Pub Date : 2025-07-17DOI: 10.1021/acsagscitech.5c00207
Cassandra L. Martin, Josephine R. Cicero, Lillian L. Springer, Dorthea A. Geroulakos, Audrey C. Moos and Daniel J. Wilson*,
From decorative houseplants to the crops that feed the world, plants are subjected to various environmental stresses over their lifetimes. Factors like changes in climate, pollution, and disease threaten plant health, requiring time-sensitive interventions to prevent widespread crop losses. We present a bioinspired colorimetric sensing strategy for measuring proline, a biomarker of stress in plants, by leveraging the condensation reaction between sinapaldehyde and proline to form a natural red pigment called nesocodin. We prepared paper-based sensors embedded with sinapaldehyde that supported nesocodin synthesis when we introduced the proline analyte. Signals range from pale yellow, indicative of unreacted sinapaldehyde, to deep red, indicative of proline-dependent formation of nesocodin. These sensors can quantitatively differentiate between 0 and 15 mM proline, which sufficiently measured relative increases in proline concentrations of plants exposed to controlled stresses. This approach highlights the opportunity to design field-deployable, user-friendly tools for agricultural monitoring, improved farming efficiency, and strengthened food security.
{"title":"Bio-Inspired Proline Sensors for the Diagnosis and Surveillance of Stress in Living Systems","authors":"Cassandra L. Martin, Josephine R. Cicero, Lillian L. Springer, Dorthea A. Geroulakos, Audrey C. Moos and Daniel J. Wilson*, ","doi":"10.1021/acsagscitech.5c00207","DOIUrl":"https://doi.org/10.1021/acsagscitech.5c00207","url":null,"abstract":"<p >From decorative houseplants to the crops that feed the world, plants are subjected to various environmental stresses over their lifetimes. Factors like changes in climate, pollution, and disease threaten plant health, requiring time-sensitive interventions to prevent widespread crop losses. We present a bioinspired colorimetric sensing strategy for measuring proline, a biomarker of stress in plants, by leveraging the condensation reaction between sinapaldehyde and proline to form a natural red pigment called nesocodin. We prepared paper-based sensors embedded with sinapaldehyde that supported nesocodin synthesis when we introduced the proline analyte. Signals range from pale yellow, indicative of unreacted sinapaldehyde, to deep red, indicative of proline-dependent formation of nesocodin. These sensors can quantitatively differentiate between 0 and 15 mM proline, which sufficiently measured relative increases in proline concentrations of plants exposed to controlled stresses. This approach highlights the opportunity to design field-deployable, user-friendly tools for agricultural monitoring, improved farming efficiency, and strengthened food security.</p>","PeriodicalId":93846,"journal":{"name":"ACS agricultural science & technology","volume":"5 9","pages":"1827–1841"},"PeriodicalIF":2.9,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsagscitech.5c00207","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145057052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-15DOI: 10.1021/acsagscitech.5c00182
Huiping Tian, Yuliang Yao, Rui Li, Shuaiqi An, Chao Huang, Jingzhe Sheng and Xin Jia*,
Carbon dioxide (CO2) is the material substance of plant photosynthesis, yet its concentration remains insufficient to meet plant photosynthesis demands. Therefore, the formation of CO2-enriched regions around leaf stomata is expected to improve the efficiency of plant photosynthesis. Herein, a photoresponsive metal–organic framework (Zr-ABTC) was constructed from azobenzene bonds, while T(n)/Zr-ABTC was prepared by the incorporation of tetraethyl pentamine (TEPA) with an adsorption ability for CO2. The photoresponsive material could capture CO2 in darkness and release it under ultraviolet irradiation, thus establishing a CO2 “enrichment-release” cycle under dark/light cycles. Upon application of Zr-ABTC onto Chinese little green leaves, scanning electron microscopy (SEM) revealed that the material is distributed around plant stomata, resulting in an 87.5% increase in crop yield compared with the blank control group not treated by Zr-ABTC (dry weight). The photothermal responsive materials created in this article may be used to improve the photosynthetic efficiency and enhance agricultural productivity.
