Co-loaded cardanol/triazole-halloysite system: characterization of the supramolecular complex and evaluation of its antiproliferative activity

Halloysite nanotubes modified with triazolium salts (f-HNT) were found to be promising drug carriers for biological molecules [1 ]. In this work we report data about f-HNT as carrier for cardanol, a molecule with interesting biological activity [2]. The interactio n between cardanol and f- HNT was highlighted by HPLC, FTIR spectroscopy, TGA , water contact angle measurements and SEM investigations. Release of cardanol from the system and cytotoxic e ffect of the complex f- HNT/Card on hepatocarcinoma cell lines were, also, evaluated. The obtained results put forward the use of halloysite as drug c arrier

Ecocompatible Halloysite/Cucurbit[8]uril Hybrid as Efficient Nanosponge for Pollutants Removal

Hybrid materials based on halloysite nanotubes (HNT) and cucurbit[8]uril (CB[8]) were prepared with the aim to obtain efficient nanosponges towards hydrocarbons both in liquid and vapor phases. The loading on both HNT surfaces and the hybrid morphology were evidenced by FTIR spectroscopy, thermogravimetric analysis and scanning electron microscopy. In order to highlight the interactions in the hybrid 13C {1H} CP-MAS NMR experiments were performed. The aqueous colloidal stability of HNT/CB[8] was highlighted through ζ potential and dynamic light scattering measurements. The HNT/CB[8] composite was employed as nanosponge to capture aromatic oils in aqueous phase as evidenced by fluorescence e…

SYNTHESIS AND CHARACTERIZATION BY THERMOGRAVIMETRIC ANALYSIS OF A NEW DRUG DELIVERY SYSTEM BASED ON HALLOYSITE NANOTUBES

Synthesis and characterization of nanomaterial based on halloysite and hectorite clay minerals covalently bridged

Halloysite is an aluminosilicate clay with a predominantly hollow tubular structure (HNTs) able to act as a nanocontainer for the encapsulation of several chemicals. However, HNTs possess low affinity for metal ions in their pristine form and they need to be modified for improving their adsorption capabilities. Therefore, to overcome this issue herein we report a straightforward approach for the covalent modification of the external surface of halloysite nanotubes with hectorite clay. Compared to halloysite, hectorite possesses a lamellar structure with higher cation exchange capacity. The covalent linkage between the two clays was verified by several techniques (FTIR spectroscopy, 13C CP-M…

Functionalized halloysite nanotubes: Efficient carrier systems for antifungine drugs

Abstract Halloysite-cyclodextrin hybrid was employed as carrier for sustained release of clotrimazole for vaginal or buccal treatment of Candidiasis. The nanocarrier was obtained by functionalization of halloysite surface with cyclodextrin moieties by means of microwave irradiation, with the final goal to obtain a scaffold for the covalent linkage of cysteamine hydrochloride. The interaction between clotrimazole and the pristine components, namely cyclodextrin and halloysite, was thoroughly investigated by several techniques such as DSC, TGA, UV–vis spectroscopy and some adsorption studies were, also, carried out. The release of the antifungine molecule was finally investigated in a medium …

Pharmaceutical properties of supramolecular assembly of co-loaded cardanol/triazole-halloysite systems

Halloysite nanotubes were explored as drug carrier for cardanol, which is considered as a promising natural anticancer active species. To this aim, besides the pristine nanoclay, a chemical modification of the nanocarrier was performed by attaching triazolium salts with different hydrophobicity at the outer surface of the hollow nanotubes. The interaction between cardanol and nanotubes was highlighted in solution by HPLC. This method proved the loading of the drug into the nanotubes. The solid dried complexes formed by pristine and modified halloysite with the cardanol were characterized by IR spectroscopy, thermogravimetric analysis as well as water contact angle to evidence the structure,…

Palladium supported on Halloysite-triazolium salts as catalyst for ligand free Suzuki cross-coupling in water under microwave irradiation

Abstract Environmental friendly halloysite-dicationic triazolium salts (second generation) obtained by subsequent click reactions of a diyne derivative in the presence of 2-azidopropyl-modified halloysite nanotubes, were used as supports for palladium catalyst. Thanks to the high triazolium loading (25%) these materials were able to support higher amount of the metal than that on the monocationic derivative (first generation). Such materials were characterized by thermogravimetric analysis, FT-IR spectroscopy and SEM investigations. The new catalytic system was employed in the ligand free Suzuki cross-coupling under microwave irradiation. A set of solvent, time and% loading of palladium was…

Multicavity halloysite-amphiphilic cyclodextrin hybrids for co-delivery of natural drugs into thyroid cancer cells

