Association thermodynamic parameters for nano Cu(NO3)2·2.5H2O with ligands at different temperatures.

Association thermodynamic parameters are important because they give information about the nature of ion-ion interaction in solution, the dielectric constant of the medium and the intermolecular hydrogen bonding between the solvent molecules. The different association thermodynamic parameters for nano copper(ii) nitrate hemi pentahydrate in the presence of 4,6-diacetylresorcinol and 4,6-bis(1-hydrazonoethyl)benzene-1,3-diol as ligands were calculated. Conductance measurements were used in different concentrations of binary mixed solvents (DMF and water) at different temperatures, 293.15, 303.15, 313.15 and 323.15 K. A comparison between association thermodynamic parameter data such as association constants (K A), degree of dissociation (α), free energies of association (ΔG A), enthalpies of association (ΔH A) and entropies of association (ΔS A) in the case of using the two ligands was done. Different calculated thermodynamic parameters indicate that the association is more favorable with 4,6-diacetylresorcinol as a ligand than 4,6-bis(1-hydrazonoethyl)benzene-1,3-diol due to the large size of 6-bis(1-hydrazonoethyl)benzene-1,3-diol.

NiII and CoII binary and ternary complexes of 3-formylchromone: spectroscopic characterization, antimicrobial activities, docking and modeling studies.

Reactions of 3-formylchromone (L) with Ni(ii) and Co(ii) ions having different anions (acetate, perchlorate, nitrate, and chloride) yielded a series of binary and ternary octahedral complexes with the general formula [ML n L' m X y (S) a ]Z y ·bS, where M = Ni or Co, n = 1-3, L' = auxiliary ligand = 8-hydroxyquinoline or 1,10-phenanthroline, m = 1 or 2, X = acetate or chloride, y = 0 or 2, S = H2O or MeOH, a = 0-2, Z = nitrate or perchlorate and b = 0-1.5. Elemental and thermal analyses and infra-red, electronic, mass, magnetic susceptibility and molar conductivity measurements were successfully utilized to characterize the structures of the chromone complexes. The chromone ligand acts as a neutral bidentate ligand through its formyl and γ-pyrone oxygen atoms. The obtained complexes were formed with molar ratios 1 : 2 and 1 : 3 M : L for the binary and 1 : 2 : 1 and 1 : 1 : 1 M : L : L' for the ternary complexes. The kinetic parameters of the thermal degradation steps were estimated and explained using the Coats-Redfern equations. The synthesized complexes showed antimicrobial activity with higher activity toward Candida albicans and Bacillus subtilis. Docking studies showed good agreement with the antimicrobial activity. Molecular modeling of the synthesized complexes was performed using Hyperchem at the PM3 level and the calculated structures correlate with the experimental data.

Bioprospecting endophytic fungi for antifeedants and larvicides and their enhancement by gamma irradiation.

The search and discovery of new natural products with antifeedant and larvicidal potentials to mitigate harmful insects are scientific pressing issues in the modern agriculture. In this paper, the antifeedant and larvicidal potentials of 69 fungal isolates were screened against the Egyptian cotton leafworm Spodoptera littoralis. A total of 17 isolates showed the insecticidal potentials with three promising isolates. These strains were Aspergillus sydowii, Lasiodiplodia theobromae, and Aspergillus flavus isolated from Ricinus communis (bark), Terminalia arjuna (Bark), and Psidium guajava (twigs), respectively. The effect of gamma irradiation on the antifeedant and larvicidal activities of the three strains was investigated. Exposure of the fungal spores to 1000 Gy of gamma rays significantly intensified both the antifeedant and larvicidal potentials. To identify compounds responsible for these activities, extracts of the three strains were fractionated by thin layer chromatography. The nature of the separated compounds namely, Penitrem A, 1, 3, 5, 8- tetramethyl- 4, 6-diethyl- 7- [2- (methoxycarbonyl)ethyl] porphyrin (from A. sydowii), Penitrem A, 2, 7, 12, 17-Tetramethyl-3, 5:8, 10:13, 15:18, 20-tetrakis (2,2-dimethylpropano) porphyrin (from A. flavus), N,N-Diethyl-3-nitrobenzamide, and Diisooctyl-phthalate (from L. theobromae) were studied by GC-MS analysis. These findings recommend endophytic fungi as promising sources of novel natural compounds to mitigate harmful insects.

