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Plant Ionomics A thoroughly up-to-date exploration of nutrient uptake in plants In Plant Ionomics: Sensing, Signaling and Regulation, accomplished botanists and researchers Dr. Vijay Singh and Dr. Manzer Siddiqui deliver an up-to-date discussion on the sensing, signaling, and regulation of nutrient uptake in plants under a variety of conditions. The book offers an accessible and easy-to-use reference for researchers with an interest in plant ionomics, combining the latest research from leading laboratories around the globe. The authors provide coverage of a variety of critical topics, including plant and soil nutrient stoichiometry, nutrient management and stress tolerance in crops, and the relationship between agricultural production and nutrient applications. Readers will also find: * A thorough introduction to nutrient regulation and abiotic stress tolerance in plants * In-depth discussions of nutrient uptake and transport in plants and the role of nutrients in ROS metabolism * Practical explorations of nutrient and sugar signaling and associated gene networks in plants * Extensive treatments of the role of nutrients in plant-microbe interactions and nutrient-use efficiency in plants Perfect for students, researchers, academics, and scientists with an interest in plant nutrition, Plant Ionomics: Sensing, Signaling and Regulation will also earn a place in the libraries of professionals in the agriculture and pharmaceutical industries.
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Cover
Title Page
Copyright Page
List of Contributors
Preface
1 Regulation of Metabolites by Nutrients in Plants
Introduction
Nitrogen (N)
Phosphorus (P)
Potassium (K)
Sulfur (S)
Magnesium (Mg)
Calcium (Ca)
Boron (B)
Chlorine (Cl)
Copper (Cu)
Iron (Fe)
References
2 Agricultural Production Relation with Nutrient Applications
Introduction
Soil as a Basic Element in Agriculture
Constituents and Ingredients of Soil
Essential Nutrients in Agriculture Especially in Plants
Beneficial/Valuable Nutrients
Issues Related to Plant Nutrition
Fertilizers and Fertilization Strategies
References
3 Role of Nutrients in the ROS Metabolism in Plants
Introduction
Oxidative Defense System
Reactive Oxygen Species (ROS) and Reactive Nitrogen Species (RNS)
ROS Generation and Functions in Plants
RNS and ROS Signaling in Plants in Response to Environmental Stresses
Antioxidant Compounds
Antioxidant‐Mediated RNS/ROS Regulation
Role of Nutrients in ROS Metabolism Under Salinity
Role of Nutrients in ROS Metabolism Under Drought
Role of Nutrients in ROS Metabolism Under Heavy Metal Stress
Role of Nutrients in ROS Metabolism Under Low‐ and High‐Temperature Stress
References
4 Polyamines Metabolism and their Regulatory Mechanism in Plant Development and in Abiotic Stress Tolerance
Introduction
Distribution, Biosynthesis, and Catabolism of Polyamines
Role of Polyamines in Plant Development
Polyamines as Biochemical Markers for Abiotic Stress Tolerance
Crosstalk of Polyamines with Other Signaling Molecules
Plant Growth Regulators
Conclusion
References
5 Mycorrhizal Symbiosis and Nutrients Uptake in Plants
Introduction
Mycorrhizal Association and Its Types
Establishment of Arbuscular Mycorrhiza in Soil
Root Modifications for Accumulation of Nutrients
Nitrogen Uptake Mechanisms of Mycorrhizal Symbionts
Phosphorus Accumulation Mechanisms of Mycorrhizal Fungus
Potassium (K) and Sodium (Na) Uptake Mechanisms of Mycorrhizal Fungi
Metabolism of Sulfur in Mycorrhizal Symbiosis
Role of Mycorrhizal Lipid Metabolism in Nutrients Accumulation
Mechanism of Micronutrients and Heavy Metal Uptake in Mycorrhizae
Carbons‐Based Triggering of Nutrients Accumulation in Mycorrhizal Symbiosis
Conclusion
References
6 Nutrient Availability Regulates Root System Behavior
Introduction
Nutrients Importance in Root Growth and Development
Morpho‐Physiological Responses of Plant Roots to Nutrients Availability
Nano Nutrients and Root System Modifications
Management Strategies for Maximizing Root Systems
Conclusions and Future Perspectives
References
7 Potassium Transport Systems at the Plasma Membrane of Plant Cells. Tools for Improving Potassium Use Efficiency of Crops
Potassium (K
+
) as a Macronutrient for Plants
K
+
Transport Systems
Key Points for K
+
Homeostasis and Transport Systems Involved
General Mechanisms of Regulation
Agriculture for the Future: K
+
Use Efficiency and Stress Tolerance
Biotechnological Approaches and Emerging Techniques for Crop Improvement
References
8 Role of Nutrients in Modifications of Fruit Quality and Antioxidant Activity
Introduction
Short Overview About Fruit Quality
Main Role of Mineral Elements on Trees Growth, Development, and Fruit Quality
The Ionomic Analysis of Fruit Crops
Requirements of Fruit Trees to Chemical Elements
The Role of Elements in the Metabolism of Fruit Trees and in Improving Quality
Conclusion and Future Prospects
References
9 Nutrients Use Efficiency in Plants
Introduction
Nutrient Use Efficiency (Concepts and Importance)
Role of Nutrient‐Efficient Plants for Improving Crop Yields
Physiological Mechanisms in Plant Nutrient Use Efficiency
Conclusion and Future Prospects
References
10 Nutrients Uptake and Transport in Plants: An Overview
Introduction
Routes from the Soil to the Stele
Passive Transport
Active Transport
Radial Transport of Mineral Ions
Long Transport of Mineral Ions
Conclusion and Future Prospects
References
11 Regulation of Phytohormonal Signaling by Nutrients in Plant
Introduction
Phytohormones: Structure, Sites of Biosynthesis, and its Effects
Interaction between Nutrient Availability and Phytohormone Signaling
Conclusions and Prospects
References
12 Nutrients Regulation and Abiotic Stress Tolerance in Plants
Introduction
How Abiotic Stresses Affect Plants
Plant’s Response to Abiotic Stress
Mineral Nutrients in the Alleviation of Abiotic Stress in Plants
Plant Growth‐Promoting Rhizobacteria (PGPR), Mineral Nutrients, and Abiotic Stress
Conclusion
References
13 Nutrient Management and Stress Tolerance in Crops
Introduction
Implications of Abiotic Stress in Plants
Role of Nutrients in Stress Tolerance
Conclusion
References
Index
End User License Agreement
Chapter 2
Table 2.1 FAO/UNESCO categorized major soil groups.
Table 2.2 Essential nutrients concentrations and forms taken up by plants....
Table 2.3 General supplement content qualities (g/kg) of crop yield, animal...
Table 2.4 Normal supplement substance of some significant fertilizers.
Chapter 6
Table 6.1 Responses of plant roots to low and high amounts of macronutrient...
Table 6.2 Responses of plant roots to low and high levels of some micronutr...
