Divalent Transition Metal Cations Research Articles

Compositional heterogeneity of secondary minerals in mine waste rock: Origins and implications for water quality.

Secondary minerals in mine waste materials impose strong controls on water quality by scavenging solutes of concern. This study investigates the mineralogical and compositional characteristics of secondary Fe(oxy)hydroxides and Ca-sulfates, two globally ubiquitous secondary precipitates, in weathered mine waste rock. Bulk analyses show that Si, Ca, Fe, Al, and S-bearing primary phases were the most abundant in the entire samples, but up to a few wt% of secondary Fe(oxy)hydroxides and Ca-sulfates were present as well. In these secondary phases, trace metal impurities like V (37 mg/kg in Ca-sulfates), Cr (23 mg/kg in Fe-oxides and 21 mg/kg in Ca-sulfates), and Cd (up to 15 mg/kg in Fe-oxides and Ca-sulfates) could not be detected by bulk techniques (XRF and XRD), but their deportment to some extent characterized by automated mineralogy, and their spatial distribution assessed at high-resolution through microscale LA-ICP-MS analysis. Element mapping revealed that metal(loid)s were generally enriched at grain rims, reflective of peripheral sequestration through surface adsorption. An exception was V, which was uniformly distributed in the studied secondary Fe-oxides, suggestive of isomorphic substitution during co-precipitation. Factor analysis revealed distinct groups of elements co-associated within each secondary mineral (e.g., divalent transition metal cations versus oxyanionic metalloids), likely caused by similar primary mineral sourcing or a comparable sequestration mechanism. Our results demonstrate the importance of secondary mineral precipitates for scavenging (trace) elements and the insights that can be gained from complementary mineralogical and element analyses for the interpretation of trace element dynamics in waste rock.

Computational Exploration of the Impact of Low‐Spin and High‐Spin Ground State on the Chelating Ability of Dimethylglyoxime Ligand on Dihalo Transition Metal: A QTAIM, EDA, and CDA Analysis

ABSTRACTWe have explored the chelation of dimethylglyoxime ligand to divalent (ndx: x = 6, 7, 8) transition metal (TM) cations in two media (gas phase and water) at the B3LYP//LANL2DZ/6–311+G (d,p) and B3LYP/def2‐TZVP level at lower multiplicity and higher multiplicity states. Majority of the 18 optimized halide (chloride and bromide) complexes prefer square planar configuration. The correlations discerned between the experimental structural data and their estimated counterparts demonstrate a good credibility for complexes at lower multiplicity state. The basis set superposition errors (BSSEs) estimated is very small which reflects the fact that the choice of different basis sets (B3LYP//LANL2DZ/6–311+G (d,p)) introduces a slight bias in the calculation of energies. The ADMP (atom‐centered density matrix propagation) simulations in water on chloride complexes indicate the irreversible nature of these M—N dissociation in trajectory simulation process. This fact explains our exclusive focus on the examination of the [glyoxime ligand]…[MX2] interactions. In addition, the solvation of (3d and 4d) transition metal chloride complexes causes a sensitive augmentation of the metal ion affinity (MIA) with an average of 0.29 and 0.24 kcal/mol. In both multiplicity states, the topological parameters have illustrated that the M—N and M—X bonds are typical metal–ligand in both media. The average ΔEorb/ΔEsteric ratio equal to 0.45 and 0.11 in gas phase and water, respectively, reveals the predominance of the contributions from non‐covalent bonding interactions (NCI) compared to those of covalent bonding. But, the maximal value equal to 6.760 is obtained for bromide rhodium complex in water. NBO analysis in both media highlights the fact that a more pronounced ionic character is observed for the majority of the chloride complexes at both spin multiplicity states because of their higher retained charges on the metal atom. For [dimethylglyoxime]…[MX2] interaction (X = Cl and Br), the charge decomposition analysis demonstrates that the lowest value of the d/b ratio is found for the chloride platinum complex at lower multiplicity state in water. This is a proof of its strong relativistic effects.