{"title":"Controlled CO2 Adsorption and Release by Photoresponsive Metal–Organic Frameworks: Enhancing Crop Yields","authors":"Huiping Tian, Yuliang Yao, Rui Li, Shuaiqi An, Chao Huang, Jingzhe Sheng and Xin Jia*, ","doi":"10.1021/acsagscitech.5c00182","DOIUrl":"https://doi.org/10.1021/acsagscitech.5c00182","url":null,"abstract":"<p >Carbon dioxide (CO<sub>2</sub>) is the material substance of plant photosynthesis, yet its concentration remains insufficient to meet plant photosynthesis demands. Therefore, the formation of CO<sub>2</sub>-enriched regions around leaf stomata is expected to improve the efficiency of plant photosynthesis. Herein, a photoresponsive metal–organic framework (Zr-ABTC) was constructed from azobenzene bonds, while T(n)/Zr-ABTC was prepared by the incorporation of tetraethyl pentamine (TEPA) with an adsorption ability for CO<sub>2</sub>. The photoresponsive material could capture CO<sub>2</sub> in darkness and release it under ultraviolet irradiation, thus establishing a CO<sub>2</sub> “enrichment-release” cycle under dark/light cycles. Upon application of Zr-ABTC onto Chinese little green leaves, scanning electron microscopy (SEM) revealed that the material is distributed around plant stomata, resulting in an 87.5% increase in crop yield compared with the blank control group not treated by Zr-ABTC (dry weight). The photothermal responsive materials created in this article may be used to improve the photosynthetic efficiency and enhance agricultural productivity.</p>","PeriodicalId":93846,"journal":{"name":"ACS agricultural science & technology","volume":"5 8","pages":"1632–1640"},"PeriodicalIF":2.9,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144860174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-15DOI: 10.1021/acsagscitech.5c00226
Almir Custodio Batista Junior, Jussara Valente Roque, Nerilson Marques Lima, Daniel de Almeida Soares, Mellissa Ananias Soler da Silva and Andréa Rodrigues Chaves*,
This study evaluated rice samples (Oryza sativa L.)─rice husk, husk and grain, polished grain, and unpolished grain─exposed to imazapyr, imazapic, and clomazone using high-performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC-HRMS) and chemometric analysis. Partial least squares discriminant analysis (PLS-DA) was applied to HPLC-HRMS data, successfully distinguishing between herbicide-treated and control samples. Additionally, variable importance in projection (VIP) scores were then computed to identify key metabolites contributing to class differentiation, with higher scores indicating the most influential m/z values. These findings revealed metabolites affected by herbicide exposure and variations in the rice matrix. Furthermore, the most relevant m/z values were putatively annotated using spectral libraries, enabling the assessment of herbicide-induced metabolomic changes in rice. Herbicide treatment resulted in reduced free sugar levels across all rice matrices and led to a decrease in flavonoid content in the husk, indicating a potential suppressive effect on flavonoid accumulation. In addition, the herbicide treatment markedly disrupted the phenylpropanoid biosynthesis pathway. Overall, the combination of HPLC-HRMS analysis with multivariate approaches proved effective in detecting significant variations in the rice metabolome cultivated under herbicide application, paving the way for understanding the effects of herbicides in crop cultivation.
{"title":"Metabolomic Changes in Rice (Oryza sativa L.) Subjected to Herbicide Application through HPLC-HRMS and Chemometrics Approaches","authors":"Almir Custodio Batista Junior, Jussara Valente Roque, Nerilson Marques Lima, Daniel de Almeida Soares, Mellissa Ananias Soler da Silva and Andréa Rodrigues Chaves*, ","doi":"10.1021/acsagscitech.5c00226","DOIUrl":"https://doi.org/10.1021/acsagscitech.5c00226","url":null,"abstract":"<p >This study evaluated rice samples (<i>Oryza sativa</i> L.)─rice husk, husk and grain, polished grain, and unpolished grain─exposed to imazapyr, imazapic, and clomazone using high-performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC-HRMS) and chemometric analysis. Partial least squares discriminant analysis (PLS-DA) was applied to HPLC-HRMS data, successfully distinguishing between herbicide-treated and control samples. Additionally, variable importance in projection (VIP) scores were then computed to identify key metabolites contributing to class differentiation, with higher scores indicating the most influential <i>m/z</i> values. These findings revealed metabolites affected by herbicide exposure and variations in the rice matrix. Furthermore, the most relevant <i>m</i>/<i>z</i> values were putatively annotated using spectral libraries, enabling the assessment of herbicide-induced metabolomic changes in rice. Herbicide treatment resulted in reduced free sugar levels across all rice matrices and led to a decrease in flavonoid content in the husk, indicating a potential suppressive effect on flavonoid accumulation. In addition, the herbicide treatment markedly disrupted the phenylpropanoid biosynthesis pathway. Overall, the combination of HPLC-HRMS analysis with multivariate approaches proved effective in detecting significant variations in the rice metabolome cultivated under herbicide application, paving the way for understanding the effects of herbicides in crop cultivation.