Hybrid Green Materials Obtained by PCL Melt Blending with Diatomaceous Earth.

In this work, diatomaceous earth (Diat) was explored as filler for polycaprolactone (PCL) to obtain composite green materials with promising viscoelastic and thermal properties. The composites were prepared by blending variable Diat amounts (5, 15 and 50 wt%) with a molten PCL matrix. The viscoelastic characteristics of PCL/Diat hybrids were studied by Dynamic Mechanical Analysis (DMA) under an oscillatory regime, while the thermal properties were determined by Differential Scanning Calorimetry (DSC) and Thermogravimetric Analysis (TGA). We detected that the presence of Diat enhances the energy storage capacity of PCL for temperatures lower than the polymer melting point. Both DMA and DSC data revealed that the PCL melting temperature is slightly affected by the Diat addition, while the TGA results showed that the thermal stability of the polymer can be significantly improved by mixing PCL with diatomaceous earth. Moreover, we observed that the dispersion of Diat into the matrix favors the crystallization process of PCL. Interestingly, the improvements of PCL properties (elasticity, thermal stability, and crystallinity) are proportional to the Diat concentration of the composites. These findings reflect the interfacial compatibility between PCL and diatomaceous earth. In conclusion, this study highlights that the preparation of PCL/Diat hybrids by melt blending is suitable for the development of composite materials for technological applications, including the remediation of air pollutants within museum environments.

Nanocomposites based on halloysite nanotubes and sulphated galactan from red seaweed Gloiopeltis: Properties and delivery capacity of sodium diclofenac.

We developed novel composite films based on biocompatible components, such as halloysite clay nanotubes and sulphated galactan (Funori) from red seaweed Gloiopeltis. The filling of the nanotubes within the sulphated galactan matrix was carried out by a green protocol (aqueous casting method) assuring that Funori/halloysite nanocomposites can be totally considered as sustainable materials. The amount of halloysite in the composites was systematically changed to explore the effects of the nanofiller concentration on the mesoscopic properties of the films. We observed that the halloysite content significantly affects the initial water contact angle and the light attenuation coefficient of the Funori based films. These results were interpreted according to SEM images, which showed that the surface morphologies of the nanocomposites depend on the halloysite amounts filled within the polymeric matrix. The mechanical characterization of the nanocomposites was conducted by tensile experiments performed using a linear stress ramp. Moreover, tensile tests were conducted in oscillatory regime at variable temperature to investigate the viscoelastic properties of the nanocomposites. Finally, we filled the biopolymeric matrix with halloysite nanotubes containing sodium diclofenac. The drug release kinetics from the nanocomposites at variable halloysite contents were studied to evaluate their suitability as oral dissolving films for pharmaceutical applications.

Thermal and Mechanical Characterization of Yarn Samples from Flemish Tapestry of the Sixteenth Century.

We propose a physico-chemical approach for theharacterization of the conservation condition of yarns from a Flemish tapestry of the sixteenth century. The aging effect on the yarns' performance was evaluated by comparison with commercial materials. Water uptake experiments highlighted the aptitude of yarns toward water sorption and their increased hydrophilicity upon aging. Thermogravimetric analysis can be considered a fast approach for the fiber identification and assessment on the material life-time. The dynamic mechanical analysis provided direct evidence on the yarns, conservation state and their performance under different mechanical stresses. The proposed characterization path can be relevant for stating the condition of the tapestry and for designing a conservation protocol for the preservation of the artwork.

Keratin/alginate hybrid hydrogels filled with halloysite clay nanotubes for protective treatment of human hair.

Keratin/alginate hydrogels filled with halloysite nanotubes (HNTs) have been tested for the protective coating of human hair. Preliminary studies have been conducted on the aqueous colloidal systems and the corresponding hydrogels obtained by using Ca2+ ions as crosslinkers. Firstly, we have investigated the colloidal properties of keratin/alginate/HNTs dispersions to explore the specific interactions occurring between the biomacromolecules and the nanotubes. Then, the rheological properties of the hydrogels have been studied highlighting that the keratin/alginate interactions and the subsequent addition of HNTs facilitate the biopolymer crosslinking. Finally, human hair samples have been treated with the hydrogel systems by the dipping procedure. The protection efficiency of the hydrogels has been evaluated by studying the tensile properties of hair fibers exposed to UV irradiation. In conclusion, keratin/alginate hydrogel filled with halloysite represents a promising formulation for hair protective treatments due to the peculiar structural and rheological characteristics.

Printable Hydrogels Based on Alginate and Halloysite Nanotubes.