Click Chemistry Derived Hexa-ferrocenylated 1,3,5-Triphenylbenzene for the Detection of Divalent Transition Metal Cations.

The 1,3-dipolar cycloaddition reaction (click chemistry approach) was employed to create a hexa-ferrocenylated 1,3,5-triphenylbenzene derivative. Leveraging the presence of metal-chelating sites associated with 1,2,3-triazole moieties and 1,4-dinitrogen systems (ethylenediamine-like), as well as tridentate chelating sites (1,4,7-trinitrogen, diethylene triamine-like) systems, the application of this molecule as a chemosensor for divalent transition metal cations was investigated. The interactions were probed voltammetrically and spectrofluorimetrically against seven selected cations: iron(II) (Fe2+), cobalt(II) (Co2+), nickel(II) (Ni2+), copper(II) (Cu2+), zinc(II) (Zn2+), cadmium(II) (Cd2+), and manganese(II) (Mn2+). Electrochemical assays revealed good detection properties, with very low limits of detection (LOD), for Co2+, Cu2+, and Cd2+ in aqueous solution (0.03-0.09 μM). Emission spectroscopy experiments demonstrated that the title compound exhibited versatile detection properties in solution, specifically turn-off fluorescence behavior upon the addition of each tested transition metal cation. The systems were characterized by satisfactory Stern-Volmer constant values (105-106 M-1) and low LOD, especially for Zn2+ and Co2+ (at the nanomolar concentration level).

Exploring electrochemical kinetic behaviors and interfacial charge transfer of pure and Ni-doped ZnFe2O4 nanoparticles-based sensing nanoplatform for ultra-sensitive detection of chloramphenicol

ZnFe2O4 (ZFO) nanomaterial was doped with a divalent transition metal cation of Ni2+ (NixZn1-xFe2O4, x=0, 0.2, 0.4, and 0.8) and characterized by various analytical techniques. Powder X-ray diffraction revealed the formation of a single-phase cubic spinel structure, while the stabilization of crystal structure for Ni2+-doped samples was observed. The average crystalline size, d-spacing, and lattice parameters increased with increasing in Ni2+ concentration within NixZn1-xFe2O4, due to differences in the ionic radius, the cation distribution at A-B sites, and the creation of surface oxygen vacancies within ZFO structure. From electrochemical measurements, NixZn1-xFe2O4-based electrodes showed excellent enhancements in charge transfer ability and conductivity with the highest rate constant (0.018 ms−1), the lowest peak-to-peak separation (206 mV), the lowest Rct (118 Ω), and the largest electrochemical active area (0.248 cm2), compared to that of bare SPE. Among them, Ni0.8Zn0.2Fe2O4/SPE provided outstanding electrochemical behaviors and achieved the best sensing performance with the widened concentration linear range from 0.25 to 50 μM and a rather low detection limit of 0.2 μM for chloramphenicol detection. The most important reason for this positive advance comes from the unique synergistic effects of Ni doping into the ZFO host structure. The excellent enhancements in adsorption capacity (Г) (1.4 times higher), number of oxygen vacancies, charge transfer rate constant (approximately 1.15 times higher), and catalytic rate constant (30 times greater) were recorded at Ni-doped ZFO-based electrodes, compared to pure ZFO-based electrode. Furthermore, the detailed hypotheses and possible mechanisms explaining these impressive enhancements were explored. Our work provides insight into the correlation between the Ni-doping and electrochemical characteristics, which has implications for tailoring the electrochemical performance of spinel ferrites across diverse applications and the design of novel spinel ferrite nanomaterials.

