Crystal Structures and Luminescent Properties of Three Coordination Polymers Based on 2,5-Furandicarboxylic Acid Ligand and 1,10-Phenanthroline

Three new coordination polymers,namely [Zn（FDA）（phen）（H2O）·H2O]n（1）,[Cd（HFDA）（phen）2（NO3）]（2） and [Cd（FDA）（phen）]n（3）（H2FDA = 2,5-furandicarboxylic acid,phen = 1,10-phenanthroline） have been synthesized by the solvothermal method and characterized by elemental analysis,IR,powder X-ray diffraction,thermogravimetric analysis and X-ray single-crystal diffraction analysis.For 1,the neighboring Zn^2＋ ions are bridged by FDA2-as linkers to form one-dimensional（1D） chains,and phen ligands are as the terminal ligands.Furthermore,the 1D chains are packed into a three-dimensional（3D） supramolecular structure through hydrogen bonds and π-π interactions.For 2,the H2FDA ligand is partial deprotonation,which is a rare phenomenon among other coordination polymers based on H2FDA.Under the synergetic effect of phen ligands and the partial deprotonation of H2FDA,the structure of 2 is discrete.For 3,the Cd^2＋ ions are linked by two carboxylates of FDA^2-ligand to give rise to 1 D zig-zag chains,and phen ligands chelate the Cd^2＋ ions like 1.In addition,solid-state luminescent spectra of three coordination polymers were also studied at room temperature.

Synthesis and Properties of Eu(Ⅲ) Complexes with Aromatic Carboxylic Acid, Dibenzoylmethane and 1, 10-phenanthroline

In order to obtain an excellent luminescent material, herein four complexes of Eu(Ⅲ) were synthesized with dibenzoylmethane (DBM), benzoic acid (BA) and phenylacetic acid (PLA) as the anion ligands, and 1, 10-phenanthroline (phen) as the neutral ligand. The complexes Eu(DBM)3phen (1), Eu(DBM)(BA)2phen (2), Eu(DBM)(PLA)2phen (3) and Eu(DBM)2(PLA)phen (4) were characterized by elemental analysis, IR and TG-DTG. In these complexes, the Eu(Ⅲ) ions are bonded to the oxygen atoms of carboxylate (or dibenzoylmethane), and the nitrogen atoms of phen. The TG-DTG analysis indicated that these complexes are thermally stable. Their excitation and luminescence spectra revealed that the complexes emitted the characteristic luminescence of Eu(Ⅲ): 579 nm (5D0→7F0), 589 nm (5D0→7F1), 610 nm (5D0→7F2). The emission peak at ca. 610 nm was the most intensive. The order of their fluorescence intensity was: Eu(DBM)2(PLA)phen (4)>Eu(DBM)(PLA)2phen (3)>Eu(DBM)3phen (1)>Eu(DBM)(BA)2phen (2).

Preparation of Ternary Lanthanide Complexes with Unsaturated Acid and 1,10-Phenanthroline, and Their Anti-Inflammatory Action

Four ternary lanthanide complexes with unsaturated acid and 1,10-phenanthroline are prepared in methanol and characterized by elemental analysis, molar conductance, UV, IR, (()~1H) NMR and XPS. The results from this paper show that the complexes Ln(phen)(SA)_3·2H_2O or Ln(phen)(CA)_3·H_2O (Ln=Ce(Ⅲ), Sm(Ⅲ) and Eu(Ⅲ), (phen=1,10-)phenanthroline, SA=Sorbate and CA=Cinnamate) has better anti-inflammatory effect than cerium nitrate and their gremores are steadier than cerium nitrate gremor. And there is a kind of medicament which can replace the cerium nitrate gremor completely in treating burn.

