Synthetic Chelators Research Articles

Removal of heavy metals from wastewater using synthetic chelating agents

Abstract The issue of heavy metal water pollution is one that concerns everyone. Both plants and humans are negatively impacted by heavy metals. Consequently, the environment and water resources require an efficient heavy metal remediation technique. In this context, a series of compounds were investigated as potential chelating agents for the removal of Cu, Zn, Cd, and Pb cations from water. By solvent extraction, it was shown that the chelating ligands’ affinity for Cu, Zn, Cd, and Pb as indicated by the extraction performance was in the following order: Cu > Zn > Cd > Pb. The size and electrical characteristics of the metal as well as the ligand structure affect how well L1–L6 extracts that metal.

Isolation, screening, characterization, and optimization of bacteria isolated from calcareous soils for siderophore production

The most effective agricultural practice to prevent iron deficiency in calcareous soils is fertilizing with synthetic chelates. These compounds are non-biodegradable, and persistent in the environment; hence, there is a risk of leaching metals into the soil horizon. To tackle iron deficiency-induced chlorosis (IDC) in crops grown on calcareous soils, environmentally friendly solutions are needed rather than chemical application as it affects the soil health further. Hence, the present work focused on isolating and screening calcareous soil-specific bacteria capable of producing iron-chelating siderophores. Siderophore-producing bacteria (SPB) was isolated from the groundnut (Arachis hypogeaL.) rhizosphere region, collected from Coimbatore district, Tamil Nadu, of which 17 bacterial isolates were positive for siderophore production assayed by chrome azurol sulphonate. The performance of SPB isolates was compared for siderophore kinetics, level of siderophore production, type of siderophore produced and iron-chelating capacity under 15mM KHCO3. Four best performing isolates were screened, with average siderophores yield ranging ∼60-80% under pH 8, with sucrose as carbon source and NH2SO4 as nitrogen source at 37°C. The four efficient SPB were molecularly identified asB. licheniformis,B. subtilis,B. licheniformis,andO. grignonensebased on 16S rDNA sequencing. The simultaneous inhibition methodshowedT.viridehas the highest antagonistic effect againstS.rolfsii,andM.phaseolinawith a reduction of mycelial growth by 69.3 and 65.1%, respectively,compared to control.Our results indicate that the optimized conditions enhanced siderophores chelation by suppressing the stem and root rot fungi, which could help in a cost-effective and environmentally friendly manner.

Experimental and theoretical studies on coordination of a flexible cyclohexane based C3-symmetric tripodal ligand with iron, aluminum and gallium

The use of a cyclohexane ring in the centre of a C3 symmetric tripodal ligand with a suitable spacer can flip between the axial and equatorial forms due to low transition energy and can facilitate the formation of stable metal complexes. Keeping this perspective in view, a new chelator, N,N′,N″-((1R,3R)-cyclohexane-1,3,5-triyl)tris(8-hydroxyquinoline-2-carboxamide), TACH2COX, comprising of a cis,cis-1,3,5-trisaminocyclohexane(TACH) as central unit and three quinolinols joined through amide linkage is developed. The brown-colored ligand has been characterized through melting point, IR, NMR (1H, 13C), ESI mass, and absorption spectroscopy. The solution coordination chemistry of the newly synthesized ligand is studied by its interaction with three bio-relevant metal ions: iron(III), aluminum (III) and gallium(III) through spectroelectrochemical technique. The high metal–ligand formation constants of the ligand indicate that TACH2COX is one of the strong metal chelators amid synthetic chelators. The structure and bonding of the complexes have been established through DFT studies. The molecular modeling studies reveal that the tripodal ligand binds to the metal ions by coordination of the ligand through three sets of N, O-coordination sites on, each from one pendant showing distorted octahedral geometry. The NBO, EDA, ETS-NOCV analysis, and absorption spectra of the ligand and its metal complexes are also described.

