Simultaneous Spectrophotometric Determination of Uranium and Thorium Using Arsenazo III by H‐Point Standard Addition Method and Partial Least Squares Regression

Simultaneous determination of uranium and thorium using arsenazo III as a chromogenic reagent at pH 1.70 by H‐point standard addition method (HPSAM) and partial least squares (PLS) calibration is described. Under optimum conditions, the simultaneous determinations of uranium and thorium by HPSAM were performed. The absorbencies at one pair of wavelengths, 649 and 669 nm, were monitored with the addition of standard solutions of uranium. The results of applying the HPSAM showed that uranium and thorium can be determined simultaneously with weight concentration ratios of uranium to thorium varying from 20:1 to 1:15 in the mixed sample. By multivariate calibration methods such as PLS, it is possible to obtain a model adjusted to the concentration values of the mixtures used in the calibration range. In this study, the calibration model is based on absorption spectra in the 600–750 nm range for 25 different mixtures of uranium and thorium. Calibration matrices contained 0.10–21.00 and 0.25–18.5 μg mL^?1 of uranium and thorium, respectively. The RMSEP for uranium and thorium were 0.7400 and 0.7276, respectively. Both proposed methods (HPSAM and PLS) were also successfully applied to the determination of uranium and thorium in several synthetic and real matrix samples.     

Silicon nitride nanoparticles for surface-assisted laser desorption/ionization of small molecules

Conventional matrix-assisted laser desorption/ionization mass spectrometry is limited to analyses of higher molecular weight compounds due to high background noise generated by the matrix in the lower mass region. Surface-assisted laser desorption/ionization (SALDI) mass spectrometry is an alternative solution to this problem. Nanoparticles, structured silicon surfaces and carbon allotropes are commonly used as SALDI surfaces. Here, for the first time, we demonstrate the application of silicon nitride nanoparticles as a suitable medium for laser desorption/ionization of small drug molecules.     

Synthesis,Thermal Behavior,and Antimicrobial Activity of a Novel Macrocycle and its Transition Metal Complexes Derived from Thiosemicarbazide

The present study reports the synthesis of Co(II), Ni(II), Mn(II), Cu(II), and Zn(II) complexes with a new macrocyclic ligand (L₂)- 1,2,8,9,11,14-hexaazacyclopentadeca-12,13-dioxo-10,15-dithione-2,7-diene. The macrocycle was derived from thiosemicabazone (L₁) and diethyloxalate that were prepared by the reaction of thiosemicarbazide and glutaraldehyde in the ratio of 2:1. The synthesized complexes and ligands were characterized by elemental analysis and molar conductance, magnetic susceptibility, ¹HNMR, IR, electronic, and thermogravimetric analyses. The molar conductance values confirmed that the Ni(II), Cu(II), Zn(II), Mn(II) and Co(II) complexes were 1:2 electrolytes. On the basis of electronic spectral studies and molar conductance measurements, the authors proposed an octahedral structure for Ni(II), Mn(II), and Co(II) complexes, tetrahedral geometry for Zn(II) complex, and square planar geometry for Cu(II) complex. The thermal behavior of the compounds was studied by TGA in a nitrogen atmosphere up to 750°C at the rate of 20°C/min. The TGA results revealed that the complexes had higher thermal stability than the macrocycle. All the synthesized compounds were screened against 4 bacteria (i.e., Streptococcus aureus, Escherichia coli, Bacillus subtillis, Salmonella typhimurium) and 2 fungi (i.e., Fusarium oryzae, Candida albicans). The results showed that the metal complexes inhibited the growth of bacteria to a greater extent as compared to the ligand.     

Regularity and Related Rings

A ring R is a Garcia ring provided that the product of two regular elements is unit-regular. We prove that every regular element in a Garcia ring R is the sum/difference of an idempotent and a unit. Furthermore, we prove that every regular element in a weak Garcia ring is the sum of an idempotent and a one-sided unit. These extend several known theorems on (one-sided) unit-regular rings to wider classes of rings with sum summand property.     

Synthesis of Pyrazolo‐[4́,3́:5,6]pyrido[2,3‐d]pyrimidine‐diones Catalyzed by a Nano‐sized Surface‐Grafted Neodymium Complex of the Tungstosilicate via Multicomponent Reaction

An inorganic–organic hybrid based on lanthanide clusters and Keggin type polyoxometalates (POMs) (Na[Nd (pydc‐OH)(H₂O)₄]₃}[SiW₁₂O₄₀]) was used the first time as trinuclear catalyst for one pot synthesis of pyrazolo[4??,3?:5,6]pyrido[2,3‐d]pyrimidine‐diones, via two different four and five‐component reactions involving hydrazine hydrate, ethyl acetoacetate, aryl aldehydes, and 6‐amino‐1,3‐dimethyl uracil or barbituric acid with ammonium acetate as alternative materials in green condition. To evaluate potential application of the as‐made hybrid in adsorption and separation processes, nitrogen adsorption was performed at 77 K through simulation study. The hybrid catalyst was further characterized via powder X‐ray diffraction (PXRD) at room temperature which indicated the good phase purity of the catalyst. The results show that the catalytic activity of the hybrid catalyst has increased relative to each parent component due to the special interaction between Keggin anions and pydc‐OH ligands.     

Photocatalytic degradation of carcinogenic Congo red dye in aqueous solution,antioxidant activity and bactericidal effect of NiO nanoparticles

Journal of the Iranian Chemical Society - Face-centered cubic structure of nickel oxide (NiO) nanoparticles with 30 nm average size was synthesized by co-precipitation method with some...     