Molecular evolution and functional diversification of metal tolerance protein families in cereals plants and function of maize MTP protein

Plants employ metal tolerance proteins (MTPs) to confer tolerance by sequestering excess ions into vacuoles. MTPs belong to the cation diffusion facilitator (CDF) family, which facilitates the transport of divalent transition metal cations. In this study, we conducted a comprehensive analysis of the MTP gene families across 21 plant species, including maize (Zea mays). A total of 247 MTP genes were identified within these plant genomes and categorized into distinct subgroups, namely Zn-CDF, Mn-CDF, and Fe/Zn-CDF, based on phylogenetic analyses. This investigation encompassed the characterization of genomic distribution, gene structures, cis-regulatory elements, collinearity relationships, and gene ontology functions associated with MTPs. Transcriptomic analyses unveiled stress-specific expression patterns of MTP genes under various abiotic stresses. Moreover, quantitative RT-PCR assays were employed to assess maize MTP gene responses to diverse heavy metal stress conditions. Functional validation of metal tolerance roles was achieved through heterologous expression in yeast. This integrated evolutionary scrutiny of MTP families in cereals furnishes a valuable framework for the elucidation of MTP functions in subsequent studies. Notably, the prioritized MTP gene ZmMTP6 emerged as a positive regulator of plant Cd tolerance, thereby offering a pivotal genetic asset for the development of Cd-tolerant crops, particularly maize cultivars.

Structural and Electronic Factors behind the Electrochemical Stability of 3D-Metal Tungstates under Oxygen Evolution Reaction Conditions.

Transition metal tungstates (TMTs) possess a wolframite-like lattice structure and preferably form via an electrostatic interaction between a divalent transition metal cation (MII) and an oxyanion of tungsten ([WO4]2-). A unit cell of a TMT is primarily composed of two repeating units, [MO6]oh and [WO6]oh, which are held together via several M-μ2-O-W bridging links. The bond character (ionic or covalent) of this bridging unit determines the stability of the lattice and influences the electronic structure of the bulk TMT materials. Recently, TMTs have been successfully employed as an electrode material for various applications, including electrochemical water splitting. Despite the wide electrocatalytic applications of TMTs, the study of the structure-activity correlation and electronic factors responsible for in situ structural evolution to electroactive species during electrochemical reactions is still in its infancy. Herein, a series of TMTs, MIIWVIO4 (M = Mn/Fe/Co/Ni), have been prepared and employed as electrocatalysts to study the oxygen evolution reaction (OER) under alkaline conditions and to scrutinize the role of transition metals in controlling the energetics of the formation of electroactive species. Since the [WO6]oh unit is common in the TMTs considered, the variation of the central atom of the corresponding [MO6]oh unit plays an intriguing role in controlling the electronic structure and stability of the lattice under anodic potential. Under the OER conditions, a potential-dependent structural transformation of MWO4 is noticed, where MnWO4 appears to be the most labile, whereas NiWO4 is stable up to a high anodic potential of ∼1.68 V (vs RHE). Potential-dependent hydrolytic [WO4]2- dissolution to form MOx active species, traced by in situ Raman and various spectro-/microscopic analyses, can directly be related to the electronic factors of the lattice, viz., crystal field splitting energy (CFSE) of MII in [MO6]oh, formation enthalpy (ΔHf), decomposition enthalpy (ΔHd), and Madelung factor associated with the MWO4 ionic lattice. Additionally, the magnitude of the Löwdin and Bader charges on M of the M-μ2-O-W bond is directly related to the degree of ionicity or covalency in the MWO4 lattice, which indirectly influences the electronic structure and activity. The experimental results substantiated by the computational study explain the electrochemical activity of the TMTs with the help of various structural and electronic factors and bonding interactions in the lattice, which has never been realized. Therefore, the study presented here can be taken as a general guideline to correlate the reactivity to the structure of the inorganic materials.

