Halloysite nanotubes as a carrier of cornelian cherry (Cornus mas L.) bioactives

Abstract Cornelian cherry fruit extract rich in anthocyanins and iridoids was encapsulated in the halloysite nanotubes in order to obtain a stable nanoscale system for better delivery and prolonged release of bioactive constituents. The cyclic vacuum technique was used for halloysite nanotubes-cornelian cherry composite preparation and the loading of 8.5 wt% was achieved. Pure cornelian cherry extract exhibited antiproliferative effect on HT-29, MCF7, and MRC-5 cells, pristine halloysite nanotubes affected the growth of MCF7 cells, while halloysite nanotubes-cornelian cherry composites demonstrated proliferative activity in all tested cells. The sustained release of anthocyanins was achieve…

Design of PNIPAAM covalently grafted on halloysite nanotubes as a support for metal-based catalysts

A thermo-responsive polymer such as poly(N-isopropylacrylamide) (PNIPAAM) was covalently grafted on the external surface of halloysite nanotubes (HNTs) by means of microwave irradiation. This nanomaterial was used as a support and stabilizer for palladium nanoparticles. The obtained HNT–PNIPAAM/PdNPs was characterized by means of TGA, SEM, EDS and TEM analyses. The palladium content of the catalyst was estimated to be 0.4 wt%. The stability of the catalytic material at different temperatures (below and above the PNIPAAM lower critical solution temperature) was tested in the Suzuki reaction under microwave irradiation. In addition, TEM analysis after five consecutive runs was performed. The …

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

Effect of a zwitterionic surfactant on the dynamics of a pH oscillator

Halloysite Nanotube with Fluorinated Lumen: Non-Foaming Nanocontainer for Storage and Controlled Release of Oxygen in Aqueous Media

Halloysite clay nanotubes were selectivity modified by adsorbing perfluoroalkylated anionic surfactants at the inner surface. The modified nanotubes formed kinetically stable dispersions due to the enhanced electrostatic repulsions exercised between the particles. We proved that the modified nanotubes can be used as non-foaming oxygen nanocontainers in aqueous media. The gas release from supersaturated dispersions can be controlled by external stimuli and system composition. In conclusion, we managed to put forward an easy strategy to develop smart materials from natural nanoclays, which can endow important applications like the storage and delivery of gas.

Characterization of the pressure induced Ringwoodite to Mg-perovskite+Mg-wuestite phase transition by Catastrophe Theory

Biopolymer-Targeted Adsorption onto Halloysite Nanotubes in Aqueous Media.

Studies on the adsorption of biopolymers onto halloysite nanotubes (HNTs) in water were conducted. Three polymers with different charges-anionic (pectin), neutral (hydroxypropyl cellulose), and cationic (chitosan)-were chosen. The thermodynamic parameters for the adsorption of polymers onto the HNT surface were determined by isothermal titration calorimetry (ITC). The experimental data were interpreted based on a Langmuir adsorption model. The standard variations in free energy, enthalpy, and entropy of the process were obtained and discussed. Turbidimetry was used to evaluate the stability of functionalized nanoparticles in water. The ζ-potential clarified the surface charge properties of …

Paper consolidation with Halloysite nanotubes. TGA, DMA and contact angle investigations

Halloysite Nanotubes and Metal Corrosion Inhibitors: A Computational and Experimental Study

Halloysite nanotubes are widely used as a substrate for the controlled release of various types of molecules in an increasing number of applications. In this work, the interactions of halloysite silicic and aluminic surfaces with corrosion inhibitor compounds, such as benzotriazole, 8-hydroxyquinoline, 2-mercaptobenzimidazole, and 2-mercaptobenzothiazole, were investigated from a computational point of view. Two new halloysite compounds with salicylaldoxime and quinaldic acid were designed. Here we propose their synthesis, evaluate amounts of loading, and analyze the adsorption behavior.

Dual drug-loaded halloysite hybrid-based glycocluster for sustained release of hydrophobic molecules

A dual drug-loaded HNT–CD glycocluster delivery system based on halloysite nanotubes and carbohydrate functionalized cyclodextrin was developed by a green protocol using solvent-free microwave irradiation. The nanohybrid was employed for concurrent load and release of silibinin and curcumin. The new delivery system was characterized by means of TGA, FT-IR spectroscopy, SEM and DLS. These techniques confirm the successful loading of the two drugs in the system. SEM and DLS measurements highlighted that the nanomaterial preserves a tubular structure with an average hydrodynamic radius of ca. 200 nm. The release of the drugs from the HNT glycocluster was investigated by means of UV-vis spectro…

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…

The role of different oxides as supports of an heteropolyacid in the catalytic and catalytic photo-assisted propene hydration

High-pressure crystal structure investigation of synthetic Fe2SiO4 spinel.

