Phase identification in a series of liquid crystalline TPP polyethers and copolyethers having highly ordered mesophase structures. 6. Structure changes from smectic to columnar phases in a series of copolyethers containing odd and even numbers of methylene units in equal molar composition

A series of liquid crystalline copolyethers has been synthesized from 1-(4-hydroxy-4'-biphenyl)-2-(4-hydroxyphenyl)propane and different alpha,omega-dibromoalkanes [coTPP(n/m)]. In this report, coTPPs having n = 5, 7, 9, 11 and m = 12 are studied, which represent copolyethers having both varying odd number and a fixed even number of methylene units. The compositions were fixed at an equal molar ratio (50/50). These coTPPs(nlm) show multiple phase transitions during cooling and heating in differential scanning calorimetry experiments. The undercooling dependence of these transitions is found to be small, indicating that these transitions are close to equilibrium, Although the coTPPs possess a high-temperature nematic (N) phase, the periodicity order along the chain direction is increasingly disturbed when the length of the odd-numbered methylene units decreases from n 11 to 5. in the coTPPs(5/12, 7/12, and 9/12), wide-angle X-ray diffraction experiments at different temperatures show that, shortly after the N phase formation during cooling, the lateral molecular packing improves toward a hexagonal lattice, as evidenced by a gradual narrowing of the scattering halo. This process represents the possible existence of an exotic N phase, which serves as a precursor to the columnar (Phi(H)) phase. A further decrease in temperature leads to a (PH phase having a long-range ordered, two-dimensional hexagonal lattice. In coTPP(11/12), the phase structures are categorized as highly ordered and tilted, smectic and smectic crystal phases, similar to homoTPPs, such as the smectic F (S-F) and smectic crystal G (SCG) phases. An interesting observation is found for coTPP(9/12), wherein a structural change from the high-temperature Phi(H) phase to the low-temperature S-F phase occurs. It can be proven that, upon heating, the well-defined layer structure disappears and the lateral packing remains hexagonal. The overall structural differences in this series of coTPPs between those of the columnar and highly ordered smectic phases are related to the disorders introduced into the layer structure by the dissimilarity of the methylene unit lengths in the comonomers.

Metal-oxo cluster-supported transition metal complexes: hydrothermal synthesis and characterization of [{M(phen)(2)}(2)(Mo8O26)] (M = Ni or Co)

Two new metal-ore supported transition metal complexes, E{M(phen)(2)}(2)(Mo8O26) (M = Ni or CO; phen = 1,10-phenanthroline) are synthesized by a hydrothermal method and characterized by X-ray crystallography, showing that the octamolybdate possesses a novel unprecedented structure and that [M(phen)(2)](2+) units are covalently bonded to the [Mo8O26](4-) cluster.

Synthesis and characterization of a water-soluble endohedral metallofullerol

A water-soluble endohedral metallofullerol, Pr@C82Om(OH)(n)(m approximate to 10 and n approximate to 10), was successfully synthesized through the reaction of a pure endohedral metallofullerene, Pr@C-82, with a concentrated nitric acid and a subsequent hydrolysis process. The formation of endohedral metallofullerols Pr@C82Om(OH)(n) is thought to involve a NO2 radical formation step, in much the same way as the reaction of empty fullerenes. FT-IR, XPS, and LD-TOF MS techniques were employed to characterize the structure of the endohedral metallofullerol from the above reaction.

Voltammetric study of vitamin K-3 at interdigitated array microelectrodes

Cyclic voltammetry of Vitamin K-3 (V-K3) was measured with Pt disk electrode, platinum interdigitated array (Pt-IDA) and Au-IDA microelectrodes in single and dual modes. The effects of pH, scan rate and collector potential on the current of generator and collector were studied. The collection efficiency of V-K3 at IDA electrodes was measured. The linear ranges for current response as a function of V-K3 concentration were found to he 10 mu M-1 mM (i(g)) and 1 mu M - 1 mM (i(c)) for the generator and collector of the Pt-IDA electrode, respectively. The effects of waiting time, potential difference and pulse electrolysis time in differential pulse voltammetry (DPV) on the peak current of V-K3 were studied to get the optimal condition at 0.1 M Na2HPO4, pH 11.50 and 11.0 for Au-IDA and Pt-IDA, respectively.

Crystal Structure of [PrAl(CF3COO)(2)(CF3CHOO)(C2H5)(2)(C4H8O)(2)](2)

[PrAl (CF3COO)(2) (CF3CHOO) (C2H5)(2) (C4H8O)(2)](2) M-r = 1420. 56, monoclinic, P2(1)/n, a = 10. 651 (6) , b = 24. 276(9), c = 11. 110(5) Angstrom, beta = 107. 650 (4)degrees , V = 2737. 4(1) Angstrom (3) , Z = 2, D-c = 3. 45 g/cm(3) , F(000) = 2816 , T = 233K, MoK alpha radiation (lambda= 0. 71069 Angstrom), mu(MoK alpha) = 38. 017 cm(-1) , R = 0. 048 for 2847 observed reflections (I greater than or equal to 3 sigma(I)). It is isostructural with [LnAl (CF3COO)(2) (CF3CHOO) -R-2 (C4H8O)(2)](2) (Ln = Ho, R = Et; Ln = Ndt Y, R = Bu-1). Pr3+ is coordinated by eight oxygen atoms from five bridging ligands and two THF forming a distorted bicap-prism.

