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Binary and ternary complex formation equilibria of copper(II) with imidazole-4-acetic acid (IMA) and some aromatic amino acids such as tryptophan and phenylalanine have been studied from 15 to 45 °C by potentiometric titration. The pH-titrations of the reaction mixtures have shown 1:1:1 (Cu:IMA:amino acid) ternary complex formation. The stability of mixed-ligand complexes was quantitatively compared with the stability of the binary complexes as Δlog K, Δlog β and log X parameters. The speciation of different species in solution has been evaluated as a function of pH. The effect of temperature on protonation of the ligands and formation of mixed ligand complexes was investigated. Thermodynamic parameters were calculated and are discussed. The effect of solvent of the protonation of IMA and Cu-IMA complex formation was also investigated and discussed. Additionally, the stoichiometric protonation constants (log β) of imidazole-4-acetic acid and its binary Cu(II)-IMA complexes were determined potentiometrically over a wide range of solvent composition. [ABSTRACT FROM AUTHOR]

The interaction of DET (diethyltin(IV)) and DVT (divinyltin(IV)) with 1-(2-aminoethyl)piperazine (AEP) was investigated potentiometrically at different temperatures in 0.1 mol·dm NaNO. The hydrolysis constants of diethyltin(IV) and divinyltin(IV) cations and the stepwise formation constants of the complexes formed in solution were calculated at different temperatures and in solutions of dioxane-water solutions of different compositions. The stoichiometries and stability constants for the complexes formed are reported. The results show formation of 1:1 complexes and the corresponding hydroxide complexes. The concentration distributions of the various complex species were evaluated as a function of pH. The thermodynamic parameters Δ H° and Δ S° calculated from the temperature dependence of the equilibrium constants were investigated for DET and DVT complexes with AEP. [ABSTRACT FROM AUTHOR]

Alzheimer's disease (AD) is one of the most common causes of dementia. Several drugs are used to improve the symptoms, but do not stop AD progression. There are more promising treatments that may have a significant role in AD diagnosis and treatment such as miRNAs and stem cells. The present study aims to develop a new approach for AD treatment by mesenchymal stem cells (MSCs) and/or acitretin with special reference to inflammatory signaling pathway as NF-kB and its regulator miRNAs in AD-like rat model. Fourty-five male albino rats were allotted for the present study. The experimental periods were divided into induction, withdrawal, and therapeutic phases. Expression levels of miR-146a, miR-155, necrotic, growth and inflammatory genes were assessed using RT-qPCR. Histopathological examination of brain tissues was performed in different rat groups. The normal physiological, molecular, and histopathological levels were restored after treatment with MSCs and/or acitretin. The present study demonstrates that the miR-146a and miR-155 might be used as promising biomarkers for AD. MSCs and/or acitretin proved their therapeutic potential in restoring the expression levels of targeted miRNAs and their related genes concerning NF-kB signaling pathway. [ABSTRACT FROM AUTHOR]

The formation of mixed ligand complexes of Cu(II) with 2,2′-bipyridyl (Bipy) in the presence of some selected aromatic diamines (L) (L = 3,4-diamino benzoic acid (DABA), 2-hydazinopyridine (hzpy) or 4-chloro- o-phenylenediamine has been studied by pH-metric titrations. Potentiometric measurements show that ternary complexes are formed in a simultaneous manner. The pH-titrations of the reaction mixtures are shown to yield 1:1:1 ternary complex formation. The equilibrium and formation constants of the resulting ternary complexes have been calculated at I = 0.1 mol·dm of NaNO. The order of stability in terms of the secondary ligands has been found to be DABA > hzpy > CAPA. The stability of ternary complexes was quantitatively compared with their corresponding binary complexes in terms of the parameters Δlog K, Δlog β and log X. The concentration distributions of various species formed in solution were also evaluated as a function of pH. In addition, the effect of temperature on both the ionization process of the ligands and complex formations for Cu-Bipy-L ternary systems was studied. The thermodynamic parameters were calculated from the temperature dependence of the equilibrium constants and are discussed. The structure of the Cu(II) complexes have been geometrically optimized using the parameterized PM3 semiempirical method. [ABSTRACT FROM AUTHOR]