Use of Parthenium hysterophorus with synthetic chelator for enhanced uptake of cadmium and lead from contaminated soils-a step toward better public health.

Parthenium hysterophorus L. is a vigorous plant species with cosmopolitan distribution. It can uptake considerable quantities of heavy metals from the soil and accrue these metals in its different tissue. The use of chelating agent i.e., Ethylenediaminetetraacetic acid (EDTA) can boost up metal uptake capacity. Pot experiment was performed to evaluate phytoextraction potential of P. hysterophorus for lead (Pb) and cadmium (Cd) with and without the aid of EDTA chelator. Shoot length, weight of root and shoot (both fresh and dry), leaves number, and chlorophyll contents of P. hysterophorus got reduced with an increase in metal uptake. The results revealed the highest concentration of Cd in shoot without and with EDTA was 283.6 and 300.1 mg kg−1, correspondingly. Increase in Pb concentration was also boosted up by the EDTA from its maximum concentration in shoot 4.30–9.56 mg kg−1. Generally, Pb and Cd concentrations were greater in shoots of P. hysterophorus than the roots regardless of EDTA in the treatments. EDTA also impacted positively the accumulation of essential ions K+, Na+, and Ca+2 in P. hysterophorus. The capacity of P. hysterophorus to accumulate Pb and Cd found to be increased with EDTA in the soil. Bringing metals level in the soil in accordance to the WHO standards can improve the ecosystem as well as public health.

Remediation of Heavy Metal-Contaminated Soils with Soil Washing: A Review

Soil with heavy metals’ contamination has caused worldwide concern, and there is an increasing interest in the application of washing agents for the remediation of soils with heavy metals’ contamination. The review summarizes the recent findings about soil washing with different washing agents. For soil washing technologies, the solubilizing capability, toxicity, and biocompatibility of agents are essential concerns. Washing agents can enhance heavy metals’ desorption and removal from soil. Inorganic acids/bases/salts, synthetic surfactants, and synthetic chelators are often limited due to their adverse effects on soil. Biosurfactants, HAs (humic acids), and LMWOA (low-molecular-weight organic acids) are suggested washing agents, but the limitation of their low production needs to be conquered. Moreover, both washing with a mixture agent and sequential washing have often been adopted to improve the overall capacity of the washing agent for decontamination. Mixture washing can obtain the synergetic effect for soil washing and increase washing efficiency. Sequential washing can apply an agent with a high heavy metals removal rate. However, this may cause environmental risks in the early stage, and then remove the washing agent injected in the early stage by the secondary washing stage. Overall, the already known cases reveal the good prospect of soil washing for soil remediation.

Chemigenetic indicators based on synthetic chelators and green fluorescent protein.

Molecular fluorescent indicators are versatile tools for dynamic imaging of biological systems. We now report a class of indicators that are based on the chemigenetic combination of a synthetic ion-recognition motif and a protein-based fluorophore. Specifically, we have developed a calcium ion (Ca2+) indicator that is based on genetic insertion of circularly permuted green fluorescent protein into HaloTag protein self-labeled with a ligand containing the Ca2+ chelator 1,2-bis(2-aminophenoxy)ethane-N,N,N',N'-tetraacetic acid. We have demonstrated the versatility of this design by also developing a sodium ion (Na+) indicator using a crown-ether-containing ligand. This approach affords bright and sensitive ion indicators that can be applicable to cell imaging. This design can enable the development of chemigenetic indicators with ion or molecular specificities that have not been realized with fully protein-based indicators.

