No abstract

Crystalline structure and molecular dynamics in α and α′ crystals of poly(L-lactide) (PLLA) and PLLA/poly(Dlactide) (PDLA) stereocomplex (sc) crystals have been investigated by the temperature-variable FTIR and solid-state 13 C CP-MAS NMR spectroscopy. The crystal forms of polylactide (PLA) have different band frequencies, correlation field splittings in FTIR spectra and different line shapes, and resonance splittings in solid-state NMR spectra, which become more distinct with cooling to the cryogenic conditions. The well-resolved splittings in NMR resonances of α crystals, attributable to the crystallographically inequivalent sites within crystal unit cell, are considered to be due to the dipolar interactions related to the carbonyl, methyl, and methine groups. The splittings in FTIR bands and NMR resonances are absent in α′ crystals, indicating the disordered conformation and loose molecular lateral packing within their crystal lattices. The significant FTIR frequency shifts of ν(CO), ν(CH 3 ), and ν(CH) modes during stereocomplex crystallization of PLLA/PDLA blend and the appearance of spectral splittings at cryogenic conditions suggest the coexistence of weak C−H···OC hydrogen bonds and dipolar interactions between PLLA and PDLA chains in the sc crystals of PLA. Below the glass transition temperature (T g ), the spin−lattice relaxation times of PLA with different crystalline structures increase in the order of amorphous ≈ α′ < α < sc.

Astragalus polysaccharides (APS), which is widely used as a remedy to promote immunity of breast cancer patients, can enhance immune responses and exert anti-tumor effects. In this study, we investigated the effects and mechanisms of APS on macrophage RAW 264.7 and EAC tumor-bearing mice. Griess reaction and ELISA assays revealed that the concentrations of nitric oxide, TNF-α, IL-1β and IL-6 were increased by APS. However, this effect was diminished in the presence of TAK-242 (TLR4 inhibitor) or ST-2825(MyD88 inhibitor). In C57BL/10J (TLR4+/+wild-type) and C57BL/6J (MyD88+/+wild-type) tumor-bearing mice, the tumor apoptosis rate, immune organ indexes and the levels of TNF-α, IL-1β and IL-6 in blood increased and the tumor weight decreased by oral administration of APS for 25 days. APS had no obvious effects on IL-12p70. However, these effects were not significant in C57BL/10ScNJ (TLR4-deficient) and C57BL/B6.129P2(SJL)-Myd88m1.1Defr/J (MyD88-deficient) tumor-bearing mice. qRT-PCR and Western blot indicated that APS stimulated the key nodes in the TLR4-MyD88 dependent signaling pathway, including TLR4, MyD88, TRAF-6, NF-κB and AP-1, both in vitro and in vivo. However, TRAM was an exception. Moreover, TRAF-6 and NF-κB were not triggered by APS in gene-deficient tumor-bearing mice. Therefore, APS may modulate immunity of host organism through activation of TLR4-mediated MyD88-dependent signaling pathway.