Dentin Bond Strength of Dental Adhesives Functionalized with Polyhedral Oligomeric Silsesquioxanes.

This study analyzed the dentin shear bond strength (SBS) of an etch-and-rinse (ER) or a self-etch (SE) adhesive incorporated with multifunctional polyhedral oligomeric silsesquioxanes (MA-POSS-8). An ER adhesive (Solobond Plus, VOCO GmbH, Cuxhaven, Germany) and a universal adhesive applied in SE mode (Scotchbond Universal, 3M, St. Paul, MN, USA) were infiltrated with MA-POSS-8 (Hybrid Plastics Inc., Hattiesburg, MS, USA) at 5 wt.% or 10 wt.%. Pure adhesives served as controls. Bovine dentin specimens were conditioned with one of the adhesives prior to the application of a nano-hybrid composite (Venus Diamond A3, Kulzer, Hanau, Germany). SBS and failure modes were determined after water storage for 24 h, 6 months, 12 months, or 24 months (each subgroup n = 20). Statistical analysis was performed using ANOVAs, Weibull statistics, and χ2 tests (p < 0.05). SBSs for the control groups after 24 h were 17.4 ± 4.9 MPa for the ER adhesive and 19.1 ± 5.2 MPa for the universal adhesive. After 24 months, the SBS of the ER adhesive was significantly higher for 5 wt.% MA-POSS-8 (17.9 ± 5.1 MPa) than for the control group (14.6 ± 3.6 MPa) and 10 wt.% MA-POSS-8 (12.8 ± 4.1 MPa), and more cohesive failures were observed. The SBS of the universal adhesive increased during aging, irrespective of the MA-POSS-8 concentration. 5 wt.% MA-POSS-8 improves the SBS of the ER adhesive and does not impair the SBS of the SE adhesive.

Ultrathin Films of MXene Nanosheets Decorated by Ionic Branched Nanoparticles with Enhanced Energy Storage Stability.

Two-dimensional (2D) materials such as MXenes have shown great potential for energy storage applications due to their high surface area and high conductivity. However, their practical implementation is limited by their tendency to restack, similar to other 2D materials, leading to a decreased long-term performance. Here, we present a novel approach to addressing this issue by combining MXene (Ti3C2Tx) nanosheets with branched ionic nanoparticles from polyhedral oligomeric silsesquioxanes (POSS) using an amphiphilicity-driven assembly for the formation of composite monolayers of nanoparticle-decorated MXene nanosheets at the air-water interface. The amphiphilic hybrid MXene/POSS monolayers allow for the fabrication of organized multilayered films with ionic nanoparticles supporting the nanoscale gap between MXene nanosheets. For these composite multilayers, we observed a 400% enhancement in specific capacitance compared to pure drop-cast MXene films. Furthermore, dramatically enhanced electrochemical cycling stability for ultrathin-film electrodes (<400 nm in thickness) with a 91% capacitance retention over 10,000 cycles has been achieved. Our results suggest that this insertion of 0D ionic nanoparticles with complementary interactions in between 2D MXene nanosheets could be extended to other hybrid 0D-2D nanomaterials, providing a promising pathway for the development of hybrid electrode architectures with enhanced ionic transport for long-term energy cycling and storage, capacitive deionization, and ionic filtration.

A Brief Review on Selected Applications of Hybrid Materials Based on Functionalized Cage-like Silsesquioxanes.

Rapid developments in materials engineering are accompanied by the equally rapid development of new technologies, which are now increasingly used in various branches of our life. The current research trend concerns the development of methods for obtaining new materials engineering systems and searching for relationships between the structure and physicochemical properties. A recent increase in the demand for well-defined and thermally stable systems has highlighted the importance of polyhedral oligomeric silsesquioxane (POSS) and double-decker silsesquioxane (DDSQ) architectures. This short review focuses on these two groups of silsesquioxane-based materials and their selected applications. This fascinating field of hybrid species has attracted considerable attention due to their daily applications with unique capabilities and their great potential, among others, in biomaterials as components of hydrogel networks, components in biofabrication techniques, and promising building blocks of DDSQ-based biohybrids. Moreover, they constitute attractive systems applied in materials engineering, including flame retardant nanocomposites and components of the heterogeneous Ziegler-Natta-type catalytic system.

POSS and SSQ Materials in Dental Applications: Recent Advances and Future Outlooks.

