Growth Response and Metal Accumulation of Sedum alfredii to Cd/Zn Complex-Polluted Ion Levels

Sedum alfredii Hance has been identified as a new Zn-hyperaccumulator native to China. In this study, responses and metal accumulation of S alfredii were examined under Zn/Cd complex polluted conditions. The results showed that optimal growth of S alfredii in terms of the maximum dry matter yield was observed at Zn/Cd complex level of 500/100 mumol/L. Plant cadmium (Cd) or zinc (Zn) concentrations increased with increasing Cd or Zn supply. During the 20 d treatment, the highest Cd concentration in the leaves reached 12.1 g/kg at Zn/Cd level of 50/400 mumol/L and that of Zn in the stems was 23.2 g/kg at Zn/Cd level of 1000/50 mumol/L. The distribution of Cd in different plant parts decreased in the order: leaf > stem greater than or equal to root, whereas that of Zn was: stem > leaf greater than or equal to root. The accumulation of Cd and Zn in the shoots and roots of S. alfredii increased with the increasing of Zn/Cd supply levels, peaked at Zn/Cd levels of 250/400 and 500/100 mumol/L, respectively. The highest Cd and Zn uptake by the shoots was approximately 5 and 11 mg/plant, and was over 20 and 10 times higher than those in the roots, respectively. Zn supply at levels less than or equal to 500 mumol/L increased plant Cd concentrations, whereas high Zn supply decreased root Cd but did not affect leaf Cd concentrations in S alfredii Low Cd supply increased Zn concentration in the leaves, but Cd supply higher than 50 mumol/L considerably reduced root Zn concentrations, especially at low Zn level. These results indicate that S. alfredii can tolerate high Zn/Cd complex levels and has an extraordinary ability to hyperaccumulate not only Zn but also Cd. It could provide a new valuable plant material for understanding the mechanisms responsible for co-hyperaccumulation of Zn and Cd as well as for phytoremediation of the Cd/Zn complex polluted soils.

Synthesis,Structure and Luminescent Property of a New Cd(Ⅱ) Complex Containing 2-Propyl-imidazole-4,5-dicarboxylate

A new Cd（Ⅱ） complex（[Cd（H2PIDC）2]n） with singly deprotonated 2-propyl-imidazole-4,5-dicarboxylate as bridging ligand was synthesized and characterized by X-ray diffraction method.Crystal data：monoclinic,space group P21/c,with a=8.2547（11）,b=10.7071（15）,c=13.9131（14）A,β=126.164（5）o,V=992.8（2）A^3,C16H18N4O8Cd,Mr=506.74,Z=2,Dc=1.695g/cm^3,F（000）=508,μ=1.151 mm^-1,R=0.0296 and wR=0.0812 for 1581 observed reflections.Singly deprotonated ligands（H2PIDC-） act as μ3-bridge and join the Cd（Ⅱ） atoms into a 2-D layer structure.The 2-D layers are further linked by intermolecular hydrogen bonds into a 3D network.The luminescent property of the complex was also investigated.

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.

Syntheses and Crystal Structures of Two New Hg(Ⅱ) and Cd(Ⅱ) Complexes with 2,3,5,6-Tetrakis-(2-pyridyl)Pyrazine

Under thermal gradient in solution phase, the reaction of Hg（Ⅱ） and Cd（Ⅱ） salts with 2,3,5,6-tetrakis-（2-pyddyl）pyrazine （tppz） in 1：1 molar ratio afforded dinuclear [{HgI2}2}- tppz）] （1） and mononuclear [CdI2（tppz）] （2） complexes. Single-crystal X-ray diffraction structural analysis reveals that the tppz acts as bis-tridentate and tridentate chelating ligands in 1 and 2, respectively. Metal（Ⅱ） ions adopt a distorted square pyramidal geometry and have the same coor- dination environment in both complexes. Based on the 1H NMR spectroscopy measurements, both complexes decompose in solution and release free tppz.

Hydrothermal Syntheses, Crystal Structures and Luminescence Properties of Cu(Ⅱ) and Cd(Ⅱ) Complexes Assembled by 6-Hydroxypicolinic Acid and 1,10-Phenanthroline

Two new complexes based on 6-hydroxypicolinic acid(H_2picO) and 1,10-phenanthroline(phen), such as [Cu_4(picO)_4(phen)_4]·12 H_2O(1) and {[Cd_4(picO)_4(phen)_4(H_2O)_2]·5H_2O}_n(2), have been synthesized and characterized by IR, elemental analyses, thermogravimetric analyses and X-ray diffraction technique. Single-crystal X-ray diffraction analyses revealed that the two complexes both crystallize in the triclinic system, space group P(16)-. For complex 1, the picO ligands adopt a tridentate coordination mode to link copper(Ⅱ) ions into dimmers. PicO ligands also adopt a tridentate mode in complex 2, which connects the cadmium(Ⅱ) to form a one-dimensional chain. Moreover, luminescent properties of 1 and 2 were also investigated.

