Efficient oxidation of sulfides to sulfoxides catalyzed by heterogeneous Zr-containing polyoxometalate grafted on graphene oxide.

In this study, a tri-component composite named Zr/SiW12/GO was meticulously prepared through an ultrasonic-assisted method. This composite incorporates zirconium nanoparticles (Lewis acid), a negatively charged Keggin type polyoxometalate, and graphene oxide, and serves as a remarkable heterogeneous catalyst. The Keggin component plays multiple roles as reducing, encapsulating, and bridging agents, resulting in a cooperative effect among the three components that significantly enhances the catalytic activity. The catalytic performance of Zr/SiW12/GO was thoroughly investigated in the oxidation of sulfides to sulfoxides under mild conditions, employing H2O2 as the oxidant. Remarkably, this composite exhibited exceptional stability and could be effortlessly recovered and reused up to four times without any noticeable loss in its catalytic activity.

Incorporating heterogeneous lacunary Keggin anions as efficient catalysts for solvent-free cyanosilylation of aldehydes and ketones.

Polyoxometalates (POMs) as efficient catalysts can be used a wide range of chemical transformations due to their tunable Brønsted/Lewis-acidity and redox properties. Herein, we reported two hybrid and heterogeneous lacunary Keggin catalysts: (TBA)7[PW11O39] (TBA-PW11) and (TBA)8[SiW11O39]·4H2O (TBA-SiW11) (TBA+: tetrabutylammonium) in which [XW11O39]n- anions were coated by TBA+ cations. In this form, TBA+ can easily trap reactants on the surface of the catalysts and increase the catalytic reaction. Therefore, the catalytic performance of both POMs was tested in cyanosilylation of numerous compounds bearing-carbonyl group and trimethylsilyl cyanide under solvent-free conditions. TBA-PW11 is more effective than TBA-SiW11, conceivably due to the higher Lewis acidity of the P than the Si center and to the higher accessibility of the metal centers in the framework structure. Noteworthy, the recyclability and heterogeneity of both POMs catalysts were also examined, and the results confirmed that they remain active at least after three recycling procedures.

Molecular design and synthesis of new dithiocarbazate complexes; crystal structure, bioactivities and nano studies.

The syntheses of a new set of metal complexes MoO2L'(CH3OH), VOL'(CH3O)(CH3OH), , , SnL'Cl2 and SnL'I2 with a new ligand (L = (2,2'(disulfanediylbis((ethylthio)methylene)bis(hydrazin-2-yl-1-ylidene)bis(methanylylidene)) diphenol; L' = S-ethyl-3-(2-hydroxyphenyl)methylenedithiocarbazate are described along with characterization by elemental analysis, mass spectrometry, spectroscopic (IR, 1H- and 13C-NMR) and TGA techniques. The crystal structures of compounds were determined by single crystal X-ray diffraction analysis and compared to powder X-ray diffraction (PXRD) patterns of the nano complexes obtained using ultrasonic methods. The PXRD results indicate that the compounds synthesized by ultrasonic methods have high crystallinity. The compounds were evaluated in an in vitro cytotoxicity study with two human cancer cell lines. The results of this study revealed that all complexes exhibit good cytotoxic activity when compared to the clinical drug, cisplatin. Interaction of the samples with human serum albumin (HSA) was investigated using fluorescence spectrophotometric methods and the Stern-Volmer quenching constant (K SV) and free energy changes (ΔG) were calculated at 298 K. The fluorescence quenching method is used to determine the number of binding sites (n) and association constants (K a) at the same temperatures.

Application of response surface methodology in enzymatic synthesis: a review.

There are very chemical reactions with very slow rates which can be catalyzed by enzymes. These biocatalysts need to moderate conditions for their catalytic activity and are stable in low temperature (between 15-50°C), average pH (5-10) and aqueous media. One of important things in enzymatic synthesis which has been recently noticed is the yield of reactions. Nowadays wide application of response surface methodology (RSM) was observed in organic chemistry. In one-variable-at-a-time technique only one parameter is changed and other parameters are kept at a constant level. It does not study the interactive effects among the variables, and does not illustrate the complete effects of the parameters on the process. Increasing the yield of product without increase in casts is carried out by modeling and optimization of reaction variables through statistical techniques such as RSM. In this paper, we reviewed some articles that used the RSM for optimization in the enzymatic synthesis.