131803-48-0Relevant articles and documents
Efficient and specific strand scission of DNA by a dinuclear copper complex: Comparative reactivity of complexes with linked tris(2-pyridylmethyl)amine moieties
Humphreys, Kristi J.,Karlin, Kenneth D.,Rokita, Steven E.
, p. 6009 - 6019 (2002)
The compound [CUII2(D1)(H2O)2] (ClO4)4 (D1 = dinucleating ligand with two tris(2-pyridylmethyl)-amine units covalently linked in their 5-pyridyl positions by a -CH2CH2- bridge) selectively promotes cleavage of DNA on oligonucleotide strands that extend from the 3′ side of frayed duplex structures at a site two residues displaced from the junction. The minimal requirements for reaction include a guanine in the n (i.e. first unpaired) position of the 3′ overhang adjacent to the cleavage site and an adenine in the n position on the 5′ overhang. Recognition and strand scission are independent of the nucleobase at the cleavage site. The necessary presence of both a reductant and dioxygen indicates that the intermediate responsible for cleavage is produced by the activation of dioxygen by a copper(I) form of the dinuclear complex. The lack of sensitivity to radical quenching agents and the high level of site selectivity in scission suggest a mechanism that does not involve a diffusible radical species. The multiple metal center exhibits a synergy to promote efficient cleavage as compared to the action of a mononuclear analogue [CuII(TMPA)-(H2O)](ClO4)2 (TMPA = tris(2-pyridylmethyl)amine) and [Cu(OP)2]2+ (OP = 1,10-phenanthroline) at equivalent copper ion concentrations. The dinuclear complex, [CuII2(D1)(H2O)2] (ClO4)4, is even capable of mediating efficient specific strand scission at concentrations where [Cu(OP)2]2+ does not detectably modify DNA. The unique coordination and reactivity properties of [CuII2(D1)(H2O)2] (ClO4)4 are critical for its efficiency and site selectivity since an analogue, [CuII2(DO)(Cl2)] (ClO4)2, where DO is a dinucleating ligand very similar to D1, but with a -CH2OCH2- bridge, exhibits only nonselective cleavage of DNA. The differences in the reactivity of these two complexes with DNA and their previously established interaction with dioxygen suggest that specific strand scission is a function of the orientation of a reactive intermediate.
Host-guest assemblies of anchoring molecular catalysts of CO2 reduction onto CuInS2/ZnS quantum dots for robust photocatalytic syngas production in water
Deng, Bo-Yi,Liu, Jing,Ren, Ying-Yi,Wang, Feng,Xia, Wu
, (2022/02/11)
Simultaneously fulfilling CO2-to-CO and 2H+-to-H2 reactions in water via photocatalyst represents an alternative to produce syngas driven by solar energy. To this end, photocatalyst having ability of simultaneously producing CO and H2 with controllable ratio should be exploited. In this work, we report a self-assembly photocatalyst C1@CD-CuInS2/ZnS quantum dots (QDs) that enabling to produce syngas robustly in CO2-saturated water under visible light irradiation. C1 is a molecular catalyst of linking an adamantine moiety to [Co(TPA)Cl]Cl (TPA = tris (2-pyridylmethyl) amine), while CD-CuInS2/ZnS QDs are semiconductor QDs with structure of CuInS2 core and ZnS shell and containing β-cyclodextrin (CD) on the surface. The C1@CD-CuInS2/ZnS QDs assemblies form by anchoring molecular cobalt catalyst C1 onto cyclodextrin (CD) modified CuInS2/ZnS quantum dots (CD-CuInS2/ZnS QDs) based on host-guest interaction between adamantine in C1 and cyclodextrin in the QDs. In which, C1 functions a molecular catalytic center mainly for CO2 reduction, and CD-CuInS2/ZnS QDs functions as both a light harvester and a hydrogen production center. The C1@CD-CuInS2/ZnS QDs system maintains syngas production activity over 200 h, and produces 184.21 μmol syngas with a CO/H2 ratio of 0.74 (ca. 2:3), exhibiting obvious advantages of syngas production efficiency in comparison to the non-assembled system and pristine CD-CuInS2/ZnS QDs system. Mechanism studies revealed that photoinduced electron transfer between CD-CuInS2/ZnS QDs and C1 occurs. The host-guest interaction improves syngas production activity and stability as well as plays positive role on stability of the molecular catalyst.
Exploration of Structure-Activity Relationship of Aromatic Aldehydes Bearing Pyridinylmethoxy-Methyl Esters as Novel Antisickling Agents
Pagare, Piyusha P.,Ghatge, Mohini S.,Chen, Qiukan,Musayev, Faik N.,Venitz, Jurgen,Abdulmalik, Osheiza,Zhang, Yan,Safo, Martin K.
, p. 14724 - 14739 (2020/11/30)
Aromatic aldehydes elicit their antisickling effects primarily by increasing the affinity of hemoglobin (Hb) for oxygen (O2). However, challenges related to weak potency and poor pharmacokinetic properties have hampered their development to treat sickle cell disease (SCD). Herein, we report our efforts to enhance the pharmacological profile of our previously reported compounds. These compounds showed enhanced effects on Hb modification, Hb-O2 affinity, and sickling inhibition, with sustained pharmacological effects in vitro. Importantly, some compounds exhibited unusually high antisickling activity despite moderate effects on the Hb-O2 affinity, which we attribute to an O2-independent antisickling activity, in addition to the O2-dependent activity. Structural studies are consistent with our hypothesis, which revealed the compounds interacting strongly with the polymer-stabilizing αF-helix could potentially weaken the polymer. In vivo studies with wild-type mice demonstrated significant pharmacologic effects. Our structure-based efforts have identified promising leads to be developed as novel therapeutic agents for SCD.
