Formation Of Coordination Complexes Research Articles

“Turn-On” Fluorescent Assay of Biothiols Based on Nitrogen-Rich Polymer Carbon Nanostrips and Its Application in Cell Imaging

In this work, a sensitive and selective turn-on fluorimetric method has been developed for the determination of biothiols based on blocking Ag+-induced fluorescence quenching of nitrogen-rich polymer carbon nanostrips (NRPCNSs). Ag+ion can induce the fluorescence quenching of NRPCNSs due to the formation of nonfluorescent coordination complexes via robust Ag-N interaction. Once addition of biothiols, such as cysteine (Cys) and glutathione (GSH), Ag+ions prefer to interact with biothiols rather than NRPCNSs, which could be attribute to the formation of Ag-S bond, thus leading to effective fluorescent recovery of NRPCNSs. Under the optimized conditions, excellent linear relationships existed between the recovery degree of the NRPCNSs and the concentrations of Cys and GSH in the range of 0.05 μM to 10 μM and 0.2 μM to 30 μM, respectively. And, the limits of detection (LODs) for Cys and GSH are 16.5 nM and 65.1 nM, respectively. The detection system also shows high selectivity against other non-thiol amino acids. Moreover, the potential in practical applications of this proposed method has been demonstrated by detecting biothiols in human serum and fluorescence imaging of biothiols in living cells.

NMR investigation of the structure and single-particle dynamics of inorganic salt solutions in a protic ionic liquid

With the aim to analyze the microstructure of the polar nanoregions of mixtures of ionic liquids and inorganic salts and the single particle dynamics of metal cations in these densely ionic environments, solutions of inorganic nitrate salts (lithium, magnesium, calcium and aluminium nitrates) in the protic ionic liquid ethylammonium nitrate have been characterized by means of nuclear magnetic resonance. The measured spectra reveal that, despite being dried under vacuum, all the studied mixtures contained variable amounts of water, but, while in those with the salt cations of lower ionic potentials (Li+, Ca2+) only bulk free water that can be almost completely removed from the mixture is found, mixtures with the cations of higher ionic potentials (Mg2+, Al3+) contain only hydration water structurally anchored in the primary solvation shells of the metal cations forming coordination complexes inside the polar nanoregions of the densely ionic solvent and, thus, non-removable under vacuum. This hydration water is not properly detected by common Karl Fisher methods and these solutions are sometimes mistakenly considered anhydrous. Moreover, our NMR measurements confirm the nanostructured solvation paradigm, since they show that the influence of the addition of salt on the chemical shifts of the signals associated to hydrogen atoms in the apolar regions of the protic ionic liquid is negligible. Single-particle dynamics of cations of low and high ionic potentials was also studied, and our observations for the diffusion coefficients of lithium and aluminium cations support the conclusion that Li+ diffusion takes place inside anhydrous [Li(NO3)4]3− complexes, while kinetic complexes with Al3+ gather around [Al(H2O)6]3+) aqua ions.

Enhanced release of palladium and platinum from catalytic converter materials exposed to ammonia and chloride bearing solutions.

The environmental levels of platinum group elements (PGEs) are steadily rising, primarily due to exhaust emissions of vehicle catalytic converter (VCC) materials containing solid PGEs. Once these VCC materials reach soil and water, the PGEs may be transported in the form of nanoparticles (dimensions 1-100 nm) or they may be mobilized by forming coordination complexes with ligands in the environment. Chloride (Cl-) and ammonia (NH3) are two ligands of particular concern due to their ubiquity as well as their potential to form the chemotherapy drug cisplatin (Pt(NH3)2Cl2) or other potentially bioactive complexes. This initial study examines the release of Pd and Pt into solutions exposed to VCC materials at pH 8 and 25 °C, using elemental analysis of metal content in post-exposure extracts. The solutions had total ammonia nitrogen concentrations (TAN, [NH4+] + [NH3]) of 0 μM, 5.56 μM, 55.6 μM and 1.13 × 105 μM (0 ppm, 0.1 ppm, 1 ppm, and 2147 ppm). The former three represent background environmental levels had a minimal effect on release. However, when combined with 1.13 × 105 μM Cl- (4000 ppm Cl-), 55.6 μM TAN induced a marked increase in metal release (∼41× for Pd). High TAN solutions induced more Pd and Pt release than equimolar NaCl solutions. Materials characterization revealed that ∼4 nm palladium-containing nanoparticles were present, spatially associated with nanoparticles of γ-Al2O3; ceria-zirconia nanoparticles were also present but did not have any metal associated with them. Platinum-containing nanoparticles were not observed.

