Intercalation Assembly, Characterization and Luminescent Properties of Novel Supramolecular Composite Materials, Tb(Ⅲ) Complex with Tetrapodal Ligand-Montmorillonite

Two kinds of Tb（ Ⅲ ） complexes with tetrapodal ligand, [TbL（NO3）]^3＋ and [TbL]^3＋ （L： 1,1, 1＇, 1＇-tera （ 2-pyridinecarboxylester ）-di （ trimethylpropane）） were intercalated into the interlayer space of montmorillonite （MT） by ion exchange and coordination reaction of L with the Tb^3＋ ion existing in the interlayer space of Tb-MT respectively. The obtained luminescent supramolecular composite materials, [ TbL （NO3） ]^2＋-MT and [TbL]^3＋-MT were characterized by elemental analysis, XRD, FT-IR, UV-vis and thermal analysis. At the same time, the luminescent properties of the materials were also studied. The results show that the intercalated materials with regular layered structure, good thermal stability and the interlayer spacing （d001） approximates to the size of the complex ions which are located in the interlayer space of MT in the form of a monolayer.

Supramolecular Terbium-SIP Complex Pillared by 4,4'-Bipyridyl,{[Tb(SIP)(H_2O)_5]_2(bpy)_3(H_2O)}n:Synthesis,Crystal Structure and Photoluminescence

The supramolecular terbium complex, {[Tb（SIP）（H2O）5]2（bpy）3（H2O）}n （NaH2SIP = 5-sulfoisophthalic acid monosodium salt and bpy = 4,4＇-bipyridyl）, has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a = 30.6840（1）, b = 10.9206（2）, c = 17.4967（3） A, β= 111.931（1）°, V = 5438.65（14） A^3, Z = 4, C46H52N6O25S2Tb2, Mr = 1470.90, Dc = 1.796 g/cm^3, p = 2.747 mm^-1, F（000） = 2928, the final R = 0.0654 and wR = 0.1322 for 3806 observed reflections with I 〉 2σ（I）. In the neutral [Tb（SIP）（H2O）5]2 motif, the Tb（III） ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H...N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Supramolecular Lead(II) Complex with 4-Nitrobenzoic Acid and 1,10-Phenanthroline

A new complex [Pb（phen）2（4-NBA）]2·2（NO3）·H2O（phen = 1,10-phenanthroline,4-NBA = 4-nitrobenzoate） has been hydrothermally synthesized and structurally determined by single-crystal X-ray diffraction,elemental analyses and IR spectroscopy.The complex crystallizes in monoclinic,space group P21/c with a = 13.416（3）,b = 14.065（3）,c = 16.845（3）（A°） ,β = 110.55（3）o,V = 2976.5（10）（A°）^3,Z = 2,Dc = 1.796 g/cm^3,F（000） = 1564,GOOF = 0.962,the final R = 0.0686 and wR = 0.1746.The crystal structure shows that the lead ion is coordinated with two carboxylate O atoms from the 4-NBA anion,and four N atoms from two phen molecules,forming a slightly distorted pentagonalbipyramidal coordination geometry.It is further extended by various supramo-lecular interactions to form a three-dimensional supramolecular network.The TG analysis result shows that this complex begins decomposing at 30 ℃ and decompounding completely at 733 ℃.

The Aggregates in LB Films of Schiff base Aluminium (III) Complex

The surface pressure-area (pi -A) isotherm of Schiff base aluminium (III), tris (2-hydroxy-5-nitro-N-dodecyl-benzylideneaminato) aluminium (III) (denoted as Al(TAl2)(3)), on pure water subphase was investigated. The molecular area, 0.48 nm(2), is one-third of expected value that indicated the aggregation took place. The Langmuir-Blodgett (LB) films of Al(TAl2), was transferred and characterized. The AFM image confirmed the formation of aggregates.

Immp2l Mutation Induces Mitochondrial Membrane Depolarization and Complex Ⅲ Activity Suppression after Middle Cerebral Artery Occlusion in Mice