Syntheses,Structures and Photoluminescent Properties of Cd(Ⅱ)Polymeric Complexes Based on 5-Aminoisophthalic Acid and Bipyridine Co-ligands

Two novel complexes, namely {[Cd（AIP）（4,4＇-bpy）]·1.3DMF}n（1） and [Cd（AIP）（2,2＇- bpy）]n（2）, have been synthesized through solvothermal reaction（H2AIP = 5-aminoisophthalic acid, 2,2＇-bpy = 2,2＇-bipyridine, 4,4＇-bpy = 4,4＇-bipyridine, and DMF = N,N＇-dimethylformamide） and structurally determined by single-crystal X-ray diffraction. Complex 1 shows a three-dimensional（3D） layer-pillar framework with rectangular channels, while complex 2 displays a two-dimensional（2D） wave net architecture. Furthermore, 1 and 2 were characterized by elemental analysis, infrared spectra（IR）, thermal gravimetric analyses（TGA） and fluorescence measurements. The luminescent properties of 1 dispersed in various organic solvents have been investigated systematically, demonstrating high selectivity for acetone via the fluorescence quenching effect.

Indirect Spectrophotometric Determination of Sulphide with the Complex of Cd(Ⅱ)-5-Br-PADAP-CPB

By the use of CPB, Cd(Ⅲ) forms a highly sensitive complex with 5-Br-PADAP in aqueous solution, molar absorptivity εis 1. 21 ×105 1. mol-1. cm-1.Trace amount of sulphide can be determined from its effect on the complex of Cd (Ⅲ)-5-Br-PADAP-CPB, sulphide in the range 0~3. 2 ×10-6mol dm-3 causes a decrease in absorption, that is a linear function of the concentration, For 13ng cm-3 sulphide, common metal ions such as Na+, K+, Ca2+, Mg2+, Al3+ and anions such as CO (24μg cm-3). S2O (22μg cm-3). PO (20μg cm-3) etc. do not interfere. A method for the indirect determination of sulphide in beer and in dustrial waste water with good selectivity and accuracy is described.

Observation of Reciprocal Induced CD between Colloidal Gold Nanoparticles and Chiral Schiff Base Zn （11） Complexes with Parallel Dipole Moments

The authors have prepared suprameolecular systems of chiral Schiffbase ZnAZSB （Zn（II） complexes with azo-groups） or without ZnSB （azo-groups） and colloidal AuNP （gold nanoparticles） of 10, 40 and 80 nm diameters. They exhibited gradual shifts of surface plasmon bands as well as fluorescence bands. The authors observed and discussed induced CD bands on gold nanoparticles from chiral ZnAZSB or ZnSB. Absence of cis-trans photoisomerization of ZnAZSB with AuNP also supported direct contact near the surface of AuNP. Quenching and splitting of fluorescence bands of ZnSB （λex = 550 nm and λem = 400 nm） depending on concentration of ZnSB and size of AuNP also suggested intermolecular （electric） interaction on the surface of AuNE Decrease of the intensity of the CD band around 380 nm resulted from reciprocal induced CD effect due to parallel arrangement of electric transition moments of ZnAZSB or ZnSB and surface of AuNP.

The First Hybrid Wells-Dawson-type Polytungstate Monosupported by Cd-coordination Complex via Di-bridging O-atom

Polyoxometalates（POMs） with Cd-coordination complexes acting as supporting units are rarely reported. The linkage of the supporting units with inorganic building block（polyanion） is generally established on terminal O-atoms, but scarcely via bridging O-atoms. By introducing liquid small organic molecule（pyridine, C5NH5） as assistant ＂structure-directing agent＂, we obtained a novel organic-inorganic hybrid polytungstate,（Hpy）4[Cd（phen）2（P2W18O62）]·nH2O（1, n ≈ 3, py = pyridine, phen = 1,10-phenanthroline）, under hydrothermal conditions. The single-crystal X-ray diffraction analysis shows that 1 is the first compound containing an asymmetric heteropolyanion, [Cd（phen）2（P2W18O62）]4–, a Wells-Dawson-type polyanion monosupported by Cd-coordination complex via di-bridging O-atoms.

