Spectroscopic and voltammetric studies of Pefloxacin bound to calf thymus double-stranded DNA

Spectral and electrochemical studies have been carried out on the interaction of pefloxacin with calf thymus double-stranded dsDNA. The voltammetric behavior of pefloxacin was investigated at glassy carbon, carbon paste and dsDNA-modified carbon paste electrodes using cyclic voltammetry. Pefloxacin was oxidized, yielding one irreversible oxidation peak. The modification of the carbon paste surface with dsDNA allowed an accumulation process to take place for pefloxacin such that higher sensitivity was achieved compared with the bare surface. The response was characterized with respect to ionic strength, accumulation time, pefloxacin concentration, and other variables. The stripping differential pulse voltammetric response showed a linear calibration curve in the range 1.0×10^–7–1.0×10^–5 mol l^–1 with a detection limit of 5.0×10^–8 mol l^–1 at the dsDNA modified electrode. The method was applied to the direct determination of pefloxacin in diluted urine samples.     

Interaction of a new cobalt(II) complex of five-coordinated chiral porphyrin with calf thymus DNA

A new template-directed chiral porphyrin [(TPP)Co(Trp)], where TPP = tetraphenylporphyrin and Trp = 1-tryptophan, was prepared and characterized by various physico-chemical methods. Interaction of [(TPP)Co(Trp)] with calf thymus DNA was studied by u.v.–vis. spectroscopy and cyclic voltammetry. The complex [(TPP)Co(Trp)], after interaction with calf thymus DNA, shows a shift in the absorption spectrum and a large hypochromicity, indicating an intercalating binding mode. This observation was further confirmed by the electrochemical behavior of [(TPP)Co(Trp)] before and after interaction with calf thymus DNA. The complex experiences a negative shift in E _1/2 and a decrease in E _p. The ratio of cathodic to anodic peak currents i _pc/i _pa was 1 for [(TPP)Co(Trp)] while for DNA bound complex i _pc/i _pa 1, suggesting that the calf thymus DNA moiety is bound strongly to the complex [(TPP)Co(Trp)]. Kinetic studies of the DNA-porphyrin complex reveal a psuedo-first order rate law as the plot of k _obs versus calf thymus DNA is linear passing through the origin.     

Spectroscopic studies of the interaction between pirimicarb and calf thymus DNA

The interaction between pirimicarb and calf thymus DNA in physiological buffer (pH 7.4) was investigated with the use of Neutral Red (NR) dye as a spectral probe by UV-vis absorption, fluorescence and circular dichroism (CD) spectroscopy, as well as viscosity measurements and DNA melting techniques. The results revealed that an intercalation binding should be the interaction mode of pirimicarb to DNA. CD spectra indicated that pirimicarb induced conformational changes of DNA. The binding constants of pirimicarb with DNA were obtained by the fluorescence quenching method. The thermodynamic parameters, enthalpy change (ΔHθ) and entropy change (ΔSθ) were calculated to be -52.13±2.04 kJ mol(-1) and -108.8±6.72 J mol(-1) K(-1) according to the van't Hoff equation, which suggested that hydrogen bonds and van der Waals forces might play a major role in the binding of pirimicarb to DNA. Further, the alternative least squares (ALS) method was applied to resolve a complex two-way array of the absorption spectra data, which provided simultaneously the concentration information for the three reaction components, pirimicarb, NR and DNA-NR. This ALS analysis indicated that the intercalation of pirimicarb into the DNA by substituting for NR in the DNA-NR complex.     

Spectroscopic studies on the interaction of pazufloxacin with calf thymus DNA

Fluorescence spectra, absorption spectra, DNA viscosity titrations, competition experiment, and iodide quenching experiment were used to study the interaction of DNA with pazufloxacin. DNA quenches the fluorescence of pazufloxacin significantly. No red shift and isobestic points are observed in UV titration experiment. DNA viscosity and iodide quenching results suggest that pazufloxacin does not intercalate into DNA. SsDNA has a stronger quenching effect on pazufloxacin than dsDNA has. Pazufloxacin interacts with DNA in a different mode from ethidium bromide, which is a typical intercalator of DNA. All these results indicate that pazufloxacin interacts with calf thymus DNA in the mode of groove binding. The quenching constant and thermodynamic constants have also been determined.     

