Copper complexes of anthrahydrazone bearing pyridyl side chain:Synthesis,crystal structure,anticancer activity,and DNA binding

To expand the study on the structures and biological activities of the anthracyclines anticancer drugs and reduce their toxic side effects,the new anthraquinone derivatives,9‑pyridylanthrahydrazone(9‑PAH)and 9,10‑bispyridylanthrahydrazone(9,10‑PAH)were designed and synthesized.Utilizing 9‑PAH and 9,10‑PAH as promising anticancer ligands,their respective copper complexes,namely[Cu(L1)Cl_(2)]Cl(1)and{[Cu_(4)(μ_(2)‑Cl)_(3)Cl_(4)(9,10‑PAH)_(2)(DMSO)_(2)]Cl_(2)}_(n)(2),were subsequently synthesized,where the new ligand L1 is formed by coupling two 9‑PAH ligands in the coordination reaction.The chemical and crystal structures of 1 and 2 were elucidated by IR,MS,elemental analysis,and single‑crystal X‑ray diffraction.Complex 1 forms a mononuclear structure.L1 coordinates with Cu through its three N atoms,together with two Cl atoms,to form a five‑coordinated square pyramidal geometry.Complex 2 constitutes a polymeric structure,wherein each structural unit centrosymmetrically encompasses two five‑coordinated binuclear copper complexes(Cu1,Cu2)of 9,10‑PAH,with similar square pyramidal geometry.A chlorine atom(Cl_(2)),located at the symmetry center,bridges Cu1 and Cu1A to connect the two binuclear copper structures.Meanwhile,the two five‑coordinated Cu2 atoms symmetrically bridge the adjacent structural units via one coordinated Cl atom,respectively,thus forming a 1D chain‑like polymeric structure.In vitro anticancer activity assessments revealed that 1 and 2 showed significant cytotoxicity even higher than cisplatin.Specifically,the IC_(50)values of 2 against HeLa‑229 and SK‑OV‑3 cancer cell lines were determined to be(5.92±0.32)μmol·L^(-1)and(6.48±0.39)μmol·L^(-1),respectively.2 could also block the proliferation of HeLa‑229 cells in S phase and significantly induce cell apoptosis.In addition,fluorescence quenching competition experiments suggested that 2 might interact with DNA by an intercalative binding mode,offering insights into its underlying anticancer mechanism.CCDC:2388918,1;2388919,2.

Synthesis,crystal structure,and DNA‑binding of binuclear lanthanide complexes based on a multidentate Schiff base ligand

Two new dinuclear lanthanidecomplexes,namely[Ln_(2)(dbm)_(2)(HL)_(2)(CH_(3)OH)_(2)]·4CH_(3)OH[Ln=Tb(1)and Dy(2),Hdbm=dibenzoylmethane]have been synthesized using prepared multidentate Schiff base ligand H_(3)L(hydroxy‑acetic acid(4‑diethylamino‑2‑hydroxy‑benzylidene)‑hydrazide)with good biological activity.Structure characterizations show that the complex comprises two Ln3+ions,two dbm-ions,two HL^(2-)ligands,two CH_(3)OH molecules,and four free methanol molecules.Each Ln^(3+)ion is eight‑coordinated.The two central Lnions are bridged by twoμ_(2)‑O atoms leading to a parallelogram[Ln2O2]core.The interaction between the compounds(H_(3)L,1,and 2)and the calf thymus DNA(CT‑DNA)has been further confirmed by UV‑Vis spectrometry,fluorescence titration,and cyclic voltammetry.The results showed that both 1 and 2 could undergo insertion with CT‑DNA.CCDC:2343005,1;2343006,2.

Catalytic Effect of Transition Metal Complexes of Triaminoguanidine on the Thermolysis of Energetic NC/DEGDN Composite

The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.