Antioxidant Properties and the Formation of Iron Coordination Complexes of 8-Hydroxyquinoline.

Background: The alkaloid 8-hydroxyquinoline (8HQ) is well-known for various biological activities, including antioxidant effects and especially for the formation of coordination complexes with various transition metals, such as iron, amongst others. Therefore, 8HQ was extensively explored as a promising antineurodegenerative agent. However, other authors noted pro-oxidant effects of 8HQ. Here, we explore the pro- and antioxidant properties of 8HQ, especially in context of coordination complexes with iron (II) and iron (III). Methods: Nano-electrospray−mass spectrometry, differential pulse voltammetry, deoxyribose degradation, iron (II) autoxidation, and brine shrimp mortality assays were used. Results: 8HQ formed a complex mixture of coordination complexes with iron (II) and iron (III). Furthermore, 8HQ showed antioxidant effects but no pro-oxidant ones. In the brine shrimp mortality assay, 8HQ demonstrated toxicity that decreased in the presence of iron (III). Conclusions: 8HQ is a potent antioxidant whose effects depend not only on the formation of the coordination complexes with iron ions, but surely on the scavenging activities due to the redox properties of the 8-hydroxyl group. No pro-oxidant effects were observed in the set of the used assays.

One-dimensional networks formed via the self-assembly of anthracenedibenzoic acid with zinc(II).

Self-assembly of metal-organic coordination polymers occurs because of enthalpically favorable interactions. In the case of the bulky 4,4'-(anthracene-9,10-diyl)dibenzoic acid ligand (abdH2), we demonstrate that the presence of numerous π-π and C-H...π interactions outweigh the formation of saturated coordination complexes with zinc, leading to the formation of a dimethylformamide (DMF) solvate, namely 4,4'-(anthracene-9,10-diyl)dibenzoic acid dimethylformamide disolvate, C28H18O4·2C3H7NO or [(abdH2)(DMF)2], at low concentrations of zinc. Meanwhile, at higher zinc concentrations, the abdH2 ligand gives rise to the nonporous one-dimensional coordination polymer catena-poly[[bis(dimethylformamide-κO)zinc(II)]-μ-4,4'-(anthracene-9,10-diyl)dibenzoato-κ2O:O'], [Zn(C28H16O4)(C3H7NO)2]n or [Zn(abd)(DMF)2]n, when assembled in dimethylformamide, while a related compound is observed when N,N-dimethylacetamide (DMA) is used as the solvent, namely catena-poly[[[bis(N,N-dimethylacetamide-κO)zinc(II)]-μ-4,4'-(anthracene-9,10-diyl)dibenzoato-κ2O:O'] N,N-dimethylacetamide monosolvate], {[Zn(C28H16O4)(C4H9NO)2]·C4H9NO}n or {[Zn(abd)(DMA)2]·DMA}n. Attempts to use other amide-based solvents did not give rise to any other assembled structures.

Application of Benzoxazine‐Based Dimers, Oligomers, and Polymers as Chelating Agents

AbstractPolybenzoxazines are a relatively new type of thermoset polymer that has primarily been used for the development of composite materials. However, there is an existing interest in expanding the applications for this family of polymers. One way of achieving this goal is by taking advantage of the molecular structure, where the presence of oxygen and nitrogen atoms with lone electron pairs allows the formation of coordination complexes and chelates between the benzoxazine oligomers and polymers with metal ions. This article is focused on studying the relationship between the spatial conformation of the polybenzoxazine and the capacity to form coordination complexes from a fundamental point of view as well as practical applications of this concept. Thus, it can be seen that use of polybenzoxazines for the removal of heavy metals from water and the use of benzoxazine dimers for the synthesis of CeO2 nanoparticles are examples of very different applications based on the same working principle.

