Alkaline earth metal ion coordination increases the radical scavenging efficiency of kaempferol

Flavonoids are used as natural additives and antioxidants in foods, and after coordination to metal ions, as drug candidates, depending on the flavonoid structure. The rate of radical scavenging of the ubiquitous plant flavonoid kaempferol (3,5,7,4′-tetrahydroxyflavone, Kaem) was found to be significantly enhanced by coordination of Mg(ii), Ca(ii), Sr(ii), and Ba(ii) ions, whereas the radical scavenging rate of apigenin (5,7,4′-trihydroxyflavone, Api) was almost unaffected by alkaline earth metal (AEM) ions, as studied for short-lived β-carotene radical cations (β-Car˙⁺) formed by laser flash photolysis in chloroform/ethanol (7 : 3) and for the semi-stable 2,2-diphenyl-1-picrylhydrazyl radical, DPPH˙, in ethanol at 25 °C. A 1 : 1 Mg(ii)–Kaem complex was found to be in equilibrium with a 1 : 2 Mg(ii)–Kaem₂ complex, while for Ca(ii), Sr(ii) and Ba(ii), only 1 : 2 AEM(ii)–Kaem complexes were detected, where all complexes showed 3-hydroxyl and 4-carbonyl coordination and stability constants of higher than 10⁹ L² mol⁻². The 1 : 2 Ca(ii)–Kaem₂ complex had the highest second order rate constant for both β-Car˙⁺ (5 × 10⁸ L mol⁻¹ s⁻¹) and DPPH˙ radical (3 × 10⁵ L mol⁻¹ s⁻¹) scavenging, which can be attributed to the optimal combination of the stronger electron withdrawing capability of the (n − 1)d orbital in the heavier AEM ions and their spatially asymmetrical structures in 1 : 2 AEM–Kaem complexes with metal ion coordination of the least steric hindrance of two perpendicular flavone backbones as ligands in the Ca(ii) complex, as shown by density functional theory calculations.

Radical scavenging activity of kaempferol is notably enhanced by Ca(ii) binding.     

A novel catalytic kinetic method for the determination of mercury(ii) in water samples

Mercury(ii) ions act as catalyst in the substitution of cyanide ion in hexacyanoruthenate(ii) by pyrazine (Pz) in an acidic medium. This property of Hg(ii) has been utilized for its determination in aqueous solutions. The progress of reaction was followed spectrophotometrically by measuring the increase in absorbance of the yellow colour product, [Ru(CN)₅Pz]³⁻ at 370 nm (λ_max, ε = 4.2 × 10³ M⁻¹ s⁻¹) under the optimized reaction conditions; 5.0 × 10⁻⁵ M [Ru(CN)₆⁴⁻], 7.5 × 10⁻⁴ M [Pz], pH 4.00 ± 0.02, ionic strength (I) = 0.05 M (KCl) and temp. 45.0 ± 0.1 °C. The proposed method is based on the fixed time procedure under optimum reaction conditions. The linear regression (calibration) equations between the absorbance at fixed times (t = 15, 20 and 25 min) and [Hg(ii)] were established in the range of 1.0 to 30.0 × 10⁻⁶ M. The detection limit was found to be 1.5 × 10⁻⁷ M of Hg(ii). The effect of various foreign ions on the proposed method was also studied and discussed. The method was applied for the determination of Hg(ii) in different wastewater samples. The present method is simple, rapid and sensitive for the determination of Hg(ii) in trace amount in the environmental samples.

Mercury(ii) ions act as catalyst in the substitution of cyanide ion in hexacyanoruthenate(ii) by pyrazine (Pz) in an acidic medium.     

Au(i)-, Ag(i)-, and Pd(ii)-coordination-driven diverse self-assembly of an N-heterocyclic carbene-based amphiphile

Au(i)-, Ag(i)-, and Pd(ii)-coordination-driven diverse self-assembly of an N-heterocyclic carbene (NHC)-based amphiphile was demonstrated herein. The transition metals had significant effects over the whole system, setting the self-assembly direction of the NHC-based amphiphile. More specifically, Au(i)- and Ag(i)-coordination to the NHC-based amphiphile promoted the formation of spherical and hexagonal structures, while Pd(ii)-coordination promoted the formation of cylindrical and lamellar structures.

