Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716, USA.
Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE 19716, USA.
J Chromatogr A. 2014 May 2;1340:33-49. doi: 10.1016/j.chroma.2014.02.072. Epub 2014 Mar 4.
A fully-mechanistic understanding of protein transport and sorption in chromatographic materials has remained elusive despite the application of modern continuum and molecular observation techniques. While measuring overall uptake rates in proteins in chromatographic media is relatively straightforward, quantifying mechanistic contributions is much more challenging. Further, at equilibrium in fully-loaded particles, measuring rates of kinetic exchange and diffusion can be very challenging. As models of multicomponent separations rely on accurate depictions of protein displacement and elution, a straightforward method is desired to measure the mobility of bound protein in chromatographic media. We have adapted fluorescence recovery after photobleaching (FRAP) methods to study transport and exchange of protein at equilibrium in a single particle. Further, we have developed a mathematical model to capture diffusion and desorption rates governing fluorescence recovery and investigate how these rates vary as a function of protein size, binding strength and media type. An emphasis is placed on explaining differences between polymer-modified and traditional media, which in the former case is characterized by rapid uptake, slow displacement and large elution pools, differences that have been postulated to result from steric and kinetic limitations. Finally, good qualitative agreement is achieved predicting flow confocal displacement profiles in polymer-modified materials, based solely on estimates of kinetic and diffusion parameters from FRAP observations.
尽管现代连续体和分子观测技术已经得到了应用,但对于蛋白质在色谱材料中的传输和吸附的完全机械理解仍然难以捉摸。虽然在色谱介质中测量蛋白质的总体吸收速率相对简单,但定量描述其机制贡献则更加困难。此外,在完全加载的颗粒中达到平衡时,测量动力学交换和扩散的速率可能会非常具有挑战性。由于多组分分离的模型依赖于对蛋白质置换和洗脱的准确描述,因此需要一种直接的方法来测量色谱介质中结合蛋白质的迁移率。我们已经采用荧光恢复后光漂白(FRAP)方法来研究单个颗粒中蛋白质在平衡状态下的传输和交换。此外,我们还开发了一种数学模型来捕获控制荧光恢复的扩散和解吸速率,并研究这些速率如何随蛋白质大小、结合强度和介质类型而变化。重点解释了聚合物改性和传统介质之间的差异,在前者中,其特征是快速吸收、缓慢置换和较大的洗脱池,这些差异被认为是由于空间和动力学限制所致。最后,仅基于 FRAP 观察得出的动力学和扩散参数的估计,就可以很好地定性预测聚合物改性材料中的流动共聚焦置换剖面。