Polymeric Hydrogels for Intervertebral Disc Replacement/Integration: Playing with the Chemical Composition for Tuning Shear Behavior and Hydrophilicity.

Damages to the intervertebral disc (IVD) due to improper loading or degeneration result in back pain, which is a common disease affecting an increasing number of patients. Different strategies for IVD remediation have been developed, from surgical treatment to disc replacement, by using both metallic and non-metallic materials. Hydrogels are very attractive materials due to their ability to simulate the properties of many soft tissues; moreover, their chemical composition can be varied in order to assure performances similar to the natural disc. In particular, for the replacement of the IVD outer ring, namely, the anulus fibrosus, the shear properties are of paramount importance. In this work, we produced hydrogels through the photo-induced crosslinking of different mixtures composed of two hydrophilic monofunctional and difunctional polymers, namely, poly(ethyleneglycol) methyl ether methacrylate (PEGMEMA) and poly(ethyleneglycol) dimethacrylate (PEGDMA), together with a hydrophobic molecule, i.e., tert-butyl acrylate (tBA). By changing the ratio among the precursors, we demonstrated the tunability of both the shear properties and hydrophilicity. The structural properties of hydrogels were studied by solid-state nuclear magnetic resonance (NMR). These experiments provided insights on both the structure and molecular dynamics of polymeric networks and, together with information obtained by differential scanning calorimetry (DSC), allowed for correlating the physical properties of the hydrogels with their chemical composition.

Ladder-like Poly(methacryloxypropyl) silsesquioxane-Al2O3-polybutadiene Flexible Nanocomposites with High Thermal Conductivity.

Ladder-like poly(methacryloxypropyl)-silsesquioxanes (LPMASQ) are photocurable Si-based gels characterized by a double-stranded structure that ensures superior thermal stability and mechanical properties than common organic polymers. In this work, these attractive features were exploited to produce, in combination with alumina nanoparticles (NPs), both unmodified and functionalized with methacryloxypropyl-trimethoxysilane (MPTMS), LPMASQ/Al2O3 composites displaying remarkable thermal conductivity. Additionally, we combined LPMASQ with polybutadiene (PB) to produce hybrid nanocomposites with the addition of functionalized Al2O3 NPs. The materials underwent thermal stability, structural, and morphological evaluations via thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), Fourier transform infrared spectroscopy (FTIR), and solid-state nuclear magnetic resonance (NMR). Both blending PB with LPMASQ and surface functionalization of nanoparticles proved to be effective strategies for incorporating a higher ceramic filler amount in the matrices, resulting in significant increases in thermal conductivity. Specifically, a 113.6% increase in comparison to the bare matrix was achieved at relatively low filler content (11.2 vol%) in the presence of 40 wt% LPMASQ. Results highlight the potential of ladder-like silsesquioxanes in the field of thermally conductive polymers and their applications in heat dissipation for flexible electronic devices.

Amino-Alcohol Organic-Inorganic Hybrid Sol-Gel Materials Based on an Epoxy Bicyclic Silane: Synthesis and Characterization.

Organic-inorganic hybrids (OIHs) are a type of material that can be obtained using the sol-gel process and has the advantages of organic and inorganic moieties in a single material. Polyetheramines have been widely used in the preparation of this type of material, particularly in combination with epoxy-based alkoxysilanes. Nevertheless, epoxyciclohexylethyltrimethoxysilane (ECHETMS) is a promising alkoxysilane with an epoxy terminal group that is quite unexplored. In this work, four novel OIH materials were synthesized using the sol-gel method. The OIHs were based on Jeffamines® of different molecular weights (D-230, D-400, ED-600, and ED-900), together with ECHETMS. The materials were characterized using multinuclear solid state NMR, FTIR, BET, UV/Vis spectroscopy, EIS, and TGA. The influence of the Jeffamine molecular weight and the suitability of these materials to act as a supporting matrix for heteroaromatic probes were assessed and discussed. The materials show interesting properties in order to be applied in a wide range of sensing applications.