Au(i)-, Ag(i)-, and Pd(ii)-coordination-driven diverse self-assembly of an N-heterocyclic carbene (NHC)-based amphiphile was demonstrated.     

Anticancer and antimicrobial properties of novel η6-p-cymene ruthenium(ii) complexes containing a N,S-type ligand,their structural and theoretical characterization

Ruthenium(ii) complexes are lately of great scientific interest due to their chemotherapeutic potential as anticancer and antimicrobial agents. Here we present the synthesis of new pyrazole carbothioamide derivatives and their four arene–ruthenium complexes. The title compounds were characterized with the application of IR, NMR, mass spectrometry, elemental analysis and X-ray diffraction. Additionally, for new complexes DFT calculations were done. Their antimicrobial activity (MIC, MBC/MFC) was examined in vitro against Staphylococcus aureus, Staphylococcus epidermidis, Enterococcus faecalis, Pseudomonas aeruginosa, Proteus vulgaris and Candida albicans. Their cytotoxic effects, using the MTT assay, against three cancer cell lines: HL-60, NALM-6, WM-115 and normal human foreskin fibroblasts (HFF-1) were also investigated. The influence of the new arene–ruthenium(ii) complexes on the DNA structure was also tested. From our results, compound 2d showed higher cytotoxicity against melanoma cell line WM-115 than cisplatin. Strong biostatic and biocidal activity of the tested complexes against Gram-positive bacteria, including S. aureus, S. epidermidis and E. faecalis was demonstrated. The new arene–ruthenium(ii) compounds could not only inhibit proliferation of cancer cells, but also protect patients against malignant wound infections.

New arene–ruthenium(ii) complexes with pyrazole derivatives as ligands were synthesized and characterized. This compounds exhibited good cytotoxic effects, and strong biostatic and biocidal activity.     

Selective removal of lead ions from aqueous solutions using 1,8-dihydroxyanthraquinone (DHAQ) functionalized graphene oxide; isotherm,kinetic and thermodynamic studies

An anthraquinone – graphene structure was fabricated and applied for the removal of lead(ii) from aqueous solution. The equilibrium occurred in about 10 min revealing the high adsorption rate at the beginning of the process. The maximum Pb(ii) adsorption capacity of the Fe₃O₄@DHAQ_GO nanocomposite was about 283.5 mg g⁻¹ that was observed at 323 K and pH 5.5. The Pb(ii) adsorption ability increased with the increasing pH. The isotherm and kinetic studies indicated that the Sips isotherm model and the linear form of the pseudo-second kinetic model had a better fit with the experimental results. The positive value of ΔH⁰ indicated endothermic interactions between Pb(ii) and Fe₃O₄@DHAQ_GO. The negative ΔG⁰ indicated that the reactions are spontaneous with a high affinity for Pb(ii). The positive ΔS⁰ values indicated increasing randomness at the solid–solute interface during the adsorption process. The selective removal of Pb(ii) by the nanocomposite confirms the presence of higher-affinity binding sites for Pb(ii) than Cd(ii), Co(ii), Zn(ii), and Ni(ii) ions. Furthermore, the Fe₃O₄@DHAQ_GO nanocomposite revealed an excellent preferential adsorbent for Pb(ii) spiked in drinking water samples containing natural ion matrices. EDTA-2NA 0.01 N was found to be a better elution agent than HCl 0.1 M for the nanocomposite regeneration. After five adsorption/desorption cycles using EDTA-2NA 0.01 N, more than 84% of the adsorbed Pb(ii) was still desorbed in 30 min. Capturing sub-ppm initial concentrations of Pb(ii) and the capability to selectively remove lead from drinking water samples make the Fe₃O₄@DHAQ_GO nanocomposite practically convenient for water treatment purposes. High adsorption capacity and facile chemical synthesis route are the other advancements.

The Fe₃O₄@DHAQ_GO nanocomposite can serve as an efficient adsorbent for the selective removal of lead from polluted water.     