Subtraction of liposome signals in cryo-EM structural determination of protein-liposome complexes

Reconstituting membrane proteins in liposomes and determining their structure is a common method for determining membrane protein structures using single-particle cryo-electron microscopy(cryo-EM).However,the strong signal of liposomes under cryo-EM imaging conditions often interferes with the structural determination of the embedded membrane proteins.Here,we propose a liposome signal subtraction method based on single-particle two-dimensional(2D)classification average images,aimed at enhancing the reconstruction resolution of membrane proteins.We analyzed the signal distribution characteristics of liposomes and proteins within the 2D classification average images of protein–liposome complexes in the frequency domain.Based on this analysis,we designed a method to subtract the liposome signals from the original particle images.After the subtraction,the accuracy of single-particle three-dimensional(3D)alignment was improved,enhancing the resolution of the final 3D reconstruction.We demonstrated this method using a PIEZO1-proteoliposome dataset by improving the resolution of the PIEZO1 protein.

Study on the Reaction Behavior of Some Trinuclear Complexes of Transition Metals: [Fe_2M(μ_3-O) (μ-O_2CCH_3)_6(H_2O)_3]·xH_2O by the Method of Probe Reaction of Acetic Acid

The reaction behaviors of the title complexes have been studied in thesystem of dinitrogen gas by means of in situ IR. It has been found that some activefragments created at some stage of the thermal decomposition process of the complexes.enable.the acetic acid both obtained from the ligand of the complexes and introducedfrom outside to convert to acetone by decarboxylation. Their optimum reaction temperatures are of 240~270℃ for [Fe2MnO(O2CCH3),(H2O)3], 290~320 C for [Fe3Q(O2CCH3)6(H2O)3], 300~330℃ for [Fe2CoO(O2CCH3),(H2O)3] and 320~ 350℃for [Fe2NiO(O2CCH3)6(H2O)3], indicating the lowering sequence of the activity of active species. At the same time it has been shown that this activity may come from thejoined contributions of both the coordinating capability of the hetero-metals in the complexes and their structural factors. On the basis of the TGA, DTA and EI-MS data,the composition of the active fragments has been tentatively inferred as [Fe2MnO(O2CCH3)3-2].

Synthesis and Physico-Chemical Characterizations of Novel Hydrazone Ligands and Their Metal Complexes against Hormone-Dependent and Independent Cancers

This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is effective against human breast cancer BT-20 and MCF-7 cell lines. At the same time, compound L2 exerts its effect on human prostate cancer PC-3 and human breast cancer MDA-MB-231 and MCF-7 cell lines respectively. The retinoid ligands exert their pleiotropic action toward retinoic acid receptors (RARs) than their metal complexes but all compounds exhibit concentration-dependent.

3,6-Bis-β-Dicarbonylsubstituted Carbazoles Bearing N-Spacers and Their Eu(III) Complexes as Immunofluorescent Labelling Agents

New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carbazole scaffold have been developed. The markers in complex with Eu3+ ions possess stability in the aqueous phase, intense and prolonged luminescence (τ 550 - 570 μs) with characteristic emission maxima in the region of 615 nm and excitation wavelengths in the region of 380 - 390 nm, which distinguishes them from most of the analogs used. In the study of marker conjugation with streptavidin, a reagent containing 4 - 5 europium labeling complexes based on spacer-containing carbazole tetraketone was obtained. The marker-doped silicate nanoparticles exhibit intense and long-lived luminescence in the characteristic region.

Structures and magnetism of dinuclear Co complexes based on imine derivatives

This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives:bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether(L1),bis-[4-(2-pyridylmethyleneamino)-phenyl]ether(L2),and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane(L3).Single-crystal X-ray diffraction analysis reveals that the complexes[Co_(2)(L1)3](ClO_(4))4·2CH_(3)CN(1),[Co_(2)(L2)3](ClO_(4))4·2CH_(3)OH(2),and[Co_(2)(L3)3](ClO_(4))4·2CH_(3)OH(3)all exhibit a dinuclear structure.Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K,with the average Co-N bond length increasing from 0.2139(3)to 0.2153(3)nm.Meanwhile,the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2.Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.CCDC:2347354,1(120 K);2347355,2(120 K);2347356,3(120 K);2347357,3(400 K).