</p>","PeriodicalId":93846,"journal":{"name":"ACS agricultural science & technology","volume":"5 8","pages":"1641–1653"},"PeriodicalIF":2.9,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsagscitech.5c00226","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144860175","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nanopesticides have emerged as a highly promising approach for plant protection. Importantly, their preparation process plays a crucial role in determining their particle characteristics and impacting crop protection efficacy. Unfortunately, current nanopesticides exhibit predominantly large size distributions and uncontrollable morphologies, leading to unpredictable protection efficacy. Microfluidics allows one to manipulate fluids in microchannels with precise controllability. Herein, we employed microfluidic technology to systematically investigate key preparation parameters and prepared the zein-loaded lambda-cyhalothrin (LC) (LC@Zein) nanopesticides successfully. The produced LC@Zein exhibited size controllability, high uniformity, excellent storage stability, and sustained release. Importantly, the insecticidal activity of LC@Zein against Spodoptera exigua was demonstrated to be higher than that of two commercial formulations, microemulsion and emulsion in water. Moreover, LC@Zein exhibited higher biological safety compared to the two commercial formulations in earthworm acute toxicity and rabbit acute eye irritation tests, suggesting its excellent eco-friendly properties and contributing to green agriculture development.
{"title":"Microfluidic Manipulation Enabling Controllable and Eco-Friendly Lambda-Cyhalothrin Nanopesticides for Highly Efficient Pest Control","authors":"Shuqin Wu, Jinshan Xie, Yufang Xu, Xuhong Qian, Weiping Zhu* and Yangyang Yang*, ","doi":"10.1021/acsagscitech.5c00231","DOIUrl":"https://doi.org/10.1021/acsagscitech.5c00231","url":null,"abstract":"<p >Nanopesticides have emerged as a highly promising approach for plant protection. Importantly, their preparation process plays a crucial role in determining their particle characteristics and impacting crop protection efficacy. Unfortunately, current nanopesticides exhibit predominantly large size distributions and uncontrollable morphologies, leading to unpredictable protection efficacy. Microfluidics allows one to manipulate fluids in microchannels with precise controllability. Herein, we employed microfluidic technology to systematically investigate key preparation parameters and prepared the zein-loaded lambda-cyhalothrin (LC) (LC@Zein) nanopesticides successfully. The produced LC@Zein exhibited size controllability, high uniformity, excellent storage stability, and sustained release. Importantly, the insecticidal activity of LC@Zein against <i>Spodoptera exigua</i> was demonstrated to be higher than that of two commercial formulations, microemulsion and emulsion in water. Moreover, LC@Zein exhibited higher biological safety compared to the two commercial formulations in earthworm acute toxicity and rabbit acute eye irritation tests, suggesting its excellent eco-friendly properties and contributing to green agriculture development.</p>","PeriodicalId":93846,"journal":{"name":"ACS agricultural science & technology","volume":"5 8","pages":"1670–1680"},"PeriodicalIF":2.9,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144860173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-11DOI: 10.1021/acsagscitech.5c00285
Elias E. Buurma, Shital R. Vaidya, Laura Pilotto, Christian O. Dimkpa, Jason C. White, Guido Fellet and D. Howard Fairbrother*,
While biopolymers have the potential to enhance agrochemical delivery and mitigate environmental impacts such as runoff, previous plant studies have often been limited to examining single biopolymers in isolation. This approach has hindered effective comparisons of plant outcomes due to variations in plant type, growth duration, and soil characteristics. The current study addresses this gap by incorporating six separate milled biopolymers: pectin, starch, chitosan, polycaprolactone (PCL), polylactic acid (PLA), or polyhydroxybutyrate (PHB) into soil and directly comparing their impacts on tomato (Solanum lycopersicum) plants cultivated under identical environmental parameters. Plant outcomes were also studied when biopolymers were modified via the inclusion of two phosphorus (P) salts, forming two types of Polymer-P-containing salt composites with amorphous CaPO4 (CaP) and CaHPO4 (DCP). Our results revealed that chitosan-based treatments significantly improved tomato root and shoot biomass, with increases of 200–300% compared to the control plants. Chitosan-CaP and Chitosan-DCP also enhanced P uptake, though the effect was significantly more