A highly selective pyridoxal-based chemosensor for the detection of Zn(ii) and application in live-cell imaging; X-ray crystallography of pyridoxal-TRIS Schiff-base Zn(ii) and Cu(ii) complexes

In a simple, one-step reaction, we have synthesized a pyridoxal-based chemosensor by reacting tris(hydroxymethyl)aminomethane (TRIS) together with pyridoxal hydrochloride to yield a Schiff-base ligand that is highly selective for the detection of Zn(ii) ion. Both the ligand and the Zn(ii) complex have been characterized by ¹H & ¹³C NMR, ESI-MS, CHN analyses, and X-ray crystallography. The optical properties of the synthesized ligand were investigated in an aqueous buffer solution and found to be highly selective and sensitive toward Zn(ii) ion through a fluorescence turn-on response. The competition studies reveal the response for zinc ion is unaffected by all alkali and alkaline earth metals; and suppressed by Cu(ii) ion. The ligand itself shows a weak fluorescence intensity (quantum yield, Φ = 0.04), and the addition of zinc ion enhanced the fluorescence intensity 12-fold (quantum yield, Φ = 0.48). The detection limit for zinc ion was 2.77 × 10⁻⁸ M, which is significantly lower than the WHO''s guideline (76.5 μM). Addition of EDTA to a solution containing the ligand–Zn(ii) complex quenched the fluorescence, indicating the reversibility of Zn(ii) binding. Stoichiometric studies indicated the formation of a 2 : 1 L₂Zn complex with a binding constant of 1.2 × 10⁹ M⁻² (±25%). The crystal structure of the zinc complex shows the same hydrated L₂Zn complex, with Zn(ii) ion binding with an octahedral coordination geometry. We also synthesized the copper(ii) complex of the ligand, and the crystal structure showed the formation of a 1 : 1 adduct, revealing 1-dimensional polymeric networks with octahedral coordinated Cu(ii). The ligand was employed as a sensor to detect zinc ion in HEK293 cell lines derived from human embryonic kidney cells grown in tissue culture which showed strong luminescence in the presence of Zn(ii). We believe that the outstanding turn-on response, sensitivity, selectivity, lower detection limit, and reversibility toward zinc ion will find further application in chemical and biological science.

The synthesis, characterization, X-ray crystallography, and live-cell imaging of pyridoxal-TRIS Schiff-base ligand which is selective as a luminescence sensor to detect Zn(ii) ion, and the corresponding Zn(ii) and Cu(ii) complexes are described.     

Electronic effects on the mechanism of the NAD+ coenzyme reduction catalysed by a non-organometallic ruthenium(ii) polypyridyl amine complex in the presence of formate

In the present study, electronic effects on the mechanism of the NAD⁺ coenzyme reduction in the presence of formate, catalysed by a non-organometallic ruthenium(ii) polypyridyl amine complex, were investigated. The [Ru^II(terpy)(ampy)Cl]Cl (terpy = 2,2′:6′,2′′-terpyridine, ampy = 2-(aminomethyl)pyridine) complex was employed as the catalyst. The reactions were studied in a water/ethanol mixture as a function of formate, catalyst, and NAD⁺ concentrations at 37 °C. The overall process was found to be 11 to 18 times slower than for the corresponding ethylenediamine (en) complex as the result of π-back bonding effects of the ampy ligand. The mechanistic studies revealed a complete set of reactions that accounted for the overall catalytic cycle based on a formate-induced hydride transfer reaction to form the reduced coenzyme, NADH. The geometries of the ruthenium(ii)-ampy complexes involved in the catalytic cycle and free energy changes for the main steps were predicted by DFT calculations. Similar calculations were also performed for the analogues ruthenium(ii)-en and ruthenium(ii)-bipy complexes (bipy = 2,2′-bipyridine). The DFT calculated energies show that both the solvent-formato exchange and the formato-hydrido conversion reactions have negative (favourable) energies to proceed spontaneously. The reactions involving the en complex have the more negative (favourable) reaction energies, followed by the ampy complex, in agreement with faster reactions for en complexes and slower reactions for bipy complexes than for ampy complexes.

The graphical abstract represents the overall catalytic cycle in which the non-organometallic Ru(ii) formato complex releases CO₂ and transfers hydride to NAD⁺ to form NADH coenzyme.     

