Influence of Laponite RD on the properties of poly(vinyl alcohol) hydrogels

Poly(vinyl alcohol) (PVA) hydrogels were prepared in the presence/absence of Laponite RD (LRD) by using glutaraldehyde (GL) as chemical crosslinker. The effect of GL concentration (CHO/OH ratio between 0.02 and 0.38) and of clay addition on the PVA hydrogel properties was investigated. The swollen hydrogels showed good transparency and flexibility. LRD incorporation into the PVA hydrogel, revealed by Fourier transform infrared spectroscopy, led to a significant increase of the roughness of the dried hydrogel surface (about two times), as established by atomic force microscopy. The swelling ability was affected in a small extent by the clay addition. The elastic modulus decreased from 4680 to 3340 Pa and from 2195 to 1603 Pa by addition of 0.5% LRD into PVA hydrogels obtained with CHO/OH ratio of 0.02 and 0.06, respectively. The LRD addition reduced the gelation time determined by in situ rheological monitoring of PVA crosslinking reaction. The experimental investigations showed that there is an optimum CHO/OH ratio of 0.02 for which the PVA/LRD hybrid hydrogel presents the properties required by a targeted application, as for example support material for wound dressings. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46661.     

Expanded Polystyrene Foam Formed from Polystyrene Beads Coated with a Nanocrystalline SiO2 Film and the Analysis of Its Moisture Adsorption and Resistance to Mechanical Stress

Conventional expanded polystyrene can absorb moisture, which significantly degrades its properties. In the present study, it was demonstrated that SiO₂ can be deposited on polystyrene beads before pre-expansion and molding steps. Under the applied test conditions, expanded polystyrene with nanocrystalline SiO₂ additives had approximately 10% lower moisture adsorption and an 8.4% better resistance to deformation. Expanded polystyrene analysis suggested that the observed improvements were caused by the hydrophobic nature of nanocrystalline SiO₂ and, even more importantly, because SiO₂ acted as an amalgamation catalyst and significantly increased adhesion between the expanded polystyrene beads during the expanded polystyrene molding process.     

Highly bright and photostable cyanine dye-doped silica nanoparticles for optical imaging: Photophysical characterization and cell tests

Spherical silica nanoparticles containing fluorescent trimethine indocyanine dyes (λ_abs = 547 nm, λ_em = 570 nm) were prepared using a water-in-oil microemulsion method. The nanoparticles were of 50 nm diameter and were almost monodispersed in aqueous solution at pH 5.5. Entrapment of dye molecules in the silica matrix stabilised photoemission over several hours of continuous irradiation. The photoemission intensity of the indocyanine was increased 13-fold over that recorded in solution. As each nanoparticle contained 110 dye molecules, the photoemission brightness of each particle was enhanced by three orders of magnitude. The fluorescent nanoparticles have been tested as imaging tools in in vitro tests. As an example of non-macrophagic cells, a highly differentiated neuronal cell line (GT1-7) was used and the results showed that the prepared nanoparticles can be incorporated into these cells with no apparent toxicity for up to three days.     

Tumor-Derived Small Extracellular Vesicles Induce Pro-Inflammatory Cytokine Expression and PD-L1 Regulation in M0 Macrophages via IL-6/STAT3 and TLR4 Signaling Pathways

Tumor-associated macrophages play a key role in promoting tumor progression by exerting an immunosuppressive phenotype associated with the expression of programmed cell death ligand 1 (PD-L1). It is well known that tumor-derived small extracellular vesicles (SEVs) affect the tumor microenvironment, influencing TAM behavior. The present study aimed to examine the effect of SEVs derived from colon cancer and multiple myeloma cells on macrophage functions. Non-polarized macrophages (M0) differentiated from THP-1 cells were co-cultured with SEVs derived from a colorectal cancer (CRC) cell line, SW480, and a multiple myeloma (MM) cell line, MM1.S. The expression of PD-L1, interleukin-6 (IL-6), and other inflammatory cytokines as well as of the underlying molecular mechanisms were evaluated. Our results indicate that SEVs can significantly upregulate the expressions of PD-L1 and IL-6 at both the mRNA and protein levels and can activate the STAT3 signaling pathway. Furthermore, we identified the TLR4/NF-kB pathway as a convergent mechanism for SEV-mediated PD-L1 expression. Overall, these preliminary data suggest that SEVs contribute to the formation of an immunosuppressive microenvironment.     