Multicavity halloysite nanotube materials were employed as simultaneous carriers for two different natural drugs, silibinin and quercetin, at 6.1% and 2.2% drug loadings, respectively. The materials were obtained by grafting functionalized amphiphilic cyclodextrin onto the HNT external surface. The new materials were characterized by FT-IR spectroscopy, SEM, thermogravimetry, turbidimetry, dynamic light scattering and ζ-potential techniques. The interaction of the two molecules with the carrier was studied by HPLC measurements and fluorescence spectroscopy, respectively. The release of the drugs from HNT-amphiphilic cyclodextrin, at two different pH values, was also investigated by means of…

Synthesis and Characterization of Halloysite-Cyclodextrin Nanosponges for Enhanced Dyes Adsorption

Inorganic-organic nanosponge hybrids based on halloysite clay and organic cyclodextrin derivatives (HNT-CDs) were developed by means of microwave irradiations in solvent-free conditions. The HNT-CDs nanomaterials characterized by FT-IR, TGA, BET, TEM, SEM, DLS, and zeta-potential have showed a hyper-reticulated network which possesses both HNT and cyclodextrin peculiarities. The new HNT-CDs nanosponge hybrids were employed as nanoadsorbents, first choosing Rhodamine B as the dye model, and furthermore for the removal of some cationic and anionic dyes, under different pH values (1.0, 4.54, and 7.4). The collected results showed that the pH solution as well as the electrostatic interactions a…

Palladium nanoparticles immobilized on halloysite nanotubes covered by a multilayer network for catalytic applications

The synthesis of pure fine chemicals for industrial purposes is one of the most attractive challenges of chemical research. The use of catalytic pathways mediated by palladium nanoparticles (PdNPs) for C-C bond formation is a useful way to obtain these kinds of compounds. To achieve this objective, the PdNPs can be efficiently loaded on a functionalized natural nanostructured support such as halloysite nanotubes (HNTs). Hybrid materials based on thiol functionalized halloysite nanotubes and highly cross-linked imidazolium salts were successfully developed and used for the stabilization of PdNPs. The HNT/Pd hybrids were thoroughly characterized from a physico-chemical point of view and teste…

1,2,3-Oligotriazoles modified halloysite nanotubes as potential active biological species: synthesis and characterization

In the last years, the development of nano-formulations for cancer treatment represents one of the major challenges of the scientific research. The prodrug strategy, that combines chemotherapeutic agents with nanocarriers such as halloysite nanotubes (HNTs), is a promising strategy both to improve the biological activity of the drug molecules and to reduce the side effects of drugs. Herein we report the synthesis and characterization of a HNTs prodrug based on 1,2,3-triazole units covalently linked to HNTs external surface, bearing different positively charged moieties, which could present interesting pharmacological activities.

SYNTHESIS AND EVALUATION OF CATALYTIC ACTIVITY IN WATER AND MICROWAVE IRRADIATION OF A NEW SUPPORT BASED ON HNT TRIAZOLIUM SALTS

In the last years SILLP (supported ionic liquid-like phase)-based materials prepared by covalent attachment have been synthesized [1]. Recently, we have synthesized a palladium-based catalytic system using halloysite nanotubes modified with octylimidazolium moieties and we have tested it in the Suzuki cross-coupling reaction under traditional heating, microwave irradiation and a very small amount of Pd catalyst [2,3]. It is known that support based on triazole motif showed superior activity to the analogous imidazole molecules [4] so, we have focused our attention to develop a new SILLP system with triazolium moiety. Herein we report the synthesis of an original Pd-dicationic triazolium sup…

Photoluminescent hybrid nanomaterials from modified halloysite nanotubes

The synthesis of photoluminescent nanomaterials based on halloysite nanotubes is described. The obtained hybrid was characterized by means of TGA, FT-IR, DLS and XPS measurements; in addition its morphology was imaged by TEM and HR-TEM. The HNT hybrid also exhibited photoluminescent properties, both in solution and in the solid state, and white-light emission (0.24, 0.36; CIE coordinates) was observed. This work could be pioneering as a new strategy for manufacturing both LEDs and fluorescent tags based on HNT nanomaterials. © 2018 The Royal Society of Chemistry.

SYNTHESIS AND CHARACTERIZATION OF POSITIVELY CHARGED FUNCTIONALIZED HALLOYSITE/CURCUMIN SYSTEMS AND EVALUATION OF THEIR ANTICANCER ACTIVITY

Phenolic compound originated from one of the main class of secondary metabolites, as curcumin and its derivatives have been studied and their biological and pharmacological activities have been evaluated, too [1,2]. Unfortunately, curcumin exhibits poor bioavailability after oral or topic administration [3]. Therefore a carefully designed carrier could significantly facilitate curcumin delivery and broaden the range of its possible pharmaceutical applications. Halloysite was found to be a viable and inexpensive nanoscale container for the encapsulation of biological active molecules [4]. In this communication we report data about a new potential curcumin carrier based on positively charged …

