Source: LOUISIANA STATE UNIVERSITY submitted to NRP
PARTNERSHIP: TUNABLE POLYMERIC NANOPARTICLE PLATFORM FOR CONTACT/SYSTEMIC CUS DELIVERY FOR CROP DISEASE MANAGEMENT
Sponsoring Institution
National Institute of Food and Agriculture
Project Status
ACTIVE
Funding Source
AFRI COMPETITIVE GRANT
Reporting Frequency
Annual
Accession No.
1030968
Grant No.
2023-67018-40722
Cumulative Award Amt.
$727,328.00
Proposal No.
2022-08636
Multistate No.
(N/A)
Project Start Date
Sep 1, 2023
Project End Date
Aug 31, 2027
Grant Year
2023
Program Code
[A1511]- Agriculture Systems and Technology: Nanotechnology for Agricultural and Food Systems
Recipient Organization
LOUISIANA STATE UNIVERSITY
202 HIMES HALL
BATON ROUGE,LA 70803-0100
Performing Department
(N/A)
Non Technical Summary
The main goal of this work is to develop tunable, biodegradable, bio-derived controlled release formulations designed to specifically deliver CuS as a contact or systemic agrochemical for plant disease management. Copper is traditionally used as a contact fungicide; to improveits ability to increase the natural defense mechanisms of plants previously documented, systemic delivery of Cu would be beneficial. Combining contact and systemic (and combining Cu and S) will be a powerfulstrategy to fight fungal/bacterial diseases more efficiently by using several modes of action and timing facilitated by the nanodelivery system. To meet this goal,a lignin-basedpolymer will be synthesized and assembled into lignin nanoparticles (LNPs) of controlled properties. The LNPs will be tested for their ability to delivery CuS to the roots/leaves as a contact or systemic agrochemical. Those LNPs deemed most efficient as delivery systems able to 1. adhere to the plant tissue where applied (leaves or roots) or 2. able to translocate from one tissue to another will be further tested. Their impact on plant and insect health, and their environmental fate and impact will be assessed.
Animal Health Component
60%
Research Effort Categories
Basic
20%
Applied
60%
Developmental
20%
Classification

Knowledge Area (KA)Subject of Investigation (SOI)Field of Science (FOS)Percent
40218202020100%
Knowledge Area
402 - Engineering Systems and Equipment;

Subject Of Investigation
1820 - Soybean;

Field Of Science
2020 - Engineering;
Goals / Objectives
This proposal will focus on biopolymer-based tunable delivery of nanoscale CuS to crops as a novel and sustainable, multifunctional crop pathogen control strategy. The following objectives are proposed: Objective 1: Synthesize amphiphilic graft polymer from bioderived lignin (LGN) and polyester poly(lactic-co-glycolic) acid (PLGA) at different LGN:PLGA ratios. Objective 2: Synthesize tunable CuS loaded LNPs of controlled properties (size, charge, targeting) from LGN-g-PLGA polymer. Objective 3: Evaluate LNPs as a potential contact/systemic delivery of CuS. Objective 4: Determine impact of LNPs on plant and insect health. Objective 5: Assess fate and impact of LNPs on the environment. The mechanisms of LNPs of various sizes, surface charges, and targeting to plant tissues will allow for specific LNP -guided CuS applications as a contact or systemic agrochemical.
Project Methods
Biodegradable, bio-derived controlled release formulations capable of contact/systemic delivery of CuS will be synthesized as follows. First, bioderived polymer lignin (LGN) will be grafted with a biodegradable hydrophobic polyester poly(lactic-co-glycolic) acid (PLGA) to form an amphiphilic LGN-g-PLGA polymer. The ratios of the two polymers will be selected based on the self-assembly tendencies of the polymer and the efficacy of the polymer to accommodate the two differently sized CuS. Given the chemistry of the polymers (lignin as a polyphenol and PLGA as a polyester), a platform of environmentally-benign LNPs will be built from the LGN-g-PLGA polymer to achieve the goal of contact or systemic delivery of entrapped CuS. Controlled parameters include type of lignin (lignosulfonate or alkaline), LGN:PLGA ratio, surfactant (DMAB, SDS, Tween) and addition or not of a stomata targeting agent. LNPs will be rationally applied to the roots of hydroponically grown lettuce and to the leaves of soil grown soybeans. Those LNP systems most successful in maintaining contact with the roots/leaves or become internalized will be further tested for their intended and unintended effects on plants, insects, and environment.

