Nano-sized Cu(II) and Zn(II) complexes and their use as a precursor for synthesis of CuO and ZnO nanoparticles: A study on their sonochemical synthesis,characterization, and DNA-binding/cleavage,anticancer, and antimicrobial activities

Two new divalent copper (C1) and zinc (C2) chelates having the formulae [M(PIMC)₂] (where M = Cu(II), Zn(II) and PIMC = Ligand [(E)-3-(((3-hydroxypyridin-2-yl)imino)methyl)-4H-chromen-4-one] were obtained and characterized by several techniques. Structures and geometries of the synthesized complexes were judged based on the results of alternative analytical and spectral tools supporting the proposed formulae. IR spectral data confirmed the coordination of the ligands to the copper and zinc centers as monobasic tridentate in the enol form. Thermal analysis, UV-Vis spectra and magnetic moment confirmed the geometry around the copper center to be tetrahedral, square pyramidal and octahedral. Study of the binding ability of the synthesized compounds with Circulating tumor DNA (CT-DNA) bas been evaluated applying UV-Vis spectral titration and viscosity measurements. The copper and zinc oxides were achieved from the copper and zinc nano-particles structures Schiff base complexes as the raw material after calcination for 5 hr at 600°C. On the other hand, synthesized of C1 and C2 NPs were used as suitable precursors to the preparation of CuO and ZnO NPs. Finally, the synthesized of the two complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to HPIMC. Among all these synthesized compounds, C1 exhibits good cleaving ability compared to other newly synthesized C2.     

Synthesis,characterization, duplex-DNA interactions,and anticancer activities of novel octahedral [Ni(phen)2(dppz-idzo)]2+ and [Co(phen)2(dppz-idzo)]3+ complexes

Two new octahedral [Ni(phen)₂(dppz-idzo)]²⁺ and [Co(phen)₂(dppz-idzo)]³⁺ complexes have been synthesized and characterized by CHN analysis, electrospray ionization-MS, nuclear magnetic resonance, and UV–Vis spectra. The DNA-binding ability of these complexes was spectrophotometrically, hydrodynamically, and electrophoretically evaluated which indicated that they strongly intercalate into the DNA double helix, and that both induced severe DNA damage in the presence of peroxide. The complexes also showed strong antiproliferative effect against HepG2 and MDA-MB-231 cells. By contrast, they were found to be inactive against the MCF-7 cell line. The ligand itself was found to be inactive against the cells tested.     

Polymer complexes. LXXVI. Synthesis,characterization, CT‐DNA binding,molecular docking and thermal studies of sulfoxine polymer complexes

Novel polymer complexes of 8‐hydroxyquinoline‐5‐sulfonic acid hydrate ( H ₂ L ) with Cu²⁺, Co²⁺ and Ni²⁺ chloride were prepared and characterized. Microanalysis, magnetic susceptibility, IR spectra, electron spin resonance, mass spectra, X‐ray, molar conductance, thermal, and UV–Vis spectra studies have been used to confirm the structure of the prepared polymer complexes. The molecular and electronic structures of the hydrogen bond conformers for ligand ( H ₂ L ) were optimized theoretically and the quantum chemical parameters were calculated. On the basis of elemental and IR data, the chemical structure of metal chelates commensurate that the tri‐dentate (H₂L) coordinate to metal chlorides through oxygen atom of phenolic OH and oxygen atom of SO₃‐H group by replacing H atoms and nitrogen of the quinoline ring. The magnetic studies suggested the octahedral geometrical structure for all produced polymer complexes with general formula {[ML (OH₂)₃] .xH₂O}_n (M = Cu²⁺, x = 1.; Co²⁺, x = 2 and Ni²⁺, x = 2) in molar ratio (1:1). Coats–Redfern and Horowitz–Metzger methods have been used for calculating the activation thermodynamic parameters of the thermal decomposition for H ₂ L and its polymer complexes. The interaction between H ₂ L and its transition metal complexes with the calf thymus DNA (CT‐DNA) was determined by UV–Vis spectra. Binding efficiency between H ₂ L with the receptors of the prostate cancer (PDB code 2Q7L Hormone) and the breast cancer (PDB code 1JNX Gene regulation) was studied by molecular docking. The inhibition behaviour of H ₂ L against the corrosion of carbon steel / HCl (2 M) solution was studied by weight loss, Tafel polarisation, electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) techniques. The adsorption isotherm was found to be Friendlish isotherm. The morphology of inhibited carbon steel? s surface was studied using scanning electron microscope (SEM) and energy dispersive X‐ray spectroscopy (EDS).     