Bioprospecting endophytic fungi for bioactive metabolites and use of irradiation to improve their bioactivities.

The search for new bioactive compounds with innovative modes of action and chemistry are desperately needed to tackle the increased emergence of drug-resistant microbes. With this view, this paper was conducted for the isolation, identification, and biological evaluation of fungal endophytes of eleven different plant species. A total of 69 endophytic strains were isolated and tested for the presence of bioactive metabolites with antifungal, antibacterial, anticancer, and antioxidant properties in their extracts. Upon screening, two promising strains were found to have all the before-mentioned activities. These strains were Aspergillus sydowii isolated from the bark of Ricinus communis and Aspergillus flavus isolated from the twigs of Psidium guajava. Major compounds present in extracts of the two strains were identified by GC-Mass analyses. Several well-known bioactive compounds as well as unreported ones were identified in the fungal extracts of the two strains. Furthermore, gamma irradiation (at 1000 Gy) of the fungal cultures resulted in improved bioactivities of extracts from the two strains. These findings recommend the two fungal strains as sources of antimicrobial, anticancer, and antioxidant compounds which may aid in the development of novel drugs. The presented research also explains the high-value of fungal endophytes as untapped sources of bioactive metabolites.

Synthesis, molecular orbital, optical and device characterization of mononuclear mixed ligand nickel(II) complex of phthalate with N,N,N',N'-tetramethylethylenediamine for photodiode applications.

In this work, a new synthesized mononuclear mixed ligand nickel(II) complex was characterized by various techniques. Crystalline characteristics of [Ni(Phth)(Me4en)(H2O)2]·4H2O were studied by using transmission electron microscope(TEM). Well crystalline structure corresponds to the hexagonal crystal system and identified by selected area electron diffraction (SAED) were achieved. Coordination of the nickel(II) ion with the functional groups of the ligands was established from the IR spectrum. Molar conductance of the current complex in DMF (10(-3)mol/L) indicated a non-electrolytic nature of the complex. Electronic spectra showed a strong band in the region 661-684nm; MeCN (661nm), CHCl3 (663nm), MeOH (667nm), Me2CO (675nm), DMSO (682nm) and DMF (684nm) which can be assigned to (3)A2g(F)→(3)T1g(F) transition of an octahedral structure around nickel(II). Multiple peaks were easily resolved from the spectral dependence of the absorption coefficient (α) measurements and the analysis near the fundamental absorption edge showed two direct allowed transition with energy gaps of 1.18 and 2.53eV. Dark current-voltage and capacitance-voltage characteristics of [Ni(Phth)(Me4en)(H2O)2]·4H2O/n-Si heterojunctions were studied to extract the main important parameters of the heterojunction device. The electrical characteristics of the heterojunction device under illumination hold the suitability of the device for optoelectronic applications.

Reactivity and molecular modeling of new solvatochromic mixed-ligand copper(II) chelates of 2-acetylbutyrolactone and dinitrogen bases.

