Investigation of the Binding Behavior between the S-heterocyclic Aromatic Palladium(II) Complex and Human Serum Albumin: Spectroscopic Approach

The interaction of 1, 10-phenanthroline octhyldithiocarbamato palladium(II) nitrate ([Pd(Oct-dtc)(phen)]NO₃) with human serum albumin (HSA) has been investigated by various spectroscopic techniques under physiological conditions. Here, HSA was titrated with the Pd(II) complex, followed by UV–Vis absorption spectroscopy to estimate a binding constant (K_b) and other thermodynamic parameters. The results indicate that the Pd (II) complex has a high affinity for bind HSA. Thermodynamic analysis showed that the enthalpy (ΔH°) and entropy changes (ΔS°) are positive and Gibbs free energy change (ΔG°) is negative which indicated that hydrophobic interactions played the predominant role in the binding process. Fluorescence spectroscopy were used to show the mechanism and binding parameters of this interaction. Utilizing the Stern–Volmer equation, the Pd(II) complex quenched the intrinsic fluorescence of HSA via a static quenching procedure. The specific binding distances between the tryptophan (donor) proteins and Pd(II) complex (acceptor) were estimated by Forster resonance energy transfer. The CD results also showed the conformational changes on serum albumin upon binding with the Pd(II) complex.     

Polypyridyl CoII-Curcumin Complexes as Photoactivated Anticancer and Antibacterial Agents

Four new Co^II complexes, [Co(bpy)₂(acac)]Cl ( 1 ), [Co(phen)₂(acac)]Cl ( 2 ), [Co(bpy)₂(cur)]Cl ( 3 ), [Co(phen)₂(cur)]Cl ( 4 ), where bpy=2,2’-bipyridine ( 1 and 3 ), phen=1,10-phenanthroline ( 2 and 4 ), acac = acetylacetonate ( 1 and 2 ), cur=curcumin monoanion ( 3 and 4 ) have been designed, synthesized and fully characterized. The X-ray crystal structures of 1 and 2 indicated that the CoN₄O₂ core has a distorted octahedral geometry. The photoactivity of these complexes was tuned by varying the π conjugation in the ligands. Curcumin complexes 3 and 4 had an intense absorption band near 435 nm, which made them useful as visible-light photodynamic therapy agents; they also showed fluorescence with λ_em≈565 nm. This fluorescence was useful for studying their intracellular uptake and localization in MCF-7 breast cancer cells. The acetylacetonate complexes ( 1 and 2 ) were used as control complexes to understand the role of curcumin. The white-light-triggered anticancer profiles of the cytosol targeting complexes 3 and 4 were investigated in detail. These non-dark toxic complexes displayed significant apoptotic photo-cytotoxicity (under visible light) against MCF-7 cells through ROS generation. The control complexes 1 and 2 did not induce significant cell death in the light or dark. Interestingly, 1-4 produced a remarkable antibacterial response upon light exposure. Overall, the reported results here can increase the boundary of the Co^II-based anticancer and antibacterial drug development.     

[Ru(L)2(3-tppp)]2 + (L = bpy,phen) stabilizes two different forms of the human telomeric G-quadruplex DNA

The binding properties of new complexes [Ru(L)₂(3-tppp)]^2 + (L = bpy, phen) towards two different forms of the human telomeric G-quadruplexes DNA have been investigated by UV–Vis spectroscopy, fluorescent indicator displacement (FID) assays, fluorescence resonance energy transfer (FRET) melting assays and molecular docking studies. The molecular docking studies indicated that both complexes interacted with 22AG with the stoichiometric ratio of 1:1, but the two complexes showed different G-quadruplexed DNA binding affinity. Complex 2 bound to the G-quadruplexes DNA more tightly than complex 1 did. Moreover, the FRET melting assay revealed that both complexes could be potential stabilizers for G-quadruplex architectures. These studies are useful not only for better understanding of the interaction between the target G-quadruplexes DNA and metal complexes but also valuable in defining the best strategy to prepare metal complexes as potential anticancer drugs.     

