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Fluorescence imaging has become an indispensable tool in the biomedical laboratory to elucidate the fundamental dynamic and structural factors regulating cellular processes. The development of fluorescent nanoprobes represents a challenge to detect any cellular process under a microscope. Herein, a fluorescent nanomaterial was synthesized by exploiting the supramolecular interaction between a halochromic switch (1Cl) and halloysite nanotubes (HNTs). The successful synthesis of a HNTs/1Cl nanomaterial was confirmed by thermogravimetric analysis and Fourier transform infrared. The aqueous mobility was investigated by dynamic light scattering and ζ-potential measurements as well. Furthermore, the morphology was imaged by transmission electron microscopy, and the interaction of the clay with 1Cl was also studied by kinetic adsorption measurements. In addition, the spectroscopy properties of the resulting nanomaterial were studied in solution and the solid state by UV-vis and fluorescence measurements. Finally, the ability of our nanomaterial to detect cancer cells was assessed with confocal laser scanning microscopy measurements on normal (hTERT) and/or tumoral cell lines (MCF-7 and HL-60R).

We describe an educational activity that can be completed with mobile media devices in order to understand the working principle of a pair of tuning forks, from the Historical Collection of Physics Instruments of the University of Palermo, and how they were used to explain acoustic interference and beats with the Lissajous optical method. This approach can be used with any tuning fork and it is a valuable teaching strategy that does not require specific laboratory equipment.

This work proposes a novel protocol for the fabrication of halloysite based geopolymers filled with beeswax microparticles obtained from Pickering emulsions. The actual filling of the microwax into the geopolymers has been demonstrated by using several techniques, including thermal analyses, spectroscopies, microscopies and contact angle experiments. According to the morphological and structural investigations, microwax spherical particles (diameter ranging between ca. 3 and 5 μm) have been homogeneously dispersed within the geopolymeric network conferring excellent properties to the hybrid geopolymers in terms of mechanical performances and heat storage capacity although their low content in the hybrid material. For comparison, we have prepared and characterized hybrid geopolymers obtained by the loading of variable amounts of beeswax within the geopolymeric matrix. Reliable enhancements of the flexural characteristics and heat absorption capacity have been achieved only with a large content of beeswax. Moreover, the removal of microvax and wax from the hybrid geopolymers has been obtained by rinsing with ethanol. The washed geopolymers have been characterized by wettability and water vapour permeability experiments, which have been proved that the beeswax has been removed and the porosity of the materials can be controlled by the initial composition of the hybrid geopolymers. In conclusion, this paper puts forward an easy strategy to fabricate composite geopolymers with heat storage capacity due to presence of phase change materials (microwax particles) confined in the geopolymeric network. Their enhanced flexural performances make the hybrid geoppolymers suitable as building materials.

The modification of chitosan represents a challenging task in obtaining biopolymeric materials with enhanced removal capacity for heavy metals. In the present work, the adsorption characteristics of chitosan modified with carboxyl groups (CTS-CAA) towards copper (II) and zinc (II) ions have been tested. The efficacy of the synthesis of CTS-CAA has been evaluated by studying various properties of the modified chitosan. Specifically, the functionalized chitosan has been characterized by using several techniques, including thermal analyses (differential scanning calorimetry and thermogravimetry), spectroscopies (FT-IR, XRD), elemental analysis, and scanning electron microscopy. The kinetics and the adsorption isotherms of CTS-CAA towards both Cu (II) and Zn (II) have been determined in the aqueous solvent under variable pH. The obtained results have been analyzed by using different adsorption models. In addition, the experiments have been conducted at variable temperatures to explore the thermodynamics of the adsorption process. The regeneration of CTS-CAA has been investigated by studying the desorption process using different eluents. This paper reports an efficient protocol to synthesize chitosan-based material perspective as regenerative adsorbents for heavy metals. © 2022 by the authors. Licensee MDPI, Basel, Switzerland. The authors express their gratitude to Princess Nourah bint Abdulrahman University Researchers Supporting Project number (PNURSP2022R13), Princess Nourah bint Abdulrahman University, Riyadh, Saudi Arabia. The work was supported by the Russian Foundation for Basic Research (RFBR) grant 18-29-12129mk. The researcher A.M. Abu El-Soad is funded by a scholarship under the Joint Executive program between the Arab Republic of Egypt and Russian Federation.

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.

The prodrug approach, as well as the development of specific systems able to deliver a chemotherapeutic agent in the target site, decreasing the side effects often associated with its administration, are still a challenging. In this context, both methotrexate drug molecules (MTX) and biotin ligand moieties, whose receptors are overexpressed on the surface of several cancer cells, were loaded on halloysite nanotubes (HNTs) to develop nanomaterial based on multifunctional and "smart" delivery systems. To highlight the crucial role played by biotin, carrier systems based on HNTs and MTX were also synthetized. In detail, several approaches were envisaged: i) a supramolecular interaction between the clay and the drug; ii) a covalent grafting of the drug onto the HNTs external surface and, iii) a combination of both approaches. The nanomaterials obtained were characterized by thermogravimetric analysis, FT-IR, and UV-vis spectroscopies, DLS and ζ-potential measurements and the morphologies were imaged by HAADF/STEM investigations. Kinetic release experiments at different pH conditions were also performed. Finally, as a proof-of-concept application of our pro-drug delivery systems based on HNTs in cancer therapy, the cytotoxic effects were evaluated on acute myeloid leukemia cell lines, HL60 and its multidrug resistance variant, HL60R. The obtained results showed that both the MTX prodrug system and the biotinylated ones played a crucial role in the biological activity and, they are promising agents for the cancer treatments.

