Polymeric aluminum porphyrin: Controllable synthesis of ultra-low molecular weight CO2-based polyols

Carbon dioxide-based polyols with ultra-low molecular weight (ULMW, M_n < 1000 g/mol) are emergent polyurethane precursors with economic and environmental benefits. However, the lack of effective proton-tolerant catalytic systems limits the development of this field. In this work, the polymeric aluminum porphyrin catalyst (PAPC) system was applied to the copolymerization of CO₂ and propylene oxide, where sebacic acid, bisphenol A, poly(ethylene glycol), and water were used as chain transfer agents to achieve the controlled synthesis of CO₂-polyols. The molecular weight of the resulting CO₂-polyols could be facilely regulated in the range of 400–930 g/mol at low catalyst loadings, fully demonstrating its catalytic advantages of high activity, high product selectivity, and excellent proton tolerance of PAPC. Meanwhile, the catalytic efficiency of PAPC could reach up to 2.1–5.2 kg/g under organic CTA conditions, even reaching 1.9 kg/g using water as the CTA. The cPC content could be controlled within 1.0 wt% under the optimized conditions, indicating the excellent controllability of the PAPC system. ULMW CO₂-polyols combines the advantages of low viscosity (∼3000 mPa s at 25 °C), low glass transition temperature (∼−73 °C), and high carbonate unit content (∼40%), which is important for the development of high-performance polyurethanes.     

多库酯类离子液体作为镁合金润滑剂的摩擦学性能及机理研究

合成了以季铵盐、季鏻盐和烷基咪唑为阳离子,琥珀酸二异辛酯磺酸为阴离子的五种多库酯类离子液体,考察了其理化性能,研究其作为钢-镁合金摩擦副润滑剂的摩擦学性能,并与常规离子液体1-丁基-3-甲基咪唑双(三氟甲基磺酰基)亚胺(L-F104)作对比. 结果表明:该类离子液体具有良好的黏温性能和热稳定性,并且与L-F104相比,对镁合金腐蚀较轻,且具有优异的减摩抗磨性能;接触电阻和磨斑表面元素分析结果表明该类离子液体能够在镁合金表面形成有效的吸附膜,且摩擦试验过程中形成了MgSO₄和MgO等物质的摩擦化学反应膜,能够阻止摩擦过程中金属表面间的直接接触,从而起到减摩抗磨效果.      

全氟聚醚羧酸铵离子液体的润滑性能及润滑机理研究

设计制备了三种全氟聚醚羧酸铵离子液体,在微动振动摩擦磨损试验机上考察了其在不同温度下对钢/铜锡合金以及钢/钢摩擦副的润滑性能,并与全氟聚醚(PFPE)和全氟聚醚羧酸(PFPEC)进行了对比. 通过测量接触角表征了所制备离子液体对金属表面的润湿性,通过测试摩擦试验过程中接触电阻的变化分析了摩擦过程中摩擦膜的变化;采用扫描电镜和X射线光电子能谱仪分别对磨斑表面形貌和元素状态进行了表征. 结果表明:作为钢/铜锡合金摩擦副的润滑剂时,全氟聚醚羧酸铵离子液体在常温下的润滑性能与PFPE和PFPEC相差不大,但在高温条件下表现出更为优异的减摩抗磨性能;而作为钢/钢摩擦副的润滑剂,其在常温、高温条件下均表现出优于PFPE以及PFPEC的减摩抗磨性能. 多种物理化学表征研究表明该类离子液体优异的减摩抗磨性能归因于其在金属表面优异的吸附性能以及稳定摩擦化学反应膜的形成.      

不同结构Cu_2O多晶的合成及其对高氯酸铵热分解的催化作用

利用均相反应器,在没有添加剂的条件下合成了具有多孔结构的Cu2O微球.考察了合成时间以及反应器旋转速度对Cu2O微球结构的影响.通过增加聚乙烯吡咯烷酮(PVP)的用量,使得Cu2O从多孔微球转变为立方体孪晶,最终形成十四面体孪晶结构.同时,将不同结构的Cu2O多晶应用于催化高氯酸铵(AP)的热分解,结果表明:多孔Cu2O微球较其它结构的Cu2O对AP的热分解具有更高的催化活性,使得AP的低温分解温度降低了37.4°C,而AP在低温阶段的分解量也由8.7%增加至49.0%.     