pronounced in the former, suggesting a synergy between chitosan and CaP. Neither Chitosan-P-containing salt treatment, however, mitigated P leaching from soil when compared to CaP or DCP applied in isolation. The two most hydrophilic biopolymers, pectin and starch, as well as their P-salt-containing counterparts, showed the most substantial reductions in biomass (∼80%) with respect to control plants, while similarly lowering P uptake and P retention in soil compared to CaP- and DCP-only plants. PCL- and PHB-based treatments also adversely influenced biomass and plant P, though these effects were not as drastic as those observed with pectin and starch. PLA-based soil amendments had no effect on any plant performance metric, though PLA-CaP, specifically, was the only treatment to appreciably mitigate P leaching (−63%). Based on these findings, subsequent tomato growth experiments were conducted over a longer 8-week period with CaP, DCP, Chitosan, Chitosan-CaP, and Chitosan-DCP. While all chitosan-treated plants showed similar enhancements in biomass, plants treated with Chitosan-CaP and Chitosan-DCP were the only ones to fruit, demonstrating the benefit of using chitosan in conjunction with a P source as compared to either treatment in isolation. These findings contribute to an expanding body of evidence that biopolymer carriers can offer a more sustainable approach to improving the precision of nutrient delivery, while also highlighting the pivotal role of biopolymer and nutrient type in the development of these carriers.
{"title":"Differential Effects of Biodegradable Polymers and Polymer-Phosphorus Composites on Tomato Performance and Phosphorus Uptake","authors":"Elias E. Buurma, Shital R. Vaidya, Laura Pilotto, Christian O. Dimkpa, Jason C. White, Guido Fellet and D. Howard Fairbrother*, ","doi":"10.1021/acsagscitech.5c00285","DOIUrl":"https://doi.org/10.1021/acsagscitech.5c00285","url":null,"abstract":"<p >While biopolymers have the potential to enhance agrochemical delivery and mitigate environmental impacts such as runoff, previous plant studies have often been limited to examining single biopolymers in isolation. This approach has hindered effective comparisons of plant outcomes due to variations in plant type, growth duration, and soil characteristics. The current study addresses this gap by incorporating six separate milled biopolymers: pectin, starch, chitosan, polycaprolactone (PCL), polylactic acid (PLA), or polyhydroxybutyrate (PHB) into soil and directly comparing their impacts on tomato (<i>Solanum lycopersicum</i>) plants cultivated under identical environmental parameters. Plant outcomes were also studied when biopolymers were modified via the inclusion of two phosphorus (P) salts, forming two types of Polymer-P-containing salt composites with amorphous CaPO<sub>4</sub> (CaP) and CaHPO<sub>4</sub> (DCP). Our results revealed that chitosan-based treatments significantly improved tomato root and shoot biomass, with increases of 200–300% compared to the control plants. Chitosan-CaP and Chitosan-DCP also enhanced P uptake, though the effect was significantly more pronounced in the former, suggesting a synergy between chitosan and CaP. Neither Chitosan-P-containing salt treatment, however, mitigated P leaching from soil when compared to CaP or DCP applied in isolation. The two most hydrophilic biopolymers, pectin and starch, as well as their P-salt-containing counterparts, showed the most substantial reductions in biomass (∼80%) with respect to control plants, while similarly lowering P uptake and P retention in soil compared to CaP- and DCP-only plants. PCL- and PHB-based treatments also adversely influenced biomass and plant P, though these effects were not as drastic as those observed with pectin and starch. PLA-based soil amendments had no effect on any plant performance metric, though PLA-CaP, specifically, was the only treatment to appreciably mitigate P leaching (−63%). Based on these findings, subsequent tomato growth experiments were conducted over a longer 8-week period with CaP, DCP, Chitosan, Chitosan-CaP, and Chitosan-DCP. While all chitosan-treated plants showed similar enhancements in biomass, plants treated with Chitosan-CaP and Chitosan-DCP were the only ones to fruit, demonstrating the benefit of using chitosan in conjunction with a P source as compared to either treatment in isolation. These findings contribute to an expanding body of evidence that biopolymer carriers can offer a more sustainable approach to improving the precision of nutrient delivery, while also highlighting the pivotal role of biopolymer and nutrient type in the development of these carriers.</p>","PeriodicalId":93846,"journal":{"name":"ACS agricultural science & technology","volume":"5 8","pages":"1709–1721"},"PeriodicalIF":2.9,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144860172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-09DOI: 10.1021/acsagscitech.5c00311
Bin Sheng, Ying Zhang, Kexin Yang, Xiaobin Wen, Zhihao Lin, Zhijian Wu, Yaowei Zhang, Jie Zhou, Xueling Ye*, Miao Wang, Ge Chen, Guangyang Liu*, Xiaomin Xu, Xin Yang, Bining Jiao and Donghui Xu*,