The design of hydrogels for the controlled release of active species is an attractive challenge. In this work, we prepared hybrid hydrogels composed of halloysite nanotubes as the inorganic component, and alginate as the organic counterpart. The reported procedure allowed us to provide the resulting materials with a peculiar wire-like shape. Both optical and scanning electron microscopy were used to characterize the morphological properties of the hydrogel wires, whose diameters were ca. 0.19 and 0.47 mm, respectively. The possibility to be exploited as drug delivery systems was carried out by loading the nanoclay with salicylic acid and by studying the release profiles. Thermogravimetric experiments showed that the amount of encapsulated drug was 4.35 wt%, and the salicylic acid was thermally stabilized after the loading into the nanotubes, as observed by the shift of the degradation peak in the differential thermograms from 193 to 267 °C. The kinetics investigation was conducted using UV-Vis spectrophotometry, and it exhibited the profound effects of both the morphology and dimensions on the release of the drugs. In particular, the release of 50% of the payload occurred in 6 and 10 h for the filiform hydrogels, and it was slower compared to the bare drug-loaded halloysite, which occurred in 2 h. Finally, an induction period of 2 h was observed in the release profile from the thicker sample.

Halloysite nanotubes as nanoreactors for heterogeneous micellar catalysis.

HYPOTHESIS: Electrostatic attractions between the anionic head group of sodium alkylsulphates and the positively charged inner surface of halloysite nanotubes (HNTs) drive to the formation of tubular inorganic micelles, which might be employed as nanoreactors for the confinement of non polar compounds in aqueous media. On this basis, sodium alkylsulphates/halloysite hybrids could be efficient nanocatalysts for organic reactions occurring in water. EXPERIMENTS: Sodium decylsulphate (NaDeS) and sodium dodecylsulphate (NaDS) were selected for the functionalization of the halloysite cavity. The composition, the structure and the surface charge properties of the hybrid nanotubes were determined. The actual formation of inorganic micelles was explored by studying the microviscosity and polarity characteristics of the surfactant modified nanotubes through fluorescence spectroscopy experiments using DiPyme as probe. The performances of the sodium alkylsulphates/halloysite composites as micellar catalysts for the Belousov-Zhabotinsky (BZ) reaction were investigated. FINDINGS: The halloysite functionalization with sodium alkylsulphates generated the formation of hydrophobic microdomains with an enhanced microviscosity. Compared to the surfactant conventional micelles, the functionalized nanotubes induced larger enhancements on the rate constant of the BZ reaction. This is the first report on the surfactant/halloysite hybrids showing their efficiencies as reusable nanocatalysts, which are dependent on their peculiar microviscosity and polarity properties.

Understanding the Effects of Crosslinking and Reinforcement Agents on the Performance and Durability of Biopolymer Films for Cultural Heritage Protection.

In the last two decades, the naturally occurring polysaccharides, such as chitosan and pectin, have gained great attention having potential applications in different sectors, from biomedical to new generation packaging. Currently, the chitosan and pectic have been proposed as suitable materials also for the formulation of films and coatings for cultural heritage protection, as well as packaging films. Therefore, the formulation of biopolymer films, considering only naturally occurring polymers and additives, is a current challenging trend. This work reports on the formulation of chitosan (CS), pectin (PC), and chitosan:pectin (CS:PC) films, also containing natural crosslinking and reinforcement agents, such as citric acid (CA) and halloysite nanotubes (HNT), through the solvent casting technique. The produced films are characterized through water contact angle measurements, infrared and UV-visible spectroscopy and tensile test, while the durability of the CS:PC films is evaluated subjecting the film to accelerated UVB exposure and monitoring the photo-oxidation degradation in time though infrared spectroscopy. All obtained results suggest that both crosslinking and reinforcement agents have beneficial effects on the wettability, rigidity, and photo-oxidation resistance of biopolymer films. Therefore, these biopolymer films, also containing naturally occurring additives, have good properties and performance and they are suitable as coverage films for cultural heritage protection.

Bionanocomposite Films Containing Halloysite Nanotubes and Natural Antioxidants with Enhanced Performance and Durability as Promising Materials for Cultural Heritage Protection.

In the last decade, the interest toward the formulation of polymer films for cultural heritage protection continuously grew, and these films must be imperatively transparent, removable, and should not react/interact with surface of the artworks. In this research, bionanocomposite films, based on chitosan (Ch) and pectin (P) and containing naturally occurring fillers and antioxidants, were formulated by solvent casting methods and were accurately characterized. The natural halloysite nanotubes (HNT) have a two-fold role, specifically, physical compatibilizer and antioxidant carrier. Therefore, the theoretical solubility between Ch and P was estimated considering Hoy's method for solubility of polymers, while the optimum ratio between biopolymer constituents was assessed by ζ-potential measurements. The transparency, wettability, and mechanical behavior of Ch:P films, also in presence of HNT without and with antioxidants, were investigated. The beneficial effects of natural antioxidants, such as vanillic acid (VA) and quercetin (Q), on Ch:P/HNT durability were found.

