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Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich., This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively., We studied the formation of polypseudorotaxanes formed with cyclodextrins (CDs) threading a copolymer chain that forms self-assembled structures in water. The size of the CD cavity was chosen such that it is block selective with respect to the formation of inclusion complexes and therefore in terms of altering the structure of the copolymer self-assemblies in a systematic fashion. Small angle neutron scattering (SANS) experiments provide a direct and clear picture of the shape and interactions of the copolymer micelles in the absence and the presence of various CDs. Moreover, the dissolution of copolymer micelles by CD addition was clearly described by a simple model which provides a tool for quantitative predictions. This study suggests the possibility of designing materials with tunable aggregation abilities in water, where the extent of aggregate formation is determined by the amount and type of added cyclodextrin.

Scientific research has been invigorated by a new class of biodegradable materials as alternatives to polymers derived from fossils. Such biomaterials can also offer economic advantages because they are derived from renewable resources. Several biopolymers (gelatin, chitin, chitosan, starch, pectin, cellulose and its modified versions, etc.) have been exploited to produce films and formulations. Their use is limited because of fast degradation, predominant hydrophilic character, and, in some cases, unsatisfactory mechanical properties. However, the properties of these polymers can be improved by using inorganic fillers such as additives. Halloysite nanotube is a promising green filler for this purpose.

Covalently functionalized halloysite nanotubes (HNTs) were successfully employed as dual-responsive nanocarriers for curcumin (Cur). Particularly, we synthesized HNT-Cur prodrug with a controlled curcumin release on dependence of both intracellular glutathione (GSH) and pH conditions. In order to obtain HNT-Cur produgs, halloysite was firstly functionalized with cysteamine through disulphide linkage. Afterwards, curcumin molecules were chemically conjugated to the amino end groups of halloysite via Schiff's base formation. The successful functionalization of halloysite was proved by thermogravimetric analysis, FT-IR spectroscopy, dynamic light scattering and scanning electron microscopy. Experimental data confirmed the presence of curcumin on HNT external surface. Moreover, we investigated the kinetics of curcumin release by UV-vis spectroscopy, which highlighted that HNT-Cur prodrug possesses dual stimuli-responsive ability upon exposure to GSH-rich or acidic environment. In vitro antiproliferative and antioxidant properties of HNT-Cur prodrug were studied with the aim to explore their potential applications in pharmaceutics. This work puts forward an efficient strategy to prepare halloysite based nanocarriers with controlled drug delivery capacity through direct chemical grafting with stimuli-responsive linkage.

In the last two decades, the naturally occurring polysaccharides have gained great attention because of their potential applications in different sectors, for example, from food to biomedical sectors. Chitosan is a cationic polysaccharide with good transparency, and currently, it has been considered also as suitable material for the formulation film and coating in cultural heritage protection. In this work, the chitosan films (Ch), with and without natural antioxidant such as citric acid (CA), are formulated considering two different processing techniques: (i) conventional solvent casting and (ii) compression molding, that is an unconventional method for this polysaccharide, giving the possibility to formulate films with extended surface and constant thickness. The effects of processing conditions and antioxidant presence on the properties and performance are evaluated by thermo-gravimetric analysis, FTIR and UV-visible spectroscopy, water contact angle measurements and tensile test. Besides, the durability of all investigated Ch and Ch/CA has been evaluated subjecting thin film to UVB exposure and monitoring their structural changes by FTIR analysis in time. All obtained results suggest that the chitosan films can be processed successfully by both solvent casting and compression molding techniques. Further, the CA presence in Ch films has a beneficial effect on the thermal resistance and durability and no negative effect on the transparency and optical properties.

A halloysite-based geopolymer filled with microwax particles was designed as a protective layer on steel substrates. Beeswax microparticles were obtained from the clay stabilized Pickering emulsions and they were homogeneously dispersed within the geopolymeric network, thus improving the coating physico-chemical properties. Specifically, this treatment changed the steel's wettability by increasing its hydrophobicity. Moreover, XRF analysis was conducted in order to have details on the chemical compositions.

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.