Ligand-Centered Borenium Reactivity in Triaminoborane-Bridged Diphosphine Complexes.

Borenium ions (i.e., three-coordinate boron cations) are known to promote a wide variety of stoichiometric and catalytic reactions because of their high Lewis acidity. As demonstrated by the growing number of chemically reactive borane ligands, there is considerable interest in developing ligands with highly electrophilic boron sites that promote multisite reactivity in metal complexes. However, there are currently few examples of ligand-centered borenium ions, especially with ligands that form coordination complexes with a wide range of metals. Here we report borenium-like reactivity on a highly versatile diphosphine ligand. Treating (PhTBDPhos)NiCl2 (1) with strong Bronsted acids such as HBF4·Et2O, HOTf, or HNTf2 resulted in fluoride or chloride abstraction from BF4- or NiCl2, respectively, to form trans N-H and B-X bonds on the ligand backbone. HCl addition to the bridgehead N-B bond is reversible, and the reactivity depends on the identity of the supporting counteranions, as observed when treating [(PhTBDPhos)NiCl]2X2, where X = NTf2- (3), OTf- (4), or BArF4- (5), with HCl. The reaction of 4 with HNTf2 instead of HCl yielded NMR evidence of the latent borenium cation in solution and showed how poor nucleophiles such as triflate bind to the borenium ion in the solid state. Remarkably, replacing the chloride ligands in 1 with chelating and less-labile thiolates or catecholates, or changing the phosphorus substituents (phenyl to isopropyl), attenuates the reactivity on the ligand backbone. Density functional theory was used to quantify the reaction free energies, and the theoretical results corroborate the experimental observations. Given the broad utility of diphosphines in homogeneous catalysis and the known benefits of strong Lewis acid promotors in many catalytic reactions, we anticipate that the results will provide new opportunities for dual-site reactivity involving boron ligands and metals.

Assembly of Robust Holmium-Directed 2D Metal-Organic Coordination Complexes and Networks on the Ag(100) Surface.

We describe the formation of lanthanide-organic coordination networks and complexes under ultra-high-vacuum conditions on a clean Ag(100) surface. The structures comprise single Ho atoms as coordination centers and 1,4-benzenedicarboxylate (from terephtalic acid, TPA) as molecular linkers. Using low-temperature scanning tunneling microscopy, we find two different chiral phases of surface-supported metal-organic structures incorporating Ho atoms. Density functional theory calculations can explain the structure of both binding motifs and give possible reasons for their varying formation under the respective Ho/TPA ratios, as well as deposition and annealing temperatures. Metal-ligand interactions drive the formation of cloverleaf-shaped mononuclear Ho-TPA4 complexes establishing supramolecular arrays stabilized through hydrogen bonding. A 2D lanthanide-organic reticulation is observed when changing the stoichiometry between the two building blocks. The combined insights from scanning tunneling microscopy and density functional theory reveal the relative stability, charge transfer, and bonding environment of both motifs.

Carbonyls in the s block

Organometallics Conventional wisdom in chemistry distinguishes transition metals from other elements by their use of d orbitals in bonding. Wu et al. now report that alkaline earth metals can slide their electrons from s- to d-orbital bonding motifs as well (see the Perspective by Armentrout). Calcium, strontium, and barium all form coordination complexes with a cubic arrangement of eight carbonyl ligands and an 18-electron valence shell. The compounds were characterized in frozen neon matrices by vibrational spectroscopy and in gas phase by mass spectrometry. Science , this issue p. [912][1]; see also p. [849][2] [1]: /lookup/doi/10.1126/science.aau0839 [2]: /lookup/doi/10.1126/science.aau6622

Cu(II), Zn(II), Cd(II) and Hg(II) Complexes of Pantroprazole (PPZH): Synthesis and Characterization