A new series of solvatochromic mononuclear mixed ligand chelates with the general formula: Cu(AcBL)(L)X; where AcBL=2-acetylbutyrolactonate, L=N,N,N',N'-tetramethylethylenediamine (Me4en), N,N,N',N'-tetramethylpropylene diamine (Me4pn), 1,10-phenanthroline (Phen) or 2,2'-bipyridyl (Bipy) and X=ClO4-, NO3- or Br- have been synthesized and characterized by the analytical and spectral methods, as well as magnetic and molar conductance measurements. The d-d absorption bands of Me4en-chelates as Nujol mulls or weak donor solvents solutions revealed square-planar, distorted octahedral and/or distorted trigonal bipyramid geometries for the perchlorate, nitrate and bromide chelates, respectively. However, an octahedral structure is identified for chelates in strong donor solvents. Perchlorate chelates show a remarkable color change from violet to green as the Lewis basicity of the donor solvent increases, whereas bromide chelates are mainly affected by the Lewis acidity of solvent. Specific and non-specific interactions of solvent molecules with the chelates were investigated on the basis of unified solvation model. Structural parameters of the free ligands and their Cu(II)-chelates have been calculated on the basis of semiempirical PM3 level and correlated with the experimental data.

Mono- and binuclear copper(II) complexes of new hydrazone ligands derived from 4,6-diacetylresorcinol: Synthesis, spectral studies and antimicrobial activity.

Two new hydrazone ligands, H2L(1) and H2L(2), were synthesized by the condensation of 4,6-diacetylresorcinol with 3-hydrazino-5,6-diphenyl-1,2,4-triazine and isatin monohydrazone, respectively. The structures of the ligands were elucidated by elemental analyses, IR, (1)H NMR, electronic and mass spectra. Reactions of the ligands with several copper(II) salts, including AcO(-), NO3(-), SO4(2-), Cl(-) and Br(-) afforded mono- and binuclear metal complexes. Also, the ligands were allowed to react with Cu(II) ion in the presence of a secondary ligand (L') [N,O-donor; 8-hydroxyquinoline, N,N-donor; 1,10-phenanthroline or O,O-donor; benzoylacetone]. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, electronic, mass and ESR spectra as well as conductivity and magnetic susceptibility measurements. The ESR spin Hamiltonian parameters of some complexes were calculated. The spectroscopic data showed that the H2L(1) ligand acts as a neutral or monobasic tridentate ligand while the H2L(2) ligand acts as a bis(monobasic tridentate) ligand. The coordination sites with the copper(II) ion are phenolic oxygen, azomethine nitrogen and triazinic nitrogen (H2L(1) ligand) or isatinic oxygen (H2L(2) ligand). The metal complexes exhibited octahedral and square planar geometrical arrangements depending on the nature of the anion. The ligands and some metal complexes showed antimicrobial activity.

Synthesis, spectroscopic characterization and antimicrobial activity of binuclear metal complexes of a new asymmetrical Schiff base ligand: DNA binding affinity of copper(II) complexes.

The 1:1 condensation of o-acetoacetylphenol and 1,2-diaminopropane under condition of high dilution gives the mono-condensed Schiff base, (E)-3-(1-aminopropan-2-ylimino)-1-(2-hydroxyphenyl)butan-1-one. The mono-condensed Schiff base has been used for further condensation with isatin to obtain the new asymmetrical dicompartmental Schiff base ligand, (E)-3-(2-((E)-4-(2-hydroxyphenyl)-4-oxobutan-2-ylideneamino) propylimino)indolin-2-one (H3L) with a N2O3 donor set. Reactions of the ligand with metal salts give a series of new binuclear complexes. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H and (13)C NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. The analytical and spectroscopic tools showed that the complexes can be formulated as: [(HL)(VO)2(SO4)(H2O)]·4H2O, [(HL)Fe2Cl4(H2O)3]·EtOH, [(HL)Fe2(ox)Cl2(H2O)3]·2H2O, [(L)M2(OAc)(H2O)m]·nH2O; M=Co, Ni or Cu, m=4, 0 and n=2, 3, [(HL)Cu2Cl]Cl·6H2O and [(L)(UO2)2(OAc)(H2O)3]·6H2O. The metal complexes exhibited octahedral geometrical arrangements except copper complexes that exhibited tetrahedral geometries and uranyl complex in which the metal ion is octa-coordinated. The Schiff base and its metal complexes were evaluated for antimicrobial activity against Gram positive bacteria (Staphylococcus aureus), Gram negative bacteria (Escherichia coli) and fungi (Candida albicans and Aspergillus flavus). The ligand and some of its complexes were found to be biologically active. The DNA-binding properties of the copper complexes (6 and 7) have been investigated by electronic absorption, fluorescence and viscosity measurements. The results obtained indicate that these complexes bind to DNA via an intercalation binding mode with an intrinsic binding constant, Kb of 1.34×10(4) and 2.5×10(4) M(-1), respectively.

