Co-reporter:Dong-Yan Zhang, Yan Nie, Hui Sang, Jing-Jing Suo, Zong-Jin Li, Wen Gu, Jin-Lei Tian, Xin Liu, Shi-Ping Yan
Inorganica Chimica Acta 2017 Volume 457() pp:7-18
Publication Date(Web):1 March 2017
DOI:10.1016/j.ica.2016.12.002
Three Cu(II) complexes of [Cu(L1)(Br)2]·CH3CN (1), [Cu(L2)2(OAc)](PF6)·2C2H5OH (2), and [Cu(L1)(L2)](PF6)2 (3) (L1 = 2-(6-(pyridine-2-yl)-4-p-tolylpyridin-2-yl)pyridine, L2 = 2-(4-(pyridine-2-yl)-6-p -tolylpyridin-2-yl)pyridine) were designed and synthesized as anti-cancer drugs. All complexes were structurally characterized by X-ray crystallography showing that three complexes were the mononuclear compounds with the triclinic crystal system p1¯ space group. The interaction between each of these three complexes and calf thymus DNA (CT-DNA) was investigated via spectroscopic techniques and viscosity measurement, which indicated that these complexes could bind to CT-DNA by intercalation. Moreover, DNA cleavage experiment showed that, in the natural light under an aerobic environment, all complexes could cleave DNA in the absence of exogenous oxidant agent, and that singlet oxygen (1O2) might serve as the major cleavage active species. Protein binding experiment indicated that 1–3 could bind to bovine serum albumin (BSA) with moderate bonding via the static quenching mechanism. In addition, the IC50 values of these three complexes were significantly lower which denoted highly anti-cancer activities in comparison to cisplatin. And each of these complexes could individually inhibit proliferation potential of cancer cells by promoting G1-phase cell cycle arrest (G1 arrest) and inducing apoptosis through the production of reactive oxygen species (ROS) and the activation of caspase-3Three Copper(II) complexes with two isomers of terpyridyl ligands could bind to DNA/BSA and exhibited good DNA cleavage activity, which arrested cells at the G0/G1 phase. And the generation of 1O2, ROS, was under the natural light in an aerobic environment, which activated the caspase family mediated mitochondrial apoptotic pathway.
Co-reporter:Lin Jiang;Yue Liu;Xin Liu;Jinlei Tian;Shiping Yan
Dalton Transactions 2017 vol. 46(Issue 37) pp:12558-12573
Publication Date(Web):2017/09/25
DOI:10.1039/C7DT02351K
Three series of NiII–LnIII complexes were synthesized with the general formulae [(μ3-CO3)2{Ni(HL)(CH3–CH2OH)Ln(CH3COO)}2]·2CH3CH2OH (1–6) (Ln = Tb (1), Dy (2), Ho (3), Er (4), Tm (5), Yb (6); H3L = N,N′-bis(3-methoxysalicylidene)-1,3-diamino-2-prop-anol), [Ni(HL)Ln(dbm)3]·CH3OH2·2CH2Cl2 (7–10) (Ln = Tb (7), Eu (8), Gd (9), Ho (10); Hdbm = 1,3-diphenyl-1,3-propanedione) and [Ni(HL)(H2O)(tfa)Ln(hfac)2] (11–15) (Ln = Tb (11), Dy (12), Eu (13), Gd (14), Ho (15); Hhfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione, tfa− = trifluoroacetate) using compartmental Schiff base ligands in conjunction with auxiliary ligands. For the NiII2LnIII2 series, the tetranuclear structure could be considered as two NiII–LnIII dinuclear subunits bridged by two carbonates derived from atmospheric carbon dioxide. The LnIII ions of complexes 1–6 were octa-coordinated with distorted triangular dodecahedral geometry, while the LnIII ions of the dinuclear complexes 7–15 were nona-coordinated with distorted muffin geometry. The magnetic properties of the three series complexes were studied using dc and ac magnetic measurements. For the NiII–GdIII complexes, the dc magnetic susceptibility measurements suggested the existence of the anticipated ferromagnetic interaction between NiII and GdIII ions. The fitting of the χMT vs. T data processed by PHI software provided the parameters g = 2.08 (J = +0.87 cm−1) for 9 and g = 2.02 (J = +1.83 cm−1) for 14. The interaction exchange was magneto-structurally correlated to the Ni–O–Gd angle (α) and Ni(μ-O)Gd dihedral angle (β). With an applied dc field, complexes 1 (Tb), 2 (Dy), 7 (Tb) and 12 (Dy) exhibited single magnetic relaxation with SMM parameters of Ueff/k = 13.60 K, 11.52 K, 7.69 K and 5.14 K, respectively. Analysis of the Cole–Cole plots for complexes 2 and 7 suggested that a single relaxation process was mainly involved in the relaxation process, with α values in the range of 0.37–0.17 and 0.14–0.11, respectively.