AbstractThe crystal structure of Fe2SiO4 spinel at room temperature was investigated at seven different pressures by X-ray diffraction, using a diamond anvil cell to examine the influence of Fe substitution on ringwoodite behaviour at high pressure. The results compared with those of a pure Mg endmember show that the substitution of Fe into the spinel structure causes only small changes in the compression rate of coordination polyhedra and the distortion of the octahedron. The data show that the compression rate for the octahedron and tetrahedron in (Mg,Fe)2SiO4 can be considered statistically equal for FeO6 and MgO6, as well as for SiO4 in both the endmembers. This shows why almost identic…

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

Halloysite Nanotubes for Cleaning, Consolidation and Protection

Herein, we report our recent research concerning the development of halloysite based protocols for cleaning, consolidation and protection purposes. Surface modification of halloysite cavity by anionic surfactants was explored to fabricate inorganic micelles able to solubilize hydrophobic contaminants. Hybrid dispersions based on halloysite and ecocompatible polymers were tested as consolidants for paper and waterlogged archaeological woods. Encapsulation of deacidifying and flame retardant agents within the halloysite lumen was conducted with aim to obtain nanofiller with a long-term protection ability. The results prove the suitability and versatility of halloysite nanotubes, which are per…

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,…

Keggin heteropolyacid H3PW12O40 supported on different oxides for catalytic and catalytic photo-assisted propene hydration

Catalytic and catalytic photo-assisted hydration of propene to form 2-propanol in gas–solid regime at atmospheric pressure and 85 1C were carried out by using a heteropolyacid (POM) supported on different oxides. Binary materials were prepared by impregnation of H3PW12O40 on different commercial and home prepared supports (TiO2, SiO2, WO3, ZrO2, ZnO, Al2O3). Some of the composites were active both for catalytic and catalytic photo-assisted reactions. The Keggin type POM was completely and partially degraded, when supported on ZnO and Al2O3, respectively, and these binary solids always resulted as inactive for both catalytic and catalytic photo-assisted reactions. The supported Keggin POM sp…

Halloysite nanotubes with fluorinated cavity: an innovative consolidant for paper treatment

AbstractHybrid material based on halloysite nanotubes (HNTs) and sodium perfluorooctanoate (NaPF8) was used as a consolidant for paper treatment. The consolidation efficiency was determined by thermogravimetry as well as by paper grammage determination. Morphological analysis of the treated paper was performed by means of scanning electron microscopy while the effect of modified HNTs on the thermal behaviour of the cellulose fibres was investigated by differential scanning calorimetry which determined the combustion enthalpy of the paper.Water contact angle measurements were performed to study the paper wettability. The physico-chemical properties investigated (mesoscopic structure, thermal…

Coffee grounds as filler for pectin: Green composites with competitive performances dependent on the UV irradiation.

Novel composite bioplastics were successfully prepared by filling pectin matrix with treated coffee grounds. The amount of coffee dispersed into the pectin was changed within a wide filler range. The morphology of the pectin/coffee hybrid films was studied by microscopic techniques in order to investigate their mesoscopic structure as well as the sizes distribution of the particles dispersed into the matrix. The micrographs showed that the coffee grounds are uniformly dispersed within the polymeric matrix. The morphological characteristics of the biocomposite films were correlated to their properties, such as wettability, water uptake, thermal behavior and mechanical performances. Dynamic m…

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…

Sonication-Induced Modification of Carbon Nanotubes: Effect on the Rheological and Thermo-Oxidative Behaviour of Polymer-Based Nanocomposites.

The aim of this work is the investigation of the effect of ultrasound treatment on the structural characteristics of carbon nanotubes (CNTs) and the consequent influence that the shortening induced by sonication exerts on the morphology, rheological behaviour and thermo-oxidative resistance of ultra-high molecular weight polyethylene (UHMWPE)-based nanocomposites. First, CNTs have been subjected to sonication for different time intervals and the performed spectroscopic and morphological analyses reveal that a dramatic decrease of the CNT's original length occurs with increased sonication time. The reduction of the initial length of CNTs strongly affects the nanocomposite rheological behavio…

WOOD TREATMENT BASED ON HALLOYSITE/HYDROXYPROPYL CELLULOSE COMPOSITE. THERMOMECHANICAL AND POROSITY CHARACTERIZATION

Clay/Non-Ionic Surfactant Hybrid Nanocomposites

This chapter gives an overview of the structural and chemical physical properties of nanocomposites formed by clay minerals and surfactants, which represent a class of materials with promising features for applications in different industrial, biomedical, and environmental applications. Due to their non-toxicity and biocompatibility, a great deal of attention is nowadays devoted to the study of non-ionic surfactants. Among them, block copolymers represent a combination of the properties of common amphiphilic molecules and long polymer chains. These macromolecules can form a great variety of supra-molecular structures generated from self-organization phenomena in aqueous media. Nanostructure…

