Synthesis,Crystal Structure,Fluorescent and Antioxidation Properties of Cerium(III) and Europium(III) Complexes with Bis(3‐methoxysalicylidene)‐3‐oxapentane‐1,5‐diamine

Two aliphatic ether Schiff base lanthanide complexes (Ln = Eu, Ce) with bis(3‐methoxysalicylidene)‐3‐oxapentane‐1,5‐diamine (Bod), were synthesized and characterized by physicochemical and spectroscopic methods. [Eu(Bod)(NO₃)₃] ( 1 ) is a discrete mononuclear species and [Ce(Bod)(NO₃)₃DMF]_∞ ( 2 ) exhibits an inorganic coordination polymer. In the two complexes, the metal ions both are ten‐coordinated and the geometric structure around the Ln^III atom can be described as distorted hexadecahedron. Under excitation at room temperature, the red shift in the fluorescence band of the ligand in the complexes compared with that of the free ligand can be attributed to coordination of the rare earth ions to the ligand. Moreover, the antioxidant activities of the two complexes were investigated. The results demonstrated that the complexes have better scavenging activity than both the ligand and the usual antioxidants on the hydroxyl and superoxide radicals.     

Synthesis,structure and antioxidant properties of manganese(II), zinc(II) and cobalt(II) complexes with bis(benzimidazol-2-ylmethyl)allylamine

Three new metal complexes, namely: [Mn(AIDB)Cl₂]·DMF (1), [Zn(AIDB)Br₂]·CH₃OH (2) and [Co(AIDB)Cl₂]·CH₃OH (3) having a ligand bis(benzimidazol-2-ylmethyl)allylamine (AIDB), have been synthesized in high yields and characterized by elemental analyses, molar conductivities, IR, UV–Vis spectra and single-crystal X-ray diffraction. The structural analysis revealed that all the three complexes 1–3 have five-coordinated trigonal bipyramid geometry where the degree of distorting is 1>3>2. In vitro antioxidant activity assay demonstrates that the complexes 1 and 3 display high scavenging activity against hydroxyl (OH·) and superoxide (O₂^−·) radicals.

     

A Schiff base ligand <Emphasis Type="Italic">N</Emphasis>-(2-hydroxylacetophenone)-3-oxapentane-1,5-diamine and its nickel(II) complex: synthesis,crystal structure,antioxidation, and DNA-binding properties

A new Schiff base ligand N-(2-hydroxylacetophenone)-3-oxapentane-1,5-diamine (HL) and its Ni complex, [Ni₂(L)₂(NO₃)₂], have been synthesized and characterized by physicochemical and spectroscopic methods. The X-ray crystal structure of [Ni₂(L)₂(NO₃)₂] shows it to be a dinuclear 2:2 complex, in which each Ni(II) atom is in a distorted octahedral geometry. The two Ni(II) atoms are dibridged by two phenoxo ligands, forming a Ni₂O₂ parallelogram-type moiety. The interactions between free HL and the complex with calf thymus DNA have been investigated, and the binding constant and linear Stern–Volmer quenching constant suggest that the two compounds bind to DNA via the intercalation mode. The binding affinity of the complex was higher than that of HL. Antioxidant assays in vitro showed that the Ni(II) complex possesses significant antioxidant activity.     

A Six-Coordinate Picrate Nickel(II) Complex Based on the V-Shaped Ligand 1,3-Bis (1-Benzylbenzimidazol-2-yl)-2-Thiapropane: Synthesis,Crystal Structure,Biological Activities

Abstract

A six-coordinate picrate nickel(II) complex based on the V-shaped ligand 1,3-bis(1-benzylbenzimidazol-2-yl)-2-thiapropane (L), with the composition [Ni(L)₂](pic)₂, has been synthesized and characterized systematically. The crystal structure of the Ni(II) complex is a six-coordinated octahedron, which is considerably close to ideal octahedral geometry with N₄S₂ donors of the two ligands. Biological activities of compounds were investigated using electronic absorption spectroscopy, fluorescence spectroscopy, and viscosity measurements. The results suggested that both ligand L and Ni(II) complex bind to DNA in an intercalative binding mode, and DNA-binding affinity of the Ni(II) complex is stronger than that of ligand L.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental files: Additional figures.]     

A highly Selective Fluorescent Sensor for Monitoring Cu<Superscript>2+</Superscript> Ion: Synthesis,Characterization and Photophysical Properties

A new fluorescent sensor, 4-allylamine-N-(N-salicylidene)-1,8-naphthalimide (1), anchoring a naphthalimide moiety as fluorophore and a Schiff base group as receptor, was synthesized and characterized. The photophysical properties of sensor 1 were conducted in organic solvents of different polarities. Our study revealed that, depending on the solvent polarity, the fluorescence quantum yields varied from 0.59 to 0.89. The fluorescent activity of the sensor was monitored and the sensor was consequently applied for the detection of Cu²⁺ with high selectivity over various metal ions by fluorescence quenching in Tris-HCl (pH = 7.2) buffer/DMF (1:1, v/v) solution. From the binding stoichiometry, it was indicated that a 1:1 complex was formed between Cu²⁺ and the sensor 1. The fluorescence intensity was linear with Cu²⁺ in the concentration range 0.5–5 μM. Moreso, the detection limit was calculated to be 0.32 μM, which is sufficiently low for good sensitivity of Cu²⁺ ion. The binding mode was due to the intramolecular charge transfer (ICT) and the coordination of Cu²⁺ with C = N and hydroxyl oxygen groups of the sensor 1. The sensor proved effective for Cu²⁺ monitoring in real water samples with recovery rates of 95–112.6 % obtained.     

