A H2O2 Self-Charging Zinc Battery with Ultrafast Power Generation and Storage.

Self-charging power systems are considered as promising alternatives for off-grid energy devices to provide sustained electricity supply. However, the conventional self-charging systems are severely restricted by the energy availability and time-consuming charging process as well as insufficient capacity. Herein, we developed an ultrafast H2O2 self-charging aqueous Zn/NaFeFe(CN)6 battery, which simultaneously integrates the H2O2 power generation and energy storage into a battery configuration. In such battery, the chemical energy conversion of H2O2 can generate electrical energy to self-charge the battery to 1.7 V through the redox reaction between H2O2 and NaFeFe(CN)6 cathode. The thermodynamically and kinetically favorable redox reaction contributes to the ultrafast H2O2 self-charging rate and the extremely short self-charging time within 60 seconds. Moreover, the rapid H2O2 power generation can promptly compensate the energy consumption of battery to provide continuous electricity supply. Impressively, this self-charging battery shows excellent scalability of device architecture and can be designed to a H2O2 single-flow battery of 7.06 Ah to extend the long-term energy supply. This work not only provides a route to design self-charging batteries with fast charging rate and high capacity, but also pushes forward the development of self-charging power systems for advanced large-scale energy storage applications.

A High-Energy Aqueous All-Sulfur Battery.

Rechargeable aqueous batteries are promising energy storage devices because of their high safety and low cost. However, their energy densities are generally unsatisfactory due to the limited capacities of ion-inserted electrode materials, prohibiting their widespread applications. Herein, a high-energy aqueous all-sulfur battery was constructed via matching S/Cu2 S and S/CaSx redox couples. In such batteries, both cathodes and anodes undergo the conversion reaction between sulfur/metal sulfides redox couples, which display high specific capacities and rational electrode potential difference. Furthermore, during the charge/discharge process, the simultaneous redox of Cu2+ ion charge-carriers also takes place and contributes to a more two-electron transfer, which doubles the capacity of cathodes. As a result, the assembled aqueous all-sulfur batteries deliver a high discharge capacity of 447 mAh g-1 based on total mass of sulfur in cathode and anode at 0.1 A g-1 , contributing to an enhanced energy density of 393 Wh kg-1 . This work will widen the scope for the design of high-energy aqueous batteries.

Six-Electron-Redox Iodine Electrodes for High-Energy Aqueous Batteries.

Iodine (I2 ) shows great promising as the active material in aqueous batteries due to its distinctive merits of high abundance in ocean and low cost. However, in conventional aqueous I2 -based batteries, the energy storage mechanism of I- /I2 conversion is only two-electron redox reaction, limiting their energy density. Herein, six-electron redox chemistry of I2 electrodes is achieved via the synergistic effect of redox-ion charge-carriers and halide ions in electrolytes. The redox-active Cu2+ ions in electrolytes induce the conversion between Cu2+ ions and I2 to CuI at low potential. Simultaneously, the Cl- ions in electrolytes activate the I2 /ICl redox couple at high potential. As a result, in our case, I2 -based battery system with six-electron redox is developed. Such energy storage mechanism with six-electron redox leads to high discharge potential and capacity, excellent rate capability, as well as stable cycling behavior of I2 electrodes. Impressively, six-electron-redox I2 cathodes can match various aqueous metal (e.g. Zn, Mn and Fe) anodes to construct metal||I2 hybrid batteries. These hybrid batteries not only deliver enhanced capacities, but also exhibit higher operate voltages, which contributes to superior energy densities. Therefore, this work broadens the horizon for the design of high-energy aqueous I2 -based batteries.

High-Energy Aqueous/Organic Hybrid Batteries Enabled by Cu2+ Redox Charge Carriers.

Lithium||sulfur (Li||S) batteries are considered as one of the promising next-generation batteries due to the high theoretical capacity and low cost of S cathodes, as well as the low redox potential of Li metal anodes (-3.04 V vs. standard hydrogen electrode). However, the S reduction reaction from S to Li2 S leads to limited discharge voltage and capacity, largely hindering the energy density of Li||S batteries. Herein, high-energy Li||S hybrid batteries were designed via an electrolyte decoupling strategy. In cathodes, S electrodes undergo the solid-solid conversion reaction from S to Cu2 S with four-electron transfer in a Cu2+ -based aqueous electrolyte. Such an energy storage mechanism contributes to enhanced electrochemical performance of S electrodes, including high discharge potential and capacity, superior rate performance and stable cycling behavior. As a result, the assembled Li||S hybrid batteries exhibit a high discharge voltage of 3.4 V and satisfactory capacity of 2.3 Ah g-1 , contributing to incredible energy density. This work provides an opportunity for the construction of high-energy Li||S batteries.

