ and EDTA2−, exploiting their strong coordination interactions [65].
In addition to the increase in loading efficiency and slow release of CPF, the synthesized nanopesticide, because of the strong interaction of alginate with plant leaves, shows a foliar adhesion property against rain rinsing that is strengthened by 86% in comparison to pristine CPF, thus reducing the overall environmental impact.
Similarly, CPF was loaded onto modified HNTs to develop a novel pesticide for the control of the growth of beet armyworm (which grows fastest at 35 °C) [66]. The modification of HNTs was achieved by the grafting of a thermo-responsive polymer, poly-isopropylacrylamide (PNIPAAM), followed by a polydopamine coating that was used to avoid fast release of CPF. The nanomaterial showed excellent thermosensitive release performance, with an average release rate of CPF at 35 °C ca. 2.5 times higher than that at 25 °C.
An emulsion of chlorantraniliprole (CAP) in xylene was added to an aqueous HNTs dispersion, forming a three-dimensional network structure that showed increased leaf adhesion, rain erosion resistance, and insecticidal effect in comparison to “free” CAP [67]. To test the insecticidal activity of the synthesized system, S. frugiperda was selected as a pest model. The experimental results showed an increased mortality in the presence of the HNTs based emulsion, indicating that the system is promising for future applications.
The loading of pyrethrum extract into HNTs’ lumen led to the synthesis of nanopesticides where, because of the presence of HNTs, the active ingredients are protected from UV light and slowly released over time. In addition, in vivo tests on two different insects, G. mellonella and T. molitor, chosen as pest models, showed that the nanomaterial was highly active on the first one at a half dose compared to a commercial pesticide [68].

References

  1. Ye, J.J.; Li, L.F.; Hao, R.N.; Gong, M.; Wang, T.; Song, J.; Meng, Q.H.; Zhao, N.N.; Xu, F.J.; Lvov, Y.; et al. Phase-change composite filled natural nanotubes in hydrogel promote wound healing under photothermally triggered drug release. Bioact. Mater. 2023, 21, 284–298.
  2. Shi, R.; Niu, Y.; Gong, M.; Ye, J.; Tian, W.; Zhang, L. Antimicrobial gelatin-based elastomer nanocomposite membrane loaded with ciprofloxacin and polymyxin B sulfate in halloysite nanotubes for wound dressing. Mater. Sci. Eng. C 2018, 87, 128–138.
  3. Meng, Y.; Wang, M.; Tang, M.; Hong, G.; Gao, J.; Chen, Y. Preparation of Robust Superhydrophobic Halloysite Clay Nanotubes via Mussel-Inspired Surface Modification. Appl. Sci. 2017, 7, 1129.
  4. Massaro, M.; Buscemi, G.; Arista, L.; Biddeci, G.; Cavallaro, G.; D’Anna, F.; Di Blasi, F.; Ferrante, A.; Lazzara, G.; Rizzo, C.; et al. Multifunctional Carrier Based on Halloysite/Laponite Hybrid Hydrogel for Kartogenin Delivery. ACS Med. Chem. Lett. 2019, 10, 419–424.
  5. Massaro, M.; Licandro, E.; Cauteruccio, S.; Lazzara, G.; Liotta, L.F.; Notarbartolo, M.; Raymo, F.M.; Sánchez-Espejo, R.; Viseras-Iborra, C.; Riela, S. Nanocarrier based on halloysite and fluorescent probe for intracellular delivery of peptide nucleic acids. J. Colloid Interface Sci. 2022, 620, 221–233.
  6. Stavitskaya, A.V.; Kozlova, E.A.; Kurenkova, A.Y.; Glotov, A.P.; Selischev, D.S.; Ivanov, E.V.; Kozlov, D.V.; Vinokurov, V.A.; Fakhrullin, R.F.; Lvov, Y.M. Ru/CdS Quantum Dots Templated on Clay Nanotubes as Visible-Light-Active Photocatalysts: Optimization of S/Cd Ratio and Ru Content. Chem.—A Eur. J. 2020, 26, 13085–13092.