Vegetable oils are sources of saturated, monounsaturated and polyunsaturated fatty acids. In this work, we studied the suitability of a mixture of vegetable oils and some fatty acids (similar to the those of the human skin) as a cosmetic emulsion. Hypericum (Hypericum perforatum L.) – 1 %, thistle (Silybum marianum (L.) Gaertn.) – 42 %, linen (Línum usitatíssimum L.) – 1.1 %, wheat germ (Triticum aestivum L.) – 1 %, sesame (Sésamum índicum L.) – 1 %, mustard (Sinápis álba L.) – 2%, pumpkin (Cucúrbita p é po L.) – 5 %, – were selected as vegetable oils. The emulsion based on the proposed mixture of vegetable oils has a higher antioxidant activity (1.623 OD) compared with that based on mineral oil (0.427 OD). Finally, the emulsion provides a good balance of moisture and fat on the skin for one hour, in contrast to the short-term effect of the emulsion based on mineral oil. The obtained data are promising for the formulation of emulsion with specific fatty acids composition.

Abstract The treatment of stone surfaces for their protection from ageing caused by natural and anthropogenic effects is an open issue in materials development for Cultural Heritage. We thought interesting to verify the suitability of a modified cellulose biofilm filled with halloysite nanotubes as wax compatibilizers to design a protecting layer. A hydraulic mortar was selected as a stone prototype. To improve the physico-chemical properties of the covering layer, wax microparticles have been incorporated to control transport, consolidation and wettability features. In particular, different application protocols have been studied, namely brushing and spraying, to assess whether the proposed procedures can be scaled up. Colorimetric analysis has been carried out to evidence the applicability in terms of color alteration after the treatment. Water adhesion was investigated by measuring the contact angle values as a function of time to obtain information on spreading and adsorption phenomena. These physico-chemical properties have been correlated to the microstructure evidenced by both electron and optical microscopies. Graphic abstract

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.

Here we report a spontaneous electrostatic coating of human hair with aqueous Fe3O4 colloids capable to tailor magnetic properties to hair, orienting and even moving them under the influence of the external magnetic field. Magnetite particles were modified by cationic and anionic polyelectrolytes and then successfully deposited in dense arrays, starting from cuticle gaps and spreading further over a major hair surface. These biocompatible and biodegradable magnetic nanoparticles may serve as carriers for drug loading and delivery for topical pharmaceutical treatments. The deposition process was imaged in real-time using dark-field microscopy. The hair specimens were further studied using a number of characterisation techniques. Under application of an external magnetic field, the nanoparticle magnetic ordering was obtained resulting in the hair alignment and attraction along the field applied. We believe the technology reported here will find a range of applications in topical drug delivery and hair care.

The development of systems able to deliver genetic material into a target site is a challenge for modern medicine. Single-stranded peptide nucleic acids have attracted attention as promising therapeutic molecules for diagnostic and gene therapy. However, their poor cell membrane permeability represents a drawback for biomedical applications. Halloysite nanotubes (HNTs) are emerging materials in drug delivery applications both for their ability to penetrate cell membranes and for enhancing the solubility of drugs in biological media. Herein, we report the first example of the use of a nanocarrier based on halloysite labelled with fluorescent switchable halochromic oxazine molecules, to deliver a single-stranded peptide nucleic acids tetramer (PNAts) into living cells. The PNAts is covalently attached to halloysite (HNTs-PNA), whereas the fluorescent probe supramolecularly interacts with HNTs. The ability of the nanomaterial to bind complementary single-stranded DNA was assessed by resonance light scattering measurements. Finally, studies of cellular uptake were carried out by confocal laser scanning microscopy on normal and tumoral cell lines. This work highlights the usefulness of the covalent approach to generate HNTs-PNA nanomaterials for the potential targeting of future specific nucleic acids in living cells, which could open the doorway to novel possibilities for theranostic and gene therapy applications.

In this work, we investigated the effects of the vacuum pumping on both the loading efficiencies and the release kinetics of halloysite nanotubes filled with drug molecules dissolved in ethanol. As model drugs, salicylic acid and sodium diclofenac were selected. For comparison, the loading of the drug molecules was conducted on platy kaolinite to explore the key role of the hollow tubular morphology on the filling mechanism of halloysite. The effects of the pressure conditions used in the loading protocol were interpreted and discussed on the basis of the thermodynamic results provided by Knudsen thermogravimetry, which demonstrated the ethanol confinement inside the halloysite cavity. Several techniques (TEM, FTIR spectroscopy, DLS and $$\zeta$$ ζ -potential experiments) were employed to characterize the drug filled nanoclays. Besides, release kinetics of the drugs were studied and interpreted according to the loading mechanism. This work represents a further step for the development of nanotubular carriers with tunable release feature based on the loading protocol and drug localization into the carrier. Graphic abstract The filling efficiency of halloysite nanotubes is enhanced by the reduction of the pressure conditions used in the loading protocol.