Spectroscopic and theoretical studies on cobalt (II) complex of maleonitriledithiolate and 5-nitro-1,10-phenanthroline

The molecular structure, electronic and infrared spectroscopic properties of the title complex Co(mnt)(5-NO(2)-phen) (mnt(2-) = maleonitriledithiolate, 5-NO(2)-phen = 5-nitro-1,10-phenanthroline) were studied in this paper. With non-empirical density functional theory (DFT) methods, the gaseous molecular geometry of the complex was optimized and corresponding vibrational spectra was obtained. A complete assignment to the IR spectra of such a complicated molecule has been exhibited. And the established scientific method could give a complete and accurate analysis about the vibrational spectra of this complex. An electronic spectra was calculated by ZINDOS/S method. The results showed that the calculated values agreed with the observed ones.     

Spectroscopic and theoretical studies on cobalt(II) complex of maleonitriledithiolate and 5-nitro-1,10-phenanthroline

The molecular structure, electronic and infrared spectroscopic properties for the title complex Co(mnt)(5-NO2-phen) (mnt2-=maleonitriledithiolate, 5-NO2-phen=5-nitro-1,10-phenanthroline) were studied in this paper. With semi-empirical PM3 and non-empirical density functional theory (DFT) methods, the gaseous molecular geometry of the complex was optimized and corresponding vibrational spectra was obtained. The calculated results of structure and frequency from DFT were more reasonable than those from PM3, and the two methods were both agreed with the experimental values. A complete assignment to the IR spectra of such a complicated molecule has been exhibited. An electronic spectra was calculated by ZINDOS/S method. The results showed that the calculated values agreed with the observed ones.     

Spectroscopic studies on the interaction of alpha‐eleostearic acid with calf thymus DNA

Interaction between alpha‐eleostearic acid (α‐ESA) and calf thymus DNA in Tris‐HCl buffer (pH = 7.4) using neutral red (NR) dye as a spectral probe was investigated using UV–Vis absorption and fluorescence spectroscopy. Spectral data matrix of the complexed reaction between α‐ESA and NR with DNA was processed with an alternative least‐squares (ALS) algorithm, the obtained concentration profiles and the corresponding pure spectra for species (NR, DNA–NR, and DNA–NR–ESA) demonstrated three kinds of reactions might occur in the system. The major groove binding between α‐ESA and DNA was further validated using circular dichroism, viscosity, DNA melting, and ionic strength effect measurements. Moreover, the calculated values of thermodynamic parameters, such as enthalpy (ΔH^θ, ?22.04 kJ/mol) and entropy change (ΔS^θ, 91.52 J K^?1 mol^?1), suggested binding between α‐ESA and DNA was mainly driven by hydrophobic interactions and hydrogen bonds without electrostatic force.     

Synthesis, cytotoxicity and spectroscopy studies of a new copper (II) complex: calf thymus DNA and T47D as targets

A water-soluble Cu (II) complex [(dien)Cu(??-1,6-DAH)Cu(dien) (NO₃)₂](NO₃)₂ has been synthesized and its effect on the carrier model DNA structure and cancer cell line proliferation was investigated. In this regard, calf thymus DNA (CT-DNA) and human breast cancer cell line, T47D, were the targets. The effect of the complex on DNA structure was investigated by means of UV/vis, fluorescence and circular dichroism (CD) spectroscopic techniques as well as dynamic light scattering (DLS), zeta potential analysis and docking assay for more analysis. The UV?Cvis absorption spectra of complex with DNA showed a slight red shift and hypochromic effect, which indicated the intercalation and electrostatic effect of complex with CT-DNA. Using ethidium bromide (EB) as a probe in fluorescence studies revealed that complex can quench the EB?CDNA fluorescence emission at different temperatures. Besides, the far UV?CCD studies displayed that the complex induces changes in the secondary structure of CT-DNA and can increase the melting temperature of DNA up to 14?°C. The DLS and zeta potential measurements confirmed the electrostatic interaction of complex with the negatively charged DNA and subsequent DNA condensation. Besides, computational studies reflect that major and minor groove binding are two modes of interaction between complex and DNA. On the other hand, growth inhibition of the complex toward T47D cell line was measured using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay, which showed no cytotoxic properties.     

