Iron tetranitrosyl complex bearing the thiosulfate ligand (TNIC) is an efficient nitrogen monoxide donor (NO). He shows antitumor properties and may be used as an original drug for the therapy of acute coronary syndro...Iron tetranitrosyl complex bearing the thiosulfate ligand (TNIC) is an efficient nitrogen monoxide donor (NO). He shows antitumor properties and may be used as an original drug for the therapy of acute coronary syndrome. In this work, the reaction of the TNIC with adenosine triphosphoric acid (ATP) was studied. Formation of the products for the reaction of ATP with TNIC was shown by electronic microscopy. The kinetics of the reaction was controlled by spectrofluorometric method, and the complexation constant was measured. The mechanism of interaction of ATP with TNIC was proposed, and the relevant kinetic model satisfactorily described the experimental data, which permitted to calculate the rate constants for these process stages. NMR, IR, and M?ssbauer studies were used for determination of the reaction product structure. NMR study showed TNIC interaction only with adenine part of ATP. The method of IR spectroscopy identified both the absence NO in the reaction products and the occurrence of new Fe-S and Fe-N bonds. M?ssbauer study showed that iron in the reaction products was presented by two forms: Fe(II) and Fe(III). Thus, the structures for the [ATP-Fe2+S] and [ATP-Fe3+S] complexes were proposed.展开更多
Developing nonprecious carbon electrocatalysts as alternatives to platinum for cathodic oxygen reduction reaction in fuel cells is of signifi- cance. Herein, an efficient precursor-controlled synthesis strategy based ...Developing nonprecious carbon electrocatalysts as alternatives to platinum for cathodic oxygen reduction reaction in fuel cells is of signifi- cance. Herein, an efficient precursor-controlled synthesis strategy based on extremely rapid nucleation and deposition process assisted by the liquid nitrogen freeze drying method is explored to anchor cheap iron-EDTA complex evenly dispersed on graphene to realize mJcrostructural homogeneity of the derived Fe-N-C oxygen reduction electrocatalyst. The prepared electrocatatyst possesses excellent performance including high activity with more positive onset and half-wave potential, a long-term stability, and anti-poisoning effect compared to commercial Pt/C. The activity correlates well with the unique sheet-shaped morphology, high surface area, hierarchical porous structure, and the introduction of Fe-Nx/C species. Especially, both the assembled practical alkaline and acid fuel cells based on the synthesized cathode catalysts reveal excellent performance with high open-circuit voltage and power density.展开更多
文摘Iron tetranitrosyl complex bearing the thiosulfate ligand (TNIC) is an efficient nitrogen monoxide donor (NO). He shows antitumor properties and may be used as an original drug for the therapy of acute coronary syndrome. In this work, the reaction of the TNIC with adenosine triphosphoric acid (ATP) was studied. Formation of the products for the reaction of ATP with TNIC was shown by electronic microscopy. The kinetics of the reaction was controlled by spectrofluorometric method, and the complexation constant was measured. The mechanism of interaction of ATP with TNIC was proposed, and the relevant kinetic model satisfactorily described the experimental data, which permitted to calculate the rate constants for these process stages. NMR, IR, and M?ssbauer studies were used for determination of the reaction product structure. NMR study showed TNIC interaction only with adenine part of ATP. The method of IR spectroscopy identified both the absence NO in the reaction products and the occurrence of new Fe-S and Fe-N bonds. M?ssbauer study showed that iron in the reaction products was presented by two forms: Fe(II) and Fe(III). Thus, the structures for the [ATP-Fe2+S] and [ATP-Fe3+S] complexes were proposed.
基金This work was financially supported by Ministry of Science and Technology of China （Nos. 2026YFB0200203 and 2017YFA0206704）, National Program on Key Basic Research Project of China （No. 2014CB932300）, Strategic Priority Research Program of the Chinese Academy of Sciences （No. XDA09010404）, Technology and Industry for National Defense of China （No. JCKY2026130B010）,and National Natural Science Foundation of China （Nos. 51771177, 21422108 and 51472232）.
文摘Developing nonprecious carbon electrocatalysts as alternatives to platinum for cathodic oxygen reduction reaction in fuel cells is of signifi- cance. Herein, an efficient precursor-controlled synthesis strategy based on extremely rapid nucleation and deposition process assisted by the liquid nitrogen freeze drying method is explored to anchor cheap iron-EDTA complex evenly dispersed on graphene to realize mJcrostructural homogeneity of the derived Fe-N-C oxygen reduction electrocatalyst. The prepared electrocatatyst possesses excellent performance including high activity with more positive onset and half-wave potential, a long-term stability, and anti-poisoning effect compared to commercial Pt/C. The activity correlates well with the unique sheet-shaped morphology, high surface area, hierarchical porous structure, and the introduction of Fe-Nx/C species. Especially, both the assembled practical alkaline and acid fuel cells based on the synthesized cathode catalysts reveal excellent performance with high open-circuit voltage and power density.