Crystal Structure and Properties of a Terbium Benzoate Complex with 1,10-Phenanthroline

A terbium benzoate complex with 1,10-phenanthroline [Tb(ba)3(phen)]2, where ba = benzoate and phen = 1,10-phenanthroline, has been prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 10.7881(5), b = 11.9262(6), c = 12.4249(6) ?, a = 105.1260(10), β = 93.6010(10), ? = 113.3350(10)o, (C33H23N2O6Tb)2, Mr = 1404.90, V = 1391.87(12) ?3, Z = 1, Dc = 1.676 g/cm3, μ(MoKα) = 2.590 mm-1, F(000) = 696, the final R = 0.0277 and wR = 0.0670 for 6085 observed reflections with I > 2σ(I). The crystal consists of binuclear molecules of the title compound. Each Tb3+ ion is nine-coordinated to one 1,10-phenan- throline molecule, one bidentate carboxylate group and four bridging carboxylate groups. The carboxylate groups are bonded to the terbium ion in three modes: the chelating bidentate, bridging bidentate and bridging-chelating tridentates. Excitation and luminescence data observed at room temperature show that the title complex emits very intensive green fluorescence under ultraviolet light. The results of thermal analysis indicate that the complex [Tb(ba)3phen]2 is very thermal stable.

Thermal Decomposition Kinetics and Mechanism of Tb(Ⅲ) m-Methylbenzoate Complex with 1,10-Phenanthroline in Static Air Atmosphere

The thermal behavior of [Tb_2( m -MBA)_6(phen)_2](H_2O)_2( m -MBA=C_8H_7O_2, methoxybenzoate; phen=C_ 12 H_8N_2, 1,10-phenanthroline) in static air atmosphere was investigated by means of TG-DTG and DTA methods. The thermal decomposition of the title compound takes place mainly in two steps. The intermediate and the residue for each decomposition were identified by the TG curve. By the kinetic method of processing thermal analysis data put forward by Malek et al ., it is defined that the kinetics model for the first-step thermal decomposition is SB( m,n ).

白细胞介素10工程化修饰人脐带间充质干细胞优效治疗炎症性肠病

背景:间充质干细胞来源广泛、易体外增殖,并可分泌一系列免疫调节因子抑制炎症、促进组织修复再生,广泛应用于各种疾病治疗研究。但是对于多种疾病,间充质干细胞的治疗效果有限。针对疾病特定发病机制或者干预靶点进行工程化修饰间充质干细胞是未来细胞治疗的重要发展方向。目的:白细胞介素10是一种典型的抗炎细胞因子,有助于调节免疫反应并诱导巨噬细胞向抗炎表型极化,该研究探讨白细胞介素10基因工程化修饰人脐带间充质干细胞对炎症性肠病的治疗效果。方法:通过电转染建立稳定过表达人白细胞介素10基因的人脐带间充质干细胞,并基于细胞治疗产品标准筛选出临床级细胞。给予C57BL/6J小鼠自由饮用5%葡聚糖硫酸钠盐水溶液建立急性结肠炎模型,分别在造模前1 d(尾静脉途径)与造模后第4天(腹腔途径)注射空质粒转染的人脐带间充质干细胞或过表达人白细胞介素10基因的人脐带间充质干细胞(1×10~6个/只)。在造模后第6天取结肠组织进行苏木精-伊红染色评估组织学变化,免疫荧光染色检测增殖细胞核抗原与CD31的表达。结果与结论:构建的稳定过表达白细胞介素10的工程化人脐带间充质干细胞,满足临床级人脐带间充质干细胞质量标准;人脐带间充质干细胞对小鼠急性结肠炎具有修复效果,过表达白细胞介素10基因的人脐带间充质干细胞的治疗效果更加优效,更显著地抑制急性结肠炎小鼠的体质量下降(P<0.05)、结肠缩短(P<0.05)以及结肠组织损伤(P<0.05);过表达白细胞介素10基因人脐带间充质干细胞组结肠组织切片中增殖细胞核抗原阳性细胞与CD31阳性细胞显著多于人脐带间充质干细胞组,表明过表达白细胞介素10基因的人脐带间充质干细胞可能通过显著促进肠组织细胞增殖和血管再生进而促进结肠组织修复。