Attenuation of tryptophan metabolism by Fe chelators: A hypothesis regarding inhibiting tumor suppressive microenvironments in pancreatic ductal adenocarcinoma

Pancreatic ductal adenocarcinoma (PDAC) is one of the most lethal cancers. Although extensive research has been conducted on chemotherapy and immunotherapy for PDAC patients, the efficacy of these treatments varies, partially due to immunosuppressive environments and the limited infiltration of effector cells into tumors. Here, we highlight the potential application of iron (Fe) chelators to inhibit immunosuppressive environments in PDAC. This assumption is based on data from published articles indicating that 1) tryptophan (TRP) plays a role in immunosuppressive microenvironments; 2) metabolism of TRP is regulated by tryptophan hydroxylase (TPH), indoleamine-2,3-dioxygenase (IDO), and tryptophan-2,3-doxygenase (TDO), all of which are Fe-dependent enzymes; and 3) wide varieties of both synthetic Fe chelators and natural products are available for clinical application. In light of these data from the literature, we hypothesize that combining Fe chelators with immunotherapeutic or chemotherapeutic agents in PDAC patients can improve treatment efficacy by inhibiting tryptophan depletion in the surrounding mesenchymal stromal cells, allowing effector cells to infiltrate the tumor, and enabling cytotoxic drugs to access the targeted cells.

De novo synthesis of ferrichrome by Fusarium oxysporum f. sp. cubense TR4 in response to iron starvation

Manipulation of iron bioavailability in the banana rhizosphere may suppress Fusarium wilt, caused by Fusarium oxysporum f. sp. cubense (Foc). However, iron starvation induced by application of synthetic iron chelators does not effectively suppress Fusarium wilt. It is unclear whether Foc can subvert iron chelators and thereby evade iron starvation through the synthesis of iron-scavenging secondary metabolites, called siderophores. In vitro studies were conducted using iron-deficient growth medium and medium supplemented with a synthetic iron chelator, 2,2′-dipyridyl, to mimic iron starvation in Foc Tropical Race 4 (Foc TR4). Concentration of extracellular siderophores increased three-fold (p < 0.05) in the absence of iron. Liquid chromatography-mass spectrometry analysis detected the hydroxamate siderophore, ferrichrome, only in the mycelia of iron-starved cultures. Moreover, iron-starved cultures exhibited a reduction in total cellular protein concentration. In contrast, out of the 20 proteinogenic amino acids, only arginine increased (p < 0.05) under iron starvation. Our findings suggest that iron starvation does not cause a remodelling of amino acid metabolism in Foc TR4, except for arginine, which is required for biosynthesis of ornithine, the precursor for siderophore biosynthesis. Collectively, our findings suggest that biosynthesis of siderophores, particularly ferrichrome, could be a counteractive mechanism for Foc TR4 to evade iron starvation.

Synthesis of a New Chelating Iminophosphorane Derivative (Phosphazene) for U(VI) Recovery.

A new synthetic chelating N–hydroxy–N–trioctyl iminophosphorane (HTIP) was prepared through the reaction of trioctylphosphine oxide (TOPO) with N–hydroxylamine hydrochloride in the presence of a Lewis acid (AlCl3). Specifications for the HTIP chelating ligand were successfully determined using many analytical techniques, 13C–NMR, 1H–NMR, FTIR, EDX, and GC–MS analyses, which assured a reasonable synthesis of the HTIP ligand. The ability of HTIP to retain U(VI) ions was investigated. The optimum experimental factors, pH value, experimental time, initial U(VI) ion concentration, HTIP dosage, ambient temperature, and eluents, were attained with solvent extraction techniques. The utmost retention capacity of HTIP/CHCl3 was 247.5 mg/g; it was achieved at pH = 3.0, 25 °C, with 30 min of shaking and 0.99 × 10−3 mol/L. From the stoichiometric calculations, approximately 1.5 hydrogen atoms are released during the extraction at pH 3.0, and 4.0 moles of HTIP ligand were responsible for chelation of one mole of uranyl ions. According to kinetic studies, the pseudo–first order model accurately predicted the kinetics of U(VI) extraction by HTIP ligand with a retention power of 245.47 mg/g. The thermodynamic parameters ΔS°, ΔH°, and ΔG° were also calculated; the extraction process was predicted as an exothermic, spontaneous, and advantageous extraction at low temperatures. As the temperature increased, the value of ∆G° increased. The elution of uranium ions from the loaded HTIP/CHCl3 was achieved using 2.0 mol of H2SO4 with a 99.0% efficiency rate. Finally, the extended variables were used to obtain a uranium concentrate (Na2U2O7, Y.C) with a uranium grade of 69.93% and purity of 93.24%.

