用于直接从空气中捕获 CO2 的氨基聚合物/氧化物复合材料的研究通常集中在作为氨基聚合物的原型聚(乙烯亚胺)(PEI)上。然而,众所周知,PEI 在升高的温度下会氧化降解。这种降解归因于仲胺的存在,仲胺在氧化时会失去其 CO2 捕获能力。在这里,我们展示了在二氧化硅支持的线性和树枝状结构中使用小分子聚(丙烯亚胺)(PPI)作为直接从空气中捕获 CO2 的吸附材料。无论胺负载或氨基聚合物结构如何,发现 PPI 基吸附剂比 PEI 基吸附剂更有效地捕获 CO2。此外,发现 PPI 比 PEI 更耐氧化降解,即使含有仲胺,如 FTIR、NMR、和 ESI-MS 研究。这些结果表明,由于对吸附剂再生条件的耐受性增加,基于 PPI 的 CO2 吸附剂可能允许更长的吸附剂工作寿命,并表明仲胺的存在可能并不意味着所有氨基聚合物都会氧化降解。
Parameters Influencing the Release of Tertiary Alcohols from the Surface of “Spherical” Dendrimers and “Linear” Stylomers by Neighbouring-Group-Assisted Hydrolysis of 2-Carbamoylbenzoates
作者:Alain Trachsel、Jean-Yves de Saint Laumer、Olivier P. Haefliger、Andreas Herrmann
DOI:10.1002/chem.200801350
日期:2009.3.9
Investigation of the controlled release of tertiaryalcoholsfrom the surface of dendrimers and “stylomers” as polymer model systems (see scheme) showed that the polarity of the conjugates and structural modifications in close proximity to the release unit have a stronger influence on the rates of hydrolysis than the size (generation) or shape (linear or spherical) of the macromolecules.
The present invention provides crosslinked amine polymers effective for binding and removing bile salts from the gastrointestinal tract. These bile acid binding polymers or pharmaceutical compositions thereof can be administered to subjects to treat various conditions, including hypercholesteremia, diabetes, pruritus, irritable bowel syndrome-diarrhea (IBS-D), bile acid malabsorption, and the like.
Influence of the distance between ionizable groups on the protonation behavior of various hexaamines
作者:Rene´ C. van Duijvenbode、Anton Rajanayagam、Ger J. M. Koper,、Michal Borkovec、Wolfgang Paulus、Ulrich Steuerle、Lukas Häu
DOI:10.1039/a907397c
日期:——
A synthesis route for N,N,N′,N′-tetraaminoethyl-1,2-ethylenediamine, N,N,N′,N′-tetraaminopropyl-1,2-ethylenediamine, N,N,N′,N′-tetraaminopropyl-1,3-propylenediamine and N,N,N′,N′-tetraaminopropyl-1,4-butylenediamine is presented. These molecules differ from each other in the number of carbon atoms between the six amino groups. This results in different protonation behavior. Potentiometric titrations are performed in 0.1 M and 1.0 M KCl, and the six macroscopic protonation constants are obtained from these curves. An Ising model with a limited number of microscopic protonation constants and short-ranged pair interactions describes the protonation behavior quantitatively. The results are compared to those of other, similar molecules. The advantage of the Ising model over empirical relations such as the Taft equations is the more systematic approach with which the titration curves of more complex molecules can be described. The values for the Ising model parameters obtained here can be used to predict the protonation behavior of more complex, in particular larger, polyamines.
本文介绍了一种合成N,N,N′,N′-四氨基乙基-1,2-乙二胺、N,N,N′,N′-四氨基丙基-1,2-乙二胺、N,N,N′,N′-四氨基丙基-1,3-丙二胺和N,N,N′,N′-四氨基丙基-1,4-丁二胺的合成路线。这些分子中六个氨基之间的碳原子数不同,导致它们具有不同的质子化行为。在0.1 M和1.0 M KCl中进行电位滴定,从这些曲线中获得了六个宏观质子化常数。采用有限数量的微观质子化常数和短程配对相互作用的Ising模型,可以定量描述质子化行为。将结果与其他类似分子的结果进行了比较。与Taft方程等经验关系式相比,Ising模型在描述更复杂分子的滴定曲线时采用了更系统的方法。这里获得的Ising模型参数值可以用于预测更复杂、特别是更大的多胺分子的质子化行为。
End-on and Side-on Nematic Liquid Crystal Dendrimers
作者:Laura Pastor、Joaquín Barberá、Mark McKenna、Mercedes Marcos、Rafael Martín-Rapún、José Luis Serrano、Geoffrey R. Luckhurst、Azizah Mainal
DOI:10.1021/ma048450p
日期:2004.12.1
A group of nematic materials based on poly(propyleneimine) dendrimers (PPI) containing two types of mesogenic subunits were synthesized. The presence of different types of mesogenic group, the topology of the attachment to the core (end-on and side-on), and the chemical nature of the linking connection to the PPI scaffold (imine or amide) were used to tailor the mesomorphic properties. The materials
合成了一组基于含两种介晶亚基的聚(亚丙基亚胺)树状大分子(PPI)的向列材料。不同类型的介晶基团的存在,与核的连接的拓扑结构(端对端和侧对面)以及与PPI支架(亚胺或酰胺)的连接连接的化学性质用于定制介晶特性。材料通过多种技术进行了表征,包括1 H,13C NMR光谱,GPC,MALDI-TOF MS,DSC,POM和X射线衍射。发现大多数材料一旦经历了第一次向各向同性相的转变,就会抑制其结晶状态。大多数化合物在接近或低于室温的温度下会显示出玻璃化转变,并伴有宽温度范围的中间相。合成的所有侧向树枝状大分子均显示向列型中间相,而端向树枝状大分子则根据介晶单元末端链的长度(n = 2、4、5为向列型)显示不同的中间相。的2使用1 H NMR技术来研究由侧置上形成树枝状向列相的对称性(ģ= 3)。这些研究表明,向列相的对称性是单轴的。它们还允许研究相的取向顺序和场致指向矢对准的速率。
Synthesis of Heterobinudear Cu(II)Ni(II) Complexes with Bis(tetraazamacrocycle)
作者:Katsura Mochizuki、Yumiko Endoh
DOI:10.1246/bcsj.62.936
日期:1989.3
A new series of heterobinudear Cu(II)Ni(II) complexes with bis(tetraazamacrocycle), i.e., 7,7′-polymethylenebis[2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),2,11,13,15-pentaene]copper(II)nickel(II) perchlorates with polymethylene bridges with a length of 2–6-C, were synthesized by a template reaction.