  7. Stavitskaya, A.; Mazurova, K.; Kotelev, M.; Eliseev, O.; Gushchin, P.; Glotov, A.; Kazantsev, R.; Vinokurov, V.; Lvov, Y. Ruthenium-Loaded Halloysite Nanotubes as Mesocatalysts for Fischer–Tropsch Synthesis. Molecules 2020, 25, 1764.
  8. Stavitskaya, A.; Glotov, A.; Pouresmaeil, F.; Potapenko, K.; Sitmukhanova, E.; Mazurova, K.; Ivanov, E.; Kozlova, E.; Vinokurov, V.; Lvov, Y. CdS Quantum Dots in Hierarchical Mesoporous Silica Templated on Clay Nanotubes: Implications for Photocatalytic Hydrogen Production. ACS Appl. Nano Mater. 2022, 5, 605–614.
  9. Massaro, M.; Colletti, C.G.; Fiore, B.; La Parola, V.; Lazzara, G.; Guernelli, S.; Zaccheroni, N.; Riela, S. Gold nanoparticles stabilized by modified halloysite nanotubes for catalytic applications. Appl. Organomet. Chem. 2019, 33, e4665.
  10. Stavitskaya, A.; Rubtsova, M.; Glotov, A.; Vinokurov, V.; Vutolkina, A.; Fakhrullin, R.; Lvov, Y. Architectural design of core–shell nanotube systems based on aluminosilicate clay. Nanoscale Adv. 2022, 4, 2823–2835.
  11. Massaro, M.; Colletti, C.G.; Guernelli, S.; Lazzara, G.; Liu, M.; Nicotra, G.; Noto, R.; Parisi, F.; Pibiri, I.; Spinella, C.; et al. Photoluminescent hybrid nanomaterials from modified halloysite nanotubes. J. Mater. Chem. C 2018, 6, 7377–7384.
  12. Micó-Vicent, B.; Martínez-Verdú, F.M.; Novikov, A.; Stavitskaya, A.; Vinokurov, V.; Rozhina, E.; Fakhrullin, R.; Yendluri, R.; Lvov, Y. Stabilized Dye–Pigment Formulations with Platy and Tubular Nanoclays. Adv. Funct. Mater. 2018, 28, 1703553.
  13. Kamalieva, R.F.; Ishmukhametov, I.R.; Batasheva, S.N.; Rozhina, E.V.; Fakhrullin, R.F. Uptake of halloysite clay nanotubes by human cells: Colourimetric viability tests and microscopy study. Nano-Struct. Nano-Objects 2018, 15, 54–60.
  14. Fakhrullina, G.I.; Akhatova, F.S.; Lvov, Y.M.; Fakhrullin, R.F. Toxicity of halloysite clay nanotubes in vivo: A Caenorhabditis elegans study. Environ. Sci. Nano 2015, 2, 54–59.
  15. Kryuchkova, M.; Danilushkina, A.; Lvov, Y.; Fakhrullin, R. Evaluation of toxicity of nanoclays and graphene oxide in vivo: A Paramecium caudatum study. Environ. Sci. Nano 2016, 3, 442–452.
  16. Konnova, S.A.; Sharipova, I.R.; Demina, T.A.; Osin, Y.N.; Yarullina, D.R.; Ilinskaya, O.N.; Lvov, Y.M.; Fakhrullin, R.F. Biomimetic cell-mediated three-dimensional assembly of halloysite nanotubes. Chem. Commun. 2013, 49, 4208–4210.
  17. Zhang, Y.; Gao, R.; Liu, M.; Shi, B.; Shan, A.; Cheng, B. Use of modified halloysite nanotubes in the feed reduces the toxic effects of zearalenone on sow reproduction and piglet development. Theriogenology 2015, 83, 932–941.
  18. Nadziakiewicz, M.; Lis, M.W.; Micek, P. The Effect of Dietary Halloysite Supplementation on the Performance of Broiler Chickens and Broiler House Environmental Parameters. Animals 2021, 11, 2040.
  19. Wang, X.; Gong, J.; Rong, R.; Gui, Z.; Hu, T.; Xu, X. Halloysite Nanotubes-Induced Al Accumulation and Fibrotic Response in Lung of Mice after 30-Day Repeated Oral Administration. J. Agric. Food Chem. 2018, 66, 2925–2933.