DNA interaction,cytotoxicity and molecular structure of cobalt complex of 4‐amino‐N‐(6‐chloropyridazin‐3‐yl)benzene sulfonamide in the presence of secondary ligand pyridine

Novel cobalt complex of 4‐amino‐N‐(6‐chloropyridazin‐3‐yl)benzene sulfonamide (sulfachloropyridazine) has been synthesized and characterized by elemental analysis, FT‐IR spectroscopy and magnetic susceptibility (VSM). Cobalt complex of Sulfachloropyridazine (Co‐SCP) crystallized in monoclinic space group P2₁/n with Z = 4. The structure is solved by direct method and refined to R = 0.099 for 4720 reflections with I ?4σ(I). The results of FT‐IR spectra suggest the binding of cobalt atom to the sulfonamide ligand which is in agreement with the crystal structure determination. In crystal structure, molecule is linked via, C‐H … π, C‐Cl … π and π … π intermolecular interactions. The computational studies like the optimization energy and root means square deviation compare with single crystal structure, frontier molecular orbital (Homo‐Lumo energy) and binding energy of the Co‐SCP has been carried out using DFT/B3LYP level of theory in gaseous phase. Hirshfeld surfaces and the 2D‐fingerprint analysis are performed to study the nature of interactions and their measurable contributions towards crystal packing. The interaction of the complex with DNA is investigated using viscosity measurement and absorption titration studies. The result shows the complex bind to DNA with intercalative mode with high DNA‐binding constant (K_b). Also, in vivo and in vitro cytotoxic studies are performed using S. pombe cells and brine shrimp lethality bioassay. DNA‐cleavage study shows better cleaving ability of the complex.     

Biological and catalytic evaluation of Ru(II)‐p‐cymene complexes of Schiff base ligands: Impact of ligand appended moiety on photo‐induced DNA and protein cleavage,cytotoxicity and C‐H activation

Two organometallic Ru(II)‐p‐cymene complexes of the type [Ru(η⁶‐p‐cymene)(L)Cl]PF₆ 1 and 2 , where L is N,N‐bis(4‐isopropylbenzylidene)ethane‐1,2‐diamine (bien, L1 ) or N,N‐bis (pyren‐2‐ylmethylene)ethane‐1,2‐diamine (bpen, L2 ) have been prepared and characterized well. Because of appended pyrenyl groups in coordinated bpen ligand, the complex 2 exhibits higher DNA and protein binding than complex 1 in which isopropylbenzyl groups are incorporated. Interestingly, the luminescent characteristic complex 2 is unique in displaying DNA cleavage after light activation by UVA light at 365 nm through oxygen dependent mechanism. AFM analysis attests the photo‐induced DNA fragmentation ability of complex 2 . Also, the complex 2 cleaves the protein after light exposure in a non‐specific manner suggesting that it can act as a protein photo cleaving agent. In contrast to the trend of DNA and protein interaction of complexes, the complex 1 exhibits cytotoxic activity against human breast carcinoma ( MCF‐7 ) and liver carcinoma ( HepG2 ) with potency higher than that of complex 2 due to enhanced hydrophobicity of isopropyl groups present in p‐cymene and bien ligands. Indeed, complex 2 is inactive against MCF‐7 and HepG2 cancer cell lines even up to 200 μM concentration. The AO/EB staining assay reveals that the complex 1 is able to induce late apoptotic mode of cell death in breast cancer cells, which is further confirmed by inter‐nucleosomal DNA cleavage. Furthermore, the complexes 1 and 2 are evaluated for their catalytic activities and found to be working well for the β‐carboline directed C–H arylation to afford the desired products in good yield (40–47%).     

In vitro biomolecular interaction studies and cytotoxic activities of copper(II) and zinc(II) complexes bearing ONS donor thiosemicarbazones

Among all the bio‐metals, zinc and copper derivatives of ONS donor thiosemicarbazone have aroused great interest because of their potential biological applications. Multisubstituted thiosemicarbazone ligand H₂dspt (3,5‐dichlorosalicylaldehyde‐N⁴‐phenylthiosemicarbazone) derived new ternary complexes like [Zn(dspt)(phen)]?DMF ( 1 ) and [Cu(dspt)(phen)]?DMF ( 2 ), and another thiosemicarbazone, H₂dsct (3,5‐dichlorosalicylaldehyde‐N⁴‐cyclohexylthiosemicarbazone), derived [Cu(dsct)(bipy)]?DMF ( 3 ). These complexes have been characterized by elemental analysis (CHNS), Fourier transform infrared (FT‐IR), ultraviolet–visible (UV–Vis) and proton nuclear magnetic resonance (¹H‐NMR) spectra. The structures of the complexes were obtained by single‐crystal X‐ray diffraction analysis. Compounds 1 and 2 got crystallized in the monoclinic P2₁/c space group. The complexes showed interesting supramolecular interaction, which in turn stabilizes the complexes. The ground state electronic configurations of the complexes were studied using the B3LYP/LANL2DZ basis set, and ESP plots of complexes were investigated. The interaction of the complexes with calf thymus DNA (CT‐DNA) was studied using absorption and fluorescence spectroscopic methods. A UV study of the interaction of the complexes with calf thymus DNA (CT‐DNA) has shown that the complexes can effectively bind to CT‐DNA, and [Cu(dspt)(phen)]·DMF ( 2 ) exhibited the highest binding constant to CT‐DNA (K_b = 3.7 × 10⁴). Fluorescence spectral studies also indicated that Complex 2 binds relatively stronger with CT DNA through intercalative mode, exhibiting higher binding constant (K_q = 4.7 × 10⁵). The DNA cleavage result showed that the complexes are capable of cleaving the DNA without the help of any external agent. Molecular docking studies were carried out to understand the binding of complexes with the molecular target DNA. Complex 2 exhibited the highest cytotoxicity against human breast cancer cell line MD‐MBA‐231 (IC₅₀ = 23.93 μg/mL) as compared to Complex 1 (IC₅₀ = 44.40 μg/mL) .     