Halloysite Nanotubes Coated by Chitosan for the Controlled Release of Khellin.

In this work, we have developed a novel strategy to prepare hybrid nanostructures with controlled release properties towards khellin by exploiting the electrostatic interactions between chitosan and halloysite nanotubes (HNT). Firstly, khellin was loaded into the HNT lumen by the vacuum-assisted procedure. The drug confinement within the halloysite cavity has been proved by water contact angle experiments on the HNT/khellin tablets. Therefore, the loaded nanotubes were coated with chitosan as a consequence of the attractions between the cationic biopolymer and the halloysite outer surface, which is negatively charged in a wide pH range. The effect of the ionic strength of the aqueous medium on the coating efficiency of the clay nanotubes was investigated. The surface charge properties of HNT/khellin and chitosan/HNT/khellin nanomaterials were determined by ζ potential experiments, while their morphology was explored through Scanning Electron Microscopy (SEM). Water contact angle experiments were conducted to explore the influence of the chitosan coating on the hydrophilic/hydrophobic character of halloysite external surface. Thermogravimetry (TG) experiments were conducted to study the thermal behavior of the composite nanomaterials. The amounts of loaded khellin and coated chitosan in the hybrid nanostructures were estimated by a quantitative analysis of the TG curves. The release kinetics of khellin were studied in aqueous solvents at different pH conditions (acidic, neutral and basic) and the obtained data were analyzed by the Korsmeyer-Peppas model. The release properties were interpreted on the basis of the TG and ζ potential results. In conclusion, this study demonstrates that halloysite nanotubes wrapped by chitosan layers can be effective as drug delivery systems.

Polysaccharides/Halloysite nanotubes for smart bionanocomposite materials.

Biopolymers as alternative to fossils-derived polymers are attracting the interest of researcher in material science. Besides the economic advantages, the sustainability makes polysaccharides ideal candidates to prepare films and formulations. The addition of Halloysite nanotubes as green inorganic fillers was exploited to improve the physico-chemical properties and to introduce smart response abilities to the material. Halloysite is a natural tubular nanomaterial with hollow cavity and large aspect ratio. The effect of polymer charge on the morphology and mesoscopic properties of polysaccharides/halloysite nanocomposites has been highlighted. Different strategies (solvent casting, lyophilization, cryoscopic technique) for the preparation of nanocomposites have been described. In addition, we present novel protocols for the fabrication of polysaccharides/halloysite nanocomposites suitable as drug delivery systems. The emerging halloysite-based bionanocomposites are addressed to applications such as biomedicine, packaging, corrosion protection and restoration of cultural heritages. This review provides an overview of the recent progress achieved on halloysite-polysaccharides nanocomposites.

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-clay tubule nanocomposite was used for the immersion treatment of hair. Three-dimensional-measuring laser scanning microscopy demonstrated that 50-60% of the hair surface coverage can be achieved with 1 wt % suspension application. Hair samples have been exposed to UV irradiation for times up to 72 h to explore the protection capacity of this coating by monitoring the cysteine oxidation products. The nanocomposites of halloysite and keratin prevent the deterioration of human hair as evident by significant inhibition of cysteic acid. The successful hair structure protection was also visually confirmed by atomic force microscopy and dark-field hyperspectral microscopy. The proposed formulation represents a promising strategy for a sustainable medical coating on the hair, which remediates UV irradiation stress.

Halloysite Nanotubes: Interfacial Properties and Applications in Cultural Heritage.

The peculiar surfaces of halloysite nanotubes and their biocompatibility are attracting the interest of researchers based on the wide range of attainable applications. The large aspect ratio of this nanotubular material ensures promising properties as a reinforcing agent in polymeric matrixes, such as cellulose and its derivatives, that entail strengthening due to, for instance, aging-induced degradation. The halloysite cavity has a suitable size for hosting a large variety of active species such as deacidifying (calcium hydroxide) and flame retardant agents (fluorinated surfactants) for a controlled and sustained release relevant to the conservation of cultural heritage. Additionally, anionic surfactants can be selectively adsorbed at the inner surface generating inorganic micelles able to solubilize hydrophobic species in a controlled cleaning protocol. We briefly discuss how the natural halloysite nanotubes can be supportive in various conservation processes of cultural heritage and present an outlook for future perspectives.