Copper Toxicity in Maize: The Severity of the Stress is Reduced Depending on the Applied Fe-Chelating Agent

The wide use of copper (Cu)-based fungicide has caused a stepwise accumulation of Cu in the environment increasing the occurrence of phytotoxicity in crops. To understand and alleviate this abiotic stress, maize seedlings were grown in hydroponic solution with different combinations of Cu and iron (Fe) forms. Results showed that maize Cu sensitivity is related to the nature of the form supplied and to the chelate-exchange processes that might involve other elements, such as Fe. The use of CuSO4 excess (100 µM) caused severe reduction of plant growth, over accumulation of Cu, high activity of antioxidant enzymes, and impairment of the acquisition of other nutrients. In presence of chelating agents (citrate and ethylenediaminetetraacetic acid, EDTA) the ability of plants to tolerate high Cu-levels depends on the Fe nutritional status. Copper phytotoxicity symptoms do not occur when Cu was supplied chelated by EDTA. The use of synthetic agent EDTA (as Cu-EDTA and Fe-EDTA) prevented the accumulation of toxic Cu-level in plants and allowed a better homeostasis among nutrients. In presence of citrate, high concentration of Cu occurred in plants but its phytotoxicity was limited when even EDTA was available in solution. Results suggest that maize plants can operate a good control of nutritional status when Cu-excess is present concomitantly with a synthetic chelator (as EDTA) even when supplied as a Fe-fertilizer. These results pave the way to provide guidelines for the fertilization managements on Cu-contaminated soils to alleviate phytotoxicity in crops.

Sorption of silver (I) ions from aqueous solutions using the synthetic sorbent

We study the sorption of silver ions from aqueous solutions by a synthetic chelating sorbent. In the presence of formaldehyde, a polymeric sorbent based on a copolymer of styrene with maleic anhydride, modified with N,N’-diphenylguanidine, was synthesized and further used for extracting Ag(I) ions. The composition and structure of the synthesized polymeric chelating sorbent were studied using IR and UV spectroscopy methods. A simple, inexpensive, and efficient method for extracting Ag(I) ions from aqueous solutions was used. The effect of various parameters on the sorption process was studied, including the acidity of the medium (pH), the initial concentration of the metal ion, the time required to establish complete sorption equilibrium, and ionic strength. The optimum pH value for the extraction of Ag(I) was found to be 6. The process is characterized by a high adsorption capacity reaching 547.2 mg/g. The research results showed that the time required to establish a complete sorption equilibrium for the sorbent modified with N,N’- diphenylguanidine is 60 min. Ag(I) adsorption increases up to the value of ionic strength of μ = 1, after which its intensity decreases. At the final stage, the process of desorption of absorbed silver ions was carried out. During desorption, the best eluting agent for the extraction of Ag(I) was determined to be 0.5 M HNO3. The sorbent can be re-used after regeneration. The copolymer of styrene and maleic anhydride modified with N,N’-diphenylguanidine has a high sorption capacity and, therefore, can be used as a potential adsorbent for the extraction of silver (I) from aqueous solutions.