Multifunctional Electrolyte Additive Enables Highly Reversible Anodes and Enhanced Stable Cathodes for Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) are charming devices for large-scale power grid energy storage because of their characteristics of environment friendliness, low cost, high abundance, and safe operation. However, the inferior reversibility of the anode and the loss of cathode capacity always hinder the application of AZIBs. Herein, we propose a simple multifunctional electrolyte additive, diethylenetriamine (DETA), which can inhibit the formation of zinc dendrites and the occurrence of side reactions on the anode, reconstruct the solvated structure and uniform ion flux in the electrolyte, restrain the dissolution of active materials, and induce the crystal transformation on the cathode concurrently. Molecular dynamics Simulation and density functional theory both verified the extraordinary efficacy of DETA. With the assistance of DETA, the Zn anode gained a life of up to 2000 h, and the cathode with commercial V2O5 retained a capacity of 125.2 mA h g-1 at the 1000th discharge process. From the perspective of practical application, this work can open up the application prospect of AZIBs in large-scale energy storage and provide reference for the subsequent works. The findings will greatly promote the application of AZIBs in large-scale energy storage and provide more inspiration for future research.

Antitumor effects of new glycoconjugated PtII agents dual-targeting GLUT1 and Pgp proteins.

A novel and highly efficient dual-targeting PtII system was designed to improve the drug delivery capacity and selectivity in cancer treatment. The dual-targeting monofunctional PtII complexes (1-8) having glycosylated pendants as tridentated ligand were achieved by introducing glycosylation modification in the thioaminocarbazone compounds with potential lysosomal targeting ability. The structures and stability of 1-8 were further established by various techniques. Molecular docking studies showed that 2 was efficiently docked into glucose transporters protein 1 (GLUT1) and P-glycoprotein (Pgp) proteins with the optimal CDocker-interaction-energy of -64.84 and -48.85 kcal mol-1. Complex 2 with higher protein binding capacity demonstrated significant and broad-spectrum antitumor efficacy in vitro, even exhibiting a half maximal inhibitory concentration (IC50) value (∼10 µM) than cisplatin (∼17 µM) against human lung adenocarcinoma cells (A549). The inhibitor experiment revealed GLUT-mediated uptake of 2, and the subcellular localization experiment in A549 also proved that 2 could be localized in the lysosome, thereby causing cell apoptosis. Moreover, cellular thermal shift assay (CETSA) confirmed the binding of 2 with the target proteins of GLUT1 and Pgp. The above results indicated that 2 represents a potential anticancer candidate with dual-targeting functions.

Synthesis, crystal structures, anticancer activities and molecular docking studies of novel thiazolidinone Cu(II) and Fe(III) complexes targeting lysosomes: special emphasis on their binding to DNA/BSA.

Novel [CuL2Cl]Cl·H2O (1) and [FeL2Cl2]Cl·MeOH·CHCl3·H2O (2) complexes of (Z)-N'-((E)-3-methyl-4-oxothiazolidin-2-ylidene)picolinohydrazonamide (L) as antitumor agents were designed and synthesized in order to explore DNA and serum albumin interaction. X-ray diffraction revealed that both 1 and 2 were a triclinic crystal system with P1̄ space group, which consisted of a positive electric main unit, a negative chloride ion and some solvent molecules. The complexes with DNA and bovine serum albumin (BSA) were studied by fluorescence and electronic absorption spectrometry. The results indicated that there was moderate intercalative binding mode between the complexes and DNA with Kapp values of 2.40 × 105 M-1 (1) and 6.49 × 105 M-1 (2). Agarose gel electrophoresis experiment showed that both 1 and 2 exhibited obvious DNA cleavage activity via an oxidative DNA damage pathway, and the cleavage activities of 1 were stronger than those of 2. Cytotoxicity assay showed that 1 had a more effective antitumor activity than 2. The two complexes were bound to BSA by a high affinity and quenched the fluorescence of BSA through a static mechanism. The thermodynamic parameters suggested that hydrophobic interactions played a key role in the binding process. The binding energy xpscore of 1 and 2 were -10.529 kcal mol-1 and -10.826 kcal mol-1 by docking studies, and this suggested that the binding process was spontaneous. Complex 1 displayed a lysosome-specific targeting behavior with a Pearson coefficient value of 0.82 by confocal laser scanning microscopy (CLSM), and accumulated in the lysosomes, followed by the disruption of lysosomal integrity.

Non-Metal Ion Co-Insertion Chemistry in Aqueous Zn/MnO2 Batteries.