VDACs Post-Translational Modifications Discovery by Mass Spectrometry: Impact on Their Hub Function

VDAC (voltage-dependent anion selective channel) proteins, also known as mitochondrial porins, are the most abundant proteins of the outer mitochondrial membrane (OMM), where they play a vital role in various cellular processes, in the regulation of metabolism, and in survival pathways. There is increasing consensus about their function as a cellular hub, connecting bioenergetics functions to the rest of the cell. The structural characterization of VDACs presents challenging issues due to their very high hydrophobicity, low solubility, the difficulty to separate them from other mitochondrial proteins of similar hydrophobicity and the practical impossibility to isolate each single isoform. Consequently, it is necessary to analyze them as components of a relatively complex mixture. Due to the experimental difficulties in their structural characterization, post-translational modifications (PTMs) of VDAC proteins represent a little explored field. Only in recent years, the increasing number of tools aimed at identifying and quantifying PTMs has allowed to increase our knowledge in this field and in the mechanisms that regulate functions and interactions of mitochondrial porins. In particular, the development of nano-reversed phase ultra-high performance liquid chromatography (nanoRP-UHPLC) and ultra-sensitive high-resolution mass spectrometry (HRMS) methods has played a key role in this field. The findings obtained on VDAC PTMs using such methodologies, which permitted an in-depth characterization of these very hydrophobic trans-membrane pore proteins, are summarized in this review.     

Preparation of nanocomposites based on PP and PA6 by direct injection molding

Nanocomposites based on polyamide 6 (PA6) and polypropylene (PP) have been prepared by melt compounding the above polymer matrices with two montmorillonite(MMT)‐type commercial organoclays which, from previous studies of ours and from some results reported in literature, resulted to be the most proper layered silicates to be dispersed in PP and PA6, respectively. The preparation of nanocomposites has followed two different approaches. In the first, melt blending was carried out by twin screw extrusion whereas, direct injection molding was used in the second method. X‐ray diffraction (WAXD) and transmission electron microscope (TEM) characterizations have evidenced that independently of the preparation approach, nanostructured material were obtained, which are intercalated in the case of PP and exfoliated in that of PA6. Also mechanical properties have demonstrated that nanocomposites prepared by applying the two methods were characterized by similar features. These findings demonstrate the effectiveness of direct injection molding in the preparation of nanocomposites, whose features are similar to those prepared by compounding. Indeed, the elongational deformation, applied in the former technique, might favor the clay dispersion in the polymer matrix. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Electrospinning: A Novel Method to Incorporate POSS Into a Polymer Matrix

The effectiveness of electrospinning as a simple approach to disperse POSS into a polymer matrix at a nm‐level has been assessed. Electrospun and cast films were prepared by dissolving CA and epoxycyclohexylisobutyl POSS in the solvent mixture acetone/DMAc. The membranes were characterized by SEM, TEM and WAXD. Whereas films produced by casting showed µm‐sized POSS crystals, thus suggesting a small affinity between the polymer matrix and the POSS molecules, those prepared by electrospinning were characterized by a nanometric POSS distribution. This is explained by considering the peculiar solvent evaporation mechanism, occurring during the electrospinning process, which allows to produce nanofibers characterized by a silsesquioxane dispersion similar to that present in solution.

     

An effective multipurpose building block for 3D electropolymerisation: 2,2′-Bis(2,2′-bithiophene-5-yl)-3,3′-bithianaphthene

Novel thiophene-based oligomer, 2,2′-bis(2,2′-bithiophene-5-yl)-3,3′-bithianaphthene (TX), was designed and synthesized, and its electrochemical and spectral properties characterised. TX was readily polymerised electrochemically to form well organized conducting homopolymer films on various solid electrode substrates. Moreover, it was successfully used for deposition by electropolymerisation of electrochemically active thin films of co-polymers with three different monomers of functionalised bis(2,2′-bithienyl)methane derivatives. It appeared that TX was an effective crosslinker and 3D promoter in these electropolymerisations involving co-monomers intrinsically showing limited aptitude for the electropolymerisation or forming polymer films of low conductivity. This attractive TX ability stems from combination of its (i) high conjugation efficiency in each of the two planar moieties, (ii) intrinsic 3D structure on account of the presence of the central node, and (iii) intrinsic regioselectivity in electropolymerisation on account of the positions of the two available free α-thiophene sites.