SUSTAINABLE WATER FREE CLEANING PROTOCOL FOR WAX REMOVAL FROM A SOLID SURFACE

A Bader’s topological approach for the investigation of the high pressure stability field of the Mg-perovskite phase

Clay Nanotube/PNIPAAM Hybrid material

SrTiO 3 -based perovskites: Preparation, characterization and photocatalytic activity in gas–solid regime under simulated solar irradiation

Strontium titanate-based perovskites have been prepared in the presence of Y and Co with the aim to substitute Sr and Ti, respectively, in the ST crystalline structure. The obtained samples have been characterized by XRD, Raman spectroscopy, FE-SEM, XPS and tested as photocatalysts in two gas-solid regime reactions: (i) 2-propanol complete mineralization and (ii) propene partial oxidation, using a system simulating solar irradiation. All the tested samples resulted active as photocatalysts but with significant differences. The lattice substitution of Sr by Y displays a beneficial effect on the 2-propanol photodegradation. Conversely, the partial presence of cobalt on the ST surface, as Co-o…

Pressure stability field of Mg-perovskite under deep mantle conditions: A topological approach based on Bader's analysis coupled with catastrophe theory

Abstract The pressure stability field of the Mg-perovskite phase was investigated by characterizing the evolution of the electron arrangement in the crystal. Ab initio calculations of the perovskite structures in the range 0–185 GPa were performed at the HF/DFT (Hartree-Fock/Density Functional Theory) exchange–correlation terms level. The electron densities, calculated throughout the ab-initio wave functions, were analysed by means of the Bader's theory, coupled with Thom's catastrophe theory. To the best of our knowledge the approach is used for the first time. The topological results show the occurrence of two topological anomalies at P~20 GPa and P~110 GPa which delineate the pressure ra…

A synergic nanoantioxidant based on covalently modified halloysite–trolox nanotubes with intra-lumen loaded quercetin

We describe the preparation and properties of the first example of a synergic nanoantioxidant, obtained by different functionalizations of the external surface and the inner lumen of halloysite nanotubes (HNTs). Trolox, a mimic of natural α-tocopherol, was selectively grafted on the HNT external surface; while quercetin, a natural polyphenolic antioxidant, was loaded into the inner lumen to afford a bi-functional nanoantioxidant, HNT–Trolox/Que, which was investigated for its reactivity with transient peroxyl radicals and a persistent 1,1-diphenyl-2-picrylhydrazyl (DPPH˙) radical in comparison with the corresponding mono-functional analogues HNT–Trolox and HNT/Que. Both HNT–Trolox and HNT/Q…

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.

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…

Halloysite nanotubes as sustainable nanofiller for paper consolidation and protection

We investigated the filling process of cellulose-based paper with natural clay nanotubes and their mixtures with hydroxypropyl cellulose (HPC) that is commonly used as glue and consolidant for degraded paper. A comprehensive characterization of the materials was carried out through morphology, wettability, thermal degradation, and tensile properties. The treatment with halloysite nanotubes generated a decrease of the paper mechanical performance and did not alter the thermal properties. The co-presence of HPC and nanoparticles generated a more uniform nanotubes distribution in the paper fibrous structure and a significant enhancement of both the mechanical properties and the surface hydroph…

Characterization of synthetic Fe-Mg silicate spinels in the gamma-(Mgx,Fe1-x)2SiO4 series by means of single crystal XRD (x=0,0.4,0.5)

ADSORPTION OF WATER MOLECULES ONTO 1:1 DIOCTAHEDRAL CLAY MINERALS: A BADER'S TOPOLOGICAL ANALYSIS OF THE AB-INITIO ELECTRON DENSITIES

Clay nanotubes for paper consolidation

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.

Steric stabilization of modified nanoclays triggered by temperature.