Several metal complexes of pantoprazole, [Cu(PPZ)(H2O)Cl], [Zn(PPZ)2], [Cd(PPZ)2].1.5H2O and [Hg(PPZ)(H2O)Cl] have been synthesized and characterized. Elemental analysis, IR, UV-Visible spectral analysis, magnetic measurement, thermogravimetric analysis, differential scanning calorimetric and cyclic voltammetric techniques were used for their characterization. The lipophilic weak base pantoprazole (PPZ) act as a potential bidentate ligand forming coordination complexes with divalent metal ions through anionic imidazolyl N- and O atom of sulfinyl >S=O group. All complexes possess tetrahedral geometry.
 Dhaka Univ. J. Sci. 66(2): 151-156, 2018 (July)

Highly Efficient Nonfullerene Polymer Solar Cells Enabled by a Copper(I) Coordination Strategy Employing a 1,3,4-Oxadiazole-Containing Wide-Bandgap Copolymer Donor.

A novel wide-bandgap copolymer of PBDT-ODZ based on benzo[1,2-b:4,5-b' ]dithiophene (BDT) and 1,3,4-oxadiazole (ODZ) blocks is developed for efficient nonfullerene polymer solar cells (NF-PSCs). PBDT-ODZ exhibits a wide bandgap of 2.12 eV and a low-lying highest occupied molecular orbital (HOMO) level of -5.68 eV, which could match well with the low-bandgap acceptor of 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone)-5,5,11,11-tetrakis(4-hexylthienyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']-dithiophene (ITIC-Th), inducing a good complementary absorption from 300 to 800 nm and a minimal HOMO level offset (0.1 eV). The PBDT-ODZ:ITIC-Th devices exhibit a large open-circuit voltage (Voc ) of 1.08 eV and a low energy loss (Eloss ) of 0.50 eV, delivering a high power conversion efficiency (PCE) of 10.12%. By adding a small amount of copper(I) iodide (CuI) as an additive to form coordination complexes in the active blends, much higher device performances are achieved due to the improved absorption and crystallinity. After incorporating 4% of CuI, the PCE is elevated to 12.34%, with a Voc of 1.06 V, a Jsc of 17.1 mA cm-2 and a fill factor of 68.1%. This work not only provides a novel oxadiazole-containing wide-bandgap polymeric donor candidate for high-performance NF-PSCs but also presents an efficient morphology-optimization approach to elevate the PCE of NF-PSCs for future practical applications.

Can Remote N-Heterocyclic Carbenes Coordinate with Main Group Elements? Synthesis, Structure, and Quantum Chemical Analysis of N+ -Centered Complexes.

Remote N-heterocyclic carbenes (rNHCs), such as N-methyl-4-pyridylidene, are known to form coordination complexes with TMs. Herein, it is established that rNHCs can also coordinate to the N+ centre. Synthesis of some novel divalent NI complexes with the general formula (rNHC)→N+ ←(NHC) and (rNHC)→N+ ←(rNHC) was achieved, and X-ray diffraction studies supported the coordination bond character between the rNHCs and the N+ centre. Quantum chemical analysis established the presence of divalent NI character at the central nitrogen in these systems.

Iron speciation in peats: Chemical and spectroscopic evidence for the co-occurrence of ferric and ferrous iron in organic complexes and mineral precipitates

The speciation of iron (Fe) in organic matter (OM)-rich environments under in situ variable redox conditions is largely unresolved. Peatlands provide a natural setting to study Fe–OM interactions. Utilizing chemical, spectroscopic and theoretical modeling approaches, we report the chemical forms, oxidation states and local coordination environment of naturally occurring Fe in the vertically redox-stratified Manning peatlands of western New York. In addition, we report dominant carbon, sulfur and nitrogen species that can potentially stabilize the various Fe species present in these peatlands. Our results provide clear direct and indirect evidence for the co-occurrence of ferrous (Fe2+) and ferric (Fe3+) iron species in peats under both oxic and anoxic conditions. Iron is mostly present within the operationally defined organic and amorphous (i.e., short range ordered, SRO) fractions; ferric iron primarily as magnetically isolated paramagnetic Fe3+ in Fe(III)-organic complexes, but also in mineral forms such as ferrihydrite; ferrous iron in tetrahedral coordination in Fe(II)-organic complexes with minor contribution from pyrite. All of the Fe species identified stabilize Fe(III) and/or Fe(II) in anoxic and oxic peats. Fundamental differences are also observed in the relative proportion of C, S and N functionalities of OM in oxic and anoxic peats. Aromatic CC, ester, phenol and anomeric C (ROCOR), as well as thiol, sulfide and heterocyclic N functionalities are more prevalent in anoxic peats. Collectively, our experimental evidence suggests iron forms coordination complexes with O-, S- and N-containing functional groups of OM. We posit the co-occurrence of organic and mineral forms of Fe(II) and Fe(III) in both oxic and anoxic peat layers results from dynamic complexation and hydrolysis-precipitation reactions that occur under variable redox conditions. Our findings aid in understanding the crucial role OM plays in determining Fe species in soils and sediments.