Mechanistic study on substitution reaction of a citrato(p-cymene)Ru(ii) complex with sulfur-containing amino acids

The reactions of a dichloro(p-cymene)ruthenium(ii) dimer, [RuCl₂(p-cymene)]₂, with citric acid and sulfur-containing amino acids gave only [Ru(L)(p-cymene)]-type complexes (L = citrate (Cit), l-penicillaminate (l-Pen), S-methyl-l-cysteinate (S-Me-l-Cys) and l-methioninate (l-Met)) in aqueous solutions at various pHs and molar ratios of the reactants, where Cit and the amino acids act as a tridentate ligand. These sulfur-containing amino acid complexes with bound nitrogen, oxygen and sulfur atoms and η⁶-p-cymene take S absolute configuration around Ru(ii) selectively, having the α-proton oriented in the opposite direction from the Ru(ii) center. The concentration dependences of the observed pseudo-first-order rate constants were provided for the substitution reactions of the citrato complex, [Ru(Cit)(p-cymene)], with a large excess of the sulfur-containing amino acids at various temperatures at pH 7.3, where solvolysis path was observed for S-Me-l-Cys and l-Met as an intercept but not for l-Pen. The activation parameters for the substitution reactions by the direct attack of the amino acids were changed significantly, indicating that the reaction mechanism varies sensitively with the amino acids from an associative mechanism to an interchange one. The pH dependences of the rate constants of the substitution reactions suggest that the carboxylate group is an attacking group for S-Me-l-Cys and l-Met under neutral conditions and the thiol group of l-Pen acts as an entering group constantly at any pH showing a considerably smaller activation energy compared with S-Me-l-Cys and l-Met. Differences in stabilities of the amino acid complexes were obtained from the equilibrium constants for the substitution reactions between the amino acids. These results indicate that the activation energies for the substitution reactions of the citrato complex with the amino acids are moderately correlated with the stabilities of the formed amino acid complexes.

Thorough kinetic study revealed characteristics of the reaction mechanism for arene ruthenium(ii) complexes with bio-related ligands.     

Extraction of Pd(ii) and Pt(ii) from aqueous hydrochloric acid with 1,3-diaminocalix[4]arene: switching of the extraction selectivity by using different extraction modes

The extraction ability of 1,3-diaminocalix[4]arene (2: H₂L) toward platinum group metals (PGMs) has been investigated, which revealed that 2 is able to extract Pd(ii) and Pt(ii) from hydrochloric acid via different extraction modes. The extraction species for Pd(ii) and Pt(ii) are [PdL] and [Pt₂Cl₆(H₃L)₂], respectively, as evidenced by equilibrium analysis and X-ray crystallography. In [PdL], the two phenoxide oxygens and two amino nitrogens of L²⁻ coordinate to the Pd ion. On the other hand, in [Pt₂Cl₆(H₃L)₂], two anionic trichloro complexes PtCl₃⁻ are sandwiched between two H₃L⁺, in which one amino nitrogen directly coordinates to a PtCl₃⁻ species and another protonated amino group forms an ion pair with another PtCl₃⁻. Utilizing the different extraction modes, switching of the extraction selectivity has been achieved in the competitive extraction between Pd(ii) and Pt(ii) by varying the concentrations of H⁺ and Cl⁻ in the aqueous phase. Finally, from the extracted organic phase, back-extraction of Pd(ii) and Pt(ii) was easily performed, respectively.

1,3-Diaminocalix[4]arene shows extraction ability toward Pd(ii) and Pt(ii), the selectivity of which can be switched by changing the concentrations of H⁺ and Cl⁻ in the aqueous phase.     

A highly sensitive,selective and renewable carbon paste electrode based on a unique acyclic diamide ionophore for the potentiometric determination of lead ions in polluted water samples

Due to the toxicity of lead(ii) to all living organisms as it destroys the central nervous system leading to circulatory system and brain disorders, the development of effective and selective lead(ii) ionophores for its detection is very important. In this work, 1,3-bis[2-(N-morpholino)acetamidophenoxy]propane (BMAPP), belonging to acyclic diamides, was applied as a highly selective lead(ii) ionophore in a carbon paste ion selective electrode for the accurate and precise determination of Pb(ii) ions even in the presence of other interfering ions. Factors affecting the electrode''s response behavior were studied and optimized. Scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and FT-IR spectroscopy were used for studying the morphology and response mechanism of the prepared sensor. The lipophilicity of the used ionophore, which contributes to the mechanical stability of the sensor, was studied using the contact angle measurement technique. The selectivity coefficients obtained by the separate solution method (SSM) and fixed interference method (FIM) confirmed the selectivity of the proposed sensor for Pb(ii) ions. The proposed sensor exhibited a Nernstian slope of 29.96 ± 0.34 mV per decade over a wide linear range of 5 × 10⁻⁸ to 1 × 10⁻¹ mol L⁻¹ and detection limit of 3 × 10⁻⁸ mol L⁻¹ for 2 months with a fast response time (<10 s) and working pH range (2.5–5.5). To further ensure the practical applicability of the sensor, it was successfully applied for the lead(ii) ion determination in different water samples and the obtained data showed an agreement with those obtained by atomic absorption spectroscopy. In addition, it was successfully applied for the potentiometric titration of Pb(ii) against K₂CrO₄ and Na₂SO₄.

