Hai-Yang Liu

Palladium-Catalyzed Redox-Neutral N-O/C(sp3)-H Functionalization of Aryl Oximes with Isocyanides

A redox-neutral palladium-catalyzed N-O/C(sp3)-H functionalization of aryl oximes with isocyanides has been developed. Various pyrrole derivatives were prepared in good to excellent yields through oxime carbamate as a key intermediate and internal oxidant in this process. Furthermore, this transformation also features readily available starting materials, good functional group tolerance, and excellent regioselectivity.

Phosphorus(V) corrole: DNA binding, photonuclease activity and cytotoxicity toward tumor cells

A new phosphorus(V) corrole, 10-(4-hydroxylphenyl)-5,15-bis(pentafluorophenyl)corrolato (trans-dihydroxo)phosphorus(V) 1-P, was synthesized and characterized. The interaction of 1-P with calf thymus DNA (CT-DNA) was studied by multi-spectroscopic methods. The photonuclease activity of this complex was examined by agarose gel electrophoresis. 1-P may bind to CT-DNA via an outside binding mode and display good photonuclease activity. 1-P displayed low dark toxicity but high photocytotoxic activity against H460 and A549 tumor cell lines.

The magnetic properties, DNA/HSA binding and nuclease activity of manganese N-confused porphyrin

The first oxidative cleavage of DNA by manganese N-confused porphyrin [chloro(2-aza-2-methyl-5,10,15,20-tetrakis(p-chlorophenyl)-21-carbaporphyrin)manganese(III), 1] using H2O2 as oxidant agent and its magnetic, calf thymus DNA(ct-DNA)- and human serum albumin (HSA) binding properties were investigated. The magnitude of the axial (D) zero-field splitting for the mononuclear Mn(III) center in 1 was determined to be approximately 2.71 cm−1 by paramagnetic susceptibility measurements. The DNA- and HSA binding experimental results showed that 1 bound to ct-DNA via an outside groove binding mode and the hydrophobic cavity located in subdomain IIA of HSA with the binding constant of 4.144 × 105 M−1 and ∼ 106 M−1, respectively. Thermodynamic parameters revealed that both DNA- and HSA binding were spontaneous process. The main driven forces were the hydrogen bond and van der Waals for the former, but hydrophobic interaction for the latter, which were further confirmed by molecular docking modeling. Manganese N-confused porphyrin 1 could cleave the supercoiled plasmid DNA efficiently in the presence of hydrogen peroxide. Hydroxyl radical (•OH) was found the active species for oxidative damage of DNA.

Photoinduced Electron Transfer between Anionic Corrole and DNA

The interaction between a water-soluble anionic Ga(III) corrole [Ga(tpfc)(SO3Na)2] and calf thymus DNA (ct-DNA) has been investigated by using femtosecond transient absorption spectroscopy. A significant broadening from 570 to 585 nm of positive absorption band of the blend of Ga(tpfc)(SO3Na)2 and ct-DNA (Ga(tpfc)(SO3Na)2-ctDNA) has been observed from 0.15 to 0.50 ps after photoexcitation of Ga(tpfc)(SO3Na)2 into the Soret band. The control experiment has been performed on the model DNA ([poly(dG-dC)]2) rich in guanine bases, which exhibits a similar spectral broadening, whereas it is absent for [poly(dA-dT)]2 without guanine bases. The molecular orbital calculation shows that HOMO of Ga(tpfc)(SO3Na)2 is lower than that of guanine bases. The results of the electrochemical experiment show the reversible electron transfer (ET) between Ga(tpfc)(SO3Na)2 and guanine bases of ct-DNA is thermodynamically favorable. The dynamical analysis of the transient absorption spectra reveals that an ultrafast forward ET from the guanine bases to Ga(tpfc)(SO3Na)2 occurs within the pulse duration (156 fs), leading to the formation of an intermediate state. The following back ET to the ground state of Ga(tpfc)(SO3Na)2 may be accomplished in 520 fs.

