Combining Medium Effects and Cofactor Catalysis: Metal‐Coordinated Synzymes Accelerate Phosphate Transfer by 108

The systematic exploration of the modification of polyethylene imine with guanidinium and octyl groups has led to the identification of a catalyst, CD6, which accelerates the phosphate transfer reaction of HPNP (2‐hydroxypropyl‐4‐nitrophenyl phosphate) in the presence of divalent metals such as Zn²⁺, Co²⁺, Mg²⁺ or Ni²⁺. CD6 exhibits saturation kinetics that are described by Michaelis–Menten parameters K_m ranging from 2.5–8 mM and k_cat ranging from 0.0014–0.09 s^?1. For Zn^II–CD6 this corresponds to an overall acceleration k_cat/k_uncat of 3.8×10⁵ and a catalytic proficiency (k_cat/K_m)/k_uncat of 1.5×10⁸. Catalysis by Zn^II–CD6 is specifically inhibited by inorganic phosphate, allowing turnover regulation by product inhibition. This effect stands in contrast to Zn^II‐catalysed transesterification of HPNP in water or by the synzymes Co^II–CD6 and Ni^II–CD6, with which no such interference by product is observed. These characteristics render synzyme Zn^II–CD6 an efficient enzyme model that reflects enzyme‐like properties in a wide range of features.     

A functional applied material on recognition of metal ion zinc based on the double azine compound

A colorimetric and fluorescent probe L has been designed and synthesized, which bearing the double azine moiety and showing a detection limit of 2.725 × 10^?7 M towards Zn²⁺. Based on the basic recognition mechanism of ESIPT and CHEF effect, the L has high selectivity and sensitivity to only Zn²⁺ (not Fe³⁺, Hg²⁺, Ag⁺, Ca²⁺, Co²⁺, Ni²⁺, Cd²⁺, Pb²⁺, Cr³⁺, and Mg²⁺) within the physiological pH range (pH = 7.0–8.4) and showed a fluorescence switch. Moreover, this detection progress occured in the DMSO/H₂O ～ HEPES buffer (80/20, v/v; pH 7.23) solution which can conveniently used on test strip.     

Construction of 0D to 3D Copper(II) MOFs based on heterocyclic carboxylic acid: Synthesis,structures, cyclic voltammograms,and luminescent properties

The crystal structures of MOFs [Cu(PDA)(Phen)(H₂O)]₂ · 5H₂O (I) and [Cu(PZCA)₂(H₂O)₂] · 2H₂O (II) (H₂PDA = pyridine-2,6-dicarboxylic acid, Phen = 1,10-phenanthroline, HPZCA = pyrazine-2-carboxylic acid, H₂PZDA = pyrazine-2,3-carboxylic acid) have been prepared under hydrothermal conditions. These MOFs have been characterized by element analysis, single-crystal X-ray diffraction, thermogravimetric analyses and IR spectroscopy. 3D frameworks of MOFs I and II are fabricated from zero-dimensional (0D) motifs through hydrogen bonds and π-π interactions. In MOF II, the PZCA ligand comes from in situ decarboxylation of the part of pyrazine-2,3-dicarboxylic acid (H₂PZDA). Luminescent emissions bands of MOF I in methanol have been measured at room temperature and it displays selectivity to Zn²⁺, Cu²⁺, Pb²⁺, and Cd²⁺ ions. Cyclic voltammetry of MOFs I and II showed that the Cu(II/I) couple is irreversible.     

Complexation of metal ions with the novel 2-hydroxy-1-naphthaldehyde-derived diamine Schiff base carrying a macrobicyclic moiety with N2O2S2 mixed donor in acetonitrile-dichloromethane

A new Schiff base containing a macrobicyclic moiety was designed and synthesized by reaction of the corresponding macrobicyclic diamine compound and 2-hydroxy-1-naphthaldehyde. The influence of metal cations such as Zn²⁺, Mn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺ and Pb²⁺ on the spectroscopic properties of the 2-hydroxy-1-naphtyl group linked to the macrobicyclic moiety with N₂O₂S₂ mixed donor was investigated in acetonitrile-dichloromethane solution (9.5/0.5) by means of absorption and emission spectrometry. Emission spectra undergo a marked blue shift and enhancement of naphtyl fluorescence in the presence of Fe³⁺ and Zn²⁺. The presence of Pb²⁺, Mn²⁺, Fe²⁺, Co²⁺ and Ni²⁺ caused a quenching of naphtyl fluorescence. Especially, the quenching was higher than 90% in case of the interaction of Ni²⁺ and Co²⁺ with the ligand. The results of spectrophotometric and spectrofluorimetric titration experiments disclosed the complexation properties of the novel ligand with Zn²⁺, Co²⁺ and Ni²⁺ cations.     