Chapter 8
Table 8.1 Elements those are essential for all higher plants including frui...
Table 8.2 Leaf composition standards for some pome and stone fruit types ba...
Chapter 11
Table 11.1 Phytohormone: pathway, site of biosynthesis and its effect.
Table 11.2 Effects of nutrients on phytohormones.
Chapter 13
Table 13.1 Information of nutrients available form, concentration in soil a...
Chapter 3
Figure 3.1 Mechanistic representation of nutrient‐mediated ROS metabolism in...
Chapter 4
Figure 4.1 Diagrammatic representation of polyamines biosynthetic pathway in...
Figure 4.2 Diagrammatic representation of crosstalk between PAs and nitric o...
Chapter 5
Figure 5.1 The anatomy of root and types of fungal interactions in angiosper...
Figure 5.2 The indirect and direct mycorrhizal associated pathways for the u...
Chapter 6
Figure 6.1 Responses of plant roots to various nutrients.
Chapter 7
Figure 7.1 K
+
transport systems in roots and specialized cells. (a) K
+
is ta...
Figure 7.2 Workflow for the generation of crops with increased K
+
use effici...
Chapter 10
Figure 10.1 The pore system of the apparent free space of cell walls contain...
Figure 10.2 The structure of a phospholipid.
Figure 10.3 Passive transport across the plasma membrane.
Chapter 11
Figure 11.1 Molecular structure of phytohormones.
Figure 11.2 NO
3
−
regulates phytohormonal signaling and pathways and im...
Chapter 12
Figure 12.1 Different abiotic stresses, their effect on plant, and plant’s s...
Figure 12.2 Differential response of plants under abiotic stress in absence ...
Cover Page
Title Page
Copyright Page
List of Contributors
Preface
Table of Contents
Begin Reading
Index
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Edited by
Vijay Pratap Singh
University of Allahabad
Prayagraj
India
Manzer H. Siddiqui
King Saud University
Riyadh
Saudi Arabia
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Saghir AbbasDepartment of BotanyFaculty of Life SciencesGovernment College UniversityFaisalabad, Pakistan
Zeeshan AhmedXinjiang Key Laboratory of Desert Plant Roots Ecology and Vegetation RestorationXinjiang Institute of Ecology and GeographyChinese Academy of SciencesUrumqi, China
State Key Laboratory of Desert and Oasis EcologyXinjiang Institute of Ecology and Geography
Chinese Academy of SciencesUrumqi, China
Cele National Station of Observation and Research for Desert‐Grassland EcosystemsCele, China
and
University of Chinese Academy of SciencesBeijing, China
AmnaDepartment of Plant SciencesFaculty of Biological SciencesQuaid‐i‐Azam UniversityIslamabad, Pakistan
Jesús AmoDepartamento de Nutrición VegetalCentro de Edafología y Biología Aplicada del Segura‐CSICMurcia, Spain
Muhammad Arslan AshrafDepartment of BotanyGovernment College University FaisalabadFaisalabad, Pakistan
Savita BhardwajDepartment of BotanySchool of Bioengineering and BiosciencesLovely Professional UniversityPhagwara, Punjab, India
Nikita BishtMicrobial Technologies DivisionCouncil of Scientific and Industrial Research‐National Botanical Research Institute (CSIR‐NBRI)Lucknow, Utter Pradesh, India
Puneet Singh ChauhanMicrobial Technologies DivisionCouncil of Scientific and Industrial Research‐National Botanical Research Institute (CSIR‐NBRI)LucknowUtter Pradesh, India
Neda DalirDepartment of Soil ScienceTarbiat Modares UniversityTehran, Iran
Salar Farhangi‐AbrizDepartment of Plant Eco‐physiologyFaculty of AgricultureUniversity of TabrizTabriz, Iran
Kazem Ghassemi‐GolezaniDepartment of Plant Eco‐physiologyFaculty of AgricultureUniversity of TabrizTabriz, Iran
Corina GracianoInstituto de Fisiología Vegetal
Consejo Nacional de InvestigacionesCientíficas y Técnicas
Universidad Nacional de La PlataBuenos Aires, Argentina
Iqbal HussainDepartment of BotanyGovernment College University FaisalabadFaisalabad, Pakistan
Mudassir Iqbal ShadDepartment of BotanyGovernment College University FaisalabadFaisalabad, Pakistan
Muhammad IqbalDepartment of BotanyGovernment College University FaisalabadFaisalabad, Pakistan
Khasan IsmoilovUniversity of Chinese Academy of SciencesBeijing, China
and
CAS Key Laboratory of Biogeography and Bioresource in Arid LandChinese Academy of SciencesUrumqi, China
Hassan Javed ChaudharyDepartment of Plant SciencesFaculty of Biological SciencesQuaid‐i‐Azam UniversityIslamabad, Pakistan
Harshita JoshiMicrobial Technologies DivisionCouncil of Scientific and Industrial Research‐National Botanical Research Institute (CSIR‐NBRI)Lucknow, Utter Pradesh, India
Dhriti KapoorDepartment of BotanySchool of Bioengineering and BiosciencesLovely Professional UniversityPhagwara, Punjab, India
Rajeev KumarDepartment of BotanySchool of Bioengineering and BiosciencesLovely Professional UniversityPhagwara, Punjab, India
Vicente MartínezDepartamento de Nutrición VegetalCentro de Edafología y Biología Aplicada del Segura‐CSIC, Murcia, Spain
Almudena Martínez‐MartínezDepartamento de Nutrición VegetalCentro de Edafología y Biología Aplicada del Segura‐CSIC, Murcia, Spain
Nebojša MiloševićDepartment of Pomology and Fruit BreedingFruit Research Institute ČačakČačak, Republic of Serbia
Tomo MiloševićDepartment of Fruit Growing and ViticultureFaculty of AgronomyUniversity of KragujevacČačak, Republic of Serbia
Ghulam MurtazaFaculty of Environmental Science and EngineeringKunming University of Science and Technology, Kunming, PR China
Manuel Nieves‐CordonesDepartamento de Nutrición VegetalCentro de Edafología y Biología Aplicada del Segura‐CSICMurcia, Spain
Rizwan RasheedDepartment of BotanyGovernment College University FaisalabadFaisalabad, Pakistan
Francisco RubioDepartamento de Nutrición VegetalCentro de Edafología y Biología Aplicada del Segura‐CSIC, Murcia, Spain
Sehrish SadiaDepartment of Biological SciencesUniversity of Veterinary and Animal Sciences‐Lahore, Pattoki, Pakistan
Muhammad ShahidDepartment of Bioinformatics and BiotechnologyGovernment College UniversityFaisalabad, Pakistan
Muhammad Sohail AkramDepartment of BotanyFaculty of Life SciencesGovernment College UniversityFaisalabad, Pakistan
Kashif TanwirDepartment of BotanyFaculty of Life SciencesGovernment College UniversityFaisalabad, Pakistan
Muhammad Tariq JavedDepartment of BotanyFaculty of Life SciencesGovernment College UniversityFaisalabad, Pakistan
Akash TariqXinjiang Key Laboratory of Desert Plant Roots Ecology and Vegetation RestorationXinjiang Institute of Ecology and Geography
Chinese Academy of SciencesUrumqi, China
State Key Laboratory of Desert and Oasis Ecology
Xinjiang Institute of Ecology and GeographyChinese Academy of SciencesUrumqi, China
Cele National Station of Observation and Research for Desert‐Grassland EcosystemsCele, ChinaandUniversity of Chinese Academy of Sciences, Beijing, China
Monika ThakurDivision BotanyDepartment of Bio‐SciencesCareer Point UniversityHamirpur, Himachal Pradesh, India
Abd UllahXinjiang Key Laboratory of Desert Plant Roots Ecology and Vegetation Restoration
