Environment Of Metal Ions Research Articles

Structural Parameters of the Solvate Environment of Metal Ions in Dimethylsulfoxide

Structural Parameters of the Solvate Environment of Metal Ions in Dimethylsulfoxide

Disentangling the Ligand and Electronic Structure in KVPO4F1-XOx Positive Electrode Materials by Valence-to-Core X-Ray Emission Spectroscopy

Among all positive electrode materials for K-ion batteries (KIBs), KVPO4F offers a high theoretical capacity of 131 mAh·g-1 and an average working potential reaching above 4.3 V vs K+/K, resulting in a theoretical energy density of up to 520 Wh·kg-1. [1] The anionic substitution of fluorine by oxygen in KVPO4F1-xOx (x = 0, 0.25, 0.5, 0.75, 1) induces an increasing working potential by activating the V3+/4+ and V4+/5+ redox couples and replacing the VO4F2 “ionic” entity by {V=O}O5 unit with a highly “covalent” vanadyl-type bond. [2] The accurate prediction of the electrode potential as well as the understanding of the mechanisms involved upon cycling requires the determination of how the coordination environment of the transition metal ion influences the ionicity/covalency of the metal-ligand bonds and thus the electronic structure. Nevertheless, discriminating these ligands remains a challenge due to the limited sensitivity to light elements of common characterization techniques such as X-ray diffraction and extended X-ray absorption fine structure. Despite the valuable information from these techniques, fundamental concerns still need to be addressed which include: i) the implication of the covalent V=O vanadyl bond in the electronic structure; ii) the difference of Vcis and Vtrans, the two different sites for V, in the electronic configuration of the material; and finally, (iii) the impact of F/O ligands on the electrochemical mechanism upon battery cycling.To address this issue, we employed valence-to-core Kβ X-ray emission spectroscopy (VtC XES) combined with ab initio modelling and conducted a systematic investigation of KVPO4F1-xOx: two distinct regions were identified in the spectra, Kβ" and Kβ2,5, which are critical to probe the electronic structure close to the Fermi level and to discriminate different ligands coordinated with the vanadium atoms. [3] Our approach allows distinguishing in KVPO4F1-xOx the contributions of V-F, V-O, and V=O bonds, with intensities at the Kβ" region highly correlated to the F- and O2- anionic composition. Additionally, the evolution of the features at the Kβ2,5 region is highly associated to the presence of short V=O bonds, strongly influencing the electrode potential of the material.Overall, we present a detailed and reliable approach for understanding the occupied electronic states of the electrode material, proving valuable for a thorough comprehension of the structural and redox mechanisms involved in batteries.AcknowledgementThis work was supported by the DESTINY Marie Skłodowska-Curie Actions COFUND PhD Programme (Grant Agreement #945357) co-funded by the European Union's Horizon2020 research and innovation program and the Synchrotron SOLEIL. ANR is also acknowledged for funding the RS2E network through the STORE-EX Labex Project ANR-10-LABX-76-01, and the ANR TROPIC project ANR-CE05-0026. Alistore-ERI network is also acknowledged.

Switchable metal extractant integrated miniaturized 3D-printed device: A semi-online multi-metal separation system for matrix-free ICP-MS analysis

