Synthesis and Characterization of New Chelating Resin: Adsorption Study of Copper(II) and Chromium (III) Ions

Acrylamide based monomer, 5-methyl-2-thiozyl methacrylamide (MTMAAm) was synthesized by the reaction of 2-Amino-5-methyl thiazole with methacryloyl chloride in the presence of triethylamine(NR₃) at 0–5°C. The monomer MTMAAm was characterized by FT-IR and ¹H-and ¹³C-NMR spectral studies. A new chelating resin, poly(5-methyl-2-thiozyl methacrylamide-co-2-acrylamido-2-methyl-1-propanesulfonic acid-co-divinylbenzene) [MTMAAm/AMPS/DVB] was synthesized. This resin was characterized by FT-IR. In order to determine the adsorption behavior of chelating resin, the adsorption isotherm of Cr(III) and Cu(II) were studied. It was found that the adsorption isotherm of the ions fitted with Langmuir-type isotherms. From the Langmuir equation, the adsorption capacity of chelating resin for Cr(III) and Cu(II) was found to be 7.77 mg g^{? 1} and 4.27 mg g^{? 1}, respectively. Binding equilibrium constant was calculated to be 0.155 L mg^{? 1} and 0.106 L mg^{? 1} for Cu(II) and Cr(III), respectively.     

Covalent Functionalization of Pristine and Ga-Doped Boron Phosphide Nanotubes with Imidazole

Abstract

Density functional theory (DFT) calculations at the B3LYP/6–31G* level were performed to investigate covalent functionalization of imidazole on pristine (in gas and H₂O phases) and Ga-doped BPNT models in terms of energetic, geometric, and electronic properties. The results show that imidazole, as a functional group, prefers to be adsorbed via its nitrogen atom on the pristine, Ga_B, and Ga_P nanotube models. The adsorption energy of imidazole on the (6,0) zigzag BPNT in gas and solvent phases is ?0.76 and ?1.11 eV, respectively, and about 0.38 and 0.43 electron are transferred from the imidazole to nanotube in the phases. The presence of a polar solvent increases the electron donor of imidazole molecule. The results show that Ga doping can significantly enhance the adsorption energy of imidazole on the nanotube models to about 95%.

Moreover, the imidazole adsorption on the pristine and Ga-doped BPNT models has not significant changes in the energy gap of the nanotube models and it is slightly changed after covalent functionalization process. This study may provide new insight to the development of functionalized boron phosphide nanotubes for generation of the new hybrid compounds especially in drug delivery systems for virtual applications.     

Oxovanadium(IV) and ruthenium(II) carbonyl complexes of ONS‐donor ligands derived from dehydroacetic acid and dithiocarbazate: Synthesis,characterization, antioxidant activity,DNA binding and in vitro cytotoxicity

A series of new complexes of oxovanadium(IV) [VO(L)(B)] and ruthenium(II) [Ru(CO)(PPh₃)₂(L)] ( 1.1- 1.3,  2.1–2.3 ) (H₂L = dehydroacetic acid Schiff base of S‐methyldithiocarbazate, H₂smdha ( 1 ) or S‐benzyldithiocarbazate, H₂sbdha ( 2 ); B = 2,2′‐bipyridine (bpy) or 1,10‐phenanthroline (phen)) have been synthesized. The structure of these complexes was authenticated using elemental analyses and spectroscopic techniques, and their magnetic properties and electrochemical behaviour were studied. The molecular structures of oxovanadium(IV) complexes [VO(smdha)(bpy)]?CH₂Cl₂ ( 1.1 ) and [VO(sbdha)(phen)]?2H₂O ( 2.2 ) were confirmed using single‐crystal X‐ray crystallography. Analytical data showed that the ligands 1 and 2 are chelated to the metal centres in a bi‐negative tridentate fashion through azomethine N, thiol S and deprotonated hydroxyl group. The antioxidant activity of the synthesized compounds was tested against 2,2‐diphenyl‐1‐picrylhydrazyl) radical, which showed that the complexes demonstrate a better scavenging activity than their corresponding ligands. The cupric ion reducing antioxidant capacity method was also employed and the total equivalent antioxidant capacity values were found to be higher for the oxovandium(IV) complexes. DNA binding affinity of the compounds was determined using UV–visible and fluorescence spectra, revealing an intercalation binding mode. Higher cytotoxicity for the complexes compared to their ligands was found against human liver hepatocellular carcinoma (HepG2) and breast adenocarcinoma (MCF7) cell lines using MTT assay.     

Selective Binding of Dopamine and Epinephrine in Water by Molecularly Imprinted Fluorescent Receptors

Catecholamines play important roles in biology but their structural similarity makes it challenging to construct synthetic receptors with selective binding. A combination of covalent and noncovalent binding groups in the hydrophobic core of water‐soluble nanoparticles enabled them to recognize dopamine and epinephrine with an association constant (K_a) of 3–4×10⁴ M^?1 in water, an order of magnitude higher than those of previously reported synthetic hosts. In addition, minute structural changes among analogues were detected including the addition or removal of a single hydroxyl or methyl group.     