Mononuclear half-sandwich nd7 metallo drug complexes based on bidentate N∩N dendritic scaffolds: DFT (B3LYP; BP86 and B3PW91) examination

Through an use of three functionals (B3PW91, B3LYP and BP86) associated to a generic basis set LanL2DZ for transition metals (as well as halogen atoms) and 6-311+G (d,p) for others atoms, an examination of the bonding properties of a series of mononuclear half-sandwich nd7 transition metal (anticancer) complexes based on N∩N dendritic scaffolds (L) has been done. Collectively, complexes studied have adopted the piano-stool environment. An examination of the performance of each functional has shown that for the most reliable geometrical analysis of Metal-Nitrogen and Metal-Halogen bonds, the B3LYP and B3PW91 functionalities are suitable respectively. Regardless of the halogen ligand adopted, the B3LYP metal-nitrogen bond lengths are the most widely overestimated. A correlation has been built between the retained charge on each divalent transition metal cation and its metal ion affinity (MIA). Topological examinations reveal the higher instability of metal-N bonds compared to metal-X ones (X = Cl and Br). By the mean of the energy decomposition analysis, a predominant electrostatic character of metal … halogen and [LCP]- … [MX]+ interaction has been demonstrated. The transition metal atom … (hydrophobic) surface (Cp*) interaction is most pronounced for the chloride rhodium complexes of rhodium (combined with (E)-N-(pyridin-2-ylmethylene) Propan-1-amine and 2,2′- dipyridylketone ligands and iridium combined with 2,2′- dipyridylketone ligand. The charge decomposition analysis displays the weakening of the [MLCP*]+−X− bonds in the studied complexes.

An investigation on carrier transport behavior of tetragonal halide perovskite: First-principles calculation

Halide perovskite is a special kind of semiconductor, which is expected to apply in solar cells and electronic devices. A key characteristic of these materials is the carrier mobility, which determines the average electron velocity caused by the driving electric field. In the face of the complexity for experimental samples, it is very important to identify mobility’s upper limit, and which parameters control it, so as to provide clear guidance for material application. In this study, the mobility for the tetragonal halide perovskite (CsSnCl3, CsPbCl3, CsSnBr3 and CsPbBr3) is predicted by semiempirical modes including both longitudinal acoustic (LA) and polar optical (PO) phonons. The results show that the mobility derived from LA phonon model is much higher than that from PO phonon model, so LA phonon is not the decisive scattering source. According to Matthiessen’s rule, the carrier mobility for these perovskites is determined by PO phonon model. The electron and hole mobilities along [0 0 1] direction are about 52 and 133 cm2V−1s−1 for CsSnCl3, 35 and 33 cm2V−1s−1 for CsPbCl3, 94 and 198 cm2V−1s−1 for CsSnBr3, and 51 and 38 cm2V−1s−1 for CsPbBr3. The mode analysis reveals that LO phonon associated with the fluctuations of divalent transition metal cations and halogen anions limits the mobility. This investigation provides some valuable information for the application of perovskite.

MntP and YiiP Contribute to Manganese Efflux in Salmonella enterica Serovar Typhimurium under Conditions of Manganese Overload and Nitrosative Stress.

ABSTRACTThe divalent transition metal cation manganese is important for protein function, particularly under conditions of iron limitation, nitrosative stress, and oxidative stress, but can mediate substantial toxicity in excess. Salmonella enterica serovar Typhimurium possesses multiple manganese importers, but the pathways for manganese efflux remain poorly defined. The S. Typhimurium ATCC 14028s genome was analyzed for putative manganese export pathways, which identified a previously uncharacterized homologue of the Escherichia coli manganese exporter mntP, stm1834, and two cation diffusion facilitator family transporters, zitB (stm0758) and yiiP (stm4061). Manganese acquisition by S. Typhimurium has been shown to occur in response to nitric oxide, an important chemical mediator of the mammalian innate immune response. However, cellular manganese can rapidly return to prechallenge levels, strongly suggesting that one or more S. Typhimurium exporters may contribute to this process. Here, we report that mntP and yiiP contribute to manganese resistance and export in S. Typhimurium. YiiP, also known as FieF, has previously been associated with zinc and iron transport, although its physiological role remains ambiguous due to a lack of zinc-sensitive phenotypes in yiiP mutant strains of S. Typhimurium and E. coli. We report that S. Typhimurium ΔmntP ΔyiiP mutants are exquisitely sensitive to manganese and show that both YiiP and MntP contribute to manganese efflux following nitric oxide exposure.IMPORTANCE Transition metal cations are required for the function of many proteins but can mediate toxicity when present in excess. Identifying transporters that facilitate metal ion export, the conditions under which they are expressed, and the role they play in bacterial physiology is an evolving area of interest for environmental and pathogenic organisms. Determining the native targets of metal transporters has proved challenging since bioinformatic predictions, in vitro transport data, and mutant phenotypes do not always agree. This work identifies two transporters that mediate manganese efflux from the Gram-negative pathogen Salmonella enterica serovar Typhimurium in response to manganese overload and nitric oxide stress. While homologues of MntP have been characterized previously, this is the first observation of YiiP contributing to manganese export.

