2-Hydroxybenzylidene-4-(4-SubstitutedPhenyl)-2-amino Thiazole and Their Pt (II) Complexes: Synthesis, Characterization and Biological Study
EGYPTIAN JOURNAL OF CHEMISTRY
Authors: Aldelfy, Zahra; Al-Shamkani, Zeki; Al-assadi, Mohammed
Abstract
NEWLY prepared Schiff bases; 2-Hydroxybenzylidene-4-x-phenyl)-2-aminothiazole, where x=H, NO2-, CH3, -OCH3, -F, and Cl- (L1-L6), and their corresponding Pt (II) complexes (Pt(L1)(2)-Pt(L6)(2)) were synthesized. The ligands and their own complexes were structurally characterized using, FT-IR, (HNMR)-H-1, (CNMR)-C-13, mass spectra, elemental analysis and SEM technique. The spectral data revealed that these bases are bonded to the Pt ion via both, the deprotonated hydroxyl and the imine groups, suggesting a square planar geometry. Human DNA interaction with Schiff bases and their metal complexes were investigated spectrophotometrically, intercalation mechanism was found to dominate those links. Antioxidant activity measurements of the prepared ligands and their platinum complexes, also, were performed by linoleic acid free radical scavenging method. The methoxy derivative, L4 was found to be the most active species relatively to BHT and the sequence of activity, apparently arranged as following order: L4> L3> L2> L5=L6> L1 Anti-proliferative activity of the bases and their Pt(II) complexes was carried out on the MCF-7 cancer cell lines following the MTT assay.
Mechanistic study of transesterification in TBD-catalyzed ring-opening polymerization of methyl ethylene phosphate
EUROPEAN POLYMER JOURNAL
Authors: Nifant'ev, Ilya E.; Shlyakhtin, Andrey V.; Tavtorkin, Alexander N.; Kosarev, Maxim A.; Gavrilov, Dmitry E.; Komarov, Pavel D.; Ilyin, Sergey O.; Karchevsky, Stanislav G.; Ivchenko, Pavel V.
Abstract
It is well known that ring-opening polymerization (ROP) of sterically unhindered cyclic ethylene phosphates, initiated by both organocatalysts and coordination catalysts, is accompanied by transesterification (TE) even at subzero temperatures. To clarify this phenomenon from the mechanistic point of view, we calculated (DFT, B3PW91/DGTZVP) the reaction profiles of the ROP for 2-methoxy-1,3,2-dioxaphospholane-2-oxide (methyl ethylene phosphate, MeOEP) and of the transesterification processes for poly(MeOEP) and trlmethyl phosphate (TMP) in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) organocatalyst. We found that the free activation energy of TE is substantially higher (10-13 kcal/mol) than the ROP activation barrier. To verify the calculation results, we investigated the chemical behavior of low molecular weight trimethyl phosphate (TMP) in the TBD-catalyzed polymerization of MeOEP. We demonstrated that TMP was not affected by transesterification, which correlates with the calculation results. However, we found that the polymerization of MeOEP in the presence of TMP leads to the formation of linear poly(MeOEP) with given P-n and narrow MWD even at > 99% monomer conversion degree. A similar pattern was revealed for the synthesis of poly(MeOEP) with the coordination catalyst of aryloxy-alkoxy magnesium complex [(BHT)mg(mu-OBn)(THF)](2) (BHT = 2,6-di-tert-butyl-4-methylphenoxy). To explain the difference in the chemical behavior of TMP and polyphosphate, we assumed that poly(MeOEP) in the solution represents a dense globule, which leads to a decrease in the entropy of transesterification. To confirm this assumption, we studied the solution behavior of poly(MeOEP) in CHCl3 and in TMP. Both CHCl3 and TMP were found to be poor solvents for poly(MeOEP) in terms of KMH solution theory (alpha = 0.53 and 0.33, respectively). We assume that it is the conformation of the polymer in the solution that determines the tendency of the polyphosphate towards transesterification.