Co-reporter:Lin Jiang;Bin Liu;Hao-Wen Zhao;Xin Liu;Shi-Ping Yan
CrystEngComm (1999-Present) 2017 vol. 19(Issue 13) pp:1816-1830
Publication Date(Web):2017/03/27
DOI:10.1039/C6CE02519F
The employment of a reduced Schiff-base ligand, 1,3-bis(3-methoxy-salicylamino)-2-propanol (H3L), with the assistance of acetate anions led to the isolation of eight heptanuclear heterometallic complexes containing [Cu5Ln2] cores. Single-crystal X-ray diffraction analyses have been performed for all the complexes and show that they all have dicationic [Cu5Ln2] cores with two nitrate or hexafluorophosphate anions to compensate the charge. The dicationic parts in 1–8 display centrosymmetric hexagonal-like arrangements in which one CuII ion sits on the inversion centre with six peripheral metal ions (two LnIII and four CuII) around it. The magnetic susceptibilities of all the complexes have been studied by dc magnetic measurements. The temperature dependent magnetic susceptibility data for the CuII–GdIII complex have been processed using PHI software. The results reveal that the magnetic exchange interactions between CuII and CuII ions are antiferromagnetic while those between CuII and GdIII ions are ferromagnetic. The magnetostructural correlations reveal that the bridging angles of Cu–O–Cu and Cu–O–Gd greatly influence the magnetic coupling of CuII–CuII and CuII–GdIII, respectively. Further, ac susceptibility studies have been carried out for DyIII and TbIII complexes and HoIII derivatives. The complexes CuII–HoIII and CuII–TbIII show slow magnetization relaxation behaviour of an SMM.
Co-reporter:Lin Jiang, Dong-Yan Zhang, Jing-Jing Suo, Wen Gu, Jin-Lei Tian, Xin Liu and Shi-Ping Yan
Dalton Transactions 2016 vol. 45(Issue 25) pp:10233-10248
Publication Date(Web):11 May 2016
DOI:10.1039/C6DT00380J
A series of NiII, CoII, ZnII and CdII complexes 1–9 with polytopic Schiff base ligands have been synthesized. The single-crystal X-ray crystallography results show that tetranuclear complexes 1–6 have common face-shared defective dicubane cores, whereas trinuclear CdII complexes 7–9 are almost linear entities. Synthesis methods (solvent evaporation and hydrothermal synthesis), reaction conditions (pH, solvents and dosage) and coligands (azide, methanol, chloride and acetate) play vital roles in determining the final structure of the complexes and therefore their magnetic properties. In complexes 1–6, the terminal and central M2+ ions are connected through mixed bridges, μ-phenoxido/μ1,1,1-X and μ-Oalphatic/μ1,1,1-X, while central two M2+ ions are linked by double bridges, μ1,1,1-X (X = azido and methoxido groups for 1 and 2–6 respectively). For complex 1, two central NiII ions are connected through two μ1,1,1-N3− which is relatively less reported. For complexes 7–9, there are two kinds of CdII, the centre CdII ions are eight-coordinated with triangle dodecahedral geometries, while the two side CdII ions are six-coordinated with trigonal prism geometries using chlorides or acetates as terminal ligands. Magnetic susceptibility measurements (χM) for compounds 1–6 have been performed, and they reveal predominant ferromagnetic exchange interactions in CoII and NiII tetramers. The photoluminescence studies show that the ZnII complex 6 and three CdII complexes 7–9 have strong fluorescence, and the lifetimes are measured to be in the 102 nanosecond timescale.