  20. Prinz Setter, O.; Segal, E. Halloysite nanotubes—The nano-bio interface. Nanoscale 2020, 12, 23444–23460.
  21. Stavitskaya, A.; Batasheva, S.; Vinokurov, V.; Fakhrullina, G.; Sangarov, V.; Lvov, Y.; Fakhrullin, R. Antimicrobial Applications of Clay Nanotube-Based Composites. Nanomaterials 2019, 9, 708.
  22. Saadat, S.; Pandey, G.; Tharmavaram, M.; Braganza, V.; Rawtani, D. Nano-interfacial decoration of Halloysite Nanotubes for the development of antimicrobial nanocomposites. Adv. Colloid Interface Sci. 2020, 275, 102063.
  23. Rapacz-Kmita, A.; Foster, K.; Mikołajczyk, M.; Gajek, M.; Stodolak-Zych, E.; Dudek, M. Functionalized halloysite nanotubes as a novel efficient carrier for gentamicin. Mater. Lett. 2019, 243, 13–16.
  24. Oun, A.A.; Bae, A.Y.; Shin, G.H.; Park, M.-K.; Kim, J.T. Comparative study of oregano essential oil encapsulated in halloysite nanotubes and diatomaceous earth as antimicrobial and antioxidant composites. Appl. Clay Sci. 2022, 224, 106522.
  25. Hendessi, S.; Sevinis, E.B.; Unal, S.; Cebeci, F.C.; Menceloglu, Y.Z.; Unal, H. Antibacterial sustained-release coatings from halloysite nanotubes/waterborne polyurethanes. Prog. Org. Coat. 2016, 101, 253–261.
  26. Krepker, M.; Prinz-Setter, O.; Shemesh, R.; Vaxman, A.; Alperstein, D.; Segal, E. Antimicrobial Carvacrol-Containing Polypropylene Films: Composition, Structure and Function. Polymers 2018, 10, 79.
  27. Stavitskaya, A.; Sitmukhanova, E.; Sayfutdinova, A.; Khusnetdenova, E.; Mazurova, K.; Cherednichenko, K.; Naumenko, E.; Fakhrullin, R. Photoinduced Antibacterial Activity and Cytotoxicity of CdS Stabilized on Mesoporous Aluminosilicates and Silicates. Pharmaceutics 2022, 14, 1309.
  28. Makaremi, M.; Pasbakhsh, P.; Cavallaro, G.; Lazzara, G.; Aw, Y.K.; Lee, S.M.; Milioto, S. Effect of Morphology and Size of Halloysite Nanotubes on Functional Pectin Bionanocomposites for Food Packaging Applications. ACS Appl. Mater. Interfaces 2017, 9, 17476–17488.
  29. Kurczewska, J.; Ratajczak, M.; Gajecka, M. Alginate and pectin films covering halloysite with encapsulated salicylic acid as food packaging components. Appl. Clay Sci. 2021, 214, 106270.
  30. Krepker, M.; Shemesh, R.; Danin Poleg, Y.; Kashi, Y.; Vaxman, A.; Segal, E. Active food packaging films with synergistic antimicrobial activity. Food Control 2017, 76, 117–126.
  31. Alkan Tas, B.; Sehit, E.; Erdinc Tas, C.; Unal, S.; Cebeci, F.C.; Menceloglu, Y.Z.; Unal, H. Carvacrol loaded halloysite coatings for antimicrobial food packaging applications. Food Packag. Shelf Life 2019, 20, 100300.
  32. Ding, X.; Wang, H.; Chen, W.; Liu, J.; Zhang, Y. Preparation and antibacterial activity of copper nanoparticle/halloysite nanotube nanocomposites via reverse atom transfer radical polymerization. RSC Adv. 2014, 4, 41993–41996.
  33. Zhang, J.; Zhang, Y.; Chen, Y.; Du, L.; Zhang, B.; Zhang, H.; Liu, J.; Wang, K. Preparation and Characterization of Novel Polyethersulfone Hybrid Ultrafiltration Membranes Bending with Modified Halloysite Nanotubes Loaded with Silver Nanoparticles. Ind. Eng. Chem. Res. 2012, 51, 3081–3090.