Synthesis and Crystal Structure of an Ion-pair Supramolecular Associate 2,9-Diformyl-1,10-phenanthrolinebis-(2,6-dimethylanil)cobalt(Ⅱ) Perchlorate

2,9-Diformyl-l, 10-phenanthrolinebis（2,6-dimethylanil）cobalt（Ⅱ） perchlorate was synthesized and demonstrated to be [COL2][ClO4]2 by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group C2/c with a = 22.294（4）, b = 15.122（3）, c = 20.640（4） A, β = 119.618（4）°, V = 6048.9（19） A^3, C63H52Cl2CoN9O9, Mr= 1208.97, F（000） = 2504, De= 1.328g/cm^3, Z = 4, μ= 0.436, the final R = 0.0712 and wR = 0.1718 for 1734 observed reflections （I 〉 2σ（I））. In its solid state the helical polymeric chains are supramolecularly associated through intermolecular and interionic hydrogen bonding interactions.

Crystal structure and properties of terbium o-methylbenzoate complex with 1,10-phenanthroline [Tb(o-CH_3C_6H_4COO)_3(C_(12)H_8N_2)]_2

A terbium o-methylbenzoate complex with 1,10-phenanthroline, Tb(o-MBA)_3phen(where o-MBA = o-methylbenzoate and phen = 1,10-phenanthroline) was prepared from ethanol solutionand its crystal structure was determined by X-ray diffraction. The crystal of the complexTb(o-MBA)_3phen belongs to triclinic crystal system and P1 (#2) space group. The crystal data are asfollows: a = 1.4371(4) nm, b = 1.7387(2) nm, c = 1.3109(2) nm, α = 96.37(1)°, β = 107.21(2)°,γ= 82.78(2)°, Ⅴ= 3.094(1) nm^3, Z= 2, M_r = 1489.12, D_c= 1.598 g·cm^(-3), μ = 2.330 mm^(-1)and F(000) = 1488.00. The final R and R_w are 0.038 and 0.047 for 8668 [Ⅰ > 2σ(Ⅰ)] uniquereflections, respectively. In the complex each Tb^(3+) ion is eight-coordinated by one1,10-phenanthroline molecule, one bidentate carboxylate group and four bridging carboxylate groups.The carboxylate groups are bonded to the terbium ion in two modes: the chelating bidentate and thebridging bidentate. Excitation and luminescence data observed at room temperature show that thetitle complex emits strong green fluorescence under ultraviolet light. The results of thermalanalysis indicate that the complex Tb(o-MBA)_3phen is quite stable to heat.

Crystal Structure and Properties of Europium m-Chlorobenzoate Complex with 1,10-Phenanthroline

A europium m-chlorobenzoate complex with 1,10-phenanthroline [Eu(m-ClBA)_3(phen)]_2 single crystal, where m-ClBA=m-chlorobenzoate and phen=1,10- phenanthroline,was prepared and structurally characterized by X-ray diffraction. It crystallizes in triclinic, space group P1- with a=1.10138(8)nm, b=(1.18606(9) nm,) c=1.32516(10) nm, α=112.5390(10)°, β=92.1700(10)°, γ=101.6220(10)°,(C_(66))H_(40)N_4O_(12)Cl_6Eu_2, M_r=1597.64, V=1.5533(2) nm^3, Z=1, D_c=1.708 g·cm^(-3), μ(Mo Kα)=2.325 mm^(-1), (F(000))= 788, the final R=0.0424 and wR=0.0899 for 6856 independent reflections with R_(int)=(0.0776.)The crystal consists of binuclear molecules of the title compound. Each Eu^(3+) ion is nine-coordinated to one 1,10-phenanthroline molecule, one bidentate carboxylate group and four bridging carboxylate groups. The carboxylate groups are bonded to the europium ion in three modes: the chelating bidentate, the bridging bidentate and bridging-chelating thridentate. Excitation and luminescence data observed at room temperature show that the title complex (emits) very intensive red fluorescence under ultraviolet light. The results of thermal analysis indicate that the complex [Eu(m-ClBA)_3(phen)]_2 is quite stable to heat.

