Ahmed A. El-Asmy

Spectroscopic characterization and biological activity of dihydrazone transition metal complexes: crystal structure of 2,3-butanedione bis(isonicotinylhydrazone).

Metal complexes of the chloride, nitrate and acetate salts of Co(II), Ni(II) Cu(II), Zn(II), Cd(II) or Hg(II) with 2,3-butanedione bis(isonicotinylhydrazone) [BBINH] have been synthesized and structurally characterized. The crystal of BBINH was solved to crystallize as monoclinic system with space group of P121/c14. The formulae of the complexes were assigned based on the elemental analysis and mass spectra. The formation of BBINH complexes depend on the metal anion used. All complexes are nonelectrolytes except for the complexes 2, 3, 4 are (1:1) and 13 and 14 which are 1:2 electrolytes. BBINH behaves as a neutral tetradentate (N2O2) in the chloride complexes of Ni(II), Cu(II), Zn(II), Cd(II) and Hg(II). In [Co2(BBINH)(H2O)Cl3]Cl⋅H2O, BBINH has the same dentate but with the two Co(II) ions. In the acetate complexes, [Ni2(BBINH-2H)(H2O)2(OAc)2]⋅3H2O and [Cu2(BBINH-2H)(OAc)2]⋅5H2O, BBINH acts as a binegative tetradentate with the two metal ions. The ligand in the nitrate complexes acts as a neutral bidentate via the two hydrazone azomethine C=NHy; the nitrate ions are ionic in the Cd(II) and Zn(II) complexes and covalent in the Ni(II) complex. The data are supported by NMR ((1)H and (13)C) spectra. The magnetic moments and electronic spectra of all complexes provide tetrahedral, square planar and/or octahedral structure. The decomposition of the complexes revealed the outer and inner solvents as well as the remaining residue based on TGA. The complexes have variable activities against some bacteria and fungi. The ligand is inactive against all tested organisms. The activity of Cd(II) and Hg(II) may be related to the geometry of the complexes.

Cloud point extraction of some precious metals using Triton X-114 and a thioamide derivative with a salting-out effect

Abstract A cloud point extraction procedure is proposed for preconcentration of trace amounts of palladium (II), silver (I) and gold (III) in aqueous medium. The metal ions in the initial aqueous solution were extracted using the non-ionic surfactant, Triton X-114 after complex formation with 4-(p-chlorophenyl)-1-(pyridin-2-yl)thiosemicarbazide at pH 6.0 in the presence of 0.3 mol L−1 sodium sulfate as a salting-out agent at 25 °C. Dilution of the surfactant-rich phase with acidified methanol was performed after phase separation, and the metal ions were determined by electrothermal atomic absorption spectrometry. The main factors affecting extraction procedure, such as pH, concentration of the ligand, and amount of Triton X-114 were studied in detail. Under the optimum experimental conditions, the calibration graphs were linear upto 125, 50 and 100 μg L−1 and the enrichment factors were 52, 46 and 56 for palladium, silver and gold, respectively. The limits of detection, based on three times of standard deviation of blank signal by 10 replicate measurements divided by the slope of calibration curves were 0.12, 0.08 and 0.30 μg L−1 for palladium, silver and gold, respectively. The accuracy of the results was verified by analyzing spiked water samples. The proposed method has been applied for the determination of the metal ions in soil and rock samples with satisfactory results.

Spectroscopic and structural study of some 2,5-hexanedione bis(salicyloylhydrazone) complexes: crystal structures of its Ni(II) and Cu(II) complexes and N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxy-benzamide.