Effect of pH on the electrochemical reduction of some heterocyclic quinones

The reduction of 1,10-phenanthroline-5,6-quinone(I), 5,8-quinolinequinone(II) and 6,7-dichloro-5,8-quinolinequinone(III) was investigated using cyclic voltammetry and coulometry at mercury electrodes and 50% dimethylsulfoxide+water solvent. Each compound is reduced to the corresponding hydroquinone in a diffusion-controlled, reversible two-electron process. The pH-dependence of the reversible potential indicated that the quinone forms were unprotonated, but the hydroquinones could be protonated at the heterocyclic nitrogen atom with pK_a = 5.3 for I and 3.5 for III. Careful analysis of the cyclic voltammetric peak shape revealed that the difference between the standard potentials for the introduction of successive electrons, E₂⁰ ? E₁⁰, was 70 ±20, >100 and 80 ± 20 mV for I–III. Investigation of the pH-dependence of E₁⁰ and E₂⁰ showed that the pK_a of the semiquinone of I was about 8.     

Ethers as ligands. Part V(1). Metal(II)-diglyme and -pentaglyme solvates

Summary Eighteen new coordination compounds are reported with diglyme (dgm) and pentaglyme (pgm) as ligands:viz. [M(dgm)₂](SbCl₆)₂ with M=Mg^II, Ca^II, Sr^II, Mn^II, Fe^II, Co^II, Ni^II, Cu^II, and Zn^II; [M(pgm)](SbCl₆)₂ with M=Mn^II, Fe^II,Co^II, Ni^II, Cu^II, and Zn^II; and [M(pgm)](SbCl₆)₂ · H₂O with M=Mg^II, Ca^II, and Sr^II. The metal(II) ions are hexacoordinated by the ether-oxygens of two diglyme molecules or of one pentaglyme molecule. The coordinated diglyme molecules are in the TGTT¯GT conformation.     

Synthesis of a Dithiocarbamate Chelate Resin and Its Oxidized form and Their Adsorption Properties for Heavy Metal Ions

A series of macroporous dithiocarbamate chelate resins, III and V, and an oxidized resin, VI, with high adsorption capacity were prepared. The influence of various reaction conditions of amination, dithiocarboxylation, and oxidation were examined. The structure and the conversion of functional groups of resins were confirmed by IR spectra and elemental analysis. The adsorption capacities of Resin II for Hg²⁺, Cu²⁺, Zn²⁺, and Cd²⁺ are 4.40, 2.44, 1.77, and 1.36 mmol/g, respectively. The adsorption capacities of Resins V and VI for Cu²⁺. Zn²⁺, Ni²⁺, Co³⁺, Ag⁺, Hg²⁺, Cd²⁺, Pb²⁺, and Au³⁺ are 4.07–0.51 and 3.81–0.59 meq ion/g, respectively. The adsorption rate and the influence of pH on the adsorption percentage of the resins for metal ions were examined. Noble metal, transitional metal, and heavy metal ions can be quantitatively adsorbed by the resins. The adsorbed Cu²⁺, Pb²⁺, Cd²⁺, Co³⁺, and Ni²⁺ can be quantitatively eluted with 5N HNO₃, and the presence of large amounts of Ca²⁺, Mg²⁺, Fe³⁺, and Al³⁺ did not interfere.     

Spektralphotometrische Ermittlung der Koordinationsverhältnisse in Kristallgittern, 2. Mitt.: Die Dimorphie von Zn7Sb2O12

