Department of Chemistry, University of Michigan, Ann Arbor, MI 48109, USA.
Analyst. 2020 Jul 7;145(13):4484-4493. doi: 10.1039/c9an02533b. Epub 2020 May 12.
Characterization of copolymers requires the measurement of two distributions-molecular weight (MW) and chemical composition (CC). Molecular weight distributions (MWD) are traditionally determined using size exclusion chromatography (SEC) run under isocratic solvent conditions. Chemical composition distributions (CCD) are often determined using liquid adsorption chromatography (LC) with solvent gradients. The use of solvent gradients, however, often limits options of compatible detectors. A gradient compatible, universal linear mass concentration detector is a longstanding unmet need. Many industrially-relevant polymers lack chromophores or other discriminating moieties requiring detectors with a universal response. Differential refractive index (dRI) is incompatible with gradient elution due to its small dynamic range. Charged aerosol detectors (CAD) and evaporative light scattering detectors (ELSD) are probably the most promising options for gradient elution detection, but both suffer from a nonlinear mass concentration response. Silicon photonic microring resonators are optical sensors that are responsive to changes in the local refractive index (RI). The substantial dynamic range of this technology makes it attractive for refractive index-based detection during solvent gradient elution. Previously, the microring resonator platform was used as a SEC detector to characterize the MWD of broadly dispersed polystyrene (PS) standards. In this study, we demonstrate the gradient compatibility of the microring resonator platform for polymer detection by quantifying the CCD of polymer blend components. Control experiments were run with UV and ELSD detection, highlighting the uniqueness of the platform as a linear mass concentration detector with a universal detector response.
共聚物的特性需要测量两个分布——分子量 (MW) 和化学组成 (CC)。分子量分布 (MWD) 传统上是使用等度溶剂条件下运行的尺寸排阻色谱 (SEC) 来测定的。化学组成分布 (CCD) 通常使用带有溶剂梯度的液相吸附色谱 (LC) 来测定。然而,溶剂梯度的使用往往限制了兼容检测器的选择。梯度兼容的通用线性质量浓度检测器是一个长期未满足的需求。许多工业相关的聚合物缺乏发色团或其他有区别的基团,需要具有通用响应的检测器。由于动态范围小,差示折射率 (dRI) 与梯度洗脱不兼容。由于其小的动态范围,带有梯度洗脱的 charged aerosol detector (CAD) 和 evaporative light scattering detector (ELSD) 可能是梯度洗脱检测最有前途的选择,但两者都存在非线性质量浓度响应。硅光子微环谐振器是对局部折射率 (RI) 变化敏感的光学传感器。该技术的大动态范围使其在溶剂梯度洗脱过程中基于折射率的检测具有吸引力。以前,微环谐振器平台被用作 SEC 检测器来表征广泛分散的聚苯乙烯 (PS) 标准的 MWD。在这项研究中,我们通过定量聚合物共混物成分的 CCD 来证明微环谐振器平台在聚合物检测方面的梯度兼容性。进行了 UV 和 ELSD 检测的对照实验,突出了该平台作为具有通用检测器响应的线性质量浓度检测器的独特性。