Sensitive Nucleic Acid Detection at NH2‐MWCNTs Modified Glassy Carbon Electrode and its Application for Monitoring of Gemcitabine‐DNA Interaction

An electrochemical dsDNA nanobiosensor was fabricated using amino‐functionalized multi walled carbon nanotubes modified glassy carbon electrode (NH₂fMWCNTs/GCE) for the sensitive detection of DNA bases and electrochemical monitoring of drug‐DNA interaction. The influence of functional groups on MWCNT was studied by MWCNT functionalized with NH₂ (NH₂fMWCNTs) and COOH (COOHfMWCNT) groups based on the signal of DNA bases. The modified electrodes were characterized by scanning electron microscopy. One layer of calf thymus double stranded deoxyribonucleic acid (ct‐dsDNA) was immobilized onto the NH₂fMWCNTs/GCE (dsDNA/NH₂fMWCNTs/GCE). The dsDNA/NH₂fMWCNTs/GCE were used to investigate the interaction between the dsDNA and the anticancer drug gemcitabine by differential pulse voltammetry in acetate buffer of pH 4.70. For the confirmation of interaction, the lowering in intensity of the current signals of guanine and adenine was considered as an indicator. Electrochemical impedance spectroscopy studies were performed for the comparison of the modified surfaces. In order to define and visualize the interaction mechanism between gemcitabine and dsDNA/NH₂fMWCNTs/GCE at the molecular level, in silico methods including docking and molecular dynamics simulations were employed.     

The Synthesis of Novel Crown Ethers, Part VII [1]. Coumarin Derivatives of Benzocrowns and Cation Binding from Fluorescence Spectra

4-[3-(1-benzopyran-2-one)] derivativesof benzo[12]crown-4, benzo[15]crown-5 andbenzo-[18]crown-6 were synthesized from4-[3-(1-benzopyran-2-one)]-1,2-dihydroxy-benzenereacting with bis-ethyleneglycol dihalides orpentaethylene glycol ditosylate in alkali carbonate/DMF/water. The original products were identified byhigh resolution EI-mass spectra as well as IR,¹H-NMR and ¹³C-NMR spectroscopy. The 1 : 1binding constants of Mg²⁺, Li⁺, Na⁺ andK⁺ with the coumarin-benzocrowns were estimated usingfluorescence emission spectroscopy in acetonitrile.The complexing enhanced quenching fluorescence spectra(CEQFS) and complexing enhanced fluorescence spectra(CEFS) exhibited the ion binding powers due tocationic recognition rules of the macrocycles.     

Novel Methods of Synthesis of Dibenzo[3n]crown-n and Their Cation Binding Studied by Fluorescence Spectroscopy. Part V

The dibenzo[3n]crown-n were synthesised starting from bis[2-(o-hydroxyphenoxy)ethyl]ether obtained from bis[2-(o-formylphenoxy)ethyl]ether via Baeyer-Villiger oxidation in H₂O₂/CH₃COOH in a good yield. The cyclic condensation ofbis[2-(o-hydroxyphenoxy)ethyl]etherwith tri- and tetraethylene glycol bisdichlorides andthe bisditosylate of pentaethylene glycol in DMF/Me₂CO₃ afforded the large cyclic ethers of dibenzo[21]crown-7, dibenzo[24]crown-8 and dibenzo[27]crown-9. The structures were analysed with IR, ¹H NMR, ¹³C NMR and low-resolution mass spectroscopy methods. The Na⁺, K⁺, Rb⁺ and Cs⁺ cations' recognition of the molecules were conducted withsteady-state fluorescence spectroscopy. The 1:1 association constants, K_a, in acetonitrile were estimated. Dibenzo[21]crown-7 was the best both for K⁺ and Rb⁺ binding but showed too small an effect on Cs⁺. Dibenzo[24]crown-8 exhibited the binding power in the order of Rb⁺ > K⁺ > Na⁺ > Cs⁺. However, dibenzo[27]crown-9 displayed marked binding with only K⁺ but not with Rb⁺ or with Cs⁺ cations probably due to the heavy atom effect of fluorescence quenching.     

光谱法研究Ge-132与DNA的作用机理

利用吸收光谱、DNA碱变性曲线、荧光光谱研究了Ge-132与DNA的相互作用。在Ge-132存在下,DNA的紫外吸收光谱产生明显的减色效应。同时,Ge-132的存在使DNA碱变性的pH值增大,变性后增色效应减小,实验结果表明,Ge-132主要是以嵌入方式与DNA结合的。     

Synthesis,Characterization, Crystal Structure,and Biological Activities of Transition Metal Complexes with 1‐Phenyl‐3‐methyl‐5‐hydroxypyrazole‐4‐methylene‐8′‐quinolineimine

The Schiff base ligand, 1‐phenyl‐3‐methyl‐5‐hydroxypyrazole‐4‐methylene‐8′‐quinolineimine, and its Cu^II, Zn^II, and Ni^II complexes were synthesized and characterized. The crystal structure of the Zn^II complex was determined by single‐crystal X‐ray diffraction, indicating that the metal ions and Schiff base ligand can form mononuclear six‐coordination complexes with 1:1 metal‐to‐ligand stoichiometry at the metal ions as centers. The binding mechanism and affinity of the ligand and its metal complexes to calf thymus DNA (CT DNA) were investigated by UV/Vis spectroscopy, fluorescence titration spectroscopy, EB displacement experiments, and viscosity measurements, indicating that the free ligand and its metal complexes can bind to DNA via an intercalation mode with the binding constants at the order of magnitude of 105–106 M ^–1, and the metal complexes can bind to DNA more strongly than the free ligand alone. In addition, antioxidant activities of the ligand and its metal complexes were investigated through scavenging effects for hydroxyl radical in vitro, indicating that the compounds show stronger antioxidant activities than some standard antioxidants, such as mannitol. The ligand and its metal complexes were subjected to cytotoxic tests, and experimental results indicated that the metal complexes show significant cytotoxic activity against lung cancer A 549 cells.