Halloysite clay nanotubes were modified through the adsorption of poly(N-isopropylacrylamide)-amine terminated (PNIPA-NH2) onto the external surface by exploiting electrostatic interactions at pH=6. In spite the amount of attached polymer is rather low (1 wt%), the properties of the nanotubes are deeply modified. The apparent specific volume and isentropic compressibilities of the hybrid nanomaterial dispersed in water evidenced the transferring of the termosensitive property from the polymer to halloysite. The hydrodynamic radius as well as the ζ-potential of the nanohybrid are consistent with the attachment of a positively charged polymer onto the negative surface of the nanotube. The col…

TiO2 in the food industry and cosmetics

Abstract The white pigment titanium dioxide is widely used in foodstuff and cosmetics mainly because it provides whitening effect, it acts as a physical filter in sunscreen products, and due to its photocatalytic properties. As food additive, it is labeled as E171 (Europe) and INS171 (United States), and its use was approved in 1966 by the US Food and Drug Administration and in 1969 by the European Union. According to a request of the European Commission, a scientific reevaluation of the safety of TiO2 when used as food additive was recently elaborated by European Food Safety Authority ANS panel. The TiO2 photocatalytic inactivation power is widely studied in order to nonthermally decontami…

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 …

Nanocomposite based on Multi-Macrocyclic Receptors and Halloysite for Volatile Organic Compounds Capture

Volatile organic compounds (VOCs) are chemicals released to the atmosphere by natural and anthropogenic sources. VOCs are hazardous air pollutants and promote formation of photochemical smog. Variety of chemicals released from pharmaceutical industry includes priority pollutants like benzene, toluene, and dichloromethane. The aim of this work was at designing, preparing and characterizing from the physico-chemical view-point a pseudo nano-sponge with low environmental impact for pollutant removal. As adsorbent material, a nanocomposite based on nanoclay and cucurbiturils, which are biocompatible materials, were investigated. Clay minerals (e.g. montmorillonite and kaolin) are important comp…

Nanoclays for Conservation

Within the conservation of artworks materials, this chapter describes innovative strategies based on clay nanoparticles that are promising for protective coating, surface cleaning, and consolidation. We present the preparation of polymer/montmorillonite nanocomposites, which are revealed as efficient protective coatings for highly porous stones, marbles, and bread-made artifacts. Anticorrosive films for metal substrates have been obtained by polymer filling with laponite and halloysite nanotubes (HNTs) containing corrosion inhibitors into their lumen. The dispersion of hydrophobically modified HNTs into chitosan matrix drives to fabricate biofilms with surface cleaning capacity. Rust stains…

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 …

Improvement of oxidation resistance of polymer-based nanocomposites through sonication of carbonaceous nanoparticles

Abstract The work aim is focused on two different aspects: first, the investigation of the effect of extended ultra-sound-assisted treatment (us) of carbonaceous nanoparticles, such as carbon nanotubes (CNTs) and carbon black (CB), on their radical scavenging activity, and second, the investigation of the oxidative resistance of polymer-based nanocomposites, containing us-treated CNTs and CB. Particularly, the CNTs and CB have been subjected to us sonication for different time intervals and the performed analysis reveals that both kinds of nanoparticles show decreased average hydrodynamic diameters and large content of surface defects. Really, the increased content of CNTs and CB defects, a…

Ordering kinetics in synthetic Mg(Al,Fe3+)2O4 spinels: Quantitative elucidation of the whole Al-Mg-Fe partitioning, rate constants, activation energies

A novel procedure, based on the application of the kinetics simulator Gepasi, has been successfully applied for modeling the cation ordering process in two synthetic Mg(Al2-yFe3+y)O4 spinels (y~ 0.39 and 0.54, samples F39 and F54, respectively). The kinetic profiles suggested a two-stage mechanism, with rapid inter-site exchange of Fe3+ with Mg followed by slow exchange of Al with Mg. The trial to apply the classical approaches, based on the explicit solutions of the differential equations corresponding to single-cation (Sha-Chappel model) or two-cation (Müller model) exchange reactions, proved not feasible in the whole time range, thus implying a lack of information about the exchange proc…

Halloysite nanotubes loaded with peppermint essential oil as filler for functional biopolymer film

Abstract The purpose of this paper is to show how a functional bionanocomposite film with both antioxidant and antimicrobial activities was successfully prepared by the filling of a pectin matrix with modified Halloysite nanotubes (HNT) containing the essential peppermint oil (PO). Firstly, HNT surfaces were functionalized with cucurbit[6]uril (CB[6]) molecules with the aim to enhance the affinity of the nanofiller towards PO, which was estimated by means of HPLC experiments. The HNT/CB[6] hybrid was characterized by several methods (thermogravimetry, FT-IR spectroscopy and scanning electron microscopy) highlighting the influence of the supramolecular interactions on the composition, therma…

Colloidal stability of halloysite clay nanotubes

Abstract The colloidal stability of halloysite clay nanotubes dispersion is reviewed showing the strategy and the mechanism to obtain stable systems in water and apolar solvents. The selective modification of halloysite inner/outer surfaces can be achieved by exploiting electrostatic interactions. The adsorption of anionic surfactants onto the halloysite cavity allows generating inorganic cylindrical micelles that can be separated from the solvent. On the other hand, the functionalization of halloysite shell by positively charged surfactants drives to obtain stable water-in-oil emulsions. The interactions with ionic and nonionic polymers alters the dispersability of halloysite due to electr…