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

Outputs
Target Audience:Academia, agrochemical companies. Changes/Problems:None What opportunities for training and professional development has the project provided?A research professor, three graduate students and four undergraduate student worked on the project. They were all trained on nanoparticle synthesis and characterization, soybean health analysis, new methodologies for nanoparticle detection in plant tissue. How have the results been disseminated to communities of interest?The results of this work have been presented at national and international conferences,and at various academic institutions. What do you plan to do during the next reporting period to accomplish the goals?Nanoparticles synthesis will be perfected to yield negatively and positively charged LNPs of controlled sizes. These particles will be tested in plants and insects by our collaborators at the University of Auckland and the Connecticut Agricultural Experiment Station, respectively.

Impacts
What was accomplished under these goals? Environmental concerns call for increasing efficiency and sustainability of current agricultural practices. This study investigated the synthesis of CuS nanoparticles using the citrate method, followed by surface modification and entrapment of hydrophobic CuS NPs in engineered lignin NPs. CuS NPs exhibited a size between 8.8±1.3 to 14.7±3.3 nm depending on the duration of the reaction, 15 to 30 min, respectively. Surface modification of CuS NPs with ODT, a thiol with 18 carbons (R-SH), resulted in hydrophobic CuS NPs. FTIR revealed a layer assembled due to arranged alkyl chains on CuS surface, confirming surface functionalization. Separately, two types of lignin, alkali lignin (ALN) and sulfonate lignin (SLN), were grafted with PLGA at different (A/S)LN:PLGA w/w ratios (1:1 and 2:1) to allow the construction of amphiphilic polymers that were further assembled into delivery systems for the CuS NPs. Hydrophobic CuS were successfully entrapped into LN-PLGA delivery systems with the goal to control the release of CuS under aqueous solutions. SLN-PLGA NPs were generally smaller (122 to 130 nm) compared to ALN-PLGA NPs (132-162 nm). Release of Cu and S in aqueous solutions were controlled over a time frame of 168 h with a total dissolution of 30.50% and 28.21% for S, higher than 0.76 and 4% for Cu for ALN-PLGA1:1 and ALN-PLGA2:1, respectively. In general, this study demonstrated the capability of LN-based NPs to control the release of modified CuS NPs. In conclusion, CuS NPs were successfully synthesized and modified, allowing their entrapment into LNP delivery systems with different properties, and controlled release over time. The lignin-based delivery systems are proposed as feasible alternatives for efficient delivery of CuS in nanoform, utilizing an abundant biodegradable resource for improving plant health. We also conducted a series of experiments to test the ability of the lignin nanoparticles as an antifungal delivery system. Lignin nanoparticles (LNP) (173.6 ± 0.9 nm, -56.5 ± 2.8 mV) with loaded azoxystrobin (AZO) (5.5 ± 0.7 wt%, respectively) were designed as antifungal delivery systems for seed treatments. LNPs followed pseudo-first-order kinetics for AZO release at 25°C, with AZO releasing faster from ZNP. Empty LNP treated seeds produced a yield of 40.35 bushels for inoculated samples, comparable to yields achieved with the commercial AZO formulation, Dynasty®. The stand per row feet for inoculated plants were significantly higher than the control, with the highest being Dynasty®, followed AZO-entrapped LNP treatments. All treatments, resulted in a statistically significant increase in yield and stand per row feet compared to the non-treated plants. LNPs developed herein for AZO delivery can be used as an alternative and sustainable solution for the delivery of other agrochemicals.

