Efficient Synthesis of Triarylamines Catalyzed by Copper(I) Diazabutadiene Complexes

Cuprous chloride was coordinated by diazabutadiene (DAB‐R) ligands to form Cu(I)‐(DAB‐R) complexes, most of which have a 1:1 ratio of Cu to DAB‐R as reported. In the case of a special DAB‐ⁱPP, N,N′‐bis(2,6‐diisopropylphenyl)‐1,4‐diaza‐1,3‐butadiene, an unexpected composition of complex was found with the formula Cu(I)Cl(DAB)₂. When employed as catalyst for triarylamine synthesis from the coupling of aryl halides with primary and secondary arylamines, the new Cu(I)‐(DAB‐ⁱPP) complex displayed high efficiency.     

TODGA/[C_2mim][NTf_2]萃取Th~(4+)

研究了N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)溶于疏水性离子液体咪唑类离子液体1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐([C2mim][NTf2])中对硝酸水溶液体系中四价钍离子(Th4+)的萃取行为。详细考察了接触时间、酸度、Th4+浓度、TODGA浓度、温度对TODGA/[C2mim][NTf2]体系萃取性能的影响。作为对比,我们还考察了TODGA在传统有机溶剂异辛烷中对Th4+的萃取。结果表明:TODGA/[C2mim][NTf2]体系对Th4+的萃取是吸热反应,且在50℃下,能在5 min内达到平衡。萃取体系随着酸度对Th4+的萃取性能先降后增大;Th4+浓度的增大,TODGA浓度的降低,对Th4+的萃取性能下降。TODGA在离子液体萃取体系中比在有机体系中有更好的Th4+萃取效果,特别是在低酸条件下。通过萃取机理研究,推测出在低酸下萃取反应是离子交换且TODGA与Th4+配比为2∶1,在高酸下萃取是中性配位。     

AM/AA/APEG/NANB共聚物的合成与性能研究

通过丙烯酰胺(AM),丙烯酸(AA),烯丙醇聚氧乙烯醚(APEG)和N,N-二烯丙基苄胺(NANB)制备共聚物P(AM/AA/APEG/NANB)。确定了最佳反应条件:m(AM)∶m(AA)=6.5∶3,APEG为5 wt%,NANB加量0.2 wt%,pH为7,反应温度40℃,引发剂0.4 wt%。通过IR和1H NMR确定了聚合物的分子结构,并对其进行性能测试。结果表明:2000 mg·L-1的AM/AA/APEG/NANB溶液具有较好的流变性能(120℃,粘度保留率:38.56%;1000 s-1,粘度保留率:17.93%)和抗盐性能(20 000 mg·L-1Na Cl,2000 mg·L-1Mg Cl2或Ca Cl2,粘度保留率分别为22.14%、18.34%和15.33%),且提高采收率可达16.12%。     

双官能单萜氧杂二环二醇乙酸酯类衍生物的合成及其除草活性

以(3R,4R)-4,7,7-三甲基-6-氧杂二环[3,2,1]辛烷-3,4-二醇(1)和乙酰氯(2)为原料,经"一锅法"制得混合物Ⅰ;Ⅰ经分离纯化得4个新型的双官能单萜氧杂二环二醇乙酸酯类衍生物(3a~3d),其结构经1H NMR,13C NMR,FT-IR和HR-MS表征。考察了物料比r[n(2)∶n(1)]和反应时间对3a~3d相对浓度的影响。结果表明,在反应条件[1 5 mmol,r=7,回流反应7 h]下,3a~3d的相对浓度分别为21.6%,15.6%,37.9%和24.9%;在反应条件[1 5 mmol,r=4,回流反应7 h]下,3a~3d的相对浓度分别为50.7%,36.6%,7.84%和4.86%。用培养皿法测试了1和3a~3d的除草活性。实验结果表明,1和3a~3d均能显著抑制一年生黑麦草胚根与胚芽生长;在用药浓度为5 mmol·L-1时,1和3a~3d对根长抑制率分别为55.1%,86.0%,84.2%,91.3%和97.5%;对芽长抑制率分别为55.1%,76.5%,92.8%,94.8%和98.4%。     

游离芳香氨基酸和半胱氨酸对光诱导高铁肌红蛋白还原的影响

肌红蛋白(Myoglobin,Mb)中血红素辅基不仅具有储氧功能,也能吸收特定波长的光而影响蛋白功能表达。实验发现,部分游离的氨基酸对光诱导高铁肌红蛋白(metM b,Fe(III)-Mb)的还原过程及还原程度都有重要作用,因此,本文采用紫外-可见吸收光谱、圆二色谱、三维荧光光谱法,在光照体系中加入拥挤试剂来模拟细胞内拥挤环境,研究芳香氨基酸[色氨酸(Trp)、苯丙氨酸(Phe)、酪氨酸(Tyr)、半胱氨酸(Cys)]对metM b还原的影响。结果表明,含-OH或-SH的氨基酸(Tyr、Cys)能使metM b发生较好的光还原,无-OH或-SH基团的氨基酸(Trp、Phe)对metM b的光还原作用较弱,氨基酸促进metM b光还原的整个过程可能是分子间电子转移的过程。metM b在拥挤环境聚蔗糖70(Ficoll 70)中的光诱导还原程度比在稀溶液中高,拥挤试剂Ficoll70对蛋白的二级结构起保护作用,能够稳定血红素微环境。     

