Some new complexes derived from VO(II), Ag(I) and Pd(II) metal ions and HNA imine ligand (L), i.e. (2‐((6‐allylidene‐2‐hydroxycyclohexa‐1,3‐dienylmethylene)amino)benzoic acid), have been prepared and their structures elucidated via molar conductance measurements, elemental analyses, infrared, NMR and electronic spectra and magnetic susceptibility estimations. Moreover, stability constants of the synthesized complexes were evaluated utilizing a spectrophotometric technique. On the basis of molar conductance and elemental analyses, the metal imine chelates have structure [M(L)], where M = Pd(II), VO(II) and Ag(I). The results indicate that the prepared HNA imine ligand acts as a tridentate moiety via nitrogen atom of azomethine group and two oxygen atoms of phenolic and carboxylic groups. All the complexes are found to be monomeric with 1:1 stoichiometry with square planar geometry for Pd(II), tetrahedral geometry for Ag(I) and distorted square pyramidal for VO(II). Theoretical density functional theory calculations were applied to verify the molecular geometry of the chelators and their metal chelates. The geometry optimization results are in agreement with experimental observations. The antimicrobial properties of the prepared HNA imine ligand and its metal chelates were evaluated against numerous plant pathogenic fungi and bacteria. The results of these studies indicate that the metal complexes exhibit a stronger antibacterial and antifungal effect compared to the imine ligand. In addition, the interaction of the metal imine chelates with calf thymus DNA was observed by way of viscosity, gel electrophoreses and spectral studies. Absorption titration studies reveal that each of the complexes is an avid binder to calf thymus DNA. Also, there are appreciable changes in the relative viscosity of DNA, which are consistent with enhanced hydrophobic interaction of the aromatic rings and intercalation mode of binding. Additionally, the cytotoxic activity of the investigated compounds against various cancer cell lines shows promising results which makes them prospective compounds for antibiotic and anticancer medicament studies. Furthermore, docking studies of the prepared compounds were conducted for confirming the biological results.
Few studies have examined the long-term outcomes and prognostic factors associated with pediatric living living-donor liver transplantation (LDLT) using reduced and hyper-reduced left lateral segment grafts. We conducted a retrospective, single-center assessment of the outcomes of this procedure, as well as clinical factors that influenced graft and patient survival. Between September 2000 and December 2009, 49 patients (median age: 7 months, weight: 5.45 kg) underwent LDLT using reduced (partial left lateral segment; n = 5, monosegment; n = 26), or hyper-reduced (reduced monosegment grafts; n = 18) left lateral segment grafts. In all cases, the estimated graft-torecipient body weight ratio of the left lateral segment was more than 4%, as assessed by preoperative computed tomography volumetry, and therefore further reduction was required. A hepatic artery thrombosis occurred in two patients (4.1%). Portal venous complications occurred in eight patients (16.3%). The overall patient survival rate at 1, 3 and 10 years after LDLT were 83.7%, 81.4% and 78.9%, respectively. Multivariate analysis revealed that recipient age of less than 2 months and warm ischemic time of more than 40 min affected patient survival. Pediatric LDLT using reduced and hyper-reduced left lateral segment grafts appears to be a feasible option with acceptable graft survival and vascular complication rates.
This study was conducted to prepare novel azomethine chelates of Cu(II), Pd(II), Zn(II) and Cr(III) with tridentate dianionic azomethine OVAP ligand 2-[(2-hydroxyphenylimino)methyl]-6-methoxyphenol. The prepared compounds were characterized using elemental analyses and spectral, conductivity, magnetic and thermal measurements. The spectroscopic data suggest that the parent azomethine ligand binds to the investigated metal ions through both deprotonated phenol oxygen and azomethine nitrogen atoms, and adopts distorted octahedral geometry in the case of Cr(III) and Cu(II) ions while tetrahedral and square planar geometries for Zn(II) and Pd(II) ions, respectively. In order to confirm the molecular geometry of the investigated azomethine chelator and its complexes, theoretical density functional theory calculations were employed. Correlation between experimental observations and theoretical calculations of geometry optimization results are in a good agreement. Absorption titration was used to explore the interaction of the investigated azomethine metal chelates with calf thymus DNA, and the binding constant as well as Gibbs free energy were evaluated. Viscosity measurements and gel electrophoresis studies suggest intercalative and replacement binding modes of the azomethine metal chelates with calf thymus DNA. Additionally, the antimicrobial activity of the complexes was screened against some pathogenic bacteria and fungi. This biological study shows that the complexes exhibit a marked inhibitory effect compared to the corresponding ligand and standard drugs.Furthermore, the effect of the novel compounds as antioxidants was determined by reduction of 1,1-diphenyl-2-picrylhydrazyl and compared with that of vitamin C. Finally, in vitro cell proliferation via MTT assay was investigated against colon carcinoma cells (HCT-116), hepatic cellular carcinoma cells (HepG-2(and breast carcinoma cells (MCF-7) to calculate the cytotoxicity of the prepared compounds. Cell proliferation is inhibited for all compounds and in a dose-dependent manner in the sequence of OVAPPd > OVAPCu > OVAPZn > OVAPCr > OVAP azomethine ligand.