Synthesis and CD Spectra of Chiral Molybdenum-fullerenyl Complexes with Pineno-bipyridine Ligands

The synthesis and characterization of two chiral fullerene complexes (+)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(RR))] 1 and (-)_(430)^(CD)-[Mo(η~2-C_(60))(CO)_3(L^(SS))] 2 were described. The CD spectra of 1 and 2 inthe visible range show weak Cotton effects, which are approximately of mirror image, indicatingthat the appended pineno-groups with opposite chirality in bipyridines can perturb the fullerenechromophores through the molybdenum centers and lead to induced CD effects.

Synthesis,Structure and Physical Properties of Mn and Cd Complexes with 1,1,2,2-Tetracarboxyl-ethylene Acid

Complex [Mn（tce） 0.5（H2O） 4]（1） was obtained from Mn（OAc） 2 and tce,where tce is 1,1,2,2-tetracarboxyl-ethane. The structure of 1 is a single molecule,in which Mn（II） is a distorted octahedron coordinated to six oxygen atoms. Complex [Cd（tce） 0.5（H2O） 3]（H2O） （2） fea-tures a pillared layer architecture. The Cd（II） atom is in an octahedral environment coordinated by six oxygen donors from water molecules and tce ligands. Cd（II） atoms are interlinked by the tce ligand to generate a 2-D wavelike layer. The layers are strutted by the intermolecular O-H···O hydrogen bonds to form a 3-D open framework. Luminescence property of complex 2 was investigated. Magnetic property of complex 1 was also studied. 1 belongs to triclinic,space group P1 with a = 6.2901（12） ,b = 8.0212（15） ,c = 8.0769（15） A,α = 108.522（3） ,β = 95.068（3） ,γ = 97.086（3） °,V = 379.92（12）A^3,Mr = 456.08,Dc = 1.993 g/cm^3,F（000） = 232,μ = 1.748 mm^-1,Z = 1,the final R = 0.0297 and wR = 0.0731 for 1575 observed reflections with I 〉 2σ（I） . 2 is of monoclinic system,space group P21/c with a = 6.4367（14） ,b = 9.495（2） ,c = 13.907（3）A,β = 117.405（8） °,V = 754.6（3） A^3,Mr = 285.51,Dc = 2.513 g/cm^3,F（000） = 556,μ = 2.905 mm^-1,Z = 4,the final R = 0.0375 and wR = 0.0737 for 1521 observed reflections with I 〉 2σ（I）.

Syntheses,Crystal Structures and Thermal Properties of Two Dicadmiun(II) Complexes Cd_2L_2X_2(HL=N-(3-Methoxylsalicylidene)-3-dimethylaminopropylamine,X = Cl(1),NCS(2))

Two Cd（Ⅱ） complexes, Cd2L2Cl2 （1） and Cd2L2（NCS）2 （2） （HL = N-（3-methoxylsalicylidene）-3-dimethylaminopropylamine） were synthesized and determined by EA, IR, TG and single-crystal X-ray diffraction. The crystallographic data are as follows： monoclinic, space group P21/n, a = 9.2710（9）, b = 18.0069（18）, c = 18.5562（19） A^°, β= 99.741（4）°, V = 3053.1（5）, Z = 4,μ = 1.605, F（000） = 1536, R = 0.0264 and wR = 0.0699 for 1; orthorhombic, space group Pca21, a = 16.196（3）, b = 11.506（2）, c = 36.126（7） A^°, V = 6732（2）, Z = 8,μ = 1.428, F（000） = 3264, R = 0.0376 and wR = 0.0877 for 2. There are two geometrically different octahedral Cd（Ⅱ） atoms, with N4O2 and O4Cl2 donor sets for 1 while N4O2 and N2O4 for 2. In the dinuclear Cd（Ⅱ） centers, the Cd（Ⅱ） atoms are held together by two deprotonted phenolate oxygen atoms from tetradentate L^- ligands. The thermal gravity data show two step decompositions with the residues of CdO for two complexes.