Proton-ligand association constants of imidazole-4-acetic acid (IMA) were determined potentiometrically in aqueous solution at different temperatures in the range 15-35 °C. The stepwise stability constants of IMA with some selected bivalent transition metal ions were also determined in 0.1 mol·dm NaNO. The stability of the complexes follows the trend Cu > Ni > Co > Mn, which is in agreement with the Irving-Williams order of the metal ions. The thermodynamic parameters for Cu(II)-IMA complex formation were derived and discussed. The ternary complexes Cu(IMA)L (IMA = imidazole-4-acetic acid, HL = amino acid, amides or DNA constituents) have been investigated. Ternary complexes of amino acids or amides are formed by a simultaneous mechanism. Amino acids form the complex Cu(IMA)L, whereas amides form two complex species Cu(IMA)L and Cu(IMA)(LH). The DNA constituents form both 1:1 and 1:2 complexes. The stabilities of ternary complexes are quantitatively compared with their corresponding binary complexes. The concentration distribution of the complexes in solution was evaluated as a function of pH. [ABSTRACT FROM AUTHOR]

The protonation constants of some α-amino acids (glycine (Gly), l-alanine (Ala), l-valine (Val), l-serine (Ser), l-leucine (Leu) and l-isoleucine (Ile)) were studied in water and DMSO-water solution mixtures containing 30, 50 and 70 vol-% DMSO; in addition the complex formation equilibria of their copper(II) complexes were studied by potentiometric technique using a combined pH electrode system calibrated in concentration units of the hydrogen ion at 25 ± 0.1 °C under a nitrogen atmosphere, and at an ionic strength of 0.10 mol·dm NaNO. The protonation constants and the overall stability constants of copper(II) complexes were influenced by changes in solvent composition, and their variations are discussed in terms of solvent and structural properties. [ABSTRACT FROM AUTHOR]

Binary and mixed-ligand complexes of zinc(II) involving 2-(aminomethyl)-benzimidazole (AMBI) and amino acids, peptides (HL) or DNA constituents have been investigated. Ternary complexes of amino acids or peptides are formed simultaneously. Amino acids form the complex Zn(AMBI)L, whereas amides form two complex species Zn(AMBI)L and Zn(AMBI)(LH). The ternary complexes of zinc(II) with AMBI and DNA are formed in a stepwise process, whereby binding of zinc(II) to AMBI is followed by ligation of the DNA constituents. The stability of ternary complexes is quantitatively compared with their corresponding binary complexes in terms of the parameters Δlog K, log β and log X. The effect of the side chains of amino acid ligands (Δ) on complex formation is discussed. The values of Δlog K indicated that the ternary complexes containing aromatic amino acids are significantly more stable than the complexes containing alkyl- and hydroxyalkyl-substituted amino acids. This may be taken as evidence for a stacking interaction between the aromatic moiety of AMBI and the aromatic side chains of the bio-active ligands. The concentration distributions of various species formed in solution were also evaluated as a function of the pH. [ABSTRACT FROM AUTHOR]

A comprehensive review of organotin(IV) hydrolysis and complex formation equilibria with amino acids, peptides and DNA constituents is presented with special reference to solution and coordination chemistry studies. The review focuses on results obtained in the author's laboratory and related work of other groups. Also, published studies on these complexes were reviewed with emphasis on their biological aspects. [ABSTRACT FROM AUTHOR]

Seven-coordinate Fe(EDTA)-L complexes, where L represents a DNA constituent (uracil, uridine, thymine, thymidine and inosine), methylamine, ammonium chloride or imidazole, were investigated to resolve the solution chemistry of this system. The results show formation of 1:1 complexes with DNA constituents and the other ligands, supporting the hepta-coordination mode of Fe(III) ion. Stability constants of the complexes were measured by potentiometric titration at 25 °C and ionic strength 0.1 mol⋅L NaNO. The hydrolysis constant of [Fe(EDTA)(HO)] and the formation constants of the complexes formed in solution were calculated using the non-linear least-squares program MINIQUAD-75. The concentration distributions of the various complex species were evaluated as a function of pH. The thermodynamic parameters Δ H and Δ S, calculated from the temperature dependence of the equilibrium constants, were determined for the Fe(EDTA)-uracil complex. The effect of dioxane as a solvent on the protonation constant of uracil, hydrolysis constants of [Fe(EDTA)(HO)], and the formation constants of the Fe(EDTA)-uracil complex are discussed. [ABSTRACT FROM AUTHOR]