Synthesis and Fluorescence Property of Eu^(3+), Tb^(3+) Perchlorate Complexes with Diphenyl Sulfoxide and 1,10-Phenanthroline

Two ternary complexes of RE(ClO_4)_3-DPSO-phen and two binary complexes of RE(ClO_4)_3-phen have been synthesized (RE=Eu, Tb; DPSO=diphenyl sulfoxide, phen=1,10-phenanthroline). Elemental analysis and TG-DTA studies suggest that the ternary complexes consist of RE(ClO_4)_3(DPSO)(phen)_3·nH_2O (n=1, 3) and binary complexes consist of RE(phen)_4(ClO_4)_3. IR spectra studies indicate that the DPSO ligand is bonded with RE(Ⅲ) through oxygen atom in sulfinyl group and phen ligand is bonded to RE(Ⅲ) through nitrogen atom. The molar conductivities measured in the acetonitrile solution indicate that two inorganic anions ClO_4^- are coordinated and binary complexes are nonelectrolyte. In the fluorescent spectra it was found that the fluorescence emission intensity of the ternary complexes more intensive than that of the binary complexes.

Synthesis and Characterization of Rare Earth Nitrates Ternary Complexes with Glycine and 1,10-Phenanthroline

Eight new complexes with the general formula of RE(Gly)(NO_3)_3(phen)_2·3H_2O (RE=La, Ce, Pr, Nd, Gd, Sm, Er, Y) were synthesized and characterized by elemental analysis, molar conductivity, IR spectra, UV spectra and thermal analysis. All the complexes are stable in air and their conductance values in acetonitrile lie in the range of 204.1～239.4 S·cm2·mol -1, indicating 1∶2 type electrolytes. The IR shows that all the COO of glycine and oxygen atom of NO_3- take part in the coordination to the RE ions. The thermal behavior of La complex shows that the weight losses at 75～120 ℃ and 145～170 ℃ correspond to the loss of two lattice water molecules and one coordinated water molecules, respectively.

Synthesis and Spectroscopic Characteriration of Transition MetalComplexes of Maleionitriledithiolene and 1,10-Phenanthroline

The title complex M (mnt) (phen), M=Fe11, Co11. Ni11, Cu11. Zn11. was respectivelysynthesized by reaction of disodium maleionitriledithiolate (Na2 (mnt) ) with corresponding metalcomplex M (phen) Cl2. Charge transfer transitions in the absorption and emission spectra have beenstuded.

Preparation, Crystal Structure and Thermal Decomposition Process of Dysprosium Benzoate Complex with 1,10-Phenanthroline

A dinuclear dysprosium（III） complex with benzoic acid and 1,10-phenanthroline, [Dy（BA）3phen]2 （BA = benzoate, PHEN = 1,10-phenanthroline） （C66H46Dy2NaO12, Mr = 1412.07） was synthesized and characterized by elemental analysis, UV, IR, X-ray diffraction, molar conductance and TG-DTG techniques. It crystallizes in triclinic, space group P1 with a = 10.773（2）, b = 11.933（3）, c = 12.417（5） A, α= 105.226（3）,β= 93.470（3）, γ= 113.475（2）°, V= 1388.0（7）, Z = 1, Dc = 1.689 g/cm3, μ（MoKa） = 2.742 mm-1 and F（000） = 698. R = 0.0210, wR = 0.0538. In the crystal, each Dy（III） ion is eight-coordinated by one bidentate chelating carboxylate group, four bidentate bridging carboxylate groups and one 1,10-phenanthroline molecule. The thermal decomposition process of [Dy（BA）3phen]2 has been determined by thermal analysis.