Xinjiang Institute of Ecology and Geography, Chinese Academy of SciencesUrumqi, China
State Key Laboratory of Desert and Oasis Ecology
Xinjiang Institute of Ecology and Geography
Chinese Academy of SciencesUrumqi, China
Cele National Station of Observation and Research for Desert‐Grassland EcosystemsCele, China
and
University of Chinese Academy of SciencesBeijing, China
Tunisha VermaDepartment of BotanySchool of Bioengineering and BiosciencesLovely Professional UniversityPhagwara, Punjab, India
Fanjiang ZengXinjiang Key Laboratory of Desert Plant Roots Ecology and Vegetation RestorationXinjiang Institute of Ecology and Geography
Chinese Academy of SciencesUrumqi, China
State Key Laboratory of Desert and Oasis Ecology
Xinjiang Institute of Ecology and Geography
Chinese Academy of SciencesUrumqi, China
and
Cele National Station of Observation and Research for Desert‐Grassl andEcosystemsCele, China
Zhihao ZhangXinjiang Key Laboratory of Desert Plant Roots Ecology and Vegetation Restoration
Xinjiang Institute of Ecology and Geography
Chinese Academy of SciencesUrumqi, China
State Key Laboratory of Desert and Oasis Ecology
Xinjiang Institute of Ecology and Geography
Chinese Academy of SciencesUrumqi, China
Cele National Station of Observation and Research for Desert‐Grassland EcosystemsCele, China
and
University of Chinese Academy of SciencesBeijing, China
Muhammad ZubairDiscipline of ZoologyUniversity of Veterinary and AnimalSciences‐Lahore, Pattoki, Pakistan
Ionome includes the role of mineral nutrients, namely phosphorus (P), nitrogen (N), calcium (Ca), potassium (K), sulfur (S), magnesium (Mg), etc., and trace metals namely iron (Fe), copper (Cu), manganese (Mn), molybdenum (Mo), cobalt (Co), zinc (Zn), etc. in plant growth and development. Although all mineral nutrients and trace elements are essential for growth and developmental processes of plants, concentration greater than the required level becomes toxic to the plants. Apart from posing toxicity at higher concentration, nutrients under safe limit play important role in alleviating toxicity induced by various stresses.
Appropriate and adequate amount of any nutrient is required at specific stage of development and time to sustain the life of the plant. Hence, in the past decade, much progress has been made in understanding the regulation of nutrients homeostasis under normal and stressed conditions. Further, on one hand an approach has been developed for generating biofortified grains and on other hand nutrients have been successfully employed for managing stress challenges in plants. Taking into account the progress made in ionomics and plants, this book has compiled recent knowledge on sensing, signaling, and regulation of nutrients uptake in plants under changing environment.
A total of 13 chapters have been compiled in this book. Chapter 1 has comprehensively complied information on the regulation of metabolites by nutrients in plants. Chapter 2 deals with agricultural production relation with nutrient applications. Chapter 3 deals with the role of nutrients in ROS metabolism in plants. Chapter 4 deals with polyamines metabolism and their regulatory mechanism in plant development and in abiotic stress tolerance. Chapter 5 narrates the mycorrhizal symbiosis and nutrients uptake in plants. Chapter 6 deals with nutrient availability and root system behavior. Chapter 7 describes in detail the potassium transport systems at the plasma membrane of plant cells and their potential roles in improving potassium use efficiency of crops. Chapter 8 narrates the role of nutrients in modifications of fruit quality and antioxidant activity. Chapter 9 deals with the nutrients use efficiency in plants. Chapter 10 describes the nutrients uptake and their transport in plants. Chapter 11 comprehensively deals with the regulation of phytohormonal signaling by nutrients in plants. Chapter 12 gives details on the nutrients regulation and abiotic stress tolerance in plants. Chapter 13 deals with nutrient management and stress tolerance in crops. Overall, we believe that this book will serve as an important source of information for students, researchers, and academicis.
Vijay Pratap Singh
Manzer H. Siddiqui
Akash Tariq1,2,3,4, Fanjiang Zeng1,2,3, Corina Graciano5, Abd Ullah1,2,3,4, Sehrish Sadia6, Zeeshan Ahmed1,2,3,4, Ghulam Murtaza7, Khasan Ismoilov4,8, and Zhihao Zhang1,2,3,4
1 Xinjiang Key Laboratory of Desert Plant Roots Ecology and Vegetation Restoration, Xinjiang Institute of Ecology and Geography, Chinese Academy of Sciences, Urumqi, China
2 State Key Laboratory of Desert and Oasis Ecology, Xinjiang Institute of Ecology and Geography, Chinese Academy of Sciences, Urumqi, China
3 Cele National Station of Observation and Research for Desert‐Grassland Ecosystems, Cele, China
4 University of Chinese Academy of Sciences, Beijing, China
5 Instituto de Fisiología Vegetal, Consejo Nacional de Investigaciones Científicas y Técnicas, Universidad Nacional de La Plata, Buenos Aires, Argentina
6 Department of Biological Sciences, University of Veterinary and Animal Sciences, Lahore, Pakistan
7 Faculty of Environmental Science and Engineering, Kunming University of Science and Technology, Kunming, PR China
8 CAS Key Laboratory of Biogeography and Bioresource in Arid Land, Chinese Academy of Sciences, Urumqi, China
Mineral nutrients are required for plant growth and metabolism. Seventeen nutrients that are essential for plant growth have been identified to date. Macronutrients or essential elements such as nitrogen (N), phosphorus (P), potassium (K), sulfur (S), and magnesium (Mg) are required in large amounts, whereas micronutrients or trace elements including chloride (Cl), copper (Cu), manganese (Mn), iron (Fe), zinc (Zn), cobalt (Co), molybdenum (Mo), and nickel (Ni) are required in smaller amounts. Some researchers also consider sodium (Na) and silicon (Si) as essential micronutrients because of their role in certain crop plants; however, whether they are essential for plant growth and metabolism remains unclear (Maathuis 2009; Marschner 2012). Plants acquire these nutrients from the soil through the roots and carbon (C) and oxygen (O2) from the air. The concentrations of the available forms of these nutrients in the soil solution are low; for example, N can be readily absorbed by plant roots in nitrate (NO3−) and ammonium (NH4+) forms and P in orthophosphate (HPO42− and H2PO4) forms (Soetan et al. 2010; Mazid et al. 2011). Their availability can be further altered in both time and space because of several environmental factors, such as precipitation, temperature, wind, and soil properties. Consequently, plants have evolved various flexible physiological and morphological mechanisms to facilitate the uptake of nutrients. Each mineral carries equal importance and a deficiency of any of them can affect growth and disrupt the plant life cycle.