Objective We previously reported that mutations in inner mitochondrial membrane peptidase 2-like(Immp2l)increase infarct volume,enhance superoxide production,and suppress mitochondrial respiration after transient cerebral focal ischemia and reperfusion injury.The present study investigated the impact of heterozygous Immp2l mutation on mitochondria function after ischemia and reperfusion injury in mice.Methods Mice were subjected to middle cerebral artery occlusion for 1 h followed by 0,1,5,and 24 h of reperfusion.The effects of Immp2l^(+/−)on mitochondrial membrane potential,mitochondrial respiratory complex III activity,caspase-3,and apoptosis-inducing factor(AIF)translocation were examined.Results Immp2l^(+/−)increased ischemic brain damage and the number of TUNEL-positive cells compared with wild-type mice.Immp2l^(+/−)led to mitochondrial damage,mitochondrial membrane potential depolarization,mitochondrial respiratory complex III activity suppression,caspase-3 activation,and AIF nuclear translocation.Conclusion The adverse impact of Immp2l^(+/−)on the brain after ischemia and reperfusion might be related to mitochondrial damage that involves depolarization of the mitochondrial membrane potential,inhibition of the mitochondrial respiratory complex III,and activation of mitochondria-mediated cell death pathways.These results suggest that patients with stroke carrying Immp2l^(+/−)might have worse and more severe infarcts,followed by a worse prognosis than those without Immp2l mutations.

Synthesis,Crystal Structure and Magnetic Properties of a Ni(Ⅱ) Supramolecular Complex Based on Aromatic Polycarboxylate Ligand

A Ni（Ⅱ） supramolecular complex,[Ni 2 （btec）（3py） 2 （H 2 O） 8 ]（H 2 O） 4 （1）,has been synthesized by Ni（ClO 4） 2 ·6H 2 O,benzene-1,2,4,5-tetracarboxylic acid （H 4 btec） and terminal ligand 3-hydroxypyridine （3py） in aqueous solution.The title compound crystallizes in triclinic system,space group P1,with a=8.5637（12）,b=9.4138（13）,c=10.3611（14）,α=67.9540（10）,β=85.1740（10）,γ=76.9890（10）°,V=754.33（18） 3,Z=2,M r=386.96,D c=1.704 Mg/m 3,μ=1.345 mm-1,F（000）=402,the final R=0.0222 and wR=0.0563 for 2675 observed reflections with I 2σ（Ⅰ）.The adjacent discrete molecules are further self-assembled by intermolecular π-π and O-H···O hydrogen bonding interactions to construct a 3D supramolecular framework.Magnetic measurement shows weak ferromagnetic interaction in the range of 2～300 K.

Synthesis,Structure and Thermal Property of a Cobalt Supramolecular Complex Containing N-[(4-Carboxyphenyl)-sulfonyl]glycine

Utilizing N-[（4-carboxyphenyl）-sulfonyl]glycine （abbreviated as cbsglyH3）,a new cobalt complex [Co（cbsglyH）（bipy）2]3H2O （bipy = 2,2＇-bipyridine） has been synthesized under mild conditions and characterized by IR,elemental analysis,thermogravimetric analysis and X-ray diffraction analysis. It crystallizes in the monoclinic system,space group C2/c with a = 34.978（3）,b = 12.0437（11）,c = 20.0041（19） ,β = 122.2990（10）°,V = 7123.0（11） 3,Z = 8,C29H28CoN5O9S,Mr = 681.55,μ = 0.593 mm-1,Dc = 1.271 Kg/m3,F（000） = 2816,the final R = 0.0434 and wR = 0.1351. The title complex is a monomeric compound which is further assembled by intermolecular hydrogen bonds into a 3-D supramolecular network. Thermogravimetric analysis illustrates that this complex begins decomposing at 100 ℃ and decompounding completely at 560 ℃.

[Co^(Ⅲ)(DIEN)(N_(3))_(3)]配合物的合成、晶体结构及量子化学研究

采用配体占位策略和分子自组装原理,选用二亚乙基三胺(DIEN)为有机配体,Co^(3+)为中心金属离子,室温下,通过溶液法合成了一例单核钴配合物[Co^(Ⅲ)(DIEN)(N_(3))_(3)](1)单晶体,利用X射线单晶衍射方法、元素分析和量子化学计算对配合物进行了结构表征和电子结构分析。结构解析表明,该配合物单晶体属于三斜晶系,■空间群,晶胞参数为:a=0.825 3(2)nm,b=0.892 0(3)nm,c=0.898 7(3)nm,α=106.497(4)°,β=90.281(4)°,γ=113.861(4)°,V=0.574 7(3)nm^(3)。中心金属离子Co(Ⅲ)位于拉长八面体配位环境中,每个配合物分子由一个Co(Ⅲ)离子、3个叠氮阴离子和1个二亚乙基三胺组成,一个叠氮离子的两个N原子位置无序,占有率各为50%。单核结构之间通过N—H…N分子间氢键和π…π堆积组装成一维链状超分子结构。此外,以X射线衍射分析得到的晶体结构为计算模型,采用密度泛函理论(DFT)对配合物1的几何构型进行了全构型结构优化和振动频率计算,分析了配合物的单点能、原子电荷分布及前线分子轨道等性质。量子化学计算结果表明该配合物构型为稳定构型,且与实验结果相吻合。

