Uncovering Fundamental Transport Principles in Novel, Ultraclean Lignin-Based Hydrogels for Bioseparations

揭示用于生物分离的新型超净木质素水凝胶的基本传输原理

• 批准号: 1915787
• 负责人: Eric Davis
• 金额: $ 46.57万
• 依托单位: Clemson University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-08-15 至 2023-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1915787&HistoricalAwards=false
• 关键词: Uncovering; Fundamental; Transport; Principles; Novel

Biological products, such as proteins and nucleic acids, must often be separated from a solution as part of an industrial purification process. One approach to this separation is to pass the fluid containing the biological product through a membrane made of hydrogels. Hydrogels are a three-dimensional network of polymeric chains that are designed to absorb water-based solutions. Lignin, a plant-based polymer, can be incorporated into the hydrogel network to enhance the membrane's ability to capture biological molecules from the solution. However, there is relatively little information on how adding lignin to the hydrogel changes the three-dimensional structure of the resulting composite membrane. Additionally, conventional methods used to recover lignin from plant material results in low-purity lignin with unpredictable chemical structure. Using heterogeneous lignin in the production of hydrogel membranes will result in composite materials with ill-defined network structures, making it difficult to design membranes for real applications. The goal of this project is to clarify how introducing lignin into hydrogels influences the resulting structure. The project will make use of a new lignin purification process to obtain ultraclean lignin with controlled molecular architecture. By systematically varying the polymeric hydrogel structure with lignin, fundamental relationships between membrane structure, molecular interactions, and protein transport through the membrane will be uncovered. The anticipated outcomes of this project have the potential substantially impact next-generation materials fabrication strategies by establishing parameters for predictive materials design of novel, composite hydrogels. Composite hydrogel membranes are finding use in applications ranging from biological molecule separation, tissue engineering, to protein delivery. The research efforts are closely tied to educational outreach initiatives that aim to engage and inspire the next generation of engineers and scientists through the development of a 'membrane module' related to bioseparations and water purification. The aim of the proposed research is to uncover the fundamental transport principles and key network structure-property relationships underlying the protein separation and immobilization performance of an emerging class of novel, lignin-based hydrogels. This aim will be achieved by leveraging fractionated lignins of low dispersity and controlled molecular weights to systematically vary the network structure (i.e., mesh size) of the composite hydrogels. By tuning both the chemical functionality and the molecular weight of the lignins, the role of both structure and molecular-scale interactions on membrane performance can be elucidated. The lignin fractions will be modified with functional groups that allow them to participate in the crosslinking reaction that forms the network structure of the hydrogel. The separation/binding efficiency of various biomacromolecules from the composite membranes will be investigated using a combination of in situ permeation experiments with longer-term, 'bind-and-release' experiments. The water transport and hydrated mechanical properties of composite membranes will be characterized using a mechanics-based technique, poroelastic relaxation indentation. Using a Darcy's law framework, the average mesh (pore) size of the hydrated network structure can be determined. The structure of the hydrated membranes will be independently characterized using small-angle neutron scattering, and the results will be compared to those obtained from indentation experiments. Additionally, molecular-level interactions between the biomacromolecules and the composite hydrogels, as well as protein dynamics within the membrane, will be captured using infrared spectroscopy and quasi-elastic neutron scattering, respectively. These findings have the potential to impact the design of new materials in several other membrane-based separations processes, such as materials for water purification and desalination. Finally, the research component of this proposal is closely tied to STEM-based outreach objectives that seek to integrate findings and materials from this research into departmental outreach efforts related to bioseparations and water purification.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