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.

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. Furthermore, waterlogged archeological wood samples are consolidated using the nanotubes/pluronic nanocomposite, and the penetration of the nanocomposites into the lignin channels is confirmed by measurements based on X-ray computed microtomography.

In this contribution, we investigate the effect of the type of counterion on the properties of dilute solutions of polyoxyethylene alkyl ether carboxylic acids. Two different surfactants, presenting an oleic acid alkyl chain and on-average five and nine ethylene oxide units, and terminated by a weakly anionic carboxymethyl group were studied. The surfactants were gradually ionized with sodium hydroxide, arginine, and choline hydroxide. The solutions properties were probed by light scattering, electrophoretic mobility, density and sound velocity measurements, as well as by small-angle neutron scattering. To our initial surprise, no specific effect arising from the nature of the counterion could be determined. We ascribe this phenomenon to the fact that the presence of the ethylene oxide units markedly dilutes the surfactant head group charge density, reducing counterion condensation and subsequent counterion specific effects. This journal is

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.

A novel material for the deacidification and protection of paper has been designed by using MgO filled halloysite nanotubes (Hal). The ability of MgO loaded nanotubes to control the acidic conditions was evaluated by pH measurements in aqueous solvent. Afterwards, paper was impregnated into hydroxypropyl cellulose dispersions containing the consolidating material. A simulation of strong acidic conditions allowed us to evaluate the deacidification effect of the composite material on the samples. In particular, the paper reaches a pH of 7.7 after 1 h exposition to HNO3 vapours when MgO-Hal nanoparticles are added to the impregnation mixture at a concentration of 10 wt% and it remains still neutral after 12 h. Dynamic mechanical analysis showed that the tensile strength of the consolidated paper is improved, since the stress at breaking increase of ca. 8% for the samples treated with MgO-Hal compared to the untreated paper. Due to the presence of halloysite loaded with the alkaline reservoir, the acidic degradation of cellulose is neutralized as suggested by the stored energy which is similar to the pristine paper without any chemical attack. Therefore, the mechanical performances of the paper are preserved during the aging together with its macroscopic aspect, as suggested by colorimetric analysis. The proposed consolidation protocol represents a further step for the self-healing and long-term protection of cellulose based artworks.

The design of multifunctional nanomaterials which can help the healing processes of skin, preventing the bacterial infections, is crucial for the development of suitable therapy for the treatment of chronic lesions. The use of clay minerals in wound healing applications is well documented since the prehistoric period and offers several advantages due to their intrinsic properties. Herein, we report the development of ciprofloxacin carrier systems based on hectorite/halloysite (Ht/Hal) hybrid hydrogels for potential wound healing applications. To achieve this objective firstly the ciprofloxacin molecules were loaded onto Hal by a supramolecular and covalent approach. The so obtained fillers were thoroughly investigated by several techniques and at molecular level by means of quantum mechanics calculations along with empirical interatomic potentials. Afterwards the modified Hal were used as filler for Ht hydrogels. The introduction of modified Hal, in hectorite hydrogel, helps the gel formation with an improvement of the rheological properties. The in vitro kinetic release from both the fillers and from the hybrid hydrogels was studied both at skin's pH (5.4) and under neutral conditions (pH 7.4); in addition, the factors controlling the ciprofloxacin release process were determined and discussed. Finally, the in vitro biocompatibility of the Hal fillers was evaluated by means of cytotoxic assays and laser scanning confocal microscopy on normal human dermal fibroblasts., The work was carried out in the frame of the PON “AIM: Attrazione e Mobilità Internazionale” No. 1808223-1 project. Authors are thankful to H.A. Duarte for providing atomic coordinates of halloysite, to the CSIC Computational Center and the University of Granada Computation Center for computation facilities, and the Andalusian project grants RNM-1897 and P18-RT-3786 , and the Spanish MINECO projects , PCIN-2017-098 , FIS2016-77692-C2-2-P and CGL2016-80833-R , for the financial support of this research.

In this paper, films based on sustainable polymers with variable charge have been investigated by non-isothermal thermogravimetry in order to predict their lifetime, which is a key parameter for their potential use in numerous technological and biomedical applications. Specifically, chitosan has been selected as positively charged biopolymer, while alginate has been chosen as negatively charged biopolymer. Among non-ionic polymers, methylcellulose has been investigated. Thermogravimetric measurements at variable heating rates (5, 10, 15 and 20 °C min−1) have been performed for all the polymers to study their degradation kinetics by using isoconversional procedures combined with ‘Master plot’ analyses. Both integral (KAS and Starink methods) and differential (Friedman method) isoconversional procedures have shown that chitosan possesses the highest energetic barrier to decomposition. Based on the Master plot analysis, the decomposition of ionic polymers can be described by the R2 kinetic model (contracted cylindrical geometry), while the degradation of methylcellulose reflects the D2 mechanism (two-dimensional diffusion). The determination of both the decomposition mechanism and the kinetic parameters (activation energy and pre-exponential factor) has been used to determine the decay time functions of the several biopolymers. The obtained insights can be helpful for the development of durable films based on sustainable polymers with variable electrostatic characteristics. Graphical abstract