BackgroundThis study tackles the critical challenges in metal analysis by presenting an innovative miniaturized metal extraction device prototype. This device features a functional nanocomposite (FNC) enhanced 3D-printed polylactic acid (PLA) metal extractant (FNC@3D PLA). The research is motivated by the constraints of traditional solid-phase extraction (SPE) methods, specifically their limitations in handling competitive metal ion environments and matrix interference during inductively coupled plasma mass spectrometry (ICP-MS) analysis. The designed prototype aims to overcome these challenges and enhance the extraction efficiency of diverse metals. ResultsThe FNC, designed to incorporate various functional groups critical for metal ion extraction efficiency, was meticulously engineered through the reaction of acid-treated and delaminated graphitic carbon nitride nanosheets (Thiol-gCN NSs) with 3-mercaptopropyl trimethoxysilane (MPTMS). The competitive metal ion extraction efficiency of FNC@3D PLA was demonstrated, showcasing notable limit of detection values of 3.2 ± 0.7 ng mL−1 and 8.57 ± 3.05 ng mL−1 for Cu and Ag, respectively. Furthermore, the miniaturized 3D-printed metal-preconcentration setup incorporating FNC@3D PLA exhibited favorable intraday relative standard deviation (RSD) percentage (%) values ranging from 1.23 to 8.6 for both Cu and Ag. Interday RSD % between 1.41 and 8.14 were observed under spiked real urine sample conditions. The sustainability and robustness of the proposed approach were underscored by substantial recovery % values exhibited by FNC@3D PLA, even after eight consecutive regeneration processes. SignificanceThis study significantly contributes to the advancement of analytical methodologies by providing a reliable and efficient platform for metal extraction and preconcentration in practical metal analysis applications. Developed FNC@3D PLA system demonstrates its potential to address the challenges associated with SPE in metal analysis, especially in complex sample matrices. We believe implications of this research can be extended to various fields, from environmental monitoring to clinical diagnostics, where accurate and reliable metal analysis is paramount.

Efficient and clean treatment of indium-bearing zinc ferrite: A new approach using a water-regulated deep eutectic solvent

Indium, a strategic key metal, is mainly recovered from zinc leaching residue. However, a challenging problem in the treatment of zinc leaching residue is how to efficiently and cleanly treat the poorly soluble phase, the indium-bearing zinc ferrite (IBZF). Here, we propose a novel strategy for the selective extraction of indium, zinc and iron from IBZF. By introducing water to regulate the coordination environment of a choline chloride-anhydrous oxalic acid based deep eutectic solvent (ChCl-Oxa based DES), efficient leaching and deep separation of indium, zinc and iron were achieved. Water, acting as both co-solvent and diluent, played a critical role in the whole process. The addition of a little water reduces the viscosity of the DES, thereby improving the leaching of indium, zinc and iron. Under specific leaching conditions (leaching temperature of 90 °C, liquid/solid ratio of 20:1 ml/g, molar ratio of ChCl:Oxa = 1:1, molar ratio of DES:H2O = 1:3 and reaction time of 3.5 h), the leaching efficiencies of indium, zinc and iron were 96.27 %, 95.55 % and 96.33 %, respectively. The subsequent addition of large amounts of water dilutes and dissociates the structure of the DES, facilitating the stepwise precipitation and deep separation of metal ions. The precipitation efficiency of zinc and iron reached 93.06 % and 98.07 %, respectively. Residual indium ions in the solution were effectively adsorbed by activated carbon, with a recovery efficiency of 75.7 % after five cycles of adsorption. The solution separated from the metal ions was well regenerated by evaporation and addition of Oxa. Our work represents a novel approach for the recycling and clean utilization of zinc leaching residue. And the regulation of the coordination environment of metal ions in DES is proved to have great potential in metal recycling.

Disentangling the ligand and electronic structure in KVPO4F1-xOx positive electrode materials by valence-to-core X-ray emission spectroscopy

Understanding the intricate crystal structure of polyanionic positive electrode materials is essential for elucidating the mechanisms involved during cycling and predicting the working potential of the electrode. To achieve this goal, a clear comprehension of how the coordination environment of the transition metal ion influences the ionicity/covalency of the metal-ligand bonds is necessary. Yet, discriminating these ligands poses challenges due to the limited sensitivity to light elements of common characterization techniques such as X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) analysis. To address this issue, we employed valence-to-core Kβ X-ray emission spectroscopy combined with ab initio modelling and conducted a systematic investigation using potassium vanadium oxyfluoride phosphate compounds with the general formula KVPO4F1-xOx (x = 0, 0.25, 0.5, 0.75, 1). Our approach allows distinguishing the contributions of VF, VO, and VO bonds at the Kβ" region, with intensities highly correlated to the F− and O2− anion composition. Additionally, the evolution of the features at the Kβ2,5 region is highly correlated to the presence of short VO bonds, strongly influencing the electrode potential of the material. Density of state (DOS) analysis based on ab initio modelling of the end member compounds KVPO4F and KVOPO4 further supports the existence of VF and VO bonding through the mixing of F/O p-DOS with V d-DOS. Overall, we present a detailed and reliable approach for understanding the occupied electronic states of the bulk material, proving valuable for a thorough comprehension of the structure of positive electrode materials in batteries.

