Methacrylate-functionalized POSS as an efficient adhesion promoter in olefin-based adhesives

This study aims to investigate the effects of methacrylate-functionalized polyhedral oligomeric silsesquioxane (MA-POSS) on polyolefin-based adhesives. The so called adhesive was synthesized by the cooligomerization of 1-decene/9-decene-1-ol monomers using a Ti amine bis-phenolate catalyst, [Ti{2,2′-(OC₆H₂-4,6-^tBu₂)₂NHC₂H₄NH(OⁱPr)₂], which was subsequentlyacrylated via a simple reaction with methacryloyl chloride. Different weight fractions of MA-POSS nanoparticles were solution blended with synthesized adhesive and undergone curing reaction with blue light. Observation of a unique tan δ peak in dynamic mechanical thermal analysis (DMTA) curve was clear evidence that two employed moieties were miscible and only one hybrid polymeric phase was created. Most noticeably, significant increase in mechanical parameters was detected in the lower inclusion compositions, 0.2-1 wt% of MA-POSS, where flexural strength and flexural modulus were increased up to 99 and 110%, respectively. Furthermore, thermal stability of the synthesized nanocomposite enhanced dramatically by increasing MA-POSS weight fraction. Influence of employed nanoparticles on adhesion properties of synthesized nanocomposites was evaluated with tensile shear bond strength and pull off analysis. According to the adhesion results, the MA-POSS causes an adhesion promotion on the fabricated adhesive/POSS nanocomposites.     

Improved interfacial adhesion with the help of functional polyhedral oligomeric silsesquioxanes in silicone rubber/rayon fiber composites: Physical,mechanical, thermal,and morphological properties

The aim of this article is to improve the interfacial adhesion between silicone rubber (SR) and Rayon fiber by the help of functional hybrid POSS nanoparticles. Two POSS types were compared, octavinyl-POSS (O-POSS) and methacryl-POSS (M-POSS), having reactive  CC double bonds that can impart in peroxide crosslinking. O-POSS is nonpolar, whereas M-POSS is polar and is able to make H-bond with Rayon fibers. POSS type and their concentrations were examined as the experimental parameters. H-adhesion tests indicated that both POSS types enhanced the adhesion of SR composites to Rayon fibers compared with control recipe. Specifically, slightly higher values were obtained with the use of M-POSS. It was observed that both O-POSS and M-POSS slowed down the curing rate but increased the degree of crosslinking. The cure extent of O-POSS containing composites was found to be higher than that of M-POSS containing ones. Thermal gravimetric analyses revealed that thermal stability of SR composites was significantly improved by the addition of POSS particles. Higher char yield and degradation temperatures were obtained with O-POSS at higher loadings with respect to M-POSS. The POSS distribution at lower loading levels was found to be homogenous for both POSS types as observed from scanning electron microscope and transmission electron microscope.     

Effect of Betaine and Arginine on Interaction of αB-Crystallin with Glycogen Phosphorylase b

Protein–protein interactions (PPIs) play an important role in many biological processes in a living cell. Among them chaperone–client interactions are the most important. In this work PPIs of αB-crystallin and glycogen phosphorylase b (Phb) in the presence of betaine (Bet) and arginine (Arg) at 48 °C and ionic strength of 0.15 M were studied using methods of dynamic light scattering, differential scanning calorimetry, and analytical ultracentrifugation. It was shown that Bet enhanced, while Arg reduced both the stability of αB-crystallin and its adsorption capacity (AC₀) to the target protein at the stage of aggregate growth. Thus, the anti-aggregation activity of αB-crystallin increased in the presence of Bet and decreased under the influence of Arg, which resulted in inhibition or acceleration of Phb aggregation, respectively. Our data show that chemical chaperones can influence the tertiary and quaternary structure of both the target protein and the protein chaperone. The presence of the substrate protein also affects the quaternary structure of αB-crystallin, causing its disassembly. This is inextricably linked to the anti-aggregation activity of αB-crystallin, which in turn affects its PPI with the target protein. Thus, our studies contribute to understanding the mechanism of interaction between chaperones and proteins.     