A new adsorbent, sulfated crosslinked chitosan (SGCH), has been synthesized for the effective extraction of beryllium ions from their aqueous solutions. In recent times, beryllium extraction has been of great importance because beryllium can be used in many applications such as in nuclear reactor, heat shields, high-technology ceramics, alloys and electronic heat sinks. SGCH has been synthesized by two successive phases. The first is the conversion of chitosan (CH) into non-soluble cross-linked chitosan (GCH) through the interaction between chitosan and glutaraldehyde. The second step is the formation of functional sulfonate groups onto the adsorbent material through the interaction of GCH with chlorosulfonic acid (sulfating agent). The role played by the sulfonate groups in the adsorption process was analyzed using FT-IR and SEM. Also, the role played by the solution pH, time, beryllium concentration and temperature on the batch adsorption process was investigated. Our results point to the successful preparation of SGCH adsorbent with high affinity for beryllium ions. The maximum sorption values of beryllium ions on the investigated biosorbent is 40.6 mg/g. The desorption of the loaded beryllium ions from the SGCH was achieved by using 1.5 M urea acidified by 0.6 M H2SO4.

Halloysite clay is a natural nanomaterial that is attracting a growing interest in colloidal science. The halloysite aqueous dispersion stability is a key aspect for the configuration of a purification protocol as well as to establish the durability of a formulation. A physico-chemical study demonstrated the role of ionic strength and nanotube characteristic sizes on the sedimentation behavior. We highlighted the importance of the electrostatic repulsions exercised between the particles in the settling process. A protocol for image analysis has been proposed to provide robust information from time resolved optical images on the suspensions. In conclusion, we managed to correlate microscopic aspect to the peculiar sedimentation process of halloysite nanotubes.

Thermal and structural properties of historical woods from apparatuses of the Historical Collection of the Physics Instruments of the University of Palermo have been investigated by FTIR spectroscopy coupled with thermogravimetric analysis. Specifically, the wooden portions of apparatuses from XIX century have been studied. The investigated woods belong to different taxa (Swietenia mahagoni, Picea abies and Juglans regia). The thermal behavior of the wooden materials has been successfully interpreted on the basis of specific indexes determined by the quantitative analysis of the FTIR spectra. The kinetics of the wood pyrolysis have been investigated by using a non-isothermal approach based on model-free isoconversional procedures, such as Kissinger–Akahira–Sunose (KAS) and Friedman methods. Interestingly, the activation energy of the pyrolysis process reflects both the peculiar composition (related to the specific wooden taxon) and the conservation state of the historical woods. In this regards, we estimated that the average activation energies obtained from KAS analysis are 203, 156 and 43 kJ mol−1 for Swietenia mahagoni, Picea abies and Juglans regia woods, respectively. The thermogravimetric parameters have been correlated to the lignin index of the woods by proper experimental equations, which can be considered as a novel protocol to estimate the preservation conditions of historical woods from different taxon.

We have fabricated ecocompatible Pickering emulsions based on halloysite nanotubes and ionic biopolymers (chitosan and pectin) from renewable resources. The effect of pectin and chitosan on the Pickering emulsion was investigated by direct visualization of the oil droplets and by the thermodynamic characterization at the interface. Pectin enhances the Pickering emulsion stability, while a phase separation and nonhomogeneous gel was observed in the presence of chitosan. We have demonstrated that the Pickering emulsion in a pectin based gel phase is suitable for wax layer removal from a marble surface. A controlled cleaning is achieved by tuning the contact time between the gel and the marble surface. Due to its nonhomogeneous structure, chitosan-based gel does not show proper wax removal ability. This work opens up a new sustainable approach in preparing cleaning formulations for conservation of cultural heritage.

Here we overview the recent advances in the fabrication of sustainable composite nanomaterials with decontamination capacity towards inorganic and organic pollutants. In this regards, we present the development of hybrid systems based on clay nanoparticles with different shapes (such as kaolinite nanosheets and halloysite nanotubes) and organic molecules (biopolymers, surfactants, cucurbituril) as efficient removal agents for both aliphatic and aromatic hydrocarbons. Due to their high specific surface area, clay nanoparticles have been successfully employed as fillers for composite membranes with excellent filtration capacity. The preparation of composite gel beads based on biopolymers (alginate and pectin) and halloysite nanotubes has been discussed and their adsorption capacities towards both heavy metals and organic dyes have been highlighted. We describe the successful preparation of kaolinite/graphene composites as well as tubular inorganic micelles obtained by the select functionalization of the halloysite cavity with anionic surfactants. Finally, recent research on Pickering emulsions (for oil spill remediation) and bioremediation technologies has been discussed.

New temperature-responsive hybrid nanomaterials based on modified halloysite nanotubes (HNTs) containing grafted polymer brushes with silver nanoparticles have been successfully fabricated. We used a three steps process including synthesis of the initiating coatings onto HNTs surface, fabrication of the POEGMA – poly(oligo(ethylene glycol)ethyl ether methacrylate) grafted brushes and synthesis of the silver nanoparticles (AgNPs). The synthesis and properties of hybrid nanomaterials were studied by FT-IR, TGA and DLS methods. It is shown that the introduction of AgNPs, formed from 0.005 M AgNO3 solution leads to a significant reduction of low critical solution temperature (LCST) of the polymer layer from 29.7 to 21.6 °C. The samples fabricated from 0.05 M AgNO3 solution did not evidence a temperature-induced transition, despite of the contents of AgNPs obtained for both solutions are almost identical (≈ 4%w). The presence of AgNPs with sizes of ca. 20 nm was confirmed in the hybrids prepared from both AgNO3 concentrations by UV–vis spectroscopy, and electron microscopy. These temperature-responsive hybrid nanomaterials may be used for conservation of solid substrates, production of advanced medical facemasks, photothermal therapy against microorganisms and tumors etc.