The co-insertion of dual ions can often offer enhanced electrochemical performance for the aqueous zinc batteries. Although the insertion of non-metallic ions has been achieved in aqueous zinc batteries, the co-insertion chemistry of non-metallic cations is still a challenge. Here, a reversible H+ /NH4 + co-insertion/extraction mechanism was developed in an aqueous Zn/MnO2 battery system. The synergistic effect between the dual cations endows the aqueous batteries with the fast kinetics of ion diffusion and the reversible structure evolution of MnO2 . As a result, the Zn/MnO2 battery displays excellent rate capability and cycling performance. This work will pave the way toward the design of aqueous rechargeable batteries with non-metallic ions.

Thermal-Gated Polymer Electrolytes for Smart Zinc-Ion Batteries.

Smart self-protection is essential for addressing safety issues of energy-storage devices. However, conventional strategies based on sol-gel transition electrolytes often suffer from unstable self-recovery performance. Herein, smart separators based on thermal-gated poly(N-isopropylacrylamide) (PNIPAM) hydrogel electrolytes were developed for rechargeable zinc-ion batteries (ZIBs). Such PNIPAM-based separators not only display a pore structure evolution from opened to closed states, but also exhibit a surface wettability transition from hydrophilic to hydrophobic behaviors when the temperature rises. This behavior can suppress the migration of electrolyte ions across the separators, realizing the self-protection of ZIBs at high temperatures. Furthermore, the thermal-gated behavior is highly reversible, even after multiple heating/cooling cycles, because of the reversibility of temperature-dependent structural evolution and hydrophilic/hydrophobic transition. This work will pave the way for designing thermal-responsive energy-storage devices with safe and controlled energy delivery.

Recent Progress in the Electrolytes of Aqueous Zinc-Ion Batteries.

Rechargeable aqueous zinc-ion batteries (ZIBs) have garnered tremendous attention in the field of next energy storage devices due to their high safety, low cost, abundant resources, and eco-friendliness. As an important component of the zinc-ion battery, the electrolyte plays a vital role in the electrochemical properties, since it will provide a pathway for the migrations of the zinc ions between the cathode and anode, and determine the ionic conductivity, electrochemically stable potential window, and reaction mechanism. In this Minireview, a brief introduction of electrochemical principles of the aqueous ZIBs is discussed and the recent advances of various aqueous electrolytes for ZIBs, including liquid, gel, and multifunctional hydrogel electrolytes are also summarized. Furthermore, the remaining challenges and future directions of electrolytes in aqueous ZIBs are also discussed, which could provide clues for the following development.

Three series of heterometallic NiII-LnIII Schiff base complexes: synthesis, crystal structures and magnetic characterization.

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 NiLn 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 (ß). 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.

Synthesis, magnetism and spectral studies of six defective dicubane tetranuclear {M4O6} (M = Ni(II), Co(II), Zn(II)) and three trinuclear Cd(II) complexes with polydentate Schiff base ligands.

A series of Ni(II), Co(II), Zn(II) and Cd(II) complexes with polytopic Schiff base ligands have been synthesized. The single-crystal X-ray crystallography results show that tetranuclear complexes have common face-shared defective dicubane cores, whereas trinuclear Cd(II) complexes 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 , the terminal and central M(2+) ions are connected through mixed bridges, µ-phenoxido/µ1,1,1-X and µ-Oalphatic/µ1,1,1-X, while central two M(2+) ions are linked by double bridges, µ1,1,1-X (X = azido and methoxido groups for and respectively). For complex , two central Ni(II) ions are connected through two µ1,1,1-N3(-) which is relatively less reported. For complexes , there are two kinds of Cd(II), the centre Cd(II) ions are eight-coordinated with triangle dodecahedral geometries, while the two side Cd(II) ions are six-coordinated with trigonal prism geometries using chlorides or acetates as terminal ligands. Magnetic susceptibility measurements (χM) for compounds have been performed, and they reveal predominant ferromagnetic exchange interactions in Co(II) and Ni(II) tetramers. The photoluminescence studies show that the Zn(II) complex and three Cd(II) complexes have strong fluorescence, and the lifetimes are measured to be in the 10(2) nanosecond timescale.

Copper complexes based on chiral Schiff-base ligands: DNA/BSA binding ability, DNA cleavage activity, cytotoxicity and mechanism of apoptosis.

Four copper(II) complexes with chiral Schiff-base ligands, [Cu(R-L(1))2]·EtOAc (1) and [Cu(S-L(1))2]·EtOAc (2), [Cu(R-L(2))2]·EtOAc (3) and [Cu(S-L(2))2]·EtOAc (4), (R/S-HL(1) = (R/S)-(1-naththyl)-salicylaldimine, R/S-HL(2) = (R/S)-(1-naththyl)-3-methoxysalicylaldimine, EtOAc = ethyl acetate) were synthesized to serve as artificial nucleases and anticancer drugs. All complexes and R/S-HL(1) 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 (1)O2. 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.

