Source: IOWA STATE UNIVERSITY submitted to NRP
MACROMOLECULAR ANALYSIS OF INDUSTRIAL PRODUCTS FROM AGRICULTURAL BIOMASS
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
ACTIVE
Funding Source
OTHER GRANTS
Reporting Frequency
Annual
Accession No.
1031417
Grant No.
2023-70410-41185
Cumulative Award Amt.
$222,050.00
Proposal No.
2023-05464
Multistate No.
(N/A)
Project Start Date
Sep 1, 2023
Project End Date
Aug 31, 2027
Grant Year
2023
Program Code
[EGP]- Equipment Grants Program
Recipient Organization
IOWA STATE UNIVERSITY
2229 Lincoln Way
AMES,IA 50011
Performing Department
(N/A)
Non Technical Summary
This project will acquire and manage a 2D HPLC-SEC system that comprehensively analyzes complex macromolecular mixtures by hydrodynamic volume (size exclusion chromatography, SEC) and chemical affinity (high performance liquid chromatography, HPLC). Such mixtures are common in the study of biological and agricultural systems. HPLC and SEC are very common and have been staples of chemistry and material science for decades with nearly all polymer research groups having one or more SECs. However, SECs are limited in the level of detail they provide, especially when exploring complex materials such as block copolymers, proteins, asphalt, and especially polymers produced from biomass.The instrument will overlap with at least 17 faculty, $30 MM in research, and at least 50 graduate students from the onset. The research supported overlaps with collaborations with other universities, private companies, non-profit organizations, and state entities. ISU maintains millions of dollars of equipment throughout individual researchers and service centers; letters of institutional support from the central administration and the Chemical and Biological Engineering (CBE) department are attached committing to the operation of the 2D Acquity. The 2D Acquity will join PolyCy (https://www.polycy.cbe.iastate.edu/lab-facilities/), a service center hosted in shared CBE lab-space managed by PI Cochran for roughly 10 years, which operates over $1.5 MM in equipment supporting polymer-related research (Rheometer, DSC, Viscometers, Extruders, Injection Molders, Flash Chromatography, SEC, FTIR, MFR, etc.). PolyCy instrumentation is protected by warranty and/or service contracts to ensure regular preventative maintenance and prompt repairs as needed. Instrument access, training, maintenance, and education is supported by four Ph. D. level scientists, including Co-PD Dr. Forrester, to ensure proper user training and compliance with operating procedures. User fees support these value-added services.
Animal Health Component
45%
Research Effort Categories
Basic
45%
Applied
45%
Developmental
10%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
40272992020100%
Knowledge Area
402 - Engineering Systems and Equipment;

Subject Of Investigation
7299 - Research equipment and methods, general/other;

Field Of Science
2020 - Engineering;
Goals / Objectives
This project will acquire a Waters Acquity / Polymer Standards Service 2D HPLC-SEC system (2D Acquity) to comprehensively analyze complex macromolecular mixtures by hydrodynamic volume (size exclusion chromatography, SEC) and chemical affinity (high performance liquid chromatography, HPLC). HPLC and SEC are very common and have been staples of chemistry and material science for decades with nearly all polymer research groups having one or more SECs. However, SECs are limited in the level of detail they provide, especially when exploring complex materials such as block copolymers, proteins, asphalt, and especially polymers produced from biomass.We have an initial user pool comprised of 17 senior investigators managing over 50 researchers from 4 colleges and 8 departments that will thrive with new capabilities offered by the 2D Acquity. It accomplishes two tandem tasks, allowing for never-before-discovered information about numerous research topics: Firstly, chemical separation through HPLC yields composition and chemical affinity information; subsequently, SEC yields the molecular weight distribution of each slice of the HPLC chromatogram to enable unparalleled insights into the macromolecular analyte. For example, two compounds with different chemical structures and similar/overlapping hydrodynamic volumes can be resolved in 2D but not 1D.17 This provides unprecedented understanding of complex mixtures that are common in research, especially with biomass products. These integrated capabilities make the instrument crucial to three Core areas of collaborative agricultural materials research: (1) Derived from Biomass (2) Biomass Modified Geotechnical and Construction Material (3) Fundamental Analysis of Complex Polymer Structures.
Project Methods
The instrument requirements will be formatted into a Request for QuotationVendors will make proposals to supply the instrumentationISU will select the bid that best meets the needs of the project.ISU will work with the vendor to install the instrumentation in Sweeney Hall and train the equipment manager and first users.The instrument details will be published athttps://www.polycy.cbe.iastate.edu/space-equipment-etc/

