Distinct Stepwise Reduction of a Nickel?Nickel‐Bonded Compound Containing an α‐Diimine Ligand: From Perpendicular to Coaxial Structures

A nickel? nickel‐bonded complex, [{Ni(μ‐L^.?)}₂] ( 1 ; L=[(2,6‐iPr₂C₆H₃)NC(Me)]₂), was synthesized from reduction of the LNiBr₂ precursor by sodium metal. Further controllable reduction of 1 with 1.0, 2.0 and 3.0 equiv of Na, respectively, afforded the singly, doubly, and triply reduced compounds [Na(DME)₃] ? [{Ni(μ‐L^.?)}₂] ( 2 ; DME=1,2‐dimethoxyethane), [Na(Et₂O)]Na[(L^.?)Ni? NiL^2?] ( 3 ), and [Na(Et₂O)]₂Na[L^2?Ni? NiL^2?] ( 4 ). Here L represents the neutral ligand, L^.? denotes its radical monoanion, and L^2? is the dianion. All of the four compounds feature a short Ni? Ni bond from 2.2957(6) to 2.4649(8) Å. Interestingly, they display two different structures: the perpendicular ( 1 and 2 ) and the coaxial ( 3 and 4 ) structure, in which the metal? metal bond axis is perpendicular to or collinear with the axes of the α‐diimine ligands, respectively. The electronic structures, Ni? Ni bonding nature, and energetic comparisons of the two structure types were investigated by DFT computations.     

Collective Total Synthesis of Englerin A and B,Orientalol E and F,and Oxyphyllol: Application of the Organocatalytic [4+3] Cycloaddition Reaction

The concise collective total synthesis of englerin A and B, orientalol E and F, and oxyphyllol has been accomplished in 10–15 steps, with the total synthesis of orientalol E and oxyphyllol being achieved for the first time. The success obtained was enabled by the realization of the [4+3] cycloaddition reaction of 9 and 10 . Other features of the synthesis include 1) the intramolecular Heck reaction to access the azulene core, 2) the epoxidation–S_N2′ reduction sequence to access the allylic alcohol, 3) the efficient regioselective and stereoselective formal hydration of the bridging C?C bond in the synthesis of englerins, and 4) the late‐stage chemo‐ and stereoselective C? H oxidation in the synthesis of orientalol E. The total synthesis of these natural products has enabled the structural revision of oxyphyllol and established the absolute stereochemical features of the organocatalytic [4+3] cycloaddition reaction. The identification of 5 as the natural product oxyphyllol, the success in converting 5 to orientalol E, along with the fact that englerins and oxyphyllol were isolated from plants of the same genus Phyllanthus gives support to our proposed biosynthetic pathways. This work may enable detailed biological evaluations of these natural products and their analogues and derivatives, especially of their potential in the fight against renal cell carcinoma (RCC).     

Preparation and characterization of cotton fabrics with antibacterial properties treated by crosslinkable benzophenone derivative in choline chloride-based deep eutectic solvents

Cotton fabrics with antibacterial properties were prepared by the treatment with 3,3′4,4′-benzophenone tetracarboxylic dianhydride (BPTCD) in a combined process of shaking immersion in dyeing machine and pad-dry-cure. Environmentally-benign choline chloride (ChCl)-based deep eutectic solvents (DESs) were mainly examined as treatment media instead of using organic solvent. The results revealed that cotton fabrics treated with BPTCD in urea-ChCl DES showed a strong ester carbonyl peak in fourier transform infrared (FTIR) analysis, indicating fixation of BPTCD on cotton cellulose. Detailed characterizations of the BPTCD-treated cotton were carried out by FTIR, thermogravimetric analysis, scanning electron microscopy, dye staining, and evaluation of hydrophilicity and strength. The treated fabrics demonstrated a high level of antibacterial characteristics before and after UV irradiation. This indicated that addition of ChCl could enhance antibacterial activity of cotton before UV irradiation. Therefore, use of ChCl-based DES along with BPTCD incorporation provided environmentally-acceptable and economically-feasible treatment process for preparation of novel antibacterial cotton.     

Durable antimicrobial cotton fabrics containing stable quaternarized N-halamine groups

A novel N-halamine precursor with tertiary amino group (5,5-dimethylhydantoinyl-3-ylethyl)-dimethylamine (DEADH), was synthesized and then covalently bonded onto cotton fabrics modified by 3-chloropropyltrimethoxysilane to form quaternarized N-halamine precursor grafted cotton fabrics which could be transferred to N-halamine structure upon exposure to dilute sodium hypochlorite solution. The grafted cotton fabrics were characterized by FT-IR, X-ray photoelectron spectroscopy, and field emission scanning electron microscope. The antimicrobial test showed that the cotton fabrics grafted with the quaternarized N-halamine were capable of 7-log inactivation of Staphylococcus aureus and Escherichia coli O157:H7 within 1 min of contact time. Very interestingly, it was found that the grafting process and following chlorination had almost no adverse effect on the tensile strength of cotton fabrics. Furthermore, the antimicrobial cotton fabrics exhibited good washing durability and stability.     

