A green approach is proposed to achieve a rapid surface functionalization of microcrystalline cellulose (MCC) in 30 min by a solvent-free "grafting from" reaction of l-lactide through compression molding without the need for an inert atmosphere. A sufficient hydrophobization of the MCC surface is achieved with an amount of grafted poly(l-lactic acid) (PLLA) oligomers of 7 wt % with respect to MCC. The obtained MCC-g-PLLA is subsequently melt-compounded with poly(lactic acid) (PLA) through extrusion and injection molding. As a result of higher compatibility and interfacial adhesion of the functionalized filler with PLA, PLA/MCC-g-PLLA biocomposites with a cellulose content ranging from 4 to 20 wt % exhibit an enhancement in important physicochemical properties (i.e., water vapor barrier, crystallinity, stiffness) compared to both pure PLA and formulations containing an equal or higher amount of nonfunctionalized MCC. At the same time, the materials retain the mechanical strength and resistance to thermal degradation of PLA. The physicochemical characteristics, excellent biocompatibility, and biodegradability of PLA and cellulose and the simplicity, rapidity, and cost-effectiveness of the grafting process render these biocomposites suitable for several applications within the plastics domain including packaging, agriculture, automotive, consumer goods, and household appliances.
Objective A relationship between thyroid and non-organ-specific autoimmunity could be relevant for Graves’ orbitopathy (GO), which affects connective tissue. We investigated the association between GO and anti-nuclear antibodies (ANAs). Methods Retrospective investigation was conducted in 265 patients with Graves’ disease (GD), 158 with and 107 without GO. Primary outcome was: prevalence of ANAs in GO vs no-GO. Secondary outcomes were: (1) relationship between ANAs and GO features; (2) prevalence of ANAs in GD compared with non-autoimmune hyperthyroidism [(78 patients with toxic nodular goiter (TNG)]; (3) distribution of ANA patterns. Results ANAs were detected in 212 (80%) GD patients, but prevalence did not differ between GO (79.7%) and no-GO (80.3%). Higher ANA titers (1:160) were more common in GO (51.5 vs 38.3%), but only nearly significantly (OR 0.5; 95% CI: 0.3–1; P = 0.059). Proptosis was lower in ANA-positive patients (mean difference: − 1.4 mm; 95% CI from − 2.5 to − 0.3; P = 0.011), in whom nearly significantly lower CAS (Mann–Whitney U: 1.5; P = 0.077) and eyelid aperture (mean difference: − 0.9 mm; 95% CI from − 2 to 0; P = 0.062) were observed. Prevalence of ANAs in GD was lower than in TNG (80 vs 91%; OR 0.3; 95% CI: 0.1–0.9; P = 0.028), but nuclear speckled pattern was more frequent (OR 22.9; 95% CI 1.3–381.3; P = 0.028). Conclusions Although ANAs are not more frequent in GO, they seem to exert a protective role on its severity and on development of GD. A switch of T cell population in ANA-positive patients, resulting in a different phenotype, may be responsible. Further studies are needed to investigate the mechanisms.
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