Due to the toxicity of lead(ii) to all living organisms destroying the central nervous system and leading to circulatory system and brain disorders, the development of effective and selective lead(ii) ionophores for its detection is very important.     

Simultaneous removal of Sb(iii) and Cd(ii) in water by adsorption onto a MnFe2O4–biochar nanocomposite

In this study, a jacobsite–biochar nanocomposite (MnFe₂O₄–BC) was fabricated and used to simultaneously remove Sb(iii) and Cd(ii) from water via adsorption. The MnFe₂O₄–BC nanocomposite was prepared via a co-precipitation method and analyzed using various techniques. The results confirm the successful decoration of the biochar surface with MnFe₂O₄ nanoparticles. The maximum Sb(iii) removal efficiency was found to be higher from bi-solute solutions containing Cd(ii) than from single-solute systems, suggesting that the presence of Cd(ii) enhances the removal of Sb(iii). The Langmuir isotherm model describes well Sb(iii) and Cd(ii) removal via adsorption onto the MnFe₂O₄–BC nanocomposite. The maximum adsorption capacities are 237.53 and 181.49 mg g⁻¹ for Sb(iii) and Cd(ii), respectively, in a bi-solute system. Thus, the prepared MnFe₂O₄–BC nanocomposite is demonstrated to be a potential adsorbent for simultaneously removing Sb(iii) and Cd(ii) ions from aqueous solutions.

In this study, a jacobsite–biochar nanocomposite (MnFe₂O₄–BC) was fabricated and used to simultaneously remove Sb(iii) and Cd(ii) from water via adsorption.     

Theoretical study of ternary silver fluorides AgMF4 (M = Cu,Ni, Co) formation at pressures up to 20 GPa

Only several compounds bearing the Ag(ii) cation and other paramagnetic transition metal cations are known experimentally. Herein, we predict in silico stability and crystal structures of hypothetical ternary silver(ii) fluorides with copper, nickel and cobalt in 1 : 1 stoichiometry at a pressure range from 0 GPa up to 20 GPa employing the evolutionary algorithm in combination with DFT calculations. The calculations show that AgCoF₄ could be synthesized already at ambient conditions but this compound would host diamagnetic Ag(i) and high-spin Co(iii). Although none of the compounds bearing Ag(ii) could be preferred over binary substrates at ambient conditions, at increased pressure ternary fluorides of Ag(ii) featuring Cu(ii) and Ni(ii) could be synthesized, in the pressure windows of 7–14 and 8–15 GPa, respectively. All title compounds would be semiconducting and demonstrate magnetic ordering. Compounds featuring Ni(ii) and particularly Co(ii) should exhibit fundamental band gaps much reduced with respect to pristine AgF₂. The presence of Cu(ii) and Ni(ii) does not lead to electronic doping to AgF₂ layers, while Co(ii) tends to reduce Ag(ii) entirely to Ag(i).

Only several compounds bearing the Ag(ii) cation and other paramagnetic transition metal cations are known experimentally. Here, we predict as yet unknown AgMF₄ phases and their stability in function of pressure.     

Cytotoxic effect,generation of reactive oxygen/nitrogen species and electrochemical properties of Cu(ii) complexes in comparison to half-sandwich complexes of Ru(ii) with aminochromone derivatives

