Tentative identification of phytochelatins, their derivatives, and Cd-phytochelatin complexes in Ocimum basilicum L. roots by Paper Spray Mass Spectrometry.

An unprecedented and direct PS-MS (paper spray ionization mass spectrometry) method was proposed for the detection of native peptides, that is, glutathiones (GSHs), homoglutathiones (hGSHs), and phytochelatins (PCs), in basil (Ocimum basilicum L.) roots before and after cadmium exposure. The roots were submitted to cold maceration followed by sonication with formic acid as the extractor solvent for sample preparation. PS-MS was used to analyze such extracts in the positive mode, and the results allowed for the detection of several GSHs, hGSHs, and PCs. Some of these PCs were not distinguished in the control samples, that is, basil roots not exposed to cadmium. Other PCs were noticed in both types of roots, uncontaminated and cadmium-contaminated, but the intensities were higher in the former samples. Moreover, long-time exposure to cadmium stimulated the formation of some of these PCs and their cadmium complexes. The results, therefore, provided some crucial insights into the defense mechanism of plants against an external stress condition due to exposure to a toxic heavy metal. The present study represents a promising alternative to investigate other crucial physiological processes in plants submitted to assorted stress conditions.

Unveiling New Arsenic Compounds in Plants via Tailored 2D-RP-HPLC Separation with ICP and ESI MS Detection.

Arsenic (As) speciation analysis is scientifically relevant due to the pivotal role the As chemical form plays in toxicity, which, in turn, directly influences the effect it has on the environment. The objective of this study was to develop and optimize a method tailored for studying As compounds in plant samples. Different extraction procedures and HPLC methods were explored to assess their efficiency, determine mass balance, and improve the resolution of compounds in the chromatograms. Conventionally applied anion-exchange chromatography facilitated the separation of well-documented As compounds in the extracts corresponding to 19 to 82% of As present in extracts. To gain insight into compounds which remain undetectable by anion chromatography (18 to 81% of As in the extracts), but still possibly metabolically relevant, we explored an alternative chromatographic approach. The procedure of sample purification and preconcentration through solid-phase extraction, facilitating the detection of those minor As compounds, was developed. The system was further refined to achieve an online 2D-RP-HPLC system, which was employed to analyze the extracts more comprehensively with ICP and ESI MS. Using this newly developed method, As(III)-phytochelatins, along with other arseno-thio-compounds, were detected and identified in extracts derived from the tree roots of seedlings grown in the presence of As(III) and As(V), and a group of arseno lipids was detected in the roots of plants exposed to As(V).

Hyperconfined bio-inspired Polymers in Integrative Flow-Through Systems for Highly Selective Removal of Heavy Metal Ions.

Access to clean water, hygiene, and sanitation is becoming an increasingly pressing global demand, particularly owing to rapid population growth and urbanization. Phytoremediation utilizes a highly conserved phytochelatin in plants, which captures hazardous heavy metal ions from aquatic environments and sequesters them in vacuoles. Herein, we report the design of phytochelatin-inspired copolymers containing carboxylate and thiolate moieties. Titration calorimetry results indicate that the coexistence of both moieties is essential for the excellent Cd2+ ion-capturing capacity of the copolymers. The obtained dissociation constant, KD ~ 1 nM for Cd2+ ion, is four-to-five orders of magnitude higher than that for peptides mimicking the sequence of endogenous phytochelatin. Furthermore, infrared and nuclear magnetic resonance spectroscopy results unravel the mechanism underlying complex formation at the molecular level. The grafting of 0.1 g bio-inspired copolymers onto silica microparticles and cellulose membranes helps concentrate the copolymer-coated microparticles in ≈3 mL volume to remove Cd2+ ions from 0.3 L of water within 1 h to the drinking water level (<0.03 µM). The obtained results suggest that hyperconfinement of bio-inspired polymers in flow-through systems can be applied for the highly selective removal of harmful contaminants from the environmental water.

Unravelling the halophyte Suaeda maritima as an efficient candidate for phytostabilization of cadmium and lead: Implications from physiological, ionomic, and metabolomic responses.