Despite the common use of salens and hydroxyquinolines as therapeutic and bioactive agents, their metal complexes are still under development. Here, we report the synthesis of novel mixed-ligand metal complexes (MSQ) comprising salen (S), derived from (2,2′-{1,2-ethanediylbis[nitrilo(E) methylylidene]}diphenol, and 8-hydroxyquinoline (Q) with Co(II), Ni(II), Cd(II), Al(III), and La(III). The structures and properties of these MSQ metal complexes were investigated using molar conductivity, melting point, FTIR, 1H NMR, 13C NMR, UV–VIS, mass spectra, and thermal analysis. Quantum calculation, analytical, and experimental measurements seem to suggest the proposed structure of the compounds and its uncommon monobasic tridentate binding mode of salen via phenolic oxygen, azomethine group, and the NH group. The general molecular formula of MSQ metal complexes is [M(S)(Q)(H2O)] for M (II) = Co, Ni, and Cd or [M(S)(Q)(Cl)] and [M(S)(Q)(H2O)]Cl for M(III) = La and Al, respectively. Importantly, all prepared metal complexes were evaluated for their antimicrobial and anticancer activities. The metal complexes exhibited high cytotoxic potency against human breast cancer (MDA-MB231) and liver cancer (Hep-G2) cell lines. Among all MSQ metal complexes, CoSQ and LaSQ produced IC50 values (1.49 and 1.95 µM, respectively) that were comparable to that of cisplatin (1.55 µM) against Hep-G2 cells, whereas CdSQ and LaSQ had best potency against MDA-MB231 with IC50 values of 1.95 and 1.43 µM, respectively. Furthermore, the metal complexes exhibited significant antimicrobial activities against a wide spectrum of both Gram-positive and -negative bacterial and fungal strains. The antibacterial and antifungal efficacies for the MSQ metal complexes, the free S and Q ligands, and the standard drugs gentamycin and ketoconazole decreased in the order AlSQ > LaSQ > CdSQ > gentamycin > NiSQ > CoSQ > Q > S for antibacterial activity, and for antifungal activity followed the trend of LaSQ > AlSQ > CdSQ > ketoconazole > NiSQ > CoSQ > Q > S. Molecular docking studies were performed to investigate the binding of the synthesized compounds with breast cancer oxidoreductase (PDB ID: 3HB5). According to the data obtained, the most probable coordination geometry is octahedral for all the metal complexes. The molecular and electronic structures of the metal complexes were optimized theoretically, and their quantum chemical parameters were calculated. PXRD results for the Cd(II) and La(III) metal complexes indicated that they were crystalline in nature.