Metabolites are chemical compounds produced during metabolism and catalyzed by different naturally occurring enzymes in the cell. Plants can produce a variety of metabolites ranging from 0.1 to 1 million, which help plants survive in diverse environments, as these metabolites play important roles in structure, defense, energy, signaling, and interactions with other organisms (Rai et al. 2017). Plant metabolites are divided into two categories (primary and secondary) according to their functions. Primary metabolites (PMs) are directly involved in growth and cellular functions; they are thus also referred to as vital metabolites because they are generally common in all plant species. These are the intermediate products of anabolic metabolism and are formed in the growth phase. PMs are produced in large amounts and can be easily extracted. Examples of PMs include carbohydrates, protein, nucleic acids, lipids, and vitamins. Secondary metabolites (SMs) are the derivatives of PMs, and they are not directly involved in growth and development, but they are ecologically relevant. SMs are formed in the stationary phase; they are also called “natural products” and are different in every plant species because of environmental and genetic differences. There are more than 30 000 SMs, but they are produced in small concentrations, and extracting them can be difficult (Baranauskiene et al. 2003). Plant SMs have diverse applications and have been used in pharmaceuticals, flavoring compounds, antimicrobial agents, dyes, antioxidants, and agrochemicals. Examples of SMs include alkaloids, terpenoids, phenolic compounds, and glycosides.
There is a strong linkage between plant metabolites and mineral nutrients, but understanding the large diversity of plant metabolites requires knowledge of their biosynthesis, degradation, regulation, and transportation processes. Their biosynthesis involves various metabolic pathways such as absorption, assimilation of C, photosynthesis, protoplast formation, respiration, transpiration, translocation, and storage, and these pathways are regulated by mineral nutrients available in different forms in the soil solution (Soetan et al. 2010). Mineral nutrient availability and composition have a profound effect on the type and amount of PMs and SMs produced. Plants growing in soil with an unbalanced composition and limited nutrient concentrations experience serious morphological, biochemical, physiological, and molecular disruptions (Amtmann and Armengaud 2009). There is an increased interest in unraveling the regulatory roles of mineral nutrients in the biosynthesis of plant metabolites. The aim of this chapter is to improve our understanding regarding the regulatory roles of mineral nutrients in the biosynthesis of plant metabolites.
N is a key plant macronutrient that accounts for nearly 4% of the total dry matter of plants. It is an important structural component of several organic compounds, including amino acids, proteins, chlorophyll pigments, and nucleic acids. N is also involved in the biochemistry of several nonprotein compounds such as polyamines, co‐enzymes, SMs, and photosynthetic pigments. N is an important plant macronutrient that is necessary for the biosynthesis of various PMs (i.e. amino acids, chlorophyll, nucleic acids, lipids, proteins, and enzymes) and SMs (i.e. flavonoids and phenolic compounds) in plants (Kováčik and Klejdus 2013; Shiwakoti et al. 2016). N availability controls plant metabolism and alters the N‐based metabolites into C‐based plant metabolites (Strissel et al. 2005; del Mar Rubio‐Wilhelmi et al. 2012a). C‐based plant metabolites mostly contain phenolic acids, anthocyanins, flavonoids, and coumarins (Kováčik et al. 2011). Phenolics consist of thousands of nonenzymatic antioxidants that are ubiquitous in plants and an integral part of human nutrition (Balasundram et al. 2006). The concentrations of flavonoids produced in the secondary metabolism of plants are affected by N, which regulates flavonoid biosynthesis by affecting the C flow allocation between primary and secondary metabolism. For example, excessive N application reduces the content of flavonoids in plants (Ballizany et al. 2012; Shiwakoti et al. 2016), and low N increases the content of carbohydrates (e.g. starch and fructose) but decreases the content of N‐rich metabolites (e.g. proteins, free amino acids, and polyamines) in plants (Paul and Driscoll 1997; Coruzzi and Bush 2001).
Soil solution carries N mainly in the form of nitrate (NO3−) and ammonium (NH4+), but, NO3−‐N is readily available for plants uptake (at high pH). Plants absorb NO3−, which is then reduced to NH4+ through enzymatic action of glutamine synthetase/glutamate synthase (GS/GOGAT) enzymes. Scheible et al. (2004) reported downregulation of most genes responsible for chlorophyll and plastid protein synthesis, photosynthesis, and upregulation of many genes involved in secondary metabolism following two days of N deprivation in Arabidopsis thaliana. It is noted that N limitation mainly governs the shift from N‐based to C‐based plant metabolites (Kováčik et al. 2011; del Mar Rubio‐Wilhelmi et al. 2012b). This effect of N limitation on phenolic metabolites is thought to be the result of reductions in other macronutrients, such as the depletion of K, and does not increase phenolic metabolites and vice versa (Nguyen et al. 2010).
Leaf N limitation generally alters the pattern of N allocation in photosynthetic organs and directly regulates the content and enzymatic activity of ribulose 1,5‐bisphosphate carboxylase/oxygenase (Rubisco) and chlorophyll, thereby affecting the photosynthetic rate. Kováčik and Klejdus (2013) noted that concentrations of phenolic metabolites (especially chlorogenic acid) and free amino acids (mainly proline and arginine) increased in Matricaria chamomilla plants upon NH4+ application. Coumarin‐related metabolites showed a similar increase under N limitation, and herniarin mainly accumulated in plants under NO3− addition and umbelliferone under NH4+ addition.
P does not exist in elemental form but is firmly fixed (>90%) in soil minerals, therefore it is unavailable to plants. P is assimilated by the plants as phosphate (H2PO4−) at a pH of 5, and it is unevenly distributed because it is relatively immobile in soils. In addition, inorganic phosphate (Pi) is an important part of several biological compounds, such as sugar phosphates, phospholipids, DNA, RNA, and nucleotides. P has a crucial role in energy metabolism and activation of various intermediates in the C cycle of photosynthesis. These are the reasons why plant growth and yield depend on the availability of P.
