The structural transition of DNA-Tris(1,10-phenanthroline) cobalt(III) complexes in ethanol-water solution

The interaction of DNA with Tris(1,10-phenanthroline) cobalt(III) was studied by means of atomic force microscopy. Changes in the morphologies of DNA complex in the presence of ethanol may well indicate the crucial role of electrostatic force in causing DNA condensation. With the increase of the concentration of ethanol, electrostatic interaction is enhanced corresponding to a lower dielectric constant. Counterions condense along the sugar phosphate backbone of DNA when e is lowered and the phosphate charge density can thus be neutralized to the level of DNA condensation. Electroanalytical measurement of DNA condensed with Co(phen)(3)(3+) in ethanol solution indicated that intercalating reaction remains existing. According to both the microscopic and spectroscopic results, it can be found that no secondary structure transition occurs upon DNA condensing. B-A conformation transition takes place at more than 60% ethanol solution.

Conformation change of horseradish peroxidase in lipid membrane

The electrochemical behavior of horseradish peroxidase (HRP) in the dimyristoyl phosphatidylcholine (DMPC) bilayer on the glassy carbon (GC) electrode was studied by cyclic voltammetry. The direct electron transfer of HRP was observed in the DMPC bilayer. Only a small cathodic peak was observed for HRP on the bare GC electrode. The electron transfer of HRP in the DMPC membrane is facilitated by DMPC membrane. UV-Vis and circular dichroism (CD) spectroscopy were used to study the interaction between HRP and DMPC membrane. On binding to the DMPC membrane the secondary structure of HRP remains unchanged while there is a substantial change in the conformation of the heme active site. Tapping mode atomic force microscopy (AFM) was first applied for the investigation on the structure of HRP adsorbed on supported phospholipid bilayer on the mica and on the bare mica. HRP molecules adsorb and aggregate on the mica without DMPC bilayer. The aggregation indicates an attractive interaction among the adsorbed molecules. The molecules are randomly distributed in the DMPC bilayer. The adsorption of HRP in the DMPC bilayer changes drastically the domains and defects in the DMPC bilayer due to a strong interaction between HRP and DMPC films.

Synthesis and structural characterization of organolanthanide complexes with 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligands

Reactions of anhydrous LnCl(3) (Ln = Nd, Gd, Dy, Er, Yb) with 2 equiv of LiCp' in THF afford the lanthanocene complexes Of CP'(2)Ln(mu-Cl)(2)Li(THF)(2) (CP' = eta(5)-t-BuC5H4, Ln = Nd (1), Gd (2), Dy (3), Er (4), Yb (5); Cp'= 1,3-eta(5)-t-Bu2C5H3, Ln = Nd (6), Gd (7), Dy (8), Er (9), Yb (10)). The molecular structures of 7 and 8 were characterized by X-ray crystallographic analysis. In these complexes, two Cp' ring centroids and two it-bridging chloride atoms around the lanthanide atoms form a distorted tetrahedron. The insertion of elemental chalcogen E (E = S, Se) into Li-C bonds of dilithium o-carborane in THF solution afforded dimers of dilithium. dichalcogenolate carboranes, [(THF)(3)LiE2C2B10H10Li(THF)](2) (E = S (12a), Se (12b)), which were confirmed by a crystal structure analysis. Reactions Of Cp'(2)Ln(mu-Cl)(2)Li(THF)(2) (1-10) with 12a or 12b gave dinuclear complexes of the formula [Li(THF)(4)](2)[Cp'(2)LnE(2)C(2)B(10)H(10)](2) (Cp'= eta(5)-t-BuC5H4, E = S, Ln = Nd (13a), Gd (14a), Dy (15a), Er (16a), Yb (17a); E = Se, Ln = Nd (13b), Gd (14b), Dy (15b), Er (16b), Yb (17b); Cp'= 1,3-eta(5)-t-Bu2C5H3 E = S, Ln = Nd (18a), Gd (19a), Dy (20a), Er (21a), Yb (22a); E = Se, Ln = Nd (18b), Gd (19b), Dy (20b), Er (21b), Yb (22b)). According to the X-ray structure analyses, the dianions of 13a and 13b contain two o-carborane dichalcogenolate bridges, and each CP'2Ln fragment is attached to one terminal and two bridging chalcogen ligands. The central Ln(2)E(2) four-membered ring is not planar, and the direct metal-metal interaction is absent.