Interplay between coordination sphere engineering and properties of nickel diketonate-diamine complexes as vapor phase precursors for the growth of NiO thin films.

NiO-based films and nanostructured materials have received increasing attention for a variety of technological applications. Among the possible strategies for their fabrication, atomic layer deposition (ALD) and chemical vapor deposition (CVD), featuring manifold advantages of technological interest, represent appealing molecule-to-material routes for which a rational precursor design is a critical step. In this context, the present study is focused on the coordination sphere engineering of three heteroleptic Ni(II) ß-diketonate-diamine adducts of general formula [NiL2TMEDA] [L = 1,1,1-trifluoro-2,4-pentanedionate (tfa), 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedionate (fod) or 2,2,6,6-tetramethyl-3,5-heptanedionate (thd), and TMEDA = N,N,N',N'-tetramethylethylenediamine]. Controlled variations in the diketonate structure are pursued to investigate the influence of steric hindrance and fluorination degree on the chemico-physical characteristics of the compounds. A multi-technique investigation supported by density functional calculations highlights that all complexes are air-insensitive and monomeric and that their thermal properties and fragmentation patterns are directly dependent on functional groups in the diketonate ligands. Preliminary thermal CVD experiments demonstrate the precursors' suitability for the obtainment of NiO films endowed with flat and homogeneous surfaces, paving the way to future implementation for CVD end-uses.

Structure of Starch-Sepiolite Bio-Nanocomposites: Effect of Processing and Matrix-Filler Interactions.

Sepiolite clay is a natural filler particularly suitable to be used with polysaccharide matrices (e.g., in starch-based bio-nanocomposites), increasing their attractiveness for a wide range of applications, such as packaging. Herein, the effect of the processing (i.e., starch gelatinization, addition of glycerol as plasticizer, casting to obtain films) and of the sepiolite filler amount on the microstructure of starch-based nanocomposites was investigated by SS-NMR (solid-state nuclear magnetic resonance), XRD (X-ray diffraction) and FTIR (Fourier-transform infrared) spectroscopy. Morphology, transparency and thermal stability were then assessed by SEM (scanning electron microscope), TGA (thermogravimetric analysis) and UV-visible spectroscopy. It was demonstrated that the processing method allowed to disrupt the rigid lattice structure of semicrystalline starch and thus obtain amorphous flexible films, with high transparency and good thermal resistance. Moreover, the microstructure of the bio-nanocomposites was found to intrinsically depend on complex interactions among sepiolite, glycerol and starch chains, which are also supposed to affect the final properties of the starch-sepiolite composite materials.

Modeling a Dynamic Printability Window on Polysaccharide Blend Inks for Extrusion Bioprinting.

Extrusion-based bioprinting is one of the most widespread technologies due to its affordability, wide range of processable materials, and ease of use. However, the formulation of new inks for this technique is based on time-consuming trial-and-error processes to establish the optimal ink composition and printing parameters. Here, a dynamic printability window was modeled for the assessment of the printability of polysaccharide blend inks of alginate and hyaluronic acid with the intent to build a versatile predictive tool to speed up the testing procedures. The model considers both the rheological properties of the blends (viscosity, shear thinning behavior, and viscoelasticity) and their printability (in terms of extrudability and the ability of forming a well-defined filament and detailed geometries). By imposing some conditions on the model equations, it was possible to define empirical bands in which the printability is ensured. The predictive capability of the built model was successfully verified on an untested blend of alginate and hyaluronic acid chosen to simultaneously optimize the printability index and minimize the size of the deposited filament.

Synthesis and Characterization of Alkoxysilane-Bearing Photoreversible Cinnamic Side Groups: A Promising Building-Block for the Design of Multifunctional Silica Nanoparticles.