Cadmium (Cd) and lead (Pb) are among the most toxic heavy metals affecting human health and crop yield. Suaeda maritima (L.) Dumort is an obligate halophyte that is well adapted to saline soil. The inbuilt salinity tolerance mechanisms of halophytes help them to survive in heavy metal-contaminated rhizospheric soil. In the present study, growth and ionomic responses, reactive oxygen species (ROS) accumulation, modulations of phytochelatins, antioxidative defense, and metabolomic responses were studied in S. maritima imposed to Cd and Pb stresses with an aim to elucidate Cd and Pb tolerance mechanisms and phytoremediation potential of this halophyte. Our results showed a reduction of biomass in S. maritima, which may serve as an energy conservation strategy for survival under heavy metal stress. The increased accumulation of ROS with concomitant higher expression of various antioxidative enzymes suggests the efficient scavenging of ROS. The metabolite profiling revealed significant up-regulation of sugars, sugar alcohols, amino acids, polyphenols, and organic acids under Cd and Pb stresses suggesting their possible role in osmotic balance, ionic homeostasis, ROS scavenging, and signal transduction for stress tolerance. In S. maritima, the translocation factors (Tf) are <1 in both Cd and Pb treatments, which indicates that this halophyte has high phytostabilization potential for Cd and Pb in roots and through restricted translocation of heavy metal ions to the aboveground part. The findings of this study offer comprehensive information on Cd and Pb tolerance mechanisms in S. maritima and suggest that this halophyte can detoxify the HMs through physiological, ionic, antioxidative, and metabolic regulations.

Phytochelatins Bind Zn(II) with Micro- to Picomolar Affinities without the Formation of Binuclear Complexes, Exhibiting Zinc Buffering and Muffling Rather than Storing Functions.

Phytochelatins (PCs) are poly-Cys peptides containing a repeating γ-Glu-Cys motif synthesized in plants, algae, certain fungi, and worms by PC synthase from reduced glutathione. It has been shown that an excess of toxic metal ions induces their biosynthesis and that they are responsible for the detoxification process. Little is known about their participation in essential metal binding under nontoxic, basal conditions under which PC synthase is active. This study presents spectroscopic and thermodynamic interactions with the PC2-PC5 series, mainly focusing on the relations between Zn(II) complex stability and cellular Zn(II) availability. The investigations employed mass spectrometry, UV-vis spectroscopy, potentiometry, competition assays with zinc probes, and isothermal titration calorimetry (ITC). All peptides form ZnL complexes, while ZnL2 was found only for PC2, containing two to four sulfur donors in the coordination sphere. Binuclear species typical of Cd(II)-PC complexes are not formed in the case of Zn(II). Results demonstrate that the affinity for Zn(II) increases linearly from PC2 to PC4, ranging from micro- to low-picomolar. Further elongation does not significantly increase the stability. Stability elevation is driven mainly by entropic factors related to the chelate effect and conformational restriction rather than enthalpic factors related to the increasing number of sulfur donors. The affinity of the investigated PCs falls within the range of exchangeable Zn(II) concentrations (hundreds of pM) observed in plants, supporting for the first time a role of PCs both in buffering and in muffling cytosolic Zn(II) concentrations under normal conditions, not exposed to zinc excess, where short PCs have been identified in numerous studies. Furthermore, we found that Cd(II)-PC complexes demonstrate significantly higher metal capacities due to the formation of polynuclear species, which are lacking for Zn(II), supporting the role of PCs in Cd(II) storage (detoxification) and Zn(II) buffering and muffling. Our results on phytochelatins' coordination chemistry and thermodynamics are important for zinc biology and understanding the molecular basis of cadmium toxicity, leaving room for future studies.

Engineered Cyanobacteria-Based Living Materials for Bioremediation of Heavy Metals Both In Vitro and In Vivo.