Microemulsion encapsulated into halloysite nanotubes and their applications for cleaning of a marble surface

Halloysite nanotubes were used to incorporate anionic surfactant micelles and an organic solvent to generate a cleaning system to be applied in Cultural Heritage restoration. The targeted adsorption is driven by electrostatic interactions based on the nanotubes peculiar charge separation. Namely anionic species are driven to the positively charged inner surface while being prevented from interacting with the halloysite outer surface that possesses a positive charge density. The hybrid organic/inorganic emulsion was characterized by dynamic light scattering. Analysis of the autocorrelation function allowed us to define the presence of surfactant aggregates inside/outside the nanotube lumen a…

Preliminary data of oxidation kinetics of Fe2+Cr2O4 synthetic spinel

Clay Nanotube/Perfluorinated Surfactant Hybrid Materials

Hydrophobically Modified Halloysite Nanotubes as Reverse Micelles for Water-in-Oil Emulsion.

An easy strategy to obtain inorganic reverse micelles based on halloysite nanotubes (HNTs) and alkyltrimethylammonium bromides has been developed. The selective modification of the HNTs external surface with cationic surfactants endows to generate tubular nanostructures with a hydrophobic shell and a hydrophilic cavity. The influence of the surfactants alkyl chain on the HNTs functionalization degree has been investigated. The dynamic behavior of the surfactant/HNT hybrids in solvents with variable polarity has been correlated to their affinity toward hydrophobic media explored through partition experiments. The water-in-oil emulsion is able to solubilize copper sulfate, proving the incorpo…

Halloysite nanotubes sandwiched between chitosan layers: novel bionanocomposites with multilayer structures

This work is a contribution to the design of multilayer biocomposites based on halloysite nanotubes (HNTs) and chitosan. Both the polymer and nanotubular inorganic additive have been selected among easily available green materials. An innovative preparation procedure based on the sequential casting of chitosan and HNTs has been proposed in order to obtain multilayer composite biofilms. A physico-chemical investigation (contact angle measurements, differential scanning calorimetry, thermogravimetry) has been conducted to characterize the bionanocomposites. As evidenced by scanning electron microscopy, the nanocomposites possess an intermediate halloysite layer between the chitosan ones. The …

A one step enhanced extraction and encapsulation system of cornelian cherry (Cornus mas L.) polyphenols and iridoids with β-cyclodextrin

Abstract The objective of this study was simultaneous extraction and encapsulation of cornelian cherry active principles. As an encapsulating agent, β-cyclodextrin (β-CD) was used to enhance the ultrasound-assisted extraction of cornelian cherry polyphenols and iridoids. Lyophilized cornelian cherry fruit was extracted by four different solvents: pure water, 50% aqueous ethanol (conventional system), 1.5% β-CD water solution and 1.5% β-CD aqueous ethanol solution. The highest enhancement of the extraction efficiency was observed for flavonoids and anthocyanins, especially for cyaniding 3-galactoside and pelargonidin 3-galactoside. Water-ethanolic extract was used to form inclusion complexes…

FeCr2O4 synthetic spinel: heating experiments and oxidation kinetics

Selective adsorption of oppositely charged PNIPAAM on halloysite surfaces: a route to thermo-responsive nanocarriers.

Halloysite nanotubes were functionalized with stimuli-responsive macromolecules to generate smart nanohybrids. Poly(N-isopropylacrylamide)-co-methacrylic acid (PNIPAAM-co-MA) was selectively adsorbed into halloysite lumen by exploiting electrostatic interactions. Amine-terminated PNIPAAM polymer was also investigated that selectively interacts with the outer surface of the nanotubes. The adsorption site has a profound effect on the thermodynamic behavior and therefore temperature responsive features of the hybrid material. The drug release kinetics was investigated by using diclofenac as a non-steroidal anti-inflammatory drug model. The release kinetics depends on the nanoarchitecture of th…

Characterization of the pressure induced Ringwoodite toMg-perovskite and Mg-wüstite phase transition by Catastrophe Theory

Olive mill wastewaters decontamination based on organo-nano-clay composites

Abstract Green composites for environmental applications were successfully prepared by intercalation of the biosurfactant Quillaja saponin onto montmorillonite mineral clay on varying pH and surfactant/clay ratio. Equilibrium adsorption isotherms were constructed and the system was characterized by performing TGA and XRD analyses. The efficiency of the surfactant-modified clay in the removal of the organic content present in olive mill wastewaters (OMW) was evaluated by means of spectrophotometric measurements. The interest for this cogent issue comes from the consideration that, despite their high pollutant content, OMW can be considered as a potential resource of several organic compounds…