This paper describes the synthesis of new 6-aminoflavone (6AFl (3)) and 6-aminochromone (6AC (4)) complexes with Cu(ii) and Ru(ii) ions ([Cu(6AC)₂Cl₂] (3a), [Cu(6AFl)₂Cl₂] (4a), [Ru(p-cymene)(6AC)Cl₂] (4b)) and comparison of their properties with the previously described 7-aminoflavone (7AFl (1)) and 7-amino-2-methylchromone (7A2MC (2)) analogues. The cytotoxic effect of all these complexes against two human leukaemia cell lines (HL-60 and NALM-6), melanoma WM-115 cells and COLO205 cells, is determined. The cytotoxicity of copper(ii) complexes, especially [Cu(6AFl)₂Cl₂] (3a) was higher than ruthenium(ii) complexes with the same ligands. Their cytotoxic potency was also stronger in comparison to the referential agents like cisplatin. The pro-oxidative properties were determined for the most active complexes and their ability to generate ROS (reactive oxygen species)/RNS (reactive nitrogen species) in cancer cells was confirmed. The type of ligand and the chemical structure of the tested complexes had an influence on the level of ROS/RNS generated in cancer cells. The redox properties of the copper complex compounds were evaluated by cyclic voltammetry, and compared with the data for Ru(ii) complexes. The reduction and oxidation processes of Ru(iii)/Ru(ii) and Cu(ii)/Cu(i) were described as quasi-reversible.

New Cu(ii)/Ru(ii) complexes with 6-aminoflavone/chromone derivatives as ligands were synthesized and characterized. Their cytotoxicity, pro-oxidative and redox properties were investigated.     

Co(ii), Ni(ii), Cu(ii) and Cd(ii)-thiocarbonohydrazone complexes: spectroscopic,DFT, thermal,and electrical conductivity studies

New and stable coordinated compounds have been isolated in a good yield. The chelates have been prepared by mixing Co(ii), Ni(ii), Cu(ii), and Cd(ii) metal ions with (1E)-1-((6-methyl-4-oxo-4H-chromen-3-yl)methylene)thiocarbonohydrazide (MCMT) in 2 : 1 stoichiometry (MCMT : M²⁺). Various techniques, including elemental microanalyses, molar conductance, thermal studies, FT-IR, ¹H-NMR, UV-Vis, and XRD spectral analyses, magnetic moment measurements, and electrical conductivity, were applied for the structural and spectroscopic elucidation of the coordinating compounds. Further, computational studies using the DFT-B3LYP method were reported for MCMT and its metal complexes. MCMT behaves as a neutral NS bidentate moiety that forms octahedral complexes with general formula [M(MCMT)₂Cl(OH₂)]Cl·XH₂O (M = Cu²⁺; (X = ½), Ni²⁺, Co²⁺; (X = 1)); [Cd(MCMT)₂Cl₂]·½H₂O. There is good confirmation between experimental infrared spectral data and theoretical DFT-B3LYP computational outcomes where MCMT acts as a five-membered chelate bonded to the metal ion through azomethine nitrogen and thiocarbonyl sulphur donors. The thermal analysis is studied to confirm the elucidated structure of the complexes. Also, the kinetic and thermodynamic parameters of the thermal decomposition steps were evaluated. The measured optical band gap values of the prepared compounds exhibited semiconducting nature. AC conductivity and dielectric properties of the ligand and its complexes were examined, which showed that Cu(ii) complex has the highest dielectric constant referring to its high polarization and storage ability.

New and stable coordinated compounds have been isolated in a good yield.     

Unraveling mechanisms of the uncoordinated nucleophiles: theoretical elucidations of the cleavage of bis(p-nitrophenyl) phosphate mediated by zinc-complexes with apical nucleophiles

A theoretical approach was used to investigate the hydrolytic cleavage mechanisms of the bis(p-nitrophenyl) phosphate (BNPP⁻) catalyzed by Zn(ii)-complexes featuring uncoordinated nucleophiles. Ligand-based and alternative solvent-based nucleophilic attack reaction models are proposed. The pK_a values of the Zn(ii)-bound water molecules or ligands in the [Zn(LⁿH)(η-H₂O)(H₂O)]²⁺ (n = 1, 2 and 3) complexes, as well as the dimerization tendency of the mononuclear Zn(ii)-complexes, were found to significantly influence the reaction mechanisms. The Zn(ii)-L³ complexes were found to be more favorable for the hydrolytic cleavage of the BNPP⁻via a ligand-based nucleophilic attack pathway. This was due to the lower pK_a value for the deprotonation of the oxime ligand, the hard dimerization of the mononuclear Zn(ii)-L³ species, and the presence of an uncoordinated nucleophile. The origins of the uncoordinated reactions were systematically elucidated. The theoretical results reported here are in good agreement with experimental observations and more importantly, help to elucidate the factors that influence intermolecular nucleophilic attack reactions with coordinated/uncoordinated nucleophiles.