In this work, we propose an easy strategy for the separation of halloysite/kaolinite mixtures in sucrose aqueous solution. Preliminarily, we investigated the influence of the sucrose addition on the colloidal stability of kaolinite nanoplates and halloysite nanotubes (HNTs) dispersed in water. Dynamic Light Scattering (DLS) measurements revealed that the HNTs aqueous mobility is dependent on the sucrose concentration, while the ζ-potential is negligibly affected by the addition of the carbohydrate in the aqueous solvent. On the other hand, any variations on the surface charge and dynamic behavior of kaolinite were detected in the presence of sucrose. The obtained ζ-potential and DLS results were useful to interpret the sedimentation kinetics of kaolinite and halloysite dispersions. In particular, the peculiar sedimentation behavior of halloysite were discussed by considering the screening effect of sucrose on the attractive interactions between the nanotubes. The latter was evaluated by the calculation of the corresponding Hamaker constants. On this basis, we estimated that the optimization of the separation between kaolinite and halloysite might be achieved in 10 wt% sucrose aqueous solution. This hypothesis was confirmed by the separation experiments, which exploited the different sedimentation behavior of halloysite and kaolinite. Thermogravimetric experiments on the separated material and kaolinite/halloysite composites with variable composition allowed us to determine the efficiency of the separation protocol. To this purpose, the differential thermogravimetric curves were accurately analysed by using split Gaussian functions. In conclusion, this paper represents a further step in the purification of natural halloysite samples exploiting the ability of sucrose to control the attractive forces of the clay nanotubes as well as the colloidal stability of kaolinite nanoplates in aqueous solvent.

In this work, non-isothermal thermogravimetric studies have been carried out on several paracetamol formulations with the aim to predict their shelf-lives under variable storage conditions. Specifically, paracetamol tablets of different brands have been investigated allowing to estimate their pharmaceutical quality by considering the specific drug stability. The proposed protocol is based on the kinetic study of thermogravimetric data by the combination of isoconversional procedures (Friedman and Kissinger-Akahira-Sunose (KAS) methods) and “Master plot” analysis. Accordingly, the kinetics of the paracetamol degradation is totally explored in terms of activation energy, pre-exponential factor and reaction mechanism of the drug decomposition. The obtained insights drive to simulate the decay time functions of paracetamol amount for the several pharmaceutical formulations. Interestingly, these simulations can be easily adapted to variable isothermal conditions providing the shelf-lives of the paracetamol tablets at different temperatures. The kinetic characteristics of the paracetamol degradation as well as the corresponding shelf-life values evidenced that the expiration date of the pharmaceutical products are significantly affected by the composition of the excipients. In conclusion, this work demonstrates that non-isothermal thermogravimetric analysis can be used as efficient and sensitive tool for the prediction of the shelf-lives of paracetamol formulations.

Modified halloysite nanotubes (HNTs-Cl) were synthesized by a coupling reaction with (3-chloropropyl) trimethoxysilane (CPTMS). The incorporation of chloro-silane onto HNTs surface creates HNTs-Cl, which has great chemical activity and is considered a good candidate as an active site that reacts with other active molecules in order to create new materials with great applications in chemical engineering and nanotechnology. The value of this work lies in the fact that improving the degree of grafting of chloro-silane onto the HNT’s surface has been accomplished by incorporation of HNTs with CPTMS under different experimental conditions. Many parameters, such as the dispersing media, the molar ratio of HNTs/CPTMS/H2O, refluxing time, and the type of catalyst were studied. The greatest degree of grafting was accomplished by using toluene as a medium for the grafting process, with a molar ratio of HNTs/CPTMS/H2O of 1:1:3, and a refluxing time of 4 h. The addition of 7.169 mmol of triethylamine (Et3N) and 25.97 mmol of ammonium hydroxide (NH4OH) led to an increase in the degree of grafting of CPTMS onto the HNT’s surface. © 2021 by the authors. Licensee MDPI, Basel, Switzerland. This research was funded by Program 211 of the Government of the Russian Federation No. 02.A03.21.0006, RFBR grants 17-03-00641 and 18-29-12129 mk, the State Task from the Ministry of the Education and Science of the Russian Federation No. 4.9514.2017/8.9.

Cyclodextrins (CDs) play an important role in self-assembly systems of amphiphiles. The structure of CDs provides distinguished physicochemical properties, including the ability to form host-guest complexes. The complexation affects the properties of guest molecules and can produce supramolecular aggregates with desirable characteristics for fundamental and practical applications. Surfactants are particularly attractive host molecules due to their wide variety, availability, responsiveness to different stimuli, and high relevance in different fields, e.g. medical, cosmetic, pharmaceutical, and food industries. The tendency of organization in higher-order supramolecular aggregates arises the interest in applying such versatile complexes in the development of novel materials. In this review, we provide a comprehensive overview of the thermodynamics aspects of surfactants and CDs inclusion complexes formation in aqueous environment, emphasizing the assessment of the interactions, thermodynamic driving forces, and structural aspects. Also, the most common analytical techniques used to gather deep insight into the aspects of CDs complexes are discussed and the perspectives for the surfactant-cyclodextrin complexes are pointed out.