Neonicotinoid insecticides face a number of challenges in improving the efficacy and mitigating resistance in Bemisia tabaci. The zeolitic imidazolate framework (ZIF) in metal–organic frameworks (MOFs) has attracted much attention in the field of nanopesticide preparation and controlled release due to its simple preparation. However, monometallic ZIFs have a simple structure and low loading capacity. To solve this problem, we doped Fe into ZIF-L and successfully synthesized a cross-stacked bimetallic ZIF nanocarrier, which can effectively load and release dinotefuran (DNF). Subsequent preparation of Zn-Fe-ZIF@DNF@MPN after encapsulation using metal–phenolic networks (MPNs) increased the DNF loading to 23.74% and achieved >99% release within 24 h. Zn-Fe-ZIF@DNF@MPN has greater resistance to UV light, retention on vegetable leaves, and resistance to rainwater washout. Dynamic residue analysis confirmed its effectiveness and persistence. In addition, it achieved 86.95% mortality against Bemisia tabaci without inhibiting cabbage seed germination. This work is of strategic importance for the development of a functional and environmentally friendly smart nanopesticide.
{"title":"MPN-Modified Bimetallic ZIF Nanopesticide Enhances Dinotefuran Loading Efficiency and Synergistically Controls Pesticide Residue and Insecticidal Activity","authors":"Bin Sheng, Ying Zhang, Kexin Yang, Xiaobin Wen, Zhihao Lin, Zhijian Wu, Yaowei Zhang, Jie Zhou, Xueling Ye*, Miao Wang, Ge Chen, Guangyang Liu*, Xiaomin Xu, Xin Yang, Bining Jiao and Donghui Xu*, ","doi":"10.1021/acsagscitech.5c00311","DOIUrl":"https://doi.org/10.1021/acsagscitech.5c00311","url":null,"abstract":"<p >Neonicotinoid insecticides face a number of challenges in improving the efficacy and mitigating resistance in <i>Bemisia tabaci</i>. The zeolitic imidazolate framework (ZIF) in metal–organic frameworks (MOFs) has attracted much attention in the field of nanopesticide preparation and controlled release due to its simple preparation. However, monometallic ZIFs have a simple structure and low loading capacity. To solve this problem, we doped Fe into ZIF-L and successfully synthesized a cross-stacked bimetallic ZIF nanocarrier, which can effectively load and release dinotefuran (DNF). Subsequent preparation of Zn-Fe-ZIF@DNF@MPN after encapsulation using metal–phenolic networks (MPNs) increased the DNF loading to 23.74% and achieved >99% release within 24 h. Zn-Fe-ZIF@DNF@MPN has greater resistance to UV light, retention on vegetable leaves, and resistance to rainwater washout. Dynamic residue analysis confirmed its effectiveness and persistence. In addition, it achieved 86.95% mortality against <i>Bemisia tabaci</i> without inhibiting cabbage seed germination. This work is of strategic importance for the development of a functional and environmentally friendly smart nanopesticide.</p>","PeriodicalId":93846,"journal":{"name":"ACS agricultural science & technology","volume":"5 7","pages":"1516–1528"},"PeriodicalIF":2.9,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144808020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-09DOI: 10.1021/acsagscitech.5c00259
Edwin Davidson, Paul Aikpokpodion, Anastasiia Pestereva, Jorge Pereira, Giulio Diracca, Allison Lloyd, Laurene Tetard, Christian Dimkpa and Swadeshmukul Santra*,
Securing global food supplies requires the use of fertilizers to sustain crop production. Current agricultural practices rely on the excessive use of phosphorus (P) fertilizers, which, unfortunately, have been implicated in surface and groundwater contamination due to their high solubility in water. This study aimed to develop a nanoenabled polymeric coating technology for pristine rock phosphate (RP) mineral. A chitosan gel matrix with tannic acid, citric acid, and nanosulfur (CTS) was designed to harness the chelating properties of organic acids and the abrasion resistance of sulfur to generate slow-release RP fertilizers. Furthermore, kinetic studies were conducted to provide insights into the surface interactions of the coatings and RP and the kinetics of phosphate desorption from the coated RP. The CTS-coated RP exhibited nonphytotoxicity, reduced P leaching, and increased plant height, plant biomass, and yield compared to a commercial P fertilizer. Loss of P from soil was reduced by 71% in CTS-coated RP treatment compared to the commercial P fertilizer application. In addition, there was a 12% enhancement in soil postharvest cation exchange capacity, corroborating the impact of the coating on the dissolution of cationic nutrients present in RP. The release kinetics elucidated a pseudo-first-order desorption process driving the available P release mechanism with a Pearson R correlation value of 0.983. Altogether, this study demonstrated the suitability of nanoenabled coating technology to develop an alternative for P fertilizers with improved P use efficiency, with benefits in sustainable crop production and reduced environmental impact.
