Synthesis of Janus polyaniline–polyelectrolyte complex membrane via in situ confined polymerization

Polyelectrolyte complex (PEC) membranes prepared from poly(styrene sulfonate) (PSS) and poly(diallyldimethylammonium chloride) (PDADMAC) were modified by crossflow polymerization of aniline (ANI). The PEC membranes were used as separators in a two-compartment setup where ANI monomer and ammonium persulfate (APS) oxidant diffused through the membranes to form polyaniline (PANI). APS and ANI having different distributions throughout the membranes, the reaction led to the asymmetric polymerization of PANI on one face of each PEC membrane thus producing Janus membranes. Due to the excess PANI content, the membrane displayed distinct asymmetric electrical conductivities on each face. Interestingly, very different ANI polymerizations were obtained when nonstoichiometric PEC membranes having different molar ratio of cationic and anionic polyelectrolytes (P⁺:P^? represents PDADMAC:PSS) were used and transport of APS was fastest through the 2:1 PEC when compared to the 1:2 PEC. In all experiments, the polymerization was most intense on the ANI side of the membranes. Also, the influence of NaCl both during PEC fabrication and during polymerization was studied and found to have some effect on the solute permeability. Results showed that a higher content of PANI was formed on PEC membranes having excess P⁺ and with no NaCl added during PEC fabrication. Although X-ray diffraction confirmed the presence of PANI on both sides of each membrane, scanning electron microscopy images demonstrated that both sides of each membrane had different PANI content deposited. Electrical conductivity measurements using a four-point probe setup also showed that the PEC–PANI exhibits asymmetric electrical property on different sides. © 2021 Society of Industrial Chemistry.     

Configurational Isomers Induced Significant Difference in All-Polymer Solar Cells

The design of polymer acceptors plays an essential role in the performance of all-polymer solar cells. Recently, the strategy of polymerized small molecules has achieved great success, but most polymers are synthesized from the mixed monomers, which seriously affects batch-to-batch reproducibility. Here, a method to separate γ-Br-IC or δ-Br-IC in gram scale and apply the strategy of monomer configurational control in which two isomeric polymeric acceptors (PBTIC-γ-2F2T and PBTIC-δ-2F2T) are produced is reported. As a comparison, PBTIC-m-2F2T from the mixed monomers is also synthesized. The γ-position based polymer (PBTIC-γ-2F2T) shows good solubility and achieves the best power conversion efficiency of 14.34% with a high open-circuit voltage of 0.95 V when blended with PM6, which is among the highest values recorded to date, while the δ-position based isomer (PBTIC-δ-2F2T) is insoluble and cannot be processed after parallel polymerization. The mixed-isomers based polymer, PBTIC-m-2F2T, shows better processing capability but has a low efficiency of 3.26%. Further investigation shows that precise control of configuration helps to improve the regularity of the polymer chain and reduce the π–π stacking distance. These results demonstrate that the configurational control affords a promising strategy to achieve high-performance polymer acceptors.     

Piezoelectric properties of PVDF-conjugated polymer nanofibers

This study presents the development and characterization of PVDF-conjugated polymer nanofiber-based systems. Five different conducting polymers (CPs) were synthesized successfully and used to create the nanofiber systems. The CPs used are polyaniline (PANI), polypyrrole (PPY), polyindole (PIN), polyanthranilic acid (PANA), and polycarbazole (PCZ). Nanofiber systems were produced utilizing the Forcespinning® technique. The nanofiber systems were developed by mechanical stretching. No electrical field or post-process poling was used in the nanofiber systems. The morphology, structure, electrochemical and piezoelectric performance was characterized. All of the nanofiber PVDF/CP systems displayed higher piezoelectric performance than the fine fiber PVDF systems. The PVDF/PPY nanofiber system displays the highest piezoelectric performance of 15.56 V. The piezoelectric performance of the PVDF/CP nanofiber systems favors potential for an attractive source of energy where highly flexible membranes could be used in power actuators, sensors and portable, and wireless devices to mention some.     