Interaction of [Rh(2)(O(2)CCH(3))(4)(H(2)O)(2)] and [Rh(2)(O(2)CCH(OH)Ph)(2)(phen)(2)(H(2)O)(2)](O(2)C-CH(OH)Ph)(2) With Sulfhydryl Compounds and Ceruloplasmin

The interaction of binuclear rhodium(II) complexes [Rh(2)(OOCCH(3))(4)(H(2)O)(2)], [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] {OOCCH(OH)Ph}(2), [Rh(2)(OOCCH(3))(2)(bpy)(2)(H(2)O)(2)](OOCCH(3))(2) and [Rh(2)Cl(2)(OOCMe)(2)(bpy)(2)](3H(2)O) with ceruloplasmin, cysteine, glutathione and coenzyme A have been investigated using. UV-Vis and CD spectroscopies. The complexes containing phen or bpy at pH = 7.4 and 4.0 are readily reduced with sulfhydryl compounds, while rhodium(II) acetate is relatively stable in these conditions. Complex [Rh(2){OOCCH(OH)Ph}(2)(phen)(2)(H(2)O)(2)] strongly changes structure of ceruloplasmin leading to the decrease of of alpha-helix content and loss of oxidase activity.     

Supramolecular Photochemistry and Photophysics. Adducts of Metal Complexes with the Natural Ionophore Lasalocid A Anion

The formation of adducts of Cr(bpy)₃³⁺, Cr (phen)₃³⁺, Ru(bpy)₃²⁺, and Pt(bpy)(NH₃)₂²⁺ (bpy = 2, 2′-bipyridine; phen = 1, 10-phenanthroline) with the lasalocid A anion (LAS-⁾ in CH₂Cl₂ solution has been investigated by means of electronic absorption and emission spectroscopy. Cr(bpy)₃³⁺ forms a 1:1 adduct with LAS⁻. In this adduct, the fluorescence of LAS⁻ is quenched, whereas the phosphorescence intensity and lifetime of Cr(bpy)₃³⁺ increase. In the case of Cr(phen)₃³⁺, only a dynamic quenching of the Cr(phen)₃³⁺ phosphorescence by LAS⁻ is observed. For Ru(bpy)₃²⁺, either no adduct is formed or the interaction is too weak to cause changes in the absorption and emission properties. For Pt(bpy)(NH₃)₂²⁺, evidence has been obtained for formation of a 1:2 Pt(bpy)(NH₃)₂²⁺ / LAS⁻ adduct, where the LAS⁻ fluorescence is statically quenched.     

Three new coordination polymers based on 4-oxo-1(4H)quinolineacetate: Synthesis,structures and luminescent properties

Reactions of 4-oxo-1(4H)-quinolineacetic acid (Hoqa) and varied metal salts of Zn(II), Cd(II) and Ag(I) resulted in the formation of three new coordination polymers, namely, [Zn(oqa)₂]·H₂O (1), [Cd(bpy)(oqa)₂(H₂O)₂]·4H₂O (2) and [Ag(bpy)(oqa)]·2H₂O (3) (bpy = 4,4′-bipyridine). Complex 1 has a three-dimensional (3D) polymeric network with diamondoid topology; compounds 2–3 exhibit one-dimensional (1D) chain structure characteristics, which are further assembled through π–π stacking attractions and hydrogen bonds, forming the 3D supramolecular frameworks. In addition, the solid-state luminescent properties of the ligand Hoqa and complexes 1–2 have been investigated at room temperature.     

Synthesis,spectral and antibacterial studies on Ni(II) and Zn(II) complexes involving N-furfuryl-N-isopropyldithiocarbamate (f iprdtc) and Lewis bases: X-ray structure of [Ni(f iprdtc)(NCS)(PPh3)]