Enhancement in photophysical properties of octacoordinated Dy(III) complexes via energy transfer from photosensitizing ligands

In this study, β-diketone (1,1,1-trifluoroacetylacetone, tfaa) based mononuclear anhydrous octacoordinated dysprosium complexes i.e. [Dy(tfaa)3(TOPO)2] (D1), [Dy(tfaa)3(phen)] (D2), [Dy(tfaa)3(NeoC)] (D3) and [Dy(tfaa)3(BathoC)] (D4) were synthesized using four different neutral ligands. The effect of different sensitizers on Dy(III) ion is analyzed using various spectroscopic and analytical techniques. The composition and bonding were examined by elemental analysis, infrared spectroscopy, NMR spectroscopy and thermal analysis (TGA). The luminescent characteristics of the synthesized complexes were further investigated. The complexes, when exposed to UV light, displayed characteristic emissions of the central Dy(III) ion. The photoluminescence spectra indicated the strongest emission intensity of D3 complex. The hyper-intense transition in all complexes is sensitive to the metal ion environment. The semiconducting nature of complexes was confirmed by optical and electronic band gap values obtained from absorption spectroscopy and cyclic voltammetric analysis, respectively. The neutral ligands (TOPO, phen and its derivatives) along with tfaa, are found to be good sensitizers for trivalent dysprosium ion. All the characteristic features of these prepared complexes show their potential applications in the fabrication of OLEDs.

A prismatic alkali-ion environment suppresses plateau hysteresis in lattice oxygen redox reactions

The prismatic environment of the alkali metal ion is demonstrated to control plateau hysteresis in lattice oxygen redox materials.

Experimental and Theoretical Survey of Intramolecular Spodium Bonds/σ/π-Holes and Noncovalent Interactions in Trinuclear Zn(II)-Salen Type Complex with OCN- Ions: A Holistic View in Crystal Engineering.

In this work, one new centrosymmetric trinuclear Zn(II) complex 1, [{(OCN)Zn(L)}2Zn], using a salen-type ligand (H2L) in the presence of OCN- was synthesized and characterized via elemental, spectral, SEM-EDX, and single-crystal X-ray diffraction (SCXRD) study. In 1, SCXRD reveals two different stereochemical environments of zinc metal ions; one terminal Zn(II) center adopts square pyramidal geometries with the Addison parameter (τ) 0.095, and the central Zn(II) is tetracoordinated tetrahedral geometry. This article provides evidence of the significance and presence of spodium bonds (SpBs) in solid-state crystal structures involving a pseudotetrahedral environment of the central Zn-atom. X-ray structures reveal intramolecular Zn···O SpBs caused by the methoxy (-OCH3) substituent O-atom adjacent to the coordinated phenoxy O-atom. These noncovalent interactions have been thoroughly studied using density functional theory calculations at the RI-BP86[2]-D3[3]/def2-TZVP level of theory that characterizes the nature of SpBs, including the Baders quantum theory of atoms-in-molecules "QTAIM", molecular electrostatic potential (MEP) surface, and noncovalent index plot (NCI). In addition, a unique complex-isomer-based theoretical model has been vividly employed to estimate the SpBs energy in the complex. Natural bond orbital (NBO) analysis also tries to establish the differentiation between σ-hole and π-hole SpBs' natures more authentically. The complex energy frameworks were used to investigate noncovalent interactions. To better understand the different intermolecular interactions, we conducted a Hirshfeld surface, which revealed N···H (15.4%) and O···H (9.1%) contacts and Zn···O (5.1%) (SpBs).