The synthesis of a new biocompatible bichromophoric system (CURBO) was developed, by connecting the skeleton of the naturally occurring curcumin to a BODIPY derivative. The system exhibited an intense fluorescence band with maximum at about 510 nm in organic solvent, while its emission spectra in aqueous solution were more complicated and slightly red-shifted, due to the effect of aggregation for the poor solubility of the dyad. To overcome these problems, the bichomophoric system has been loaded into the halloysite nanotubes (HNT). The HNT/CURBO nanocomposite, suspended in aqueous solution, showed an intensity of emission in the red region of the spectrum higher than the one exhibited by the pristine CURBO. The biocompatibility and photophysical behavior of HNT/CURBO nanocomposite were studied using ASC52Telo, h-TERT immortalized adipose-derived mesenchymal stem cells. To investigate the localization of the CURBO alone and in HNT/CURBO, fluorescence epimicroscopy was performed. The HNT/CURBO nanocomposite showed a high propensity to cross cell membranes, resulting in a massive cell uptake around the cell nucleus. Moreover, it lighted up ASC52Telo cells both with intense green and red fluorescence while excited in the blue portion of the electromagnetic spectrum, a phenomenon that could not be observed for the free CURBO. Dual-channel emissions dyes and, in particular, materials, such as the HNT/CURBO nanocomposite, emitting in the red portion of the spectrum have become, in recent decades, particularly fascinating since they can minimize the autofluorescence detection of the cell medium and allow interesting microscopy applications.

The design of novel nanocomposite films based on hydroxypropyl cellulose (HPC) and wax/halloysite hybrid microspheres has been reported. In particular, we first prepared wax/clay Pickering emulsions which were characterized by thermogravimetric analysis and microscopy. SEM images allowed more detailed insights on the nanotubes disposition at the wax/water interface, acting as an outer stabilizing shell. Therefore, the cellulosic biopolymer was added, and it was found that HPC enhances the colloidal stability of the particles, preventing their coalescence and sedimentation. The preparation of the composite films was carried out by the solvent casting method, which enabled the development of very homogeneous materials. Contact angle and sliding angle measurements showed that the increasing amount of wax/halloysite microparticles into the biopolymeric matrix is responsible for an enhanced hydrophobic nature of the films and, at the same time, it facilitates the rolling process of droplets on the surfaces, thus making the prepared materials promising protective coatings. These findings were also confirmed by the decrease of the vapor permeability of the nanocomposites, which can act as a gas barrier. Moreover, the effect of the composition on the optical properties, namely transparency and colorimetric features, was investigated together with the thermal properties of the films. Results demonstrated that the presence of wax/halloysite microspheres as fillers within the HPC matrix has profound effects on the prepared systems, which were evaluated to be good energy storage and heat reservoir materials. In light of these aspects, the new HPC/wax/halloysite nanocomposites represent promising tools for the surface modification.

This study evidences the adsorption of model nonionic polymers onto aluminogermanate imogolite nanotubes, attractive porous nanofillers with potential molecular loading and release applications. We resolve the underlying mechanisms between nanotubes and polyethylene glycols with different molecular weights by means of nanoisothermal titration calorimetry. The analysis of the results provides a direct thermodynamic characterization, allowing us to propose a detailed description of the energetics involved in the formation of polymer/imogolite complexes. The affinity toward the nanotube surface is enthalpy-driven and strongly depends on the polymer chain length, which significantly affects the polymer configuration and the flow properties of the resulting complexes, probed by small-angle neutron scattering and rheology, respectively. These findings open new avenues for the rational design of these hybrid mixtures for advanced applications.

Chitosan is one of the most studied cationic polysaccharides. Due to its unique characteristics of being water soluble, biocompatible, biodegradable, and non-toxic, this macromolecule is highly attractive for a broad range of applications. In addition, its complex behavior and the number of ways it interacts with different components in a system result in an astonishing variety of chitosan-based materials. Herein, we present recent advances in the field of chitosan-based materials from a physico-chemical perspective, with focus on aqueous mixtures with oppositely charged colloids, chitosan-based thin films, and nanocomposite systems. In this review, we focus our attention on the physico-chemical properties of chitosan-based materials, including solubility, mechanical resistance, barrier properties, and thermal behaviour, and provide a link to the chemical peculiarities of chitosan, such as its intrinsic low solubility, high rigidity, large charge separation, and strong tendency to form intra- and inter-molecular hydrogen bonds.

Besides surfactants, which decrease the interfacial tension between two immiscible liquids, also interfacially active particles can successfully stabilize an emulsion system by attaching at the liquid–liquid interface. The preparation of the resulting Pickering emulsions has been so far investigated starting from the study of the interactions arising between the dispersed droplets and the stabilizers, till the application of these systems in a wide range of different fields. This work is intended to provide an overall overview about the development of Pickering emulsions by considering the most general aspects and scanning the diverse types of solid stabilizers. Among them, Halloysite nanotubes play a major role as naturally derived clay with emulsifying capability owing to their cheap, abundant, green and biocompatible properties. Therefore, the design of Halloysite stabilized Pickering emulsions is the main content of this review, which will survey the role of nanotubes in providing colloidal stability and will comprehensively sum up the use of these particles in technological and industrial purposes: from environmental to catalytic, from health to cultural heritage related applications.