A novel magnetically separable laccase-mediator catalyst system for the aerobic oxidation of alcohols and 2-substituted-2,3-dihydroquinazolin-4(1H)-ones under mild conditions

In this study, a magnetically reusable artificial metalloenzyme has been constructed by co-immobilization of palladium nanoparticles as a strong oxidizing catalyst and laccase as an oxygen-activating enzyme into the cavities of magnetic mesocellular foams silica (Pd-Laccase@MMCF). The combination of Pd-Laccase@MMCF and hydroquinone (HQ) act as electron-transfer mediator system and make stepwise electron transfer from substrate to molecular oxygen. This catalyst system was used for the aerobic (i) oxidation of alcohols to the corresponding carbonyl compounds and (ii) dehydrogenation of 2-substituted-2,3-dihydroquinazolin-4(1H)-ones in phosphate buffer (0.1 M, pH 4.5, 4 mL)/THF (4%, 1 mL) as solvent under mild conditions. The co-immobilization of both laccase and Pd onto high surface area mesoporous support, high catalytic activity and magnetically separable and reusable make the present catalyst system superior to other currently available electron-transfer mediator systems.     

Synthesis,characterization and in vitro DNA binding studies of a new copper(II) complex containing an antiviral drug,valganciclovir

A new complex, [Cu(valcyte)₂(NO₃)₂], in which valcyte served as a valganciclovir drug, was synthesized and characterized by different physicochemical methods. Optimization of ligand structures and their complexes with Cu²⁺ were performed by semi-empirical and DFT methods. Binding interaction of this complex with calf-thymus DNA (ct-DNA) was explored by emission, absorption, circular dichroism and viscosity techniques. Additionally, cell line targeting was studied and cytotoxic effects of [Cu(valcyte)₂(NO₃)₂] (0.0–160 μg) on AGS and MCF-7 cell lines were reported. Percentage of Cell Viability and Apoptotic Index were assessed. The complex displayed significant binding properties to ct-DNA. Undertaking fluorometric studies, the binding mode of the complex with ct-DNA was explored utilizing Hoechst as a fluorescence probe, indicating the binding to be of groove mode. The DNA viscosity altered slightly in presence of the complex. Enthalpy and entropy changes during the interaction showed that the process is endothermic, with the complex mainly bound to ct-DNA by hydrophobic attraction. Values of ΔG revealed a spontaneous reaction between DNA and the complex. Optimized docked model of DNA–complex mixture confirmed the experimental results. The results of MMFF94 calculations indicated stability of [Cu(valcyte)₂(NO₃)₂] after docking with the modeled DNA profile, as compared to the DNA profile and valganciclovir results before the docking process. Cytotoxicity studies showed that an increase in [Cu(valcyte)₂(NO₃)₂] may result in a significant decrease in cell viability and increase apoptosis index in the treated cells, as compared to valganciclovir treated cells (p < 0.05). The findings further showed that [Cu(valcyte)₂(NO₃)₂] has potential for use in cancer therapy.     

A combined theoretical and thermal analysis study on the solid state linkage isomerization of Ni(II)-nitrite complexes with ethylenediamine derivatives*

Solid state stepwise nitro–nitrito linkage isomerization of trans-[dinitrobis(ethylenediamine)nickel(II)], [Ni(en)₂(NO₂)₂] (N,N-en), trans-[dinitrobis(N,N′-dimethylethylenediamine)nickel(II)], [Ni(N,N′-dmen)₂(NO₂)₂] (N,N-dmen), and trans-[dinitritobis(N,N-dimethylethylenediamine)nickel(II)], [Ni(N,N-dmen)₂(ONO)₂] (O,O-udmen) were investigated by performing non-isothermal differential scanning calorimetry (DSC) analyses and the thermodynamic and thermokinetic parameters of isomerization were determined using DSC curves. Both N,N-en and N,N-dmen DSC curves show an endothermic peak at elevated temperatures, attributed to dinitro-to-dinitrito linkage isomerization. Similar exothermic peaks were observed in the cooling cycle, assigned to the reverse dinitrito-to-dinitro isomerization. The O,O-udmen isomer is more stable than the corresponding dinitro one at ambient temperatures, but an exothermic dinitrito-to-dinitro isomerization occurs upon cooling down to ?70 °C and reverts endothermically to dinitrito isomer upon heating up to ambient temperature. The overlapping DSC peaks associated with stepwise linkage isomerization were resolved using nonlinear fitting method. The peak temperature and the enthalpy changes of linkage isomerization are inversely dependent on the steric hindrance provided by diamine ligands, which increases in the order udmen > dmen > en. The results showed that the steric factor of the co-ligands also influences the kinetic parameters of isomerization, so that more bulky ligand substituent leads to higher isomerization rate constants. A DFT and TD-DFT calculations have been carrid out on both dinitro complexes of this investigation .     

Synthesis,Characterization, and DNA Binding Studies of a New Pt(II) Complex Containing the Drug Levetiracetam: Combining Experimental and Computational Methods

The water-soluble platinum(II) complex, [Pt(LV)(dmso)Cl]Cl (LV is Levetiracetam an anti-epileptic drug belonging to the pyrrolidine family) was synthesized and characterized using physico-chemical, spectroscopic and computational methods. Multi-spectroscopic methods used to study the interaction of Pt(II) complex with calf thymus (ct-DNA) in Tris–HCl buffer solution (pH 7.4). The Pt(II) complex was found to be a minor groove binder with a preference for the A-T region compared to the G-C region. This was substantiated by displacement studies with Hoechst 33258, a known minor groove binder. The mean binding constant obtained from the spectroscopic techniques was 7?×?10⁴ M^?1. In comparison with the previous study, the binding constant of Pt(II) complex is 15 times greater than the corresponding value of levetiracetam. These results indicate that the binding affinity of Pt(II) complex is stronger than levetiracetam.