Coprecipitation Synthesis of V2o5 Nanoribbons on Reduced Graphene Oxide Nanosheets Through Divalent Transition Metal Cations for High-Capacity and Stable Aqueous Zinc Ion Batteries

Coprecipitation Synthesis of V2o5 Nanoribbons on Reduced Graphene Oxide Nanosheets Through Divalent Transition Metal Cations for High-Capacity and Stable Aqueous Zinc Ion Batteries

Differential Surface Capping Effects on the Applications of Simple Amino-Acid-Capped ZnS:Mn Nanoparticles.

Water-dispersible ZnS:Mn nanoparticles (NPs) were prepared by capping their surface with simple structured amino acids: l-alanine (Ala), l-glycine (Gly), and l-valine (Val) molecules, which have very similar structures except for the terminal organic functional groups. The detailed characterization works for the prepared colloidal NPs were performed using various spectroscopic methods. In particular, the NPs commonly showed UV/visible absorption peaks around 325 nm and PL emission peaks around 590 nm, corresponding to the wavelength of orange color light. In this study, these amino-acid-capped NPs were applied as optical photosensors in the detection of specific divalent transition metal cations in the same conditions. Consequently, all three NPs showed exclusive fluorescence quenching effects upon the addition of Cu (II) metal ions, whereas their quenching efficiencies were quite different to each other. These experimental results indicated that the Gly-ZnS:Mn NPs (k = 4.09 × 105 M−1) can be the most effective optical photosensor for the detection of Cu2+ ions in water among the three NPs in the same conditions. This study showed that the steric effect of the capping ligand can be one of the key factors affecting the sensor activities of the ZnS:Mn NPs.

Transition metal cation inhibition of Mycobacterium tuberculosis esterase RV0045C.

Mycobacterium tuberculosis virulence is highly metal-dependent with metal availability modulating the shift from the dormant to active states of M. tuberculosis infection. Rv0045c from M. tuberculosis is a proposed metabolic serine hydrolase whose folded stability is dependent on divalent metal concentration. Herein, we measured the divalent metal inhibition profile of the enzymatic activity of Rv0045c and found specific divalent transition metal cations (Cu2+ ≥ Zn2+ > Ni2+ > Co2+ ) strongly inhibited its enzymatic activity. The metal cations bind allosterically, largely affecting values for kcat rather than KM . Removal of the artificial N-terminal 6xHis-tag did not change the metal-dependent inhibition, indicating that the allosteric inhibition site is native to Rv0045c. To isolate the site of this allosteric regulation in Rv0045c, the structures of Rv0045c were determined at 1.8Å and 2.0Å resolution in the presence and absence of Zn2+ with each structure containing a previously unresolved dynamic loop spanning the binding pocket. Through the combination of structural analysis with and without zinc and targeted mutagenesis, this metal-dependent inhibition was traced to multiple chelating residues (H202A/E204A) on a flexible loop, suggesting dynamic allosteric regulation of Rv0045c by divalent metals. Although serine hydrolases like Rv0045c are a large and diverse enzyme superfamily, this is the first structural confirmation of allosteric regulation of their enzymatic activity by divalent metals.

