Simple N‐Heterocyclic Carbenes as Ligands in Ullmann‐Type Ether and Thioether Formations

A simple N‐heterocyclic carbene (NHC) derived from 1‐methyl‐3‐ethylimidazolium tetrafluoroborate was found to be an efficient ligand for a range of copper‐catalyzed cross‐coupling reactions, leading to the formation of aromatic ethers and thioethers.

     

EDTA辅助制备高活性费托合成催化剂

费托合成（FTS）对天然气、煤炭和生物质向清洁运输燃料和增值化学品的转化至关重要。传统上,用于FTS的负载型铁催化剂主要是以氧化铝和二氧化硅为载体。然而,金属与载体的相互作用阻碍了活性相碳化铁的形成,使得催化剂活性较低。本文通过乙二胺四乙酸（EDTA）络合浸渍制备了Fe/Al₂O₃催化剂,通过带正电荷的羟基（OH{}_{\mathrm{2}}^{+}）与[Fe(EDTA)]^-配合物阴离子之间的库仑相互作用来提高氧化铝载体上铁物种的分散度。采用X射线衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、比表面积（BET）、原位红外（In-situ IR）等手段进行表征分析。结果表明,添加EDTA有助于增强Fe的抗烧结性。在煅烧络合浸渍制备样品的过程中,EDTA可以分解为具有还原性质的有机小分子,将催化剂中的铁物种还原为Fe²⁺,有利于催化剂的还原;更多活性中心增强了催化剂对CO的吸附量。原位红外实验表明,EDTA辅助制备的催化剂更容易富集活性物种,从而提高CO的转化率。调节体系中碱金属钠的含量改善了烃内产物分布。在较低的氢碳比（H₂/CO=1/1）下,EDTA络合制备的Fe-Na/Al₂O₃催化剂显示出高的CO转化率（88.5%）以及最大的C₂~C₄=和C₅~C₁₁选择性,总选择性达71.2%。     

前驱体结构对多环芳烃选择性开环Pt/Beta催化剂的影响

以海绵铂为原料合成出［Pt（NH₃）₆］Cl₄络合物,采用热重分析（TG）、扫描电镜-能谱（SEM-EDS）、紫外-可见分光光度计（UV-Vis）、质谱（MS）、X射线光电子能谱（XPS）等手段确定了［Pt（NH₃）₆］Cl₄的结构组成;以H₂PtCl₆、Pt（NH₃）₄Cl₂和［Pt（NH₃）₆］Cl₄为前驱体,采用等体积浸渍法制得Pt/Beta催化剂,采用X射线衍射（XRD）、X射线荧光光谱（XRF）、氨程序升温脱附（NH₃-TPD）、氢氧滴定（H₂-O₂）、透射电镜（TEM）、氢气程序升温脱附（H₂-TPD）等表征了Pt/Beta催化剂的物化性质,并考察了Pt/Beta催化剂的多环芳烃选择性开环性能。结果表明,［Pt（NH₃）₆］Cl₄络合物具有更高的“抗自还原”能力,可从前驱体结构上降低铂氨前驱体受热分解时的自还原现象。前驱体结构对铂纳米颗粒的几何尺寸及分布有较大影响,一方面络合物的价态显著影响前驱体与分子筛间的静电作用,进而影响铂纳米颗粒的落位与尺寸;另一方面络合物的空间结构影响前驱体在分子筛微孔中的分布,影响铂纳米颗粒的Ostwald熟化速率。前驱体结构可调变Pt/Beta催化剂的双功能匹配关系,显著影响Pt/Beta催化剂转化甲基萘的活性、稳定性,采用［Pt（NH₃）₆］Cl₄前驱体制备的Pt/Beta催化剂具有更优的活性及长周期稳定性。     