Solvent-dependent formation of di- and trinuclear rhodiurn and iridium complexes bridged by N,N '-donor ligands

Reactions of Rh and Ir hydrido complexes. [Rh(H)(2)(PPh3)(2)(solv)(EtOH)]ClO4 (solv = Me2CO, 1a; EtOH, 1b) and [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]BF4 (2), with various N,N'-donor bridging ligands, such as pyrazine (pyz), 4,4'-trimethylenedipyridine (tmdp) and di(4-pyridyl) disulfide (dpds), in some solvents were examined, and their reaction products were characterized by X-ray crystal structure analysis. IR, H-1 NMR and UV-vis spectra. Rh hydrido complexes, la or 1b, formed a dinuclear Rh complex, [Rh-2(PPh3)(2) {(eta(6)-C6H5PPh2}(2)] (ClO4)(2).6CH(2)Cl(2) (3.6CH(2)Cl(2)), in dichloromethane with a reductive elimination of hydrogen. The reactions of 1a or 1b with the pyz ligand in dichloromethane and tetrahydrofuran gave triangular Rh-3 complexes, [Rh-3(PPh3)(6)(pyz)(3)](ClO4)(3).CH2Cl2 (5.CH2Cl2) and [Rh-3(PPh3)(6)(pyz)(3)](ClO4)(3).EtOH (5.EtOH), respectively, in contrast to the formation of a dinuclear Rh hydrido complex, [Rh-2(H)(4)(PPh3)(4)(Me2CO)(2)(pyz)](ClO4)(2).EtOH A-EtOH). in acetone. The reactions of la or 1b with the tmdp ligand in dichloromethane and 3-methyl-2-butanone also afforded dinuclear Rh complexes, [Rh-2(PPh3)(4)(tmdp)(2)](ClO4)(2) (6) and [Rh-2(PPh3)(4)(tmdp)(2)](ClO4)(2).4MeCOCHMe(2) (6.4MeCOCHMe(2)), respectively. On the other hand, Ir hydrido complex 2 reacted with pyz and dpds ligands in dichloromethane to afford dinuclear Ir complexes, [Ir-2(H)(4)(PPh3)(4)(Me2CO)(2)(pyz)]- (BF4)(2).3CH(2)Cl(2) (7.3CH(2)Cl(2)) and [Ir-2(H)(4)(PPh3)(4)(dpds)(2)](BF4)(2).3CH(2)Cl(2).H2O (8.3CH(2)Cl(2).H2O), respectively, without any reductive elimination of hydrogen. Based on structural studies in solution and in the solid state. it was demonstrated that various Rh and Ir complexes were selectively produced depending on the choice of solvents and N,N'-donor bridging ligands.

Synthesis and characterization of a novel hybrid single crystal [Ga-3(PO4)(3)F-2]H3O center dot (H3NCH2CH2)(2)NH2

A novel three-dimensional fluorinated gallium phosphate has been hydrothermally,synthesized by using diethylenetriamine as an organic structure-directing agent. X-ray single crystal structure analysis indicates this compound crystallizes in the orthorhombic space group P-bca, a = 1. 605 6 (7) nm, b = 1.011 4 (4) nm, c=1. 854 6(5) nm, V=3. 011 6(19) nm(3), Z=4. The three-dimensional framework based on linkage of corner-sharing polyhedron PO4, GaO4F and GaO4F2 delimit ten-ring channels along b axis in which the triply protonated amines are located serving as charge compensating guests and supporters.

Synthesis and characterization of metallocenes containing tert-butyl substituted cyclopentadienyl ligands and their activities in ethylene polymerization

The metallocene complexes ((BuC5H4)-Bu-t)(2)MCl2 (M=Ti (1a), Zr (1b), Hf (1c)) and (tBu2C5H3)(2)MCl2 (M=Ti (2a), Zr (2b), Hf (2c)) were synthesized by the react ions of Li (BuC5H4)-Bu-t and (LiBu2C5H3)-Bu-t with metal tetrachloride in THF solution. The complexes were characterized by their IR, H-1-NMR and EI-MS. The molecular structure of Ic was determined by X-ray single-crystal structure analysis. The complexes (1a similar to 2c) exhibited high activities for ethylene polymerizatin (up to 3.2x10(6) gPE/mol.h) in the presence of methylaluminoxane (MAO) at room temperature.

Synthesis and characterization of polynuclear half-sandwich lanthanoid complexes [Na(THF)(6)](2)[(Cp6Sm6Se13)-Sm-t] and [Li(LHF4](2)[Cp6Nd6Se13]

The half-sandwich tert-butyl cyclopentadienyl lanthanoid complexes {[Cp ' Ln(THF)](2)(mu (2)-Cl)(2)(mu (3)-Cl)(3)Na(THF)}(n) [Cp ' = eta (5)-' BuC5H4; Ln = Nd (1a), Sm (1b), Gd (1c), Yb (1d)] are prepared by the reaction of anhydrous lanthanoid trichloride, LnCl(3), with NaCp ' in THF solution. Complex 1b reacts with Na2Se5 to give hexanuclear samarium polyselenide complexes [Na(THF)(6)](2)[Cp-6' SM6(mu (6)-Se)(mu -Se-2)(6)] (2). An analogous cyclopentadienyl neodymium polyselenide complex [Li(THF)(4)](2)[Cp6Nd6(mu (6)-Se)(mu -Se-2)(6)] (3) is synthesized by the reaction of [CpNdCl2. 2LiCl . 5THF] with Na2Se5 in THF solution. The molecular structures of 1a and 2 were determined by X-ray crystal structure analysis. Complex 2 contains an interstitial selenium atom which is coordinated with six samarium atoms. (C) 2001 Elsevier Science BN. All rights reserved.