Co-reporter:Xue-Quan Zhou, Yang Li, Dong-Yan Zhang, Yan Nie, Zong-Jin Li, Wen Gu, Xin Liu, Jin-Lei Tian, Shi-Ping Yan
European Journal of Medicinal Chemistry 2016 Volume 114() pp:244-256
Publication Date(Web):23 May 2016
DOI:10.1016/j.ejmech.2016.02.055
•Four mononuclear copper(II) complexes with chiral Schiff-base ligands were synthesized and characterized.•These complexes exhibited excellent anticancer ability with IC50 values in micromole magnitude.•Chiral enantiomers 3 and 4 induced cancer cell apoptosis via different pathway.Four copper(II) complexes with chiral Schiff-base ligands, [Cu(R-L1)2]·EtOAc (1) and [Cu(S-L1)2]·EtOAc (2), [Cu(R-L2)2]·EtOAc (3) and [Cu(S-L2)2]·EtOAc (4), (R/S-HL1 = (R/S)-(1-naththyl)-salicylaldimine, R/S-HL2 = (R/S)-(1-naththyl)-3-methoxysalicylaldimine, EtOAc = ethyl acetate) were synthesized to serve as artificial nucleases and anticancer drugs. All complexes and R/S-HL1 ligands were structurally characterized by X-ray crystallography. The interaction of these complexes with CT-DNA was researched via several spectroscopy methods, which indicates that complexes bind to CT-DNA by moderate intercalation binding mode. Moreover, DNA cleavage experiments revealed that the complexes exhibited remarkable DNA cleavage activities in the presence of H2O2via the generation of hydroxyl radical. Particularly, complex 4 also could nick DNA with the production of 1O2. And all complexes exhibited excellent cytotoxicity to MDA-MB-231, A549 and Hela human cancer cells in micromole magnitude. Furthermore, complex 4 exhibited comparable cytotoxic effect to cisplatin against the proliferation of MDA-MB-231 and A549 cancer cells, as well as showed better anticancer ability to the three cancer cells than the other complexes. The results of cell cycle analysis indicated that complexes 3–4 could induce G2/M phase cell cycle arrest. Furthermore, MDA-MB-231 cells treated with 3 and 4 were subjected to apoptosis and death by generation of ROS and the activation of caspase-3. Interestingly, the chiral complexes 3 and 4 may induce cell apoptosis through extrinsic and mitochondrial intrinsic pathway, respectively.Chiral enantiomers 3 and 4 induced cancer cell apoptosis via different pathway.
Co-reporter:Xue-Quan Zhou, Qian Sun, Lin Jiang, Si-Tong Li, Wen Gu, Jin-Lei Tian, Xin Liu and Shi-Ping Yan
Dalton Transactions 2015 vol. 44(Issue 20) pp:9516-9527
Publication Date(Web):07 Apr 2015
DOI:10.1039/C5DT00931F
Six novel copper(II) complexes of [CuL1Cl]ClO4 (1), [CuL1(acac)]PF6 (2), [CuL2(R)Cl]2(PF6)2 (3), [CuL2(S)Cl]2(PF6)2 (4), [CuL2(R)(acac)]PF6 (5) and [CuL2(S)(acac)]PF6 (6), (L1 = 1-naphthyl-N,N-[bis(2-pyridyl)methyl]amine, L2 = R/S-1-naphthyl-N,N-[bis(2-pyridyl)methyl]ethanamine, acac = diacetone) were synthesized to serve as artificial nucleases. All complexes were structurally characterized using X-ray crystallography. The crystal structures showed the presence of distorted square-planar CuLCl (1, 3 and 4) and distorted tetragonal-pyramidal CuL(acac) (2, 5 and 6) geometry. The interaction of these complexes with calf thymus DNA (CT-DNA) was researched by means of several spectroscopy methods, which indicated that the complexes were bound to CT-DNA by an intercalation binding mode. DNA cleavage experiments revealed that the complexes exhibited remarkable DNA cleavage activities in the presence of H2O2, and single oxygen (1O2) or hydroxyl radicals may serve as the major cleavage active species. In particular, the in vitro cytotoxicity of the complexes on four human cancer cell lines (HeLa, MCF-7, Bel-7404 and HepG-2) demonstrated that the six compounds had broad-spectrum anti-cancer activity with low IC50 values. The stronger cytotoxicity and DNA cleavage activity of the chiral enantiomers compared with chiral analogues verified the influence of chirality on the antitumor activity of complexes. Meanwhile, the protein binding ability was revealed by quenching of tryptophan emission with the addition of complexes using BSA as a model protein. The results indicated that the quenching mechanism of BSA by the complexes was a static process.