The interaction of trimethyltin(IV) (TMT) with imino-bis(methylphosphonic acid) (IDP), abbreviated as HL, was investigated at 25 °C and at ionic strength 0.1 mol⋅dm (NaNO) using a potentiometric technique. The formation constants of the complexes formed in solution were calculated using the nonlinear least-squares program MINIQUAD-75. The stoichiometry and stability constants are reported for the complexes formed. The results show the formation of 110, 111, 112 and 11-1 complexes for the TMT-IDP system. The concentration distribution of the various complex species was evaluated. The effect of dioxane as a solvent, on both the protonation constants and the formation constants of trimethyltin(IV) complexes with IDP, is discussed. The thermodynamic parameters Δ H and Δ S calculated from the temperature dependence of the equilibrium constants were evaluated. The effect of ionic strength on the protonation constants of IDP is also discussed. [ABSTRACT FROM AUTHOR]

The kinetics of base hydrolysis of the alanine ethyl ester, in addition to glycine, histidine and methionine methyl esters in the presence of the Zn-NTP complex, were studied in aqueous solution by the pH-potentiometric technique, where NTP denotes the nitrilo-tris(methyl phosphonic acid) ligand. The kinetic data fits assumed that hydrolysis proceeds through formation of a M-OH complex, followed by an intramolecular OH attack. The effect of an organic solvent on the hydrolysis of coordinated esters was investigated by measuring the rate of hydrolysis in dioxane-water solutions of different compositions at t=25.0 °C and I=0.1 mol⋅dm. The kinetics of base hydrolysis of the glycine methyl ester was studied at different temperatures. Activation parameters for the base hydrolysis of the complexes were evaluated. [ABSTRACT FROM AUTHOR]

Formation equilibria of cobalt(II) complexes of 2-(aminomethyl)-benzimidazole (AMBI) and the ternary complexes Co(AMBI)L (L = aliphatic or aromatic dicarboxylic acids) were investigated in aqueous solutions at 25 °C and 0.1 mol⋅dm ionic strength. Stoichiometry and stability constants are reported for the complexes formed. The speciation of the complexes was resolved. Values of $\log_{10}\ (K_{\mathrm{Co(AMBI)L}}^{\mathrm{Co(AMBI)}})$ and Δlog K are calculated and discussed. The effect of chelate ring size of the dicarboxylic acid complexes on their stability constants was examined. The effect of temperature on the dissociation constant of AMBI, CBDCA, and the formation constant of Co(AMBI) and Co(AMBI)-CBDCA complexes was studied and the thermodynamic parameters were calculated. Formation of the metal complexes has been found to be spontaneous, exothermic and entropically favorable. The solid complexes of [Co(AMBI)L] (L = oxalic acid, 1,1-cyclobutanedicarboxylic acid (CBDCAH) and malonic acid) have been synthesized and characterized by elemental analysis, infrared, spectra, magnetic and conductance measurements. Electronic spectra and μ values suggest a tetrahedral geometry for Co(II)-complexes. The isolated metal chelates have been screened for their antibacterial activities and the complexes show a significant antibacterial activity against Pseudomonas fluorescence (Gram −ve) and Bacillus subtilis (Gram +ve). The activity increases at higher concentration of the compounds. [ABSTRACT FROM AUTHOR]

Binary and ternary complexes of zinc(II) involving nitrilo-tris(methyl phosphonic acid (H6A) and amino acids, peptides (HL), or DNA constituents have been investigated. The stoichiometry and stability constants for the complexes formed are reported. The results show that ternary complexes are formed in a stepwise manner whereby nitrilo-tris(methylphosphonic acid) binds to zinc(II), which is then followed by coordination of an amino acid, peptide or DNA. Zinc(II) was found to form ZnA and ZnAH n complex species where n=3, 2 or 1. The stabilities of the ternary complexes are compared with the stabilities of their corresponding binary complexes. The concentration distributions of the various complex species have been evaluated. The kinetics of the base hydrolysis of glycine methyl ester in the presence of Zn(II)-NTP complexes was studied in aqueous solution using a pH-stat technique. The p Ka for ionization of the coordinated water molecule is 9.14 as determined from the kinetic results, while direct potentiometric titration of the complex [Zn(NTP)(H2O)] gave 9.98 (±0.02). The rate constant for the intramolecular attack of coordinated hydroxide on the ester is k=(2.65×10−4±0.003) dm3⋅mol−1⋅s−1. [ABSTRACT FROM AUTHOR]

