RESUMO
Two solvent-free polymorphs of a chiral iron(ii) complex have been obtained, and their polymorphism dependent spin-crossover and ferroelectric properties have been demonstrated. Polymorph I shows a gradual spin-crossover behavior, whereas polymorph II remains in a high-spin state but shows a typical ferroelectric feature.
RESUMO
A new class of chiral tetrahedral iron(II) cages were prepared from subcomponent self-assembly with high diastereoselectivity. The cages can be interconverted through imine exchange. The chiral cages displayed a spin transition close to room temperature, and the transition temperatures were affected by the substituent and uncoordinated solvents.
Assuntos
Compostos Ferrosos/química , Cristalografia por Raios X , Modelos Moleculares , Solventes , Estereoisomerismo , Temperatura de TransiçãoRESUMO
Three dinuclear nickel triple-stranded supramolecular cylinders [Ni2(L1)3][ClO4]4 (1), [Ni2(L2)3][ClO4]4 (2) and [Ni2(L3)3][ClO4]4 (3) with bis(pyridylimine) Schiff base containing triphenyl groups in the spacers as ligands were synthesized and characterized. The human telomeric G-quadruplexes binding properties of cylinders 1-3 were evaluated by means of UV-Vis spectroscopy, circular dichroism (CD) spectroscopy and fluorescence resonance energy transfer (FRET) melting assay. UV-Vis studies revealed that the supramolecular cylinders 1-3 could bind to G-quadruplex DNA with high binding constants (Kb values ranging from 0.11-2.2×10(6) M(-1)). FRET melting studies indicated that the cylinders 1-3 had much stronger stabilizing effect on G-quadruplex DNA (ΔTm up to 24.5°C) than the traditional cylinder Ni2L3(4+) just containing diphenylmethane spacers (ΔTm=10.6 °C). Meanwhile, cylinders 1-3 were found to have a modest degree of selectivity for the quadruplex DNA versus duplex DNA in competition FRET assays. Moreover, CD spectroscopy revealed that complex 1 could induce G-quadruplex formation in the absence of metal ions solution and convert antiparallel G-quadruplex into hybrid structure in Na(+) solution. These results provided a new insight into the development of supramolecular cylinders as potential anticancer drugs targeting G-quadruplex DNA.
Assuntos
Quadruplex G , Modelos Moleculares , Níquel/química , Animais , Bovinos , Dicroísmo Circular , Simulação por Computador , DNA/metabolismo , Transferência Ressonante de Energia de Fluorescência , Humanos , Espectrofotometria Ultravioleta , Telômero/metabolismo , TermodinâmicaRESUMO
OBJECTIVE: To deeply explore the effects of microcystins (MC-LR) on Bax and Bcl-2 during the course of MC-LR promoting liver tumor. METHODS: applied to set up the animal model, and the effect of MC-LR promoting liver tumor was evaluated by the Albertgamma-GT methods. And then, the immunohistochemical technique, RT-PCR and image analysis were used to study the expression of the Bcl-2 and Bax during the course of promoting tumor. RESULTS: (1) MC-LR might enhance the positive reaction rate of GGT. The positive reaction rate of GGT in DEN + pure toxin group was 100%, it was significantly higher than the DEN control group 22.22% (P < 0.05). (2) The intension and areas of the protein expression of Bcl-2 in DEN + pure toxin group were 0.0977 and 0.0315, and in DEN control group were 0.0460 and 0.0205, respectively. The expression level of Bcl-2 protein in DEN + pure toxin group were significantly higher than in DEN control group (P < 0.05). Simultaneously, the protein expression of Bax was significantly decreased by MC-LR (P < 0.05). The intension and areas of the expression of Bax in DEN + pure toxin group were 0.0283 and 0.0073, and in DEN control group were 0.0655 and 0.0244 respectively. (3) The mRNA expression of Bcl-2 was significantly increased by MC-LR. The intension of Bcl-2 mRNA expression in DEN + pure toxin group was 2.244, being significantly higher than in the other groups (P < 0.05). However, the mRNA expression of Bax showed no significant difference between DEN + pure toxin and the other groups. CONCLUSION: The expression change of Bcl-2 and Bax should possibly play an important role in the course of MC-LR promoting liver tumor.