Aside from its structural roles, P is involved in reversible protein phosphorylation (facilitated by kinases and phosphatases) to modulate protein activity. In this mechanism, terminal Pi from ATP or GTP nucleotide is transferred to Ser or the protein residues. ATP is an important energy compound with a pyrophosphate bond. Pyrophosphate is an energy‐rich bond and participates in active ion uptake and the synthesis of various PMs and SMs during hydrolysis (30 kJ mol−1). GTP, CTP, and UTP are energy‐rich phospho‐nucleotides which also regulate the nucleic acid metabolism. CTP provides energy during phospholipid biosynthesis, and UTP is the main structural constituent of sucrose, starch, and cellulose (Maathuis and Diatloff 2013). Pi also regulates various enzymes involved in carbohydrate metabolism (Ashihara and Stupavska 1984; Avigad and Bohrer 1984). P is a constituent of energy metabolism, and the phospho groups are responsible for the activation of enzymes and metabolic intermediates. For example, P activates intermediates in the photosynthetic carbon cycle and during the entire primary metabolism. P limitations have a substantial effect on plants at the morphological, physiological, biochemical, and molecular levels (Secco et al. 2013; Pant et al. 2015). Morcuende et al. (2007) determined the metabolite levels, transcripts, and maximum enzyme activity in the seedlings of Arabidopsis grown under P‐added and P‐depleted liquid culture. Reduction occurred in the levels of ATP and hexose phosphates (Glc6P, Fru6P, and Glc1P), owing to P limitation, recovered immediately after restocking with a knock‐on effect on UDP‐glucose, which took few hours for its completion. Tricarbonic acids such as 3‐phosphoglyceric acid (3PGA) and phosphoenolpyruvate (PEP), accumulated due to P limitation, are rapidly used after restocking and lead to the quick initiation of glycolysis. However, reduction in organic acids (malate, 2‐oxoglutarate, citrate, and fumarate) and storage carbohydrates (starch and sucrose) due to P limitation did not get back to their normal state within 24 hours of restocking. These findings clearly show that in response of P restocking, plants do modifications to retrieve their energy stores and the biosynthesis of phosphorylated substrates for glycolysis.
Soil contains extremely low concentrations of Pi (~0.1–1 mM), and P limitation is likely widespread in agriculture. Several studies revealed that P deficiency affects numerous PMs and SMs in soybean and Arabidopsis (Hurry et al. 2001; Morcuende et al. 2007; Hernandez et al. 2009). However, how the metabolite profile during P limitation and in mutants is affected during the P‐deprivation response remains unclear.
Morcuende et al. (2007) noted that P limitation in A. thaliana can induce or suppress more than1000 genes involved in many metabolic processes. P limitation leads to the accumulation of carbohydrates, amino acids, and organic acids. P‐limited plants also show significant variations in the expression of many genes associated with secondary metabolism and carbon assimilation. Upon P deficiency, plants generally recycle P from organic molecules (Yuan and Liu 2008). P limitation can induce substantial variations in gene expression in plants, but the diversity of these metabolic alterations and their regulation procedure have been poorly studied. Pant et al. (2015) profiled nearly 350 PMs and SMs of P‐added and P‐deficient A. thaliana, wild‐type, and mutants of the central P‐signaling components (PHR1 and PHO2, and microRNA399 overexpressor). P availability has a significant effect on the metabolite profile in the roots and shoots of A. thaliana wild‐type, phr1, pho2, and miR399OX seedlings. The concentrations of many glucosinolates, phenylpropanoids, flavonoids, flavonoid glycosides, esculetin, ferulic acid, caffeic acid, kaempferol glucuronide, kaempferol 3‐O‐glucoside, kaempferol 3‐O‐rutinoside, and many other glucosinolates markedly increased in wild‐type A. thaliana under P limitation.
K is a vital macro‐mineral element (inorganic cation) that is necessary for the optimal growth and development of plants. K being an abundant cation in plant tissues plays fundamental role in numerous biochemical and biophysical processes, such as osmoregulation, ion homeostasis, enzyme activation, and protein formation. Nonstomatal inhibition of photosynthesis, such as the inhibition of chlorophyll synthesis, is often observed during unfavorable conditions, and the K supply can positively affect chlorophyll biosynthesis (Tiwari et al. 1998), the chloroplastic CO2 level, and the electron transport system. The free ionic form of K (K+) plays a fundamental role in regulating many physiological processes, such as membrane polarization, protein synthesis, and osmotic adjustments, and thus controls osmotically driven processes such as phloem transport and stomatal function (Zorb et al. 2014). When K+ is sufficient, carboxylation and the overall photosynthetic rate lead to normal growth and yield. K‐limitation reduces photosynthetic rates because of the low concentration of CO2 stemming from stomatal closure (Jin et al. 2011). In contrast, a sufficient K level can improve the photosynthetic rate by regulating stomatal and gas exchange attributes and enzymes such as Rubisco (Erel et al. 2015). Furthermore, K‐induced increases in photosynthesis might also stem from a reduction in reactive oxygen species. For example, the K supply can decrease oxidative damage by increasing the activities of key enzymes of the antioxidant system, such as SOD, POD, and CAT (Ahanger and Agarwal 2017a, 2017b). Plants have developed efficient mechanisms for K uptake to guarantee normal growth under K‐limited conditions. For example, main strategies for efficient K uptake capacity include potassium redistribution between cytosol and vacuole for cellular homeostasis and adaptation of the root system. Execution of these strategies needs accurate regulatory signaling pathways and mechanisms. The accumulation of sugars and amino acids increased in both leaves and roots, but organic acids showed reduction upon low K stress. Moreover, amino acids with negative charges (Asp and Glu) and most organic acids were decreased while amino acids carrying positive charge (Lys and Gln) increased in all three genotypes (Ashley et al. 2006). The selective reductions in acidic amino acids can facilitate the maintenance of the charge balance upon low K stress. Armengaud et al. (2009) noted the responses of shoot and roots of two‐week old Arabidopsis (A. thaliana) plant species to K availability. The concentrations of nitrate, pyruvate, organic acids (2‐oxoglutarate and malate), glutamate, and aspartate (negatively charged amino acids) were significantly reduced in the roots, but the concentrations of soluble carbohydrates (e.g. glucose, sucrose, and fructose) and numerous amino acids such as glycine, arginine, and glutamine (positively charged amino acids) and those with a high N:C ratio were significantly increased in the roots. In addition, metabolite alterations under K depletion were observed later in the shoots than in the roots. Carbohydrates (sucrose and reducing sugars) and organic acids were increased in the shoots. Moreover, N‐rich and basic amino acids like arginine, glutamine, asparagine, lysine, and histidine largely increased in shoots relative to the roots.
Although K is not metabolized, but there are numerous metabolic processes that are highly K‐dependent. For example, (i) direct enzyme activation of enzymes: vacuolar PPase isoforms, which are responsible for the accumulation of protons in the vacuolar lumen, are largely dependent on the K+ level; (ii) translation: ribosome‐mediated protein synthesis also depends on a sufficient K+ concentration; and (iii) transportation: both across membranes and over long distances, among other important roles (Wyn Jones and Pollard 1983; Marschner 1995). These processes assist in observing the metabolic impairments especially under K‐deficient conditions.