Complexation of biopolymers with halloysite nanotubes (HNTs) can greatly affect their applicability as materials building blocks. Here we have performed a systematic investigation of fabrication of halloysite nanotubes complexes with nucleotides and genomic DNA. The binding of DNA and various nucleotide species (polyAU, UMP Na2, ADP Na3, dATP Na, AMP, uridine, ATP Mg) by halloysite nanotubes was tested using UV-spectroscopy. The study revealed that binding of different nucleotides to the nanoclay varied but was low both in the presence and absence of MgCl2, while MgCl2 facilitated significantly the binding of longer molecules such as DNA and polyAU. Modification of the nanotubes with DNA and nucleotide species was further confirmed by measurements of &zeta, potentials. DNA-Mg-modified nanotubes were characterized using transmission electron (TEM), atomic force (AFM) and hyperspectral microscopies. Thermogravimetric analysis corroborated the sorption of DNA by the nanotubes, and the presence of DNA on the nanotube surface was indicated by changes in the surface adhesion force measured by AFM. DNA bound by halloysite in the presence of MgCl2 could be partially released after addition of phosphate buffered saline. DNA binding and release from halloysite nanotubes was tested in the range of MgCl2 concentrations (10&ndash, 100 mM). Even low MgCl2 concentrations significantly increased DNA sorption to halloysite, and the binding was leveled off at about 60 mM. DNA-Mg-modified halloysite nanotubes were used for obtaining a regular pattern on a glass surface by evaporation induced self-assembly process. The obtained spiral-like pattern was highly stable and resisted dissolution after water addition. Our results encompassing modification of non-toxic clay nanotubes with a natural polyanion DNA will find applications for construction of gene delivery vehicles and for halloysite self-assembly on various surfaces (such as skin or hair).

Herein, we describe an open-source, Python-based, script to treat the output of differential scanning calorimetry (DSC) experiments, called pyDSC, available free of charge for download at https://github.com/leonardo-chiappisi/pyDSC under a GNU General Public License v3.0. The main aim of this program is to provide the community with a simple program to analyze raw DSC data. Key features include the correction from spurious signals, and, most importantly, the baseline is computed with a robust, physically consistent approach. We also show that the baseline correction routine implemented in the script is significantly more reproducible than different standard ones proposed by proprietary instrument control software provided with the microcalorimeter used in this work. Finally, the program can be easily applied to large amount of data, improving the reliability and reproducibility of DSC experiments.

Prodigiosin, a bioactive secondary metabolite produced by Serratia marcescens, is an effective proapoptotic agent against various cancer cell lines, with little or no toxicity toward normal cells. The hydrophobicity of prodigiosin limits its use for medical and biotechnological applications, these limitations, however, can be overcome by using nanoscale drug carriers, resulting in promising formulations for target delivery systems with great potential for anticancer therapy. Here we report on prodigiosin-loaded halloysite-based nanoformulation and its effects on viability of malignant and non-malignant cells. We have found that prodigiosin-loaded halloysite nanotubes inhibit human epithelial colorectal adenocarcinoma (Caco-2) and human colon carcinoma (HCT116) cells proliferative activity. After treatment of Caco-2 cells with prodigiosin-loaded halloysite nanotubes, we have observed a disorganization of the F-actin structure. Comparison of this effects on malignant (Caco-2, HCT116) and non-malignant (MSC, HSF) cells suggests the selective cytotoxic and genotoxic activity of prodigiosin-HNTs nanoformulation.

A new design for halloysite nanotube materials was obtained by grafting chemically modified cyclodextrin units onto the nanotube surface. In particular, grafted cyclodextrins were decorated with thiosaccharide pendants, in order to mimic the well-known binding of sugars to proteins and the glyco-cluster effect occurring during cellular recognition events. The obtained materials were characterized by using a combination of varied techniques (FT-IR spectroscopy, thermogravimetric analysis, scanning electron microscopy, dynamic light scattering, turbidimetry), and their potential drug-delivery abilities were tested by studying their interactions with the common naturally occurring anticancer agent curcumin. A suitable model describing the interaction between our materials and curcumin is proposed.

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.

The structural properties of halloysite/biopolymer aqueous mixtures were firstly investigated by means of combining different techniques, including small-angle neutron scattering (SANS), electric birefringence (EBR) and fluorescence correlation spectroscopy (FCS). Among the biopolymers, non-ionic hydroxypropylcellulose and polyelectrolytes (anionic alginate and cationic chitosan) were selected. On this basis, the specific supramolecular interactions were correlated to the structural behavior of the halloysite/biopolymer mixtures. SANS data were analyzed in order to investigate the influence of the biopolymer adsorption on the halloysite gyration radius. In addition, a morphological description of the biopolymer-coated halloysite nanotubes (HNTs) was obtained by the simulation of SANS curves. EBR experiments evidenced that the orientation dynamics of the nanotubes in the electric field is influenced by the specific interactions with the polymers. Namely, both variations of the polymer charge and/or wrapping mechanisms strongly affected the HNT alignment process and, consequently, the rotational mobility of the nanotubes. FCS measurements with fluorescently labeled biopolymers allowed us to study the aqueous dynamic behavior of ionic biopolymers after their adsorption onto the HNT surfaces. The combination of EBR and FCS results revealed that the adsorption process reduces the mobility in water of both components. These effects are strongly enhanced by HNT/polyelectrolyte electrostatic interactions and wrapping processes occurring in the halloysite/chitosan mixture. The attained findings can be useful for designing halloysite/polymer hybrids with controlled structural properties.