Structure and spectral performance of Co(II) and Co(III) complexes for DNA-binding: Synthesis, characterization and comparison

There have been many literatures reporting the binding performance of transition metal complexes towards DNA, aiming at anti-cancer and anti-tumor drugs. However, most of these references focused on divalent transition metal cations, such as Co(II), Ni(II), Cu(II) and Zn(II). Only a few efforts have been devoted to high-valent transition metal cations. In this paper, we synthesized two Co(II) and Co(III) complexes, tris{2-(pyridin-2-yl)benzo[d]imidazole-1-ide}-cobalt(III) [denoted as Co(L)3] and bis{2-(pyridin-2-yl)benzo[d]imidazole-1-ide}-{2-(pyridin-2-yl)-1H-benzo[d]imidazole}-cobalt(II) [denoted as Co(HL)(L)2], using a diamine ligand 2-(pyridin-2-yl)-1H-benzo[d]imidazole (denoted as HL). Their molecular structure was identified with their single crystals, MS and NMR spectra. Co(L)3 and Co(HL)(L)2 share the same crystal system (monoclinic) and space group (P21/c). Their crystal cell parameters were found rather similar to each other owing to their rather similar ligands, showing a slightly distorted octahedron coordination geometry. No intramolecular interaction, superamolecular interactions and π-π staking between neighboring Co(L)3 molecules or neighboring Co(HL)(L)2 molecules were found, forming a clean coordination environment. Density functional theory calculation on their single crystals suggested that they had similar onset electronic transitions. Their thermal stability, absorption and emission were compared. Owing to their rather similar molecular structures, most of their features were similar. Their binding performance for calf thymus DNA (CT-DNA) was then analyzed and compared. The binding mode between two Co complexes and CT-DNA was analyzed and confirmed by means of viscosity monitoring, circular dichroism analysis, SEM and XRD comparison. Their binding constants were determined as 974.89 M-1 for Co(L)3 and 829.25 M-1 for Co(HL)(L)2, respectively. We found a hydrogen bond between Co(L)3 and CH3OH. No hydrogen bonds were found in Co(HL)(L)2. This result suggested that the Co(L)3 interact with Ct-DNA via the combination of hydrogen bond and weak intermolecular interaction with DNA, while Co(HL)(L)2 interacts with Ct-DNA via only weak intermolecular interaction with DNA. These values were two fold higher than those of literature values (<450 M−1), indicating their potential for DNA treatment.

3d Transition-Metal-Mediated Columbite Nanocatalysts for Decentralized Electrosynthesis of Hydrogen Peroxide.

Decentralized electrosynthesis of hydrogen peroxide (H2 O2 ) via oxygen reduction reaction (ORR) can enable applications in disinfection control, pulping and textile bleaching, wastewater treatment, and renewable energy storage. Transition metal oxides are usually not efficient catalysts because they are more selective to produce H2 O. Here, it is shown that divalent 3d transition metal cations (Mn, Fe, Co, Ni, and Cu) can control the catalytic activity and selectivity of columbite nanoparticles. They are synthesized using polyoxoniobate (K7 HNb6 O19 ·13H2 O) and divalent metal cations by a hydrothermal method. The optimal NiNb2 O6 holds an H2 O2 selectivity of 96% with the corresponding H2 O2 Faradaic efficiency of 92% in a wide potential window from 0.2 to 0.6V in alkaline electrolyte, superior to other transition metal oxide catalysts. Ex situ X-ray photoelectron and operando Fourier-transformed infrared spectroscopic studies, together with density functional theory calculations, reveal that 3d transition metals shift the d-band center of catalytically active surface Nb atoms and change their interactions with ORR intermediates. In an application demonstration, NiNb2 O6 delivers H2 O2 productivity up to 1 molH2O2 gcat -1 h-1 in an H-shaped electrolyzer and can yield catholytes containing 300× 10-3 m H2 O2 to efficiently decomposing several organic dyes. The low-cost 3d transition-metal-mediated columbite catalysts show excellent application potentials.