Two novel µ6-O(2-) bridged Co14/Ni14 hydroxamate clusters packed in distorted face-centered cubic patterns.

Two novel clusters [Co(µ6-O(2-))(sbha)12(sba)2 (DMF)7(DMA)]·(DMF)8 (1) and [Ni(µ6-O(2-))(sbha)12(sba)2(DMF)8] (2) (sH2bha = 4-bromo-benzohydroximic acid; sHba = 4-bromobenzene carboxylic acid; DMF = N,N-dimethylformamide; DMA = dimethylamine) have been synthesized. The novel body-centred µ6-O(2-) bridged Co14 and Ni14 clusters are packed in distorted face-centered cubic (FCC) patterns with different symmetries. Magnetic studies confirmed the antiferromagnetic exchange interactions between magnetic centers.

Synthesis, characterization, DNA/BSA interactions and anticancer activity of achiral and chiral copper complexes.

Six novel copper(ii) complexes of [CuCl]ClO4 (), [Cu(acac)]PF6 (), [CuCl]2(PF6)2 (), [CuCl]2(PF6)2 (), [Cu(acac)]PF6 () and [Cu(acac)]PF6 (), ( = 1-naphthyl-N,N-[bis(2-pyridyl)methyl]amine, = 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 (, and ) and distorted tetragonal-pyramidal CuL(acac) (, and ) 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 ((1)O2) 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.

Bio-relevant cobalt(II) complexes with compartmental polyquinoline ligand: synthesis, crystal structures and biological activities.

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-η(1), η(1), η(1)-CrO4(2-) 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.

Synthesis, crystal structure, and biological activities of two chiral mononuclear Mn((III)) complexes.

Two new chiral mononuclear Mn((III)) complexes, [MnL((R)) Cl (C2 H5 OH)]•C2 H5 OH () and [MnL((S)) (CH3 OH)2 ]Cl•CH3 OH (), {H2 L = (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 (R-enantiomer) > (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.

Synthesis, characterization, and biological activities of two Cu(II) and Zn(II) complexes with one polyquinoline ligand.

Two new complexes, [CuLCl]ClO4 (1) and [Zn2L2SO4(H2O)2](ClO4)2 (2) [L=N,N-bis(quinolin-2-ylmethyl)quinolin-8-amine], have been synthesized and structurally characterized. The interactions of two complexes with CT-DNA have been investigated by UV absorption, fluorescence spectroscopy, viscosity measurements and gel electrophoresis under physiological conditions. Results show that the complexes bind to CT-DNA with a moderate intercalative mode and exhibit efficient DNA cleavage activity on UV-A light of 365 nm. Furthermore, two complexes could quench the intrinsic fluorescence of BSA in a static quenching process based on BSA binding experiments. Notably, in vitro cytotoxicity study of two complexes on four human tumor cells lines (7404, HeLa, MCF-7, and HepG-2) indicate that both of them have the potential to act as effective anticancer drugs with low IC50 values.

Two water-soluble copper(II) complexes: synthesis, characterization, DNA cleavage, protein binding activities and in vitro anticancer activity studies.

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 ((1)O2) 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 0.43-1.85µM. Based on the cell cycle experiments, 1 and 2 could delay or inhibit cell cycle progression through the S phase.

A series of rare earth complexes with novel non-interpenetrating 3D networks: synthesis, structures, magnetic and optical properties.

A series of metal-organic framework {Ln(BCPBA)(H2O)}n {Ln = Nd (1), Sm (2), Eu (3), Tb (4), Dy (5)}; {[Ln(BCPBA)(H2O)](H2O)}n {Ln = Pr (6), Gd (7)} have been synthesized through the hydrothermal synthesis method. These compounds possess non-interpenetrating 3D networks with 10.1438 Å× 17.9149 Å rhombic channels along the [001] direction. The results of temperature-dependent magnetic susceptibility measurements indicate that compounds 4 and 7 exhibit Ln(III)Ln(III) antiferromagnetic interactions, while compound 5 exhibits Ln(III)Ln(III) ferromagnetic interactions. Frequency dependent out-of-phase signals were observed in alternating current (ac) magnetic susceptibility measurements which indicate that they have slow magnetic relaxation characteristics. The luminescent properties of 1, 2, 3, 4, and 5 are also discussed. Due to the good match between the lowest triplet state of the ligand and the resonant energy level of the lanthanide ion, compound 4 has longer fluorescence lifetime (τ1 = 400.0000 ms, τ2 = 1143.469 ms) and higher quantum yield (Φ = 42%) compared with other compounds.