[Ni(fⁱprdtc)₂] (1), [Ni(fⁱprdtc)(PPh₃)(NCS)] (2), [Ni(fⁱprdtc)(PPh₃)₂]ClO₄ (3), [Zn(fⁱprdtc)₂] (4), [Zn(fⁱprdtc)₂(1,10-phen)] (5) and [Zn(fⁱprdtc)₂(2,2′-bipy)] (6) (f ⁱprdtc=N-furfuryl-N-isopropyldithio- carbamate, 1,10-phen=1,10-phenanthroline and 2,2′-bipy=2,2′-bipyridine) complexes were prepared and characterized by elemental analysis, electronic, IR and NMR spectra and the structure of 2 was determined by single-crystal X-ray crystallography. UV–Vis spectral data of 1–3 are consistent with the formation of square planar complexes. IR spectra of the complexes show the contribution of the thioureide form to the structure. A single-crystal X-ray structural analysis of 2 proved four-coordinated nickel in a distorted square planar arrangement with a S₂PN donor set. Significant asymmetry in Ni–S bond distances was observed in [Ni? S1=2.1655(8); Ni? S2=2.2120(8) Å]. This observation clearly supports the less effective trans of SCN^? over PPh₃. The observed shielding in N¹³CS₂ chemical shifts of heteroleptic nickel complexes 2 and 3 when compared with homoleptic nickel complex 1 indicates the effect of PPh₃ on the mesomeric drift of electron density toward nickel through the thioureide C? N bond. The N¹³CS₂ chemical shift of 5 and 6 are additionally deshielded compared with 4 owing to the increase in coordination number. Complexes were screened for in vitro antibacterial activity and significant activity has been found.     

Properties of Binuclear Rhodium(II) Complexes and Their Antibacterial Activity

Binuclear rhodium(II) complexes [Rh(2)Cl(2)(mu-OOCR)(2)(N-N)(2)], [Rh(2)(mu-OOCR)(2)(N-N)(2)(H(2)O)(2)](RCOO)(2) and [Rh(2)Cl(2)(mu-OOCCH(3))(terpy)(2)](H(3)O)Cl(2).9H(2)O (R = H, Me, Bu(n), ph, PhCHOH; N-N = 2,2'-bipyridine (bpy), 1,10-phenanthroline (phen), 2,9-dimethyl-1,10-phenanthroline (dmp) and 6,7-dimethyl-2,3- di(2-pyridyl)quinoxaline (dmpq); terpy 2,2':6',2'-terpyridine) have been synthesized and their structure and properties have been studied by electronic, IR and (1)H NMR spectroscopy. Antibacterial activity of these complexes against Staphylococcus aureus and Escherichia coli has been investigated. The most active antibacterial agents against S. aureus were [Rh(2)(OOCPh)(2)(phen)(2)(H(2)O)(2)](2+), [Rh(2)(OOCPh)(2)(dmpq)(2)(H(2)O)(2)](2+), [Rh(2)(OOCBu)(2)(phen)(2)(H(2)O)(2)](2+) and [Rh(2)-(OOCBu)(2)(bpy)(2)(H(2)O)(2)](2+) which were considerably more active than the appropriate nitrogen ligands. The complexes show rather low activity against E. coli.     

A series of novel indium complexes derived from aromatic carboxylic acids: Hydrothermal syntheses,crystal structures,supramolecular networks and fluorescent properties

Five new compounds with mixed-ligand formulated as (H₄bptc)(phen) (1), [In(phen)₂Cl₂](H₄bptc)(NO₃)(H₂O) (2), [In(Hbptc)(phen)(H₂O)]₂ (3), In(2,6-pydc)(phen)(H₂O)Cl (4), and {[In(2,6-pydc)(Ox)_0.5(H₂O)₂](H₂O)}₂ (5) have been synthesized under hydrothermal conditions. Compounds 1–5 display white, green and blue fluorescence at 298 K in the solid state, respectively. It is shown that 1 assumes solvent-dependent photoluminescence. By contrast, the different polarities of solvents do not alter the luminescence position of 3 and 5. The thermogravimetric curves show that binuclear compounds 3 and 5 have excellent thermal stability, whose structures are stable up to 190 and 272 °C, respectively.     