Metallic antitumor drugs with heterocyclic ligands, such as novel AMI (amino methyl imidazole) complexes [Pd(AMI)Cl2](1), [Cu(AMI)L1](2), and [Cu(AMI)L2·2H2O](3) where L1 = oxalate and L2 = malonate, were synthesized and characterized. Assessments included elemental analyses, mass spectrometry, Fourier transform-infrared spectroscopy, ultraviolet–visible spectroscopy, and thermal analysis. The cytotoxicity of AMI complexes compared to cisplatin was assessed using MTT (3-[4,5-dimethylthiazol-2-yl] 2,5diphenyl tetrazolium bromide) assay with breast (MCF-7) and cervical (HeLa) cancer cell lines. After treating these cells with the AMI complexes' IC50 values for 48 h, malondialdehyde levels and catalase activity were used to assess oxidative stress, antioxidant activity was evaluated with DPPH radical scavenging method, comet assays assessed DNA damage, and DNA fragmentation was evaluated using the gel electrophoresis. In vitro, antimicrobial activity was assessed using a disc diffusion method. The anticancer activity results showed that IC50 (half-maximal inhibitory concentration) values of complex one, two, and three against MCF-7 and HeLa cancer cells are 0.156 ± 0.0006, 0.125 ± 0.001, 0.277 ± 0.002 μM respectively for MCF-7 cells and 0.222 ± 0.0005, 0.126 ± 0.0009, 0.152 ± 0.001 μM respectively for HeLa cells. Complex two demonstrated strong anticancer activity against MCF-7 and Hela cells. The study of oxidative stress parameters revealed that Malondialdehyde levels increased in cancer cell lines treated with complexes compared to untreated cells. Catalase activity decreased in cells treated with palladium chelate. The DPPH radical scavenging assay results identified that complex one was a more potent antioxidant in MCF-7 and Hela cells than other complexes with SC50 values of 227.5 ± 0.28 and 361 ± 1.2 μL/mL, respectively. The comet assay results showed that complex two caused significant DNA damage in MCF-7 and HeLa cancer cells treated. Antimicrobial assays identified complex three as the most effective. Copper complexes give better antifungal activity against A. flavus than the palladium complex. We conclude that complex two is the most active in both cell types and might be assessed as a clinically useful drug for breast cancer treatment. The significance of the current study is the synthesis of antitumor drugs containing heterocyclic ligands, such as novel AMI complexes, and the study of their biological activities. [ABSTRACT FROM AUTHOR]

The interaction of diethyltin(IV), DET, with selected bioligands having a variety of model functional groups was investigated at 25 °C and ionic strength 0.1 mol·dm −3 NaCl using the potentiometric technique. The hydrolysis constants of the DET cation and the formation constants of the complexes formed in solution were calculated using the MINIQUAD-75 program. The stoichiometry and stability constants for the complexes formed are reported. The results show the formation of 1:1 and 1:2 complexes with amino acids and DNA constituents. The dicarboxylic acids form 1:1 complexes. The peptides form both 110 complexes and the corresponding deprotonated amide species [Et 2Sn(LH −1)] (11-1). The participation of different ligand functional groups in binding to organotin is discussed. The concentration distributions of the various complex species were evaluated as a function of pH. The standard thermodynamic parameters Δ H° and Δ S°, calculated from the temperature dependence of the equilibrium constants, were investigated for the interaction of DET with thymine as a representative example of DNA constituents. The effect of ionic strength and solvent on hydrolysis constants of DET, protonation equilibria of thymine and its complex formation with DET were investigated and discussed. [ABSTRACT FROM AUTHOR]

Hexyl carbazole derivatives are one of the most prominent dye scaffolds in the dye-sensitized solar cells (DSSCs). New substituted carbazole dyes such as DRA-HC, DCA-HC, and DTC-HC were synthesized for DSSCs. These dyes are containing hexyl moiety as electron donor and rhodanine-3-acetic acid, cyanoacetic acid and tetracyanoethylene as an electron acceptor linked to carbazole moiety. The relation between dye structures, photophysical/electrochemical, molecular structure and DSSC manufacturing had been discussed. All structures showed more positive ground-state oxidation potential than I−/I−3 and more negative excited state oxidation potential than the conduction band edge of the semiconductor. The highest efficiency of the DSSCs was obtained in the case of DCA-HC dye (η = 1.41%, VOC = 708 mV, FF = 0.81, and JSC = 2.45 mA cm−2 with 100 mW cm−2) compared to other synthesized dyes. [ABSTRACT FROM AUTHOR]