Fenton-Mediated Chlorophenol Degradation by Iron-Reducing Compounds Isolated from Endophytic Fungi in Atacama Puna Plateau Lecanicillium ATA01

Low-molecular-mass iron-reducing compounds (IRCs) were produced by entomopathogenic endophytic fungi Lecanicillium sp. ATA01 in liquid cultures. The extracellular hydrophilic extract contained three IRCs formed by peptides, iron and phenolate structures with molecular masses of 1207, 567 and 550 Da. These compounds were able to chelate and mediate the reduction of Fe+3 to Fe+2 and oxidized recalcitrant lignin-model substrates such as veratryl alcohol (VA), 2,6-dimethoxyphenol (DMP), and 2,2′-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid (ABTS) with or without hydrogen peroxide. Besides, IRCs can promote the degradation of chlorophenols. The maximal degradation of p-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, and pentachlorophenol was conducted at optimal degradation conditions for IRCs (pH 3.5, iron 100 mM, and H2O2 10 mM). Furthermore, Fenton-like reactions using the synthetic iron chelates DTPA and EDTA and free Fe+2 and Fe+3 were also carried out in order to compare with the reaction mediated by IRCs. The ferric IRCs displayed the ability to enhance the hydroxylation of chlorophenols as a part of a degradation mechanism of the IRC-assisted Fenton reaction. The complexed iron was more efficient than free iron in the Fenton-like reaction, and between them, the fungal chelates were more efficient than the synthetic mill chelates.

Chelating agents for diluted geothermal brine reinjection

“Blue energy” could be produced by exploiting the large salinity gradient between geothermal fluids and freshwater through a SaltPower system. This study is an attempt to select the most favorable chemicals to avoid injectivity issues when a diluted geothermal fluid resulting from the SaltPower system is returned to the reservoir. Three synthetic chelating agents (oxalic acid, EDTA, and EDDS) and one natural (humic acid) were evaluated through speciation simulations and isothermal titration calorimetry (ITC) experiments. The speciation simulation results indicate that the degree of complexing is highly dependent on pH and chelating agent type. The ITC experiments show that the total heat for the formation of soluble metal–ligand complexes in the rock + geothermal brine system follows: EDTA > EDDS > oxalic acid > humic acid. The simulations and calorimetry results suggest that EDTA could be used to avoid the precipitation of Fe(III) oxides and other minerals (e.g., calcite and dolomite) inside the porous media upon the reinjection of diluted geothermal brine coming from SaltPower electricity production.

Integrated review of the nexus between toxic elements in the environment and human health.

Emerging pollutants in the environment due to economic development have become a global challenge for environmental and human health management. Potentially toxic elements (PTEs), a major group of pollutants, have been detected in soil, air, water and food crops. Humans are exposed to PTEs through soil ingestion, consumption of water, uptake of food crop products originating from polluted fields, breathing of dust and fumes, and direct contact of the skin with contaminated soil and water. The dose absorbed by humans, the exposure route and the duration (i.e., acute or chronic) determine the toxicity of PTEs. Poisoning by PTEs can lead to excessive damage to health as a consequence of oxidative stress produced by the formation of free radicals and, as a consequence, to various disorders. The toxicity of certain organs includes neurotoxicity, nephrotoxicity, hepatotoxicity, skin toxicity, and cardiovascular toxicity. In the treatment of PTE toxicity, synthetic chelating agents and symptomatic supportive procedures have been conventionally used. In addition, there are new insights concerning natural products which may be a powerful option to treat several adverse consequences. Health policy implications need to include monitoring air, water, soil, food products, and individuals at risk, as well as environmental manipulation of soil, water, and sewage. The overall goal of this review is to present an integrated view of human exposure, risk assessment, clinical effects, as well as therapy, including new treatment options, related to highly toxic PTEs.

Fast Determination of a Novel Iron Chelate Prototype Used as a Fertilizer by Liquid Chromatography Coupled to a Diode Array Detector.

