Calcium l-Malate and d-Tartarate Frameworks as Adjuvants for the Sustainable Delivery of a Fungicide

Nurul Farhana Ahmad Aljafree; Mohamad Firdaus Ahmad; Umar Abd Aziz; Mostafa Yousefzadeh Borzehandani; Adila Mohamad Jaafar; Norhayu Asib; Ha L Nguyen; Mohamed Ibrahim Mohamed Tahir; Muhammad Alif Mohammad Latif; Kyle E Cordova; Mohd Basyaruddin Abdul Rahman

doi:10.1021/acsami.3c11697

Calcium l-Malate and d-Tartarate Frameworks as Adjuvants for the Sustainable Delivery of a Fungicide

ACS Appl Mater Interfaces. 2023 Dec 18. doi: 10.1021/acsami.3c11697. Online ahead of print.

Authors

Nurul Farhana Ahmad Aljafree^{1

2}, Mohamad Firdaus Ahmad³, Umar Abd Aziz¹, Mostafa Yousefzadeh Borzehandani^{1

2}, Adila Mohamad Jaafar^{1

4}, Norhayu Asib^{1

3}, Ha L Nguyen⁵, Mohamed Ibrahim Mohamed Tahir^{1

2}, Muhammad Alif Mohammad Latif^{1

4}, Kyle E Cordova^{1

2

6}, Mohd Basyaruddin Abdul Rahman^{1

2}

Affiliations

¹ Foundry of Reticular Materials for Sustainability, Institute of Nanoscience and Nanotechnology, Universiti Putra Malaysia, Serdang 43400, Selangor, Malaysia.
² Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, Serdang 43400, Selangor, Malaysia.
³ Department of Plant Protection, Faculty of Agriculture, Universiti Putra Malaysia, Serdang 43400, Selangor, Malaysia.
⁴ Centre of Foundation Studies for Agricultural Science, Universiti Putra Malaysia, Serdang 43400, Selangor, Malaysia.
⁵ Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States.
⁶ Integrated Materials Systems (iMS) Research Unit, Advanced Research Centre, Royal Scientific Society, Amman 11941, Jordan.

PMID: 38109287
DOI: 10.1021/acsami.3c11697

Abstract

Agrichemical adjuvants that combine a highly selective, efficient, and active mode of operation are critically needed to realize a more sustainable approach to their usage. Herein, we report the synthesis and full characterization of two new metal-organic frameworks (MOFs), termed UPMOF-1 and UPMOF-2, that were constructed from eco-friendly Ca²⁺ ions and naturally occurring, low-molecular weight plant acids, l-malic and d-tartaric acid, respectively. Upon structural elucidation of both MOFs, a widely used fungicide, hexaconazole (Hex), was loaded on the structures, reaching binding affinities of -5.0 and -3.5 kcal mol^-1 and loading capacities of 63% and 62% for Hex@UPMOF-1 and Hex@UPMOF-2, respectively, as a result of the formation of stable host-guest interactions. Given the framework chemistry of the MOFs and their predisposition to disassembly under relevant agricultural conditions, the sustained release kinetics were determined to show nearly quantitative release (98% and 95% for Hex@UPMOF-1 and Hex@UPMOF-2, respectively) after >500 h, a release profile drastically different than the control (>80% release in 24 h), from which the high efficiency of these new systems was established. To confirm their high selectivity and activity, in vitro and in vivo studies were performed to illustrate the abilities of Hex@UPMOF-1 and Hex@UPMOF-2 to combat the known aggressive pathogen Ganoderma boninense that causes basal stem rot disease in oil palm. Accordingly, at an extremely low concentration of 0.05 μg mL^-1, both Hex@UPMOF-1 and Hex@UPMOF-2 were demonstrated to completely inhibit (100%) G. boninense growth, and during a 26 week in vivo nursery trial, the progression of basal stem rot infection was completely halted upon treatment with Hex@UPMOF-1 and Hex@UPMOF-2 and seedling growth was accelerated given the additional nutrients supplied via the disassembly of the MOFs. This study represents a significant step forward in the design of adjuvants to support the environmentally responsible use of agrichemical crop protection.

Keywords: agrichemicals; crystalline structures; delivery systems; porous materials; reticular chemistry.

Publication types

Review