The reaction between 2,5-hexanedione and salicylic acid hydrazide produced two compounds: 2,5-hexanedione bis(salicyloylhydrazone) [HDSH] (ethanol insoluble) and N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxybenzamide [DPH] (ethanol soluble). HDSH formed complexes with Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II) and Pd(II) which are characterized by elemental analyses, spectra (IR, (1)H NMR, ESR and MS), thermal and magnetic measurements. The crystals of [Ni(HDSH-2H)(EtOH)(H2O)] and [Cu(HDSH-2H)] were solved having octahedral and square-planar geometries, respectively. The other complexes have the formulae [Co(HDSH-2H)(H2O)2], [Cu(HDSH-H)2], [Zn(HDSH-2H)(H2O)2], [Cd2(HDSH-4H)(H2O)4], [Cd2(HDSH-2H)(H2O)4Cl2]; [Hg(HDSH-2H)] and [Pd2(HDSH-4H)(H2O)4]. The obtained complexes are stable in air and non-hygroscopic. The magnetic moments and electronic spectra of the complexes provide different geometries. The ESR spectra support the mononuclear geometry for [Cu(HDSH-2H)] and [Cu(HDSH-H)2]. The thermal decomposition of the complexes revealed the coordinated waters as well as the end product which is in most cases the metal oxide. The crystal structure of N-(2,5-dimethyl-1H-pyrrol-1-yl)-2-hydroxybenzamide is solved by X-ray technique.

Coordination of Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) with 2,5-hexanedione bis(thiosemicarbazone), HBTS: Crystal structure of cis-[Pd(HBTS)]Cl2 and 1-(2,5-dimethyl-1H-pyrrol-yl)-thiourea

Metal complexes of Fe3+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Hg2+, Pd2+ or Pt2+ with 2,5-hexanedione bis(thiosemicarbazone), HBTS; have been prepared and spectroscopically investigated. The empirical formulae of the complexes were suggested based on the elemental analysis. Single crystal of Pd(II) has been solved to be cis-form of square-planar geometry by the X-ray crystallography. 1H and 13C NMR spectra have been recorded for HBTS, Zn(II), Cd(II), Hg(II), Pd(II) and Pt(II) complexes, in DMSO-d6, showing the mode of chelation. The ligand acts as a neutral or a binegative tetradentate (N2S2) or neutral bidentate on the basis of FT-IR. The magnetic moments and electronic spectra provide information about the geometry of the complexes which supported by calculating the ligand field parameters for the Co(II) and Fe(III) complexes. The Ni(II) complex has subnormal magnetic moment (0.71 BM) indicative of a mixed stereochemistry of square-planar and tetrahedral structure. [Cu(HBTS-2H)] measured 0.93 BM indicating high interaction between the copper centers. The ligand may be ordered at the top of the spectrochemical series which giving high ligand field splitting energy (10 Dq=17,900 cm(-1) for Co2+ complex). The mass spectra of some complexes proved their stable chemical formulae while the TGA depicts the degradation steps and the final residue. In evaporating the mother liquor during the preparation of HBTS, new compound is obtained naming 1-(2,5-dimethyl-1H-pyrrol-yl)thiourea and its crystal was solved.

Synthesis, spectral, thermal and biological studies on N(-)(2,4-dinitro-phenyl)-2-mercaptoacetohydrazide and its metal complexes.

Complexes of VO(2+), Cr(3+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+) and Hg(2+) ions with N(-)(2,4-dinitrophenyl)-2-mercaptoacetohydrazide (H2L) have been prepared and characterized on the basis of elemental analysis, molar conductance, thermal (TGA, DTGA), spectral (IR, NMR, UV-Visible, MS) and magnetic measurements. The IR spectra show that H2L behaves in a mononegative and/or binegative bidentate manner. The sulfate bridged the two complex molecules in [Cu(HL)(H2O)2(½SO4)]⋅3H2O. The acetate functions as a monodentate in [Ni(HL)(OAc)(H2O)3] and [Cr(HL)(OAc)2(H2O)(EtOH)]. Different stereochemistries are proposed: octahedral for Cr(III), Ni(II), Hg(II) and [Cu(HL)(H2O)2(SO4)0.5]⋅3H2O, square-based pyramid for [VO(HL)2]⋅EtOH, square-planar for [Co(L)(EtOH)(H2O)]⋅H2O, [Cu(L)(H2O)2] and tetrahedral for [Zn(L)(EtOH)(H2O)], [Cd(L)(EtOH)(H2O)] and [Cu2(HL)(H2O)6]Cl3⋅H2O according to the data of electronic spectra and magnetic measurements. The TGA data support the formula and indicate the outer and inner solvents as well as the final residue. The thermodynamic parameters are calculated using the Coats-Redfern and Horowitz-Metzger methods. H2L and [Zn(L)(EtOH)(H2O)] showed the highest cytotoxic activity while H2L has a higher antioxidant activity than ascorbic acid. The ionization constant of the ligand and the stability constant of the Cu(II)H2L in absence and presence of hexamine buffer were calculated.