The NMR-spectroscopic and X-ray crystal-structural characterization of two Cp*Ir halfsandwich complexes containing the 1,2-dicarba-closo-dodecaborane-1,2-diselenolato ligand

The reaction of [Cp*IrCl2](2) with dilithium 1,2-orthocarborane-1,2-diselenolate 3 leads to the green 16-electron diselenolene complex [Cp*Ir{Se2C2(B10H10)}] (4) which takes up two-electron ligands such as trimethylphosphane to give the 18-electron diselenolate derivative [Cp*Ir(PMe3)-{Se2C2(B10H10)}] (5). The molecular structures of 4 and 5 were determined by X-ray crystal structure analysis. The Se-77-nuclear shielding in 4 is lower by almost 500 ppm relative to that in 5.

A new dinuclear molybdenum(V)-sulfur complex containing citrate ligand: synthesis and characterization of K2.5Na2NH4[Mo2O2S2(cit)(2)].5H(2)O

The complex, K2.5Na2NH4[Mo2O2S2(cit)(2)]. 5H(2)O (1), was obtained by crystallization from a solution of (NH4)(2)MoS4, potassium citrate (K(3)cit) and hydroxyl sodium in methanol and water under an atmosphere of pure nitrogen at ambient temperature. The crystals are triclinic, space group , a = 7.376 (3)Angstrom, b = 14.620 (2) Angstrom, c = 14.661 (1) Angstrom, alpha = 71.10 (1)degrees, beta = 81.77 (1)degrees, gamma = 78.27(2)degrees, R = 0.0584 for 2545 observed (I > 2 sigma (I)) reflections. Single crystal structure analysis reveals that citrate ligand coordinated to molybdenum atom through two carboxylato oxygens and one deprotonated hydroxyl oxygen together with two bridging sulfur atoms and a terminal oxygen atom completes distorted coordination octahedron around each molybdenum atom. Principal dimensions are: Mo = O-t, 1.707 Angstrom (av); Mo-S-b, 2.341 Angstrom (av); Mo-O-(hydroxyl), 2.021 Angstrom (av); Mo-O(alpha-carboxyl), 2.1290 Angstrom (av) and Mo-O(beta-carboxyl), 2.268(av) Angstrom. IR spectrum is in agreement with the structure.

Synthesis and polymerization of some macrocyclic (arylene ether sulfone) containing cardo groups and macrocyclic (arylene ether ketone sulfone) oligomers

Some novel macrocyclic (arylene ether sulfone) containing cardo groups and (arylene ether ketone sulfone) oligomers have been synthesized in high yields by a nucleophilic aromatic substitution reaction of 4,4'-difluorophenylsulfone with bisphenols in the presence of anhydrous potassium carbonate under a pseudo-high-dilution condition. Detailed structural characterization of these oligomers by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry (MALDI-TOF-MS), fast atom bombardment mass spectrometry (f.a.b.-m.s.), nuclear magnetic resonance spectrometry (n.m.r.) and single-crystal X-ray structure analysis confirms their cyclic nature, and the composition of the oligomeric mixtures is provided by g.p.c. analysis. Ring polymerization of cyclic oligomers 3a to a high molecular weight polymer with M-w of 59.1 k was achieved by heating at 290 degrees C for 40 min in the presence of a nucleophilic initiator. (C) 1998 Elsevier Science Ltd. All rights reserved.

A new crystal modification of gutta percha

Single chain and pauci chain single crystals of gutta percha in nanometer size were prepared by a dilute solution spraying method. A new crystal modification of gutta percha was found. The unit cell of the new modification of gutta percha was determined by electron diffraction crystal structure analysis to be a hexagonal form with cell dimensions: a = b = 0.695 nm, c = 0.661 nm, alpha = beta = 90 degrees, gamma =120 degrees; the space group is P6. The molecular packing in the unit cell was determined by computer modelling with Cerius(2) 2.0 software. (C) 1998 Elsevier Science Ltd. All rights reserved.