The pollution caused by heavy metals (HMs) represents a global concern due to their serious environmental threat. Photosynthetic cyanobacteria have a natural niche and the ability to remediate HMs such as cadmium. However, their practical application is hindered by a low tolerance to HMs and issues related to recycling. In response to these challenges, this study focuses on the development and evaluation of engineered cyanobacteria-based living materials for HMs bioremediation. Genes encoding phytochelatins (PCSs) and metallothioneins (MTs) were introduced into the model cyanobacterium Synechocystis sp. PCC 6803, creating PM/6803. The strain exhibited improved tolerance to multiple HMs and effectively removed a combination of Cd2+, Zn2+, and Cu2+. Using Cd2+ as a representative, PM/6803 achieved a bioremediation rate of approximately 21 µg of Cd2+/OD750 under the given test conditions. To facilitate its controllable application, PM/6803 was encapsulated using sodium alginate-based hydrogels (PM/6803@SA) to create "living materials" with different shapes. This system was feasible, biocompatible, and effective for removing Cd2+ under simulated conditions of zebrafish and mice models. Briefly, in vitro application of PM/6803@SA efficiently rescued zebrafish from polluted water containing Cd2+, while in vivo use of PM/6803@SA significantly decreased the Cd2+ content in mice bodies and restored their active behavior. The study offers feasible strategies for HMs bioremediation using the interesting biomaterials of engineered cyanobacteria both in vitro and in vivo.

Cryo-EM structure of cadmium-bound human ABCB6.

ATP-binding cassette transporter B6 (ABCB6), a protein essential for heme biosynthesis in mitochondria, also functions as a heavy metal efflux pump. Here, we present cryo-electron microscopy structures of human ABCB6 bound to a cadmium Cd(II) ion in the presence of antioxidant thiol peptides glutathione (GSH) and phytochelatin 2 (PC2) at resolutions of 3.2 and 3.1 Å, respectively. The overall folding of the two structures resembles the inward-facing apo state but with less separation between the two halves of the transporter. Two GSH molecules are symmetrically bound to the Cd(II) ion in a bent conformation, with the central cysteine protruding towards the metal. The N-terminal glutamate and C-terminal glycine of GSH do not directly interact with Cd(II) but contribute to neutralizing positive charges of the binding cavity by forming hydrogen bonds and van der Waals interactions with nearby residues. In the presence of PC2, Cd(II) binding to ABCB6 is similar to that observed with GSH, except that two cysteine residues of each PC2 molecule participate in Cd(II) coordination to form a tetrathiolate. Structural comparison of human ABCB6 and its homologous Atm-type transporters indicate that their distinct substrate specificity might be attributed to variations in the capping residues situated at the top of the substrate-binding cavity.

Mitigating Effect of Trans-Zeatin on Cadmium Toxicity in Desmodesmus armatus.

Phytohormones, particularly cytokinin trans-zeatin (tZ), were studied for their impact on the green alga Desmodesmus armatus under cadmium (Cd) stress, focusing on growth, metal accumulation, and stress response mechanisms. Using atomic absorption spectroscopy for the Cd level and high-performance liquid chromatography for photosynthetic pigments and phytochelatins, along with spectrophotometry for antioxidants and liquid chromatography-mass spectrometry for phytohormones, we found that tZ enhances Cd uptake in D. armatus, potentially improving phycoremediation of aquatic environments. Cytokinin mitigates Cd toxicity by regulating internal phytohormone levels and activating metal tolerance pathways, increasing phytochelatin synthase activity and phytochelatin accumulation essential for Cd sequestration. Treatment with tZ and Cd also resulted in increased cell proliferation, photosynthetic pigment and antioxidant levels, and antioxidant enzyme activities, reducing oxidative stress. This suggests that cytokinin-mediated mechanisms in D. armatus enhance its capacity for Cd uptake and tolerance, offering promising avenues for more effective aquatic phycoremediation techniques.

Complexation and immobilization of arsenic in maize using green synthesized silicon nanoparticles (SiNPs).

Arsenic (As) is a heavy metal that is toxic to both plants and animals. Silicon nanoparticles (SiNPs) can alleviate the detrimental effects of heavy metals on plants, but the underlying mechanisms remain unclear. The study aims to synthesize SiNPs and reveal how they promote plant health in Arsenic-polluted soil. 0 and 100% v/v SiNPs were applied to soil, and Arsenic 0 and 3.2 g/ml were applied twice. Maize growth was monitored until maturity. Small, irregular, spherical, smooth, and non-agglomerated SiNPs with a peak absorbance of 400 nm were synthesized from Pycreus polystachyos. The SiNPs (100%) assisted in the development of a deep, prolific root structure that aided hydraulic conductance and gave mechanical support to the maize plant under As stress. Thus, there was a 40-50% increase in growth, tripled yield weights, and accelerated flowering, fruiting, and senescence. SiNPs caused immobilization (As(III)=SiNPs) of As in the soil and induced root exudates Phytochelatins (PCs) (desGly-PC2 and Oxidized Glutathione) which may lead to formation of SiNPs=As(III)-PCs complexes and sequestration of As in the plant biomass. Moreover, SiNPs may alleviate Arsenic stress by serving as co-enzymes that activate the antioxidant-defensive mechanisms of the shoot and root. Thus, above 70%, most reactive ROS (OH) were scavenged, which was evident in the reduced MDA content that strengthened the plasma membrane to support selective ion absorption of SiNPs in place of Arsenic. We conclude that SiNPs can alleviate As stress through sequestration with PCs, improve root hydraulic conductance, antioxidant activity, and membrane stability in maize plants, and could be a potential tool to promote heavy metal stress resilience in the field.