Copper(II) Furancarboxylate Complexes with 5-Nitro-1,10-Phenanthroline as Promising Biological Agents

The reaction of copper(II) acetate with 2-furancarboxylic (HFur)/5-nitro-2-furancarboxylic (HNfur) acids and 5-nitro-1,10-phenanthroline (Nphen) in methanol resulted in the formation of the binuclear coordination compounds [Cu2(L)4(Nphen)2]·X (L = Fur (I), Nfur (II); X = H2O (I)), which were structurally studied by direct X-ray diffraction (CCDC no. 2244205 (I) and 2244206 (II)). According to X-ray diffraction data, the coordination environment of the central metal ion in I and II is composed of two nitrogen atoms of Nphen and three oxygen atoms of the acid anions, which thus form the {CuN2O3} tetragonal pyramid in which the copper coordination number is five. Intermolecular hydrogen bonds and stacking interactions between the Nphen aromatic rings provide supramolecular stabilization of I and II. A characteristic feature of supramolecular organization of II is the presence of a coordination bond between the Cu2+ cation and oxygen of the Nphen NO2- group of parallel chains. A biological activity assay for complexes I and II concerning the cytotoxic properties against a human ovarian adenocarcinoma cell line (SKOV3) and the mycobacterial strain Mycolicibacterium smegmatis showed an efficient suppression of cell viability. The results of mathematical modeling of the probability of Cu2+ binding to amino acid residues of M. smegmatis proteins suggested the affinity of the Cu(II) ion to a number of amino acids in polypeptide sites. It was shown that metal ion binding in mycobacterial proteins is more characteristic of histidine- and glutamic acid-containing moieties.

Dynamic Changes and Characterization of the Metal Ions in the Silk Glands and Silk Fibers of Silkworm

Metal ions are involved in the conformational transition of silk fibroin and influence the structure and mechanical properties of silk fibers. However, the dynamic characteristics of metal ions during the formation of silk fibers remain unclear. In this study, we found that the silk glands of silkworms contain various metal elements, with varying levels of the metal elements in different zones of the glands and higher levels in the anterior silk glands. Additionally, the content of various metallic elements in the silk glands varied greatly before and after spinning, similar to their content in different cocoon layers, thus, indicating that the anterior silk glands maintain a certain metal ion environment for the transport and conformational transformation of the silk proteins. Most of the metallic elements located in fibroin were confirmed using degumming experiments. For the first time, a scanning electron microscope energy spectrometry system was used to characterize the metal elements in the cross-section of silk and cocoons. These findings have deepened our understanding of the relationship between the overall metal ion environment and silk fiber formation and help us further conceptualize the utilization of metal ions as targets to improve the mechanical properties of the silk fibers.

Metalation of Tellurophene: Reactivity of 21,23-Ditelluraporphodimethene toward Palladium(II), Platinum(II), and Rhodium(I).

Ditelluraporphodimethene, a nonaromatic porphyrinoid containing two tellurophene rings, reacted with palladium(II), platinum(II), and rhodium(I) following two different paths. Palladium(II) formed bonds to two tellurium donors of the macrocycle, yielding a side-on coordination compound, with a square planar (Te2Cl2) metal ion environment. An alternative reaction path has been observed for ditelluraporphodimethene with platinum(II) or rhodium(I) in high boiling solvents. These conditions led to the profound transformation, that is, one tellurium atom to a metal atom exchange, resulting in the formation of organometallic species containing metallacyclopentadiene rings, that is, 21-platina-23-telluraporphodimethene and 21-rhoda-23-telluraporphodimethene. The substitution reaction proceeded selectively at the tellurophene ring within the conjugated part of the molecule, that is, the tellurophene ring bound to two sp2 meso-carbon atoms. In the case of platinum, the exchange was accompanied by one meso-aryl ring fusion with the formed platinacyclopentadiene ring, and the platinum(II) macrocycle underwent reversible oxidation with chlorine. The products are stable and represent first nonaromatic examples of metalloporphyrinoids, with a metallacyclopentadiene ring incorporated into a porphodimethene skeleton.