The present study reports on the synthesis of a new alkoxysilane-bearing light-responsive cinnamyl group and its application as a surface functionalization agent for the development of SiO2 nanoparticles (NPs) with photoreversible tails. In detail, cinnamic acid (CINN) was activated with N-hydroxysuccinimide (NHS) to obtain the corresponding NHS-ester (CINN-NHS). Subsequently, the amine group of 3-aminopropyltriethoxysilane (APTES) was acylated with CINN-NHS leading to the generation of a novel organosilane, CINN-APTES, which was then exploited for decorating SiO2 NPs. The covalent bond to the silica surface was confirmed by solid state NMR, whereas thermogravimetric analysis unveiled a functionalization degree much higher compared to that achieved by a conventional double-step post-grafting procedure. In light of these intriguing results, the strategy was successfully extended to naturally occurring sepiolite fibers, widely employed as fillers in technological applications. Finally, a preliminary proof of concept of the photoreversibility of the obtained SiO2@CINN-APTES system has been carried out through UV diffuse reflectance. The overall outcomes prove the consistency and the versatility of the methodological protocol adopted, which appears promising for the design of hybrid NPs to be employed as building blocks for photoresponsive materials with the ability to change their molecular structure and subsequent properties when exposed to different light stimuli.

Barium Titanate Functionalization with Organosilanes: Effect on Particle Compatibility and Permittivity in Nanocomposites.

Barium titanate (BT) recently gained new interest in the preparation of dielectric and piezoelectric lead-free materials for applications in sensors, electronics, energy harvesting and storage fields. Barium titanate nanocomposites can achieve attractive performance, provided that the compatibility between ceramic particles and polymeric matrices is enhanced to the benefit of the physical properties of the final composite. Tuning the particle-matrix interface through particle functionalization represents a viable solution. In this work, surface functionalization of BT nanoparticles (NPs), obtained by hydrothermal synthesis, with 3-glycidyloxypropyltrimethoxysilane, 2-[(acetoxy(polyethyleneoxy)propyl]triethoxysilane and triethoxysilylpropoxy(polyethyleneoxy)dodecanoate, was performed after optimizing the hydroxylation process of the NPs to improve their surface reactivity and increase the yield of grafting. Solid-state nuclear magnetic resonance and thermogravimetric analysis were used to quantify the molecules grafted onto the ceramic nanoparticles. Both bare and functionalized particles were employed in the realization of epoxy- and polydimethylsiloxane (PDMS)-based nanocomposites. Functionalization was proven to be beneficial for particle dispersibility and effective for particle alignment in the PDMS matrix. Moreover, the dielectric constant measurements revealed the potential of PDMS-based nanocomposites for applications in the field of dielectric elastomers.

Silica hairy nanoparticles: a promising material for self-assembling processes.

"Hairy" nanoparticles (HNPs), i.e. inorganic NPs functionalized with polymer chains, are promising building blocks for the synthesis of advanced nanocomposite (NC) materials having several technological applications. Recent evidence shows that HNPs self-organize in a variety of anisotropic structures, resulting in an improvement of the functional properties of the materials, in which are embedded. In this paper, we propose a three-step colloidal synthesis of spherical SiO2-HNPs, with controlled particle morphology and surface chemistry. In detail, the SiO2 core, synthesized by a modified Stöber method, was first functionalized with a short-chain amino-silane, which acts as an anchor, and then covered by maleated polybutadiene (PB), a rubbery polymer having low glass transition temperature, rarely considered until now. An extensive investigation by a multi-technique analysis demonstrates that the synthesis of SiO2-HNPs is simple, scalable, and potentially applicable to different kind of NPs and polymers. Morphological analysis shows the overall distribution of SiO2-HNPs with a certain degree of spatial organization, suggesting that the polymer coating induces a modification of NP-NP interactions. The role of the surface PB brushes in influencing the special arrangement of SiO2-HNPs was observed also in cis-1,4-polybutadiene (cis-PB), since the resulting NC exhibited the particle packing in "string-like" superstructures. This confirms the tendency of SiO2-HNPs to self-assemble and create alternative structures in polymer NCs, which may impart them peculiar functional properties.