Zusammenfassung Im System ZnO–Sb₂O₅ existieren zwei Spinellphasen (I) und (III) gleicher Zusammensetzung Zn₇Sb₂O₁₂. Außerdem konnte noch eine weitere Modifikation (II) mit einer niedrigsymmetrischen Struktur aufgefunden werden.In (II) und (III) wurden Cu²⁺, Ni²⁺ und Co²⁺ als farbgebende Kationen eingebaut. Die spektralphotometrische Untersuchung ergab, daß Zn²⁺ in (II) sowohl oktaedrisch als auch tetraedrisch koordiniert ist. Im Spinell (III) wird Cu²⁺ sowohl in Tetraeder-und Oktaederlücken, Ni²⁺ nur in Oktaeder- und Co²⁺ vorwiegend in Oktaederlücken eingebaut.In the system ZnO–Sb₂O₅ exist two phases (I) and (III) with the spinel structure and the same composition Zn₇Sb₂O₁₂. Besides these another modification (II) with a structure of lower symmetry could be found.The colouring cations Cu²⁺, Ni²⁺, Co²⁺ have been incorporated in (II) and (III). The spectrophotometrical investigation shows that Zn²⁺ occupies in (II) octahedral and tetrahedral sites. In the spinel (III) Cu²⁺ is incorporated tetrahedrally and octahedrally, Ni²⁺ only octahedrally and Co²⁺ predominantly octahedrally.Mit 4 Abbildungen1. Mitt.:H. Kasper, Z. anorg. allgem. Chem. (im Druck).     

A highly selective turn-on fluorescent chemosensor for copper(II) ion

A new pyrene derivative (1) containing a diaminomaleonitrile moiety exhibits high selectivity for Cu²⁺ detection. Significant fluorescence enhancement was observed with chemosensor 1 in the presence of Cu²⁺. However, the metal ions Ag⁺, Ca²⁺, Cd²⁺, Co²⁺, Fe²⁺, Fe³⁺, Hg²⁺, Mg²⁺, Mn²⁺, Ni²⁺, Pb²⁺, and Zn²⁺ produced only minor changes in fluorescence values for the system. The apparent association constant (K_a) of Cu²⁺ binding in chemosensor 1 was found to be 5.55×10³ M⁻¹. The maximum fluorescence enhancement caused by Cu²⁺ binding in chemosensor 1 was observed over the pH range 5-7.5.     

Anthroneamine based chromofluorogenic probes for Hg2+ detection in aqueous solution

Anthroneamine derivatives 1–3 (H₂O:DMSO; 9:1, HEPES buffer, pH 7.0 ± 0.1) undergo highly selective fluorescence quenching with Hg²⁺. The observed linear fluorescence intensity change allows the quantitative detection of Hg²⁺ between 200 nM/40 ppb—12 μM/2.4 ppm even in the presence of interfering metal ions viz. Na⁺, K⁺, Mg²⁺, Ca²⁺, Ba²⁺, Cr³⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Ag⁺, Cd²⁺, Pb²⁺. Probes 1–3 and their Hg²⁺ complexes also show the broad pH resistance for their practical applicability.     

Complexation of late transition metal(II) ions (M = Co,Ni, Cu,and Zn) by a macrocyclic thiacrown ether studied by means of electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry (ESI‐MS) is used to probe the metal‐binding selectivity of a macrocyclic thiacrown ether (C₄₄H₃₂S₂₀) towards Co^II, Ni^II, Cu^II, and Zn^II. In homogeneous 1:1 v/v methanol/dichloromethane solutions, it is found that the thia ligand very selectively binds traces of copper even in the presence of an excess of the other metal ions. The large selectivity is ascribed to the redox‐active nature of copper which enables a reduction from Cu^II to Cu^I, occurring upon ESI‐MS, whereas Co^II, Ni^II and Zn^II cannot undergo similar redox reactions. Copyright © 2009 John Wiley & Sons, Ltd.     

New fluorescent chemosensor for Zn2+ ions on the basis of 3,3′-bis(dipyrrolylmethene)

Luminescence study of the reaction of 3,3′-methanediylbis(2,4,7,8,9-pentamethyldipyrrolylmethene) (H₂L) with a number of metal salts showed that this compound is an efficient fluorescent chemosensor for Zn²⁺ ions in organic solvents. The selectivity and sensitivity of H2L were estimated in various solvents in the presence of other metal cations (Na⁺, Mg²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺, Hg²⁺, Pb²⁺).     

Transition metal complexes derived from ethyl-α-(N-phenylthiocarbamyl)cyanoacetate

Summary Complexes of Co^II, Ni^II, Cu^II, Zn^II, Pd^II, Cd^II, Hg^II and Cu^I with ethyl--(N-phenylthiocarbamyl)cyanoacetate (HETCA) have been synthesized and characterized. The i.r. spectra show that HETCA behaves as a mononegative bidentate ligand, in the thiol tautomeric form. HETCA reduces CuCl₂ to give a diamagnetic Cu^I complex. A tetrahedral structure is proposed for the Co^II complex, while a square-planar structure is proposed for the Ni^II, Cu^II, and Pd^II complexes.     

