NMR RELAXIVITY AND IMAGING OF NEUTRAL MACROMOLECULAR POLYESTER GADOLINIUM(Ⅲ)COMPLEXES

Five neutral macromolecular polyester gadolinium (Ⅲ) complexes with pendant hydrophobic alkyland aromatic functional groups were prepared. The longitudinal relaxation rates of these complexes weremeasured. One of these Gd (Ⅲ) complexes was chosen for the acute toxicity test and T_1-weighted imagingmeasurement. Preliminary results showed that. compared with Gd-DTPA. the neutral macromoleculargadolinium (Ⅲ) complexes provide higher T_1 relaxivity enhancement and longer function duration.

Synthesis and Crystal Structure of a Binuclear Gadolinium（Ⅲ） Complex Bridged by Cucurbit[6]uril

A new cucurbit[6]uril bridsed binuclear complex {[Gd（H2O）6]2[Q6（H2O）]}C16·4H2O, where Q6 represents cucurbit[6]uril, has been synthesized and characterized by X-ray diffraction. The crystal structure shows that the complex has an extended cucurbit[6]uril-bridged structure consisting of two gadolinium（Ⅲ） ions, in which each gadolinium（Ⅲ） ion is coordinated with two neighboring carbonylic oxygen atoms of Q6 and six oxygen atoms of water molecules that leans toward one side of the portal. One disordered guest water molecule resides in the Q6 molecule cavity and occupies two different positions. Hydrogen bonds assemble the complcx to threedimensional supramolecular structure.

Syntheses and Crystal Structures of Two Gd(Ⅲ) Hydrogen Supramolecules Based on p-Sulfonatothiacalix[4]arene

Two novel polymeric complexes, [Gd（HsTCAS）（H2O）7]·4H2O 1 and [Gd（HsTCAS） （CH3COCH3）（H2O）6]·6H2O 2 （H4TCAS = p-sulfonatothiacalix[4]arene）, have been synthesized and characterized by single-crystal X-ray diffraction analyses. Complex 1 crystallizes in monoclinic, space group C2/m with a = 20.2308（12）, b = 19.0894（10）, c = 12.2448（7）A, β = 101.847（3）°, V = 4628.1（5）A^3, C24H43GdO27S8, Mr = 1169.25, Z = 4, Dc = 1.690 g/cm^3, F（000） = 2380,μ = 1.879 mm^-1, the final R = 0.0404 and wR = 0.1038 for 5127 observed reflections with I 〉 2σ（I）. Complex 2 is pseudo-isostructural with complex 1.

Composition, Stability and Probable Structure of a Colourless Organometallic Complex (Gd(III)-Malic Acid)

The formation of colourless gadolinium complexes (x,y,z), between x gadolinium ions, y ligands and z protons, of some organic acids, has been studied in aqueous solution. In this work we present the results of investigations on the interaction of the gadolinium ion (Gd3+) with malic acid (C4H6O5, a-hydroxyl dicarboxylic acid), in dilute aqueous solution for pH values between 5.5 and 7.5. Colourless gadolinium complexes of malate ions have no absorption band UV-visible, the indirect photometric detection (IPD) technique was used and studies have identified a major tri-nuclear complex of malate ion (﹣OOC-CH2-CHOH-COO﹣). The formation of this new colourless complex is derived from three Gd(III) ions that react with two malate ions and two hydronium ions (H3O+), giving for this colourless complex, a (3,2,2) composition and apparent stability constant depends on the acidity of the medium, with logK'322 = 18.88 ± 0.05 at pH = 6.30. To complement previous results and to propose a probable structure for this new complex detected in solution, studies of IR spectroscopy have been conducted to identify the chelation sites for both ligands. The results were analysed and show that this organometallic gadolinium complex, contains two different sites, respectively, two lateral tetradentate mono-nuclear sites and a single central bidentate mono-nuclear site. From these results, the reaction of formation, the stability constant and the probable structure of this new colourless organometallic gadolinium complex are proposed.

Fabrication of Green Electroluminescent Devices

A gadolinium ternary complex, tris(1 phenyl 3 methyl 4 isobutyryl 5 pyrazolone) (2, 2′ dipyridyl) gadolinium Gd(PMIP) 3(Bipy) was synthesized and used as a light emitting material in the organic electroluminescent devices. The devices exhibited the green electroluminescent (EL) emission peaking at 513 nm, originating from the Gd(PMIP) 3(Bipy). By improving the configuration, the device with a structure of ITO/poly(N vinylcarbazole) (PVK) (40 nm)/Gd(PMIP) 3(Bipy) (40 nm)/tris (8 hydroxyquinoline) aluminum (ALQ) (40 nm)/Mg∶Ag(200 nm)/Ag(100 nm) showed higher performance and a maximum luminance of 340 cd·m -2 at 18 V.