Physicochemical and Analytical Studies of Some Monomer and Polymer Complexes Derived from Selected Aroyl Hydrazone

New solid complexes derived from the reaction of aroyl hydrazones, 2-hydroxy-1-naphthaldehyde benzene sulphonyl hydrazone (HNB), and 2-hydroxy-1-naphthaldehyde p-toluene sulphonyl hydrazone (HNT), with Co2+, Ni2+, and Cu2+ salts have been isolated and characterized using elemental analyses, spectral (UV-vis., IR), molar conductivity and magnetic measurements. The modes of bonding as well as the stereochemistry of the isolated solid complexes were discussed. The results suggested that both HNB and HNT coordinated with the metal ions in a bidentate manner forming a polymeric chain in the case of HNB while monocular complexes were formed in the case of HNT. The amounts of solvent in the solid complexes were determined by TGA measurements. Also, spectral studies of HNT with Co2+ and Fe3+ ions in solution were carried and the ratio of complexes was determined by continuous variation, molar ratio, and slope ratio methods. Moreover, the results suggest the formation of 1:1 (M:L) for Co2+ ions while three species with ratios of 1:1, 1:2, and 2:1 (M:L) have been observed in the case of Ni2+ and Cu2+. Finally, conductance titration of HNB and HNT with Co2+ ion elucidates the formation of two species with ratios 1:1 and 1:2 (M:L) in the case of the Co2+-HNB while 1:1 (M:L) belongs to the Co2+-HNT system.

Two novel Cu(Ⅰ)complexes based on diimide and bisphosphine ligands:synthesis,crystal structure and spectroscopic properties

Two Cu(Ⅰ)complexes[Cu(Bphen)(dppBz)]ClO_(4)·2CH_(3)OH(1)and[Cu_(2)(Bphen)_(2)(dpppda)]BF_(4)(2){Bphen=4,7-diphenyl-1,10-phenanthroline,dppBz=1,2-Bis(diphenylphosphino)benzene,dpppda=N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamin}were synthesized using a one-pot method.X-ray crystallography was used to elucidate their crystal structures and photophysical properties.A series of characterization tests including elemental analysis,NMR,FT-IR,UV-Vis absorption spectroscopy,fluorescence spectroscopy,thermal gravimetric analysis and terahertz time-domain spectroscopy(THz-TDS)were used to further investigate their properties.The results show that complex 1 structure is mononuclear containing two solvent molecules per unit cell,while complex 2 structure is binuclear containing two metal centers per unit cell.According to photophysical properties and density functional theory(DFT)calculations,their luminescence properties can be attributed to metal-to-ligand charge transfer(MLCT).Both complexes have a unique stability,which is confirmed by thermal gravimetric analysis.

Resonance Raman Spectra of Purified PS Ⅱ Core Antenna Complexes CP43 and CP47

PSⅡ core antenna complexes, CP43 and CP47, were purified from spinach (Spinacia oleracea L.) by DEAE Fractogel TSK 650S anion exchange chromatography. Their normal temperature (298 K) resonance Raman spectra were measured. The results suggest that all β carotenoids bound to CP43 and CP47 are in all trans configuration and likely in twisted conformations.

Preparation,physicochemical properties and antioxidant activity of genistein phospholipid complexes

Genistein phospholipid complex(GS-PC)was produced in order to increase the solubility and antioxidant activity of genistein(GS),an insoluble natural polyphenol compound.By using the solvent evaporation process,GS-PC was produced.Several characteristics techniques were used to confi rm the production of GS-PC,and its physicochemical characteristics and antioxidant activity were investigated.The outcome showed that GS-PC had a recombination rate of 96.84%±0.51%.The characterization results confi rmed that GS-PC was formed by the intermolecular interaction between GS and phospholipids.In vitro antioxidant studies showed that GS-PC had a certain scavenging ability on DPPH free radicals,ABTS free radicals and hydroxyl free radicals.In summary,the results of this study indicated that GS-PC could be used as a formula to improve its solubility and antioxidant activity.