1,8-萘酰亚胺为发色团的Zn2+荧光探针的合成及性能研究

合成了以1,8-萘酰亚胺为发色团,以联吡啶为离子受体的Zn²⁺荧光探针,并进行了表征及离子识别性能的研究。研究表明该化合物对Zn²⁺具有良好的识别性能,同时相对于Ca²⁺, Cd²⁺, Co²⁺, Cu²⁺, Hg²⁺, Fe³⁺, Mn²⁺, Ni²⁺, Pb²⁺等金属离子具有良好的选择性。     

Complex formation equilibria between mercury(II) complexes of pencillamine and glutathione and transition metal ions

Summary The interaction between Hg^II complexes of the thiols pencillamine and glutathione and some transition metal ions has been investigated potentiometrically. Mixedmetal complexes of the forms Hg(ps)₂M and Hg(gs)₂M (where M=Co or Ni), were detected. The complexes formed between glutathione disulphide with bivalent metal ions Zn^II, Ni^II, Co^II and Cd^II have also been studied. Zn^II and Ni^II form the complexes M(gssg)H and M(gssg), while Co^II and Cd^II form only the fully deprotonated complex M(gssg). The formation constants of the complexes were determined at 25°C and I=0.1 M (NaNO₃). The concentration distribution of various complex species as a function of pH was evaluated.     

Syntheses,Structures, and Bioactivities Evaluation of some Transition Metal Complexes with 4,4'-Diacetylcurcumin

Stoichiometric reactions of 4,4'-diacetylcurcumin ( HL ) with series of transition metal ions, namely Fe³⁺, Co²⁺, Ni²⁺ and Zn²⁺, in methanol result in the corresponding homoleptic metal complexes. All the obtained complexes were characterized by elemental analysis, high resolution mass spectrometry, IR spectroscopy, magnetic moment and single-crystal X-ray diffraction. Structural analyses are unprecedentedly performed for the Fe^III, Co^II, and Ni^II complexes and reveal octahedral mononuclear complexes with the compositions [Fe(L)₃] and [M(L)₂(MeOH)₂] (M = Co²⁺, Ni²⁺, Zn²⁺) for trivalent and divalent metal ions, respectively. In all complexes, the deprotonated ligands serve as monoanionic and bidentate ligands with (O,O)-chelating β-diketonate moieties. The free ligand HL exhibits considerable antiproliferative effects for the human MCF-7 breast and HepG2 liver cancer cells with IC₅₀ values of 20.91 ± 2.16 μg · mL^–1 and 12.85 ± 1.85 μg · mL^–1, respectively. The Co^II and Zn^II complexes with IC₅₀ values in the range of 14.53–20.80 μg · mL^–1 for MCF-7 breast and 8.48–10.68 μg · mL^–1 for HepG2 liver cancer cells show stronger antiproliferative effects than HL, the Fe^III and Ni^II complexes cause weaker reductions of the growth of the two tested cancer cell lines.     

Reversible formation of binuclear complexes between pyridine-2-carboxylato(tetraethylenepentamine)cobalt(III) and nickel(II)/cobalt(II) in aqueous solution. Anomalous behaviour in the dissociation of binuclear complexes

The kinetics of the reversible formation of binuclear species between M(OH₂) ₆ ²⁺ (M = Ni^II and Co^II) and oxygen-bonded (tetren)Co(pycH)³⁺ (tetren = tetraethylenepentamine, pycH = N-protonated pyridine-2-carboxylate) have been investigated by stopped-flow spectrophotometry at 25°C, I = 0.3 mol dm^-3. Both the protonated (pyridine-N) and deprotonated forms of the Co^III complex were involved in the formation of the binuclear complex (tetren)Co(pyc)Co⁴⁺, whereas only the deprotonated form of the complex was involved in the formation of (tetren)Co(pyc)Ni⁴⁺. The rate date forthe formation of the binuclear complex are consistent with an Id mechanism. Interestingly, the dissociation of the binuclear Co^II complex (tetren)Co(pyc)Co⁴⁺ was acid-catalysed while that with Ni^II was acid-independent. A suitable explanation for this anomalous behaviour has been discussed.     