The pleiotropic role of Salinicoccus bacteria in enhancing ROS homeostasis and detoxification metabolism in soybean and oat to cope with pollution of triclosan.

Triclosan has been extensively used as a preservative in cosmetics and personal care products. However, its accumulation represents a real environmental threat. Thus, its phytotoxic impact needs more consideration. Our study was conducted to highlight the phytotoxic effect of triclosan on the growth, ROS homeostasis, and detoxification metabolism of two different plant species i.e., legumes (Glycine max) and grass (Avena sativa). Moreover, we investigated the potentiality of plant growth-promoting bacteria (ST-PGPB) in mitigating the phytotoxic effect of triclosan. Triclosan induced biomass (fresh and dry weights) reduction in both plants, but to a higher extent in oats. This decline was associated with a noticeable increment in the oxidative damage (e.g., MDA and H2O2) and detoxification metabolites such as metallothionein (MTC), phytochelatins (PCs), and glutathione-S-transferase (GST). This elevation was associated with a remarkable reduction in both enzymatic and non-enzymatic antioxidants. On the other hand, the bioactive strain of ST-PGPB, Salinicoccus sp. JzA1 significantly alleviated the harmful effect of triclosan on both soybean and oat plants by enhancing their biomass, photosynthesis, as well as levels of minerals (K, Ca, P, Mn, and Zn). In parallel, a striking quenching in oxidative damage and an obvious improvement in non-enzymatic (polyphenols, tocopherols, flavonoids) and enzymatic antioxidants were observed. Furthermore, Salinicoccus sp. JzA1 augmented the detoxification metabolism by enhancing the levels of phytochelatins, metallothionein, and glutathione-S-transferase (GST) activity in a species-specific manner which is more apparent in soybean rather than in oat plants. To this end, stress mitigating impact of Salinicoccus sp. JzA1 provides a basis to improve the resilience of crop species under cosmetics and personal care products toxicity.

Phytochelatin-Mediated Cultivar-Dependent Cd Accumulations of Lactuca sativa and Implication for Cd Pollution-Safe Cultivars Screening.

Cd pollution-safe cultivar (Cd-PSC) is a feasible strategy to minimize Cd contamination in leafy vegetables. The shoot Cd concentrations of 23 Lactuca sativa cultivars under Cd stress ranged from 0.124 to 2.155 mg·kg-1 with a maximum cultivar difference of 8 folds. Typical Cd-PSC C16 (L) and high-Cd-accumulating cultivar C13 (H) were screened to investigate the mechanisms of Cd accumulations in L. sativa through determining Cd concentrations, Cd subcellular distributions, phytochelatin profiles, and phytochelatin biosynthesis-related genes' expressions. Higher Cd distribution in a heat stable fraction in C13 (H) indicated that the high Cd accumulation trait of C13 (H) mainly depended on the Cd-phytochelatin complexes. Root phytochelatin concentrations were significantly elevated in C13 (H) (5.83 folds) than in C16 (L) (2.69 folds) (p < 0.05) under Cd stress. Significantly downregulated expressions of glutathione S-transferase rather than the regulation of phytochelatin synthesis genes in the root of C13 (H) might be responsible for sufficient glutathione supply for phytochelatins synthesis. These findings suggested that phytochelatin elevation in C13 (H) would favor the Cd root to shoot transportation, which provides new insights into the phytochelatin-related cultivar-dependent Cd accumulating characteristic in L. sativa.

Phenomic profiling to reveal tolerance mechanisms and regulation of ascorbate-glutathione cycle in wheat varieties (Triticum aestivum L.) under arsenic stress.