Porous organic polycarbene nanotrap for efficient and selective gold stripping from electronic waste

The role of N-heterocyclic carbene, a well-known reactive site, in chemical catalysis has long been studied. However, its unique binding and electron-donating properties have barely been explored in other research areas, such as metal capture. Herein, we report the design and preparation of a poly(ionic liquid)-derived porous organic polycarbene adsorbent with superior gold-capturing capability. With carbene sites in the porous network as the “nanotrap”, it exhibits an ultrahigh gold recovery capacity of 2.09 g/g. In-depth exploration of a complex metal ion environment in an electronic waste-extraction solution indicates that the polycarbene adsorbent possesses a significant gold recovery efficiency of 99.8%. X-ray photoelectron spectroscopy along with nuclear magnetic resonance spectroscopy reveals that the high performance of the polycarbene adsorbent results from the formation of robust metal-carbene bonds plus the ability to reduce nearby gold ions into nanoparticles. Density functional theory calculations indicate that energetically favourable multinuclear Au binding enhances adsorption as clusters. Life cycle assessment and cost analysis indicate that the synthesis of polycarbene adsorbents has potential for application in industrial-scale productions. These results reveal the potential to apply carbene chemistry to materials science and highlight porous organic polycarbene as a promising new material for precious metal recovery.

Tunable electronic structure of heterosite FePO4: an in-depth structural study and polaron transport.

The development of better electrode materials for lithium-ion batteries has been intensively investigated both due to their fundamental scientific aspects as well as their usefulness in technological applications. The present technological development of rechargeable batteries is hindered by fundamental challenges, such as low energy and power density, short lifespan, and sluggish charge transport kinetics. Among the various anode materials proposed, heterosite FePO4 (h-FP) has been found to intercalate lithium and sodium ion hosts to obtain novel rechargeable batteries. The h-FP has been obtained via the delithiation of triphylite LiFePO4 (LFP), and its structural and electronic properties have been investigated with different crystallite sizes. The synchrotron XRD measurements followed by Rietveld refinement analysis reveal lattice expansion upon the reduction of crystallite size of h-FP. In addition, the decrease in the crystallite size enhances surface energy contributions, thereby creating more oxygen vacancies up to 2% for 21 nm crystallite size. The expansion in the lattice parameters is reflected in the vibrational properties of the h-FP structure, where the red-shift has been observed in the characteristic modes upon the reduction of crystallite size. The local environment of the transition metal ion and its bonding characteristics have been elucidated through soft X-ray absorption spectroscopy (XAS) with the effect of crystallite size. XAS unequivocally reveals the valence state of iron 3d electrons near the Fermi level, which is susceptible to local lattice distortion and uncovers the detailed information on the evolution of electronic states with crystallite size. The observed local lattice distortion has been considered to be as a result of the decrease in the level of covalency between the Fe-3d and O-2p states. Further, we demonstrate the structural advantages of nanosized h-FP on the transport properties, where an enhancement in the polaronic conductivity with decreasing crystallite size has been observed. The polaronic conduction mechanism has been analyzed and discussed on the basis of the Mott model of polaron conduction along with an insightful analysis on the role of the electronic structure. The present study provides spectroscopic results on the anode material that reveal the evolution of electronic states for fingerprinting, understanding, and optimizing it for advanced rechargeable battery operations.

Recent advances and future perspectives in MOF-derived single-atom catalysts and their application: a review

This article discusses the relationship between single-atom sites and the catalytic mechanism of functional MOFs which is related to the coordination environment of metal ions, and also summarizes the research progress of MOF-derived SACs in recent years.

