Yiding Cao,Zhenzhen Liu,Bixia Zheng,Rongxian Ou,Qi Fan,Liping Li,Chuigen Guo,Tao Liu,Qingwen Wang
Sustainable thermosetting polyurethane (PU) anticorrosive coatings based on renewable biomass resources with long-lasting corrosion protection is highly desired. Herein, thermosetting lignin-based polyurethanes (LPU) coatings with superior corrosion resistance and high content of lignin were prepared by polymerization of lignin-based polyol (OH-EL) with hexamethylene diisocyanate (HDI) in absence of catalysts. In order to increase the reactivity and solubility of OH-EL when reacting with isocyanates, the phenolic hydroxyls of enzymatic hydrolysis lignin were selectively converted to primary aliphatic hydroxyls by sequential alkylation and thiol-ene reaction. Due to the well dispersion and crosslinking reactivity of OH-EL in the polyurethane networks, the resulting LPUs presented high thermal stability and excellent mechanical properties . Remarkably, LPU-3 with the content of OH-EL of 54.8 wt%, exhibited high T g of 112 °C, high char residue percentage of 26.3% at 600 °C, high tensile strength up to 81.6 MPa and tensile modulus of 1.4 GPa. Moreover, the LPU-3 coating on carbon steel substrate exhibited low corrosion current density I corr of 7.58 × 10 −11 A cm −2 , positive corrosion voltage E corr of 118 mV, and high impedance modulus |Z| 0.01Hz of 8.3 × 10 10 Ω cm 2 after immersing in 3.5 wt% NaCl solution for 0.5 h, and the |Z| 0.01Hz remained at 3.9 × 10 10 Ω cm 2 after 40 days immersion, displaying superior corrosion resistance than other reported bio-based polymer coatings . These results demonstrate that the synthesis of highly reactive lignin-based polyols based on thiol-ene chemistry is an effective and facile strategy, which is vital for the development of high-performance bio-based polyurethane anticorrosive coatings.
Radiotherapy (RT)-induced in situ vaccination greatly promotes the development of personalized cancer vaccines owing to the massive release of antigens initiated by tumor-localized RT eliciting the tumor-specific immune response. However, its broad application in cancer treatment is seriously impeded by poor antigen cross-presentation, low response rate, and short duration of efficacy. Herein, the tumor-antigen-capturing nanosystem dAuNPs@CpG consisting of gold nanoparticles, 3,5-cyclohexanedione (CHD), and immunoadjuvant CpG were fabricated to enhance RT-induced vaccination. Taking advantage of the specific covalent binding between CHD and sulfenic acids of antigen proteins, we show that this nanoplatform has an unexpected potential to capture the sulfenylated tumor-derived protein antigens (TDPAs) induced by RT to in situ generate a vaccination effect, achieving significant growth suppression of both primary and distant tumors in combination with PD-1 blockade. We thus believe that our work presents a powerful and effective means to improve the synergistic tumor radioimmunotherapy.
Summary H 2 O 2 affects the expression of genes that are involved in plant responses to diverse environmental stresses; however, the underlying mechanisms remain elusive. Here, we demonstrate that H 2 O 2 enhances plant freezing tolerance through its effect on a protein product of low expression of osmotically responsive genes2 ( LOS2 ). LOS2 is translated into a major product, cytosolic enolase2 (ENO2), and sometimes an alternative product, the transcription repressor c-Myc-binding protein (MBP-1). ENO2, but not MBP-1, promotes cold tolerance by binding the promoter of C-repeat/DRE binding factor1 ( CBF1 ), a central transcription factor in plant cold signaling, thus activating its expression. Overexpression of CBF1 restores freezing sensitivity of a LOS2 loss-of-function mutant. Furthermore, cold-induced H 2 O 2 increases nuclear import and transcriptional binding activity of ENO2 by sulfenylating cysteine 408 and thereby promotes its oligomerization . Collectively, our results illustrate how H 2 O 2 activates plant cold responses by sulfenylating ENO2 and promoting its oligomerization, leading to enhanced nuclear translocation and transcriptional activation of CBF1 .
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