Cu(II) and Zn(II)-Pyridine-2,3-Dicarboxylate Complexes with 2-Methylimidazole: Syntheses, Crystal Structures, Spectroscopic and Thermal Analyses

Two new Cu(II) and Zn(II)-pyridine-2,3-dicarboxylate (pydc) complexes with 2-methylimidazole (2-Meim), [Cu(pydc)(2-Meim)₃]·H₂O (1) and {[Zn(μ-pydc)(H₂O)(2-Meim)]·H₂O}_n (2) have been synthesized and characterized by elemental, spectral (IR and UV–Vis.) and thermal analyses. The molecular structures of mononuclear (1) and polynuclear (2) complexes have been determined by the single crystal X-ray diffraction. Compound 1 crystallizes in the triclinic P ? 1 space group, while compound 2 crystallizes in the monoclinic P2₁/c space group. The pyridine-2,3-dicarboxylate ligand acts in two different coordination modes; namely, bidentate-(N,O) for 1 and μ-tridentate-(N,O,O) for 2, the latter displaying a 1D polynuclear structure. The crystal packing of the complexes exhibit 3D supramolecular frameworks including channels by C–H···π, π···π, and N–H···O interactions. Water molecules occupy the channels by O–H···O hydrogen bonds.     

Copper(II) Complexes Containing Natural Flavonoid Pomiferin Show Considerable In Vitro Cytotoxicity and Anti-inflammatory Effects

A series of new heteroleptic copper(II) complexes of the composition [Cu(L)(bpy)]NO₃·2MeOH (1), [Cu(L)(dimebpy)]NO₃·2H₂O (2), [Cu(L)(phen)]NO₃·2MeOH (3), [Cu(L)(bphen)]NO₃·MeOH (4), [Cu(L)(dppz)]NO₃·MeOH (5) was prepared, where HL = 3-(3,4-dihydroxyphenyl)-5-hydroxy-8,8-dimethyl-6-(3-methylbut-2-ene-1-yl)-4H,8H-benzo[1,2-b:3,4-b′]dipyran-4-one, (pomiferin) and bpy = 2,2′-bipyridine, dimebpy = 4,4′-dimethyl-2,2′-bipyridine, phen = 1,10-phenanthroline, bphen = 4,7-diphenyl-1,10-phenanthroline, and dppz = dipyrido[3,2-a:2′,3′-c]phenazine. The complexes were characterized using elemental analysis, infrared and UV/Vis spectroscopies, mass spectrometry, thermal analysis and conductivity measurements. The in vitro cytotoxicity, screened against eight human cancer cell lines (breast adenocarcinoma (MCF-7), osteosarcoma (HOS), lung adenocarcinoma (A549), prostate adenocarcinoma (PC-3), ovarian carcinoma (A2780), cisplatin-resistant ovarian carcinoma (A2780R), colorectal adenocarcinoma (Caco-2) and monocytic leukemia (THP-1), revealed the complexes as effective antiproliferative agents, with the IC₅₀ values of 2.2–13.0 μM for the best performing complexes 3 and 5. All the complexes 1–5 showed the best activity against the A2780R cells (IC₅₀ = 2.2–6.6 μM), and moreover, the complexes demonstrated relatively low toxicity on healthy human hepatocytes, with IC₅₀ > 100 μM. The complexes were evaluated by the Annexin V/propidium iodide apoptosis assay, induction of cell cycle modifications in A2780 cells, production of reactive oxygen species (ROS), perturbation of mitochondrial membrane potential, inhibition of apoptosis and inflammation-related signaling pathways (NF-κB/AP-1 activity, NF-κB translocation, TNF-α secretion), and tested for nuclease mimicking activity. The obtained results revealed the corresponding complexes to be effective antiproliferative and anti-inflammatory agents.     

Synthesis,structures and properties of Cu and Cd complexes with 1,10-phenanthroline

Three new Cu and Cd complexes, namely [Cu(phen)(isca)(EtOH)] (1)，[Cu(phen)₂(HCOOH)] (2) and [Cd(phen)Cl₂](3) (phen = 1, 10-phenanthroline, isca = isophthalic acid) have been synthesized, which are characterized by elemental analysis, infrared spectrum and x-ray crystal diffraction. While strong hydrogen bonds play central roles in the formation of the 3D structure, the combined influence of the weak interactions such as C-H···O bonds, C-H···π and lone pair···π interactions are also evident in the structures. The preliminary investigation on the thermal and fluorescence property of the complexes are presented.     