STUDY ON THE ANTI-TUMOR EFFICACY INDUCED BY HEAT SHOCK PROTEIN 70-PEPTIDE COMPLEXES DERIVED FROM TUMOR CELLS

OBJECTIVE: To study the efficacy and explore the mechanism of the anti-tumor immunity elicited by heat shock protein 70-peptide complexes (HSP70-PC) derived from tumor cells. METHODS: Cells culture, flow cytometric analysis, affinity chromatography for protein purification, SDS-PAGE, Western-blotting and animal experiment were used. RESULTS: HSP70-PC immunization rendered protective effect to both naive tumorl-bearing mice. All of the naive mice obtained complete resistance to Hcaf cell attack; 40% of the tumor-bearing mice survived for over 90 days, whereas the mice of control group died within 2 weeks (P

Synthesis and Photophysical Properties of Dy^(3+) and Gd^(3+) Polymeric Complexes with Functionalized Polybenzimidazole Containing β-Diketone Side Group

The polymeric ligand PBIa （functionalized polybenzimidazole containing β-diketone side group） was successfully synthesized via the reaction of polybenzimidazole （PBI） with 3-Br-acetylacetone in DM SO solvent using Nail as the deprotonation reagent. Its corresponding polymeric complexes of Dy^3＋ and Gd^3＋ were prepared and characterized by FT-IR, ^1H NMR, molar conductance measurements, and thermal analysis. The photoluminescence properties and the probable mechanism of the Dy and Gd complexes were studied. The measurement and analysis of the thermal properties showed that these were thermal stable.

Theoretical Studies on Structures and Spectroscopic Properties of Highly Efficient Phosphorescent [Ru（terpy）（phen）X]＋ Complexes

The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru（II） complexes [Ru（terpy）（phen）X]＋ （terpy=2,2＇,6＇,2″-terpyridine, phen=l,10-phenanthroline, and X=-C-=CH （1）, X=Cl （2）, X-CN （3）） were investigated theoretically using the density functional theory method. The ground and excited state geometries have been fully optimized at the B3LYP/LanL2DZ and UB3LYP/LanL2DZ levels, respectively. The absorption and emission spectra of the com- plexes in CHaCN solutions were calculated by time-dependent density functional theory with the PCM solvent model. The calculated bond lengths of Ru-C, Ru-N, and Ru-Cl in the ground state agree well with the corresponding experimental results. The highest occupied molecular orbital were dominantly localized on the Ru atom and monodentate X ligand for 1 and 2, Ru atom and terpy ligand for a, while the lowest unoccupied molecular orbital were π＊（terpy） type orbital. Therefore, the lowest-energy absorptions of 1 and 2 at 688 and 631 nln are attributed to a dyz （Ru）＋Tr/p（X）--π＊ （terpy） transition with MLCT/XLCT （metal-to-ligand charge transfer/X ligand to terpy ligand charge transfer） character, whereas that of 3 at 529 nm is related to a dyz （Ru）＋π（terpy）-π＊ （terpy） transition with MLCT and ILCT transition character. The calculated phosphorescence of three complexes at 1011 nm （1）, 913 nm （2）, and 838 nm （3） have similar transition properties to that of the lowest-lying absorption. It is shown that the lowest lying absorptions and emissions transition character of these Ru（II） complexes can be tuned by changing the electron-withdrawing ability of the monodentate ligand.

