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Special Issue "Recent Research Advance in the Halloysite Nanotubes Field"

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A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (28 February 2023) | Viewed by 21206

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Dr. Serena Riela

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Department of Biological, Chemical and Pharmaceutical Sciences and Technologies (STEBICEF), University of Palermo Viale delle Scienze, 90128 Palermo, Italy
Interests: organic chemistry; synthesis; drug delivery; coniugates; hallosyte nanotubes; carrier systems; nanomaterials; biocompatible materials
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Dr. Marina Massaro

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Guest Editor

Department of Biological, Chemical and Pharmaceutical Sciences and Technologies, University of Palermo, Palermo, Italy
Interests: clay minerals; halloysite nanotubes; surface modification
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Halloysite (HNT) is a promising natural nanosized tubular clay mineral that has many important uses in different industrial fields. It is naturally occurring, biocompatible, and available in thousands of tons at low cost. As a consequence of a hollow cavity, HNT is mainly used as nanocontainer for the controlled release of several chemicals. The surface chemistry of HNTs is versatile for the targeted chemical modification of the inner lumen and outer surface and opens up several strategies to obtain novel nanomaterials of potential practical interest.

This Special Issue is focused on current research on halloysite-based nanomaterial from the state-of-the-art to the most recent advancements, with a special focus on the design of modified halloysite hybrids and their applications in biomedical, bioremediation, food packaging, and polymeric fields. Original contributions addressing the synthesis and characterization of HNT hybrids and related mechanisms involved in adsorption and release of active molecules, and/or metal nanoparticles as well as practical biological, industrial, or environmental applications, in the form of full papers or communications, are welcome. Mini-reviews presenting an overview of the state-of-the-art with projections on future perspectives and trends in this domain will also be considered.

Assoc. Prof. Dr. Serena Riela
Dr. Marina Massaro
Guest Editors

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Keywords

Halloysite nanotubes
HNT modification
Catalytic supports
Drug carrier and delivery
Filler for polymeric matrices

Published Papers (5 papers)

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Research

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Open AccessArticle

Cell Membrane-Coated Halloysite Nanotubes for Target-Specific Nanocarrier for Cancer Phototherapy

and

Molecules 2021, 26(15), 4483; https://doi.org/10.3390/molecules26154483 - 25 Jul 2021

Cited by 9 | Viewed by 1867

Abstract

Naturally-occurring halloysite nanotubes (HNTs) have many advantages for constructing target-specific delivery of phototherapeutic agents. Here, HNTs were labeled with fluorescein isothiocyanate (FITC) and loaded with the type-II photosensitizer indocyanine green (ICG) for phototherapy. HNTs-FITC-ICG was structurally stable due to presence of HNTs as the nanocarrier and protective agent. The nanocarrier was further wrapped with red blood cell membrane (RBCM) to enhance the biocompatibility. The HNTs-FITC-ICG-RBCM nanocarrier show high cytocompatibility and hemocompatibility. Due to the photothermal effect of ICG, a significant temperature rising was achieved by irradiation of the nanocarrier using 808 nm laser. The photothermal temperature rising was used to kill the cancer cells effectively. The HNTs-FITC-ICG-RBCM nanocarrier was further linked with anti-EpCAM to endow it with targeting therapy performance against breast cancer, and the anti-EpCAM-conjugated nanocarrier exhibited significantly tumor-specific accumulation. The RBCM-coated and biocompatible HNTs nanocarrier is a promising candidate for target-specific therapy of cancer. Full article

(This article belongs to the Special Issue Recent Research Advance in the Halloysite Nanotubes Field)

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Open AccessArticle

Theoretical Study of Retinol, Niacinamide and Glycolic Acid with Halloysite Clay Mineral as Active Ingredients for Topical Skin Care Formulations

Ana Borrego-Sánchez

Claro Ignacio Sainz-Díaz

Luana Perioli

and

César Viseras

Molecules 2021, 26(15), 4392; https://doi.org/10.3390/molecules26154392 - 21 Jul 2021