光谱法和电化学法研究中性红与小牛胸腺DNA的相互作用

利用紫外 可见和圆二色光谱(CD)法和伏安方法,研究了小分子染料中性红(NR)与小牛胸腺DNA(CTDNA)的相互作用。实验表明在NR低浓度下,NR能嵌入至核酸双螺旋的碱基内部在G C处与核酸结合,而在较高浓度情况下,嵌入的NR分子与后来的在核酸双螺旋外部的NR分子相互作用发生聚集,从而堆积在DNA双螺旋的表面,同时使核酸的构象由B型转变为Z型。用光谱滴定的方法获得NR与CTDNA作用内部结合常数,分别为:Ka1=2 4×104mol·L-1·cm-1和Ka2=2 1×10-2mol·L-1·cm-1。     

Spectroscopic and voltammetric study on the binding of aluminium(III) to DNA.

Cyclic voltammetry (CV) and ultraviolet (UV) spectroscopy were used, for the first time, to study the interaction between aluminium(III) and calf thymus DNA under neutral pH conditions. Thus obtained data confirmed the existence of a relatively strong interaction between Al(III) and DNA. The binding site for aluminium(III) on DNA chains is not the bases, but the phosphate groups on the DNA backbones, the same as that for [Co(phen)3](3+/2+) that binds non-specifically and electrostatically to the deoxyribose phosphate backbone of DNA. When coexisting, Al(III) binds more favorably to DNA than [Co(phen)3](3+/2+), which implies the relatively strong binding of Al(III) to the phosphate backbone of DNA under neutral pH conditions. The nature of the binding of Al(III) to DNA is also discussed.     

Spectroscopic, thermal and voltammetric studies of crystalline complex trans-N,N'-bis(salicylidene)-1',2'-cyclohexanediamine with Cu(II)

The dimeric complex, [C20H20CuN2O2]2, has been prepared and characterized by thermal analysis, IR spectroscopy and single-crystal X-ray diffraction techniques. The Cu atom in the binuclear complex exists in a distorted square-pyramidal configuration, defined by three O atoms and two N atoms. The crystal structure is stabilized by intermolecular C-H...O hydrogen bonding interaction. The electrochemical property of the complex was investigated in CH2Cl2 by cyclic voltammetry at 100 mV s(-1) scan rate.     

Spectroscopic studies on polymeric cobalt(II) and nickel(II) complexes with bridging succinonitrile and succinonitrile isotopomer ligands

A series of cobalt(II) and nickel(II) complexes were synthesized using succinonitrile and its [1,4-13C2], [15N2]-, [2,2,3,3-2H4]- and [1,4-13C,-2,2,3,3-2H4]- isotopomers as bridging ligands. Spectroscopic studies, as well as X-ray powder diffraction profiles, were used to identify the nature of the octahedral coordination sphere of the central metal ions and to assign the vibrational spectra in full detail. The succinonitrile ligands were found to be in trans configuration in all the complexes studied and to be coordinated via the lone pairs of their nitrile nitrogens. The rule of mutual exclusion was found to be fulfilled for the succinonitrile ligands under the Ci symmetry of the complexes and the vibrations of the succinonitrile ligands were found to appear in either the infrared or the Raman spectra. All succinonitrile isotopomers exhibited blue-shifts of 43-71 cm(-1) upon coordination, while most of the other vibrations remained unchanged or underwent small shifts of only a few wavenumbers. The mass differences of the succinonitrile isotopomers were found to shift mainly the vibrations of the respective affected part of the molecules in comparison with the normal succinonitrile. The exchange of the halides, which are coordinated to the central metal ion, was also found to influence the vibrations of the associated water molecules and we could identify vibrational bands arising due to the H-bond interaction between the halides and the water molecules. Finally, we showed that all complexes under consideration have, spectroscopically, the same symmetry.     

Thermal,spectral, and thermodynamic studies for evaluation of calf thymus DNA interaction activity of some copper(II) complexes

The square-pyramidal copper(II) complexes with ciprofloxacin in the presence of bipyridine derivatives have been synthesized and characterized using elemental analysis, magnetic moment measurement, thermal analysis (TG), IR, mass and reflectance spectra. The thermal denaturation study has been used for evaluating calf thymus DNA interaction activity. Spectral and hydrodynamic measurements have been used for validating the DNA interaction study. The thermodynamic profile was established for proper understanding of DNA binding Gibbs free energy.     