Co-reporter:Jun-Ling Li, Lin Jiang, Bi-Wei Wang, Jin-Lei Tian, Wen Gu, Xin Liu, Shi-Ping Yan
Journal of Inorganic Biochemistry 2015 Volume 145() pp:19-29
Publication Date(Web):April 2015
DOI:10.1016/j.jinorgbio.2014.11.003
•With same ligand, three structural difference complexes have been synthesized.•1, with two rare μ3 -η1, η1, η1-CrO42− moieties, is a tetranuclear complex.•Complexes show effective DNA binding and cleavage activity.•Complexes could quench fluorescence of BSA in a static quenching process.•1 shows about 6-fold higher anticancer activity against HeLa cell than cisplatin.Three new Co(II) complexes, [Co4(L)2(μ3-CrO4)2](ClO4)2 · 2CH3CN (1), [Co2(L)(μ2-na)(H2O)](ClO4)2 (2) and [Co2(L)(μ2-ba)](ClO4)2 · 0.5CH3CN (3) (Hna = nicotinic acid, Hba = benzoic acid, HL = N,N,N′,N′-tetrakis (2-quinolylmethyl)-1,3-diaminopropan-2-ol), have been synthesized and characterized by various physicochemical techniques. The Co(II) centers are connected by endogenous alkoxy bridge from L− and various extrinsic auxiliary linkers, some of which display coordination number asymmetry (5, 6-coordinated for 1 and 2; 5, 5-coordinated for 3). It is worth mentioning that complex 1 contains two rare reported μ3-η1, η1, η1-CrO42− moieties. Susceptibility data of three complexes indicated intramolecular antiferromagnetic coupling of high-spin Co(II) atoms with exchange integral values (J) − 14.94 cm− 1, − 11.26 cm− 1 and − 13.66 cm− 1 for 1, 2 and 3, respectively. Interaction of compounds with calf thymus DNA (CT-DNA) have been investigated by absorption spectral titration, ethidium bromide (EB) displacement assay and viscosity measurement, which revealed that compounds bound to CT-DNA with a moderate intercalative mode, accompanied the affinities order: 1 > 2 ≈ 3. Three complexes exhibit oxidative cleavage of pBR322 plasmid DNA including a reliance on H2O2 as the activator. Compound 1 demonstrates an increased DNA cleavage activity as compared with 2 and 3, which could degrade super coiled DNA (SC DNA) into nicked coiled DNA (NC DNA) in lower concentration (5 μM). Moreover, all compounds could quench the intrinsic fluorescence of bovine serum albumin (BSA) in a static quenching process. Complex 1 also shows higher anticancer activity than cisplatin with lower IC50 value of incubation for both 24 h and 48 h.The tetranuclear CoII complex, containing two rare μ3 -η1, η1, η1-CrO42− moieties and bearing coordination number asymmetry, displays good DNA cleavage activity in a low concentration (5 μM) in the presence of H2O2.
Co-reporter:Chun-Yan Gao, Zhong-Ying Ma, Yong-Po Zhang, Si-Tong Li, Wen Gu, Xin Liu, Jin-Lei Tian, Jing-Yuan Xu, Jin-Zhong Zhao and Shi-Ping Yan
RSC Advances 2015 vol. 5(Issue 39) pp:30768-30779
Publication Date(Web):20 Mar 2015
DOI:10.1039/C4RA16755D
Four closely related mononuclear nickel(II) complexes [Ni(L)(diimine)Cl](ClO4) (1–4), where L is a tridentate polypyridyl ligand of 4-methyl-N,N-bis(pyridin-2-ylmethyl)aniline and diimine is 2,2′-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2), dipyrido[3,2-d:20,30-f]quinoxaline (dpq, 3) or dipyrido[3,2-a:20,30-c]phenazine (dppz, 4), have been synthesized and characterized using various physico-chemical techniques. All Ni centers adopt a distorted octahedral geometry with N5Cl donor sets. From 1 to 4, the dihedral angles between the benzene ring of L and the plane of the diimine gradually decline (52.5–6.8°), leading to increasing steric encumbrance. The interactions of the complexes with CT-DNA and BSA have been explored using absorption and emission spectral methods. These complexes display binding propensity to CT-DNA in the order: 4 (dppz) > 3 (dpq) > 2 (phen) > 1 (bpy), and the quenching mechanisms of BSA by all the complexes are static procedures. In the absence of any external agents, only 1 (bpy) and 4 (dppz) exhibit apparent DNA cleavage activity, while with the addition of GSH or on the irradiation with UV-A light of 365 nm, the DNA cleavage abilities of the complexes are obviously enhanced, which vary as 1 > 2 > 3 > 4 (GSH) and 4 > 3 > 2 > 1 (UV-A). In addition, the in vitro cytotoxicity of the complexes on tumor cells lines (MCF-7, HepG-2 and SGC-7901) have been examined by MTT and the morphological assessment obtained using Hoechst 33342 staining reveals that 4 induces apoptosis against HepG-2.
Co-reporter:Jun-Ling Li, Lin Jiang, Bi-Wei Wang, Jin-Lei Tian, Wen Gu, Xin Liu and Shi-Ping Yan
New Journal of Chemistry 2015 vol. 39(Issue 1) pp:529-538
Publication Date(Web):30 Oct 2014
DOI:10.1039/C4NJ00876F
Two new mononuclear complexes [CuL(η2-SO4)] (1) and [NiL(η-SO4)(H2O)2]·3(H2O)·CH3CH2OH (2), where L is bis(2-quinolinyl methyl) benzyl-amine, have been synthesized and characterized by X-ray crystallography, ESI-MS and elemental analysis techniques. Complex 1 possesses a distorted square pyramidal geometry while complex 2 possesses distorted octahedral geometry. Interestingly, 2 dissolves in DMF–H2O mixed solvent, while 1 shows good water solubility. Both electronic absorption and EB displacement assay show that these complexes could bind to CT-DNA through partial intercalation. Though the DNA-binding abilities of 1 and 2 are similar, their chemical nuclease activities exhibit a great difference. Under physiological conditions, 1 could effectively convert pBR322 plasmid DNA from Form I to Form II at about 50 μM without any external agent, which shows self-oxidation cleavage activity; however, 2 shows poor DNA cleavage activity at 75 μM even in the presence of H2O2. At the same time, 1 also displays about 11-fold potential than 2 against HeLa cells with IC50 values 6.89 μM (1) and 74.85 μM (2). The IC50 value of 1 is even lower than the widely used drug cisplatin. The redox activity of Cu(II) and Ni(II) may play a main role in the biological activity of the two complexes, but the exact mechanism is still unclear. In addition, interactions of complexes with BSA have also been explored by fluorescence and UV-visible spectroscopic methods. The results indicated that complexes could quench the intrinsic fluorescence of BSA in a static quenching process.