Binary and ternary copper(II) complexes of a tridentate ONS ligand derived from 2-aminochromone-3 carboxaldehyde and thiosemicarbazide: synthesis, spectral studies and antimicrobial activity.

A tridentate ONS donor ligand, HL, was synthesized by the condensation of 2-aminochromone-3-carboxaldehyde with thiosemicarbazide. The structure of the ligand was elucidated by elemental analyses, IR, (1)H and (13)C NMR, electronic and mass spectra. Reaction of the ligand with several copper(II) salts, including AcO(-), NO3(-), SO4(2-), Cl(-), Br(-) and ClO4(-) afforded different metal complexes that reflect the non-coordinating or weakly coordinating power of the ClO4(-) and Br(-) anions as compared to the strongly coordinating power of AcO(-), SO4(2-), Cl(-) and NO3(-) anions. Also, the ligand was allowed to react with Cu(II) ion in the presence of a secondary ligand (L') [N,O-donor; 8-hydroxyquinoline or N,N-donor; 1,10-phenanthroline]. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, electronic, mass and EPR spectra as well as conductivity and magnetic susceptibility measurements. The EPR spin Hamiltonian parameters of some complexes were calculated. The metal complexes exhibited octahedral and square planar geometrical arrangements depending on the nature of the anion. The ligand and most of its metal complexes showed antibacterial activity towards Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis), Gram-negative bacteria (Salmonella typhimurium and Escherichia coli), yeast (Candida albicans) and fungus (Aspergillus fumigatus).

Synthesis, spectroscopic studies, molecular modeling and antimicrobial activity of binuclear Co(II) and Cu(II) complexes of 4,6-diacetylresorcinol.

Reactions of 4,6-diacetylresorcinol with different cobalt(II) and copper(II) salts viz., OAc(-), Cl(-), NO3(-) and SO4(2-), yielded a new series of binuclear metal complexes. Reactions of the ligand with these metal ions in the presence of a secondary ligand (L') [O,O-donor; acetylacetone, N,O-donor; 8-hydroxyquinoline or N,N-donor; 1,10-phenanthroline and N,N,N',N'-tetramethylethylenediamine] in 1:2:2 (L:M:L') molar ratio yielded mixed-ligand complexes with different molar ratios. The metal complexes were characterized by elemental and thermal analyses, IR, electronic, ESR and mass spectra as well as conductivity and magnetic susceptibility measurements. The analytical and spectroscopic data suggested that the H2L ligand behaves as a neutral, monobasic or dibasic tetradentate ligand, depending on the type of the anion and secondary ligand used, through the two phenolic and two carbonyl groups. Electronic spectra, magnetic and conductivity measurements showed that all complexes are octahedral with non-electrolytic nature. The profile of ESR spectra of copper(II) complexes suggested the octahedral geometry and the spin Hamiltonian parameters of the complexes were calculated and discussed. Molecular orbital calculations were performed for metal complexes using Hyperchem 7.52 program on the bases of PM3 level and the results correlated with the experimental data. The free ligand and some of its metal complexes showed antimicrobial activity towards some of Gram-positive and Gram-negative bacteria, yeast (Candida albicans) and fungus (Aspergillus fumigatus).

Zinc(II) Thiosemicarbazone Complex As a Ligand Towards Some Transition Metal Ions: Synthesis, Spectroscopic and Antimicrobial Studies.