卡尔费休法测定液态氯乙烯中水含量的研究

采用卡尔费休法测定了液态氯乙烯单体中的水含量。试验确定了采样工具、样品的预处理方式及选用溶剂的最优方案,并进行了精密度与准确度的验证。结果表明卡尔费休法测定液态氯乙烯单体中的水含量准确、快速,可以用来准确、及时地指导生产。     

Discovery of New Antiproliferative Imidazopyrazole Acylhydrazones Able To Interact with Microtubule Systems

Even though immunotherapy has radically changed the search for anticancer therapies, there are still many different pathways that are open to intervention with traditional small molecules. To expand our investigation in the anticancer field, we report here a new series of compounds in which our previous pyrazole and imidazopyrazole scaffolds are linked to a differently decorated phenyl ring through an acylhydrazone linker. Preliminary tests on the library were performed at the National Cancer Institute (USA) against the full NCI 60 cell panel. The best compounds among the imidazopyrazole series were then tested by immunofluorescence staining for their inhibition of cell proliferation, apoptosis induction, and their effect on the cell cycle and on microtubules. Two compounds, in particular 4-benzyloxy-3-methoxybenzyliden imidazopyrazole-7-carbohydrazide showed good growth inhibition, with IC₅₀ values in the low-micromolar range, and induced apoptosis. Both compounds altered the cell-cycle phases with the appearance of polyploid cells. Immunofluorescence analysis evidenced microtubules alterations; tubulin polymerization assays and docking studies suggested the tubulin system to be the possible, although not exclusive, target of the new acylhydrazone series reported here.     

Temperature- and pH-sensitive core–shell nanogels as efficient carriers of doxorubicin with potential application in lung cancer treatment

Temperature- and pH-sensitive core–shell nanogels were prepared by one-pot soapless emulsion polymerization of N-isopropylacrylamide and 2-methacryloyloxy benzoic acid with the aid of a crosslinker (core) using poly(ethylene glycol) methyl ether methacrylate as stabilizer (shell). The size of nanogels depended on the crosslinker used, being considerable smaller (around 100?nm) with the use of the acid-labile crosslinker 9-divinyl-2,4,8,10-tetraoxaspiro[5.5]-undecane (DVA). Doxorubicine (DOX) was loaded in nanogels with good efficiency. The empty nanogels were biocompatible for a lung cancer cell line (NCI-H1437), while the DOX-loaded, DVA-crosslinked nanogels resulted with efficient cytotoxicity for that cell line.     

抗冲ACR树脂的合成及其性能评价

采用种子乳液聚合法,以丙烯酸丁酯为核层单体、甲基丙烯酸甲酯为壳层单体、甲基丙烯酸烯丙酯为交联剂制备了抗冲ACR树脂。考察了不同加料方式对ACR乳液粒径及对PVC冲击性能的影响,结果表明:连续滴加方式可实现乳液粒径的稳定控制,并能得到性能优异的抗冲ACR树脂。     

Random poly(ε‐caprolactone‐L‐alanine) by direct melt copolymerization

A series of random polyesteramides (PEAs) with a range of molar composition from 90/10 to 50/50 were synthesized by direct melt polycondensation of ε‐caprolactone and l ‐alanine. Their structure was fully characterized by Fourier transform IR and NMR spectroscopy. The resulting copolymers are completely amorphous with the exception of PEA‐90/10 which possesses a semicrystalline structure. These PEAs present increasing glass transition temperatures at increasing l ‐alanine contents and exhibit fairly good thermal stability with 10% mass loss temperatures reaching 315 °C. © 2020 Society of Industrial Chemistry     

半纤维素基阿维菌素载药微囊的制备及性能

目前阿维菌素以高效性、无污染和低抗药性等特点而得到广泛应用，但是其稳定性较差，易降解导致使用量较大从而造成浪费。为解决上述问题，本文以半纤维素为基体，利用原位聚合法制备阿维菌素载药微囊（HDCM），通过制备条件、热降解性、储存稳定性和释放动力学研究，确定了HDCM的载药量、热稳定性及释放性能。结果表明，在芯壁比为1∶34（质量比），温度为65℃，pH为3.5的制备条件下，HDCM的载药量可达66.5%，粒径较小且分散均匀。HDCM的热降解性能和恒温热稳定性能较阿维菌素原药有所提高，最高热分解温度从261℃增加到272℃，阿维菌素原药10h后降解率达到12.1%，而载药量为66.5%的HDCM降解率仅为5.2%。HDCM的释放机理满足Fick扩散，阿维菌素原药在水中的累积释放率在12h之内达到83.8%，而HDCM的累积释放率在24h之后才有所增大，12h内其释放率仅为33.7%，表明HDCM具有极好的缓释性能。