{"title":"Development of a Nanosulfur–Biopolymeric Coating Composite for Rock Phosphate: Transforming a Mineral into a Fertilizer","authors":"Edwin Davidson, Paul Aikpokpodion, Anastasiia Pestereva, Jorge Pereira, Giulio Diracca, Allison Lloyd, Laurene Tetard, Christian Dimkpa and Swadeshmukul Santra*, ","doi":"10.1021/acsagscitech.5c00259","DOIUrl":"https://doi.org/10.1021/acsagscitech.5c00259","url":null,"abstract":"<p >Securing global food supplies requires the use of fertilizers to sustain crop production. Current agricultural practices rely on the excessive use of phosphorus (P) fertilizers, which, unfortunately, have been implicated in surface and groundwater contamination due to their high solubility in water. This study aimed to develop a nanoenabled polymeric coating technology for pristine rock phosphate (RP) mineral. A chitosan gel matrix with tannic acid, citric acid, and nanosulfur (CTS) was designed to harness the chelating properties of organic acids and the abrasion resistance of sulfur to generate slow-release RP fertilizers. Furthermore, kinetic studies were conducted to provide insights into the surface interactions of the coatings and RP and the kinetics of phosphate desorption from the coated RP. The CTS-coated RP exhibited nonphytotoxicity, reduced P leaching, and increased plant height, plant biomass, and yield compared to a commercial P fertilizer. Loss of P from soil was reduced by 71% in CTS-coated RP treatment compared to the commercial P fertilizer application. In addition, there was a 12% enhancement in soil postharvest cation exchange capacity, corroborating the impact of the coating on the dissolution of cationic nutrients present in RP. The release kinetics elucidated a pseudo-first-order desorption process driving the available P release mechanism with a Pearson <i>R</i> correlation value of 0.983. Altogether, this study demonstrated the suitability of nanoenabled coating technology to develop an alternative for P fertilizers with improved P use efficiency, with benefits in sustainable crop production and reduced environmental impact.</p>","PeriodicalId":93846,"journal":{"name":"ACS agricultural science & technology","volume":"5 7","pages":"1483–1496"},"PeriodicalIF":2.9,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144807871","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-08DOI: 10.1021/acsagscitech.5c00177
Ming Chang, Tesfaye Abebe Geleta, Hong-Jhang Chen and Yang-hsin Shih*,
The widespread use of tris(1,3-dichloropropyl) phosphate (TDCPP), a phosphorus flame retardant, has raised significant environmental concerns because of its persistence and toxicity. This study examines the photodegradation of TDCPP (0.25 mg/L) using titanium dioxide (TiO2) nanoparticles (P25 NPs) (50 mg/L) under UV irradiation, focusing on the effects of electrolytes, such as NaCl and NaBr, pH, and temperature. TiO2 NPs degraded TDCPP within 60 min, achieving nearly complete mineralization and release of chloride ions (Cl−). The degradation rate decreased with higher initial TDCPP concentrations but increased with higher TiO2 dosages. Acidic conditions enhanced photodegradation, while the presence of electrolytes caused nanoparticle aggregation, increasing the particle size and reducing the photocatalytic efficiency. Chloride (Cl−) and bromide ions (Br−) acted as radical scavengers, inhibiting the formation of reactive hydroxyl radicals (HO•). Notably, 89% of the total organic carbon (TOC) was eliminated from TDCPP after 60 min of UV illumination, indicating mineralization into carbon dioxide and water. The degradation intermediates were analyzed using ultrahigh-performance liquid chromatography (UHPLC), and two byproducts were identified after 10 min of treatment. Acute and chronic toxicity analyses revealed that TDCPP’s intermediates were nontoxic. Density functional theory (DFT) calculations provide insights into electronic structures and degradation pathways. This research contributes to strategies for mitigating the environmental impact of hazardous flame retardants such as TDCPP.