高效液相色谱法测定硫酸沙丁胺醇

利用高效液相色谱仪-电子捕获检测器(HPLC-ECD)测定了市售片剂硫酸沙丁胺醇的含量.结果表明,利用HPLC-ECD技术测定硫酸沙丁胺醇的线性范围为0.944~33.8mg·L-1(r=0.999 6);回收率为99.0%~107.8%(RSD≤4.6%).该法可用于测定片剂的硫酸沙丁胺含量.     

A 2D Wavy Parquet Architecture Based on the Biphenyl-3,3’,4,4’-tetracarboxylic Acid and Bis(2-benzimidazole)alkanes Ligands

A double-T-shaped ligand (H4BPTC) and bis(2-benzimidazole)alkanes as the spacers have been firstly used to direct the assembly of a 2D coordination polymer with wavy parquet network topology, [Zn(BPTC)0.5(H2C2EIm)(H2O)]n (1, C24H18ZnN4O5, Mr = 507.79, H4BPTC = biphenyl-3,3',4,4'-tetracarboxylic acid, H2C2EIm = 2,2'-(1,2-ethanediyl)-bis(1H-benzi- midazole), which was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/n with a = 1.1844(5), b = 1.4019(5), c = 1.4026(5) nm, β = 108.359(5)°, V = 2.2104(15) nm3, Z = 4, Dc = 1.526 g/cm3, μ(MoKα) = 1.156 mm-1, F(000) = 1040, S = 1.038, the final R = 0.0427 and wR = 0.0793 for 3834 reflections with I > 2σ(I). The compound units are linked through BPTC ligands into a wavilness parquet 2D layer and further connected into a 3D framework via π-π packing interactions between the adjacent H2C2EIm ligands and weak N-H…O hydrogen bonding between uncoordinated carboxylate and the nitrogen atoms of H2C2EIm as well as the free water molecules.     

羧酸配体取代基对席夫碱型双核镝(Ⅲ)配合物结构和磁性的影响

以N-(2-羟基-3-甲氧基亚苄基)氨基脲(H2hms)与不同取代基的羧酸(RCOOH)为配体,合成了3例席夫碱类的中心对称双核镝基配合物[Dy₂(Hhms)₂(C(CH₃)₃COO)₂(H₂O)₄](NO₃)₂(1)、[Dy₂(Hhms)₂(C₁₄H₉COO)₂(C₂H₅OH)₂(CH₃OH)₂][ZnCl₄](2)和[Dy₂(Hhms)₂(C₆H₃(NH₂)₂COO)₂Cl₂]·2CH₃CN(3),并对其进行了结构和磁性表征。结构分析表明,配合物1和2保持了相似的单帽四方反棱柱配位构型,但1与2中羧酸与Dy(Ⅲ)键合的方式不同;配合物2和3保持了相似的酚氧和羧酸桥联结构,但由于配位小分子的不同,配合物3中Dy(Ⅲ)离子的配位几何构型与2有所不同。磁性测试结果表明,配合物3在零场下观察到显著的单分子磁体行为,具有磁翻转有效能垒96 K。相反,配合物1仅表现了快的量子隧穿弛豫行为,甚至配合物2没有单分子磁体的弛豫信号。借助结构特点和各向异性轴取向等关键信息,对3例配合物的磁构效关系进行了讨论。研究结果表明利用羧酸配体取代基能够实现对分子磁各向异性以及对称性的良好调控,从而提高镧系单分子磁体磁弛豫行为。     

Thermodynamic properties of laburnine in saline and glucose solutions

Laburnine’s dissolution behaviors in glucose and saline solution were studied by a micro-calorimetry method. The measured integral and differential heats of solution were utilized to build equations of the solute and the heat, so that dissolution thermodynamic equations and half-time periods, Δ_sol H _m, Δ_sol G _m, and Δ_sol S _m were obtained. The results show that this study does not only provide a simple method for the determination of the half-life period for a drug but also offer a theoretical reference for the clinical application of laburnine.     

Magnesium bistrifluoromethanesulfonimide as an efficient catalyst for the hydroalkylation of aromatic olefins with 1,3-diketones under solvent-free conditions

An efficient magnesium bistrifluoromethanesulfonimide[Mg(NTf_2)_2]catalyzed hydroalkylation of aromatic olefins with 1,3- diketones under solvent-free conditions has been developed.The reactions proceed smoothly to give the desired products in good yields in short reaction times.