Structural Analysis of Peptides of PSⅡ Light-harvesting Complexes in Siphonous Green Algae, Codium fragile

Peptide composition and arrangement of 4 major light-harvesting complexes LHCP 1-3 and LHCP 3′ isolated from siphonous green algae (Codium fragile (Sur.) Hariot.) were investigated. LHCP 1 showed five main peptides, 34.4, 31.5, 29.5, 28.2 and 26.5 kD in SDS-PAGE, the 34.4 and 31.5 kD peptides were never found in higher plants. LHCP 3 contained the other four kinds of LHCP 1 peptides except 34.4 kD, while LHCP 3′ consisted of only 28.2 and 26.5 kD peptides. We found that 34.4, 28.2 and 26.5 kD peptides were easy to decompose from LHCP 1 when subjected to SDS-PAGE without pretreatment. They might be located at the exterior of LHCP 1, while the 31.5 and 29.5 kD peptides were at the central part. The 28.2 and 26.5 kD peptides often occurred in CPa, the center complex of PSⅡ. They are possibly the LHCⅡ peptides tightly associated with CCⅡ. According to the results described above, a peptide map of LHCP 1 was sketched.

Spectral Properties and Characterization of the Modified PSⅡ Core Complexes

用组氨酸的特异性修饰剂 (DEPC)对PSⅡ核心复合物进行了化学修饰 ,并对其光谱性质进行了研究。研究结果表明 :修饰后的PSⅡ核心复合物的吸收光谱在红区发生了很大变化 ,随修饰时间的增加 ,6 80nm处的吸收逐渐下降。修饰后的PSⅡ核心复合物的荧光光谱在最初的 1min内出现荧光上升现象 ,然后逐渐下降 ,峰位蓝移。这些研究结果表明 ,组氨酸残基的修饰导致了原初电子供体P6 80结构的破坏 ,并对其功能产生了影响。

Purification and Spectral Characteristics of Cytochrome b-559 from Oxygen-evolving Photosystem Ⅱ Core Complexes of Spinach and Rice

Cytochrome b_559 in photosystem Ⅱ reaction center was purified from spinach ( Spinacia oleracea L.) and rice ( Oryza sativa L.) by a rapid and simple procedure. Their low temperature fluorescence emission and excitation spectra, ultraviolet fluorescence spectra and absolute absorption spectra were presented. The author's purification methods, which enhanced the yield of pure protein and shorted the time for isolation, have several advantages: 1. use of oxygen_evolving PSⅡ core complexes as the starting material in order to avoid disturbing from other cytochromes; 2. isocratic elution of cytochrome b_559 from a DEAE_Sephacel column for eliminating the impurity and yielding the protein in pure state; 3. a simple column procedure for removal of excess Triton X_100. Purified cytochromes b_559 from these species have similar optical spectra and mobility during gel electrophoresis under native conditions. From the results of novel electrophoresis (Tricine_SDS_PAGE), cytochrome b_559 from both spinach and rice reveal two polypeptide bands (apparent molecular weight 9 kD and 4 kD, respectively). By measuring of 77 K fluorescence spectra, it was shown that for the purified cytochrome b_559 there were two excitation peaks at 439 nm and 413 nm, and two emission peaks at 563 nm and 668 nm. This is the first indication that Cyt b_559 is able to emit fluorescence and also transfer excited electrons to chlorophyll. By the use of ultraviolet fluorescence spectra, it was demonstrated for the first time that the location of Trp residue could be in the hydrophobic transmembrane region of cytochrome b_559.

STUDIES ON COMPLEXES OF RARE EARTHS WITH CROWN ETHERS(V)-SYNTHESIS AND CHARACTERIZATION OF THE COMPLEXES OF RARE EARTH NITRATES WITH 2,2'-DINITRO-4,5,4',5'-BIS-(15-CROWN-5)-DIBENZO DISULFIDE

Three new solid complexes of macrocyclic polyether ligand 2, 2'-dinitro-4, 5, 4', 5'bis-(15- crown-5)-dihenzo disulfide(L) with trivalent rare earth nitrates having composition of RE(NO_3)_3·L ·6H_2O(RE=Ce, Pr, Nd) have been synthesized in acetonitrile. All the isolated complexes have been characterized by elementary analysis, IR and UV spectra, differential thermal and thermogravimetric analysis, X-ray powder diffraction analysis, molar conductance and measurements of solubility in some general solvents.