The environmental risk of the application of synthetic chelates has favored the implementation of new biodegradable ligands to correct Fe-deficient plants. This study developed and validated an analytical method for determination of a new prototype iron chelate—Fe(III)-benzeneacetate, 2-hydroxy-α-[(2-hydroxyethyl)amino]—(BHH/Fe3+) based on liquid chromatography with diode array detection, as a potential sustainable alternative. Chromatographic analysis was performed on a LiChrospher RP-18 in reverse-phase mode, with a mobile phase consisting of a mixture of acetonitrile (solvent A) and sodium borate buffer 0.20 mM at pH = 8 (solvent B) at a flow rate of 1.0 mL/min in isocratic elution mode. This method was fully validated and found to be linear from the limit of quantification (LOQ) to 50 mg/L and precise (standard deviation below 5%). The proposed method was demonstrated to be selective, precise, and robust. The developed methodology indicated that it is suitable for the quantification of iron chelate BHH/Fe3+.

Biochelator Assisted Phytoremediation for Cadmium (Cd) Pollution in Paddy Field

To evaluate the efficacy of biochelators for phytoremediation of cadmium (Cd), effects of biochelators (humic acid, HA; polyaspartic acid, PASP; rhamnolipid, RLs) and synthetic chelator (sodium tripolyphosphate, STPP) on the growth, accumulation, and antioxidant index of Cd were investigated in Iris sibirica L. The results indicated that the addition of HA increased the dry weight of leaves and stems, and the addition of PASP, RLs, and STPP increased the growth of leaves but inhibited the growth of stems. The determination of Cd accumulation indicated that HA decreased the content of Cd in all tissues, while the addition of PASP, RLs, and STPP increased the accumulation of Cd in stems and roots. In addition, the determination of superoxide dismutase (SOD), peroxidase (POD), and catalase (CAT) activities indicated that the treatment of PASP and RLs increased the activities of antioxidant enzymes, which might be beneficial to the resistance of Cd for Iris sibirica L. Overall, these results indicated that biochelators may improve the phytoremediation efficacy of Iris sibirica L. on Cd polluted paddy field. Among the tested chelators, PASP exhibited the best comprehensive efficacy and the highest commercial potential.

Capturing an elusive but critical element: Natural protein enables actinium chemistry.

Actinium-based therapies could revolutionize cancer medicine but remain tantalizing due to the difficulties in studying and limited knowledge of Ac chemistry. Current efforts focus on small synthetic chelators, limiting radioisotope complexation and purification efficiencies. Here, we demonstrate a straightforward strategy to purify medically relevant radiometals, actinium(III) and yttrium(III), and probe their chemistry, using the recently discovered protein, lanmodulin. The stoichiometry, solution behavior, and formation constant of the 228Ac3+-lanmodulin complex and its 90Y3+/natY3+/natLa3+ analogs were experimentally determined, representing the first actinium-protein and strongest actinide(III)-protein complex (sub-picomolar Kd) to be characterized. Lanmodulin’s unparalleled properties enable the facile purification recovery of radiometals, even in the presence of >10+10 equivalents of competing ions and at ultratrace levels: down to 2 femtograms 90Y3+ and 40 attograms 228Ac3+. The lanmodulin-based approach charts a new course to study elusive isotopes and develop versatile chelating platforms for medical radiometals, both for high-value separations and potential in vivo applications.

A synthetic phytosiderophore analog, proline-2\u2032-deoxymugineic acid, is efficiently utilized by dicots