Co-reporter:Bi-Wei Wang;Lin Jiang;Si-Sheng Shu;Bo-Wen Li;Zhang Dong;Wen Gu;Xin Liu
Chirality 2015 Volume 27( Issue 2) pp:142-150
Publication Date(Web):
DOI:10.1002/chir.22403
Abstract
Two new chiral mononuclear Mn(III) complexes, [MnL(R)Cl (C2H5OH)]•C2H5OH (1) and [MnL(S) (CH3OH)2]Cl•CH3OH (2), {H2L = (R,R)-or (S,S)-N,N’-bis-(2-hydroxy-1-naphthalidehydene)-cyclohexanediamine} were synthesized and characterized by various physicochemical techniques. Bond valence sum (BVS) calculations and the Jahn-Teller effect indicate that the Mn centers are in a +3 oxidation state. The statuses of the two complexes in the solution were confirmed as a pair of enantiomers by electrospray ionization, mass spectrometry (ESI-MS) spectrum. The binding ability of the complexes with calf thymus CT-DNA was investigated by spectroscopic and viscosity measurements. Both of the complexes could interact with CT-DNA via an intercalative mode with the order of 1 (R-enantiomer) >2 (S-enantiomer). Under the physiological conditions, the two compounds exhibit efficient DNA cleavage activities without any external agent, which also follows the order of R-enantiomer > S-enantiomer. Interestingly, the concentration-dependent DNA cleavage experiments indicate an optimal concentration of 17.5 μM. In addition, the interaction of the compounds with bovine serum albumin (BSA) was also investigated, which indicated that the complexes could quench the intrinsic fluorescence of BSA by a static quenching mechanism. Chirality 27:142-150, 2015. © 2014 Wiley Periodicals, Inc.
Co-reporter:Jing Lu, Qian Sun, Jun-Ling Li, Lin Jiang, Wen Gu, Xin Liu, Jin-Lei Tian, Shi-Ping Yan
Journal of Inorganic Biochemistry 2014 Volume 137() pp:46-56
Publication Date(Web):August 2014
DOI:10.1016/j.jinorgbio.2014.03.015
Two water-soluble ternary copper(II) complexes of [Cu(L)Cl](ClO4) (1) and [Cu(L)Br2] (2) (L = (2-((quinolin-8-ylimino)methyl)pyridine)) were prepared and characterized by various physico-chemical techniques. Both 1 and 2 were structurally characterized by X-ray crystallography. The crystal structures show the presence of a distorted square-pyramidal CuN3Cl2 (1) or CuN3Br2 (2) geometry in which Schiff-base L acts as a neutral tridentate ligand. Both complexes present intermolecular π–π stacking interactions between quinoline and pyridine rings. The interaction of two complexes with CT-DNA (calf thymus-DNA) and BSA (bovine serum albumin) was studied by means of various spectroscopy methods, which revealed that 1 and 2 could interact with CT-DNA through intercalation mode, and could quench the intrinsic fluorescence of BSA in a static quenching process. Furthermore, the competition experiment using Hoechst 33258 indicated that two complexes may bind to CT-DNA by a minor groove. DNA cleavage experiments indicate that the complexes exhibit efficient DNA cleavage activities without any external agents, and hydroxyl radical (HO) and singlet oxygen (1O2) may serve as the major cleavage active species. Notably, the in vitro cytotoxicity of the complexes on three human tumor cells lines (HeLa, MCF-7, and A549) demonstrates that two compounds have broad-spectrum antitumor activity with quite low IC50 ranges of 0.43–1.85 μM. Based on the cell cycle experiments, 1 and 2 could delay or inhibit cell cycle progression through the S phase.The complexes exhibit efficient DNA cleavage activity without any external agents. They could quench the intrinsic fluorescence of BSA in a static quenching process.