Structure and spectroscopic studies of homo-and heterometallic complexes of adipic acid dihydrazide.

A single crystal of adipic acid dihydrazide, ADH, has been analyzed. Its reaction with Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+), Ag(+), Pd(2+) and/or Pt(2+) gave homometallic and heterometallic complexes which are characterized by partial elemental analysis, spectra (MS, ESR, (1)H NMR, electronic; IR), thermal analysis and magnetic measurements. Some complexes: Zn(0.73)Cu(ADH)Cl4·H2O; Zn(0.71)Hg(0.36)(ADH)Cl4·H2O; Zn(0.65)Cd(0.46)(ADH)Cl4·½H2O; Zn(0.75)Co(0.41)(ADH-2H)Cl2·3H2O; Cd0.85Co0.43(ADH)Cl4·½EtOH were isolated having nonstiochiometric metal ratios. The ligand behaves as a neutral (bidentate or tetradentate) and/or binegative tetradentate. A square-pyramid, square-planar and tetrahedral structures were proposed for the homo Co(II), Cu(II) and Ni(II) complexes, respectively. A similar and different stereochemistry around each metal ion (tetrahedral+tetrahedral; tetrahedral+square-planar; tetrahedral+tetrahedral and/or tetrahedral+octahedral) was suggested for the heterometallic complexes. Some complexes were found highly stable with stability point >240 °C; the most stable is [HgNi(ADH-2H)Cl2]. The presence of diamagnetic atom (Zn, Cd or Hg) reduces the magnetic moments and gave anomalous moments. The degradation steps and the hydrated complexes are confirmed through the TGA study. The order of covalency of [Zn(0.73)Cu(ADH)Cl4]·H2O, [CdCu(ADH)Cl4]·H2O and [HgCu(ADH-2H)Cl2] matches with the size of the second metal (Zn complex>Cd complex>Hg complex). Some heterometallic complexes were found nonstoichiometric through the analysis of their metal content and supported by TGA.

Crystal structure, complexation, spectroscopic characterization and antimicrobial evaluation of 3,4-dihydroxybenzylidene isonicotinyl-hydrazone.

A single crystal of 3,4-dihydroxybenzylidene isonicotinylhydrazone, HBINH, has been grown and solved by X-ray crystallography. The VO(2+), Zr(4+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+) and Pd(2+) complexes of HBINH have been prepared and spectroscopically characterized. The data confirmed the formulae [Co(HBINH)(H2O)Cl]Cl·H2O, [Pd(HBINH)Cl2], [Zn(HBINH)2Cl2], [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)], [Ni2(HBINH)(H2O)6Cl2]Cl2, [Cu2(HBINH-3H)(H2O)2(OAc)]·3H2O, [Zr2(HBINH-3H)Cl4]Cl, [Hg2(HBINH)Cl4] and the dimer {[Cu(HBINH)Cl]Cl}2. Most of the complexes have intense colors and high melting points and some are electrolytes in DMSO solution. The ligand behaves as a neutral bidentate in the Co(II), Cu(II), Pd(II), Zn(II) and Cd(II) complexes; dibasic tetradentate in [Ni2(HBINH)(H2O)6Cl2]Cl2 and tribasic tetradentate in [Cu2(HBINH-3H)(OAc)]·5H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Zr2(HBINH-3H)Cl4]Cl by the loss of 3H(+) due to the deprotonation of the two hydroxyl groups and the enolization of the amide (OCNH) group. A tetrahedral geometry was proposed for the Co(II), Cu(II), Zn(II) and Hg(II) complexes; square-planar for the Pd(II) complex; square-pyramid for the VO(2+) complex and octahedral for the Ni(II) and Cd(II) complexes. The complexes [Cd(HBINH)(H2O)2Cl2]·1½H2O, [(VO)2(HBINH-3H)(OH)(H2O)] and [Cu2(HBINH-3H)-(H2O)2(OAc)]·3H2O have activities against Bacillus sp. M3010, Candida albicans, Escherichia coli, Staphylococcus aureus and Slamonella sp. PA393.