The potential of arsenic (As) tolerant and sensitive varieties of wheat (Triticum aestivum L.) has yet to be explored despite of alarming situation of arsenic toxicity. To fill this gap, the study aimed to explore the role of antioxidants, phytochelatins, and ascorbate-glutathione for As tolerance in wheat. A total of eight varieties were exposed to different arsenate treatments (0, 1, 5, 10, 50, 100, 200, 500, 1000, 2000, and 10,000 µM) initially to screen effective treatment as well as contrasting varieties via Weibull distribution frequency for further analysis. The Weibull analysis found 200 µM as the most effective treatment in the present study. Selected varieties were analyzed for accumulation of total As and As speciation, oxidative stress (malondialdehyde, hydrogen peroxide), antioxidants (superoxide dismutase, catalase, peroxidase), phytochelatins, and ascorbate-glutathione cycle (glutathione-S-transferase, glutathione reductase, glutathione peroxidase, ascorbate peroxidase). Tolerant varieties showed less accumulation and translocation of total As, arsenate, and arsenite to the shoots compared with sensitive varieties under 200 µM treatment. Low concentration in tolerant varieties correlated with better growth and development response. Tolerant varieties showed higher induction of metabolites (glutathione, phytochelatins) compared to sensitive ones. Furthermore, tolerant varieties showed better performance of antioxidant and ascorbate-glutathione cycle enzymes in response to As exposure. The findings of the present study provided great insight into the wheat tolerance mechanism upon As exposure between contrasting varieties.

Detoxification role of amino acids and phytochelatins on two populations of harmel plant under silver stress.

Two non-metallicolous and metallicolous populations of harmel plants were compared regarding the role of proline, cysteine, reducing sugars, hydrogen peroxide (H2O2), glutathione, thiol compounds, organic acids, total free amino acids, and lipid peroxidation in detoxification and tolerance of silver stress (0, 1, 2.5, 5, 10 ppm Ag). The results of the present research state that the effects of Ag were increased total free amino acids, glutathione, organic acids, proline, reducing sugars, thiol compounds, and cysteine, so the accumulation of these compounds was higher in metallicolous populations than non-metallicolous. On the other hand, non-metallicolous populations showed higher content of lipid peroxidation and H2O2 than metallicolous populations under Ag stresses. Also, the accumulation of phytochelatins (PC) was observed with increasing Ag concentration, which shows that compared to glutathione, non-protein thiols have a higher concentration. The number of organic acids (malic acids, fumaric, oxalic, and citric) except acetic acid increased in the leaves of harmel in both populations. According to the results of this research, the harmel metallophilic population has a crucial role in the tolerance and detoxification of Ag stress, so the antioxidant responses of the plant against Ag stress in the non-metallicolous population were lower than the metallicolous population. Based on the above results, it can be concluded that the harmel plant has a detoxification mechanism to deal with high concentrations of Ag.

Coupling of different antioxidative systems in rice under the simultaneous influence of selenium and cadmium.

Selenium (Se) elevates the antioxidant ability of rice against cadmium (Cd) stress, but previous studies only focused on the variation in antioxidant enzymes or nonenzymatic substances induced by Se under Cd stress and ignored the relationships between different antioxidant parameters during the interaction. Here, hydroponic experiments with rice were performed by adding both Cd and Se at doses in the range of 0-50 µM to explore the physiological responses of rice and their relationships in the presence of different levels of Se and Cd. Exogenous Cd markedly promoted the activity of antioxidant enzymes with the exception of catalase (CAT) and the concentration of nonenzymatic substances in aerial parts. Se enhanced the antioxidant capacity by improving the activities of all the enzymes tested in this study and increasing the concentrations of nonenzymatic compounds. The couplings among different antioxidant substances within paddy rice were then determined based on cluster and linear fitting results and their metabolic process and physiological functions. The findings specifically highlight that couplings among the ascorbic acid (AsA)-glutathione (GSH) cycle, glutathione synthase (GS)-phytochelatin synthetase (PCS) coupling system and glutathione peroxidase (GPX)-superoxide dismutase (SOD) coupling system in aerial parts helps protect plants from Cd stress. These coupling systems form likely due to the fact that one enzyme generated a product that could be the substrate for another enzyme. Noticeably, such coupling systems do not emerge in roots because the stronger damage to roots than other organs activates the ascorbate peroxidase (APX)-GPX-CAT and PCS-GS-SOD systems with distinct functions and structures. This study provides new insights into the detoxification mechanisms of rice caused by the combined effect of Se and Cd.