Preparation and Spectroscopic Study of Different Stoichiometric Solid Supramolecular Inclusion Complexes of β-Cyclodextrin with Short Chain Aliphatic Amines

-cyclodextrin 的稳固的超分子的建筑群(有 ethylenediamine 的 -CD) 1， diethylenetriamine 2 并且 triethylamine 3 被获得并且描绘了使用元素的分析，粉末 X 光检查衍射，红外线的光谱学， thermogravimetric 分析，和 1H 原子磁性的回声光谱学。基于元素的分析和 1H NMR 的结果，三稳固的建筑群的客人主人 stoichiometries 决心为 3- 是为为 2--CD, 和 1:3 的 1--CD, 1:1 的 5:2 CD。收益相对到 CD 洞的客人的臼齿的体积比率，并且在顺序增加了：1--CD<2--CD<3- CD。包括建筑群的 X 光检查衍射模式由于在 CD 和客人之间的分子间的 complexations 不仅在衍射山峰的地点而且在形状和山峰的衍射紧张给了很好的展览。主人客人包括建筑群的形成展出了象 1 和 3 那样的 complexed 客人的显然提高的阶段变化温度。当所有另外的质子经历了更低的移动时，在 CD 洞内在更狭窄的边界定位的 H-5 质子在包括之上经历了更高的移动。

Preparation for Supramolecular Complexes of Chiral Diols BDPDD, DMBDPD and BINOL with Some Prochiral Compounds

Interaction between chiral diols BDPDD, DMBDPD and BINOL with prochiral compounds was examined and some new supramolecular complexes were prepared. It was found that these chiral hosts could include prochiral guests, a, b-unsaturated compounds or piper- azinedione derivatives to give inclusion crystals in different molar ratio. Formations of these supramolecular complexes were characterized by the data of IR and 1H NMR spectra.

Supramolecular Sheet Co(Ⅱ) Complex Assembled by Hydrogen Bond

The title complex, [ [ Co （Py） 2 （H20） 2 （ NO3 ）2 ] ] n （ 1 ） was synthesized by liquid/liquid diffusion method at room temperature. The complex crystallizes in monoclinic, space group P2 （1）/C, with a = 0.8775（6）nm, b=1.171 5（8）nm, c=0.7518（5）nm, V=0.739 3（9）nm3, C10H14CoN4O8, Mr= 377.18, Dc=1.694g/cm^3, μ=1.210mm^-1, F（000）=386, Z=2, the final R=0.0229 and wR= 0.066 1 for 3 137 observed reflections （I〉2σ（I））. In the structure of 1, the center atom of cobalt revealed a centrosymmetric, six-coordinate structure, with two Py ligands, two monodentate nitrate groups and two water molecules. It is notable that a series of hydrogen bonds （O-H…O） formed two kinds of rings exist in the structure, which linked neighboring six-coordinate polymer into a two-dimensional H-bonding network, and then assembled into a three-dimensional supramolecular architecture through electrostatic and hydrophobic interaction. In the structure, supramolecular sheet was observed, which contains alte .rnative organic and inorganic layers.

Synthesis, Crystal Structure and Characterization of a One-dimensional Supramolecular Rare Earth Complex of N-(6-(4-Methylpyridinyl))ketoacetamide

A one-dimensional （1D） supramolecular rare earth complex [Nd（NO3）2L2-（C3H6O）][NdL（NO3）4]} （L=N-（6-（4-methylpyridinyl））ketoacetamide） has been prepared and characterized by elemental analysis, IR and electronic spectroscopy, and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system, space group P1^- with a=0.9146（6）, b=1.2581（8）, c=2.2316（14） nm, α=99.352（10）,β=97.209（9）, γ=103.935（9）°, V=2.422（3） nm3, Dc=1.776 g/cm^3, C33H42N12Nd2O25, Mr=1295.27, Z=2, F（000）=1288, μ=2.217 mm-1, R=0.0508and wR=0.1046 for 5173 observed reflections （I 〉 2σ（I））. In the structure of the title complex,one-dimensional supramolecular double-chains are formed by intermolecular hydrogen bonding interactions.

Novel Properties of Supramolecular Complexes Formed by Pairing Cationic Porphyrin and Anionic Metal-Oxo Cluster

MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.

