Tubular Nanocontainers for Drug Delivery

Halloysite Nanotubes: Controlled Access and Release by Smart Gates

© 2017 by the authors. Licensee MDPI, Basel, Switzerland. Hollow halloysite nanotubes have been used as nanocontainers for loading and for the triggered release of calcium hydroxide for paper preservation. A strategy for placing end-stoppers into the tubular nanocontainer is proposed and the sustained release from the cavity is reported. The incorporation of Ca(OH) 2 into the nanotube lumen, as demonstrated using transmission electron microscopy (TEM) imaging and Energy Dispersive X-ray (EDX) mapping, retards the carbonatation, delaying the reaction with CO 2 gas. This effect can be further controlled by placing the end-stoppers. The obtained material is tested for paper deacidification. We…

Selective Cytotoxic Activity of Prodigiosin@halloysite Nanoformulation

Prodigiosin, a bioactive secondary metabolite produced by Serratia marcescens, is an effective proapoptotic agent against various cancer cell lines, with little or no toxicity toward normal cells. The hydrophobicity of prodigiosin limits its use for medical and biotechnological applications, these limitations, however, can be overcome by using nanoscale drug carriers, resulting in promising formulations for target delivery systems with great potential for anticancer therapy. Here we report on prodigiosin-loaded halloysite-based nanoformulation and its effects on viability of malignant and non-malignant cells. We have found that prodigiosin-loaded halloysite nanotubes inhibit human epithelia…

Core/Shell Gel Beads with Embedded Halloysite Nanotubes for Controlled Drug Release

The use of nanocomposites based on biopolymers and nanoparticles for controlled drug release is an attractive notion. We used halloysite nanotubes that were promising candidates for the loading and release of active molecules due to their hollow cavity. Gel beads based on chitosan with uniformly dispersed halloysite nanotubes were obtained by a dropping method. Alginate was used to generate a coating layer over the hybrid gel beads. This proposed procedure succeeded in controlling the morphology at the mesoscale and it had a relevant effect on the release profile of the model drug from the nanotube cavity.

Composite films of natural clay nanotubes with cellulose and chitosan

Composite films based on cellulose, chitosan and halloysite clay nanotubes were prepared using a solution casting method, which allowed for a uniform distribution of nanotubes within the material and provided control over the morphology of the composite. The mechanical performance of these bio nanocomposites is influenced by humidity and the nanotubes showed a plasticisation effect on the polymeric matrix. The composites of chitosan and halloysite nanotubes (HNTs), with modified hydrophobic inner lumens, resulted in a technique for controlled and sustainable surface cleaning. Lignocellulose wood microfibres modified with HNTs were also produced by a layer-by-layer assembly. The obtained ma…

Nanohydrogel Formation within the Halloysite Lumen for Triggered and Sustained Release

An easy strategy to obtain nanohydrogels within the halloysite nanotube (HNTs) lumen was investigated. Inorganic reverse micelles based on HNTs and hexadecyltrimethylammonium bromides were dispersed in chloroform, and the hydrophilic cavity was used as a nanoreactor to confine the gel formation based on alginate cross-linked by calcium ions. Spectroscopy and electron microscopy experiments proved the confinement of the polymer into the HNT lumen and the formation of calcium-mediated networks. Biological tests proved the biocompatibility of the hybrid hydrogel. The nanogel in HNTs was suitable for drug loading and sustained release with the opportunity of triggered burst release by chemical …

Selective Antimicrobial Effects of Curcumin@Halloysite Nanoformulation: A Caenorhabditis elegans Study

Alterations in the normal gastrointestinal microbial community caused by unhealthy diet, environmental factors, and antibiotic overuse may severely affect human health and well-being. Novel antimicrobial drug formulations targeting pathogenic microflora while not affecting or even supporting symbiotic microflora are urgently needed. Here we report fabrication of a novel antimicrobial nanocontainer based on halloysite nanotubes loaded with curcumin and protected with a dextrin outer layer (HNTs+Curc/DX) and its effective use to suppress the overgrowth of pathogenic bacteria in Caenorhabditis elegans nematodes. Nanocontainers have been obtained using vacuum-facilitated loading of hydrophobic …

Organic-nanoclay composite materials as removal agents for environmental decontamination

Here we overview the recent advances in the fabrication of sustainable composite nanomaterials with decontamination capacity towards inorganic and organic pollutants. In this regards, we present the development of hybrid systems based on clay nanoparticles with different shapes (such as kaolinite nanosheets and halloysite nanotubes) and organic molecules (biopolymers, surfactants, cucurbituril) as efficient removal agents for both aliphatic and aromatic hydrocarbons. Due to their high specific surface area, clay nanoparticles have been successfully employed as fillers for composite membranes with excellent filtration capacity. The preparation of composite gel beads based on biopolymers (alg…