Overexpression of LSU1 and LSU2 confers cadmium tolerance by manipulating sulfur metabolism in Arabidopsis.

Phytoremediation using plants is an environmentally friendly and cost-effective strategy for removing cadmium (Cd) from soil. Plants used for phytoremediation must have a high Cd accumulation capacity and strong Cd tolerance. Therefore, understanding the molecular mechanism of Cd tolerance and accumulation in plants is of great interest. In response to Cd exposure, plants produce various thio-rich compounds, such as glutathione, phytochelatins, and metallothioneins, which play important roles in Cd immobilization, sequestration, and detoxification. Therefore, sulfur (S) metabolism is crucial for Cd tolerance and accumulation. In this study, we report that the overexpression of low-S responsive genes, LSU1 and LSU2, confers Cd tolerance in Arabidopsis. First, LSU1 and LSU2 promoted S assimilation under Cd stress. Second, LSU1 and LSU2 inhibited the biosynthesis and promoted the degradation of aliphatic glucosinolates, which could limit the consumption and enhance the release of S, thus, facilitating the production of the S-rich metabolites, glutathione, phytochelatins, and metallothioneins. We further demonstrated that the Cd tolerance mediated by LSU1 and LSU2 was dependent on the myrosinases BGLU28 and BGLU30, which catalyze the degradation of aliphatic glucosinolates. In addition, the overexpression of LSU1 and LSU2 improved Cd accumulation, which has great potential for the phytoremediation of Cd-contaminated soil.

Regulatory mechanisms of sulfur metabolism affecting tolerance and accumulation of toxic trace metals and metalloids in plants.

Soil contamination with trace metals and metalloids can cause toxicity to plants and threaten food safety and human health. Plants have evolved sophisticated mechanisms to cope with excess trace metals and metalloids in soils, including chelation and vacuolar sequestration. Sulfur-containing compounds, such as glutathione and phytochelatins, play a crucial role in their detoxification, and sulfur uptake and assimilation are regulated in response to the stress of toxic trace metals and metalloids. This review focuses on the multi-level connections between sulfur homeostasis in plants and responses to such stresses, especially those imposed by arsenic and cadmium. We consider recent progress in understanding the regulation of biosynthesis of glutathione and phytochelatins and of the sensing mechanism of sulfur homeostasis for tolerance of trace metals and metalloids in plants. We also discuss the roles of glutathione and phytochelatins in controlling the accumulation and distribution of arsenic and cadmium in plants, and possible strategies for manipulating sulfur metabolism to limit their accumulation in food crops.

The glutathione-dependent alarm triggers signalling responses involved in plant acclimation to cadmium.

Cadmium (Cd) uptake from polluted soils inhibits plant growth and disturbs physiological processes, at least partly due to disturbances in the cellular redox environment. Although the sulfur-containing antioxidant glutathione is important in maintaining redox homeostasis, its role as an antioxidant can be overruled by its involvement in Cd chelation as a phytochelatin precursor. Following Cd exposure, plants rapidly invest in phytochelatin production, thereby disturbing the redox environment by transiently depleting glutathione concentrations. Consequently, a network of signalling responses is initiated, in which the phytohormone ethylene is an important player involved in the recovery of glutathione levels. Furthermore, these responses are intricately connected to organellar stress signalling and autophagy, and contribute to cell fate determination. In general, this may pave the way for acclimation (e.g. restoration of glutathione levels and organellar homeostasis) and plant tolerance in the case of mild stress conditions. This review addresses connections between these players and discusses the possible involvement of the gasotransmitter hydrogen sulfide in plant acclimation to Cd exposure.

Phytochelatins: Sulfur-Containing Metal(loid)-Chelating Ligands in Plants.