The pressure-induced ringwoodite to Mg-perovskite and periclase post-spinel phase transition: a Bader’s topological analysis of the ab initio electron densities

In order to characterize the pressure-induced decomposition of ringwoodite (c-Mg2SiO4), the topological analysis of the electron density q(r), based upon the theory of atoms in molecules (AIM) developed by Bader in the framework of the catastrophe theory, has been performed. Calculations have been carried out by means of the ab initio CRYSTAL09 code at the HF/DFT level, using Hamiltonians based on the Becke- LYP scheme containing hybrid Hartree– Fock/density functional exchange–correlation terms. The equation of state at 0 K has been constructed for the three phases involved in the post-spinel phase transition (ringwoodite -> Mg-perovskite + periclase) occurring at the transition zone–lower…

Halloysite Nanotubes Loaded with Calcium Hydroxide: Alkaline Fillers for the Deacidification of Waterlogged Archeological Woods

A novel green protocol for the deacidifying consolidation of waterlogged archaeological woods through aqueous dispersions of polyethylene glycol (PEG) 1500 and halloysite nanotubes containing calcium hydroxide has been designed. First, we prepared functionalized halloysite nanotubes filled with Ca(OH)2 in their lumen. The controlled and sustained release of Ca(OH)2 from the halloysite lumen extended its neutralization action over time, allowing the development of a long-term deacidification of the wood samples. A preliminary thermomechanical characterization of clay/polymer nanocomposites allows us to determine the experimental conditions to maximize the consolidation efficiency of the wood…

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…

Selective (photo)catalytic formation of 2-propanol from propene by using an heteropolyacid supported on different oxides

Halloysite Nanotubes/Perfluoroctanote: an efficient consolidant and flame retardant for paper

Effect of the Biopolymer Charge and the Nanoclay Morphology on Nanocomposite Materials

This work represents a contribution to the design, preparation, and characterization of nanocomposite materials based on biocompatible components. The effects of composition, filler geometry, and polymer charge were highlighted, and their role on the final properties of the nanocomposites was revealed. We combined some biopolymers (methylcellulose, alginate, chitosan) with two nanoclays (kaolinite sheets and halloysite nanotubes) to prepare nanocomposites by means of the casting method from water. The thermal stability, the surface wettability, and the mechanical properties of the obtained films were studied. SEM micrographs highlighted the surface morphology of the biocomposite materials. …

Hybrid supramolecular gels of Fmoc-F/halloysite nanotubes: Systems for sustained release of camptothecin

Supramolecular gel hybrids obtained by self-assembly of Fmoc-L-phenylalanine (Fmoc-F) in the presence of functionalized halloysite nanotubes (f-HNT) were obtained in biocompatible solvents and employed as carriers for the delivery of camptothecin (CPT) molecules. The synthesis of the new f-HNT material as well as its characterization are described. The properties of the hybrid hydrogels and organogels were analyzed by several techniques. The presence of small amounts of f-HNT allows good dispersion of the tubes and the subsequent formation of homogeneous gels. The experimental results show that f-HNT functions only as an additive in the hybrid gels and does not demonstrate gelator behavior.…

Synthetic and natural chromium bearing spinels: an optical spectroscopy study

Four samples of synthetic chromium-bearing spinels of (Mg, Fe2+)(Cr, Fe3+)2O4 composition and four samples of natural spinels of predominantly (Mg, Fe2+)(Al, Cr)2O4 composition were studied at ambient conditions by means of optical absorption spectroscopy. Synthetic end-member MgCr2O4 spinel was also studied at pressures up to ca. 10 GPa. In both synthetic and natural samples, chromium is present predominantly as octahedral Cr3+ seen in the spectra as two broad intense absorption bands in the visible range caused by the electronic spin-allowed 4A2g → 4T2g and 4A2g → 4T1g transitions (U- and Y-band, respectively). A distinct doublet structure of the Y-band in both synthetic and natural spine…

Halloysite nanotubes/pluronic nanocomposites for waterlogged archeological wood: thermal stability and X-ray microtomography

Filling a polymer with halloysite nanotubes is considered a promising strategy to generate nanocomposites with tailored physicochemical properties. We have focused our attention on pluronic block copolymer/halloysite nanocomposites prepared by melt blending. The effect of composition on thermal stability and polymer crystallinity was investigated by thermogravimetry and differential scanning calorimetry. Electron microscopy was used to monitor the nanoparticle distribution in the polymeric matrix. The pluronic thermal stability is reduced by the clay nanoparticles. Concerning the polymer crystallinity, it is slightly decreased even if the melting temperature is lowered by halloysite. Furthe…