Toward explicit anion transport nanochannels for osmotic power energy using positive charged MXene membrane via amination strategy

The reverse electrodialysis (RED) is a potential technique to harvest osmotic energy caused by different salinities. Owing to the negative surface-charged controlling effects of nanofluidic channel in 2D membrane, the power density has been achieved with high energy conversion efficiency for cations (Na+ with the counterpart of Cl−). However, anion-selective nanofluidic channel is rare but still required for promising application of RED due to its high higher diffusion rate resulting in desirable osmotic power energy. In this work, we constructed a two-dimensional layered MXene membrane with positive charge via amination strategy of 3-aminopropyltriethoxysilane (APTES) toward anion selectivity for efficient osmotic power harvesting. The power density of the resultant membrane can achieve a maximum of 10.98 W m−2 at a natural salinity gradient, higher than the commercial benchmark of 5 W m−2. Under regulating environmental conditions including operation temperatures, pH and the existence of pollutants (heavy metal ions and organic pollution) of the simulated electrolyte solution, a higher power density of 20.66 W m−2 can be reached through Cl− transmembrane transport. During 10-h testing, the attenuation of output power density was just 3%. The applicable stability still maintains under the contaminative environment of heavy metal ions or organic pollution. These results will bring an innovative design of anion-selective membrane for osmotic energy conversion and widen the practical application in ion selectivity.

Potential effects of metal ion induced two-state allostery on the regulatory mechanism of add adenine riboswitch

Riboswitches normally regulate gene expression through structural changes in response to the specific binding of cellular metabolites or metal ions. Taking add adenine riboswitch as an example, we explore the influences of metal ions (especially for K+ and Mg2+ ions) on the structure and dynamics of riboswitch aptamer (with and without ligand) by using molecular dynamic (MD) simulations. Our results show that a two-state transition marked by the structural deformation at the connection of J12 and P1 (CJ12-P1) is not only related to the binding of cognate ligands, but also strongly coupled with the change of metal ion environments. Moreover, the deformation of the structure at CJ12-P1 can be transmitted to P1 directly connected to the expression platform in multiple ways, which will affect the structure and stability of P1 to varying degrees, and finally change the regulation state of this riboswitch.

A High-Rate, Durable Cathode for Sodium-Ion Batteries: Sb-Doped O3-Type Ni/Mn-Based Layered Oxides.

O3-Type layered oxides are widely studied as cathodes for sodium-ion batteries (SIBs) due to their high theoretical capacities. However, their rate capability and durability are limited by tortuous Na+ diffusion channels and complicated phase evolution during Na+ extraction/insertion. Here we report our findings in unravelling the mechanism for dramatically enhancing the stability and rate capability of O3-NaNi0.5Mn0.5-xSbxO2 (NaNMS) by substitutional Sb doping, which can alter the coordination environment and chemical bonds of the transition metal (TM) ions in the structure, resulting in a more stable structure with wider Na+ transport channels. Furthermore, NaNMS nanoparticles are obtained by surface energy regulation during grain growth. The synergistic effect of Sb doping and nanostructuring greatly reduces the ionic migration energy barrier while increasing the reversibility of the structural evolution during repeated Na+ extraction/insertion. An optimized NaNMS-1 electrode delivers a reversible capacity of 212.3 mAh g-1 at 0.2 C and 74.5 mAh g-1 at 50 C with minimal capacity loss after 100 cycles at a low temperature of -20 °C. Such electrochemical performance is superior to most of the reported layered oxide cathodes used in rechargeable SIBs.

Rapid preparation of melamine based magnetic covalent triazine polymers for highly efficient extraction of copper(II), chromium(III) and lead(II) ions from environmental and biological samples