Biohybrid materials were prepared by co-assembling the three following components: nanotubular halloysite, microfibrous sepiolite, and cellulose nanofibers dispersed in water, in order to exploit the most salient features of each individual component and to render homogeneous, flexible, yet strong films. Indeed, the incorporation of halloysite improves the mechanical performance of the resulting hybrid nanopapers and the assembly of the three components modifies the surface features concerning wetting properties compared to pristine materials, so that the main characteristics of the resulting materials become tunable with regard to certain properties. Owing to their hierarchical porosity together with their diverse surface characteristics, these hybrids can be used in diverse biomedical/pharmaceutical applications. Herein, for instance, loading with two model drugs, salicylic acid and ibuprofen, allows controlled and sustained release as deduced from antimicrobial assays, opening a versatile path for developing other related organic-inorganic materials of potential interest in diverse application fields., The authors thank the MINECO (Spain) and FEDER (EU) for financial support (project MAT2015-71117-R). LL and GDL acknowledge the University of Palermo for the “UOB21 Borse di studio finalizzate alla ricerca” grants. BW thanks the MINECO for the IJCI contract (IJCI-2015-23886). We acknowledge support of the publication fee by the CSIC Open Access Support Initiative through its Unit of Information Resources for Research (URICI)

Clay minerals are phyllosilicates of nanoscale dimensions. According to their ability to entrap and release organic moieties, they have found applications in several fields, such as drug carrier and delivery, support for catalyst, environmental remediation and filler for polymeric matrices. The possibility to modify, by covalent linkage, their surfaces gives the possibility to form new nanomaterials with improved properties respect to the pristine clay minerals. In this chapter, the modifications of the siloxane surfaces of the most representative clay minerals, namely montmorillonite, sepiolites, laponite and halloysite were reviewed and discussed.

In this article, halloysite nanoclay (Hal) was used as porogen for the synthesis of nitrogen doped porous carbon material with high specific surface area and pore volume. To this purpose, polymerization of melamine and terephthalaldehyde (MT) was performed in the presence of amine-functionalized carbon coated Hal (Hal@Glu-2N) that was prepared from hydrothermal treatment of Hal and glucose. Then, the prepared nanocomposite was palladated and carbonized to afford Pd@Hal@C. To further improve the textural properties of the nanocomposite, and introduce more pores in its structure, Hal nanotubes were etched. The characterization of the resulting compound, Pd@C, and comparing it with Pd@Hal@C, showed that etching of Hal significantly increased the specific surface area and pore volume in Pd@C. Pd@C was successfully used as a heterogeneous catalyst for promoting hydrogenation of nitroarens in aqueous media using hydrogen with atmospheric pressure as a reducing agent. The comparison of the structural features and catalytic activity of the catalyst with some control catalysts, including, Pd@Hal, Pd@Hal@Glu, Pd@Hal@Glu-MT and Pd@Hal@C confirmed that nitrogen groups in C could improve the Pd anchoring and suppress its leaching, while etching of Hal and introduction of more pores could enhance the catalytic activity through facilitating the mass transfer.

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&rsquo, s method for solubility of polymers, while the optimum ratio between biopolymer constituents was assessed by &zeta, 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.

A hybrid catalyst, Pd@Hal-pDA-NPC, with the utility for promoting both C–C coupling reactions (Sonogashira, Heck and Suzuki reactions) and hydrogenation of nitrocompounds is prepared through two main steps. First, Pd(0) nanoparticles was immobilized on the poly-dopamine decorated halloysite nanotubes (Hal-pDA) and then Pd@Hal-pDA was hybridized with the layers of a novel multi-N-doped porous carbon monolayer derived from 4,4′,4″-((1,3,5-triazine-2,4,6-triyl)tris(azanediyl))tribenzonitrile. The results established that the catalyst could catalyze all the reactions efficiently under mild reaction condition. Moreover Pd@Hal-pDA-NPC exhibited high recyclability (up to ten reaction runs). Using various control catalysts, precise stuy was performed to elucidate the role of NPC and p-DA in the catalysis and suppressing Pd leaching. The results confirmed that both NPC and p-DA could improve Pd loading, while supress its leaching. Moreover, it was proved that incorporation of NPC was more effective than graphitic carbon nitride, g-G3N4, and grapheme oxide, GO.

In this article, a magnetic carbon-coated halloysite nanoclay (Hal) was prepared through introduction of hydrothermally carbonized glucose (Glu) on Hal followed by the immobilization of magnetic nanoparticles (MNPs) and incorporation of resorcinol-formaldehyde polymeric shell (RF) and carbonization. The resulting composite was then successfully applied for the immobilization of Pd nanoparticles to afford Pd@Hal@Glu-Fe-C that could efficiently promote hydrogenation of nitroarenes in the aqueous media at low temperature. The catalyst exhibited high selectivity toward nitro group. Moreover, it was highly recyclable with low MNPs and Pd leaching. To elucidate the contribution of each component of the support to the catalysis, a precise study was carried out by preparing several control catalysts and comparing their catalytic activities with that of Pd@Hal@Glu-Fe-C. Furthermore, the effect of carbon source used for the formation of hydrothermally derived carbon -wrapped Hal and the order of incorporation of metallic nanoparticles on the catalytic activity of the final catalyst was investigated.