Density functional theory calculations were performed in order to investigate the formation of silanol groups on the outer surface of halloysite nanotubes, as possible products of the reactions with water in alkaline environments. The results, discussed in terms of energy release and structural properties of the modified surface, suggest that the formation of various kinds of silanol group constellations, and even the extraction of orthosilicic acid, are highly exothermic reaction in the presence of hydroxide ions. Thermogravimetric analysis, FT-IR, XRD and X-ray fluorescence spectrometry performed on halloysite treated at high pH conditions indicate that the adsorption of water on the outer surface occurs with higher percentage after the treatment, confirming the increased number of silanols groups.

The grafting of silane groups on clay surfaces has been recently investigated in order to fabricate versatile compounds with new potential applications in materials science and ecological engineering. This work explored the influence of variety of solvents with variable polarity on the silanization of halloysite nanoclay (HNT) surface by (3-Glycidyloxy propyl) trimethoxy silane. To this purpose, the functionalization of HNT by 3-Glycidyloxypropyltrimethoxysilane (GOPTMS) has been conducted in Ethanol (polar protic solvent), Tetrahydrofuran (THF) and Acetonitrile (polar aprotic solvents), and Hexane, 1,4-Dioxane and Toluene (non polar solvents). The silane grafted materials were characterized by using several techniques, including Fourier Transform Infrared Spectroscopy (FT-IR), elemental analysis, Scanning Electron Microscopy (SEM), Thermogravimetry (TGA), X-ray Diffraction Analysis (XRD) and Nitrogen adsorption/desorption isotherms. The largest silane loading has been detected for the hybrid nanomaterials prepared in Hexane as a dispersing medium. Graphic Abstract: [Figure not available: see fulltext.]

A novel green protocol for the consolidation and protection of waterlogged archeological woods with wax microparticles has been designed. First, we focused on the development of halloysite nanotubes (HNTs) based Pickering emulsions using wax as the inner phase of the oil-in-water droplets. The optimization of the preparation strategy was supported by both optical microscopy and scanning electron microscopy, which allowed us to show the morphological features of the prepared hybrid systems and their structural properties, i.e., the distribution of the clay at the interface. Also, the dependence of the overall dimensions of the prepared systems on the halloysite content was demonstrated. Microdifferential scanning calorimetry (μ-DSC) was conducted in order to assess whether the thermal properties of the wax are affected after its interaction with HNTs. Then, the Pickering emulsions were employed for the treatment of waterlogged wooden samples. Compared to the archeological woods treated with pure wax, the addition of nanotubes induced a remarkable improvement in the mechanical performance in terms of stiffness and flexural strength. The proposed protocol is environmentally friendly since water is the only solvent used throughout the entire procedure, even if wax is vehiculated into the pores at room temperature. As a consequence, the design of wax/halloysite Pickering emulsions represents a promising strategy for the preservation of wooden artworks, and it has a great potential to be scaled up, thus becoming also exploitable for the treatments of shipwrecks of large size.

In this work, we studied the formation of supramolecular inclusion complexes (pseudopolyrotaxanes) generated by the interactions between L35 Pluronic (PEO-PPO-PEO triblock copolymer) and hydroxyl propyl-modified cyclodextrins (HP-alpha-CD and HP-beta-CD). The structural characteristics of the L35/CD composites were investigated by X-ray diffraction spectroscopy, which highlighted the effective inclusion of the copolymer. The thermodynamic properties of the pseudopolyrotaxanes were determined through density and speed of sound experiments conducted on aqueous mixtures with various L35/CD compositions, while turbidimetric analyses allowed the investigation of the kinetics of the threading process of L35 polymeric chains within the cavity of the cyclodextrins. Both thermodynamic and kinetic features were explored at various temperatures (20, 25, 30 and 35 degrees C). According to the negative values of the Gibbs free energies, we observed that the formation of the pseudopolyrotaxanes is spontaneous for both cyclodextrins. Specifically, the inclusion process is more favoured for HP-beta-CD. This result was supported by the peculiar effects of the cyclodextrins on the interfacial characteristics of the copolymer at the air/water interface. In conclusion, this paper provides an extensive description of L35/HP-alpha-CD and L35/HP-beta-CD complexes that have potential as thermo-sensitive nanocarriers with controlled release properties.