Objective: Our aim is to assess the surgical management of intramedullary spinal cord tumours (IMSCTs) and evaluate factors associated with surgical outcomes in our hospitals. Patient and methods: Between June 2013 and June 2016, a retrospective study was conducted on 16 consecutive cases of IMSCTs. All patients provided their signed consent, and MRI was performed. The patients were surgically treated and were evaluated pre- and post-operatively by the modified McCormick scale (MMS). Appropriate statistical analysis was conducted. Results: The mean patient age was 50.4 years, and the median follow-up was 15 months. The most common histological origin was ependymoma (n = 9, 56.25%). A cervical tumour was detected in eight patients, and a dorsal tumour was detected in seven. Post-operatively, the score was clinically but not statistically improved in seven cervical (87.5%) and four dorsal (57.1%) tumours (p = 0.334). Ten patients underwent total resection. Post-operative MMS scores showed improvement in all cases of total resection (n = 10, 100%). This improvement was clinically and statistically significant on last follow-up (p = 0.008). Fewer than four segments were involved in 9 cases, and more than four segments were involved in 7 cases. Post-operatively, all 9 patients (100%) with fewer than four involved segments improved, while only three patients (42.9%) with more than 4 involved segments improved (p = 0.019). Low-grade tumours such as ependymomas were correlated with good surgical outcomes, while high-grade tumours such as astrocytomas were correlated with poor surgical outcomes (p = 0.022). Conclusions: Total tumour resection coupled with good preoperative clinical condition for tumours localised in the cervical or conus region predicts good neurological outcomes. Tumour localisation in the dorsal region with multi-segmental extension and high-grade tumour pathology predicts poor neurological outcomes. [ABSTRACT FROM AUTHOR]

The stoichiometry and stability constants of the complexes formed between [Pd(MAMP)(HO)] and various biologically relevant ligands containing different functional groups were investigated. The ligands used are amino acids, peptides and DNA constituents. The results show the formation of 1:1 complexes with amino acids and peptides and the corresponding deprotonated amide species. Structural effects of peptides on amide deprotonation were investigated. The purine and pyrimidine bases uracil, uridine, cytosine, inosine, inosine 5′-monophosphate (5′-IMP) and thymine form 1:1 and 1:2 complexes. The concentration distribution of the various complex species was calculated as a function of pH. The effect of chloride ion concentration on the formation constant of CBDCA with Pd(MAMP) was also reported. The results show ring opening of CBDCA and monodentate complexation of the DNA constituent with the formation of [Pd(MAMP)(CBDCA-O)DNA], where (CBDCA-O) represents cyclobutane dicarboxylate coordinated by one carboxylate oxygen. The equilibrium constant of the displacement reaction of coordinated inosine, as a typical DNA constituent, by SMC and/or methionine was calculated. The results are expected to contribute to the chemistry of antitumor agents. The calculated parameters of the optimized complexes support the measured formation constants. [ABSTRACT FROM AUTHOR]

Mononuclear copper(II), cobalt(II) and nickel(II) complexes of cetirizine (CTZ = 2-[2-[4-[(4-chlorophenyl)phenyl methyl]-piperazine-1-yl]-ethoxy]acetic acid) in the presence of 2-aminomethyl-benzimidazole·2HCl (AMBI), as a representative example of heterocyclic bases, were synthesized and studied by different physical techniques. All mixed-ligand complexes have been fully characterized with the help of elemental analyses, molecular weight determinations, molar conductance, magnetic moments and spectroscopic data. The formulae of the isolated complexes are [M(AMBI)(CTZ)(NO)(HO)]· nHO where AMBI is the neutral bidentate 2-aminomethylbenzimidazole, CTZ the deprotonated cetirizine and n = 1 for Co(II) or 0 for Cu(II) and Ni(II) complexes. The measured molar conductance values in DMSO indicate that the complexes are non-electrolytes. The formation equilibria of the ternary complexes have been investigated. Ternary complexes are formed by a simultaneous mechanism. Stoichiometry and stability constants for the complexes formed are reported. The concentration distribution of the complexes in solution was evaluated as a function of pH. The thermodynamic parameters were calculated from the temperature dependence of the equilibrium constants and are discussed. The synthesized metal chelates have been screened for their antimicrobial activities against the selected types of Gram-positive (G) and Gram-negative (G) bacteria. They were found to be more active against Gram positive than Gram negative bacteria. The antimicrobial activity in terms of metal ions obeys this order: Cu(II) > Ni(II) > Co(II). [ABSTRACT FROM AUTHOR]