K+ limitation can lead to low chlorophyll and photosynthetic activity, the accumulation of simple carbohydrates, and a decrease in plant growth and yield. Therefore, sufficient K+ must be present in the soil to facilitate sufficient absorption and transportation, since its distribution to different plant organs depends on its availability and significantly affects the biosynthesis, conversion, and allocation of plant metabolites (Sorger et al. 1965; Evans and Sorger 1966). K+‐deficient conditions can also increase the sensitivity of plants to unfavorable environmental conditions. The plant K level decreases the occurrence of pests and diseases by regulating the production of organic compounds having large molecular weight, such as proteins, cellulose, and starch (Marschner 1995). The availability and level of K+ also regulate plant metabolism through transcriptional and posttranscriptional regulation of metabolic enzymes. Studies on K+‐deficient A. thaliana plants gave insight into the induction of GS/GOGAT pathway, malic enzyme, and the suppression of nitrate uptake (Amtmann and Blatt 2009; Armengaud et al. 2009). K limitation in cultivated land has emerged as a major factor negatively affecting the sustainable growth and production of crop plants worldwide. K‐sufficient conditions help sustain the normal metabolism and growth of plants (Sharma et al. 2006). K‐limited plants accumulate numerous basic or neutral amino acids, show minor rise in total amino acids and proteins, and contain few acidic amino acids and nitrate. K also plays a key role as an inorganic osmotic solute as well as in the synthesis of other compatible solutes required for stomatal movement and maintenance of water relations. Potassium also governs the loading of photo‐assimilates and the functioning of key metabolic enzymes (Ahanger et al. 2014; 2015; Erel et al. 2015). Furthermore, a significant reduction in pyruvic acid was observed in the roots. Most metabolites returned to their prealteration levels within 24 hours of K re‐stocking; the exception was sucrose, glucose, and fructose in the shoots. However, in roots, pyruvic acid recovered within minutes, but 2‐oxoglutaric acid and malic acid recovered more slowly. K limitation also reversibly changed the activities of many enzymes engaged in sugar metabolism (glucokinase, fructokinase, and invertase), glycolysis (glyceraldehyde 3‐phosphate dehydrogenase [GAPDH]), Krebs cycle (malic enzyme), and N assimilation (NR, GS, GDH, and Fd‐GOGAT). The noticeable build‐up of sugars, the reduction of pyruvic acid in the root cells, and the swift restoration of root sugar and pyruvic acid level suggest that K level in root cytoplasm could be the first one to be recovered upon K re‐supply (Leigh and Wyn Jones 1984). Alterations in the shoot metabolite profile (e.g. sugar accumulation and nitrate reduction) are likely derived from the same alterations in the roots. However, following K re‐supply, changes in some amino acids were specific to the shoots and took place even before K accumulated, specifying the presence of a root/shoot signal from K itself. Based on the determined metabolite profile, glutamic acid appears to play a vital role in the long‐distance signaling of tissue K status (Lacombe et al. 2001; Davenport 2002). K limitation has also been shown to decrease the scopolin content in sunflower (Lehman and Rice 1972), oxylipins in A. thaliana (Troufflard et al. 2010), and galanthamine in Narcissus bulbs (Lubbe and Verpoorte 2011). These findings suggest that K availability has crucial role in regulating the production of SMs in plants. Low K also induces oxidative stress owing to overproduction of reactive oxygen species (ROS), which damages cell membrane stability. Proline and ascorbate, which are important nonenzymatic antioxidants, have been found to mount up in plants against low K stress to protect plants from oxidative stress damage (Zeng et al. 2018).
S is another essential mineral element and a central component of plant metabolism. Autotrophic organisms require sulfur for the biosynthesis of various PMs and SMs for their growth and development. The acquisition and assimilation of S in plants have received increased research interest, especially in the context of crop improvement. Any changes in S acquisition and assimilation can lead to drastic metabolic changes that affect sulfur‐containing pools of both PMs and SMs.
Sulfur is an integral part of an array of plant metabolites including proteins and amino acids (cysteine, methionine), antioxidants (reduced glutathione), phytohormones, vitamins, sulfolipids, phytochelatins, iron‐sulfur (Fe‐S) clusters, glucosinolates, and cofactors (biotin and thiamine) having ability to potentially modify the physiological processes in plants (Takahashi et al. 2011; Asgher et al. 2014; Fatma et al. 2016). S application decreases the production of excess ROS and thus protects plants from oxidative damage (Fatma et al. 2014; Khan et al. 2015). Once absorbed by the roots, S becomes assimilated into some key organic metabolites, such as thiol (‐SH) groups in cysteine or nonprotein thiol such as glutathione. Glutathione helps to remove excess ROS, which protects the cells from oxidative damage.
S limitation inhibits chlorophyll biosynthesis, Rubisco content, photosynthesis, N assimilation, and protein synthesis and eventually disturbs plant metabolism (Honsel et al. 2012). Lunde et al. (2008) reported that S limitation decreases the concentrations of glucose, fructose, and the glycolytic intermediate PEP but increases the content of starch, flavonoids, and anthocyanins. The consumption of carbohydrates was more strongly inhibited compared with photosynthesis in S‐limited plants. The reduction in monosaccharides can be linked to the reduction in photosynthesis, and the increase in starch accumulation is considered a general response to nutrient deficiency. S‐limitation has been shown to markedly decrease the concentration of lipids (especially sulfolipids), protein, RNA, S‐adenosyl‐methionine (SAM), and chlorophyll (which requires SAM for biosynthesis), as well as the photosynthetic rate (Nikiforova et al. 2005). S deprivation decreases total glucosinolates and downregulates the genes involved in glucosinolate biosynthesis (Aghajanzadeh 2015). Indole‐acetonitrile, a breakdown product of glucosinolate, is produced from Trp and it acts as a precursor in the biosynthesis of indole‐3‐acetic acid (auxin), which is also upregulated by S‐deficiency (Kutz et al. 2002). The increase in the auxin level could explain the increase in lateral root growth in S‐deficient plants.