Design of a Zn Single-Site Curing Activator for a More Sustainable Sulfur Cross-Link Formation in Rubber.

ZnO is a worldwide used activator for a rubber vulcanization process, which promotes fast curing kinetics and high cross-linking densities of rubber nanocomposites (NCs). However, its extended use together with leaching phenomena occurring during the production and life cycle of rubber products, especially tires, entails potential environmental risks, as ecotoxicity toward aquatic organisms. Pushed by this issue, a novel activator was developed, which introduces highly dispersed and active zinc species in the vulcanization process, reducing the amount of employed ZnO and keeping high the curing efficiency. The activator is constituted by Zn(II) single sites, anchored on the surface of SiO2 nanoparticles (NPs) through the coordination with functionalizing amino silane groups. It behaves as a double-function material, acting at the same time as a rubber reinforcing filler and a curing activator. The higher availability and reactivity of the single-site Zn(II) centers toward curative agents impart faster kinetics and higher efficiency to the vulcanization process of silica/isoprene NCs, compared to conventionally used ZnO activators. Moreover, the NCs show a high cross-linking degree and improved dynamic mechanical properties, despite the remarkably lower amount of zinc employed than that normally used for rubber composites in tires. Finally, the structural stability of Zn(II) single sites during the curing reactions and in the final materials may represent a turning point toward the elimination of zinc leaching phenomena.

A novel and selective silk fibroin fragmentation method.

In the tissue-engineering field silk fibroin can be tailored to the target applications by modifying its secondary structure and molecular weight, and functionalizing the molecule with specific active groups linked to the amino acid side chains. To better tune the silk fibroin molecular weight and structural properties, we propose the creation of a lower molecular weight fibroin-derived material through a selective and tunable enzymatic attack on the fibroin chain. Cleavage at specific amino acid sites leads to precise silk fibroin fragmentation and, thus, lower molecular weight materials whose length and properties can be tuned with the enzyme concentration. The cleavage increased the presence of free amino groups, hence reactivity, and aqueous solutions of the resulting polymer remained stable for up to seven days. Films of fragmented fibroin were prepared and characterized, demonstrating that the fragmentation did not affect ß-sheet formation after methanol treatment, but differences were detected after the water-vapor annealing process, confirmed by structural and thermal analyses. The adopted fragmentation method is fast, controllable and precise, allowing the creation of a silk-derived material class that is stable in water, with a tunable molecular weight and secondary structure rearrangements, and is thus a versatile tool for the further tunability and modulation of bioengineered constructs.

Facile preparation of a cobalt diamine diketonate adduct as a potential vapor phase precursor for Co3O4films.

Co3O4 thin films and nanosystems are implemented in a broad range of functional systems, including gas sensors, (photo)catalysts, and electrochemical devices for energy applications. In this regard, chemical vapor deposition (CVD) is a promising route for the fabrication of high-quality films in which the precursor choice plays a key role in the process development. In this work, a heteroleptic cobalt complex bearing fluorinated diketonate ligands along with a diamine moiety [Co(tfa)2·TMEDA; tfa = 1,1,1-trifluoro-2,4-pentanedionate and TMEDA = N,N,N',N'-tetramethylethylenediamine] is investigated as a potential Co molecular precursor for the CVD of Co3O4 systems. For the first time, the compound is characterized by crystal structure determination and comprehensive analytical studies, focusing also on its thermal properties and fragmentation patterns, important figures of merit for a CVD precursor. The outcomes of this investigation, accompanied by detailed theoretical studies, highlight its very favorable properties for CVD applications. In fact, growth experiments under oxygen atmospheres containing water vapor revealed the suitability of Co(tfa)2·TMEDA for the fabrication of high-quality, phase-pure Co3O4 thin films. The versatility of the proposed strategy in tailoring Co3O4 structural/morphological features highlights its potential to obtain multi-functional films with controllable properties for a variety of eventual technological end-uses.