OUTLIER RECOGNITION AND ROBUST WEIGHTING PROCEDURES APPLIED IN CATION ORDERING-DISORDERING KINETIC DATA PROCESSING

Filling of Mater-Bi with Nanoclays to Enhance the Biofilm Rigidity

We investigated the efficacy of several nanoclays (halloysite, sepiolite and laponite) as nanofillers for Mater-Bi, which is a commercial bioplastic extensively used within food packaging applications. The preparation of Mater-Bi/nanoclay nanocomposite films was easily achieved by means of the solvent casting method from dichloroethane. The prepared bio-nanocomposites were characterized by dynamic mechanical analysis (DMA) in order to explore the effect of the addition of the nanoclays on the mechanical behavior of the Mater-Bi-based films. Tensile tests found that filling Mater-Bi with halloysite induced the most significant improvement of the mechanical performances under traction force, …

Mixed aggregates based on tetronic-fluorinated surfactants for selective oils capture

Abstract An aqueous star-like copolymer solution was titrated with perfluoro carboxylic acids at various compositions to prepare a polymeric surfactant composed of fluorinated nano-domains. The copolymer is X-shaped where each arm contains ethylene oxide and propylene oxide repetitive units linked to a central ethylenediamine group. The aggregation behavior of the hybrid macromolecule was studied from the physico-chemical point of view by changing parameters like temperature and composition. The solubilization of perfluorinated and hydrogenated alcohols in mixed self-assembled structure revealed that a selectivity toward the fluorinated moiety can be done. The self-assembled structures are …

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…

Thermal and dynamic mechanical properties of beeswax-halloysite nanocomposites for consolidating waterlogged archaeological woods

Abstract Thermal and mechanical properties were determined for the halloysite nanotubes (HNT)/beeswax composites at various compositions. The beeswax degradation temperatures and time course, provided by thermogravimetry (TG), evidenced the improvement of the thermal properties operated by HNT. Differential scanning calorimetry (DSC) allowed us to determine the enthalpy of melting as well as the time course of the melting process for beeswax. A slight loss of beeswax crystallinity was observed upon HNT addition. The dynamical mechanical analysis (DMA) provided the loss and the storage modulus for the nanocomposites upon heating and it was shown that the nanoclays create an inorganic framewo…

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…

Modified Halloysite Nanotubes: Nanoarchitectures for Enhancing the Capture of Oils from Vapor and Liquid Phases

We prepared hybrid halloysite nanotubes (HNT/sodium alkanoates) in which the inner cavity of the nanoclay was selectively modified. Physicochemical studies evidenced the interactions between HNT and sodium alkanoates, ruled out clay exfoliation, quantified the amount of the loaded substance, and showed an increase of the total net negative charge, allowing us to obtain rather stable aqueous nanoclay dispersions. These dispersions were exploited as inorganic micelles to capture hydrocarbon and aromatic oils in the vapor and liquid states and were revealed to be nonfoaming but very efficient in encapsulating oils. Here, we have fabricated biocompatibile and low-cost inorganic micelles that ca…

Colloidal stability and self-assembling behavior of nanoclays

Abstract Currently, nanoclays are attracting the attention of a wide part of the scientific community, due to some of their most peculiar features that make them good candidates for applications in different fields. In light of this, some strategies can be pursued in order to obtain stable colloidal dispersions of nanoclays with the aim to improve their features and to expand their use. Hence, this chapter presents an overview on the structural and morphological characteristics, the physico-chemical properties and the main approaches that are taken into account for the preparation of homogeneous suspensions of Halloysite, Imogolite and Laponite in both aqueous and apolar solvent media. In p…

Nanocomposites based on esterified colophony and halloysite clay nanotubes as consolidants for waterlogged archaeological woods

We have designed an innovative protocol for the consolidation of waterlogged archaeological woods by using acetone mixtures of halloysite clay nanotubes and a chemically modified colophony (Rosin). Firstly, we have investigated the thermal properties of HNTs/Rosin nanocomposites, which have been prepared by means of the casting method from acetone. The HNTs content have been systematically changed in order to study the influence of the inorganic filler on the thermal stability and glass transition process of Rosin. We have observed that the thermal properties of the hybrids are affected by the specific HNTs/Rosin interactions. Then, acetone dispersions of HNTs/Rosin composites at variable f…

Stability of Halloysite, Imogolite, and Boron Nitride Nanotubes in Solvent Media

Inorganic nanotubes are attracting the interest of many scientists and researchers, due to their excellent application potential in different fields. Among them, halloysite and imogolite, two naturally-occurring aluminosilicate mineral clays, as well as boron nitride nanotubes have gained attention for their proper shapes and features. Above all, it is important to reach highly stable dispersion in water or organic media, in order to exploit the features of this kind of nanoparticles and to expand their applications. This review is focused on the structural and morphological features, performances, and ratios of inorganic nanotubes, considering the main strategies to prepare homogeneous col…