Low Mg availability negatively affects morphogenesis, development, and the productivity of plants. Mg is another essential macronutrient element required for plant growth and development. Mg has vital role in carbon fixation being a key constituent of chlorophyll molecule. Mg2+ holds central place in the chlorophyll molecule, surrounded by four N atoms from the porphyrin ring. The important regulatory role of Mg2+ in photosynthesis is well established. Changes in Mg2+ concentration in the chloroplast control the functioning of many important enzymes involved in photosynthesis. Mg2+ plays an important role in photosynthesis because it can promote light reactions operating in the stroma. Light triggers the entry of Mg2+ into the stroma of the chloroplast in exchange for H+, thus establishing an optimum level for the carboxylase reaction. Mg2+ acts as a cofactor and activates the ribulose bisphosphate carboxylase (RuBP carboxylase,) and fructose‐1,6‐bisphosphatase. Thus, Mg2+ plays a fundamental role in CO2 assimilation and related metabolic processes, such as sugar and starch production (Marschner 2012). Mg2+ also acts as a cofactor in almost all the enzymes activating phosphorylation processes. Mg2+ links the pyrophosphate structure of ATP or ADP to the enzyme molecule. Hence, the activation of ATPase by Mg2+ is brought about by this linking function (Balke and Hodges 1975). Mg2+ is also required for the activation of dehydrogenases and enolase, the aggregation of ribosomes, the modulation of ionic currents across the chloroplast, and vacuolar membranes (i.e. the organelle that regulates ion balance in the cell and stomatal opening (Maathuis and Diatloff 2013).
Mun et al. (2020) examined the effects of excess Mg on Perilla frutescens leaves and noted higher chlorophyll, carbohydrates (glucose, xylose, maltose, adonitol, xylitol, glycerol, gluconic acid, glyceric acid, maltose, and fructose), and amino acids (threonine, glycine, serine, and GABA) but low antioxidant metabolites (ABTS, DPPH, and FRAP). In contrast, tryptophan, sucrose, and some organic acids (oxoglutaric acid and lactic acid), flavonoids (apigenin‐7‐O‐diglucuronide, apigenin‐7‐O‐glucuronide, luteolin‐7‐O‐diglucuronoide, apigenin‐6,8‐diglucoside, luteolin‐7‐O‐glucoside, and liquiritigenin), sagerinic acid, cinnamic acid derivatives (dimethoxycinnamic acid, caffeic acid, and salvianolic acid C), and triterpenoids (tormentic acid and corosolic acid) were significantly reduced in Mg‐oversupplied plants compared to control plants. In contrast, previous studies have shown that plant SMs (flavonoids and phenolic compounds) also serve the purpose of antioxidants and assist in reducing the oxidative damage induced by abiotic stress (Nakabayashi et al. 2014).
Ca is an abundant element existing in the lithosphere having a mean value of approximately 3.5% Ca. However, soils composed of chalk or limestone are usually rich in CaCO3 (calcite) and possess 50% Ca. Plant roots absorb Ca in the form of divalent ion (Ca2+) and account for approximately 0.5% of plant dry matter. Inside plant tissues, Ca2+ has a high affinity for plant metabolites with a negative charge. Therefore, Ca cannot be remobilized from old plant organs; hence, if Ca availability is low in the soil solution, the Ca concentration can decrease below critical levels and have negative effects on growth and productivity. A sharp decrease in Ca levels, especially in fast‐growing tissues, can lead to diseases such as “blossom end rot” in tomatoes, “black heart” in celery, “tip burn” in lettuce, or “bitter‐pit” in apples, even when plants are growing in the presence of sufficient amounts of Ca in soil (White 2000; Demidchik and Maathuis 2007; Bárcena et al. 2019).
Ca has a crucial role in cell division, structure and permeability of plasma membrane, cell transduction and elongation, translocation of carbohydrate, and nitrogen metabolism (White 2000; El‐Beltagi and Mohamed 2013. Ca plays a role in maintaining the structure of the cell wall and membranes. It readily form complexes with several anionic substances such as the phosphates and carboxyls of phospholipids, sugars and proteins. For example, in plant cell walls, the cross‐linking of pectins and glycans occurs through electrostatic coordination of Ca. Ca acts as “glue” that not only contributes to cell wall structure and strength but also decreases the risk of pathogen penetration (Marschner 1995; Maathuis and Diatloff 2013).
This complexation mainly occurs outside the cell membrane and requires a high concentration of apoplastic Ca. Replacement of Ca with other cations or elimination of apoplastic Ca can compromise membrane strength and lead to cellular electrolyte leakage. Since Ca can form insoluble salts with phosphates and sulfates easily, therefore concentration of free Ca in the cytoplasm is normally kept low nearly around ca. 100 nM. This makes Ca an ideal secondary messenger, and various stimuli have been shown to evoke rapid changes in cytosolic free Ca in plants, including responses to biotic and abiotic stress, stomatal regulation, and physical damage (Haynes 1980; Wallace and Mueller 1980). Ca also participates in photosynthetic water oxidation in PSII, which requires a metal cluster that contains a Ca ion (Hochmal et al. 2015). In contrast, optimal amounts of Ca have been shown to significantly improve the production of chlorophylls and carotenoids and maintain high photosynthetic efficiency and stomatal conductance (Elkelish et al. 2019). Ca also plays a role in polyphenolic metabolism. For example, Ca takes part in the biosynthesis of polyphenolic compounds. The application of Ca can increase the phenylalanine ammonia‐lyase activity, which leads to the accumulation of polyphenols (Castaneda and Perez 1996; Juric et al. 2020).
In addition, Ca deprivation has been reported to inhibit the photosynthesis and N metabolism of spinach plants by reducing the content of chlorophyll and activities of Rubisco, GDH, GS, and GPT (Chao et al. 2008). Under Ca deficiency, plants face the problem of an enhanced electrolyte leakage rate and decreased AsA content (da Silva et al. 2021). The increase in malondialdehyde might enhance the activity of pectolytic enzymes (Olle and Bender 2009) and lipid peroxidation (Chao et al. 2009).
B is an important trace mineral nutrient necessary for physiological processes in higher plants. B plays important roles in cell division and elongation, sugar transport, carbohydrate metabolism, N metabolism, cytoskeletal proteins, cell wall synthesis, and lignification, as well as in maintaining the integrity of bio‐membranes. Ions (K+, H+, Ca2+, KPO43−, and Rb+) are transported across the membranes, and plasmalemma‐bound enzymes, polyamines, nucleic acids, ascorbic acid, and phytohormones (indoleacetic acid) are important for mediating ion transport (Shireen et al. 2018). Plant growth and metabolism are adversely affected due to B deficiency. B deficiency or toxicity usually leads to carbohydrate accumulation (hexose sugars (glucose, fructose) and starch contents become high, but the accumulation of sucrose is low. Ruuhola et al. (2011a) reported that B availability affects carbohydrate and phenol metabolism in summer leaves and autumn buds of one‐year‐old birch seedlings (Betula pendula Roth) when treated with three different B levels: B‐0 (control), B‐30 (low level), and B‐100 (high level). B‐100 in summer leaves increased the starch accumulation and caused a reduction in hexose sugars (glucose and fructose). In contrast, B‐0 seedlings accumulated more hexose sugar (mainly glucose) and less starch content. The autumn buds of B‐30 seedlings accumulated fewer sugars (glucose and raffinose) along with total polyols, mainly due to the deposition of other metabolites (i.e. phenols). Moreover, the highest accumulation of condensed tannins was detected in B‐30. Similarly, severe boron limitation enhanced the level of hexoses, starch, and sucrose in tobacco (Nicotiana tabacum L.) (Camacho‐Cristóbal and González‐Fontes 1999; Camacho‐Cristóbal et al. 2004). The accumulation of sugar in response to B availability might have occurred due to decrease in sink demand because of a reduction in growth (Han et al. 2008, 2009).