生物产物（例如蛋白质和核酸）通常必须与溶液分离，作为工业纯化过程的一部分。这种分离的一种方法是通过含有水凝胶制成的膜通过含有生物产物的液体。水凝胶是一个三维聚合链网络，旨在吸收水基溶液。木质素是一种基于植物的聚合物，可以掺入水凝胶网络中，以增强膜从溶液中捕获生物分子的能力。但是，关于如何在水凝胶中添加木质素如何改变所得复合膜的三维结构的信息相对较少。另外，用于从植物材料中回收木质素的常规方法会导致低纯木质素具有不可预测的化学结构。在水凝胶膜的生产中使用异质性木质素将导致具有不确定的网络结构的复合材料，因此很难为实际应用设计膜。该项目的目的是阐明将木质素引入水凝胶中如何影响所得结构。该项目将利用新的木质素纯化工艺来获得具有控制分子结构的超级木质素。通过系统地用木质素改变聚合物水凝胶结构，将发现膜结构，分子相互作用和通过膜传输之间的基本关系。该项目的预期结果具有潜在的潜在影响下一代材料制造策略，通过建立用于新型复合水凝胶的预测材料设计的参数。复合水凝胶膜正在发现从生物分子分离，组织工程到蛋白质递送的应用。研究工作与教育外展计划紧密相关，旨在通过开发与生物散热和水净化有关的“膜模块”来吸引和激发下一代工程师和科学家。拟议研究的目的是揭示蛋白质分离和固定性能的基本运输原理和关键的网络结构 - 基于新兴的基于木质素水凝胶的蛋白质分离和固定性能。通过利用低色散性和受控分子量的分离木质素来实现此目标，以系统地改变复合水凝胶的网络结构（即网状尺寸）。通过调整木质素的化学功能和分子量，可以阐明结构和分子尺度相互作用对膜性能的作用。木质素馏分将通过功能组进行修改，使它们可以参与形成水凝胶网络结构的交联反应。将使用与长期，“结合及释放”实验的原位渗透实验的组合研究各种生物ac骨分子与复合膜的分离/结合效率。复合膜的水传输和水合力学特性将使用基于机械的技术，孔隙弹性弛豫凹痕进行表征。使用Darcy的法律框架，可以确定水合网络结构的平均网格（孔）大小。水合膜的结构将使用小角度的中子散射独立表征，并将结果与​​从压痕实验获得的结果进行比较。此外，将分别使用红外光谱和准弹性中子散射来捕获生物大分子与复合水凝胶以及膜内蛋白质动力学之间的分子水平相互作用。这些发现有可能在其他几种基于膜的分离过程中影响新材料的设计，例如用于净水和脱盐的材料。最后，该提案的研究组成部分与基于STEM的外展目标紧密相关，该目标试图将这项研究的发现和材料整合到与生物份额和水净化有关的部门外展工作中。该奖项反映了NSF的法定任务，并认为通过使用该基金会的知识分子和更广泛的影响来通过评估来获得支持，并被认为是值得的。

项目成果

Ultraclean hybrid poplar lignins via liquid–liquid fractionation using ethanol–water solutions

使用乙醇-水溶液通过液-液分馏获得超净混合杨木质素

• DOI: 10.1557/s43579-021-00090-4
• 发表时间: 2021
• 期刊: MRS Communications
• 影响因子: 1.9
• 作者: Tindall, Graham;Lynn, Bronson;Fitzgerald, Carter;Valladares, Lucas;Pittman, Zachariah;Bécsy-Jakab, Villő;Hodge, David;Thies, Mark
• 通讯作者: Thies, Mark

Fractionating and Purifying Softwood Kraft Lignin with Aqueous Renewable Solvents: Liquid–Liquid Equilibrium for the Lignin–Ethanol–Water System

使用水性可再生溶剂分馏和纯化软木硫酸盐木质素：木质素-乙醇-水系统的液-液平衡

• DOI: 10.1002/cssc.202000701
• 发表时间: 2020
• 期刊: ChemSusChem
• 影响因子: 8.4
• 作者: Tindall, Graham W.;Chong, Josh;Miyasato, Evan;Thies, Mark C.
• 通讯作者: Thies, Mark C.

Novel composite hydrogels containing fractionated, purified lignins for aqueous-based separations

• DOI: 10.1039/d0ta09046h
• 发表时间: 2021-01-14
• 期刊: JOURNAL OF MATERIALS CHEMISTRY A
• 影响因子: 11.9
• 作者: Gregorich, Nicholas;Ding, Junhuan;Davis, Eric M.
• 通讯作者: Davis, Eric M.

Liquefying Lignins: Determining Phase-Transition Temperatures in the Presence of Aqueous Organic Solvents

液化木质素：测定水性有机溶剂存在下的相变温度

• DOI: 10.1021/acs.iecr.1c02044
• 发表时间: 2021
• 期刊: Industrial & Engineering Chemistry Research
• 影响因子: 4.2
• 作者: Tindall, Graham W.;Temples, Spencer C.;Cooper, Mikhala;Bécsy-Jakab, Villő Enikő;Hodge, David B.;Nejad, Mojgan;Thies, Mark C.
• 通讯作者: Thies, Mark C.

Comparison of Bulk- vs Layer-by-Layer-Cured Stimuli-Responsive PNIPAM–Alginate Hydrogel Dynamic Viscoelastic Property Response via Embedded Sensors

• DOI: 10.1021/acsapm.2c00634
• 发表时间: 2022-07
• 期刊: ACS Applied Polymer Materials
• 影响因子: 5
• 作者: Yang Liu;Keturah Bethel;Manjot Singh;Junru Zhang;R. Ashkar;E. Davis;Blake N. Johnson