Molecular Fingerprint of Human Pathological Synoviocytes in Response to Extractive Sulfated and Biofermentative Unsulfated Chondroitins

Pharma-grade extractive chondroitin sulfate (CS) is widely used for osteoarthritis (OA) treatment. Recently, unsulfated biofermentative chondroitin (BC) proved positive effects in OA in vitro model. This study, based on primary pathological human synoviocytes, aimed to analyze, by a multiplex assay, a panel of OA-related biomarkers in response to short-term treatments with bovine (CS_b), pig (CS_p) and fish (CS_f) chondroitins, in comparison to BC. As expected, all samples had anti-inflammatory properties, however CS_b, CS_f and especially BC affected more cytokines and chemokines. Based on these results and molecular weight similarity, CS_f and BC were selected to further explore the synoviocytes’ response. In fact, Western blot analyses showed CS_f and BC were comparable, downregulating OA-related biomarkers such as the proteins mTOR, NF-kB, PTX-3 and COMP-2. Proteomic analyses, performed by applying a nano-LC-MS/MS TMT isobaric labelling-based approach, displayed the modulation of both common and distinct molecules to chondroitin treatments. Thus, CS_f and BC modulated the biological mediators involved in the inflammation cascade, matrix degradation/remodeling, glycosaminoglycans’ synthesis and cellular homeostasis. This study helps in shedding light on different molecular mechanisms related to OA disease that may be potentially affected not only by animal-source chondroitin sulfate but also by unsulfated biofermentative chondroitin.     

Cutaneous vasculitis, mixed cryoglobulinemia in a patient with non-secreting monolateral pheochromocytoma. A likely paraneoplastic syndrome

We describe a patient who presented with purpuric lesions over his legs, asthenia and arthralgias. The patient was diagnosed as having cryoglobulinemia and no secreting monolateral pheochromocytoma. Two months after the removal of the tumour, the vasculitic lesions disappeared but the cryoglobulins were still present in the patient's serum. The cryoglobulins, which varied from 30 mg/dl to 60 mg/dl, persisted even during the following year. We consider this case noteworthy because the association among leukocytoclastic vasculitis, cryoglobulinemia and no secreting monolateral pheochromocytoma has not been previously described.     

Novel Absorbent Materials Created via Ice Templating

Ice‐templated aerogels made from water soluble/dispersible raw materials are formed through an environmentally friendly freeze‐drying process. The structures that result from ice templating are capable of absorbing liquids into their large void volume. The effects of polymer chemistry and material loading on the absorption into the dried materials are studied. Low‐density samples were able to absorb liquids rapidly but the liquid‐saturated structures lacked mechanical integrity. The higher‐density samples absorbed liquids more slowly and again retained little structural integrity. The addition of fibers and firing of low‐density clay aerogels into ceramics provide multiple routes to creating structures exhibiting rapid absorption and a rigid, stable structure when saturated.

     

Oil absorption performance of polymer/clay aerogel materials

Oil absorption performance of aerogels produced from poly(amide‐imides), epoxies, and acrylic polymers were dependent upon freezing conditions, which in turn dictated solid state structures of these materials. Denser aerogels have less void space, and are more efficient at filling that space with oil, supporting the hypothesis that capillary spacing plays a vital role in determining oil absorption. Lower molecular weight epoxy‐based polymers produced aerogels with small capillary radii, again allowing increasing amounts of the liquid to penetrate between the aerogel layers. Aerogels produced from acrylic emulsions outperformed the other two systems tested in terms of volume per volume absorption. The initial difficulty with these materials, the fact that they still retain some hydrophilicy and absorb water, was overcome by simple post curing treatment, which was able to reduce water absorption to near zero levels. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45844.     

Morphology and Thermomechanical Properties of Melt‐Mixed Polyoxymethylene/Polyhedral Oligomeric Silsesquioxane Nanocomposites

The influence of the functionalization of fully condensed POSS cages on the properties of POM‐based nanocomposites is studied. POSS with different organic substituents [glycidylethyl, aminopropylisobutyl, and poly(ethylene glycol)] are taken into account and melt mixed with POM. Good dispersion was achieved upon the addition of amino functionalized POSS, leading to an increase on the thermal decomposition temperature under nitrogen atmosphere up to 50 °C. However, µm‐size aggregates were observed for other nanocomposites. There is no significant change in other thermal properties of the nanocomposites. The relationships among these effects and the morphological characteristics of the systems were analyzed.