一种新型双吡啶悬臂Mn(Ⅱ)配合物的合成、晶体结构及DNA结合能力研究

通过3,3′-((乙烷-1,2-二基双(2-甲基吡啶杂氮二基)双(亚甲基))双(2-羟基-5-甲基苯甲醛)与2-羟基-1,3-丙二胺的缩合反应得到一种具有双吡啶悬臂的双核锰配合物。通过X射线单晶衍射确定了该配合物结构,结果显示其分子式为[Mn₂(C₃₇H₄₃N₆O₆)]·(ClO₄)₂。该配合物属于单斜晶系,P2₁/c空间群,晶胞参数为:a=1.096 50(19) nm, b=1.419 5(3) nm, c=3.109 4(5) nm, β=108.153(5)°。进一步分析表明两个二价锰离子分别与(N_amine)₂(N_imine)₂O₃和(N_imine)₂O₄体系配位,它们与配位原子形成的几何构型分别是十面体和扭曲的八面体。两个中心锰离子距离为0.331 6 nm,由酚氧原子和醋酸根共同桥联。另外,本文也利用伏安法和黏度法对该配合物与小牛胸腺DNA的结合能力进行研究,实验结果表明它们之间的结合方式为弱的插入作用。     

Excited-State Dynamics of Thienoguanosine,an Isomorphic Highly Fluorescent Analogue of Guanosine

Thienoguanosine (^thG) is an isomorphic analogue of guanosine with promising potentialities as fluorescent DNA label. As a free probe in protic solvents, ^thG exists in two tautomeric forms, identified as the H1, being the only one observed in nonprotic solvents, and H3 keto–amino tautomers. We herein investigate the photophysics of ^thG in solvents of different polarity, from water to dioxane, by combining time-resolved fluorescence with PCM/TD-DFT and CASSCF calculations. Fluorescence lifetimes of 14.5–20.5 and 7–13 ns were observed for the H1 and H3 tautomers, respectively, in the tested solvents. In methanol and ethanol, an additional fluorescent decay lifetime (≈3 ns) at the blue emission side (λ≈430 nm) as well as a 0.5 ns component with negative amplitude at the red edge of the spectrum, typical of an excited-state reaction, were observed. Our computational analysis explains the solvent effects observed on the tautomeric equilibrium. The main radiative and nonradiative deactivation routes have been mapped by PCM/TD-DFT calculations in solution and CASSCF in the gas phase. The most easily accessible conical intersection, involving an out-of plane motion of the sulfur atom in the five-membered ring of ^thG, is separated by a sizeable energy barrier (≥0.4 eV) from the minimum of the spectroscopic state, which explains the large experimental fluorescence quantum yield.     

Determination of Anti-Parkinson Drug Pramipexole Using a Label-free Biosensor and Evaluation of its Interaction with ds-DNA

In this study, we fabricated an effective and sensitive DNA biosensor based on flower-like Pt/NiCo₂O₄ modified carbon paste electrode (FL-Pt/NiCo₂O₄/CPE) for detection of pramipexole (PPX). Spectrophotometry, differential pulse voltammetry (DPV) and docking methods were employed to evaluate the interaction of DNA-PPX. Moreover, the DPV technique was chosen to monitor the electrochemical response of guanine on the DNA biosensor. The relationship between the concentration of PPX and the oxidation signal of guanine was linear in the range of 0.4 to 310.0 μM and a limit of detection (LOD) of 0.09 μM was calculated.     

Biomolecular Release Stimulated by Electrochemical Signals at a Very Small Potential Applied

DNA release electrochemically stimulated by applying ?10 mV on the modified electrode was studied. The release process was based on the local (interfacial) pH change produced upon H₂O₂ reduction electrocatalyzed by the immobilized microperoxidase‐11. SiO₂ nanoparticles attached to the electrode surface and functionalized with trigonelline and boronic acid species changed their electrical charge from positive to negative upon the interfacial pH change, thus allowing electrostatic adsorption of negatively charged DNA on the positive interface and then its repulsion/release from the negative interface. The loaded/released DNA molecules were labeled with a fluorescent dye to allow easy detection of the released DNA molecules. The important feature of the developed system is the controlled DNA release upon applying very small electrical potential on the modified electrode.