Source: CORNELL UNIVERSITY submitted to
SWELLABLE SORBENT SHEETS FOR SIMPLE EXTRACTION, SHIPMENT, AND STORAGE OF BIOACTIVE COMPOUNDS FROM PERISHABLE AGRICULTURAL SAMPLES
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
EXTENDED
Funding Source
Reporting Frequency
Annual
Accession No.
1026427
Grant No.
2021-67034-34971
Project No.
NYC-143947
Proposal No.
2020-09988
Multistate No.
(N/A)
Program Code
A7101
Project Start Date
Jun 1, 2021
Project End Date
May 31, 2024
Grant Year
2021
Project Director
Rafson, J. P.
Recipient Organization
CORNELL UNIVERSITY
(N/A)
ITHACA,NY 14853
Performing Department
Food Science
Non Technical Summary
To proactively ensure high-quality and safe agriculture and food products, there is a system-level need for affordable technologies capable of rapid, trace-level (sub-ppm) chemical characterization of large numbers of samples. Existing analytical approaches, e.g. mass spectrometry (MS), are relatively slow because of the need for prior sample extraction and pre-concentration, and are often unsuitable for routine, near-real time quality assurance. These sample preparation approaches are generally slow, expensive, technically challenging, and/or require large volumes of hazardous solvents. Smaller producers may also need to send samples for MS analysis to external service labs, which creates additional costs and logistical challenges for perishable samples. The overall goal of this research proposal is to create a novel, broadly applicable technology that addresses the need for convenient and inexpensive extraction and storage of bioactive compounds (toxins, flavor compounds, nutrients) from foods or other agricultural products prior to analytical analysis (e.g. mass spectrometry). Briefly, a sorbent polymer is "swelled" (expanded) with an appropriate solvent and then immersed in a sample, allowing for the direct extraction of trace-level compounds. The Swellable Sorbent Sheets can then be conveniently analyzed in-house or shipped by standard mail to service labs for analysis by MS or other techniques, eliminating the need for shipping or storage of perishable samples. In this proposed project, I will build a Swellable Sorbent Sheet device capable of parallel extraction for up to 24 samples and will broaden the range of extractable target analyses. This project specifically addresses the AFRI Farm Bill priority area "agriculture systems and technology." This technology will assist both small- and large-scale producers in scaling up analytical analyses as part of systems level testing.
Animal Health Component
0%
Research Effort Categories
Basic
(N/A)
Applied
(N/A)
Developmental
100%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
40472992000100%
Goals / Objectives
The overall goal of this research proposal is to create a novel, broadly applicable technology that addresses the need for convenient and inexpensive extraction, shipment, and storage of bioactive compounds (toxins, flavor compounds, nutrients) in foods or other agricultural products prior to analysis.The specific objectives of this project are:Develop a novel, durable, swellable device capable of performing simple, convenient, parallel trace-level extractions for food and agricultural analyses.Develop Swellable Sorbent Sheet devices for parallel extraction using a multi-parameter optimization approach.Validate Swellable Sorbent Sheet performance using carotenoids and volatiles from tomato samples and maize.Expand the range of extractable compounds by incorporating a second polymer into the sorbent layer of the extraction device and by exploring different solvent/polymer combinations.Expand the polarity of the extraction system using a multi-parameter optimization (both multipolymer and swelling solvent).Validate multipolymer Swellable Sorbent Sheet performance using semi-polar smoke-taint off-aromas in grapes.
Project Methods
For Objective 1:Physical characteristic data collected on the device will be used to determine durability and number of maximum uses. I will use absorbance data from a colorimeter or MS data and ANOVAs to compare the quantities of extracted compounds throughout the optimization process. In the validation study, I will calculate the correlation coefficients between the Swellable Sorbent Sheet method and LC-UV/VIS using the carotenoid data. For stability experiments, I will fit a regression on the colorimeter data to determine storage capabilities.For Objective 2:I will use ANOVAs to compare the differences in the quantities of extracted smoke-taint compounds (using MS data) from grapes based on various solvent and polymer combinations. The optimized system will be compared to the PDMS-only version from Objective 1 using a t-test. Finally, in the validation study, I will calculate at the correlation coefficients between the multipolymer Swellable Sorbent Sheet method and SPME-GC-MS using the smoke-taint data.

Progress 06/01/21 to 08/04/22

Outputs
Target Audience:The target audiences for this work are food producers, plant breeders, analytical chemists, and other scientists. Changes/Problems:The initial design of the devices was modified to avoid tearing during the swelling process. This was expected to be a challenge and was able to be solved by grafting the polymer coating to a mesh device which could easily undergo over 40 swelling cycles with no visible signs of damage. Additionally, the fellowship was shortened due to a job offer which was accepted (research chemist position at the FDA), this narrowed the scope of the project due to time constraints with graduation. What opportunities for training and professional development has the project provided? Nothing Reported How have the results been disseminated to communities of interest?Results were published as a completed PhD dissertation. Additionally, a journal publication about the research conducted is currently under review; the manuscript has been revised and resubmitted after receiving peer review comments. What do you plan to do during the next reporting period to accomplish the goals? Nothing Reported

Impacts
What was accomplished under these goals? During this fellowship most of these goals were accomplished. I created a novel, broadly applicable technology that addresses the need for convenient and inexpensive extraction, shipment, and storage of bioactive compounds (carotenoids and volatiles) by coating stainless-steel meshes with high molecular weight polydimethylsiloxane. By using a custom stainless-steel holder, the swellable sorbent devices could be positioned in a 24-wellplate for parallel extractions. Extraction and desorption methods were optimized for carotenoids and volatiles and were reported in my completed dissertation and journal publication that has been revised and resubmitted after peer review. For objective 1, carotenoids were extracted from tomato and carrot samples with minimal solvent usage (<200 µL per sample). The swelled sorbent extraction was compared to a traditional solvent extraction and the carotenoid profiles produced by both were well correlated (R2 > 0.94). The devices were stored under ambient conditions for 4 weeks with minimal carotenoid degradation. Due to time constraints, objective 2 was scaled back but still explored. Swellable devices that had a multipolymer (polydiphenyldimethylsiloxane) coating were used to extract a variety of volatile compounds that ranged in polarity. As expected, the addition of a second, more polar polymer improved extraction of all volatiles but had a greater effect on semi-polar compounds (such as furfural, guaiacol, and 4-ethylphenol). Compared to a headspace extraction using non-swelled, single polymer (polydimethylsiloxane) swellable devices, a swelled sorbent extraction using a multipolymer coating increased signal intensity by ~125×. Future work will explore the use of these multipolymer devices in real food samples and will determine the stability of volatiles during storage.

Publications

  • Type: Journal Articles Status: Under Review Year Published: 2022 Citation: Rafson JP, Sacks GL. Swellable Sorbent Coatings for Parallel Extraction, Storage, and Analysis of Plant Metabolites. Under Review.
  • Type: Journal Articles Status: Published Year Published: 2021 Citation: Rafson JP, Sacks GL. Rapid Analysis of Volatile Phenols from Grape Juice by Immersive Sorbent Sheet Extraction Prior to Direct Analysis in Real-Time Mass Spectrometry (DART-MS). J Agric Food Chem. 2021 Oct 20;69(41):12344-12353. doi: 10.1021/acs.jafc.1c04197.
  • Type: Theses/Dissertations Status: Published Year Published: 2021 Citation: Rafson J. Novel Extractions of Trace-Level Compounds using PDMS Sorbent Polymers for High-Throughput Analyses and Mass Spectral Imaging. 2021 Dec. https://doi.org/10.7298/2frx-qg02.