A theoretical approach was used to investigate the hydrolytic cleavage mechanisms of the bis(p-nitrophenyl) phosphate (BNPP⁻) catalyzed by Zn(ii)-complexes featuring uncoordinated nucleophiles.     

A multifunctional composite Fe3O4/MOF/l-cysteine for removal,magnetic solid phase extraction and fluorescence sensing of Cd(ii)

Fe₃O₄/MOF (metal organic framework)/l-cysteine was synthesized and applied for the removal of Cd(ii) from wastewater. The adsorption kinetics and isotherms were investigated, and the results indicated that the adsorption obeyed the pseudo-second-order kinetic model and Langmuir isotherm. The maximum adsorption capacity was calculated to be 248.24 mg g⁻¹. Fe₃O₄/MOF/l-cysteine was further applied to determine trace amounts of Cd(ii) in real water samples using ICP-AES (inductively coupled plasma-atomic emission spectroscopy) based on magnetic solid-phase extraction (MSPE). The determination limit was 10.6 ng mL⁻¹. Additionally, Fe₃O₄/MOF/l-cysteine can also be used as a fluorescent sensor for “turn-off” detection of Cd(ii), and the detection limit was 0.94 ng mL⁻¹.

Fe₃O₄/MOF (metal organic framework)/l-cysteine was synthesized and applied for the removal of Cd(ii) from wastewater.     

Experimental and theoretical evaluation on the antioxidant activity of a copper(ii) complex based on lidocaine and ibuprofen amide-phenanthroline agents

A new copper(ii) complex, [Cu(LC)(Ibu-phen)(H₂O)₂](ClO₄)₂ (LC: lidocaine, Ibu-phen: ibuprofen amide-phenanthroline), was synthesized and characterized. The antioxidant activities of the free ligands and the copper(ii) complex were evaluated by in vitro experiments and theoretical calculations using density functional theory (DFT). Structures of the ligand Ibu-phen and the complex were identified by ¹H and ¹³C NMR, FT-IR spectroscopies, mass spectrometry, thermogravimetric analysis and elemental analysis. The antioxidant potentials of LC and Ibu-phen ligands as well as copper(ii) complex were also evaluated by DPPH˙, ABTS˙⁺, HO˙ essays and EPR spectroscopy. The experimental results show that the radical scavenging activity (RSA) at various concentrations is decreased in the following order: copper(ii) complex > ascorbic acid > LC > Ibu-phen. Structural and electronic properties of the studied compounds were also analyzed by DFT approach at the M05-2X/6-311++g(2df,2p)//M05-2X/LanL2DZ level of theory. ESP maps and NPA charge distributions show that the highly negative charge regions found on the N and O heteroatoms make these sites more favorable to bind with the central copper ion. Frontier orbital distributions of copper(ii) complex indicate that HOMOs are mainly localized at Ibu-phen, while its LUMOs are distributed at LC. Based on natural bond orbitals (NBO) analyses, Cu(ii) ion plays as electron acceptor in binding with the two ligands and two water molecules. Thermochemical properties including bond dissociation enthalpy (BDE), ionization energy (IE), electron affinity (EA), proton affinity (PA) characterizing three common antioxidant mechanisms i.e. hydrogen transfer (HT), single electron transfer (SET) and proton loss (PL) were finally calculated in the gas phase and water solvent for two ligands and the copper(ii) complex at the same level of theory. As a result, the higher EA and lower BDE and PA values obtained for copper(ii) complex show that the complex shows higher antioxidant potential than the free ligands.

The copper(ii) complex of lidocaine and ibuprofen amide-phenanthroline was synthesized and characterized in order to study antioxidant activity by experimental and theoretical evaluations.     