A Bio-inspired Multifunctionalized Silk Fibroin.

A bio-inspired multifunctionalized silk fibroin (BMS) was synthesized in order to mimic the interaction of nidogen with the type IV collagen and laminin of basement membranes. The designed BMS consists of a motif of laminin α-chain-derived, called IK peptide, and type IV collagen covalently bound to the silk fibroin (SF) by using EDC/NHS coupling and a Cu-free click chemistry reaction, respectively. Silk fibroin was chosen as the main component of the BMS because it is versatile and biocompatible, induces an in vivo favorable bioresponse, and moreover can be functionalized with different methods. The chemical structure of BMS was analyzed by using X-ray photoelectron spectroscopy, attenuated total reflection-Fourier transform infrared, cross-polarization magic angle spinning nuclear magnetic resonance techniques, and colorimetric assay. The SF and BMS solutions were cross-linked by sonication to form hydrogels or casted to make films in order to evaluate and compare the early adhesion and viability of MRC5 cells. BMS hydrogels were also characterized by rheological and thermal analyses.

A community-built calibration system: The case study of quantification of metabolites in grape juice by qNMR spectroscopy.

Nuclear Magnetic Resonance (NMR) is an analytical technique extensively used in almost every chemical laboratory for structural identification. This technique provides statistically equivalent signals in spite of using spectrometer with different hardware features and is successfully used for the traceability and quantification of analytes in food samples. Nevertheless, to date only a few internationally agreed guidelines have been reported on the use of NMR for quantitative analysis. The main goal of the present study is to provide a methodological pipeline to assess the reproducibility of NMR data produced for a given matrix by spectrometers from different manufacturers, with different magnetic field strengths, age and hardware configurations. The results have been analyzed through a sequence of chemometric tests to generate a community-built calibration system which was used to verify the performance of the spectrometers and the reproducibility of the predicted sample concentrations.

Effect of the Organic Functional Group on the Grafting Ability of Trialkoxysilanes onto Graphene Oxide: A Combined NMR, XRD, and ESR Study.

The functional properties displayed by graphene oxide (GO)-polymer nanocomposites are strongly affected by the dispersion ability of GO sheets in the polymeric matrix, which can be largely improved by functionalization with organosilanes. The grafting to GO of organosilanes with the general formula RSi(OCH3)3 is generally explained by the condensation reactions of silanols with GO reactive groups. In this study, the influence of the organic group on the RSi(OCH3)3 grafting ability was analyzed in depth, taking into account the interactions of the R end chain group with GO oxidized groups. Model systems composed of commercial graphene oxide reacted with 3-aminopropyltrimethoxysilane (APTMS), 3-mercaptopropyltrimethoxysilane (MPTMS), and 3-methacryloxypropyltrimethoxysilane, (MaPTMS), respectively, were characterized by natural abundance 13C, 15N and 29Si solid state nuclear magnetic resonance (NMR), x-ray diffraction (XRD), and electron spin resonance (ESR). The silane organic tail significantly impacts the grafting, both in terms of the degree of functionalization and direct interaction with GO reactive sites. Both the NMR and XRD proved that this is particularly relevant for APTMS and to a lower extent for MPTMS. Moreover, the epoxy functional groups on the GO sheets appeared to be the preferential anchoring sites for the silane condensation reaction. The characterization approach was applied to the GO samples prepared by the nitric acid etching of graphene and functionalized with the same organosilanes, which were used as a filler in acrylic coatings obtained by cataphoresis, making it possible to correlate the structural properties and the corrosion protection ability of the layers.

Docosane-Organosilica Microcapsules for Structural Composites with Thermal Energy Storage/Release Capability.

