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.     

聚乙烯醇对芳纶复合纱聚苯胺导电层耐久性影响

为提高聚苯胺导电层与基材之间的黏结牢度,以聚乙烯醇为共混高聚物,通过连续原位聚合法在对位芳纶纱线表面形成聚乙烯醇/聚苯胺导电层,制备得到芳纶/聚苯胺/聚乙烯醇复合导电纱。分析了导电纱的结构与性能,并研究了聚乙烯醇对聚苯胺导电层耐水洗和耐磨性的影响。结果表明:适量添加聚乙烯醇有助于提高导电纱导电层的结构规整性及电导率,随着聚乙烯醇质量分数的提高,导电纱的电导率呈先上升后下降的趋势,当聚乙烯醇占苯胺的质量分数为4.30%时,制得的复合导电纱线的电导率最高,达到(1.120±0.198) S/cm;聚乙烯醇的添加和质量分数的提高,有助于聚苯胺导电层耐水洗性及在较小外力作用下的耐磨性的提高。     

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.     

预处理过程产生的抑制剂对纤维素酶酶解效率的影响

在木质纤维产乙醇研究中,原料在稀磷酸浸渍+蒸汽爆破预处理过程中容易产生糠醛、5-羟甲基糠醛、对苯二酚和间苯二酚等抑制剂,这些抑制剂会影响纤维素酶酶解效率,导致还原糖浓度下降从而影响乙醇生产。通过单因素实验和正交实验,确定了纤维素酶酶解的最优条件为:酶解温度50℃、酶液载入量30 U/mL、酶解固液比1∶11、酶解pH值4. 8;选取预处理过程中产生的上述4种抑制剂,测定其浓度分别为:糠醛0. 031 g/L、5-羟甲基糠醛0. 029 g/L、对苯二酚1. 51 g/L、间苯二酚1. 242 g/L,探讨上述抑制剂单独或复配后对纤维素酶酶解效率的影响。结果表明,预处理过程中产生的酚类抑制剂高于醛类,在酶解过程中酚类抑制剂对酶解产生的影响高于醛类抑制剂;多种抑制剂的协同作用对酶解的影响高于单一种类抑制剂对酶解的影响;酶解液中抑制剂对酶解的影响强度按对苯二酚、间苯二酚、5-羟甲基糠醛、糠醛依次减弱。     

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。