Synthesis and Crystal Structure of a Novel Terpyridine-based Cd(Ⅱ) Complex

A novel terpyridine-based complex CdL＇S2 （L＇ = oxide of L; L = 10-hexyl-3-（2,6- di（pyridine-2-yl）pyridine-4-yl）-10H-phenothiazine） has been solvothermally synthesized and characterized by FT-IR spectroscopy, elemental analysis, 1HNMR and X-ray crystallography. The sulfur of phenothiazine moiety was oxidized when the crystal is formed. The complex C36H37CdN5O2S3 crystallizes in triclinic, space group P1 with a = 9.4452（9）, b = 13.0181（14）, c = 14.6721（18） A, a = 73.872（1）, β = 81.531（1）, y = 87.547（2）°, V= 1714.2（3） A3, Mr = 780.29, Dc= 1.512 g.cm-3,μ = 0.861 mm-l, F（000） = 800, Z = 2, the final R = 0.0456 and wR = 0.1059 for I 〉 2σ-（I）. The Cd（II） is coordinated by two terminal sulfur ions and three pyridyl nitrogen atoms in a distorted trigonal bipyramidal geometry. Universal hydrogen bonds between the neighboring molecules have generated a supramolecular arrangement which contributes to the stability of the title complex. Fluorescence property and thermogravimetry of the complex have also been investigated and discussed.

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,Crystal Structure and Magnetic Property of a New Cd(Ⅱ) Complex with Four Nitronyl Nitroxide Radicals

A new Cd（Ⅱ） complex with four nitronyl nitroxide radicals [Cd（NIT4Py）4Cl2]（NIT4Py = 2-（4＇-pyridinyl）-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide） has been synthesized and structurally characterized by X-ray diffraction analysis.It crystallizes in triclinic,space group P1 with a = 7.2441（4）,b = 13.6964（8）,c = 13.7354（8） ,α = 89.8610（10）,β = 77.9180（10）,γ = 87.2250（10）°,V = 1331.01（13） 3,C48H64CdCl2N12O8,Mr = 1120.41,Z = 1,Dc = 1.398 g/cm3,μ（MoKα） = 0.573 mm-1,F（000） = 582,S = 1.043,the final R = 0.0257 and wR = 0.0641 for 4333 observed reflections（I 〉2σ（I））.The title complex exists in the mononuclear-metal structures,in which each Cd（Ⅱ） ion adopts a distorted octahedral geometry and is coordinated by two Cl-anions and four pyridyl-N atoms from four NIT4Py ligands.The magnetic measurements show weak antiferromagnetic interactions between the nitroxide radicals.

A Porous 3D Supramolecular Architecture of Cd(II) Complex with Water Clusters as Pillars

A supramolecular complex of Cd（II） with 1D water tapes as pillars[Cd2（dpa）2（phen）2（H2O）2]·6H2O 1 （H2dpa = diphenic acid, phen = phenanthroline）, has been synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1^- with a = 9.7029（4）, b = 11.9601（5）, c = 12.1788（4） A, α = 71.6990（10）, β = 71.8740（10）, γ = 74.4680（10）°, V = 1252.39（8） A^3, C52H48Cd2N4O16, Mr = 1209.76, Z= 1, Dc = 1.604 g/cm^3,μ = 0.925 mm^-1, F（000） = 612, R = 0.0679 and wR = 0.2514 for 3870 observed reflections （I 〉 2σ（I））. Two intramolecular Cd（II） centers of this complex are encircled by two dpa^2- ligands forming an 18-membered ring, which is further assembled into a pillared three-dimensional （3D） supramolecular architecture through the synergetic effect of intermolecular face-to-face π…π stacking and weak O-H…O hydrogen-bonding interactions. Moreover, this complex exhibits photoluminescence with the main emission bands located at about 456 nm upon excitation at 355 nm in the solid state at room temperature.

Solvothermal Synthesis and Crystal structure of a Two-dimensional Cd(Ⅱ) Complex Based on a Flexible Carboxylate Ligand

A two-dimensional Cd（Ⅱ） coordination polymer, [Cd（dtb）]n （dtb = 5,5 ＇-dithiobis（2- nitrobenzoic acid）, has been solvothermally synthesized and characterized by elemental analysis, IR, TG analysis and single-crystal X-ray diffraction analysis. The complex crystallizes in the monoclinic P21/c space group, with a = 10.7147（10）, b = 7.4518（7）, c = 22.053（2） A, β = 95.477（2）°, V = 1752.7（3） A3, Z = 4, Mr = 524.74, Dc= 1.989 g/cm3 and F（000） = 1032. The final R = 0.0453 and wR = 0.1201 for 2950 observed reflections with 1 〉 2σ（I）. In the complex, the Cd（Ⅱ） ion is coordinated with six oxygen atoms from four different carboxylate groups of dtb ligands and one lattice water molecule. The adjacent Cd centers are interconnected by the flexible carboxylate ligand to form a two-dimensional （2D） structure.

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 = ß-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).