Über die Extrahierbarkeit von Metallverbindungen der Diphenylarsinsäure

Zusammenfassung Es wird über die Möglichkeit berichtet, Metallionen aus wäßriger Lösung mit Hilfe organischer Lösungsmittel als Verbindungen der Diphenylarsinsäure extrahieren zu können. Von den untersuchten Ionen Fe³⁺, Al³⁺, Bi³⁺, Cr³⁺, UO₂ ²⁺, Zn²⁺, Cd²⁺, Cu²⁺, Co²⁺, Ni²⁺, Mn²⁺, Be²⁺, Pb²⁺, Ca²⁺ und Mg²⁺ sind mit Chloroform nur Pb²⁺, Bi³⁺, Be²⁺, Zn²⁺ und Al³⁺ extrahierbar. Mit Trichloräthylen ist praktisch nur mehr Pb²⁺ extrahierbar, während Benzol und Essigester keinerlei Extraktionswirkung zeigen. Vergleiche mit dem Verhalten aliphatischer Arsinsäuren werden angestellt.

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Summary A report is given concerning the possibility of extracting metal ions from aqueous solution by means of organic liquids as compounds of diphenylarsinic acid. The ions investigated included Fe³⁺, Al³⁺, Bi³⁺, UO₂ ²⁺, Zn²⁺, Cr³⁺, Cd²⁺, Cu²⁺, Co²⁺, Ni²⁺, Mn²⁺, Be²⁺, Pb²⁺, Ca²⁺, and Mg²⁺. Of these only Pb²⁺, Bi³⁺, Be²⁺, Zn³⁺ and Al³⁺ are extractable with chloroform. With trichloro ethylene only Pb²⁺ is extractable, whereas benzene and acetic ester show no extraction action. Comparisons were made with the behavior of aliphatic arsinic acids.

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Résumé On décrit la possibilité d'extraction d'ions métalliques à l'état de composés de l'acide diphénylarsinique, à partir de leur solution aqueuse, à l'aide d'un solvant organique. Parmi les ions étudiés, Fe³⁺, Al³⁺, Bi³⁺, Cr³⁺, UO₂ ²⁺, Zn²⁺, Cd²⁺, Cu²⁺, Co²⁺, Ni²⁺, Mn²⁺, Be²⁺, Pb²⁺, Ca²⁺ et Mg²⁺, seuls Pb²⁺, Bi³⁺, Be²⁺, Zn²⁺ et Al³⁺ peuvent être extraits par le chloroforme. Le trichloréthyléne ne permet que l'extraction du Pb²⁺, cependant que le benzène et l'ester acétique ne manifestent aucune activité d'extraction. On établit une comparaison avec le comportement des acides arsiniques aliphatiques.

     

Versatility in the coordination behavior of a hexatopic compartmental Schiff-base ligand in the architecture of binuclear transition metal(II) complexes

Condensation of 1H-pyrazole-3,5-dicarboxylic hydrazide with 1H-indole-2,3-dione (isatin) yield the compartmental ligand, which is capable of encapsulating two transition metal ions namely Co^II, Ni^II, Cu^II, and Zn^II. The ligand is a binuclear hexadentate chelate with N₄O₂ donating sites. The pyrazole core provides the diazine fragment, which serves as an endogenous bridge between the two metal centers. In Co^II and Ni^II complexes, the ligand is in the imidol form and the subsequent coordination through the imidol oxygen. In other complexes, the lactonic oxygen takes part in ligation. All the complexes are non-electrolytes and soluble in DMSO, DMF, and acetonitrile. Spectral and magnetic studies along with analytical data suggest octahedral geometry for the Co^II and Ni^II complexes, whereas the Cu^II and Zn^II complexes are assigned square pyramidal geometry. The Cu^II and Ni^II complexes show one electron redox behavior and the rest are electrochemically inactive.     

Synthesis and spectroscopic studies on 3-isonicotinamidorhodanine complexes of some bivalent metal ions

Summary 3-Isonicotinamido-rhodanine (HINRd) reacts with metal ions to yield complexes of the types M(INRd)OH·nH₂O (where M=Co^II, Ni^II, Zn^II or Cd^II and n=1 or 2), Cu(HINRd)X·2H₂O (where X=Cl or Br), Pd(HINRd)Cl₂ and Cd(HINRd)X₂·H₂O (where X=Cl or Br), depending on the metal salt used and the reaction conditions. The metal complexes have been characterized by elemental analysis, molar conductivities, molecular weights, magnetic susceptibility, visible, and i.r. studies. The i.r. spectra show that HINRd binds in a bidentate or monodentate manner. The spectral and magnetic studies suggest a tetrahedral arrangement for Co^II, octahedral for Ni^II and square-planar for Pd^II. HINRd behaves as a reducing agent towards Cu^II chloride or bromide forming diamagnetic Cu^I complexes.