含柔性插入配体的钌（Ⅱ）配合物的合成及其与DNA作用研究

设计合成一个柔性插入配体dcpip（dcpip=2-（2,3-环己烯基眯唑并[4,5-f]邻菲咯啉）及其钌（Ⅱ）多吡啶配合物[Ru（bpy）2（dcpip）]（ClO4）2（bpy=2,2＇-联吡啶）和[Ru（phen）2（dcpip）]（ClO4）2（phen=1,10-邻菲咯啉）。采用元素分析和质谱对其进行表征。用电子吸收光谱、荧光光谱和粘度测试研究配合物与DNA作用。研究结果表明,配合物与DNA之间通过插入作用结合。     

Preparation,photophysical, and electrochemical properties of three novel trinuclear Ru(II) polypyridyl complexes based on diazafluorenes

Three tripodal ligands 2,2′,2″-tris[(4,5-diazafluoren-9-ylimino)phenoxyethyl]amine (L¹), 1,3,5-tris[(4,5-diazafluoren-9-ylimino)phenoxymethyl]-2,4,6-trimethylbenzene (L²), 1,1′,1″-tris[(4,5-diazafluoren-9-ylimino)phenoxymethyl]-1″′-(p-tosyloxymethyl)-methane (L³), and corresponding Ru(II) complexes [(bpy)₆L^1–3(Ru^II)₃](PF₆)₆ (Ru-L^1–3) have been prepared. Cyclic voltammetry of the three complexes are consistent with one Ru(II)-centered quasi-reversible oxidation and three ligand-centered reductions. Photophysical behaviors are investigated by UV–Vis absorption and fluorescence spectrometry. The three complexes display metal-to-ligand charge transfer absorption at 445 nm and emission at 578 nm.     

Two novel Zn(II) helical chain polymers containing both bridging and terminal carboxylato groups

Two novel carboxylato-bridged Zn(II) polymeric complexes [Zn(L)(CCl₃COO)]_n and [Zn(L)(CF₃COO)]_n, where [L=2-N-(2^′-pyridylimine)benzoic acid] have been synthesized and structurally characterized. The structures of the two complexes are similar with the Zn(L)(Cl₃CCO₂) or Zn(L)(F₃CCO₂) units being repeated to form infinite helical chains. In each structure, the neighbouring Zn atoms are bridged sequentially by syn–anti carboxylate groups of the Schiff base.     

Synthesis, Crystal Structures and Thermal Stabilities of Lanthanide Coordination Polymers with 5-Nitroisophthalate

Two new lanthanide coordination polymers, namely, [Ho(ox)_0.5(nip)(H₂O)₃]·2H₂O (1) and [Gd(nip)(Hnip)(phen)] (2) (nip = 5-nitroisophthalate, ox = oxalate and phen = 1,10-phenanthroline) were synthesized under hydrothermal conditions. They crystallize in triclinic, P−1 space group and exhibit 1D structure features: complex 1 possesses a 1D parallel ladder structure bridged by oxalate and nip anions and compound 2 has 1D loop-like chain structure. Moreover, intermolecular attractions such as H-bonds and π–π stacking result in the high-dimensional supramolecular frameworks. The different coordination modes of the nip anions, the appropriate choice of multidentate bridging ligands and the intermolecular forces affect the topological structures. In addition, the thermal behavior of the complexes is investigated in air.     

Different Hemi-Salen/Salan Ligand Containing Binuclear Boron-Fluoride Complexes: Synthesis,Spectroscopy, Fluorescence Properties,and Catalysis

A family of hemi-salen (L₁H–L₆H) and hemi-salan (L_1aH–L_2aH) ligands-based N,O-chelated binuclear boron-fluoride [L_n(BF₂)₂] (n = L₁–L₆ or L_1a–L_2a) complexes have been prepared and characterized by a variety of spectroscopic techniques (¹H, ¹³C and ¹⁹F NMR, FT-IR, UV-Vis, LC-MS, and fluorescence spectra) and elemental analysis. All of the binuclear boron-fluoride complexes exhibit strong absorption bands due to S₀→S₁ transitions and strong fluorescence properties were observed at room temperature in the solution. The binuclear boron complexes containing two naphthyl groups are significantly red-shifted in comparison with the other binuclear boron-fluoride complexes. After the structures are characterized, these hemi-salen and salan ligand-based N, O-chelated binuclear boron-fluoride complexes were utilized to the transfer hydrogenation of the different acetophenone derivatives conversion to 1-phenylethanol derivatives as catalysts.     