Co-reporter:Qian Sun;Jing Lu;Jun-Ling Li;Lin Jiang;Wen Gu;Xin Liu;Shi-Ping Yan
Applied Organometallic Chemistry 2014 Volume 28( Issue 4) pp:259-266
Publication Date(Web):
DOI:10.1002/aoc.3118
Three new mononuclear cobalt(II) complexes containing ligands with extended planar quinoxaline moieties, {dipyrido[3,2-a:2′,3′-c]phenazine (dppz) or dipyrido[3,2-d:2′,3′-f]quinoxaline (dpq)}, viz. [Co(dppz)(acac)2] · CH3OH (1), [Co(dpq)(tfnb)2] (2) and [Co(dpq)(dbm)2] (3), where acac = acetylacetonate, tfnb = benzoyltrifluoroacetone and dbm = dibenzoylmethane, have been synthesized and structurally characterized as octahedral complexes. The binding ability of the complexes with calf thymus (CT)-DNA has been investigated by spectroscopic and viscosity measurements. Results indicate that all complexes bind to CT-DNA via intercalative mode, and the DNA binding affinity of dppz complex 1 is apparently stronger than that of dpq complexes 2 and 3. Furthermore, DNA photocleavage experiments indicate that these complexes are efficient DNA cleaving agents in UV-A (365 nm) and hydroxyl radical (HO·), singlet oxygen (1O2) and superoxide anion (1O2−) serve as the major cleavage active species. In addition, interaction of the complexes with bovine serum albumin (BSA) was investigated using UV − visible and fluorescence methods, which indicated that all complexes could quench the intrinsic fluorescence of BSA in a static quenching process. Copyright © 2014 John Wiley & Sons, Ltd.
Co-reporter:Jing Lu, Jun-Ling Li, Qian Sun, Lin Jiang, Wen Gu, Xin Liu, Jin-Lei Tian, Shi-Ping Yan
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 2014 130() pp: 390-396
Publication Date(Web):
DOI:10.1016/j.saa.2014.04.018
Co-reporter:Gong-Jun Chen, Zhi-Gang Wang, Xin Qiao, Jing-Yuan Xu, Jin-Lei Tian, Shi-Ping Yan
Journal of Inorganic Biochemistry 2013 Volume 127() pp:39-45
Publication Date(Web):October 2013
DOI:10.1016/j.jinorgbio.2013.06.002
•Some lanthanide-based complexes have been synthesized and structurally characterized.•The compounds exhibit efficience photo-induced DNA cleavage activities.•The compounds have the potential to act as effective anticancer drugs.As a continuing investigation of our previous studies about the influence of the different rare earth metal ions on the bioactivity, a family of heavy rare earth metal complexes, [RE(acac)3(dpq)] (RE = Tb (1), Dy (2), Ho (3), Er (4), Tm (5), Yb (6), Lu (7)) and [RE(acac)3(dppz)]·CH3OH (RE = Tb (8), Dy (9), Ho (10), Er (11), Tm (12), Yb (13), Lu (14) viz. acetylacetonate (acac), dipyrido[3,2-d:20,30-f]quinoxaline (dpq), dipyrido[3,2-a:20,30-c] phenazine (dppz)), has been synthesized and their biological activities were also investigated. On the irradiation with UV-A light of 365 nm or ambient light, all complexes exhibit efficient DNA cleavage activity via the mechanistic pathway involving the formation of singlet oxygen and hydroxyl radical as the reactive species. In addition, the in vitro cytotoxicity of these complexes on HeLa cells has been examined by MTT assay, which indicate that these compounds have the potential to act as effective anticancer drugs. The results of the above biological experiments also reveal that the choice of different rare earth metal ions has little influence on the DNA binding, DNA cleavage and cytotoxicity.A family of heavy rare earth complexes, [RE(acac)3(dpq)] and [RE(acac)3(dppz)]CH3OH have been synthesized, their DNA binding and photo-induced DNA cleavage activity are investigated.DNA binding, DNA cleavage and cytotoxicity not have affected by rare earth metal elements.