Influence of ligand architecture on the structure of coordination centre in dimeric europium carboxylates with 1,10-phenanthroline

Methods of optical spectroscopy and X-ray crystallography data were used to examine the effect of architecture of carboxylate anions on structure of the Eu3＋ coordination centre in europium earboxylates with 1,10-phenanthroline Eu（RCOO）3·Phen. Luminescence spectra of europium acetate, nitropropionate, benzoate, naphthylcarboxylates, phenylacetates, phenoxyacetate, triphenylpropionate were investigated. A few of europium carboxylates with 2,2＇-bipyridine Eu（RCOO）3·Bpy and europium salts Eu（RCOO）3·nH2O were also studied. Vibrational IR and Raman spectra of phenylacetate family were analyzed. The crystal structure of nitropropionate Eu（NO2C2H4COO）3·Phen was solved by X-my diffraction method. The predominant influence of steric hindrances on Eu^3＋ coordination centre was observed at increase of the size of aromatic flagment of carboxylate anions. It was demonstrated, that introduction of the methylene bridges between the carboxylic group and aromatic rings of ligand weakens the effect of steric factor.

Preparation and Structural Analysis of Lanthanide Complexes with α-Hydroxyl-phenyl-acetic Acid and 1,10-Phenanthroline as Ligands

A series of ternary lanthanide complexes Ln （C6H5CHOHCOO）3（phen） （H2O） （Ln= La, Ce, Pr, Nd, Sm, Eu） were synthesized with α-hydroxyl-phenyl-acetic acid and 1, 10-phenanthroline （phen） as ligands. The sturcture and property of complexes were characterized by elemental analysis, IR, 1^H-NMR, UV and TGA, and the coordinate mede of both ligands was discussed. It was shown that the co-ordinate mode of 1, 10-phenanthroline was chelated, while α-hydraxyl-phenyl-acetate ion was monedentate or bridging. The mechanism of thermal determinde by thermogravimetry was indicated that the degree of co-ordinate ability of ligand was： α-hydroxyl-phenyl-acetate ion 〉 1, 10- phenanthroline（phen）.

Potassium bisperoxo(1,10-phenanthroline) oxovanadate suppresses proliferation of hippocampal neuronal cell lines by increasing DNA methyltransferases

Bisperoxo(1,10-phenanthroline) oxovanadate(BpV) can reportedly block the cell cycle. The present study examined whether BpV alters gene expression by affecting DNA methyltransferases(DNMTs), which would impact the cell cycle. Immortalized mouse hippocampal neuronal precursor cells(HT_(22)) were treated with 0.3 or 3 μM BpV. Proliferation, morphology, and viability of HT_(22) cells were detected with an IncuCyte real-time video imaging system or inverted microscope and 3-(4,5-dimethylthiazol-2-yl)-5(3-carboxymethonyphenol)-2-(4-sulfophenyl)-2H-tetrazolium, respectively. mRNA and protein expression of DNMTs and p21 in HT_(22) cells was detected by real-time polymerase chain reaction and immunoblotting, respectively. In addition, DNMT activity was measured with an enzyme-linked immunosorbent assay. Effects of BpV on the cell cycle were analyzed using flow cytometry. Results demonstrated that treatment with 0.3 μM BpV did not affect cell proliferation, morphology, or viability; however, treatment with 3 μM BpV decreased cell viability, increased expression of both DNMT3B mRNA and protein, and inhibited the proliferation of HT_(22) cells; and 3 μM BpV also blocked the cell cycle and increased expression of the regulatory factor p21 by increasing DNMT expression in mouse hippocampal neurons.