吲哚席夫碱类衍生物的合成及其抗HIV-1活性研究

设计、合成吲哚席夫碱类衍生物并研究其抗HIV-1活性。以3-吲哚甲醛衍生物为原料,在碱催化下与芳香胺发生缩合反应合成吲哚席夫碱类化合物,并采用通过 MTT 法测试了目标化合物在MT-4 细胞内的抗 HIV-1病毒株的活性。 合成了32个吲哚席夫碱类衍生物,其结构均通过1H NMR和MS加以确证。初步的生物活性结果测试表明,所合成的吲哚席夫碱类化合物对HIV-1均有优秀的抑制活性,并具有广谱的抗HIV-1活性。其中化合物31 (EC50 = 0.06 mol/L)展现出了最强的抗HIV-1活性,与阳性药物地拉韦啶 (DLV, EC50 = 0.57 mol/L)相当;同时,化合物31具有非常低的毒性,选择指数 (SI)高达2500,明显高于地拉韦啶 (DLV, SI = 1272.9)和依法韦仑 (EFV, SI = 321)。将吲哚和席夫碱两个药效团,能够得到高效、低毒的HIV-1逆转录酶抑制剂,为今后发展新型的HIV-1抑制剂提供了新思路。     

填充油中多环芳烃含量的测定

建立采用核磁共振波谱法测定填充油中多环芳烃湾区氢(H_Bay)含量的方法。结果表明,在称样量为0.1 g、处理方式为样品经硅胶柱纯化后用氘代氯仿溶解的条件下,采用核磁共振波谱法进行测定,并按给定公式计算得到H_Bay含量,该方法的测试结果具有很好的重复性和再现性。     

Asymmetric Contribution of Aromatic Interactions Stems from Spatial Positioning of the Interacting Aryl Pairs in β‐Hairpins

Isolated aromatic interactions in designed octapeptide β‐hairpin scaffolds display a near‐universal T‐shaped face‐to‐edge geometry in all positional permutations, with the exception of aryl‐Trp interactions. The heterogeneous asymmetric indole ring of Trp competes for a “shielding” face geometry, which lowers the scaffold stability in FtE aryl‐Trp pairs. Assessment of the contributions of aryl pairs (in the absence of solvent‐driven interactions) to the overall β‐hairpin structure reveals the superiority of Trp‐Phe and Trp‐Tyr contributions over the well‐established scaffold stabilization by Trp‐Trp.     

异丙氧基官能化聚芳酰胺高温热处理高效制备聚对苯撑苯并双噁唑

针对高性能纤维聚对苯撑苯并双噁唑（PBO）现有制备方法单体合成困难、聚合工艺复杂及纺丝难度大等问题,采用高温热处理方法制备PBO. 合成4,6-二异丙氧基-1,3-二氨基苯作为单体,将其与对苯二甲酰氯缩聚制得PBO前驱体-异丙氧基官能化聚芳酰胺;该前驱体通过静电纺丝制成纳米纤维薄膜,并在350 ℃与氩气气氛等条件下,通过热处理成功实现了前驱体主链的分子内环化、制得目标PBO,制备出的PBO具有高达562 ℃的热降解温度。该方法摆脱了对传统易氧化4,6-二氨基-间苯二酚单体的依赖,显著降低了聚合和成型难度,丰富了PBO的制备方法学。     

Thermal stabilities and flame retardancies of phloroglucinol‐based organo phosphates when applied to polycarbonate

A series of organo phosphorus flame retardants (FRs) based on aromatic phosphate and cyclic phosphate were synthesized in an attempt to develop an efficient FR for polycarbonate. Their successful synthesis was confirmed by FT‐IR and ¹ H and ³¹P NMR. Their thermal stability and flame retarding efficiency as a single‐component additive were investigated and compared with the commercial FR, resorcinol bis(diphenyl phosphate). The thermogravimetric analysis results revealed that the aromatic phosphate synthesized in this study, phloroglucinol diphenyl phosphate (PDP), shows a higher thermal degradation temperature and better flame retardancy even though it has a lower P content than cyclic phosphate‐based FRs. The flame retarding efficiency was evaluated by the UL‐94 test method. The V‐0 rating was achieved at a PDP loading of 2 wt% in polycarbonate in the presence of an anti‐dripping agent (1 wt%), which is better than that of resorcinol bis(diphenyl phosphate) and cyclic phosphate‐based FRs. The high thermal stability and P–OH generation tendency is responsible for the better flame‐retarding performance of PDP. The degradation path of PDP is also discussed. Copyright © 2012 John Wiley & Sons, Ltd.