Synthesis of Stable [28π] m-Benzihexaphyrins (1.0.0.1.1.1).

Four new expanded [28π] m-benziporphyrins (1.0.0.1.1.1) were synthesized by [3+3] condensation of 10,10'-bis[(p-toly)hydroxymethyl]-1,3-bis(2-thienyl)benzenediol with various 16-tripyrranes such as 16-thiatripyrrane, 16-oxatripyrrane, 16-azatripyrrane, and 16-selenatripyrrane under mild trifluoroacetic acid-catalyzed reaction conditions. The macrocycles are freely soluble in common organic solvents, and their identities were confirmed by HRMS and detailed 1D and 2D NMR spectroscopy. The macrocycles showed one sharp Soret-type band at ∼500 nm and broad ill-defined Q-type band(s) in the region 600-950 nm, which supports their nonaromatic nature. Upon protonation, the macrocycles exhibited bathochromically shifted absorption bands with a distinct change in the color of the solutions. The preliminary studies carried out with one of the macrocycles indicated that the macrocycles have a weak tendency to form coordination complexes.

Self-Assembly of Giant Spherical Liquid-Crystalline Complexes and Formation of Nanostructured Dynamic Gels that Exhibit Self-Healing Properties.

Supramolecular self-assembly of 24 forklike mesogenic ligands and 12 transition metal ions led to the formation of giant spherical coordination complexes that exhibit liquid-crystalline (LC) phases. Self-healing LC supramolecular gels were also obtained through the introduction of these LC nanostructured supramolecular giant spherical complexes into dynamic covalent networks formed by cross-linkers and bifunctional polymers. The giant spherical structures of the PdII complexes with 72 rodlike moieties on the periphery were characterized by NMR, diffusion-ordered NMR spectroscopy, and mass spectrometry. These complexes are stable and exhibit lyotropic LC behavior, while the mesogenic ligands show thermotropic LC properties. The self-assembled LC structures of the spherical complexes can be tuned by the length of the rodlike moieties.

Self‐Assembly of Giant Spherical Liquid‐Crystalline Complexes and Formation of Nanostructured Dynamic Gels that Exhibit Self‐Healing Properties

AbstractSupramolecular self‐assembly of 24 forklike mesogenic ligands and 12 transition metal ions led to the formation of giant spherical coordination complexes that exhibit liquid‐crystalline (LC) phases. Self‐healing LC supramolecular gels were also obtained through the introduction of these LC nanostructured supramolecular giant spherical complexes into dynamic covalent networks formed by cross‐linkers and bifunctional polymers. The giant spherical structures of the PdII complexes with 72 rodlike moieties on the periphery were characterized by NMR, diffusion‐ordered NMR spectroscopy, and mass spectrometry. These complexes are stable and exhibit lyotropic LC behavior, while the mesogenic ligands show thermotropic LC properties. The self‐assembled LC structures of the spherical complexes can be tuned by the length of the rodlike moieties.