Tetrapropylammonium Tribromocupurate Complex[(C3H7)4N]CuBr3(II) - Synthesis, Thermal and Spectral Characterization

Due to their interesting physical properties like ferroelastic, ferroelectric and commensurate – incommensurate phases at low temperatures, the importance of ABX3 complex (A=univalent cation, NH4(+) and its alkyl derivatives; B= divalent transition metal cation and X=halogen) has been gained more interest in recent years. Materials in good crystalline form are needed in modern technologies using semiconductors, magnetic garnets and ultraviolet and infrared solid-state lasers. The TTPATBr-Cu complex type ABX3 was grown by a slow evaporation process at room temperature. The synthesised complex is characterised by an elementary analysis, powder X-ray diffraction, thermogravimetric and differential thermal analysis. The synthesised complex is analysed by FTIR, proton and carbon-13 NMR spectrally. Elemental analysis data obtained for the complex confirm the molecular formulae [(CH3CH2CH2)4N]2CuBr3(II). The IR spectrum of the complex confirms the presence of methyl and methylene groups in the complex. The IR spectra also confirm the presence of C-C and C-N bonds. The NMR spectra suggest the presence of N-propyl group in the complex. TG-DTG thermogram indicates that the final decomposition of the complex starts from 809°C to form the end product. The prepared complex can be used for optical and biological applications.

The cation diffusion facilitator protein MamM's cytoplasmic domain exhibits metal-type dependent binding modes and discriminates against Mn2+

Cation diffusion facilitator (CDF) proteins are a conserved family of divalent transition metal cation transporters. CDF proteins are usually composed of two domains: the transmembrane domain, in which the metal cations are transported through, and a regulatory cytoplasmic C-terminal domain (CTD). Each CDF protein transports either one specific metal or multiple metals from the cytoplasm, and it is not known whether the CTD takes an active regulatory role in metal recognition and discrimination during cation transport. Here, the model CDF protein MamM, an iron transporter from magnetotactic bacteria, was used to probe the role of the CTD in metal recognition and selectivity. Using a combination of biophysical and structural approaches, the binding of different metals to MamM CTD was characterized. Results reveal that different metals bind distinctively to MamM CTD in terms of their binding sites, thermodynamics, and binding-dependent conformations, both in crystal form and in solution, which suggests a varying level of functional discrimination between CDF domains. Furthermore, these results provide the first direct evidence that CDF CTDs play a role in metal selectivity. We demonstrate that MamM's CTD can discriminate against Mn2+, supporting its postulated role in preventing magnetite formation poisoning in magnetotactic bacteria via Mn2+ incorporation.

Differential Photosensor Activities for the L-Cysteine and L-Serine Capped ZnS:Mn Nanocrystals in the Detection of Divalent Transition Metal Ions in Aqueous Solution.

Colloidal ZnS:Mn nanocrystals (NCs) were synthesized in water by capping the NC surface with conventional amino acids: L-cysteine (Cys) and L-serine (Ser) molecules, which have very similar structures but different terminal functional groups. The optical properties were investigated by using UV-Visible and photoluminescence (PL) spectroscopy. The PL spectra for both ZnS:Mn-Cys and ZnS:Mn-Ser NCs showed broad emission peaks at 590 nm. The measured average particle size from the high-resolution transmission electron microscopy (HR-TEM) images were 4.38 nm (ZnS:Mn-Cys) and 5.57 nm (ZnS:Mn-Ser), which were also supported by Debye-Scherrer calculations. In addition, the surface charge of the NCs in aqueous solutions were measured using zeta-particle size analyzer spectroscopy, which showed formation of negatively charged surface for the ZnS:Mn-Cys (-43.93 mV) and ZnS:Mn-Ser (-8.21 mV) NCs in water. In this present study those negatively charged NCs were applied as photosensors for the detection of specific divalent transition metal cations in aqueous solution at the same condition. Consequently, the ZnS:Mn-Cys and ZnS:Mn-Ser NCs showed totally different photosensor activities upon the addition of first-row divalent transition metal ions. The former NCs showed luminescence quenching for most added metal ions except for Zn (II) ions; whereas the latter NCs showed exclusive quenching effect for Cu (II) ions at the same conditions. These results suggested that those NCs can be applied as Zn2+ and Cu2+ ion sensors in water.