Co-reporter:Gong-Jun Chen, Zhi-Gang Wang, Ying-Ying Kou, Jin-Lei Tian, Shi-Ping Yan
Journal of Inorganic Biochemistry 2013 Volume 122() pp:49-56
Publication Date(Web):May 2013
DOI:10.1016/j.jinorgbio.2013.01.010
A family of Phterpy complexes, [Mn(Phterpy)2][N(CN)2]2·0.5H2O (1), [Fe(Phterpy)2](NO3)2 (2), [Ni(Phterpy)2](NO3)2 (3), [Ni(Phterpy)2]Cl2·10H2O (4), [Cd(Phterpy)2](NO3)2·2H2O (5) and [Zn(Phterpy)Cl2] (6) (Phterpy = 4′-phenyl-2,2′:6′,2″-terpyridine), have been synthesized and structurally characterized, and their DNA binding and photo-induced DNA cleavage activities have been investigated. These complexes display binding propensity to the CT-DNA giving a relative order: 1 > 4 > 3, 5, 2, 6. Under dark or ambient lighting conditions, all complexes show no efficient DNA cleavage activity to pBR322 DNA. While on irradiation with UV-A light of 365 nm, complexes of 1, 3 and 4 exhibit significant cleavage activities. In the presence of H2O2 as a revulsant or an activator, the cleavage ability of complex 2 is obviously enhanced. Complexes 5 and 6 do not exhibit any apparent chemical nuclease activities under irradiation conditions or with the addition of H2O2. The DNA photo-induced cleavage activities are consistent with the number of single-electron in the central metal ion of complexes and singlet oxygen and hydroxyl radical are found as the reactive oxygen species.In attempt to obtain more insight on the selectivity and efficiency of DNA cleavage with different transition metal complexes, herein, we have prepared a series of mononuclear d-metal complexes and investigated their DNA cleavage activities.Highlights► A family of Phterpy complexes have been synthesized and structurally characterized. ► Their DNA binding and photo-induced DNA cleavage activities have been studied. ► Singlet oxygen and hydroxyl radical are found as the reactive oxygen species.
Co-reporter:Gong-Jun Chen, Xin Qiao, Chun-Yan Gao, Guang-Jun Xu, Zhi-Ling Wang, Jin-Lei Tian, Jing-Yuan Xu, Wen Gu, Xin Liu, Shi-Ping Yan
Journal of Inorganic Biochemistry 2012 Volume 109() pp:90-96
Publication Date(Web):April 2012
DOI:10.1016/j.jinorgbio.2011.12.009
A family of light rare earth complexes, [RE(acac)3(dpq)] (RE = La (1), Ce (2), Pr (3), Nd (4), Sm (5)) and [RE(acac)3(dppz)].CH3OH (RE = La (6), Ce (7), Pr (8), Nd (9), Sm (10) viz. acetylacetonate (acac), dipyrido[3,2-d:20,30-f]quinoxaline (dpq), dipyrido[3,2-a:20,30-c] phenazine (dppz)), have been synthesized and structurally characterized. Binding interactions of these complexes with CT-DNA and their photo-induced DNA cleavage activity with pBR 322 DNA are also investigated. These complexes have strong DNA binding interaction (Kb ≈ 105 M− 1 and Kapp ≈ 105 M− 1)and the binding propensity to CT-DNA decrease with the order: dppz complexes > dpq complexes. Furthermore, DNA photocleavage experiments indicate that these complexes are efficient DNA cleaving agents in UV-A (365 nm) and ambient light in the absence of any external reagents. Hydroxyl radical (HO•) and singlet oxygen (1O2) are the major cleavage active species from the machanistic studies. Moreover, cell cytotoxicity studies of these complexes on HeLa, K562 and MDA-MB-231 cells indicate that they have the potential to act as effective metal-based anti-cancer drugs.A family of light rare earth complexes, [RE(acac)3(dpq)] and [RE(acac)3(dppz)]CH3OH have been synthesized and their DNA binding and photo-induced DNA cleavage activity are investigated.The light rare earth metal elements have less effect in the DNA binding, DNA cleavage and cytotoxicity.
Co-reporter:Jing Qian, Liping Wang, Wen Gu, Xin Liu, Jinlei Tian and Shiping Yan
Dalton Transactions 2011 vol. 40(Issue 20) pp:5617-5624
Publication Date(Web):05 Apr 2011
DOI:10.1039/C0DT01659D
Two water-soluble zinc complexes, [Zn(L)Cl2] (1) and [Zn2(L)2(μ-C2O4)(H2O)2]·(ClO4)2·CH3OH (2) (L = N,N-bis(2-pyridylmethyl)methylamine), were prepared to serve as nuclease mimics. The complexes were characterized by X-ray, IR and UV-vis spectroscopy as well as ESI-MS. The electrospray mass spectrum of 2 in solution indicates that dinuclear ion [Zn2(L)2(μ-C2O4)(ClO4)]+ (3) is the active species. UV-Vis absorption and fluorescence spectroscopy studies show that the complexes partially intercalate to CT-DNA. In the absence of reducing agent, supercoiled plasmid DNA cleavage by the complexes 1 and 3 was performed and the hydrolytic mechanism was demonstrated by adding standard radical scavengers.