{"title":"Rapid Tris(1,3-dichloropropyl) Phosphate Degradation and Detoxification via TiO2 Nanoparticles under UV Light: Kinetics and Mechanism, Environmental Implications, and Insights into DFT","authors":"Ming Chang, Tesfaye Abebe Geleta, Hong-Jhang Chen and Yang-hsin Shih*, ","doi":"10.1021/acsagscitech.5c00177","DOIUrl":"https://doi.org/10.1021/acsagscitech.5c00177","url":null,"abstract":"<p >The widespread use of tris(1,3-dichloropropyl) phosphate (TDCPP), a phosphorus flame retardant, has raised significant environmental concerns because of its persistence and toxicity. This study examines the photodegradation of TDCPP (0.25 mg/L) using titanium dioxide (TiO<sub>2</sub>) nanoparticles (P25 NPs) (50 mg/L) under UV irradiation, focusing on the effects of electrolytes, such as NaCl and NaBr, pH, and temperature. TiO<sub>2</sub> NPs degraded TDCPP within 60 min, achieving nearly complete mineralization and release of chloride ions (Cl−). The degradation rate decreased with higher initial TDCPP concentrations but increased with higher TiO<sub>2</sub> dosages. Acidic conditions enhanced photodegradation, while the presence of electrolytes caused nanoparticle aggregation, increasing the particle size and reducing the photocatalytic efficiency. Chloride (Cl−) and bromide ions (Br−) acted as radical scavengers, inhibiting the formation of reactive hydroxyl radicals (HO•). Notably, 89% of the total organic carbon (TOC) was eliminated from TDCPP after 60 min of UV illumination, indicating mineralization into carbon dioxide and water. The degradation intermediates were analyzed using ultrahigh-performance liquid chromatography (UHPLC), and two byproducts were identified after 10 min of treatment. Acute and chronic toxicity analyses revealed that TDCPP’s intermediates were nontoxic. Density functional theory (DFT) calculations provide insights into electronic structures and degradation pathways. This research contributes to strategies for mitigating the environmental impact of hazardous flame retardants such as TDCPP.</p>","PeriodicalId":93846,"journal":{"name":"ACS agricultural science & technology","volume":"5 7","pages":"1400–1412"},"PeriodicalIF":2.9,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsagscitech.5c00177","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144807960","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-08DOI: 10.1021/acsagscitech.5c00191
Jafar Fathi-Qarachal, S. Ali Moosawi-Jorf*, Mansoor Karimi-Jashni and Maryam Nikkhah,
Wheat stem rust, caused by Puccinia graminis f. sp. tritici, is a devastating disease that inflicts significant global damage annually. To combat this disease, chitosan nanoparticles (CNPs) were combined with the fungicide cyproconazole (CYP) and applied as a foliar spray 24 h postinoculation (hpi) with fungal urediniospores. Plant samples were analyzed to assess fungal progression by examining pustule formation and quantifying fungal DNA content in leaf tissues. Treatment with CNPs and the cyproconazole-chitosan nanocomposite (C-CYP) resulted in significantly smaller pustules or their absence and reduced fungal DNA levels compared to controls. Additionally, enzyme assays revealed that the activities of peroxidase, catalase, polyphenol oxidase, and phenylalanine ammonia-lyase significantly increased 24 h post-treatment with CNPs compared to controls. Furthermore, transcription levels of WAK-2, NPR-1, and Chitinase genes were notably upregulated in plants treated with CNPs and C-CYP at 24 h post-treatment. These findings suggest that the combination of chitosan nanoparticles and cyproconazole not only effectively controls wheat stem rust but also reduces environmental hazards by requiring lower chemical dosages.