Phytochelatins (PCs) are small cysteine-rich peptides capable of binding metal(loid)s via SH-groups. Although the biosynthesis of PCs can be induced in vivo by various metal(loid)s, PCs are mainly involved in the detoxification of cadmium and arsenic (III), as well as mercury, zinc, lead, and copper ions, which have high affinities for S-containing ligands. The present review provides a comprehensive account of the recent data on PC biosynthesis, structure, and role in metal(loid) transport and sequestration in the vacuoles of plant cells. A comparative analysis of PC accumulation in hyperaccumulator plants, which accumulate metal(loid)s in their shoots, and in the excluders, which accumulate metal(loid)s in their roots, investigates the question of whether the endogenous PC concentration determines a plant's tolerance to metal(loid)s. Summarizing the available data, it can be concluded that PCs are not involved in metal(loid) hyperaccumulation machinery, though they play a key role in metal(loid) homeostasis. Unraveling the physiological role of metal(loid)-binding ligands is a fundamental problem of modern molecular biology, plant physiology, ionomics, and toxicology, and is important for the development of technologies used in phytoremediation, biofortification, and phytomining.

Iron-based nanomaterials reduce cadmium toxicity in rice (Oryza sativa L.) by modulating phytohormones, phytochelatin, cadmium transport genes and iron plaque formation.

Rice is known to accumulate cadmium (Cd) in its grains, causing a severe threat to billions of people worldwide. The possible phytotoxicity and mechanism of 50-200 mg/L hydroxyapatite NPs (nHA), iron oxide NPs (nFe2O3) or nano zero valent iron (nZVI) co-exposed with Cd (100 µM) in rice seedlings were investigated. Three types of nanoparticles significantly reduced the bioaccumulation of Cd in rice shoots by 16-63%, with nZVI showing the greatest effect, followed by nHA and nFe2O3. A decrease in Cd content in the roots was observed only in the nZVI treatment, with values ranging from 8 to 19%. Correspondingly, nZVI showed the best results in promoting plant growth, increasing rice plant height, shoot and root biomass by 13%, 29% and 42%. In vitro studies showed that nZVI reduced the content of Cd in the solution by 20-52% through adsorption, which might have contributed to the immobilization of Cd in root. Importantly, the nZVI treatment resulted in 267% more iron plaques on the root surface, which acted as a barrier to hinder the entry of Cd. Moreover, all three nanoparticles significantly reduced the oxidative stress induced by Cd by regulating phytohormones, phytochelatin, inorganic homeostasis and the expression of genes associated with Cd uptake and transport. Overall, this study elucidates for the first time the multiple complementing mechanisms for some nanoparticles to reduce Cd uptake and transport in rice and provides theoretical basis for applying nanoparticles for reducing Cd accumulation in edible plants.

Nitrate enhances cadmium accumulation through modulating sulfur metabolism in sweet sorghum.

Sweet sorghum deploys tremendous potential for phytoremediation of cadmium (Cd)-polluted soils. Nitrate increases Cd accumulation in sweet sorghum, but the mechanism underlying this is still elusive. Sulfur-containing metabolites have been corroborated to play important roles in Cd tolerance in plants. Thus, whether sulfur metabolism contributed to nitrate-increased Cd accumulation in sweet sorghum was investigated in the present study. Two-way ANOVA analysis showed that most sulfur-containing metabolites concentrations and relevant enzymes activities were regulated by nitrate, Cd and interplay of nitrate and Cd. By using grey correlation analysis and Pearson correlation coefficient, Cd accumulation in shoots as affected by nitrate was also mainly ascribed to sulfur metabolism. ATP sulfurylase (ATPS) activities and non-protein thiol (NPT) concentrations in leaves were the two prominent factors that positively correlated with Cd accumulation in shoots. Excess nitrate elevated ATPS activities in leaves which contributed to increased NPT and phytochelatins (PCs) concentrations in leaves. Nitrate enhanced Cd accumulation in shoots of sweet sorghum under a low level of Cd treatment. Intriguingly, Cd accumulation in shoots of sweet sorghum was similar between a low level and a high level of Cd treatment. Principal Components Analysis (PCA) based on 34 parameters failed to separate the low Cd treatment from the high Cd treatment either, suggesting sweet sorghum is exclusively suitable for phytoremediation of slight Cd-polluted arable lands. Taken together, enhanced Cd accumulation in shoots of sweet sorghum by excess nitrate application is closely correlated with sulfur metabolism containing elevated ATPS activities, NPT and PCs concentrations in leaves.