Although salens and imidazoles are well-studied motifs among bioactive and therapeutic agents, their properties when combined in transition metal complexes are not well developed. To explore the structure/reactivity of this class of compounds, a salen-based ligand, namely (2,2 0-{1,2-ethanediylbis[nitrilo(E) methylylidene]}diphenol, S), and its binary (MS) and ternary (MSI) complexes (I = imidazole; M = Co (II), Ni (II), Cu (II), Cd (II), Al (III), and La (III)) have been synthesized and fully characterized by standard physicochemical and theoretical methods. Evidence from structural analysis tools along with DFT modeling revealed an unusual monobasic tridentate salen binding mode, involving the phenolic oxygen, the nitrogen of the azomethine group, and NH group formed via phenol-to-cyclohexadienone tautomerization, giving rise to a general molecular formula of MSI complexes as [M(S)(I) 2 (Cl)] for M (II) = Co, Ni, Cu and Cd or [M(S)(I)(Cl) 2 ] for M (III) = Al and La, respectively. The antimicrobial activities of S, MS, and MSI were screened against several bacterial and fungal strains. Of all tested complexes, CdS and CuSI were the most effective antimicrobials, giving larger inhibition zones than the reference antibiotics. The antimicrobial efficacy for the MS complexes follows the order: CdS > gentamicin > CuS > NiS > CoS > LaS > AlS > S, whereas MSI complex, potencies are ordered as CuSI > gentamicin > CdSI >NiSI > CoSI > LaSI > AlSI > S. In vitro cytotoxicity screening of MSI complexes disclosed that both CuSI and CdSI exhibited higher activity against human liver (Hep-G2) and breast (MDA-MB231) carcinoma cell lines than the reference (cisplatin) drug. The satisfactory bioactivities observed for several of these compounds supports the underlying design idea for combining important bioactive motifs for possible therapeutic benefit.
An organometallic azomethine ferrocenyl ligand (FCAP) and its transition metal complexes ([M (FCAP)2], where M = VO2+, Mn2+ cations, and [M (FCAP) (CH3COO− or NO3−)], where M = Zn2+ and Pd2+ cations) were prepared. Their structures were confirmed via various spectral and physicochemical studies performed. The crystallinity of the investigated metal chelates was confirmed by X‐ray diffraction data. The spectral data of the FCAP azomethine ligand and its metal chelates were explained concerning the structural changes due to complex formation. From the electronic spectra and the magnetic moments, the information about geometric structures can be concluded. The activation thermodynamic parameters of the thermal degradation for FCAP complexes were calculated utilizing the method of Coats–Redfern. in vitro antimicrobial, anticancer, and antioxidant activities of FCAP azomethine ligand and its complexes were screened. All the investigated metal chelates exhibited superiority on the free FCAP ligand in successful treatment. Moreover, the binding nature of the investigated complexes with calf thymus DNA (ctDNA) was examined by various methods such as spectrophotometry, viscosity, and, gel electrophoresis. Their binding feature to ctDNA was proposed to be electrostatic, intercalation, or replacement mode. Furthermore, molecular docking inspection has been conducted to clarify the nature of the binding and binding affinity of protein synthesized compounds (PDB:3hb5).
The new NO bidentate imine ligand, namely, (2‐[(3‐nitro‐benzylidene)‐amino]‐benzoic acid) (NBA) imine ligand (L), and its Pd (II) and VO (II) complexes have been synthesized and characterized by utilizing different physiochemical methods including elemental analyses, Fourier transform infrared (FT‐IR), nuclear magnetic resonance (NMR), molar conductance, and magnetic susceptibility measurements. The stability constant of these complexes has also been determined. In studies of these complexes, they were found to have [M(L)] composition where the ligand acts as a bidentate and coordinates with the various metal ions through azomethine and one oxygen atom. Moreover, the suggested geometrical structure of Pd (II) and VO (II) complexes is square planar and a distorted square pyramid, respectively. Density functional theory (DFT) calculations for the different metal complexes were studied and show a good agreement with the experiment data. The minimum inhibitory concentration method has been applied to evaluate the in vitro antimicrobial activity. Furthermore, the interaction of calf thymus DNA with the metal‐imine chelates has been assessed, and Pd (II) complex showed the strongest interaction with DNA for a binding constant value of (9.72 × 104 kcal mol−1). The cytotoxic activity of the new metal chelates has been evaluated against three human cancer cell lines (hepatic carcinoma HepG2 cells, breast carcinoma cells MCF‐7, and colon carcinoma cells HCT‐116). It has found that NBAPd complex exhibited a significant decrease in the time and dose of the cell viability than did the reference drug vinblastine. The antioxidant activity of the tested compounds was determined and compared with that of vitamin C as a standard drug. It has been found that the metal complexes exhibit higher activity than the free ligand. The finding from this investigation revealed that the new compounds are considered to be prospective antibiotic and anticancer agents.
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