Publications

  • Type: Journal Articles Status: Published Year Published: 2024 Citation: Fannyuy V. K, Astete, C. E., Nde, D. B., Eberhard, J. R., Constant, D. W., Sabliov, C. M. Lignin cationization for the removal of phosphates and nitrates from effluents of wastewater treatment plants. Environ. Sci.: Adv., 2024, DOI: 10.1039/D4VA00312H.
  • Type: Journal Articles Status: Published Year Published: 2024 Citation: Trif, E., Astete, C.E., Libi S., Pall, E., Tripon, S., Coman, C., Olah, D. Pot�rniche, V. A. Sabliov, C. M., Cerbu C. (2024). Development and in vitro evaluation of a lignin-PLGA nanocarrier for florfenicol delivery. Veterinary Research Communications.
  • Type: Journal Articles Status: Published Year Published: 2024 Citation: Hanna, E. A., Astete, C. E., Price, T., Tamez, C., Mendez, O. E., Garcia, A., Kewir, F. V., White, J. C., & Sabliov, C. M. (2024). Antifungal Efficacy of Nanodelivered Azoxystrobin against Rhizoctonia solani in Soybean. ACS Agricultural Science & Technology, 4(3), 330-336. https://doi.org/10.1021/acsagscitech.3c00469
  • Type: Journal Articles Status: Published Year Published: 2023 Citation: Kah, M., Sabliov, C., Wang, Y., & White, J. C. (2023). Nanotechnology as a foundational tool to combat global food insecurity. One Earth, 6(7), 772-775. https://doi.org/10.1016/j.oneear.2023.06.011
  • Type: Other Status: Accepted Year Published: 2024 Citation: White, J.C. et al. September 2024. CAES, Nanotechnology, And Agriculture: How We Got Here and Where We Are Going. The Connecticut Agricultural Experiment Station public seminar series. In person.
  • Type: Other Status: Accepted Year Published: 2024 Citation: White, J.C. et al. June 2024. Nano-enabled agriculture: A path to global food security in a changing climate. National Academies of Sciences, Engineering, and Medicines Committee on the Quadrennial Review of the National Nanotechnology Initiative. Washington DC. In person.
  • Type: Other Status: Accepted Year Published: 2024 Citation: Sabliov, C. M. March 2024. Nanotechnology and how I became interested in science and nanotechnology. NNI Women History month.
  • Type: Other Status: Accepted Year Published: 2024 Citation: White, J. Nanometrology for Food, Agriculture, and the Environment: Nano-enabled Agriculture. Public presentation for the National Nanotechnology Initiative Nanometrology Webinar Series: Nanometrology for Food, Agriculture, and the Environment. February 2024.
  • Type: Other Status: Accepted Year Published: 2023 Citation: White, J. Revolutionizing how we grow, distribute, & store food. NSF Center for Sustainable Nanotechnology podcast. November 2023. https://sustainablenano.simplecast.com/episodes/ep-43-jason-white-2
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2024 Citation: White, J.C. et al. August 2024. Nanobiotechnology-based Strategies for Climate Resilient Crops. The American Chemical Society, Denver CO (in person).
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2024 Citation: White, J.C. et al. August 2024. Nanobiotechnology-based Strategies for Enhanced Crop Resilience. The Joint Conference of ISEH ICEPH & ISEG on Environment and Health, Galway, Ireland (in person)
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2024 Citation: White, J.C. et al. April 2024. Nanobiotechnology-based Strategies for Enhanced Crop Resilience. NanoFlorida 2024 International Conference (remote).
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2024 Citation: White, J.C. et al. August 2024. Nano-enabled Agriculture: A Path to Global Food Security in a Changing Climate. 5th International Conference on Agriculture, Food Security, and Safety in Colombo, Sri Lanka (remote)
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2024 Citation: Sabliov, C. M., C. E. Astete, J. Davis, J. White, M. Kah, Y. Wang. June 2024. Tunable Polymeric Nanoparticle Platform for Contact/Systemic CuS Delivery for Crop Disease Management. GRC. Manchester, New Hampshire, United States.
  • Type: Conference Papers and Presentations Status: Accepted Year Published: 2024 Citation: White, J. January 2024. Nanobiotechnology based strategies for enhanced crop stress resilience. Invited presentation at the 6th International Conference on Agriculture for Sustainable Development at the National Rice Research Institute. Cuttack, India .
  • Type: Other Status: Accepted Year Published: 2024 Citation: White, J.C. et al. July 2024. Nano-enabled agriculture: A path to global food security in a changing climate. Central South University of Forestry and Technology, Changsha China (in person).
  • Type: Other Status: Accepted Year Published: 2024 Citation: White, J.C. et al. July 2024. Nano-enabled agriculture: A path to global food security in a changing climate. Guangdong University of Technology, Guangzhou China (in person).
  • Type: Other Status: Accepted Year Published: 2024 Citation: White, J. February 2024. Nano-enabled agriculture: A path to global food security in a changing climate. Invited seminar at the University of Connecticut.
  • Type: Other Status: Accepted Year Published: 2024 Citation: White, J. February 2024. Nano-enabled agriculture: A path to global food security in a changing climate. Invited seminar at the New Jersey Institute of Technology.
  • Type: Other Status: Accepted Year Published: 2023 Citation: White, J. November 2023. Sustainable Agriculture: Nano-enabled strategies for food security in a changing climate. Invited seminar at the University of Athens as part of a Sustainability Masterclass.
  • Type: Other Status: Accepted Year Published: 2023 Citation: White, J. October 2023. Nano-enabled agriculture: A path to global food security in a changing climate. Invited seminar at the University of Rhode Island.
  • Type: Other Status: Accepted Year Published: 2023 Citation: White, J. October 2023. Nano-enabled agriculture: A path to global food security in a changing climate. Invited seminar at the University of Delaware.
  • Type: Other Status: Accepted Year Published: 2023 Citation: White, J. October 2023. Nanotechnology-enabled agriculture: A path to global food security? Invited seminar at the University of Minnesota 9-9-9 program.