Department of Chemical Sciences, University of Trieste, Trieste, Italy.
Magn Reson Chem. 2011 Apr;49(4):195-8. doi: 10.1002/mrc.2732. Epub 2011 Mar 9.
DOSY is a recognized, efficient technique in the analysis of mixtures. It relies on the differences in self-diffusion coefficients, which are determined by the molecular size. Nowadays, efforts are directed towards devising matrices able to interact with the components of the mixture with differential affinity, and therefore capable to interfere with the diffusion processes and to display resolving power towards species of close, or even equal molecular weight, like isomers. Usually, commercial nonionic surfactants are mixtures of oligomeric species, since the head group, which is a short polyoxyehtylene chain, is somewhat polydisperse. The embedment of Igepal CA-520, 5 polyoxyethylene iso-octylphenyl ether, in an inverse microemulsion led to the separation of (1)H signals of the various oligomeric components. This ensued from the differential partitioning between the oil and the surface of the inverse micelles, which depends on the ethyleneoxide number (EON) of the head groups. Thus, it was possible to ascertain that the length distribution of the polyethyleneoxide chains is ingood agreement with the Poisson distribution theoretically predicted for the polymerization of ethylene oxide. The DOSY spectrum contributed to the assignment of the signals and afforded the partition degree, between the two environments, for each individual oligomeric species, providing further insight into nonionic inverse microemulsions, at present widely employed reaction media in the nanotechnological syntheses.
DOSY 是混合物分析中一种公认的高效技术。它依赖于自扩散系数的差异,而自扩散系数由分子大小决定。如今,人们致力于设计能够与混合物的成分以不同亲和力相互作用的基质,从而能够干扰扩散过程,并对具有相近甚至相等分子量的物质(如异构体)显示出分辨率。通常,商业非离子表面活性剂是低聚物的混合物,因为亲水头基(短的聚氧乙烯链)在某种程度上是多分散的。非离子表面活性剂 Igepal CA-520(5 聚氧乙烯异辛基苯基醚)在反胶束中的嵌入导致了各种低聚物成分的(1)H 信号的分离。这是由于油相与反胶束表面之间的不同分配,这取决于头基的乙氧基化数(EON)。因此,可以确定聚氧乙烯链的长度分布与理论上预测的乙氧化聚合的泊松分布非常吻合。DOSY 光谱有助于信号的分配,并提供了每个低聚物物种在两种环境之间的分配程度,进一步深入了解非离子反胶束,目前在纳米技术合成中广泛使用的反应介质。