Heterobinuclear complexes have been synthesized by stepwise reactions using the mononuclear complex, [Zn(Tsc)2] • H2O, as a complex ligand towards the metal ions, vanadyl(IV), manganese(II), iron(III), cobalt(II), nickel(II) and copper(II). The complex ligand was synthesized by the reaction of zinc acetate dihydrate with salicylaldehyde followed by the condensation with thiosemicarbazide. The structures of the complex ligand and the prepared complexes were elucidated by elemental analyses, IR, electronic, mass, 1H and 13C NMR spectra as well as molar conductivity and magnetic susceptibility measurements. All the complexes exhibited octahedral geometrical arrangements formulated as [Zn(Tsc)2VO(SO4)(H2O)], [Zn(Tsc)2MCl2(H2O)2] (M = Mn, Fe and Co) and [Zn(Tsc)2Fe(ox)Cl2] except the nickel(II) and copper(II) complexes, [Zn(Tsc)2CuCl(H2O)], [Zn(Tsc)2NiCl2], which have square planar geometries. The complex ligand and some of its heterobinuclear complexes showed antibacterial activity against the sensitive organisms Staphylococcus aureus as Gram-positive bacteria, Escherichia coli as Gram-negative bacteria and antifungal activity against the fungi Candida albicans and Aspergillus flavus.

Synthesis, spectral and magnetic studies of mono- and bi-nuclear metal complexes of a new bis(tridentate NO2) Schiff base ligand derived from 4,6-diacetylresorcinol and ethanolamine.

A new bis(tridentate NO2) Schiff base ligand, H(4)L, was prepared by the reaction of the bifunctional carbonyl compound; 4,6-diacetylresorcinol (DAR) with ethanolamine. The ligand reacted with iron(III), cobalt(II), nickel(II), copper(II), zinc(II), cadmium(II), cerium(III) and uranyl(VI) ions, in absence and in presence of LiOH, to yield mono- and bi-nuclear complexes with different coordinating sites. The ligand and its metal complexes were characterized by elemental analyses, IR, (1)H NMR, electronic, ESR and mass spectra, conductivity and magnetic susceptibility measurements as well as thermal analyses. In absence of LiOH, mononuclear complexes (2, 3 and 5-9) as well as binuclear complexes (1 and 4) were obtained. In mononuclear complexes, the ligand acted as a neutral, mono- and di-basic/bi- and tetra-dentate ligand while in binuclear complexes (1 and 4), the ligand acted as a bis(mono- or di-basic/tridentate) ligand. On the other hand, in presence of LiOH, only binuclear complexes (10-15) were obtained in which the ligand acted as a bis(dibasic tridentate) ligand. The metal complexes exhibited different geometrical arrangements such as octahedral, tetrahedral, square planar, square pyramidal and pentagonal bipyramidal arrangements.

Synthesis and spectroscopic studies of binuclear metal complexes of a tetradentate N2O2 Schiff base ligand derived from 4,6-diacetylresorcinol and benzylamine.

A tetradentate N2O2 donor Schiff base ligand, H2L, was synthesized by the condensation of 4,6-diacetylresorcinol with benzylamine. The structure of the ligand was elucidated by elemental analyses, IR, 1H NMR, electronic and mass spectra. Reaction of the Schiff base ligand with nickel(II), cobalt(II), iron(III), cerium(III), vanadyl(IV) and uranyl(VI) ions in 1:2 molar ratio afforded binuclear metal complexes. Also, reaction of the ligand with several copper(II) salts, including Cl-, NO3-, AcO-, ClO4- and SO42- afforded different metal complexes that reflect the non-coordinating or weakly coordinating power of the ClO(4)(-) anion as compared to the strongly coordinating power of SO42- and Cl- anions. Characterization and structure elucidation of the prepared complexes were achieved by elemental and thermal analyses, IR, 1H NMR, electronic, mass and ESR spectra as well as magnetic susceptibility measurements. The metal complexes exhibited different geometrical arrangements such as square planar, octahedral, square pyramidal and pentagonal bipyramidal arrangements. The variety in the geometrical arrangements depends on the nature of both the anion and the metal ion.