Thermoanalytical study of linkage isomerism in coordination compounds: Part I. Reinvestigation of thermodynamic and thermokinetic of solid state interconversion of nitrito (ONO) and nitro (NO2) isomers of pentaaminecobalt(III) chloride by means of DSC

Solid state thermal isomerization of [Co(NH₃)₅(ONO)]Cl₂ (nitrito isomer) to [Co(NH₃)₅(NO₂)]Cl₂ (nitro isomer) and reverse reaction were investigated by non-isothermal differential scanning calorimetry (DSC) and found to be essentially an equilibrium process. The interconversions are accelerated at above 65 °C and reach to equilibrium state at about 155 °C. After establishment of the equilibrium the relative amounts of two isomers at any temperature are governed by Gibbs free energy relationship. The experimental enthalpy changes of isomerization of pure nitrito and nitro solid samples to the equilibrium state are −4.67 (±0.19) and 0.99 (±0.05) kJ mol⁻¹, respectively. From these values, total enthalpy change was calculated as: ΔH°=−5.66(±0.20) kJ mol⁻¹. Using Gibbs free energy relationship, equilibrium constant, total free energy and entropy changes were estimated at 60 °C as: K=7.72(±0.8),  kJ mol⁻¹ and  J K⁻¹ mol⁻¹.An initial rate method has been developed to determine the kinetic parameters of these reactions from non-isothermal DSC data. Both nitro to nitrito and reverse reactions obey first order kinetic law in solid state. Estimated activation parameters of forward and reverse paths at 60 °C are , , and , respectively. The negative activation entropy of both directions support the intramolecular mechanism of isomerization, including formation of a seven coordinate transition state, which formerly suggested based on spectral and X-ray methods.     

Three component reactions：An efficient and green synthesis of 3, 4-dihydropyrimidin-2-(1H)-ones and thiones using silica gel-supported L-pyrrolidine-2-carboxylic acid-4-hydrogen sulfate

An environmentally benign aqueous protocol for the synthesis of 3,4-dihydropyrimidin-2-(1H)-ones and thiones promoted by a green catalyst,silica gel-supported L-pyrrolidine-2-carboxylic acid-4-hydrogen sulfate,has been developed.The use of nontoxic,thermally stable and inexpensive amino acid catalyst makes the process simple with minimal amount of chemical waste.Compared with classical Biginelli reaction conditions,this new method has the advantages of high yields and simple workup procedures.     

Green synthesis of ZnCo<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles by <Emphasis Type="Italic">Aloe albiflora</Emphasis> extract and its application as catalyst on the thermal decomposition of ammonium perchlorate

This work aimed the evaluation of pH influence in the obtainment of composites from palygorskite (PAL) and chitosan (CS). The materials PAL/CS-1 and PAL/CS-2 were obtained by similar methodology with modified pHs: 5.0 ± 0.5 and 11.0 ± 0.5, respectively. Both materials were evaluated for specific surface area analysis, elemental analysis, XRD, FTIR, thermal analysis, MEV and interaction drug composite, using 5-aminosalicylic acid (5-ASA) as model. The surface area analysis data showed the reduction in PAL/CS-2 related to CS presence on surface in contrast with PAL/CS-1, which corroborate with elemental analysis present nine times more of CS in PAL/CS-2 composition. Regarding to XRD data, the interaction of CS with PAL did not cause modification in clay structure in PAL/CS-2. These results were confirmed by FTIR data with the N–H deformation vibration in PAL/CS-2 while PAL/CS-1 was invariable to PAL. In thermal analysis, results were observed 60.2% residual mass to PAL/CS-2, which it was lower than PAL (87.2%) and PAL/CS-1 (86.7%), due to CS decomposition which had enthalpy energy of 62.1 J g^?1 K^?1, confirming the data previously cited. PAL/CS-2 presented 5-ASA adsorption of 7.9 mg g^?1, which was inferior to others probably caused by scarcity of active sites of PAL already occupied by CS. These results showed that pH control was fundamental to enhance efficiency of obtainment of composite in basic pH because the decrease in CS protonation degree increasing interaction between this one and PAL, although it contributed to decrease in 5-ASA adsorption due to low availability of interaction sites.     

Effect of monomer and hydrocarbon content and polarity of the medium on the preparation of nonspherical particles via seeded dispersion polymerization in the presence of saturated hydrocarbon droplets

In this work, the preparation of micron-sized polymer particles with nonspherical shapes via seeded dispersion polymerization of 2-ethylhexyl methacrylate (EHMA) with polystyrene (PS) seed particles in the presence of decane droplets and evaporation of decane after the polymerization under various polymerization conditions was discussed. The effect of monomer and decane content and polarity of the medium on the shape of the obtained particles was investigated. The experimental results showed that decreasing the amount of monomer and hydrocarbon volume of PEHMA/hydrocarbon domains, the particles decreased but they grew symmetrically, resulting in symmetric shapes. Furthermore, it was suggested that because of changing the solubility of the oligoradicals and hydrocarbon in the medium, the shape of the particles changed with changing the polarity of the medium. With decreasing the polarity of the medium, solubility of the oligoradicals in the medium increases and bigger polymer domains form on the surface of PS particles which can absorb higher amounts of decane. All of these can contribute to an increase in volume reduction after extraction of PEHMA/decane, resulting in various particle shapes. Further decreasing in polarity of the medium leads to an increase in the solubility of decane in the medium and decreasing the absorbed amount of decane by PS particles and PEHMA domains, resulting in lower volume reduction after evaporation of decane.     

Preparation of a dual-functionalized fumed silica nanoparticle catalysis for synthesis of azaluorenone derivatives

Research on Chemical Intermediates - A dual-functional silica-based catalyst was prepared by treating fumed silica with amino-containing silane then 1,4-butane sultone. The presence of functional...     

Decorations of graphene oxide with cisplatin toward investigation of fluorescence quencher on regulatory sequence of BRCA1 and BRCA2

Journal of the Iranian Chemical Society - Herein, we investigated the interaction of cisplatin loaded on GO (GO@CDDP) with two regulatory sequences, BRCA1 and BRCA2, synthesized from ssDNA based on...