A Raman spectroscopy study of the oxidation processes in synthetic chromite FeCr2O4

Abstract A crystal of synthetic chromite FeCr2O4 has been annealed in air at 700 °C for 50 days at room pressure in order to study physical-chemical changes. After the annealing treatment, Scanning Electron Microscopy (SEM) images of the polished surface of the sample showed areas of different composition. Detailed Raman mapping revealed that the annealed chromite undergoes an oxidation process, proceeding inwards from the outer surface and leading to the transformation of chromite to magnetite, and ultimately to hematite. The oxidation process also leads to the formation of trellis-like lines, arguably via stress-related mechanisms associated with the phase transformation and consequent vo…

Incorporation of the [(pentamethylcyclopentadienyl) (2,2-bipyridyl)(aquo)rhodium(III)] complex into DPPC vesicles studied by a kinetic method

Simultaneous Removal and Recovery of Metal Ions and Dyes from Wastewater through Montmorillonite Clay Mineral

The main objective of this work was to evaluate the potential of Montmorillonite nanoclay (Mt), readily and inexpensively available, for the simultaneous adsorption (and removal) of two classes of pollutants: metal ions and dyes. The attention was focused on two &ldquo

MODIFICAZIONI COVALENTI DI NANOTUBI DI ALLOSITE PER APPLICAZIONE NEL DRUG DELIVERY

Nell'ampio scenario dei nanomateriali, i sistemi nanotubolari godono di un consolidato e crescente interesse sia nell'ambito scientifico che industriale. Fra la miriade di sistemi tubolari, recentemente i nanotubi allosite (HNT) hanno attirato l’attenzione della comunità scientifica.1 Grazie alla presenza di una cavità vuota, gli HNT trovano, principalmente, applicazione come nanocontainer per il rilascio controllato di composti chimici, in particolare, farmaci. L’introduzione di modificazioni covalenti su entrambe le superfici permette di modulare le proprietà dell’allosite, aumentando così i suoi campi di applicazione. In questa comunicazione verranno presentati recenti risultati ottenuti…

Biocompatible Poly(N-isopropylacrylamide)-halloysite Nanotubes for Thermoresponsive Curcumin Release

The grafting of poly(N-isopropylacrylamide) (PNIPAAM) onto the halloysite external surface is proposed in order to obtain a novel thermoresponsive drug carrier for curcumin delivery. The new nanomaterial is characterized by means of FT-IR spectroscopy, thermogravimetric analysis, and SEM investigations. A high density of polymer chain was achieved at the nanoparticle surface. The PNIPAAM dehydration phenomenon was observed in water above 32 °C that is nearly coincident with the lower critical solution temperature for the polymer. The colloidal stability as well as the wettability of the obtained nanomaterial may be triggered by temperature stimuli. In vitro tests simulating the gastro-intes…

Kinetic studies on the aerobic reduction of a Rh(III)-complex by formiate ions in the presence of DPPC vesicles

Bioactive Co(II), Ni(II), and Cu(II) Complexes Containing a Tridentate Sulfathiazole-Based (ONN) Schiff Base

New Co(II), Ni(II), and Cu(II) complexes were synthesized with the Schiff base ligand obtained by the condensation of sulfathiazole with salicylaldehyde. Their characterization was performed by elemental analysis, molar conductance, spectroscopic techniques (IR, diffuse reflectance and UV–Vis–NIR), magnetic moments, thermal analysis, and calorimetry (thermogravimetry/derivative thermogravimetry/differential scanning calorimetry), while their morphological and crystal systems were explained on the basis of powder X-ray diffraction results. The IR data indicated that the Schiff base ligand is tridentate coordinated to the metallic ion with two N atoms from azomethine group and thiazole ring a…

Dynamic evolution of the hemin – hydrogen peroxide – sulfite reaction upon addition of a zwitterionic surfactant

Crystallinity of block copolymer controlled by cyclodextrin

We report a differential scanning calorimetry study to investigate the effect of cyclodextrins (CD) on the crystallinity of a copolymer. Tetronics was selected as copolymer with star-like shape formed by four polyethylene oxide flanked by four polypropylene oxide blocks linked to ethylenediamine central group. The use of CD with different cavity size was exploited for a block selective inclusion. A model for supramolecular association was considered for a quantitative description of the enthalpy data. The polymer chain incorporation into the CD cavity generates a loss of crystallinity. The stoichiometry of the CD/copolymer aggregates can be tuned by changing the CD cavity size. The investig…

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…

A BADER’S TOPOLOGICAL APPROACH FOR THE CHARACTERIZATION OF PRESSURE INDUCED PHASE TRANSITIONS