Synthesis, characterization and study of covalently modified triazole LAPONITE® edges

Abstract LAPONITE® (Lap) clay mineral was successful functionalized by triazole groups in a two steps procedure. First, the Lap edges were modified with 3-azidopropyltrimethoxysilane by traditional heating and microwave irradiation. Microwave irradiation allowed us to obtain high loading onto the Lap edges in lower times compared to those obtained through conventional method. Afterwards, the triazole moieties were obtained by reaction between azido functionalized Lap and propargyl alcohol. The successful functionalization of Lap was proved by thermogravimetric analysis, FT-IR spectroscopy, dynamic light scattering and ζ-potential measurements. Finally, the effects of the surface modificatio…

The Use of Some Clay Minerals as Natural Resources for Drug Carrier Applications

The goal of modern research is to use environmentally preferable materials. In this context, clay minerals are emerging candidates for their bio- and ecocompatibility, low cost and natural availability. Clay minerals present different morphologies according to their layer arrangements. The use of clay minerals, especially in biomedical applications is known from ancient times and they are regaining attention in recent years. The most representative clay minerals are kaolinit, montmorillonite, sepiolites and halloysite. This review summarizes some clay minerals and their derivatives for application as nanocontainer for biologically active species.

Halloysite nanotubes as support for metal-based catalysts

Halloysite nanotubes (HNTs) are clay minerals with a hollow nanotubular structure. There is growing interest in these nanomaterials, due to their biocompatibility, potential applications and availability. The surface chemistry of HNTs is versatile for the targeted chemical modification of the inner lumen and outer surface. Functionalized halloysite constitutes a valuable support for metal nanoparticles, promoting catalytic applications with tunable properties. The peculiar tubular shape of HNTs favors the dispersion and surface availability of the supported metal nanoparticles that are active in the catalytic path. Moreover, the presence of an empty lumen opens new perspectives for the prod…

Materiali ibridi a base di nanotubi di allosite per la rimozione d’inquinanti

L’allosite (HNT) è un interessante materiale argilloso allumino-silicato naturale, non tossico e biocompatibile, con la caratteristica forma tubolare cava dotata di parziale carica positiva interna e negativa esterna.Combinando le peculiarità di un composto organico con le proprietà di un materiale inorganico, è possibile ottenere sistemi ibridi organici–inorganici con interessanti proprietà e vasti campi di applicazione. Sono un esempio delle “nanospugne” capaci di adsorbire efficacemente potenziali inquinanti. In questo contesto sono stati preparati, dei materiali ibridi “spugna” costituiti da unità ciclodestriniche e allosite e ancora un sistema ibrido HNT-Cucurbit[8]uril. Il primo possi…

HALLOYSITE NANOTUBES AS SUPPORT FOR METAL NANOPARTICLES FOR CATALYTIC APPLICATION

Halloysite (HNT) is a natural clay that, in the last years, has shown an important increasing on various applications in different field of interesting. Chemically similar to kaolin, it shows the predominately rolled shape, to form multilayers tubes of nanometric dimensions. The different chemical composition of the inside lumen (Al-OH) surface and outside (Si-O) give to the tubes a partial negative charge outside and positive inside. In this way, it is possible to get different interactions of different molecules or systems selectivity on one or another surface. The selective functionalization, covalent or not, of the HNT lumen or outer surface, gives the possibility to the nanotubes to fu…

Halloysite nanotubes for efficient loading, stabilization and controlled release of insulin

Hypothesis: Oral insulin administration is not actually effective due to insulin rapid degradation, inactivation and digestion by proteolytic enzymes which results in low bioavailability. Moreover insulin is poorly permeable and lack of lipophilicity. These limits can be overcome by the loading of protein in some nanostructured carrier such as halloysite nanotubes (HNTs). Experiments: Herein we propose an easy strategy to obtain HNT hybrid materials for the delivery of insulin. We report a detailed description on the thermal behavior and stability of insulin loaded and released from the HNTs hybrid by the combination of several techniques. Findings: Release experiments of insulin from the H…

FUNZIONALIZZAZIONE E CARATTERIZZAZIONE DI NANOTUBI DI ALLOSITE UTILIZZATI PER LO STUDIO DELL’INCAPSULAMENTO DI DERIVATI FENOLICI

I composti fenolici fanno parte dei metaboliti secondari delle piante e tra questi la curcumina è stata ampiamente studiata per le sue intrinseche proprietà farmacologiche.1-4 La curcumina [bis(4-idrossi-3-metossi-fenil)-1,6-eptadiene-3,5-dione] isolata sotto forma di pigmento giallo dal rizoma secco della curcuma longa è stata utilizzata in presenza di sistemi delivery per applicazioni farmaceutiche.5 Uno degli svantaggi della curcumina è la sua scarsa biodisponibilità in ambiente acquoso;6 problema che può essere risolto incapsulandola in nanocontenitori. Tra i sistemi nanodelivery naturali che non presentano citotossicità vi sono i nanotubi di allosite. I nanotubi di allosite sono…