{"title":"Impact of Combining Chitosan Nanoparticles and Cyproconazole in Controlling Wheat Stem Rust","authors":"Jafar Fathi-Qarachal, S. Ali Moosawi-Jorf*, Mansoor Karimi-Jashni and Maryam Nikkhah, ","doi":"10.1021/acsagscitech.5c00191","DOIUrl":"https://doi.org/10.1021/acsagscitech.5c00191","url":null,"abstract":"<p >Wheat stem rust, caused by <i>Puccinia graminis</i> f. sp. <i>tritici</i>, is a devastating disease that inflicts significant global damage annually. To combat this disease, chitosan nanoparticles (CNPs) were combined with the fungicide cyproconazole (CYP) and applied as a foliar spray 24 h postinoculation (hpi) with fungal urediniospores. Plant samples were analyzed to assess fungal progression by examining pustule formation and quantifying fungal DNA content in leaf tissues. Treatment with CNPs and the cyproconazole-chitosan nanocomposite (C-CYP) resulted in significantly smaller pustules or their absence and reduced fungal DNA levels compared to controls. Additionally, enzyme assays revealed that the activities of peroxidase, catalase, polyphenol oxidase, and phenylalanine ammonia-lyase significantly increased 24 h post-treatment with CNPs compared to controls. Furthermore, transcription levels of WAK-2, NPR-1, and Chitinase genes were notably upregulated in plants treated with CNPs and C-CYP at 24 h post-treatment. These findings suggest that the combination of chitosan nanoparticles and cyproconazole not only effectively controls wheat stem rust but also reduces environmental hazards by requiring lower chemical dosages.</p>","PeriodicalId":93846,"journal":{"name":"ACS agricultural science & technology","volume":"5 7","pages":"1413–1424"},"PeriodicalIF":2.9,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144807923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-07-08DOI: 10.1021/acsagscitech.5c00068
Jaume Béjar-Grimalt, David Pérez-Guaita*, Ángel Sánchez-Illana*, Rodolfo García-Contreras, Rashmi Kataria, Sylvie Bureau, Miguel de la Guardia and Frédéric Cadet,
This work aimed to investigate using ATR–FTIR spectroscopy combined with machine learning to classify eight apricot varieties. Traditionally, variety identification relies on physicochemical property measurements, which are time-consuming and require laboratory analysis. Instead, we used the ATR–FTIR spectra from 731 apricots divided into calibration (512) and test (219) sets and three machine learning models (i.e., partial least-squares-discriminant analysis (PLS-DA), support vector machine (SVM), and random forest (RF)) to accurately predict 97% of the test samples. Additionally, careful inspection of the PLS-DA regression vectors revealed a strong correlation between the spectra and biochemical composition in sugar and organic acids, validating ATR–FTIR spectroscopy as a viable alternative for variety identification. Finally, to validate the results, additional models were constructed using the physicochemical data from the apricots. These reference models were then tested using the same data splits as the spectroscopic data used as a reference method, obtaining similar results with both approaches.
{"title":"Classification of Apricot Varieties by Infrared Spectroscopy and Machine Learning","authors":"Jaume Béjar-Grimalt, David Pérez-Guaita*, Ángel Sánchez-Illana*, Rodolfo García-Contreras, Rashmi Kataria, Sylvie Bureau, Miguel de la Guardia and Frédéric Cadet, ","doi":"10.1021/acsagscitech.5c00068","DOIUrl":"10.1021/acsagscitech.5c00068","url":null,"abstract":"<p >This work aimed to investigate using ATR–FTIR spectroscopy combined with machine learning to classify eight apricot varieties. Traditionally, variety identification relies on physicochemical property measurements, which are time-consuming and require laboratory analysis. Instead, we used the ATR–FTIR spectra from 731 apricots divided into calibration (512) and test (219) sets and three machine learning models (i.e., partial least-squares-discriminant analysis (PLS-DA), support vector machine (SVM), and random forest (RF)) to accurately predict 97% of the test samples. Additionally, careful inspection of the PLS-DA regression vectors revealed a strong correlation between the spectra and biochemical composition in sugar and organic acids, validating ATR–FTIR spectroscopy as a viable alternative for variety identification. Finally, to validate the results, additional models were constructed using the physicochemical data from the apricots. These reference models were then tested using the same data splits as the spectroscopic data used as a reference method, obtaining similar results with both approaches.</p>","PeriodicalId":93846,"journal":{"name":"ACS agricultural science & technology","volume":"5 7","pages":"1373–1381"},"PeriodicalIF":2.9,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12309246/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144755345","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}