Synthesis, characterization, analgesic and anti-inflammation activity of new phthalazines and their Cu(II) and Zn(II) complexes

Abstract1,4-Dioxo-3, 4, 4e, 5, 10, 10a-hexahydro-1H-5,10-benzenobenzo [g] phthalazin-2-yl-thioamide [6a]; 1,4-dioxo-3, 4, 4e, 5, 10, 10a-hexahydro-1H-5, 10-benzenobenzo [g] phthalazin-2-yl-N-pyridylthioamide [6b] and 1,4-dioxo-3, 4, 4e, 5, 10, 10a-hexahydro-1H-5, 10-benzenobenzo[g]phthalazin-2-yl-N-ethylthioamide [6c] and their [Cu(6a-H)(OAc)], [Zn(6a-H)(OAc)], [Cu(6b-H)(H2O)2(OAc)]·3H2O and [Zn(6b-H)(OAc)], [Cu2(6c-H)](OAc)3]·2H2O and [Zn(6c-H)(OAc)] complexes have been synthesized via a reaction between phthalazinedione 6a–c derivatives and the acetate salt of Cu(II) or Zn(II). These compounds were characterized by elemental analysis, spectra (UV–Vis, IR, 1H NMR, 13C NMR, ESR), conductance, thermal analysis and magnetic moments.

Synthesis, characterization, biological activity of binuclear Co(II), Cu(II) and mononuclear Ni(II) complexes of bulky multi-dentate thiosemicarbazide.

The chelation behavior of 9,10-dihydro-9,10-ethanoanthracene-11,12-dicarbonyl) bis (N-ethylhydrazine-1-carbothioamide) (H6ETS)(1) towards Co(2+), Ni(2+)and Cu(2+) have been studied. The spectral data revealed that the ligand acts as a bi- and/or mono-negative multi-dentate. The isolated Ni(II) and Cu(II) complexes are square-planar while the Co(II) is tetrahedral. EPR spectrum of Cu(II) complex confirmed simulated an axial spin-Hamiltonian exhibiting a four-line pattern with nitrogen super-hyperfine couplings originating from imine hydrazinic nitrogen atoms and possess a significant amount of tetrahedral distortion leading to a pseudo-square-planar geometry with unpaired electron has d(x(2)-y(2)) ground state. Also, the thermal behavior and kinetic parameters were determined. Furthermore, the title compounds were investigated for their antibacterial activity using inhibition zone diameter and for DNA degradation, superoxide-scavenging activity as well as hydroxyl radicals that generated by the oxidation of cytochrome c in L-ascorbic acid/CuSO4-cytochrome c system.

Biosorption of Pb2+ from Natural Water using Date Pits: A Green Chemistry Approach

Removal of Pb2+ ions from aqueous solutions by adsorption onto Date Pits (DP) has been investigated. The date pits (sorbent) may represent an environmental problem. The characteristic parameters (solution pH, initial concentration of Pb2+, sorbent dose, shaking time and temperature) influencing the adsorption process have been examined. pH=7 is found the best one having high floatability of 6 g l-1 dose of DP. The Freundlich and Langmuir were applied. The change in Gibbs free energy change (ΔGo), enthalpy (ΔHo) and entropy (ΔSo) were also calculated. Under the optimum experimental conditions employed, the removal of ~95% of Pb2+ was attained. The procedure was successfully applied to remove Pb2+ from natural water samples. The SEM image of DP before and after lead adsorption shows complete adsorption.