Cited by 6 | Viewed by 4521

Abstract

The adsorption of retinol, niacinamide and glycolic acid active ingredients on the internal surface of halloysite in an aqueous environment was explored at the molecular level by means of calculations based on quantum mechanics and force fields from empirical interatomic potentials. These active ingredients are stably adsorbed on the internal surface of halloysite forming hydrogen bonds between the hydrogen, oxygen and nitrogen atoms with the hydroxyl groups of the inner surface of the halloysite. In addition, electrostatic interaction between these active ingredients with the water molecules was observed. Therefore, the theoretical results indicate that the adsorption of these active principles is favourable in the halloysite nanotube, which allows directing future experimental investigations for the development and design of retinol, niacinamide and glycolic acid with halloysite nanotubes systems, which may be topical formulations for skincare. Full article

(This article belongs to the Special Issue Recent Research Advance in the Halloysite Nanotubes Field)

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Open AccessArticle

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

Läysän Nigamatzyanova

Vladimir Evtugyn

Elvira Rozhina

and

Rawil Fakhrullin

Molecules 2020, 25(15), 3557; https://doi.org/10.3390/molecules25153557 - 04 Aug 2020

Cited by 22 | Viewed by 3358

Abstract

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). Full article

(This article belongs to the Special Issue Recent Research Advance in the Halloysite Nanotubes Field)

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Open AccessEditor’s ChoiceArticle

Ruthenium-Loaded Halloysite Nanotubes as Mesocatalysts for Fischer–Tropsch Synthesis

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Molecules 2020, 25(8), 1764; https://doi.org/10.3390/molecules25081764 - 11 Apr 2020

Cited by 26 | Viewed by 3751

Abstract

Halloysite aluminosilicate nanotubes loaded with ruthenium particles were used as reactors for Fischer–Tropsch synthesis. To load ruthenium inside clay, selective modification of the external surface with ethylenediaminetetraacetic acid, urea, or acetone azine was performed. Reduction of materials in a flow of hydrogen at 400 °C resulted in catalysts loaded with 2 wt.% of 3.5 nm Ru particles, densely packed inside the tubes. Catalysts were characterized by N₂-adsorption, temperature-programmed desorption of ammonia, transmission electron microscopy, X-ray fluorescence, and X-ray diffraction analysis. We concluded that the total acidity and specific morphology of reactors were the major factors influencing activity and selectivity toward CH₄, C_2–4, and C₅₊ hydrocarbons in the Fischer–Tropsch process. Use of ethylenediaminetetraacetic acid for ruthenium binding gave a methanation catalyst with ca. 50% selectivity to methane and C_2–4. Urea-modified halloysite resulted in the Ru-nanoreactors with high selectivity to valuable C₅₊ hydrocarbons containing few olefins and a high number of heavy fractions (α = 0.87). Modification with acetone azine gave the slightly higher CO conversion rate close to 19% and highest selectivity in C₅₊ products. Using a halloysite tube with a 10–20-nm lumen decreased the diffusion limitation and helped to produce high-molecular-weight hydrocarbons. The extremely small C₂–C₄ fraction obtained from the urea- and azine-modified sample was not reachable for non-templated Ru-nanoparticles. Dense packing of Ru nanoparticles increased the contact time of olefins and their reabsorption, producing higher amounts of C₅₊ hydrocarbons. Loading of Ru inside the nanoclay increased the particle stability and prevented their aggregation under reaction conditions. Full article

(This article belongs to the Special Issue Recent Research Advance in the Halloysite Nanotubes Field)

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Review

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Open AccessReview

Past, Present and Future Perspectives on Halloysite Clay Minerals

Marina Massaro

Renato Noto

and

Serena Riela

Molecules 2020, 25(20), 4863; https://doi.org/10.3390/molecules25204863 - 21 Oct 2020

Cited by 77 | Viewed by 6871

Abstract

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. Full article

(This article belongs to the Special Issue Recent Research Advance in the Halloysite Nanotubes Field)

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