Synthesis and Crystal Structure of Lanthanide Heteropolymolybdate Complex(NH_(4))_(11)Gd[Gd_(4)Mo_(29)O_(100)(H_(2)O)_(23)]·25.75H_(2)O

The title complex crystallizes in the triclinic system, space group P1 with a=16.9568(5), b=18.8631(6), c=24.1640(8), α=100.110(1), β=92\^330(1), γ=113.368(1)°, V=7602.54(4)~3, D_c=3.002 g/cm^3, F(000)=5893, M_r=6245.25, μ(Mo Kα)=5.010mm^-1, Z=2 and final R=0.0722 and wR=0\^1960 for 16015 observed reflections with I≥2σ(I). The Gd(Ⅲ) ion is coordinated by nine oxygen atoms, forming a distorted mono-capped square antiprism, while the Mo(Ⅵ) ions have their different coordination numbers such as 4,5 and 6 with different configurations such as tetrahedron, square pyramid and octahedron, respectively.

Structure and magnetic properties of homobinuclear gadolinium (Ⅲ) complex of isonicotinoyl hydrazone

The crystal structure of [Gd2(μ-L)3(H2O)2].1.5(NO3).1.5 (OH)-5H2O (where L is an-ion of N, N'-Diisonicotinoyl-2-hydroxy-5-methyl-isophthalaIdehyde dihydrazone) has been determined by X-ray diffraction method. The complex crystallizes in the monoclinic system, space group P21/c with a=1.6654(3), b=1.6904(3), c=2.8039(6) nmβ=91.30(3)°, final R factor is 6.3%. The structrue consists of [Gd2(μ-L)3(H2O)2]3+ cation, one and a half nitrate and 1.5 hydroxyl anions and five water molecules. Within dinuclear cation, Gd(Ⅲ)-Gd(Ⅲ) is bridged by oxygen and nitrogen atoms of the three ligands, resulting in Gd...Gd distance of 0.36353(2) nm. Gd(Ⅲ) exhibits a distorted 1333 stack coordination environment. Magnetic susceptibility measurements in the temperature range 300-4 K revealed the occurrence of weak antiferromagnetic exchange interaction between two Gd(Ⅲ) ions with a J value of -0.22, and g of 1.93.

Dopamine-containing gadolinium complex as magnetic resonance imaging contrast agent

Gadolinium diethylenetriamine-pentaacetic bisdopamide （Gd-DTPA-2DA） was synthesized by the incorporation of dopamine to diethylenetriaminepentaacetic acid （DTPA） and further reaction with gadolinium chloride. In vitro and in vivo properties were also evaluated. Gadolinium complex Gd-DTPA-2DA possessed higher relaxation effectiveness and less cytotoxicity to HeLa cells than that of Gd-DTPA. Moreover, Gd-DTPA-2DA greatly enhanced the contrast of MR images of the brains, provided prolonged intravascular duration, and pro- duced highly contrasted visualization of the brain.

Liver-targeting macromolecular MRI contrast agents

Macromolecular ligands with liver-targeting group (pyridoxamine, PM) PHEA-DTPA-PM and PAEA-DTPA-PM were prepared by the incorporation of different amount of diethylenetria-minepentaacetic acid monopyridoxamine group (DTPA-PM) into poly-α, β-[N-(2-hydroxyethyl)-L-aspartamide] (PHEA) and poly-α, β-[N-(2-aminoethyl)-L-aspartamide] (PAEA). The macromolecular ligands thus obtained were further complexed with gadolinium chloride to give macromolecular MRI contrast agents with different Gd(III) contents. These macromolecular ligands and their gadolinium complexes were characterized by1H NMR, IR, UV and elementary analysis. Relaxivity studies showed that these polyaspartamide gadolinium complexes possess higher relaxation effectiveness than that of the clinically used Gd-DTPA. Magnetic resonance imaging of the liver in rats and experimental data of biodistribution in mice indicate that these macromolecular MRI contrast agents containing pyridoxamine exhibit liver-targeting property.

Crystal Structure and Bioactivity of Complex [Gd（C10H9N2O4）（C10H8N2O4）（H2O）3]2·phen·4H2O

A novel gadolinium（Ⅲ） complex with N-（2-propionic acid）-salicyloyl hydrazone （C10H10N2O4, H3L） and 1,10-phenanthroline （C12H8N2, phen） was prepared and characterized. The crystal structure of [Gd（H2L）（HL）- （H2O）3]2·phen·4H2O was determined by X-ray single crystal diffractometry. The crystal complex crystallizes in the triclinic system with space group P-1. There are two 9-coordinated structure units in every complex molecule, in which Gd（Ⅲ） is coordinated by two tridentate ligands （H2L and HL forms） and three water molecules and both the structural units take a distorted monocapped square antiprism. There is a free 1,10-phenanthroline connecting with coordinated water by hydrogen bonds in the crystal. The bioactivity tests indicate that the complex is an inhibitor against three bacteria.