Organic phase change materials (PCMs) represent an effective solution to manage intermittent energy sources as the solar thermal energy. This work aims at encapsulating docosane in organosilica shells and at dispersing the produced capsules in epoxy/carbon laminates to manufacture multifunctional structural composites for thermal energy storage (TES). Microcapsules of different sizes were prepared by hydrolysis-condensation of methyltriethoxysilane (MTES) in an oil-in-water emulsion. X-ray diffraction (XRD) highlighted the difference in the crystalline structure of pristine and microencapsulated docosane, and 13C solid-state nuclear magnetic resonance (NMR) evidenced the influence of microcapsules size on the shifts of the representative docosane signals, as a consequence of confinement effects, i.e., reduced chain mobility and interaction with the inner shell walls. A phase change enthalpy up to 143 J/g was determined via differential scanning calorimetry (DSC) on microcapsules, and tests at low scanning speed emphasized the differences in the crystallization behavior and allowed the calculation of the phase change activation energy of docosane, which increased upon encapsulation. Then, the possibility of embedding the microcapsules in an epoxy resin and in an epoxy/carbon laminate to produce a structural TES composite was investigated. The presence of microcapsules agglomerates and the poor capsule-epoxy adhesion, both evidenced by scanning electron microscopy (SEM), led to a decrease in the mechanical properties, as confirmed by three-point bending tests. Dynamic mechanical analysis (DMA) highlighted that the storage modulus decreased by 15% after docosane melting and that the glass transition temperature of the epoxy resin was not influenced by the PCM. The heat storage/release properties of the obtained laminates were proved through DSC and thermal camera imaging tests.

Silk Fibroin Porous Scaffolds Loaded with a Slow-Releasing Hydrogen Sulfide Agent (GYY4137) for Applications of Tissue Engineering.

Hydrogen sulfide (H2S) is a physiological gasotransmitter known to possess a regulatory role in several tissues, including bone. The exogenous administration by injection of solutions of H2S-releasing compounds (e.g., GYY4137) has been previously investigated as a novel therapeutic approach for the treatment of bone diseases. Here, GYY4137 was embedded into fibroin sponges, previously shown to be suitable as scaffolds for bone, thanks to their biocompatibility, scalable porous structure, and biodegradability rate. Fibroin porous scaffolds were produced by solvent casting and the particulate leaching method, and GYY4137 was successively incorporated by using dimethyl sulfoxide (DMSO) as vehicle. The process used to produce GYY4137-loaded scaffolds allowed the incorporation of different controlled amounts of GYY4137 into fibroin matrices. The loading process preserved the properties of the system components in the final products, as assessed by SEM, FT-IR, NMR, and different thermal analyses techniques. Release of H2S from GYY4137 incorporated into the scaffolds was monitored upon incubation in saline solution at physiological pH: H2S-release kinetic was found to be dependent on the amount of GYY4137. To ensure biocompatibility, mouse fibroblasts and human primary bone marrow stromal cells were seeded onto scaffolds, and short-term viability assays were performed. Results showed that the GYY4137-loaded scaffold did not induce cytotoxicity in any of the cell type tested. Our findings demonstrate that embedding an H2S-releasing donor in silk fibroin scaffold is a suitable strategy to achieve a long-lasting release of H2S that preserves cell viability and allows local delivery at sites of tissue injury.

Unveiling the hybrid interface in polymer nanocomposites enclosing silsesquioxanes with tunable molecular structure: Spectroscopic, thermal and mechanical properties.

Organic-inorganic nanobuilding blocks (NBBs) based on silsesquioxanes (SSQs) have potential applications as nanofillers, thermal stabilizers, and rheological modifiers, which can improve thermomechanical properties of polymer hosts. The possibility to tune both siloxane structure and pendant groups can promote compatibilization and peculiar interactions with a plethora of polymers. However, the control on SSQs molecular architecture and functionalities is usually delicate and requires careful synthetic details. Moreover, investigating the influence of NBBs loading and structure on the hybrid interface and, in turn, on the polymer chains mobility and mechanical properties, may be challenging, especially for low-loaded materials. Herein, we describe the preparation and characterization of polybutadiene (PB) nanocomposites using as innovative fillers thiol-functionalized SSQs nanobuilding blocks (SH-NBBs), with both tailorable functionality and structure. Swelling experiments and, more clearly, solid-state NMR, enlightened a remarkable effect of SH-NBBs on the molecular structure and mobility of the polymeric chains, envisaging the occurrence of chemical interactions at the hybrid interface. Finally, thermal and DMTA analyses revealed that nanocomposites, even containing very low filler loadings (i.e. 1, 3 wt%), exhibited enhanced thermomechanical properties, which seem to be connected not only to the loading, but also to the peculiar cage or ladder-like architecture of SH-NBBs.