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 "model" pollutants: Ce(III) and crystal violet (CV). The choice is due to the fact that they are widespread in wastewaters of various origins. These characteristics, together with their effect on human health, make them ideal for studies on water remediation. Moreover, when separated from wastewater, they can be recycled individually in industrial production with no or simple treatment. Clay/pollutant hybrids were prepared under different pH conditions and characterized through the construction of the adsorption isotherms and powder X-ray diffraction. The adsorption behavior of the two contaminants was revealed to be significantly different: the Langmuir model reproduces the adsorption isotherm of Ce(III) better, thus indicating that the clay offers a unique adsorption site to the metal ions, while the Freundlich model proved to be the most reliable for the uptake of CV which implies heterogeneity of adsorption sites. Moreover, metal ions do not adsorb at all under acidic conditions, whereas the dye is able to adsorb under all the investigated conditions. The possibility to modulate the adsorption features by simply changing the pH conditions was successfully employed to develop an efficient protocol for the removal and separation of the different components from aqueous solutions mimicking wastewaters.

Why does vacuum drive to the loading of halloysite nanotubes? The key role of water confinement.

The filling of halloysite nanotubes with active compounds solubilized in aqueous solvent was investigated theoretically and experimentally. Based on Knudsen thermogravimetric data, we demonstrated the water confinement within the cavity of halloysite. This process is crucial to properly describe the driving mechanism of halloysite loading. In addition, Knudsen thermogravimetric experiments were conducted on kaolinite nanoplates as well as on halloysite nanotubes modified with an anionic surfactant (sodium dodecanoate) in order to explore the influence of both the nanoparticle morphology and the hydrophobic/hydrophilic character of the lumen on the confinement phenomenon. The analysis of the desorption isotherms allowed us to determine the water adsorption properties of the investigated nanoclays. The pore sizes of the nanotubes' lumen was determined by combining the vapor pressure of the confined water with the nanoparticles wettability, which was studied through contact angle measurements. The thermodynamic description of the water confinement inside the lumen was correlated to the influence of the vacuum pumping in the experimental loading of halloysite. Metoprolol tartrate, salicylic acid and malonic acid were selected as anionic guest molecules for the experimental filling of the positively charged halloysite lumen. According to the filling mechanism induced by the water confinement, the vacuum operation and the reduced pressure enhanced the loading of halloysite nanotubes for all the investigated bioactive compounds. This work represents a further and crucial step for the development of halloysite based nanocarriers being that the filling mechanism of the nanotube's cavity from aqueous dispersions was described according to the water confinement process.

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, while DMA measurements under the oscillatory regime showed that the polymer glass transition was not affected by the addition of the nanoclay. The tensile properties of the Mater-Bi/halloysite nanotube (HNT) films were competitive compared to those of traditional petroleum plastics in terms of the elastic modulus and stress at the breaking point. Both the mechanical response to the temperature and the tensile properties make the bio-nanocomposites appropriate for food packaging and smart coating purposes. Here, we report a preliminary study of the development of sustainable hybrid materials that could be employed in numerous industrial and technological applications within materials science and pharmaceutics.

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 samples. The penetration of the halloysite-Ca(OH)2/PEG composite within the wooden pores conferred the robustness of the archaeological woods based on the clay/polymer composition of the consolidant mixture. Compared to the archeological woods treated with pure PEG 1500, the addition of modified nanotubes in the consolidant induced a remarkable improvement in the mechanical performance in terms of flexural strength and rigidity. The pH measurements of the treated woods showed that the halloysite-Ca(OH)2 are effective alkaline fillers. Accordingly, the modified nanotubes provided a long-term protection for lignin present in the woods that are exposed to artificial aging under acidic atmosphere. The attained knowledge shows that an easy and green protocol for the long-term preservation of wooden artworks can be achieved by the combination of PEG polymers and alkaline tubular nanostructures obtained through the confinement of Ca(OH)2 within the halloysite cavity.

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 the PNIPAAM/halloysite based material. In particular, diclofenac release was slowed down above the LCST for PNIPAAM-co-MA/halloysite. Opposite trends occurred for halloysite functionalized with PNIPAAM at the outer surface. This work represents a further step toward the opportunity to extend and control the delivery conditions of active species, which represent a key point in technological applications.

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 stimuli. Here, we propose a new strategy based on inorganic reverse micelles for nanohydrogel formation, which are suitable for industrial and biological applications as well as for selective and triggered adsorption and/or release.

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 perspective inorganic nanoparticles within materials science, remedation and conservation of cultural heritage fields.

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 carrier and delivery systems, as fillers for hydrogels, in tissue regeneration and in the gene delivery field. Furthermore the loading and release of specific molecules have been also investigated for environmental purposes. This review summarizes the main developments in the halloysite modifications in the last 20 years with a particular attention to the development in the past two years.