稀土镧在腈纶纤维化学镀银中的应用及其电化学性能

采用化学镀法(镀液中加入适量的稀土镧)在硅烷偶联剂改性后的腈纶纤维表面沉积金属银,由粒径分析、X射线衍射、扫描电子显微镜、阴极极化曲线以及循环伏安曲线等方法对其进行表征,研究了硝酸镧对化学镀银沉积速度、镀层质量和电化学性能的影响。结果表明,镀银液中加入适宜的硝酸镧,银的沉积速率和腈纶纤维表面银镀层的表面质量均有不同程度的提高。电化学测试表明,镀银液中增大硝酸镧的浓度(0～0.01 g/L),阴极极化曲线极化度增大,氧化还原峰的电流上升,电沉积的速度加快。     

化学发光分析与高效液相色谱联用检测酪氨酸

在强碱性条件下,KMnO4氧化酪氨酸产生自由基,自由基氧化Luminol产生强化学发光,酪氨酸浓度与相对发光强度呈线性关系。选用C18反相色谱柱、CH3OH、KH2PO4混合液为流动相,酪氨酸能很好分离。基于此,建立CL-HPLC检测酪氨酸的新方法,线性范围为1.2×10-3～5.0×10-2g/L、线性相关系数为0.9994、RSD为2.37%、检测限为3.3×10-4g/L。方法已于检测实际样品氨基酸口服液,并与UV光度法,结果一致。本文探讨了酪氨酸增强KMnO4-Luminol化学发光机理。     

建筑用梳形共聚物分散剂溶液行为的光散射研究

采用激光光散射研究了一种主链为聚丙烯酸侧链为聚乙二醇的梳形共聚物分散剂的一些溶液行为.从静态光散射得出了较为合理的表观重均分子量、均方旋转半径等参数.动态光散射给出了流体力学半径分布及其角度和浓度依赖性.结合静态和动态光散射,上述梳形共聚物分散剂在溶液中的构象也得到初步的表征.通过与描述梳形聚合物的Gay-Raphae模型进行比较表明,这类梳形共聚物溶液在低盐离子和低pH值条件下存在聚集行为,形成以PAA主链为核PEG为壳层的类胶束聚集.     

成核剂及其完善剂对聚乳酸结晶行为的影响

通过POM、DSC以及流变测试系统考察了成核剂(PPZn)及其完善剂(E61)对PLA结晶形貌及其结晶能力的影响.POM结果表明PPZn和E61对PLA的结晶形态的影响随两者含量的变化而变化.加入低含量的PPZn可诱导PLA得到一定完善程度的球晶,而较高含量的PPZn能够诱导PLA基体得到针状晶体.通过添加少量E61可使在PPZn较高含量下的PLA针状晶体转变为球晶.但更高含量E61的添加却使PPZn的成核作用受到抑制,再次生成针状晶体,且E61含量越高,抑制作用越明显.DSC和流变测试进一步证明PPZn可显著提高PLA的结晶能力、有效地缩短基体结晶时间,而E61的添加对PLA的结晶速率影响不大.     

含芳酰胺结构的新型甲壳型液晶高分子PMPACS的聚合反应动力学研究

采用称量法和GPC,研究了以二甲基乙酰胺为溶剂,偶氮二异丁腈为引发剂,自由基溶液聚合制备含芳酰胺结构的新型甲壳型液晶高分子聚[乙烯基对苯二甲酸二(4-甲氧基苯胺)](PMPACS)的聚合反应动力学.研究发现,(1)MPACS的聚合反应在60℃时主要为双基偶合终止,所以反应后期聚合物分子量明显增大,分子量分布变窄;(2)该反应的聚合反应速率方程为Rp=kp[M][I]1/2,表观活化能Eα=44 kJ/mol,在60℃时的聚合反应常数kp=1.04 L·mol-1·h-1;(3)相同聚合条件下,单体的转化率和数均分子量随单体初始浓度[M]0的增加而增大,当引发剂浓度[I]0增加时,聚合物的分子量随之降低,分子量分布增大;(4)该研究虽采用普通自由基聚合,所得聚合物的分子量分布却较窄,仅为1.1～1.4.     

高耐热PLLA/PDLA共混物的热性能和结晶结构研究

通过熔融共混法制备了一系列等比例聚左旋乳酸(PLLA)/聚右旋乳酸(PDLA)共混试样,采用差示扫描量热法(DSC)、核磁共振(13C-NMR)及广角X射线衍射(WAXD)等方法对共混产物进行了表征和研究分析.结果表明,等比例PLLA和PDLA熔融共混生成了立构复合物(stereocomplex,sc),同时部分均聚物发生酯交换反应,生成了立体嵌段物(stereoblock,sb),从而在DSC升温曲线上sc晶体处出现特殊的熔融双峰现象;随着熔融共混温度升高,sc晶体的生成率和结晶度逐渐下降;聚乳酸立构复合物的加工稳定性较好,二次加工后,sc晶体熔点基本不变,生成率和结晶度提高;由于sc晶体的存在,PLLA/PDLA共混物的耐热性能提高,退火热处理后耐热性能得到进一步提高.这对于开发高耐热聚乳酸及其加工应用具有重要的应用价值.