Co-reporter:Lin Jiang, Dong-Yan Zhang, Jing-Jing Suo, Wen Gu, Jin-Lei Tian, Xin Liu and Shi-Ping Yan
Dalton Transactions 2016 - vol. 45(Issue 25) pp:NaN10248-10248
Publication Date(Web):2016/05/11
DOI:10.1039/C6DT00380J
A series of NiII, CoII, ZnII and CdII complexes 1–9 with polytopic Schiff base ligands have been synthesized. The single-crystal X-ray crystallography results show that tetranuclear complexes 1–6 have common face-shared defective dicubane cores, whereas trinuclear CdII complexes 7–9 are almost linear entities. Synthesis methods (solvent evaporation and hydrothermal synthesis), reaction conditions (pH, solvents and dosage) and coligands (azide, methanol, chloride and acetate) play vital roles in determining the final structure of the complexes and therefore their magnetic properties. In complexes 1–6, the terminal and central M2+ ions are connected through mixed bridges, μ-phenoxido/μ1,1,1-X and μ-Oalphatic/μ1,1,1-X, while central two M2+ ions are linked by double bridges, μ1,1,1-X (X = azido and methoxido groups for 1 and 2–6 respectively). For complex 1, two central NiII ions are connected through two μ1,1,1-N3− which is relatively less reported. For complexes 7–9, there are two kinds of CdII, the centre CdII ions are eight-coordinated with triangle dodecahedral geometries, while the two side CdII ions are six-coordinated with trigonal prism geometries using chlorides or acetates as terminal ligands. Magnetic susceptibility measurements (χM) for compounds 1–6 have been performed, and they reveal predominant ferromagnetic exchange interactions in CoII and NiII tetramers. The photoluminescence studies show that the ZnII complex 6 and three CdII complexes 7–9 have strong fluorescence, and the lifetimes are measured to be in the 102 nanosecond timescale.
Co-reporter:Jing Qian, Liping Wang, Wen Gu, Xin Liu, Jinlei Tian and Shiping Yan
Dalton Transactions 2011 - vol. 40(Issue 20) pp:NaN5624-5624
Publication Date(Web):2011/04/05
DOI:10.1039/C0DT01659D
Two water-soluble zinc complexes, [Zn(L)Cl2] (1) and [Zn2(L)2(μ-C2O4)(H2O)2]·(ClO4)2·CH3OH (2) (L = N,N-bis(2-pyridylmethyl)methylamine), were prepared to serve as nuclease mimics. The complexes were characterized by X-ray, IR and UV-vis spectroscopy as well as ESI-MS. The electrospray mass spectrum of 2 in solution indicates that dinuclear ion [Zn2(L)2(μ-C2O4)(ClO4)]+ (3) is the active species. UV-Vis absorption and fluorescence spectroscopy studies show that the complexes partially intercalate to CT-DNA. In the absence of reducing agent, supercoiled plasmid DNA cleavage by the complexes 1 and 3 was performed and the hydrolytic mechanism was demonstrated by adding standard radical scavengers.
Co-reporter:Xue-Quan Zhou, Qian Sun, Lin Jiang, Si-Tong Li, Wen Gu, Jin-Lei Tian, Xin Liu and Shi-Ping Yan
Dalton Transactions 2015 - vol. 44(Issue 20) pp:NaN9527-9527
Publication Date(Web):2015/04/07
DOI:10.1039/C5DT00931F
Six novel copper(II) complexes of [CuL1Cl]ClO4 (1), [CuL1(acac)]PF6 (2), [CuL2(R)Cl]2(PF6)2 (3), [CuL2(S)Cl]2(PF6)2 (4), [CuL2(R)(acac)]PF6 (5) and [CuL2(S)(acac)]PF6 (6), (L1 = 1-naphthyl-N,N-[bis(2-pyridyl)methyl]amine, L2 = R/S-1-naphthyl-N,N-[bis(2-pyridyl)methyl]ethanamine, acac = diacetone) were synthesized to serve as artificial nucleases. All complexes were structurally characterized using X-ray crystallography. The crystal structures showed the presence of distorted square-planar CuLCl (1, 3 and 4) and distorted tetragonal-pyramidal CuL(acac) (2, 5 and 6) geometry. The interaction of these complexes with calf thymus DNA (CT-DNA) was researched by means of several spectroscopy methods, which indicated that the complexes were bound to CT-DNA by an intercalation binding mode. DNA cleavage experiments revealed that the complexes exhibited remarkable DNA cleavage activities in the presence of H2O2, and single oxygen (1O2) or hydroxyl radicals may serve as the major cleavage active species. In particular, the in vitro cytotoxicity of the complexes on four human cancer cell lines (HeLa, MCF-7, Bel-7404 and HepG-2) demonstrated that the six compounds had broad-spectrum anti-cancer activity with low IC50 values. The stronger cytotoxicity and DNA cleavage activity of the chiral enantiomers compared with chiral analogues verified the influence of chirality on the antitumor activity of complexes. Meanwhile, the protein binding ability was revealed by quenching of tryptophan emission with the addition of complexes using BSA as a model protein. The results indicated that the quenching mechanism of BSA by the complexes was a static process.