Synthesis of mono- and di-[12]aneN3 ligands and study on the catalytic cleavage of RNA model 2-hydroxypropyl-p-nitrophenyl phosphate with their metal complexes

Abstract

A series of mono- and di-[12]aneN(3) ligands 1-6, which contain different substituents on the coordinating backbone, different linkers between two [12]aneN(3) units and different N-methylation on the [12]aneN(3) units, have been synthesized and fully characterized. The catalytic activities of their metal complexes on the cleavage of RNA model phosphate 2-hydroxypropyl-p-nitrophenyl phosphate (HPNPP) varied with the structures of the ligands and metal ions. Click reactions afforded an efficient method to prepare a series of [12]aneN(3) ligands, however, the incorporation of triazole moieties reduced the catalytic activities due to their coordination with metal ions and the strong inhibition from the triflate counter ion. Dinuclear zinc(II) complexes containing an m-xylyl bridge showed higher catalytic activities with synergistic effects up to 700-fold. Copper(II) complexes with the ligands without triazole moieties proved to be highly reactive and showed strong cooperativity between the two copper(II) ions. In terms of k(2), dinuclear complexes Zn(2)-3b, Zn(2)-3d, Zn(2)-4b, and Cu(2)-4b afforded activities of 7.9 × 10(5), 3.9 × 10(4), 9.0 × 10(4), and 8.1 × 10(4)-fold higher than that of methoxide. The ortho arrangement of the two [12]aneN(3) units and the presence of 5- or 2-positioned substituents in the benzene ring as well as N-methylation of [12]aneN(3) units greatly reduced the catalytic activities due to the steric effects. These results clearly indicate that the structures of the linker between two [12]aneN(3) units play very important role in their catalytic synergistic effects.

[12]aneN3-based BODIPY as a selective and sensitive off–on sensor for the sequential recognition of Cu2+ ions and ADP

“…As a binding unit, macrocyclic polyamines have been frequently applied in the development of artificial nucleases [9][10][11][12] and a number of chemical sensors to monitor biologically-and environmentally-relevant metal and anion ions [13][14][15][16]. Our group has recently focused on the design and synthesis of various macrocyclic polyamine [12]aneN 3 compounds and their applications in artificial nucleases, DNA condensation agents, non-viral gene vectors, and chemical sensors [17][18][19][20][21].…”

Synthesis and cytotoxic activities of 2-substituted (25R)-spirostan-1,4,6-triene-3-ones via ring-opening/elimination and ‘click’ strategy

“…Considering the unique characteristics and antitumor applications of the steroidal dimmers, 25,26 1,4-xylyldiazide 27 was also used for the synthesis of bis-steroidal triazole derivatives. When equimolar of 4e and 1,4-xylyldiazide were added, a steroidal triazole 5d (yield 50%) and a bis-steroidal triazole 5e (yield 20%) were spontaneously isolated in the reaction.…”

Synthesis and Biological Evaluation of Novel 99mTc(CO)3-Labeled Thymidine Analogs as Potential Probes for Tumor Proliferation Imaging

“…Compound 1a was synthesized according to the literature [31]. Compound 4 was synthesized according to the literature [32].…”