A pyrene-based dual chemosensor for colorimetric detection of Cu2+ and fluorescent detection of Fe3+

A pyrene based chemosensor was designed and synthesized. The pyrene fluorophore was connected with a pyridine unit through a Schiff base structure to give the sensor (L). L was tested with a variety of metal ions and exhibited high colorimetric selectivities for Cu2+ and Fe3+ over other ions. Upon binding with Cu2+ or Fe3+, L showed an obvious optical color change from colorless to pink for Cu2+ or orange for Fe3+ over a wide pH range from 3 to 12. Moreover, the fluorescence of L at 370nm decreased sharply after bonding with Fe3+, while other metal ions including Cu2+ had no apparent interference. Thus, using such single chemosensor, Cu2+ and Fe3+ can be detected independently with high selectivity and sensitivity. The limits of detection toward Cu2+ and Fe3+ were 8.5 and 2.0μM, respectively. DFT calculation results also proved the formation of stable coordination complexes and the phenomenon of fluorescence quenching by Fe3+. Furthermore, L was also successfully used as a bioimaging reagent for detection of Fe3+ in living cells.

A(nother) Modification of the Ammonia Fountain Demonstration

A modification of the ammonia fountain demonstration is presented which does not use dyes. The procedure illustrates both the solubility of ammonia as well as the formation of coordination complexes and drives the reaction toward completion by removing a product.

Role of zeolite's exchangeable cations in phosphate adsorption onto zirconium-modified zeolite

To determine the role of zeolite's exchangeable cations such as Ca2+ and Na+ in the adsorption of phosphate on zirconium-modified zeolite (ZrMZ), the adsorption behaviors and mechanisms of phosphate on ZrMZ, NaCl-treated ZrMZ and CaCl2-treated ZrMZ in the absence and presence of ammonium were comparatively investigated in this study. Results showed that coexisting ammonium promoted the adsorption of phosphate on the raw, NaCl-treated and CaCl2-treated ZrMZs. In the absence of ammonium, the treatment of ZrMZ with NaCl inhibited the phosphate adsorption, but the treatment of ZrMZ with CaCl2 enhanced the adsorption of phosphate. In the presence of ammonium, the treatment of ZrMZ with NaCl suppressed the adsorption of phosphate, but the effect of CaCl2 treatment on the phosphate adsorption depended upon coexisting ammonium amount. In the presence of a certain amount of ammonium (5–30mg N/L), the treatment of ZrMZ with CaCl2 improved the phosphate adsorption efficiency. The mechanism for phosphate adsorption onto ZrMZ was the exchange of surface hydroxyl groups with phosphate ions and the formation of phosphate inner-sphere coordination complexes, and the enhancement of phosphate adsorption onto ZrMZ by coexisting Ca2+ could be attributed to the formation of CaHPO40 species in the calcium/phosphate solution and the formation of phosphate-bridged ternary complex (Zr)(OPO3H)Ca on the adsorbent surface. The increased phosphate adsorption induced by CaCl2 treatment could be attributed to the increase in the amount of released Ca2+ from ZrMZ, and the decreased phosphate adsorption induced by NaCl treatment could be attributed to the decrease in the amount of released Ca2+ from ZrMZ. This work suggests that the exchangeable Ca2+ in ZrMZ plays an important role in the phosphate adsorption, and its release enhances the adsorption of phosphate.

Silver ion coordination countercurrent chromatography: Separation of β-elemene from the volatile oil of Curcumae Rhizoma.

In this work, the antitumor constituent β-elemene was selectively separated from the volatile oil of the Curcumae Rhizoma by countercurrent chromatography with silver nitrate as selective reagent based on the formation of coordination complexes. A biphasic solvent system composed of n-hexane/methanol/water (2:1.5:0.5, v/v/v) was selected, in which 0.15mol/L of silver nitrate was added to the aqueous phase. The aqueous phase was used as the stationary phase for separation of β-elemene by countercurrent chromatography after it was partially purified from the volatile oil by silica gel column chromatography. An enriched β-elemene fraction was obtained by silica gel column chromatography to improve the percentage of β-elemene from 16.5 to 46.1%. Subsequently, β-elemene was further purified from 445mg of the partially purified sample of volatile oil by countercurrent chromatography with silver nitrate as a selective reagent, yielding 145mg of β-elemene with greater than 99% purity, as determined by gas chromatography mass spectrometry. The recovery of β-elemene from the crude volatile oil through two steps was around 63.6%.