Quaternary Structure and Hetero-Oligomerization of Recombinant Human Small Heat Shock Protein HspB7 (cvHsp)

In this study, a reliable and simple method of untagged recombinant human HspB7 preparation was developed. Recombinant HspB7 is presented in two oligomeric forms with an apparent molecular weight of 36 kDa (probably dimers) and oligomers with an apparent molecular weight of more than 600 kDa. By using hydrophobic and size-exclusion chromatography, we succeeded in preparation of HspB7 dimers. Mild oxidation promoted the formation of large oligomers, whereas the modification of Cys 126 by iodoacetamide prevented it. The deletion of the first 13 residues or deletion of the polySer motif (residues 17–29) also prevented the formation of large oligomers of HspB7. Cys-mutants of HspB6 and HspB8 containing a single-Cys residue in the central part of the β7 strand in a position homologous to that of Cys137 in HspB1 can be crosslinked to the wild-type HspB7 through a disulfide bond. Immobilized on monoclonal antibodies, the wild-type HspB6 interacted with the wild-type HspB7. We suppose that formation of heterodimers of HspB7 with HspB6 and HspB8 may be important for the functional activity of these small heat shock proteins.     

Enhancing aerogel mechanical properties with incorporation of POSS

Silica aerogels consisting of nanoparticles and numerous nano-pores have many attractive attributes. However, the weak mechanical properties severely limited the practical application of the silica aerogel. In this work, a facile approach was employed to strengthen the silica aerogel while the multi-alkoxy polyhedral oligomeric silsesquioxane (POSS) joined with methyltriethoxysilane (MTES) as the co-precursor. Three kinds of stiff core POSS with different amount of alkoxy groups were chosen to prepare aerogels. The result attributes showed all aerogels owned mesoporous structure (10–20 nm), high specific surface area (760–877 m² g⁻¹) and good thermal stability. Moreover, with the introduction of POSS, the mechanical properties had been apparently enhanced. The suitable addition of functional groups and the adjustment of cross-linking density made the aerogel own more room to deform and the skeleton still strong enough to endure large deformation. In addition, new peaks appeared in the XRD patterns at the same time. The preparation strategy of composite aerogels may guide a facile way to regulate the aerogel attributes. Furthermore, the aerogel potential application in oil-water separation has also been investigated.     

Synthesis and characterizations of a vinyl-terminated benzoxazine monomer and its blending with polyhedral oligomeric silsesquioxane (POSS)

Benzoxazine was synthesized through the Mannich condensation of phenol, formaldehyde, and primary amines through ring-opening polymerization. Polybenzoxazines are phenolic-like materials that possess dimensional and thermal stability, and they release no toxic byproducts during their polymerization. To further improve the thermal stability of polybenzoxazines, a hydrosilane-functionalized polyhedral oligomeric silsesquioxane (H-POSS) was incorporated into the vinyl-terminated benzoxazine monomer (VB-a) which we then subjected to ring-opening polymerization. In addition, we also prepared hybrids from a non-reactive POSS (IB-POSS) and VB-a. The glass transition temperature (T_g) of a regular polymerized VB-a (i.e. PVB-a) is 307 °C, while the hybrid containing 5 wt% of H-POSS is 333 °C. The IB-POSS modified PVB-a hybrids, in general, results in lower T_g than the pure PVB-a due to poor missibility.     

Syntheses, thermal properties, and phase morphologies of novel benzoxazines functionalized with polyhedral oligomeric silsesquioxane (POSS) nanocomposites

We have successfully synthesized a novel benzoxazine ring-containing polyhedral oligomeric silsesquioxane (BZ-POSS) monomer by two routes: (1) hydrosilylation of a vinyl-terminated benzoxazine using the hydro-silane functional group of a polyhedral oligomeric silsesquioxane (H-POSS) and (2) reaction of a primary amine-containng POSS (Amine-POSS) with phenol and formaldehyde. The benzoxazine-containing POSS (BZ-POSS) monomer can be copolymerized with other benzoxazine monomers through ring-opening polymerization under conditions similar to that used for polymerizing pure benzoxazines. Thermal properties of these POSS-containing organic/inorganic polybenzoxazine nanocomposites have been improved over the pure polybenzoxazine analyzed by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The BZ-POSS monomer is poorly miscible with the benzoxazine monomer and tends to aggregate and forms its own domains, both before and after polymerization. At a higher BZ-POSS content, gross aggregation occurs and results in a lower than expected improvement in the thermal properties.     