  34. Barman, M.; Mahmood, S.; Augustine, R.; Hasan, A.; Thomas, S.; Ghosal, K. Natural halloysite nanotubes/chitosan based bio-nanocomposite for delivering norfloxacin, an anti-microbial agent in sustained release manner. Int. J. Biol. Macromol. 2020, 162, 1849–1861.
  35. Naz, M.; Jabeen, S.; Gull, N.; Ghaffar, A.; Islam, A.; Rizwan, M.; Abdullah, H.; Rasool, A.; Khan, S.; Khan, R. Novel Silane Crosslinked Chitosan Based Electrospun Nanofiber for Controlled Release of Benzocaine. Front. Mater. 2022, 9, 826251.
  36. Fatahi, Y.; Sanjabi, M.; Rakhshani, A.; Motasadizadeh, H.; Darbasizadeh, B.; Bahadorikhalili, S.; Farhadnejad, H. Levofloxacin-halloysite nanohybrid-loaded fibers based on poly (ethylene oxide) and sodium alginate: Fabrication, characterization, and antibacterial property. J. Drug Deliv. Sci. Technol. 2021, 64, 102598.
  37. Roy, S.; Rhim, J.-W. Effect of chitosan modified halloysite on the physical and functional properties of pullulan/chitosan biofilm integrated with rutin. Appl. Clay Sci. 2021, 211, 106205.
  38. De Silva, R.T.; Dissanayake, R.K.; Mantilaka, M.M.M.G.P.G.; Wijesinghe, W.P.S.L.; Kaleel, S.S.; Premachandra, T.N.; Weerasinghe, L.; Amaratunga, G.A.J.; de Silva, K.M.N. Drug-Loaded Halloysite Nanotube-Reinforced Electrospun Alginate-Based Nanofibrous Scaffolds with Sustained Antimicrobial Protection. ACS Appl. Mater. Interfaces 2018, 10, 33913–33922.
  39. Kim, H.; Lee, J.; Sadeghi, K.; Seo, J. Controlled self-release of ClO2 as an encapsulated antimicrobial agent for smart packaging. Innov. Food Sci. Emerg. Technol. 2021, 74, 102802.
  40. Boro, U.; Priyadarsini, A.; Moholkar, V.S. Synthesis and characterization of poly(lactic acid)/clove essential oil/alkali-treated halloysite nanotubes composite films for food packaging applications. Int. J. Biol. Macromol. 2022, 216, 927–939.
  41. Saadat, S.; Rawtani, D.; Rao, P.K. Antibacterial activity of chitosan film containing Syzygium aromaticum (clove) oil encapsulated halloysite nanotubes against foodborne pathogenic bacterial strains. Mater. Today Commun. 2022, 32, 104132.
  42. Lu, L.; Su, Y.; Xu, J.; Ning, H.; Cheng, X.; Lu, L. Development of gas phase controlled-release antimicrobial and antioxidant packaging film containing carvacrol loaded with HNT-4M (halloysite nanotubes etched by 4 mol/L hydrochloric acid). Food Packag. Shelf Life 2022, 31, 100783.
  43. Wu, M.; Liu, W.; Yao, J.; Shao, Z.; Chen, X. Silk microfibrous mats with long-lasting antimicrobial function. J. Mater. Sci. Technol. 2021, 63, 203–209.
  44. Cyphert, E.L.; Zhang, N.; Learn, G.D.; Hernandez, C.J.; von Recum, H.A. Recent Advances in the Evaluation of Antimicrobial Materials for Resolution of Orthopedic Implant-Associated Infections In Vivo. ACS Infect. Dis. 2021, 7, 3125–3160.
  45. Wei, W.; Abdullayev, E.; Hollister, A.; Mills, D.; Lvov, Y.M. Clay Nanotube/Poly(methyl methacrylate) Bone Cement Composites with Sustained Antibiotic Release. Macromol. Mater. Eng. 2012, 297, 645–653.