Shift in pKa of 1,10-Phenanthroline in TBAB and PEG-400 Micellar Media: A Potentiometric Study

The acid-base equilibrium of 1,10-phenanthroline (1,10-phen) in the presence of polyethylene glycol 400 (PEG-400, non-ionic) and tetrabutylammonium bromide (TBAB, ionic) micellar media has been studied by Calvin-Wilson titration technique at different mole fractions (0.5% - 2.5%) of PEG-400 and TBAB micellar solutions at an ionic strength of 0.16 mol dm-3 NaCl and at a temperature of 298 K. The pH metric data were subjected to SCPHD program to obtain correction factor and Kw which were given as initial inputs for MINIQUAD75 program to refine protonation constants. HySS program was then used to generate the species distribution diagrams versus pH using the results obtained from the MINIQUAD75 program and SIM run data. The difference in values of protonation constants in aqueous medium (logβ1 = 4.93 & logβ2 = 6.22) and in the micellar media (PEG-400, logβ1 = 4.89 & logβ2 = 5.91 and TBAB, logβ1 = 4.84 & logβ2 = 5.73) is attributed to different intrinsic solvent characteristics of micelles. In case of ionic surfactants, the electrostatic micellar surface is an additional contributing factor.

Synthesis of 5-Substituted 2, 9-Dimethyl-1,10-Phenanthroline Dialdehydes and Their Schiff Bases with Sulfur-Containing Amines

Eight new Schiff bases of 5-nitro and 5-bromo-substituted 1,10-phenanthroline-2,9-dicarboxaldehydes with sulfur-containing amines, thiosemicarbazide, S-alkyl/aryl dithiocarbazates and 2-mercaptoaniline have been synthesized and characterized by a variety of spectroscopic methods. The condensation reactions of the dialdehydes with the amines were carried out both in the presence and absence of conc. sulfuric acid. A significant increase in yield of the Schiff bases was observed when the reactions were carried out in the presence of sulfuric acid.

Antibacterial Activities of New Schiff Bases and Intermediate Silyl Compounds Synthesized from 5-Substituted-1,10-phenanthroline- 2,9-dialdehyde

Schiff bases are known to possess anticancer, antibacterial, antifungal, antitubercular, anti-inflammatory, antimicrobial and antimalarial properties. In this paper antibacterial studies against variety of plants and human pathogenic bacteria with eight newly synthesized Schiff bases and several intermediate silyl compounds have been reported. The antibacterial activities of the synthesized compounds were primarily determined by paper disc diffusion method. The minimum inhibitory concentration (MIC) of each compound was also determined by tube dilution process. Seven different human pathogenic bacteria and eighteen different plant pathogenic bacteria were used for the antibacterial activity studies. While all synthesized compounds have shown significant antibacterial activity, one intermediate silyl compound has shown remarkably high antibacterial property. 5-substituted derivatives have shown relatively higher activity than non-substituted compounds. Polar substituent which increases hydrophilicity may have a positive impact on the antibacterial property.

Synthesis and Crystal Structure of[Copper(1,10-phenanthroline)_2(pyridine)]perchlorates

The complex [Cu(phen)2py](ClO4)2 was obtained by the reaction of 1,10-phenanthroline with Cu(ClO4)2·6H2O in water and by recrystallization from pyridine. A single-crystal X-ray study shows that the complex is a square pyramidal arrangement of five nitrogen atoms from the two 1,10-phenanthroline ligands and one pyridine ligand, respectively. The compound is orthorhombic, C29H21N5Cl2O8Cu, Mr = 701.958, with space group Pbcn, a = 29.9593(3), b = 16.1240(3), c = 11.9183(6) ?, V = 5757.3(3) ?3, Z = 8, Dc = 1.409g/cm3, μ =1.121 mm-1, F(000) = 2465, R = 0.0539, Rw = 0.1380 for 4293 reflections with I >2σ(I). The bond lengths of Cu(1)－N(1), Cu(1)－N(2), Cu(1)－N(3) and Cu(1)－N(4) are 2.223(3), 2.017(3), 2.013(3) and 2.038(3) ?, respectively. The distance from copper to pyridine N(5) is 2.012(3) ?. The angles N(2)－Cu(1)－N(3) and N(4)－Cu(1)－N(5) are 176.1(1) ° and 160.9(1)°, respectively. The angles between axial position nitrogen atom N (1) and four square position nitrogen atoms N(2), N(3), N(4), N(5) are 79.3(1), 98.3(1), 90.7(1), 108.4(1)°, respectively.