Modification of hydrogenated Bisphenol A epoxy adhesives using nanomaterials

Color-stable hydrogenated Bisphenol A (HBA) epoxy adhesives, containing organic-inorganic hybrid nanomaterials, were prepared and their properties investigated. Poly(propylene glycol)bis(2-aminopropyl ether) (D230) was used as the room temperature curing agent, and functional organic-inorganic hybrid nanomaterials, to tailor the adhesives, were prepared by a sol-gel reaction of 3-glycidoxypropyltrimethoxysilane and tetraethoxysilane. The commercial polyhedral oligomeric silsesquioxanes (POSS) having epoxy functional groups were also used. The concentration dependence of different nanomaterials, containing epoxy functional group for HBA/D230 adhesives, was studied. The tensile strength increased with the addition of nanomaterials having glycidyl epoxy group; however, the dependence varied with the size, the number of functional groups, and the amount of the addition. HBA/D230 adhesives containing different amounts of nanomaterials, whose compositions are similar to that of granite, were applied to the Korean granite and the results were compared with those obtained by using commercial adhesives, which have the problem of significant color change and high viscosity. The mechanical properties of HBA/D230 adhesives, containing POSS having glycidyl epoxy group, are found to be similar to those of commercial adhesives. Besides, it has low viscosity and long-term color stability.     

功能化POSS对硅橡胶力学性能的影响及机理研究

研究了八聚笼型倍半硅氧烷(POSS)功能化侧基的种类和用量对硅橡胶力学性能的影响。结果表明,POSS的加入使硅橡胶的拉伸强度和断裂伸长率均下降,硬度均提高。乙烯基POSS的加入显著延长了硅橡胶的正硫化时间。POSS的加入能显著降低硅橡胶的压缩永久变形,乙烯基POSS的效果比甲基POSS好;且乙烯基含量越高,压缩永久变形越小。分析了功能化POSS对硅橡胶力学性能的影响机理。     

Methacryl-polyhedral oligomeric silsesquioxane as a crosslinker for expediting photo-crosslinking of Poly(propylene fumarate): Material properties and bone cell behavior

We present photo-crosslinkable hybrid organic-inorganic composites of poly(propylene fumarate) (PPF), an injectable and biodegradable polyester, and methacryl-polyhedral oligomeric silsesquioxane (mPOSS), which has eight methacryl groups tethered with a cage-like hybrid inorganic-organic nanostructure, for bone tissue engineering applications. Two PPF samples, one with a higher molecular weight (HPPF) and one with a lower molecular weight (LPPF), were blended with mPOSS at various mPOSS compositions. We emphasize on the role of mPOSS in modifying the photo-crosslinking kinetics of PPF and the physical properties of crosslinked products, and in regulating mouse pre-osteoblastic MC3T3-E1 cell behavior on the crosslinked substrates. The viscoelastic behavior of uncrosslinked PPF/mPOSS and the mechanical, degradation, and surface characteristics of photo-crosslinked PPF/mPOSS samples have been investigated. The crosslinking kinetics of PPF/mPOSS was characterized using the gel fraction and rheological properties such as storage modulus and viscosity of the samples crosslinked for 0.5-5 min. Blending mPOSS with PPF was found to decrease the viscosity of PPF and expedite the photo-crosslinking process, both of which are important in formation of PPF networks. In addition, tensile modulus was increased by crosslinking PPF with mPOSS up to the mPOSS composition of 15%, above which phase separation occurred. The degradation rate in 1 N NaOH solution could also be regulated by varying the mPOSS composition, while crosslinked PPF/mPOSS samples did not show detectable degradation in one week in phosphate buffered saline (PBS) and mPOSS did not significantly alter surface wettability and serum protein adsorption. MC3T3 cell adhesion, spreading, proliferation, differentiation, and gene expression were examined on crosslinked PPF/mPOSS disks. Addition of mPOSS did not introduce cytotoxicity or influence cell behavior evidently. It is interesting to note that crosslinked HPPF/mPOSS showed distinct physical properties and promoted MC3T3 cell functions compared with their LPPF counterparts possibly because of higher crosslinking densities.