Some researchers have examined the B availability effects on polyol accumulation in leaves. Leite and Mather (2008) detected high amount of sorbitol, myo‐inositol, mannitol, scyllo‐inositol, and arabinose in the leaves of B‐supplied Eucalyptus grandis seedlings compared with B‐deprived seedlings. The phenolic content may constitute about 30–40% part of the total plant biomass (dry weight), which represents a major path to properly channelize the carbon (Ossipov et al. 2001). Phenolic metabolism is also involved in the production of different precursors needed for the biosynthesis of various phenolic metabolites through the shikimate pathway. Extreme B deprivation facilitates phenolic accumulation in different herbaceous species (Camacho‐Cristóbal et al. 2002; Hajiboland and Farhanghi 2010). However, moderate B limitation did not affect the accumulation of phenolics in a woody plant (silver birch, Ruuhola et al. 2011b).
Chloride (Cl) is an important mineral nutrient highly important for higher plants. It mainly occurs as Cl anion in soil and plants. Glycophytes usually contain 1–20 mg Cl g dw−1 (Marschner 2011). Although the demand for Cl for normal growth is low, Cl deprivation occurs when the Cl level is below 20 μmol kg−1 dw−1, indicating that Cl is a micronutrient (Clarkson and Hanson 1980). However, the thresholds vary among crop plants. For example, the threshold level of barley (Hordeum vulgare) and wheat (Triticum aestivum) is below 1.2–4.0 mg g dw−1; for lettuce (Lactuca sativa) and spinach, it is 0.14 mg g dw−1; that for rice is 3 mg g shoot dw−1; and that for maize (Zea mays) is 0.05–0.11 mg Cl g dw−1 (Xu et al. 2000)
Cl has been found in more than 130 organic compounds isolated from higher plants and ferns. It is actively involved in a variety of plant physio‐biochemical processes such as osmotic adjustment and stomatal regulation, the oxygen evolution during photosynthetic process, and disease resistance and tolerance (Chen et al. 2010). Cl can also promote the evolution of oxygen and photophosphorylation (Bove et al. 1963). Cl is indirectly involved in stomatal regulation as opening and closing of guard cells are regulated by potassium and anions (Cl). Cl− is a nonassimilating highly mobile anion, and therefore regulates the cell’s osmolarity and the electrical charge balance of cations (Flowers 1988; Marschner 2012). Specifically, it can balance the electric charges of important cations, including calcium (Ca2+), potassium (K+), and protons (H+); Cl− thus plays a critical role in stabilizing the electric potential of cell membranes and the regulation of pH gradients and electrical excitability. It also affects the absorption and utilization of other important plant nutrients, including nitrogen (N), phosphorus (P), potassium (K),magnesium (Mg), calcium (Ca), manganese (Mn), silicon (Si), zinc (Zn), sulfur (S), copper (Cu), and iron (Fe)in higher plants (Zhong and Ma 1993). Cl reduces NO3− uptake by the roots and facilitates the incorporation of N into organic compounds in the leaves of Catharanthus rhoeus (Flores et al. 2000). However, Cl can improve N assimilation and increase N use efficiency in tobacco plants (Rosales et al. 2020). Several enzymes are known to be stimulated by Cl (e.g. ATPase, α‐Amylase, and asparagine synthetase, and it also promotes starch accumulation in potatoes (Fixen Paul 1993; Geilfus 2018).
Although plants require Cu in low concentrations, it is critically important to plant life. Its concentrations in most plants generally range from 2 to 20 ppm in dry plant material. Two oxidation states Cu1+ (unstable) and Cu2+ of copper normally prevail that can be substituted with each other; therefore, Cu functions as a redox agent in biochemical reactions. Copper plays essential roles in photosynthesis and mitochondrial respiration, C/N metabolism, lignification, and protection against oxidative stress. Cu acts as cofactor for plastocyanin, cytochrome‐c oxidase, copper/zinc superoxide dismutase (Cu/ZnSOD), apoplastic oxidases: ascorbate oxidase, polyphenol oxidase, and diamine oxidase (Yruela 2009). It is also part of the ethylene receptor (Rodriguez et al. 1999) and facilitates the biosynthesis of molybdenum cofactor (Kuper et al. 2004). In contrast, the excessive accumulation of Cu is potentially harmful and can increase malondialdehyde and thus oxidative stress by decreasing the concentration of antioxidant enzymes, including CAT, APX, and GPX, and negatively affecting mineral nutrition (Bankaji et al. 2015). It can also catalyze the synthesis of free radicals and thus damage DNA, proteins, and other biomolecules. Therefore, Cu ions are bound by scavenging proteins such as metallothioneins to prevent their accumulation (Hansch and Ralf 2009). Approximately 70% of the total copper in leaves is bound to various cell organelles/components. The copper bounded by plastocyanin (an electron carrier protein photosystem I) accounts for approximately 50% of plastidic copper (Pilon et al. 2006).
Fe is the second most abundant element in the Earth’s crust. Although it is hardly present in living matter (50–100 μg·g−1 dry matter), it is still an essential micronutrient that is critical for plant life because of its involvement in plant metabolism, including photosynthesis, respiration, and DNA synthesis, hormone biosynthesis (ethylene, gibberellic acid, and jasmonic acid), N assimilation, osmoprotection, the scavenging of reactive oxygen species, and pathogen defense (Hansch and Ralf 2009). Fe is an active cofactor of many enzymes that are important for the biosynthesis of plant hormones, including ethylene, lipoxygenase, and 1‐aminocyclopropane acid‐1‐carboxylic oxidase (Siedow 1991). The activity of amylase reduces when a large amount of iron accumulates because iron forms complexes with carbohydrates such as maltose (Hofner 1970). A high degree of iron accumulation may lead to the iron‐induced deprivation of other essential nutrients (e.g. Mn, P, K, Ca, and Mg) in plants (Howeler 1973; Ottow et al. 1982). The assimilation of NH4+ into amino acids occurs via the joint action of the GS/GOGAT cycle, which is a primary route of N assimilation in plants. Any reduction in the activities of these enzymes reduces the production of amino acids and thus N assimilation in plants. Amylase invertase, aspartate aminotransferase, and glutamate synthase have been reported to be significantly affected in tea plants under a surplus of Fe (Hemalatha and Venkatesan 2011). In addition, high Fe concentrations decreased the amount of photosynthetic pigments, such as chlorophyll and carotenoids. Monteiro and Winterbourn (1988) reported that high iron levels catalyze the generation of active O2‐free radical species, which may oxidize chlorophyll and subsequently reduce the chlorophyll content.
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