DNA-Binding, Photocleavage, and Photodynamic Anti-cancer Activities of Pyridyl Corroles

The DNA-binding, photocleavage, and antitumor activity of three free base pyridyl corroles 1, 2, and 3 have been investigated. The binding affinity toward CT-DNA decreases with increasing number of pentafluorophenyl, whereas the photocleavage activity toward pBR322 DNA becomes more efficient. Singlet oxygen was demonstrated as active species responsible for DNA cleavage. These corroles exhibited high cytotoxicity against three tested cancer cells (Hela, HapG2, and A549) and the cytotoxicity could be further enhanced under irradiation. Intracellular reactive oxygen species level was also monitored using HeLa Cells upon the combined treatment of corroles and light. These corroles could be absorbed by HeLa cells at low concentration. They can induce the decrease of mitochondrial membrane potential and apoptosis of tumor cells under irradiation.

DNA Binding, Photonuclease Activity and Human Serum Albumin Interaction of a Water-Soluble Freebase Carboxyl Corrole

The DNA binding property of 5,10,15-Tris(4-carboxyphenyl) corrole (TCPC) was studied by UV-Visible, fluorescence and circular dichroism (CD) spectroscopic methods. TCPC can bind to ct-DNA via an outside binding mode with the binding constant of Kb = 1.05 × 105 M−1. TCPC also displayed good photonuclease activity, which involves singlet oxygen species (1O2). The binding constant between TCPC and human serum albumin (HSA) is KA = 2.24 × 105 M−1 with a simulated binding distance of 2.06 nm. The fluorescence quenching of HSA by TCPC followed a static quenching process. Site marker competitive displacement experiments indicated that warfarin site I is the main binding site. The secondary structure of HSA was changed upon interaction with TCPC, which was confirmed by UV-Visible and CD spectroscopy.

Study on the preparation of the CdSxSe1−x@ZrSiO4 red ceramic pigments and its properties

The color of the CdSxSe1−x@ZrSiO4 red ceramic pigment is associated with the condensed CdSxSe1−x particles, which is incorporated into zirconium silicate microcrystals as a robust inclusion body. The pigments were prepared via the gel co-precipitation method. The as-prepared pigments were characterized by X-ray diffraction, CIE-L*a*b* color measurement, scanning electron microscopy, acoustic particle sizer, dynamic laser scattering particle size analysis and polarized optical microscopy, respectively. The results indicate that the pigments prepared in ethanolamine solution show a more intensive tinting capacity, superior thermal stability and the finer particle size than those prepared in prevailing pure water. The prepared red pigments can be potential applied as a promising ink material for inkjet printing.Graphical AbstractDiagram of acid picking pores on pigment encapsulation

Oxygen atom transfer reactions from sterically encumbered brominated (oxo)manganese(V) corroles to styrene

Seven A3- and trans-A2B manganese(III) corroles (1–7-Mn) differing widely in their electronic and steric features were synthesized and transformed to their corresponding β-brominated manganese(III) corroles derivatives (1a–7a-Mn). Their corresponding (oxo)manganese(V) corroles 1–7-Mn(oxo) and 1a–7a-Mn(oxo) were further prepapred by treating with iodosylbenzene (PhIO). The reactivity for the oxygen atom transfer from 1–7-Mn(oxo) to styrene followed the order of 1-Mn(oxo) > 2-Mn(oxo) > 7-Mn(oxo) > 4-Mn(oxo) > 3-Mn(oxo) > 6-Mn(oxo) ≈5-Mn(oxo). The same pattern was observed for their β-brominated analogs 1a–7a-Mn(oxo), albeit their reactivity was remarkably higher. The steric protection of MnV ≡O moiety by ortho–ortho′-dibromophenyl substituents was found to enhance the stability of (oxo)manganese(V) corroles significantly.