Synthesis,characterization and interaction of mixed polypyridyl ruthenium(II) complexes with calf thymus DNA

New mixed polypyridyl {HPIP = 2-(2-hydroxyphenyl)imidazo[4,5-f][1,10]phenanthroline, phen = 1,10-phenanthroline, dmp = 2,9-dimethyl-1,10-phenanthroline, dmb = 4,4-dimethyl-2,2-bipyridine} ruthenium(II) complexes [Ru(phen)₂(HPIP)]²⁺, [Ru(dmp)₂(HPIP)]²⁺ and [Ru(dmb)₂(HPIP)]²⁺ were synthesized and characterized by elemental analyses ¹H-n.m.r., u.v.–vis. spectroscopy and cyclic voltammetry. Their DNA-binding properties were demonstrated by absorption, luminescence titrations, steady-state emission quenching and viscosity measurements. The results suggested that all the examined complexes bind with CT-DNA intercalatively. Methyl groups substituted at the 4,4-positions of bpy has no obvious effect on its DNA binding, whereas substituents at the 2- and 9-positions of phen have an impressive effect on its DNA-binding, as revealed by the decreased binding affinity.     

多种光谱方法研究除草剂利谷隆与DNA的相互作用

在生理条件下(pH 7.4),采用紫外-可见光谱法、荧光光谱法、圆二色谱法(CD)和傅里叶红外光谱法(FT-IR)并结合粘度实验和熔点测量技术,研究了利谷隆与小牛胸腺DNA(DNA)的相互作用。实验发现,利谷隆可以置换出嵌入DNA中的亚甲基蓝,并使DNA的熔点和粘度升高,表明二者发生了嵌插作用。利谷隆的存在引起DNA的CD光谱收缩,表明DNA发生了B构象向C构象的转变;红外光谱分析表明嵌入DNA双链的利谷隆芳环主要作用于G、A碱基。     

Spectroscopic studies of zinc(II)tetraphenylporphyrin molecular complex with 1,4-dioxane

The molecular complex of zinc(II)tetraphenylporphyrin with 1,4-dioxane has been obtained. The IR spectra of the [Zn(TPhP)(1,4-dioxane)2] stabile molecular complex between 4000 and 50cm(-1) have been studied. An interpretation is given on the base the "chair" conformation of 1,4-dioxane molecule.     

Synthesis and spectroscopic studies of the cobalt(II) complex with methyl 2-pyridylmethylidenehydrazinecarbodithioate (HNNS)

A new cobalt(II) complex with the Schiff base methyl 2-pyridylmethylidenehydrazinecarbodithioate (HNNS), Co(NNS)₂, has been synthesized and characterized using single-crystal X-ray diffraction and spectroscopy (IR, UV–Vis, MS and EA). Complex [Co(NNS)₂] crystallizes in the orthorhombic, space group Pna2(1). The coordination geometry around Co(II) in the complex is distorted octahedral and the two ligands in the mer-configuration (S and tertiary N atom cis to each other and the iminic N atoms trans). Furthermore, the neutral molecule unit Co^II(NNS)₂ is connected by hydrogen bonds C–H ··· S and forms a three dimensional ordered network structure.     

Spectroscopic,NMR and PMR studies on monoadducts of cobalt(II) and nickel(II) diaryldithiophosphinates with oxygen donor ligands

The high-spin CoS₄O core is stabilized in monoadducts of composition Co(X)₂(L), (X = diphenyldithiophosphinate or its p-tolyl analogue; L = pyridine N-oxide, γ-picoline N-oxide, dimethylformamide and dimethylsulfoxide). A pentacoordinate stereochemistry has been assigned on the basis of spectral and magnetic properties. Assignments of some IR frequencies in the region 4000-400 cm⁻¹ have been made. The corresponding addition complexes of planar Ni(X)₂ were studied spectroscopically in solution and the occurrence of ligand field bands around 13,500 and 21,000 cm⁻¹ in solutions containing amine-oxide is due to the formation of monoadducts Ni(X)₂(L). The contact shifts observed for the protons of the amine-oxides in these complexes have been studied to understand the spin-transfer mechanism. The results indicate that a π-mechanism is operative and comparison of the experimental data with the theoretically calculated spin densities (INDO approach) suggest that the HBO (Highest Bonding Orbital) is involved in the spin transfer mechanism. The shift pattern for the Co(X)₂(L) is influenced by a dipolar contribution and we conclude that the shifts are the net result of π-delocalization and negative dipolar contribution.