  46. Guarch-Pérez, C.; Shaqour, B.; Riool, M.; Verleije, B.; Beyers, K.; Vervaet, C.; Cos, P.; Zaat, S.A.J. 3D-Printed Gentamicin-Releasing Poly-ε-Caprolactone Composite Prevents Fracture-Related Staphylococcus aureus Infection in Mice. Pharmaceutics 2022, 14, 1363.
  47. Bernabe, E.; Marcenes, W.; Hernandez, C.R.; Bailey, J.; Abreu, L.G.; Alipour, V.; Amini, S.; Arabloo, J.; Arefi, Z.; Arora, A.; et al. Global, Regional, and National Levels and Trends in Burden of Oral Conditions from 1990 to 2017: A Systematic Analysis for the Global Burden of Disease 2017 Study. J. Dent. Res. 2020, 99, 362–373.
  48. Ribeiro, J.S.; Bordini, E.A.F.; Ferreira, J.A.; Mei, L.; Dubey, N.; Fenno, J.C.; Piva, E.; Lund, R.G.; Schwendeman, A.; Bottino, M.C. Injectable MMP-Responsive Nanotube-Modified Gelatin Hydrogel for Dental Infection Ablation. ACS Appl. Mater. Interfaces 2020, 12, 16006–16017.
  49. Barot, T.; Rawtani, D.; Kulkarni, P. Development of Chlorhexidine Loaded Halloysite Nanotube Based Experimental Resin Composite with Enhanced Physico-Mechanical and Biological Properties for Dental Applications. J. Compos. Sci. 2020, 4, 81.
  50. Marinelli, L.; Cacciatore, I.; Eusepi, P.; Dimmito, M.P.; Di Rienzo, A.; Reale, M.; Costantini, E.; Borrego-Sánchez, A.; García-Villén, F.; Viseras, C.; et al. In Vitro Wound-Healing Properties of Water-Soluble Terpenoids Loaded on Halloysite Clay. Pharmaceutics 2021, 13, 1117.
  51. Zhao, P.; Feng, Y.; Zhou, Y.; Tan, C.; Liu, M. nanotubes-chitin composite hydrogel with antibacterial and hemostatic activity for wound healing. Bioact. Mater. 2023, 20, 355–367.
  52. Chawla, R.; Sivakumar, S.; Kaur, H. Antimicrobial edible films in food packaging: Current scenario and recent nanotechnological advancements—A review. Carbohydr. Polym. Technol. Appl. 2021, 2, 100024.
  53. Jang, S.-H.; Jang, S.-R.; Lee, G.-M.; Ryu, J.-H.; Park, S.-I.; Park, N.-H. Halloysite Nanocapsules Containing Thyme Essential Oil: Preparation, Characterization, and Application in Packaging Materials. J. Food Sci. 2017, 82, 2113–2120.
  54. Gorrasi, G. Dispersion of halloysite loaded with natural antimicrobials into pectins: Characterization and controlled release analysis. Carbohydr. Polym. 2015, 127, 47–53.
  55. Biddeci, G.; Cavallaro, G.; Di Blasi, F.; Lazzara, G.; Massaro, M.; Milioto, S.; Parisi, F.; Riela, S.; Spinelli, G. Halloysite nanotubes loaded with peppermint essential oil as filler for functional biopolymer film. Carbohydr. Polym. 2016, 152, 548–557.
  56. Viscusi, G.; Lamberti, E.; D’Amico, F.; Tammaro, L.; Gorrasi, G. Fabrication and Characterization of Bio-Nanocomposites Based on Halloysite-Encapsulating Grapefruit Seed Oil in a Pectin Matrix as a Novel Bio-Coating for Strawberry Protection. Nanomaterials 2022, 12, 1265.
  57. De Silva, R.T.; Pasbakhsh, P.; Lee, S.M.; Kit, A.Y. ZnO deposited/encapsulated halloysite–poly (lactic acid) (PLA) nanocomposites for high performance packaging films with improved mechanical and antimicrobial properties. Appl. Clay Sci. 2015, 111, 10–20.