Hybrid Coatings Enriched with Tetraethoxysilane for Corrosion Mitigation of Hot-Dip Galvanized Steel in Chloride Contaminated Simulated Concrete Pore Solutions.

Hybrid sol-gel coatings, named U(X):TEOS, based on ureasilicate matrices (U(X)) enriched with tetraethoxysilane (TEOS), were synthesized. The influence of TEOS addition was studied on both the structure of the hybrid sol-gel films as well as on the electrochemical properties. The effect of TEOS on the structure of the hybrid sol-gel films was investigated by solid state Nuclear Magnetic Resonance. The dielectric properties of the different materials were investigated by electrochemical impedance spectroscopy. The corrosion behavior of the hybrid coatings on HDGS was studied in chloride-contaminated simulated concrete pore solutions (SCPS) by polarization resistance measurements. The roughness of the HDGS coated with hybrids was also characterized by atomic force microscopy. The structural characterization of the hybrid materials proved the effective reaction between Jeffamine® and 3-isocyanate propyltriethoxysilane (ICPTES) and indicated that the addition of TEOS does not seem to affect the organic structure or to increase the degree of condensation of the hybrid materials. Despite the apparent lack of influence on the hybrids architecture, the polarization resistance measurements confirmed that TEOS addition improves the corrosion resistance of the hybrid coatings (U(X):TEOS) in chloride-contaminated SCPS when compared to samples prepared without any TEOS (U(X)). This behavior could be related to the decrease in roughness of the hybrid coatings (due TEOS addition) and to the different metal coating interaction resulting from the increase of the inorganic component in the hybrid matrix.

Hydrophobic Coatings by Thiol-Ene Click Functionalization of Silsesquioxanes with Tunable Architecture.

The hydrolysis-condensation of trialkoxysilanes under strictly controlled conditions allows the production of silsesquioxanes (SSQs) with tunable size and architecture ranging from ladder to cage-like structures. These nano-objects can serve as building blocks for the preparation of hybrid organic/inorganic materials with selected properties. The SSQs growth can be tuned by simply controlling the reaction duration in the in situ water production route (ISWP), where the kinetics of the esterification reaction between carboxylic acids and alcohols rules out the extent of organosilane hydrolysis-condensation. Tunable SSQs with thiol functionalities (SH-NBBs) are suitable for further modification by exploiting the simple thiol-ene click reaction, thus allowing for modifying the wettability properties of derived coatings. In this paper, coatings were prepared from SH-NBBs with different architecture onto cotton fabrics and paper, and further functionalized with long alkyl chains by means of initiator-free UV-induced thiol-ene coupling with 1-decene (C10) and 1-tetradecene (C14). The coatings appeared to homogeneously cover the natural fibers and imparted a multi-scale roughness that was not affected by the click functionalization step. The two-step functionalization of cotton and paper warrants a stable highly hydrophobic character to the surface of natural materials that, in perspective, suggests a possible application in filtration devices for oil-water separation. Furthermore, the purification of SH-NBBs from ISWP by-products was possible during the coating process, and this step allowed for the fast, initiator-free, click-coupling of purified NBBs with C10 and C14 in solution with a nearly quantitative yield. Therefore, this approach is an alternative route to get sol-gel-derived, ladder-like, and cage-like SSQs functionalized with long alkyl chains.