Potent trophic activity of spermidine supramolecular complexes in in vitro models

AIM:To test the growth-promoting activity of the polyamine spermidine bound to various polymeric compounds in supramolecular complexes.METHODS:A thiazolyl blue cell viability assay was used to determine the growth-promoting potency of spermidine-supramolecular complexes in a human skin fibroblast cell line exposed to spermidine and different spermidine-supramolecular complexes that were obtained by combining spermidine and polyanionic polymers or cyclodextrin.Reconstituted human vaginal epithelium was exposed to a specific spermidinesupramolecular complex,i.e.,spermidine-hyaluronan(HA)50,and cell proliferation was determined by Ki-67immunohistochemical detection.Transepithelial electrical resistance and histological analysis were also performed on reconstituted human vaginal epithelium to assess tissue integrity.RESULTS:The effect of spermidine and spermidinesupramolecular complexes was first tested in skin fi-broblasts.Spermidine displayed a reverse dose-related mode of activity with mmol/L growth inhibition,whereas 30%stimulation over basal levels was detected at mol/L and nmol/L levels.Novel spermidine-supramolecular complexes that formed between spermidine and polyanionic polymers,such as HA,alginate,and polymaleate,were then tested at variable spermidine concentrations and a fixed polymer level(0.1%w/v).Spermidine-supramolecular complexes stimulated the cell growth rate throughout the entire concentration range with maximal potency(up to 80%)at sub-mol/L levels.Similar results were obtained with spermidine-(-cyclodextrin),another type of spermidine-supramolecular complex.Moreover,the increased expression of Ki-67 in the reconstituted human vaginal epithelium exposed to spermidine-HA 50 showed that the mode of action behind the spermidine-supramolecular complexes was increased cell proliferation.Functional and morphological assessments of reconstituted human vaginal epithelium integrity did not show significant alterations after exposure to spermidine-HA,thus supporting its safety.CONCLUSION:Spermidine found in spermidine-supramolecular complexes displayed potentiated regenerative effects.Safety data on reconstituted human vaginal epithelium suggested that assessing spermidinesupramolecular complex efficacy in atrophic disorders is justified.

Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co(4,4'-bipy)_2(H_2O)_4]·[Co_2(4,4'-bipy)_3(H_2O)_8]·2TST·2(4,4'-bipy)·4H_2O and [Co(4,4'-bipy)_2(H_2O)_4]DSNT·4,4'-bipy

Two new cobalt（II） supramolecular complexes [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O 1 and [Co（4,4＇-bipy）2（H2O）4]DSNT·4,4＇-bipy 2 based upon the assembly of Co（II）, 4,4＇-bipyridine （4,4＇-bipy） and two new multifunctional organic ligands, 2,4,6-tris（4-sulfophenyl- amino）-1,3,5-triazine （H3TST） and 2,4-bis（p-sulfanilato）-6-diethylamino-1,3,5-triazine （H2DSNT）, have been prepared by hydrothermal method and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal structure of 1 is of monoclinic, space group P21/n with a = 13.599（4）, b = 18.988（6）, c = 22.995（7） A, β = 90.273（6）°, V = 5938（3）A^3, Z = 4, C56H59Co1.5N13O17S3, Mr = 1370.74, Dc = 1.533 g/cm^3, μ = 0.613 mm^-1, F（000） = 2842, GOOF = 1.018, the final R = 0.0796 and wR = 0.1498 for 9019 observed reflections with I 〉 2σ（I）. The crystal structure of 2 belongs to the monoclinic system, space group C2/c with a = 18.864（6）, b = 14.283（5）, c = 20.246（7）A, β = 107.799（6）°, V = 5194（3）A^3, Z = 4, C49H52CoN12O10S2, Mr = 1092.08, Dc = 1.397 g/cm^3, μ = 0.480 mm^-1, F（000） = 2276, GOOF = 1.059, the final R = 0.0665 and wR = 0.1900 for 4887 observed reflections with I 〉 2σ（I）. The results of X-ray crystal structure analysis revealed that complexes 1 and 2 exhibit layered supramolecular frameworks stabilized by electrostatic interactions, π-π interactions and hydrogen bonds.

STUDY ON BINUCLEAR COPPER(I)COMPLEXES III.SYNTHESIS,CHARACTERIZATION AND ELECTROCHEMISTRY OF DICHLORO-TRIS(4-VINYLPYRIDINE)-DICOPPER(I)COMPLEX

Recent years,many novel complexes have been prepared by using hetero-bidentate ligands.However,complexes with such ligands as 4-vinylpyridine which has two different coordinating sites have not been reported,and only a few complexes of Cu(I)have been published^(1-3).The title complex Cu_2(C_5H_4N·CH=CH_2)_3Cl was prepared and characterized by elemental analyses,ICP,IR,and electronic spectra.Its conductivity,oxidation potential and reduction potential were measured.