Characterization of the structural and functional changes of hemoglobin in dimethyl sulfoxide by spectroscopic techniques

Circular dichroism (CD), fourier transform infrared (FTIR), and fluorescence spectroscopy were used to explore the effect of dimethyl sulfoxide (DMSO) on the structure and function of hemoglobin (Hb). The native tertiary structure was disrupted completely when the concentration of DMSO reached 50% (v/v), which was determined by loss of the characteristic Soret CD spectrum. Loss of the native tertiary structure could be mainly caused by breaking the hydrogen bonds, between the heme propionate groups and nearby surface amino acid residues, and by disorganizing the hydrophobic interior of this protein. Upon exposure of Hb to 52% DMSO for ca. 12 h in a D2O medium no significant change in 1652 cm(-1) band of the FTIR spectrum was produced, which demonstrated that alpha-helical structure predominated. When the concentration of DMSO increased to 57%: (1) the band at 1652 cm(-1) disappeared with the appearance of two new bands located at 1661 and 1648 cm(-1); (2) another new band at 1623 cm(-1) was attributed to the formation of intermolecular beta-sheet or aggregation, which was the direct consequence of breaking of the polypeptide chain by the competition of S=O groups in DMSO with C=O groups in amide bonds. Further increasing the DMSO concentration to 80%, the intensity at 1623 cm(-1) increased, and the bands at 1684, 1661 and 1648 cm(-1) shifted to 1688, 1664 and 1644 cm(-1), respectively. These changes showed that the native secondary structure of Hb was last and led to further aggregation and increase of the content of 'free' amide C=O groups. In pure DMSO solvent, the major band at 1664 cm(-1) indicated that almost all of both the intermolecular beta-sheet and any residual secondary structure were completely disrupted. The red shift of the fluorescence emission maxima showed that the tryptophan residues were exposed to a greater hydrophilic environment as the DMSO content increased. GO-binding experiment suggested that the biological function of Hb was disrupted seriously even if the content of DMSO was 20%. (C) 1998 Elsevier Science B.V. All rights reserved.

Synthesis and structures of the complexes of beta-alkoxycarbonylethyltin trichlorides with N-aryl-2-hydroxyacetophenylideneimines

Sixteen novel beta-alkoxycarbonylethyltin trichlorides and the corresponding N-aryl-2-hydroxyacetophenylideneimines complexes have been synthesized and characterized. An X-ray crystal structure analysis of the complex of beta-methyloxycarbonylethyltin trichloride and N-4-methylphenyl-2-hydroxyacetophenylideneimine has been performed, The crystal belongs to space group , The cell parameters are: a = 1.0201(6) nm, b = 1.082 2(4) nm, c = 1.394 9(6) nm, alpha = 99.88(3)degrees, beta = 98.63(4)degrees, gamma = 97.86(4)degrees, Z = 2, The ligands coordinate to tin atom via phenolic oxygen atom. Coordination of carbonyl oxygen atom to tin atom still exists in the complexes, The coordination number of tin atom is 6.

INTERACTIONS OF RARE-EARTH LENS WITH BOVINE BLOOD CU(ZN)-SUPEROXIDE DISMUTASE

The interactions of lanthanium trichloride and terbium trichloride with bovine blood Cu (Zn)-superoxide dismutase [Cu(Zn)-SOD] in the aqueous solution of hexamethylenetetrarnine buffer (pH = 6.3) have been studied by using fluorescece, CD and ESR spectra. The results indicated that rare earth ions were coordinated to the carboxyl groups of acidic amino acid residues which were far from active center of the Cu(Zn)-SOD molecule and only lightly disturbed the secondary structure of the enzyme protien, and made the coordination structure of enzyme-bound CU2+ come from the rhombchedron to the axial shape at 77 K and the activity of Cu(Zn)-SOD enzyme was not nearly changed at room temperature.

SYNTHESES AND CRYSTAL-STRUCTURES OF (C8H8)ND(C5H9C5H4)(THF)(2) AND [(C8H8)GD(C5H9C4H4(THF)][(C8H8)GD(C5H9C5H4(THF)(2)]

LnCl(3) (Ln = Nd, Gd) reacts with C5H9C5H4Na (or K2C8H8) in THF (C5H9C5H4 = cyclopentylcyclopentadienyl) in the ratio of 1:1 to give (C5H9C5H4)LnCl(2)(THF)(n) (or (C8H8)LnCl(2)(THF)(n)], which further reacts with K2C8H8 (or C5H9C5H4Na) in THF to form the title complexes. If Ln = Nd the complex (C8H8)Nd(C5H9C5H4)(THF)(2) (a) was obtained: when Ln = Gd the 1:1 complex [(C8H8)Gd(C5H9C5H4)(THF)][(C5H8)Gd(C5H9C5H4)(THF)(2)] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)(2) (Ln = Nd or Gd), the Cyclopentylcyclopentadienyl (eta(5)), cyclooctatetraenyl (eta(8)) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp') in C5H9C5H4 group, cyclooctatetraenyl centroid (COT) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (eta(5)), cyclooctatetraenyl (eta(8)) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp', COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. - 0.0144 Angstrom).