Restoration of a XVII Century’s predella reliquary: From Physico-Chemical Characterization to the Conservation Process

We report on the restoration of a XVII century’s predella reliquary, which is a part of a larger setup that includes a wall reliquary and a wooden crucified Christ, both belonging to the church of “Madre Maria SS. Assunta”, in Polizzi Generosa, Sicily, Italy. The historical/artistic and paleographic research was flanked successfully by the scientific objective characterization of the materials. The scientific approach was relevant in the definition of the steps for the restoration of the artefact. The optical microscopy was used for the identification of the wood species. Electron microscopy and elemental mapping by energy-dispersive X-ray (EDX) was successful in the identification of the l…

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 an…

Magnetic coiffure: Engineering of human hair surfaces with polyelectrolyte-stabilised magnetite nanoparticles

Here we report a spontaneous electrostatic coating of human hair with aqueous Fe3O4 colloids capable to tailor magnetic properties to hair, orienting and even moving them under the influence of the external magnetic field. Magnetite particles were modified by cationic and anionic polyelectrolytes and then successfully deposited in dense arrays, starting from cuticle gaps and spreading further over a major hair surface. These biocompatible and biodegradable magnetic nanoparticles may serve as carriers for drug loading and delivery for topical pharmaceutical treatments. The deposition process was imaged in real-time using dark-field microscopy. The hair specimens were further studied using a …

Mesoporous inorganic nanoscale particles for drug adsorption and controlled release.

The review provides an overview of the mesoporous inorganic particles employed as drug delivery systems for controlled and sustained release of drugs. We have classified promising nanomaterials for drug delivery on the basis of their natural or synthetic origin. Nanoclays are available in different morphologies (nanotubes, nanoplates and nanofibers) and they are typically available at low cost from natural resources. The surface chemistry of nanoclays is versatile for targeted modifications to control loading and release properties. Synthetic nanomaterials (imogolite, laponite and mesoporous silica) present the advantages of well-established purity and availability with size features that …

Pickering Emulsion Gels Based on Halloysite Nanotubes and Ionic Biopolymers: Properties and Cleaning Action on Marble Surface

We have fabricated ecocompatible Pickering emulsions based on halloysite nanotubes and ionic biopolymers (chitosan and pectin) from renewable resources. The effect of pectin and chitosan on the Pickering emulsion was investigated by direct visualization of the oil droplets and by the thermodynamic characterization at the interface. Pectin enhances the Pickering emulsion stability, while a phase separation and nonhomogeneous gel was observed in the presence of chitosan. We have demonstrated that the Pickering emulsion in a pectin based gel phase is suitable for wax layer removal from a marble surface. A controlled cleaning is achieved by tuning the contact time between the gel and the marble…

Clay-based drug-delivery systems: what does the future hold?

Clays for drug delivery have been used from ancient time due to the large availability of clay minerals and their unprecedented properties. The empirical use of nanoclays from the past is converted in a stimulating scientific task aimed at building up nanoarchitectonic vehicles for drug delivery in a targeted and stimuli-responsive fashion. Here the historical aspects are discussed; next the modern examples of applications of different clay-based materials are discussed. A special focus is given to halloysite clay nanotubes, which are an emerging and very promising nanomaterial for drug-delivery purposes due to its special morphology and unique chemical properties. Advantages and limitatio…

Halloysite/Keratin Nanocomposite for Human Hair Photoprotection Coating

We propose a novel keratin treatment of human hair by its aqueous mixtures with natural halloysite clay nanotubes. The loaded clay nanotubes together with free keratin produce micrometer-thick protective coating on hair. First, colloidal and structural properties of halloysite/keratin dispersions and the nanotube loaded with this protein were investigated. Above the keratin isoelectric point (pH = 4), the protein adsorption into the positive halloysite lumen is favored because of the electrostatic attractions. The ζ-potential magnitude of these core-shell particles increased from -35 (in pristine form) to -43 mV allowing for an enhanced colloidal stability (15 h at pH = 6). This keratin-cla…

An assembly of organic-inorganic composites using halloysite clay nanotubes

Halloysite is natural tubular clay suitable as a component of biocompatible nanosystems with specific functionalities. The selective modification of halloysite inner/outer surfaces can be achieved by exploiting supramolecular and covalent interactions resulting in controlled colloidal stability adjusted to the solvent polarity. The functionalized halloysite nanotubes can be employed as reinforcing filler for polymers as well as carriers for the sustained release of active molecules, such as antioxidants, flame-retardants, corrosion inhibitors, biocides and drugs. The tubular morphology makes halloysite a perspective template for core-shell metal supports for mesoporous catalysts. The cataly…