新型低共熔溶剂的制备、表征及物性研究

以氯化1-丁基-3-甲基咪唑鎓([Bmim]Cl)和二元羧酸为原料,由不同摩尔比混合制备了一类新型低共熔溶剂,采用红外光谱对[Bmim]Cl和二元羧酸之间的作用进行了分析。分别测定了其粘度、电导率、密度、折射率等物理性质,并研究了温度、二元羧酸结构和摩尔比对这些物理性质的影响。结果表明,新型低共熔溶剂的粘度随温度的升高而降低,电导率随温度的升高而增加。温度对两者的影响可以采用VTF方程进行精确地拟合。新型低共熔溶剂的密度随温度的升高而呈线性下降。对新型低共熔溶剂的过量摩尔体积进行计算的结果表明,过量摩尔体积均为正值,二元羧酸对过量摩尔体积的贡献远大于[BMIM]Cl,而结构特性的贡献多于物理作用。折射率和密度随二元羧酸碳数的变化趋势基本相似。     

二价与四价金属离子等摩尔共掺杂的锂离子电池正极材料LiMn1.9Mg0.05Ti0.05O4的制备与表征

以氢氧化锂、乙酸锰、硝酸镁和钛酸丁酯为原料, 以柠檬酸为螯合剂, 采用溶胶-凝胶法制备了二价镁离子与四价钛离子等摩尔共掺杂的尖晶石型锂离子电池正极材料LiMn_1.9Mg_0.05Ti_0.05O₄. 采用热重分析(TGA), X射线衍射(XRD), 扫描电子显微镜(SEM), 透射电子显微镜(TEM)和电化学性能测试(包括循环伏安(CV)和电化学交流阻抗谱(EIS)测试)对所得样品的结构、形貌及电化学性能进行了表征. 结果表明: 780℃下煅烧12 h 得到了颗粒均匀细小的尖晶石型结构的LiMn_1.9Mg_0.05Ti_0.05O₄材料, 该材料具有良好的电化学性能, 在室温下以0.5C倍率充放电, 在4.35-3.30 V电位范围内放电比容量达到126.8 mAh·g^-1, 循环50 次后放电比容量仍为118.5mAh·g^-1, 容量保持率为93.5%. 在55℃高温下循环30次后的放电比容量为111.9 mAh·g^-1, 容量保持率达到91.9%, 远远高于未掺杂的LiMn₂O₄的容量保存率. 二价镁离子与四价钛离子等摩尔共掺杂LiMn₂O₄, 改善了尖晶石锰酸锂的电子导电和离子导电性能, 使其倍率性能和高温性能都得到了明显的提高.     

α-四(对磺酸钠苯氧基)酞菁锌(钴,镍)光敏剂的光动力性质研究

采用UV-Vis光谱、红外吸收光谱、CHN元素分析及激光解析飞行时间质谱对α-四(对磺酸钠苯氧基)酞菁锌(钴,镍)[α-PhSPcZn(Co,Ni)]进行表征.在光诱导条件下,采用四甲基偶氮唑蓝比色法(MTT法),考察了光敏剂的中心原子、浓度和光照时间等条件下对癌细胞的抑制作用.结果显示,光照15min、浓度为0~100mg·L-1范围内时,α-PhSPcZn的抑瘤率高于α-PhSPcCo和α-PhSPcNi.抑瘤率均随光照时间和配合物浓度的增加而升高,α-PhSPcZn的抑制率可达54%,其IC50值为75mg·L-1.     

Shape-memory poly(p-dioxanone)-poly(ε-caprolactone)/sepiolite nanocomposites with enhanced recovery stress

Shape-memory poly(p-dioxanone)-poly(ε-caprolactone)/sepiolite (PPDO-PCL/OSEP) nanocomposites with different OSEP nanofiber loading were fabricated by chain-extending the PPDO-diol and PCL/OSEP precursors. The precursors and the composites were characterized by ¹H NMR, FT-IR, GPC, SEM and TEM. The results demonstrate that a part of PCL segments grafted on the surface of OSEP and composites display a fine dispersion of OSEP fiber in nanoscale with low OSEP content. The shape memory effect (SME) was evaluated by DMA, the results reveal that the PPDO-PCL/OSEP nanocomposites exhibit desirable shape-memory performance. The reinforcement of composites by incorporation of trace OSEP nanofiber evokes an effective improvement in shape-memory recovery stress.     

Synthesis and performances for treating oily wastewater produced from polymer flooding of new demulsifiers based on polyoxyalkylated N,N‐dimethylethanolamine

Usually, oily wastewater produced from polymer flooding (OWPF) was treated by cationic polymer in oilfield. In this paper, six block copolymers of ethylene oxide and propylene oxide were prepared by using N,N‐dimethylethanolamine (DMEA) as the acceptor (DMEA‐mnp and DMEA‐mnpq, n:m:p:q represented the weight ratio of different blocks). Most of DMEA products could perform well for treating OWPF, especially DMEA1231. Their performances were mainly affected by temperature. The reason of increasing oil removal performance of DMEA1231 with temperature was the decrease of interfacial dilational modulus (ε) with increasing temperature. When temperature raised up to 55°C, the ε of DMEA1231 had the minimum (1.5 l mN/m). Therefore, the OiW had the minimum (90 mg/l). Because DMEA1231 had the best performance, its flocculation kinetics was studied systemically. The results showed that the optimum condition for DMEA1231 was as follows: dosage was 300 mg/l, temperature was 55°C, stirring speed was 200 rpm and stirring time was 5 min. At last, the offshore oil field test was carried out to check the DMEA1231 performance. The result showed that at the optimum condition, DMEA1231 could perform as well as the cationic polymer. The most important thing was that flocs of DMEA1231 were not viscous and floated on the surface of the water. The results obtained by this paper provide a good choice for the treatment of OWPF in offshore oilfield to avoid the formation of viscous flocs. Copyright © 2014 John Wiley & Sons, Ltd.