Synthesis,crystal structures,antioxidant activities,and DNA-binding studies of two silver(I) complexes with 1,3-bis(1-ethylbenzimidazol-2-yl)-2-thiapropane,and α,β-unsaturated carboxylates

Two new ternary complexes of silver(I) with 1,3-bis(1-ethylbenzimidazol-2-yl)-2-thiapropane (bebt) and two ·α,β-unsaturated carboxylates, [Ag(bebt)(crotonate)] (1) and [Ag(bebt)₂](o-coumarate)·CH₃CN·2C₂H₅OH (2), have been synthesized, and characterized by physicochemical and spectroscopic methods. Single-crystal X-ray diffraction revealed that the coordination environment of 1 can be described as trigonal planar, while 2 has a distorted tetrahedral geometry. Experimental studies of the DNA-binding properties indicated that the free ligand and both complexes bind to DNA via intercalation, and the order of the binding affinity is 1 > bebt > 2. Antioxidant activity experiments show that 2 possesses significant antioxidant activity against hydroxyl radicals, with more efficient hydroxy radical scavenging compared with mannitol and vitamin C.     

Synthesis,Characterization, DNA‐binding Properties,and ­Antioxidant Activity of a Copper(II) Complex with 1, 3‐Bis­(1‐allaylbenzimidazol‐2‐yl)‐2‐oxopropane

A new complex of copper(II) picrate (pic) with 1, 3‐bis(1‐allaylbenzimidazol‐2‐yl)‐2‐oxopropane (aobb), with the composition [Cu(aobb)₂](pic)₂, was synthesized and characterized. The crystal structure of the copper(II) complex revealed that the coordination environment around the central copper(II) atom is a distorted octahedral arrangement. Electronic absorption spectroscopy, ethidium bromide displacement experiments and viscosity measurements indicate that the ligand and the Cu^II complex can strongly bind to calf thymus DNA, presumably by an intercalation mechanism. Furthermore, the antioxidant activity of the Cu^II complex was determined by superoxide and hydroxyl radical scavenging method in vitro, which indicate that the Cu^II complex has the activity to suppress OH ^· and O₂ ^{· –}.     

单细胞拉曼光谱分析地中海贫血红细胞的氧合态和去氧态

应用光镊拉曼光谱系统俘获单个红细胞并收集其拉曼光谱,选择I1638/I1547比值为区分红细胞氧合及去氧态指标,比较分析地中海贫血HbH-CS和健康个体单个红细胞的氧循环过程的氧合和去氧能力及去氧态群体红细胞.结果发现,在氧循环的去氧态中,地中海贫血HbH-CS的I1638/I1547显著高于正常对照;氧合态的I1638/I1547也略高于正常对照.群体统计中,若以小于正常对照I1638/I1547的平均值为去氧态基准,则正常对照46%的红细胞达到去氧态.而地中海贫血HbH-CS仅有15%,表明地中海贫血HbH-CS红细胞的氧合能力较强,但去氧能力显著低于正常对照,而且地中海贫血HbH-CS红细胞个体差异较大.该研究在单细胞水平上,揭示了地中海贫血HbH-CS红细胞氧合,去氧能力以及细胞个体差异性,以评价其携氧功能,为诊断治疗提供一定的理论依据.     

超氧化物歧化酶模型化合物的合成、表征及其SOD活性研究

合成了 4种过渡金属硝酸盐与三 (2 苯并咪唑亚甲基 )胺 (ntb)和水杨酸 (Hsal)的新固体配合物 ,经元素分析确定其组成分别为 [M2 (ntb) 2 (Hsal) 2 ](NO3 ) 2 ·H2 O(M =Zn ,Co)、[M2 (ntb) 2 (Hsal) ](NO3 ) 3 ·3H2 O(M =Cu)和 [M(ntb) (Hsal) ](NO3 )·2H2 O(M =Ni) ,进行了摩尔电导率、热重、红外与紫外可见光谱、1HNMR等性质的表征。研究了配合物的模拟SOD活性 ,用IC50 表征配合物的模拟SOD活性的大小。     

Synthesis, structure, DNA-binding properties and antioxidant activity of silver(I) complexes containing V-shaped bis-benzimidazole ligands

A V-shaped ligand bis(2-benzimidazol-2-ylmethyl)benzylamine L(1) with its two derivatives bis(N-methylbenzimidazol-2-ylmethyl)benzylamine L(2) and bis(N-benzylbenzimidazol-2-ylmethyl)benzylamine L(3) have been prepared. Reaction of these shape-specific designed ligands with Ag(pic) (pic = picrate) afforded three novel complexes, namely, [Ag(2)L(1)(2)](pic)(2)1, [Ag(2)L(2)(2)](pic)(2)·2DMF 2 and [AgL(3)(pic)] 3. The ligands and complexes were characterized on the basis of elemental analysis, UV-Vis, IR, NMR spectroscopy and X-ray crystallography. Complex 1 is a dinuclear metallacycle with a 2-fold rotational symmetry in which two syn-conformational L(1) ligands are connected by two linearly coordinated Ag(I) atoms. Due to the strong interaction between two adjacent Ag(I) atoms, the coordination mode of the central Ag(I) atom can be described as T-shaped. Complex 2 consists of a centrosymmetric dinuclear pore canal structure assembled from two nearly linearly coordinated Ag(I) atoms and two L(2) ligands. The structure of complex 3 adopts a four-coordinate environment for AgN(2)O(2), with the counterion participating in an eight-shaped geometry. In order to explore the relationship between the structure and biological properties, the DNA-binding properties have been investigated by viscosity measurements, electronic absorption, and fluorescence. The results suggest that the ligands and complexes bind to DNA in an intercalation mode, and their binding affinities for DNA are also different. Moreover, the three Ag(I) complexes also exhibited potential antioxidant properties in vitro studies.