Interaction of Ruthenium(II)-dipyridophenazine Complexes with CT-DNA: Effects of the Polythioether Ancillary Ligands

The complexes [Ru([9]aneS(3))(dppz)Cl]Cl 1 and [Ru([12]aneS(4))(dppz)]Cl(2)2 ([9]aneS(3) = 1,4,7- trithiaciclononane and [12]aneS(4) = 1,4,7,10-tetrathiaciclododecane) were synthesised and fully characterised. These complexes belong to a small family of dipyridophenazine complexes with non-polypyridyl ancillary ligands . Interaction studies of these complexes with CT-DNA (UV/Vis titrations, steady-state emission and thermal denaturation) revealed their high affinity for DNA . Intercalation constants determined by UV/Vis titrations are of the same order of magnitude (10(6)) as other dppz metallointercalators, namely [Ru(II)(bpy)(2)dppz]S(2+). Differences between l and2 were identified by steady-state emission and thermal denaturation studies . Emission results are in accordance with structural data, which indicate how geometric distortions and different donor and/or acceptor ligand abilities affect luminescence. The possibility of noncovalent interactions between ancillary ligands and nucleobases by van der Waals contacts and H-bridges is discussed . Furthermore, complex l undergoes aquation under intra-cellular conditions and an equilibrium with the aquated form l' is attained . This behaviour may increase the diversity of available interaction modes.     

Polyoxometalates functioned as ligands: Synthesis and crystal structure of a new hybrid compound constructed from metatungstate and metal complex units

A new organic–inorganic hybrid compound, [Zn(bpy)₃]_1.5[H₃W₁₂O₄₀Zn(bpy)₂(H₂O)]·0.5H₂O (bpy = 2,2′-bipyridine) has been synthesized hydrothermally from ZnCl₂, Na₆[H₂W₁₂O₄₀], and 2,2′-bipyridine, and has been analyzed using X-ray crystallography, thermogravimetric analysis and UV–Vis spectroscopy. The compound contains an anionic complex [H₃W₁₂O₄₀Zn(bpy)₂(H₂O)]^3? in which α-metatungstate ion [H₃W₁₂O₄₀]^5? coordinated to a [Zn(bpy)₂(H₂O)]²⁺ unit through a bridging oxo group.     

Electrochemical,spectroscopic and molecular docking studies of 4-methyl-5-((phenylimino)methyl)-3H- and 5-(4-fluorophenyl)-3H-1,2-dithiole-3-thione interacting with DNA

Cyclic voltammetry (CV) and UV–Visible spectroscopy (UV–Vis) techniques were used to calculate binding parameters of 4-methyl-5-((phenylimino)methyl)-3H-1,2-dithiole-3-thione (MPDT) and 5-(4-fluorophenyl)-3H-1,2-dithiole-3-thione (FPDT) with DNA. The results obtained from both techniques were confirmed by computational molecular docking using AutoDock molecular docking software. The anodic peak potential shift in CV indicated an intercalative mode of binding. The binding constants (M^?1) of the adducts MPDT-DNA and FPDT-DNA obtained from voltammetric measurements were found to be 8.0?×?10⁴ and 2.4?×?10⁴, respectively, with binding free energy being ?27.99 and ?25.01?KJ?mol^?1, respectively. These results are in good agreement with those obtained from UV–Visible spectroscopic studies. The diffusion coefficients of MPDT and FPDT (2.06?×?10^?10 and 2.42?×?10^?9, respectively) were found to be higher than those of DNA-bound compounds (1.27?×?10^?10 and 1.65?×?10^?9?cm²/s, respectively). The binding free energy of MPDT and FPDT to DNA was also calculated by molecular docking study. The docking study gave excellent approximation with experimental results, shedding light on the sites of binding.