Halloysite Nanotubes as Support for Metal-Based Catalysts

Halloysite nanotubes (HNTs) are a natural, biocompatible, environmental friendly and cheap double-layered aluminosilicate mineral that has a predominantly hollow tubular structure. The general stoichiometry of halloysite is Al2Si2O5·4(H2O). The layer units consist of a tetrahedral SiOH sheet stacked with an edge shared octahedral AlO6 sheet with an internal aluminol group AlOH. A water layer exists between the adjacent two layers. Thanks to their structural features, HNTs are suitable for a potential application as support for catalytic composites. Recently, we reported the synthesis of novel palladium-based catalytic systems using halloysite nanotubes modified with imidazolium or triazoliu…

Gold nanoparticles stabilized by modified halloysite nanotubes for catalytic applications

Chemical modification of halloysite nanotubes for controlled loading and release.

Clay minerals have been used for medical purposes from ancient times. Among them, the halloysite nanotube, an aluminosilicate of the kaolin group, is an emerging nanomaterial which possesses peculiar chemical characteristics. By means of suitable modifications, such as supramolecular functionalization or covalent modifications, it is possible to obtain novel nanomaterials with tunable properties for several applications. In this context the covalent grafting of suitable organic moieties on the external surface or in the halloysite lumen has been exploited to improve the loading and release of several biologically active molecules. The resulting hybrid nanomaterials have been applied as drug…

Caratterizzazione e valutazione dell’attività anti proliferativa di nuovi sistemi per il drug carrier Allosite-sali triazolici/cardanolo

Da precedenti studi è stato valutato che i nanotubi di allosite modificati con sali triazolici (f-HNT), sono dei promettenti sistemi carrier per molecole biologiche1. In questo lavoro si riportano i risultati ottenuti studiando gli f-HNT come carrier per il cardanolo, molecola con interessanti attività biologiche. L’interazione fra il cardanolo e gli f-HNT è stata valutata tramite HPLC, spettroscopia FTIR, analisi termogravimentrica, misure di angolo di contatto e microscopia a scansione elettronica. Infine sono stati studiati sia il rilascio del cardanolo dal sistema che gli effetti citotossici del complesso f-HNT/Cardanolo verso linee cellulari di epatocarcinoma. I dati sperimentali otten…

Development and characterization of co-loaded curcumin/triazole-halloysite systems and evaluation of their potential anticancer activity.

Abstract Positively charged halloysite nanotubes functionalized with triazolium salts (f-HNT) were employed as a carrier for curcumin molecules delivery. The synthesis of these f-HNT new materials is described. Their interaction with curcumin was evaluated by means dynamic light scattering (DLS) and UV–vis spectroscopy in comparison with pristine unmodified HNT (p-HNT). The curcumin load into HNT was estimated by thermogravimetric analysis (TGA) measurements, while the morphology was investigated by scanning electron microscopy (SEM) techniques. Release of curcumin from f-HNT, at three different pH values, by means of UV–vis spectroscopy was also studied. Furthermore, different cancer cell …

Synthesis, Characterization, and Study, of New Nanostructured Materials

Chemical and biological evaluation of cross-linked halloysite-curcumin derivatives

Abstract Well designed and safe nano drug carrier systems are an important tool in biomedical applications. The combination of two or more drugs has been used in medicine both to enhance the therapeutic effect and to decrease the side effects of drugs. Biocompatible halloysite nanotubes, that possess two different surfaces, are a suitable nanomaterial for a simultaneous carrier and release of two drugs that can exert a synergistic effect against cancer cells. In this study, three curcumin derivatives and doxorubicin were loaded by supramolecular and covalent linkage at the lumen and external surface of the halloysite nanotubes. The obtained multifunctional systems were characterized by seve…

CHEMICAL MODIFICATIONS OF HALLOYSITE NANOTUBES FOR THE DEVELOPMENT OF SMART NANOMATERIALS

Halloysite nanoclays (HNTs) are promising nanomaterials because of their versatile properties, such as hollow tubular morphology and tunable surface chemistry. HNTs are biocompatible, no toxic and abundantly available at low cost. Due to these characteristics HNTs are suitable for development of hybrid sustainable materials, which are perspective for wastewater remediation, green packaging and drug delivery. HNTs are quite polydisperse in size with a length of ca. 1 m, while the external diameter and the lumen range between 50-80 nm and 10-15 nm, respectively. Chemically, halloysite is composed of gibbsite octahedral sheet (Al-OH) groups on the inner surface and siloxane (Si−O−Si) groups o…