Recently, silsesquioxanes (SSQ) and polyhedral oligomeric silsesquioxanes (POSS) have gained much interest in the area of biomaterials, mainly due to their intrinsic properties such as biocompatibility, complete non-toxicity, the ability to self-assemble and to form a porous structure, facilitating cell proliferation, creating a superhydrophobic surface, osteoinductivity, and ability to bind hydroxyapatite. All the above has resulted in new developments in medicine. However, the application of POSS-containing materials in dentistry is still at initial stage and deserves a systematic description to ensure future development. Significant problems, such as reduction of polymerization shrinkage, water absorption, hydrolysis rate, poor adhesion and strength, unsatisfactory biocompatibility, and corrosion resistance of dental alloys, can be addressed by the design of multifunctional POSS-containing materials. Because of the presence of silsesquioxanes, it is possible to obtain smart materials that allow the stimulation of phosphates deposition and repairing of micro-cracks in dental fillings. Hybrid composites result in materials exhibiting shape memory, as well as antibacterial, self-cleaning, and self-healing properties. Moreover, introducing POSS into polymer matrix allows for materials for bone reconstruction, and wound healing. This review covers the recent developments in the field of POSS application in dental materials and gives the future perspectives within a promising field of biomedical material science and chemical engineering.

Characterization of Octa-aminopropyl polyhedral oligomeric silsesquioxanes (OA-POSS) nanoparticles and their effect on sweet basil (Ocimum basilicum L.) response to salinity stress.

Salt stress is of the most detrimental abiotic stress factors on either crop or non-crop species. Of the strategies employed to boost the performance of the plants against harmful impacts of salt stress; application of novel nano-engineered particles have recently gained great attention as a promising tool. Octa-aminopropyl polyhedral oligomeric silsesquioxanes nanoparticles (OA-POSS NPs) were synthesized and then a foliar-application of OA-POSS NPs were carried out on sweet basil plants subjected to the salt stress. In that context, interactive effects of OA-POSS NPs (25, 50 and 100 mg L-1) and salinity stress (50 and 100 mM NaCl) were assayed by estimating a series of agronomic, physiological, biochemical and analytical parameters. OA-POSS NPs decreased the harmful effects of salinity by increasing photosynthetic pigment content, adjusting chlorophyll fluorescence, and triggering non-enzymatic (phenolic content) and enzymatic antioxidant components. The findings suggested that 25 mg L-1 OA-POSS NPs is the optimum concentration for sweet basil grown under salt stress. Considering the essential oil profile, estragole was the predominant compound with a percentage higher than 50% depending on the treatment. In comparison to the control group, 50 mM NaCl did not significantly affect estragole content, whilst 100 mM NaCl caused a substantial increase in estragole content. Regarding OA-POSS NPs treatments, increments by 16.8%, 11.8% and 17.5% were observed following application with 25, 50 and 100 mg L-1, respectively. Taken together, the current study provides evidence that POSS NPs can be employed as novel, 'green' growth promoting agents in combating salt stress in sweet basil.

Slick Synthetic Approach to Various Fluoroalkyl Silsesquioxanes-Assessment of their Dielectric Properties.

We present a smart and efficient methodology for the synthesis of a variety of fluorinated silsesquioxanes (SQs) with diverse Si-O-Si core architecture. The protocol is based on an easy-to-handle and selective hydrosilylation reaction. An investigation on the placement of the reactive Si-HC=CH2 vs. Si-H in the silsesquioxane, as well as silane vs. olefin structure, respectively, on the progress and selectivity of the hydrosilylation process, was studied. Two alternative synthetic pathways for obtaining a variety of fluorine-functionalized silsesquioxanes were developed. As a result, a series of mono- and octa- T8 SQs, tri- 'open-cage' T7 SQs, in addition to di- and tetrafunctionalized double-decker silsesquioxane (DDSQ) derivatives, were obtained selectively with high yields. All products were characterized by spectroscopic (NMR, FTIR) techniques. Selected samples were subjected to the measurements revealing their dielectric permittivity in a wide range of temperatures (from -100 °C to 100 °C) and electric field frequencies (100-106 Hz).

The Effect of Various Polyhedral Oligomeric Silsesquioxanes on Viscoelastic, Thermal Properties and Crystallization of Poly(ε-caprolactone) Nanocomposites.

Polyhedral oligomeric silsesquioxane POSS nanoparticles can be applied as reinforcing additives modifying various properties of biodegradable polymers. The effects of aminopropylisobutyl POSS (amine-POSS), trisilanolisooctyl-POSS (HO-POSS) and glycidyl-POSS (Gly-POSS) on the viscoelastic, thermal properties and crystallization of biodegradable poly(ε-caprolactone) PCL were studied. The analysis of the viscoelastic properties at ambient temperature indicated that aminopropylisobutyl POSS (amine-POSS) and glycidyl-POSS (Gly-POSS) enhanced the dynamic mechanical properties of PCL. The increase in the storage shear modulus G' and loss modulus G″ was observed. The plasticizing effect of trisilanolisooctyl POSS (HO-POSS) due to the presence of long isoctyl groups was confirmed. As a result, the crystallization of PCL was facilitated and the degree of crystallinity of χc increased up to 50.9%. The damping properties and the values of tan δ for PCL/HO-POSS composition increased from 0.052 to 0.069. The TGA results point out the worsening of the PCL thermal stability, with lower values of T0.5%, T1% and T3%. Both HO-POSS and Gly-POSS facilitated the relaxation of molten PCL. The presence of Gly-POSS influenced the changes that occurred in the viscoelastic properties of the molten PCL due to the thermo-mechanical degradation of the material; a positive impact was observed.