In this work, melamine based magnetic covalent triazine polymers (MCTPs) was prepared by decoration of melamine based triazine polymers on the surface of magnetic Fe3O4@SiO2 nanoparticles. The polymer decoration is realized by nucleophilic substitution reaction between melamine (as functional monomer) and 1,4-dibromobutane (as crosslinking agent), which is simple, rapid and cost effective. The resultant MCTPs showed good affinity toward Cu2+, Cr3+ and Pb2+ with fast adsorption kinetic (7 min) and high adsorption capacities (38.3, 33.9 and 49.7 mg g−1 for Cu2+, Cr3+ and Pb2+, respectively). Besides, the prepared MCTPs can be reused after adsorption, desorption and regeneration steps, and the phase separation is highly efficient with the addition of an external magnet. Thus, MCTPs was employed as a magnetic solid-phase extraction (MSPE) sorbent for the extraction of trace Cu2+, Cr3+ and Pb2+ followed by graphite furnace atomic absorption spectrometry (GFAAS) determination. Then the extraction conditions of the above-mentioned MSPE-GFAAS method were optimized, including sample pH, extraction/elution time, sample volume, etc. Under the optimized conditions, the MCTPs based MSPE-GFAAS method exhibit the following merits: short extraction/elution time (10/3 min), high enrichment factor (125 folds) and low detection limit (2.9, 1.4 and 6.1 ng L-1 for Cu2+, Cr3+ and Pb2+, respectively). Finally, the proposed method was successfully employed for the determination of trace Cu2+, Cr3+ and Pb2+ in tap water, river water, lake water, human urine and human hair samples. The adequate recoveries of 85 ∼ 105% in spiked samples were achieved, suggesting the promising potential of MCTPs based MSPE-GFAAS method as an effective method for evaluating the environment and biological effect of metal ions.

A metal ion–dependent conformational switch modulates activity of the Plasmodium M17 aminopeptidase

The metal-dependent M17 aminopeptidases are conserved throughout all kingdoms of life. This large enzyme family is characterized by a conserved binuclear metal center and a distinctive homohexameric arrangement. Recently, we showed that hexamer formation in Plasmodium M17 aminopeptidases was controlled by the metal ion environment, although the functional necessity for hexamer formation is still unclear. To further understand the mechanistic role of the hexameric assembly, here we undertook an investigation of the structure and dynamics of the M17 aminopeptidase from Plasmodium falciparum, PfA-M17. We describe a novel structure of PfA-M17, which shows that the active sites of each trimer are linked by a dynamic loop, and loop movement is coupled with a drastic rearrangement of the binuclear metal center and substrate-binding pocket, rendering the protein inactive. Molecular dynamics simulations and biochemical analyses of PfA-M17 variants demonstrated that this rearrangement is inherent to PfA-M17, and that the transition between the active and inactive states is metal dependent and part of a dynamic regulatory mechanism. Key to the mechanism is a remodeling of the binuclear metal center, which occurs in response to a signal from the neighboring active site and serves to moderate the rate of proteolysis under different environmental conditions. In conclusion, this work identifies a precise mechanism by which oligomerization contributes to PfA-M17 function. Furthermore, it describes a novel role for metal cofactors in the regulation of enzymes, with implications for the wide range of metalloenzymes that operate via a two-metal ion catalytic center, including DNA processing enzymes and metalloproteases.

Facile synthesis of electrocatalytically active bismuth oxide nanosheets for detection of palladium traces in pharmaceutical wastewater

Current synthesis routes of bismuth oxide nanosheets (BiONS) are relatively complicated, requiring the use of halogens or metalloids. Herein, a facile method to synthesize BiONS without the addition of halogens or other metalloids was developed. The synthesized BiONS were identified to have flake-shaped structures (300–1000 nm in width) with the thickness of 6–10 nm, which were predominantly made of β-Bi2O3. Such BiONS were applied to modify the surface of screen-printed carbon electrodes (BiONS-SPCEs) for the development of a robust palladium (Pd2+) sensor. After optimizing the electrochemical parameters of the sensor, it was found that the linear sensor response range and limit of detection for Pd2+ were 40–400 and 1.4 ppb, respectively. The electrocatalytic activity of the Pd2+-sensor was validated in the competing environment of other metal and metalloid ions. Real samples collected during a Pd recovery process from pharmaceutical wastewater were used to verify the application of BiONS-SPCEs in control of palladium recovery process. The quantitative results of post recovery palladium concentrations obtained using BiONS-SPCEs in treated pharmaceutical wastewater samples were in good agreement with those obtained by inductively coupled plasma-optical emission spectrometry (ICP-OES). Thus, such Pd2+-sensor provided the possibility of on-site process control of complex industrial samples for obtaining near-instant information that would lead to better management of resources used in the process, and same time assure environmental standards for both recovered products and processed discharge.