Progress 09/01/24 to 08/31/25

Outputs
Target Audience:We have an initial user pool comprised of 17 senior investigators managing over 50 researchers from 4 colleges and 8 departments that will thrive with new capabilities offered by the 2D Acquity. It accomplishes two tandem tasks, allowing for never-before-discovered information about numerous research topics: Firstly, chemical separation through HPLC yields composition and chemical affinity information; subsequently, SEC yields the molecular weight distribution of each slice of the HPLC chromatogram to enable unparalleled insights into the macromolecular analyte. For example, two compounds with different chemical structures and similar/overlapping hydrodynamic volumes can be resolved in 2D but not 1D.17 This provides unprecedented understanding of complex mixtures that are common in research, especially with biomass products. These integrated capabilities make the instrument crucial to three Core areas of collaborative agricultural materials research: (1) Derived from Biomass (2) Biomass Modified Geotechnical and Construction Material (3) Fundamental Analysis of Complex Polymer Structures. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?A Ph.D. student has been deeply involved in developing and optimizing separation methods, gaining expertise in instrument calibration, method validation, and understanding the principles of both chromatographic selectivity and size exclusion behavior. The student is further gaining experience with partition coefficients of different polymer systems, which govern how macromolecules interact with the stationary and mobile phases in the first-dimension separation. This training has provided him with foundational knowledge in molecular interaction mechanisms key for designing targeted separation strategies for new and unexplored material systems. ? How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?Over the next year, the instrument will support several projects where 2D GPC will provide unique insights. Some of the polymeric systems for the future pipeline for analysis and method development would include biobased block copolymers, such as systems composed of methacrylate and acrylate blocks, which exhibit minimal differences in partition coefficients and are difficult to resolve using conventional techniques. A specific focus will be on quantifying the degree of conversion from the first block to the second, providing critical insight into structure-property relationships and the synthetic fidelity of radical-mediated block copolymerization. Additional efforts will target systems incorporating functional comonomeric units intended for post-polymerization modification, with the goal of quantitatively assessing comonomer incorporation. Furthermore, as the core users and facility manager gain expertise with the instrument, we will more actively reach out to the user base to onboard additional users.

Impacts
What was accomplished under these goals? The instrument was acquired in Feb 2024 and installed in June 2024. The facility manager and a graduate student have been developing methodologies and standard operating procedures. As of August 2024, the instrument is ready for initial data acquisition experiments with a small set of initial users. One of the initial projects involved analyzing a PolyLactic Acid (PLA) blend designed to improve toughness by incorporating amorphous polyhydroxyalkanoates (aPHA). These materials are particularly challenging to separate using conventional SEC due to similar size-exclusion behavior. We developed an initial methodology using a normal-phase HPLC column that enabled consistent and uniform separation of the blend into three segments: PLA homopolymer, chain-extended/blended PLA with aPHA, and aPHA homopolymer. This represents a major breakthrough in enabling quantitative analysis of blend composition and structural variation, paving the way for advanced 2D chromatographic mapping. Further completion of the full 2D chromatographic map is expected to provide detailed structural insights, including chain grafting levels and their correlation with mechanical properties

Publications


    Progress 09/01/23 to 08/31/24

    Outputs
    Target Audience:The audience is prospective users of the 2D HPLC/GPC equipment. Changes/Problems: Nothing Reported What opportunities for training and professional development has the project provided?A Ph. D. student has learned valuable chromatography method development and equipment knowledge. How have the results been disseminated to communities of interest? Nothing Reported What do you plan to do during the next reporting period to accomplish the goals?Over the next year, the instrument will support several projects where 2D GPC will provide unique insights. As the core users and facility manager gain expertise with the instrument, we will more actively reach out to the user base to onboard additional users.

    Impacts
    What was accomplished under these goals? The instrument was acquired in Feb 2024 and installed in June 2024. The facility manager and a graduate student have been developing methodologies and standard operating procedures. As of August 2024, the instrument is ready for initial data acquisition experiments with a small set of initial users.

    Publications