Facile transmetallation of [SbIII(DOTA)]− renders it unsuitable for medical applications

The antimony(iii) complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate (DOTA) has been prepared and its exceptionally low stability observed. The Sb(iii) ion in Na[Sb(DOTA)]·4H₂O shows an approximately square antiprismatic coordination geometry that is close to superimposable to the Bi(iii) geometry in [Bi(DOTA)]⁻ in two phases containing this anion, Na[Bi(DOTA)]·4H₂O, [H₃O][Bi(DOTA)]·H₂O for which structures are also described. Interestingly, DOTA itself in [(H₆DOTA)]Cl₂·4H₂O·DMSO shows the same orientation of the N₄O₄ metal binding cavity reflecting the limited flexibility of DOTA in an octadentate coordination mode. In 8-coordinate complexes it can however accommodate M(iii) ions with r_ion spanning a relatively wide range from 87 pm (Sc(iii)) to 117 pm (Bi(iii)). The larger Bi³⁺ ion appears to be the best metal–ligand size match since [Bi(DOTA)]⁻ is associated with greater complex stability. In the solution state, [Sb(DOTA)]⁻ is extremely susceptible to transmetallation by trivalent ions (Sc(iii), Y(iii), Bi(iii)) and, significantly, even by biologically important divalent metal ions (Mg(ii), Ca(ii), Zn(ii)). In all cases just one equivalent is enough to displace most of the Sb(iii). [Sb(DOTA)]⁻ is resistant to hydrolysis; however, since biologically more abundant metal ions easily substitute the antimony, DOTA complexes will not be suitable for deployment for the delivery of the, so far unexploited, theranostic isotope pair ¹¹⁹Sb and ¹¹⁷Sb.

The antimony(iii) complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetate (DOTA) has been prepared and its exceptionally low stability observed.     

Synthesis and physicochemical,DFT, thermal and DNA-binding analysis of a new pentadentate N3S2 Schiff base ligand and its [CuN3S2]2+ complexes

A new N₃S₂ pentadentate Schiff base ligand derived from 5-bromothiophene-2-carbaldehyde, (E)-N1-((5-bromothiophen-2-yl)methylene)-N2-(2-((E)-((5-bromothiophen-2-yl)-methylene amino) ethyl ethane-1,2-diamine, is prepared. The ligand and its complexes are subjected to extensive physical and theoretical analyses and the results are consistent with their predicted compositions. Dicationic Cu(ii) complexes ([CuN₃S₂]X₂) with a coordination number of 5 are proposed on the basis of the spectral data with N₃S₂ serving as a pentadentate ligand. The prepared complexes display a square pyramidal geometry around the Cu(ii) center. TG shows different thermal behavior for the N₃S₂ ligand and its complexes. Solvatochromism of the complexes is promoted by the polarity of the solvent used. A one-electron transfer Cu(ii)/Cu(i) reversible redox reaction is promoted by CV. SEM and EDS of the free ligand and its complexes support the morphology and composition changes observed upon the complexation of Cu(ii). As an outstanding goal to develop anticancer new metal chemotherapy, preliminary studies of the binding of the desired complexes with DNA were carried out, as it is through judging the strength of interactions that a future drug can be designed and synthesized. The viscosity and absorption results obtained for complex 1 indicated its enhanced CT-DNA binding properties as compared to those of complex 2 with K_b values of 3.2 × 10⁵ and 2.5 × 10⁵ M⁻¹, respectively.

A new N₃S₂ pentadentate Schiff base ligand derived from 5-bromothiophene-2-carbaldehyde, (E)-N1-((5-bromothiophen-2-yl)methylene)-N2-(2-((E)-((5-bromothiophen-2-yl)-methylene amino) ethyl ethane-1,2-diamine, is prepared.     

The (CF3C(O)NH)(C6H5CH2NH)2P(O) phosphoric triamide as a novel carrier with excellent efficiency for Cu(ii) in a liquid membrane transport system

Transport of Ag(i), Cd(ii), Co(ii), Cu(ii), Ni(ii), Pb(ii) and Zn(ii) cations across a bulk liquid membrane (BLM) containing N,N′-dibenzyl-N′′-(2,2,2-trifluoroacetyl)-phosphoric triamide (PTC) as a new carrier is studied by atomic absorption spectrometry. The results show selective and efficient transport of the copper(ii) cation from aqueous solution in the presence of the other cations. Various factors are optimized in order to obtain maximum transport efficiency. The PTC ligand is characterized by single crystal X-ray diffraction analysis, IR, NMR (¹⁹F, ³¹P, ¹H, ¹³C) and mass spectroscopy. The complex formation reaction between copper(ii) and PTC is studied by a conductometric method, which shows the 1 : 1 stoichiometry for ligand and copper(ii).

Selective transport of Cu(ii) cation in the presence of six other cations across a bulk liquid membrane containing a novel phosphoric triamide carrier is studied.