Aerogels from copper (II)-cellulose nanofibers and carbon nanotubes as absorbents for the elimination of toxic gases from air

A novel deodorizer that is capable of selectively eliminating the odorous chemicals, such as ammonia, trimethylamine, hydrogen sulfide and methyl mercaptan, is described. The deodorizer is a nanostructured aerogel by nature, consisting of 2,2-6,6-tetramethylpiperidine-1-oxyl (TEMPO) oxidized cellulose nanofibrils (CNF), transition metal divalent cations (M2+), and multi-walled carbon nanotubes (CNT) as the constitutive elements. CNF are firstly mixed with M2+ (M2+, in this paper, typifies Ni2+, Co2+ and Cu2+) to form CNF-M2+ complexes, monodispersed CNT is then mixed to prepare CNT/CNF-M2+ waterborne slurries; CNT/CNF-M2+ hybridized aerogels are finally obtained via freezing-drying of the CNT/CNF-M2+ waterborne slurries. The CNT/CNF-M2+ aerogels are a foam-like structure consisting of CNF and CNT as backbones and M2+ as linkers. The aerogels show higher capabilities (in comparison with activated carbon) for selectively adsorbing ammonia, trimethylamine, hydrogen sulfide and methyl mercaptan. Computing simulations suggest a theoretical conclusion that the odorous chemicals are absorbed in a preferring manner of bimolecular absorptions via the M2+ moieties. The CNT/CNF-M2+ hybridized aerogels are lightweight, eco-friendly, and easy to produce in industrial scales. Our new finding, as is described in this paper, demonstrates potential applications of the TEMPO-oxidized CNF to the field of deodorizations.

Zeolites that prefer alkynes

Separations Alkenes such as ethylene and propene must be separated from alkynes before they can be converted in polymers. Drawbacks in current methods, such as hydrogenation of alkynes producing unwanted alkanes, has spurred interest in sorption separation methods. Zeolites have generally been inefficient, given the similar sizes and volatilities of the molecules. Chai et al. incorporated atomically dispersed divalent transition metal cations into faujasite zeolite and found that the nickel-containing analog efficiently removed alkynes from olefins through chemoselective binding at open nickel(II) sites. At ambient conditions in the presence of water and carbon dioxide, the zeolites retained separation selectivities of 100 and 92, respectively, for acetylene over ethylene and propyne over propylene for 10 adsorption-desorption cycles. Science , this issue p. [1002][1] [1]: /lookup/doi/10.1126/science.aay8447

Control of zeolite pore interior for chemoselective alkyne/olefin separations

The efficient removal of alkyne impurities for the production of polymer-grade lower olefins remains an important and challenging goal for many industries. We report a strategy to control the pore interior of faujasite (FAU) zeolites by the confinement of isolated open nickel(II) sites in their six-membered rings. Under ambient conditions, Ni@FAU showed remarkable adsorption of alkynes and efficient separations of acetylene/ethylene, propyne/propylene, and butyne/1,3-butadiene mixtures, with unprecedented dynamic separation selectivities of 100, 92, and 83, respectively. In situ neutron diffraction and inelastic neutron scattering revealed that confined nickel(II) sites enabled chemoselective and reversible binding to acetylene through the formation of metastable [Ni(II)(C2H2)3] complexes. Control of the chemistry of pore interiors of easily scalable zeolites has unlocked their potential in challenging industrial separations.