Chitosan/POSS Hybrid Hydrogels for Bone Tissue Engineering.

Hybrid hydrogels composed of chitosan (CS) have shown great potential in bone tissue engineering and regeneration. The introduction of polyhedral oligomeric silsesquioxanes (POSS) in the biopolymeric matrix has been demonstrated to improve the rheological and biological properties of the hybrid composites. In this work, we have integrated the favourable features of chitosan (CS) and POSS nanoparticles to design new nanocomposites for bone tissue regeneration, focusing our attention on the effect of POSS concentration within the CS matrix (0.5, 1, and 1.5 equivalents in weight of POSS with respect to CS) on the chemical, physical, rheological, and in vitro biological properties of the final composites. The drug release ability of the synthesized hydrogel scaffolds were also investigated using, as the model drug, ketoprofen, that was included in the scaffold during the gelling procedure, showing a more controlled release for the hybrids with respect to CS (86-91% of drug released after two weeks). The results of the in vitro biological tests performed on human fetal osteoblastic cells (hFOB 1.19) culture demonstrated the great biocompatibility of the hybrid materials. The hybrids, at the different POSS concentrations, showed values of cell mortality superimposable with control cells (11.1 vs. 9.8%), thus revealing the CS/POSS hydrogels as possible candidates for bone tissue engineering applications.

Biocompatibility Computation of Muscle Cells on Polyhedral Oligomeric Silsesquioxane-Grafted Polyurethane Nanomatrix.

This study was performed to appraise the biocompatibility of polyhedral oligomeric silsesquioxane (POSS)-grafted polyurethane (PU) nanocomposites as potential materials for muscle tissue renewal. POSS nanoparticles demonstrate effectual nucleation and cause noteworthy enhancement in mechanical and thermal steadiness as well as biocompatibility of resultant composites. Electrospun, well-aligned, POSS-grafted PU nanofibers were prepared. Physicochemical investigation was conducted using several experimental techniques, including scanning electron microscopy, energy dispersive X-ray spectroscopy, electron probe microanalysis, Fourier transform infrared spectroscopy, and X-ray diffraction pattern. Adding POSS molecules to PU did not influence the processability and morphology of the nanocomposite; however, we observed an obvious mean reduction in fiber diameter, which amplified specific areas of the POSS-grafted PU. Prospective biomedical uses of nanocomposite were also appraised for myoblast cell differentiation in vitro. Little is known about C2C12 cellular responses to PU, and there is no information regarding their interaction with POSS-grafted PU. The antimicrobial potential, anchorage, proliferation, communication, and differentiation of C2C12 on PU and POSS-grafted PU were investigated in this study. In conclusion, preliminary nanocomposites depicted superior cell adhesion due to the elevated free energy of POSS molecules and anti-inflammatory potential. These nanofibers were non-hazardous, and, as such, biomimetic scaffolds show high potential for cellular studies and muscle regeneration.

Viscoelastic Properties of Epoxidized Natural Rubber/Poly(lactic acid) PLA/ENR Blends Containing Glycidyl-POSS and Trisilanolisooctyl-POSS as Functional Additives.

The glycidyl-POSS (Polyhedral Oligomeric Silsesquioxanes, Polysilsesquioxane, POSS) (Gly-POSS) and trisilanolisooctyl-POSS (HO-POSS) were applied as functional additives influencing on the viscoelastic properties of the dynamic vulcanized PLA/ENR (poly(lactic acid)/epoxidized natural rubber) blends. The plasticizing effect of HO-POSS on PLA/ENR melt, leading to the decrease of complex viscosity at 160 °C, was observed. After the incorporation of Gly-POSS into PLA/ENR blends the complex viscosity increased confirming that the epoxy groups of Gly-POSS were able to react with the functional groups of ENR and the groups present at the end of PLA chains. The incorporation of Gly-POSS into 40:60 PLA/ENR blend provided significant enhancement of the storage shear modulus G' at 30 °C. Furthermore, the glass transition temperatures Tg of ENR phase for PLA/ENR/Gly-POSS blends were shifted to higher values of temperature as compared with blends modified by HO-POSS. Strong reduction of the elongation at break Eb for 40:60 PLA/ENR/Gly-POSS blend indicated that Gly-POSS particles acted as multifunctional cross-links reducing elasticity of the material. The modification of 40:60 PLA/ENR blend by HO-POSS molecules led to lower values of composting coefficient KC indicating stronger deterioration of the mechanical properties that resulted from more intense degradation processes occurring during disposal in soil.