PurposePhytosiderophores (PS) from grasses solubilize sparingly soluble iron (Fe), and the resultant PS-Fe is an Fe source even for dicots. Recently, the synthetic PS proline-2′-deoxymugineic acid (PDMA) has been developed as a moderately biodegradable Fe fertilizer for grasses. We aimed to investigate whether PDMA-Fe is also a good Fe source for dicots.MethodsThe availability of PDMA-Fe to cucumber was evaluated in a calcareous substrate and hydroponic cultures at pH 7.0–9.0 by determining chlorophyll level, PSII activity, and Fe uptake. EDDHA-Fe, EDTA-Fe, and citrate-Fe were used as controls. The reducibility of Fe chelates by roots was measured to determine the mechanism underlying differences in availability. Expressions of Fe deficiency-inducible genes were analyzed to estimate the Fe status in plants.ResultsThe application of PDMA-Fe and EDDHA-Fe to a calcareous substrate reduced Fe-deficient chlorosis to a similar extent; however, the shoot Fe concentration was higher in the PDMA-Fe treatment. In the hydroponic culture, the availability of PDMA-Fe was higher than that of the other chelates at all pH levels, and this was confirmed by higher PSII activity and lower expression of Fe deficiency-inducible genes. The reducibility assay revealed that the reduction level of PDMA-Fe was greater than that of EDTA-Fe and citrate-Fe under alkaline pH.ConclusionsPDMA-Fe is utilized by cucumber roots more efficiently than traditional synthetic chelates in both calcareous substrate and hydroponic cultures. The higher availability of PDMA-Fe may be attributed to its higher reducibility. Our findings suggest that PDMA-Fe could be a good Fe fertilizer for dicots.

Biodegradable, metal-chelating compounds as alternatives to EDTA for cultivation of marine microalgae

Iron (Fe) is an essential nutrient for microalgal metabolism. The low solubility of Fe in oxic aquatic environments can be a growth-limiting factor for phytoplankton. Synthetic chelating agents, such as ethylenediaminetetraacetic acid (EDTA), are used widely to maintain Fe in solution for microalgal cultivation. The non-biodegradable nature of EDTA, combined with sub-optimal bioavailability of Fe-EDTA complexes to microalgae, indicates opportunity to improve microalgal cultivation practices that amplify production efficiency and environmental compatibility. In the present study, the effects of four organic chelating ligands known to form readily bioavailable organic complexes with Fe in natural aquatic environments were investigated in relation to growth and biochemical composition of two marine microalgae grown as live feeds in shellfish hatcheries (Chaetoceros calcitrans and Tisochrysis lutea). Three saccharides, alginic acid (ALG), glucuronic acid (GLU), and dextran (DEX), as well as the siderophore desferrioxamine B (DFB), were compared to EDTA. Organic ligands characterized by weaker binding capacity for cationic metals (i.e., ALG, GLU, DEX) significantly improved microalgal growth and yields in laboratory-scale static batch cultures or bubbled photobioreactors. Maximal microalgal growth enhancement relative to the control (e.g., EDTA) was recorded for GLU, followed by ALG, with 20–35% increase in specific growth rate in the early stages of culture development of C. calcitrans and T. lutea. Substitution of EDTA with GLU resulted in a 27% increase in cellular omega 3-polyunsaturetd fatty acid content of C. calcitrans and doubled final cell yields. Enhanced microalgal culture performance is likely associated with increased intracellular Fe uptake efficiency combined with heterotrophic growth stimulated by the organic ligands. Based upon these results, we propose that replacement of EDTA with one of these organic metal-chelating ligands is an effective and easily implementable strategy to enhance the environmental compatibility of microalgal cultivation practices while also maximizing algal growth and enhancing the nutritional quality of marine microalgal species commonly cultured for live-feed applications in aquaculture.

Enhancing Metal-binding with Noncanonical Coordinating Amino Acids.

More than 50% of proteinogenic amino acid sidechains can bind metal ions, enabling proteins and peptides to bear these ions as cofactors. Nevertheless, post-translational modifications and incorporation of noncanonical amino acids bestow peptides and proteins myriads of other coordination capabilities, thanks to an enhanced metal binding. Here we summarize selected examples of natural and artificial systems that contain one or more noncanonical amino acids coordinating a metal ion and subsequently achieve a new or enhanced function. We report on a wide array of systems: from disease-related proteins that undergo sulfurylation or phosphorylation through natural metallophores that selectively capture precious essential ions to synthetic selfassembly strategies, biocatalysts, and chelating agents against toxic metals. Regardless of their (bio)synthetic routes, all possess unique metal-binding properties that could not be effectively achieved by systems composed of canonical residues.