CRYSTAL STRUCTURE OF A 2D SHEET－LIKE μ－CYANIDO－OXAMIDATO BRIDGED Fe（III）－Cu（II） HETERNUCLEAR COMPLEX

The synthesis is and crystal structure are reported for the sheet-like compourd [CU2(oxpn)Fe(CN )5(NO)]. there oxpn is the dianion of M, M'-bis(3-aminopropyl)oxamide. This compound crustallizes in the orthogonal space group Puma. with a=11 .413(4), b=22.242(5), c=7.736(2) A, and Z=4.The structure was refined to conventionat discrepancy factors R=0.047 and Pw=0.054. The Cu(II ) and Fe(III)centers are bridged by oxpn and cyanide, the formal behaves as a his-terdentate tigand bound to cooper(II)ion to form (II) dimers. whereas the latter bridges Cu(II) and Fe(III) centers in both symmetric and asymetric end- to-end bis-monodentate fashions, spreading out along be plane to form a 20 network. The Structure is made up of CuFe unit with Cu(II) and Fe(III) ions locating in a distorted square-based pyramid and a compressed octahedron, respectively.

Synthesis, characterization, and stability of iron (III) complex ions possessing phenanthroline-based ligands

It has previously been demonstrated that phenanthroline-based ligands used to make gold metallotherapuetics have the ability to exhibit cytotoxicity when not coordinated to the metal center. In an effort to help assess the mechanism by which these ligands may cause tumor cell death, iron binding and removal experiments have been considered. The close linkage between cell proliferation and intracellular iron concentrations suggest that iron deprivation strategies may be a mechanism involved in inhibiting tumor cell growth. With the creation of iron (III) phen complexes, the iron binding abilities of three polypyridal ligands [1,10-phenanthroline (phen), 2,9-dimethyl-1, 10-phenanthroline (methylphen), and 2,9-di-sec-butyl-1, 10-phenanthroline (sec-butylphen)] can be tested via a competition reaction with a known iron chelator. Therefore, iron (III) complexes possessing all three ligands were synthesized. Initial mass spectrometric and infrared absorption data indicate that iron (III) tetrachloride complex ions with protonated phen ligands (RphenH+) were formed: [phenH][FeCl4], [methylphenH][FeCl4], [sec-butylphenH][FeCl4]. UV-vis spectroscopy was used to monitor the stability of the complex ions, and it was found that the sec-butylpheniron complex was more stable than the phen and methylphen analogues. This was based on the observation that free ligand was observed immediately upon the addition of EDTA to the [phenH][FeCl4] and [methylphenH] [FeCl4] complex ions.

Periodate Oxidation of a Ternary Complex of Nitrilotriacetatochromium(III) Involving ß-Alanine as Co-Ligand

The kinetics of the periodate oxidation of chromium(III)-complex, [CrIII(NTA)(Ala)(H2O)]-(NTA = Nitrilotriacetate and Ala = &#223;-alanine) to Cr(VI) have been carried out for the temperature range 15°C - 35°C under pseudo-first order conditions, >>?[complex]. Reaction obeyed first order dependence with respect to and [Cr(III)], and the rate of reaction increases with increasing of pH for the range 3.40 - 4.45. Experimentally, the mechanism of this reaction is found to be consistent with the rate law in which the hydroxo species, [CrIII(NTA)(Ala)(OH)]2- is considerably much more reactive than their conjugate acid. ΔH* and ΔS* have been calculated. It is proposed that electron transfer occurs through an inner-sphere mechanism via coordination of to chromium(III).

FERROMAGNETICALLY COUPLED Gd(III)Cu(II)Gd(III)TRINUCLEAR COMPLEXES

Three new heterotrinuclear complexes have been synthesized and characterized, namely {[Gd(L)(2)](2)[Cu(pbaOH)]}(ClO4)(4), where pbaOH denotes 2-hydroxy-1,3-propylenebis(oxamato), L stands for 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen) or 2,2'-bipyridyl (bpy). The temperature dependence of the magnetic susceptibility of ([Gd(phen)(2)(ClO4)](2)[Cu(pbaOH)])(ClO4)(2) has been studied in the 4-300K range, giving the exchange integral J = 6.69 cm(-1). This indicates a weak ferromagnetic interaction between the copper(II) and gadolinium(III) ions.