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, model&rdquo, 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.

In this study, environmental friendly halloysite nanotubes and their amino derivatives were used as adsorbent materials for lead(II) ions. The adsorption ability of both nanomaterials towards Pb2+ ions has been studied in NaClaq, at I = 0.1 mol L−1, in the pH range 3–6. Moreover, the effect of ionic strength on the adsorption process was evaluated at the pH of maximum efficiency of the adsorbent materials. Kinetic and equilibrium experiments were carried out by using the Differential Pulse Anodic Stripping Voltammetry (DP-ASV) technique to check the metal ion concentration in solution after contact with the two adsorbents. Different isotherm and kinetic equations were used to fit the experimental data. The speciation of metal ion and the characterization of the adsorbents with different techniques were considered in order to establish the suitable experimental conditions for the metal ion removal. The collected data showed that the functionalization of halloysite enhances the adsorption ability of the clay mineral and it makes the nanoclay a good candidate for metal removal from aqueous solutions.

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. © 2018 American Chemical Society.

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. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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.

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 multilayer morphology of the prepared chitosan/HNT nanocomposites has been confirmed by water contact angle measurements, which revealed that the hybrid films present a hydrophobic surface. The peculiar sandwich-like morphology of the chitosan/HNT hybrid materials has been correlated to their thermal behavior under inert and oxidative atmospheres. The kinetic aspects of chitosan degradation have been studied by a non-isothermal thermogravimetric approach (Friedman's method), while the suitability of HNTs as flame retardant fillers of multilayer nanocomposites has been estimated by the thermodynamic parameters of oxidative degradation. According to the thermogravimetric data, the formation of a well-compacted middle layer of HNTs has induced a reliable decrease in the activation energy of the degradation of chitosan. Differential scanning calorimetry experiments showed that the nanocomposites possess an enhanced ignition temperature compared with pure chitosan. This paper opens new sustainable prospects for the preparation of novel nanocomposites with layered structures that can be strategic for packaging, tissue engineering, and pharmaceutical applications. © 2018 The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.

The synthesis and characterization of a new class of 1,2,4-oxadiazolylpyridinium as a cationic scaffold for fluorinated ionic liquid crystals is herein described. A series of 12 fluorinated heterocyclic salts based on a 1,2,4-oxadiazole moiety, connected through its C(5) or C(3) to an N-alkylpyridinium unit and a perfluoroheptyl chain, differing in the length of the alkyl chain and counterions, has been synthesized. As counterions iodide, bromide and bis(trifluoromethane)sulfonimide have been considered. The synthesis, structure, and liquid crystalline properties of these compounds are discussed on the basis of the tuned structural variables. The thermotropic properties of this series of salts have been investigated by differential scanning calorimetry and polarized optical microscopy. The results showed the existence of an enantiotropic mesomorphic smectic liquid crystalline phase for six bis(trifluoromethane)sulfonimide salts.

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.

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 filler content have been employed as consolidants for waterlogged archaeological woods. The quantitative analysis of the thermogravimetric curves have provided the amount of consolidants entrapped into the wood structure. These results have been successfully correlated to the consolidation efficiencies estimated from the analysis of the wood shrinkage volume upon drying. The attained knowledge represents the basic step to develop a green protocol for the long term protection of wooden art-works. © 2017, Springer Science+Business Media B.V.

Pectin bionanocomposite films filled with various concentrations of two different types of halloysite nanotubes were prepared and characterized in this study as potential films for food packaging applications. The two types of halloysite nanotubes were long and thin (patch) (200-30 000 nm length) and short and stubby (Matauri Bay) (50-3000 nm length) with different morphological, physical, and dispersibility properties. Both matrix (pectin) and reinforcer (halloysite nanotubes) used in this study are considered as biocompatible, natural, and low-cost materials. Various characterization tests including Fourier transform infrared spectroscopy, field emission scanning electron microscopy, release kinetics, contact angle, and dynamic mechanical analysis were performed to evaluate the performance of the pectin films. Exceptional thermal, tensile, and contact angle properties have been achieved for films reinforced by patch halloysite nanotubes due to the patchy and lengthy nature of these tubes, which form a bird nest structure in the pectin matrix. Matauri Bay halloysite nanotubes were dispersed uniformly and individually in the matrix in low and even high halloysite nanotube concentrations. Furthermore, salicylic acid as a biocidal agent was encapsulated in the halloysite nanotubes lumen to control its release kinetics. On this basis, halloysite nanotubes/salicylic acid hybrids were dispersed into the pectin matrix to develop functional biofilms with antimicrobial properties that can be extended over time. Results revealed that shorter nanotubes (Matauri Bay) had better ability for the encapsulation of salicylic acid into their lumen, while patchy structure and longer tubes of patch halloysite nanotubes made the encapsulation process more difficult, as they might need more time and energy to be fully loaded by salicylic acid. Moreover, antimicrobial activity of the films against four different strains of Gram-positive and Gram-negative bacteria indicated the effective antimicrobial properties of pectin/halloysite functionalized films and their potential to be used for food packaging applications. © 2017 American Chemical Society.