     

Thin-film polymerization and ‘RIS’ Metropolis Monte Carlo simulation of fluorinated aromatic copoly(ester-amide)s

In this study, wholly aromatic main chain copoly(ester-amide)s containing tetrafluorophthalic acid (TFPA-ortho), tetrafluoroisophthalic acid (TFIA-meta) and tetrafluoroterephthalic acid (TFTA-para) were synthesized to study the effects of kinks on the formation of mesophase and crystal texture. The effects of kink moieties on these copoly(ester-amide)s were also investigated by the ‘RIS’ metropolis Monte Carlo simulation. Computational results indicate that all systems form thermotropic liquid crystalline polymers (LCPs) because the calculated persistence ratios for the ortho-, meta- and para-linkage systems are 6.51, 7.64 and 10.49, respectively. Both simulation and experimental results agree that ABA/AAA/TFTA (para) system has the greatest tendency to yield the liquid crystal (LC) phase due to its greater persistence ratio, linearity, and chain stiffness. The incorporation of TFPA (ortho) moiety can effectively reduce 30% of the molar stiffness function and 23% of the persistence length as compared to those of the TFTA (para) system. Yet, the ABA/AAA/TFPA system may form LC texture because of its large, rigid, disk-like TFPA moiety and the crankshaft structure induced by cis-configuration between AAA and TFPA moieties. The meta-linkage system has a slower LC growth rate, but it has a much higher tendency to form LC than the ortho-linkage. Both meta- and para-linkage systems have close critical ABA content to form LC texture. When comparing the requirements of critical ABA content between ABA/AAA/TFIA and ABA/AAA/IA (isophthalic acid) systems, we surprisingly observed that the former has a much lower critical ABA content than the latter. The four fluorine substituents of TFIA definitely help chain rigidity and stabilize the LC mesogens. Even though these fluorinated moieties exhibit different conformations and configurations, they yield similar end-stage crystalline structure. The spherulites are grown from the dark brushes around a single disclination, indicating that these are the lowest energy for crystallization.     

Pressure‐Sensitive Chromogenic Polyesters

Cyano‐OPV moieties were covalently incorporated into a PETG backbone to create ductile amorphous polymers which change their PL and absorption color as a function of deformation. The cyano‐OPV concentration was systematically varied, and the composition was related to the material's optical response. This approach afforded PETG/dye copolymers which upon annealing display characteristics of aggregated dye molecules. The materials exhibit a significant color change upon compression, consistent with disassembly of the dye aggregates. This mechanochromic response is irreversible and can be detected by the unassisted eye.

     

Formation of high conductivity glasses in the system AgIAg2OB2O3

Glass phases showing high ionic conductivity at room temperature were prepared through a rapid quenching of the molten mixtures of the system AgIAg₂OB₂O₃ (a fixed Ag₂O/B₂O₃ = 1 molar ratio was always considered): the obtained specimens were homogeneous and transparent cylindrical blocks.Disk shaped cells prepared with such specimens did not show any grain-grain effect as supported by the comparison between four electrodes dc and ac conductivity determinations.A less than 10^?9(ohm cm)^?1 electronic conductivity was found.According to X-rays diffraction and DTA investigations, X_AgI > 0.8 samples contained crystallized AgI, whereas 0.1 < X_AgI < 0.8 samples could be considered actual vitreous homogeneous phases.AgI contents lower than 10 mole% were not considered due to the observed presence of segregated metallic silver.Room temperature density and conductivity data showed a regular behaviour vs X_AgI in the vitreous phases range, whereas an evident discontinuity was observed about X_AgI = 0.8.Linear fits in the Arrhenius plots of the bulk conductivity were obtained in the 120 K?T_g (glass transition temperature) range: the corresponding activation energies, as well as the high room temperature conductivities, allowed to closely compare these vetrous phases with the so called “superionic” conductors.     

Physico‐optical properties of a crosslinked hyaluronic acid scaffold for biomedical applications

Optical techniques are increasingly employed for monitoring cell–matrix interactions in suitably prepared 3D scaffolds. The ability of designing and realizing synthetic extracellular matrix with well‐controlled optical properties is a crucial need in this field. For this purpose, a crosslinked hyaluronic acid (HA) scaffold is prepared. Fourier transform infrared and ultraviolet–visible spectroscopies enable to monitor the scaffold preparation process and to evidence scaffold high transparency and low fluorescence in the visible range. 3D optical characteristics of the HA scaffold are tested by two‐photon microscopy (TPM) imaging of embedded fluorescent microbeads and alive keratinocytes labeled with vital PKH67 dye at different depths from the scaffold surface. Some useful indications about the potentiality of TPM measurements for the determination of attenuation coefficient of turbid media are also reported. Moreover, the use of the presented HA scaffold for preparing tissue phantoms for fluorescence imaging or diffuse imaging is proposed. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45243.