  58. Giannakas, A.E.; Salmas, C.E.; Moschovas, D.; Baikousi, M.; Kollia, E.; Tsigkou, V.; Karakassides, A.; Leontiou, A.; Kehayias, G.; Avgeropoulos, A.; et al. Nanocomposite Film Development Based on Chitosan/Polyvinyl Alcohol Using and Hybrid Nanostructures for Active Food Packaging Applications. Nanomaterials 2022, 12, 1843.
  59. Cui, R.; Zhu, B.; Yan, J.; Qin, Y.; Yuan, M.; Cheng, G.; Yuan, M. Development of a Sodium Alginate-Based Active Package with Controlled Release of Cinnamaldehyde Loaded on Halloysite Nanotubes. Foods 2021, 10, 1150.
  60. Li, Q.; Ren, T.; Perkins, P. The development and application of nanocomposites with pH-sensitive “gates” to control the release of active agents: Extending the shelf-life of fresh wheat noodles. Food Control 2022, 132, 108563.
  61. Tan, C.; Zhao, P.; Zhou, Y.; Liu, M. Hydrophobic Halloysite Nanotubes via Ball Milling for Stable Pickering Emulsions: Implications for Food Preservation. ACS Appl. Nano Mater. 2022, 5, 11289–11301.
  62. Bellani, L.; Giorgetti, L.; Riela, S.; Lazzara, G.; Scialabba, A.; Massaro, M. Ecotoxicity of halloysite nanotube–supported palladium nanoparticles in Raphanus sativus L. Environ. Toxicol. Chem. 2016, 35, 2503–2510.
  63. Huang, X.; Huang, Y.; Wang, D.; Liu, M.; Li, J.; Chen, D. Cellular response of freshwater algae to halloysite nanotubes: Alteration of oxidative stress and membrane function. Environ. Sci. Nano 2021, 8, 3262–3272.
  64. Chen, L.; Guo, Z.; Lao, B.; Li, C.; Zhu, J.; Yu, R.; Liu, M. Phytotoxicity of halloysite nanotubes using wheat as a model: Seed germination and growth. Environ. Sci. Nano 2021, 8, 3015–3027.
  65. Teng, G.; Chen, C.; Jing, N.; Chen, C.; Duan, Y.; Zhang, L.; Wu, Z.; Zhang, J. Halloysite nanotubes-based composite material with acid/alkali dual pH response and foliar adhesion for smart delivery of hydrophobic pesticide. Chem. Eng. J. 2023, 451, 139052.
  66. Qin, Y.; An, T.; Cheng, H.; Su, W.; Meng, G.; Wu, J.; Guo, X.; Liu, Z. Functionalized halloysite nanotubes as chlorpyrifos carriers with high adhesion and temperature response for controlling of beet armyworm. Appl. Clay Sci. 2022, 222, 106488.
  67. Chen, L.; Huang, J.; Chen, J.; Shi, Q.; Chen, T.; Qi, G.; Liu, M. Halloysite Nanotube-Based Pesticide Formulations with Enhanced Rain Erosion Resistance, Foliar Adhesion, and Insecticidal Effect. ACS Appl. Mater. Interfaces 2022, 14, 41605–41617.
  68. Massaro, M.; Pieraccini, S.; Guernelli, S.; Dindo, M.L.; Francati, S.; Liotta, L.F.; Colletti, G.C.; Masiero, S.; Riela, S. Photostability assessment of natural pyrethrins using halloysite nanotube carrier system. Appl. Clay Sci. 2022, 230, 106719.
More
© Text is available under the terms and conditions of the Creative Commons Attribution (CC BY) license; additional terms may apply. By using this site, you agree to the Terms and Conditions and Privacy Policy.
Upload a video for this entry
Information
Subjects: Chemistry, Medicinal; Nanoscience & Nanotechnology
Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register :
Marina Massaro
,
Rebecca Ciani
,
Giuseppe Cinà
,
Carmelo Giuseppe Colletti
,
Federica Leone
,
Serena Riela
View Times: 539
Entry Collection: Biopharmaceuticals Technology
Revisions: 2 times (View History)
Update Date: 08 Jan 2023
Table of Contents
    1000/1000
    Hot Most Recent
    ScholarVision Creations
    Feedback