Luminescent properties of divalent samarium-doped strontium hexaborate

The valence change of samarium from trivalent to divalent in strontium hexaborate (SrB6O10) prepared in air is observed. The temperature dependence of the luminescence and vibronic transitions of Sm2+ are studied. The Sm2+ ions occupy three crystallographic sites. With increasing temperature, the D-5(0)-->F-7(0) transition line exhibits red shifts, and the half-width increases. At room temperature, due to the thermal population through the 4f(5)5d channel, the D-5(1)-->F-7(J) transitions are observed even though the vibrational energy is very close to the energy gap between the D-5(1) and D-5(0) levels in the host. A coupled phonon energy of about 108 cm(-1) is determined from the vibronic transitions of Sm2+ in the host.

A simple method for the selective enrichment of endohedral metallofullerenes

The concentration of a polar solvent DMF extract was found to be very effective for the selective enrichment of endohedral metallofullerenes against empty fullerenes. As the solvent evaporated, endohedral metallofullerenes were effectively enriched in the solution, while most of empty fullerenes (especially C-60 and C-70) were precipitated because of their scant solubility in DMF. Matrix-assisted laser-desorption-ionization time-of-fligh mass spectrometry analysis indicated that the purity of endohedral metallofullerenes increased dramatically after concentration of the DMF extract solution. Upon transferring the extract into toluene, a solution containing significantly enriched endohedral metallofullerenes was obtained. The different solubilities of endohedral metallofullerenes versus empty fullerenes are considered to account for this selective enrichment of endohedral metallofullerenes.

Fabrication and characterization of heteropolyanion Langmuir-Blodgett films

The possibility of the formation of Langmuir-Blodgett (LB) films with dimethyldioctadecylammonium (DODA) after the addition of cobalt(II)-substituted Dawson-type tungstodiphosphate anion (briefed as (H2O)(CoP2W17O618-)-P-11) in the subphase has been explored. Marked modifications of the compression isotherms are observed when this anion is dissolved in the subphase, which demonstrates that the polyanions interact with the monolayers. LB films have been readily obtained from this system. The adsorption Fourier transform IR (FT IR) spectroscopy, atomic force microscopy (AFM), X-ray diffraction (XRD) and cyclic voltammetry (CV) have been used to investigate the morphological and molecular structure of the deposited film. The FT IR results showed the presence of the polyanion within the LB films, and the shift for its characteristic bands may be related to the presence of positively charged DODA. AFM measurement reveals that the LB films of DODA/(H2O)(CoP2W17O618)-P-II are regularly and uniformly deposited on the substrate. XRD experiments prove that the lamellar structure of the LB films of DODA/(H2O)(CoP2W17O618-)-P-II is well-defined. The LB films of DODA/(H2O)(CoP2W17O618-)-P-II immobilized onto an indium-oxide (ITO) glass, in aqueous solutions of pH 2.0-5.0, show quite facile redox reactions even for multilayers. All the experiments carried out in the present study suggest that the new materials of heteropolyanions can be formed by LB techniques and beneficial physicochemical properties of heteropolyanions can be maintained/enhanced through molecular-level design. (C) 1999 Elsevier Science S.A. All rights reserved.

Evaluation of luminol-H2O2-KIO4 chemiluminescence system and its application to hydrogen peroxide, glucose and ascorbic acid assays

(A) novel chemiluminescence (CL) system was evaluated for the determination of hydrogen peroxide, glucose and ascorbic acid based on hydrogen peroxide, which has a catalytic-cooxidative effect on the oxidation of luminol by KIO4. Hydrogen peroxide can be directly determined by luminol-KIO4 -H2O2 CL system. The detection limit was 3.0 x 10(-8) mol l(-1) and the calibration graph was linear over the range of 2.0 x 10(-7)-6.0 x 10(-4) mol l(-1). The relative standard deviation of H2O2 was 1.1% for 2.0 x 10(-6) mol l(-1) (N = 11). Glucose was indirectly determined through measuring the H2O2 generated by the oxidation of glucose in the presence of glucose oxidase at pH 7.6. The present method provides a source for H2O2, which, in turn, coupled with the luminol-KIO4-H2O2 CL reaction system. The CL was linearly correlated with glucose concentration of 0.6-110 mu g ml(-1). The relative standard deviation was 2.1% for 10 mu g ml(-1) (N = 11). Detection limit of glucose was 0.08 mu g ml(-1). Ascorbic acid was also indirectly determined by the suppression of luminol-KIO4-H2O2 CL system. The calibration curve was linear over the range of 1.0 x 10(-7)-1.0 x 10(-5) mol l(-1) of ascorbic acid. The relative standard deviation was 1.0% for 8.0 x 10(-7) mol l(-1) (N = 11). Detection limit of ascorbic acid was 6.0 x 10(=8) mol l(-1). These proposed methods have been applied to determine glucose, ascorbic acid in tablets and injection. (C) 1999 Elsevier Science B.V. All rights reserved.

Structural analysis of nonlinearities of Ca4ReO(BO3)(3) (Re = La, Nd, Sm, Gd, Er, Y)

From the chemical bond viewpoint, second-order nonlinear optical (NLO) tensor coefficients of the family of new oxoborates Ca4ReO(BO3)(3) (CReOB, Re = La, Nd, Sm, Gd, Er, and Y) have been theoretically predicted. The d(11) tensor coefficient of CReOB is predicted to be -11 d(36)(KDP), which is the largest d(ij) tensor that has been found in borate crystals. From the structural characteristic of CReOB, we find the isolated BO33- clusters play a dominant role in contributions to the total nonlinearity, and the largest d(11) tensor of CReOB-type crystals is also ascribed to these BO33- clusters. We also find the NLO property of this family does not change dramatically for different rare-earth elements. The details of the calculation of CGdOB only are presented.

Stability and luminescence properties of Tb (III) complexes with adrenaline

Stability and luminescence properties of Tb (III) complexes with adrenaline have been studied. The Tb (III) complexes with adrenaline are quite stable. The fluorescence spectra of the Tb (III) complexes with adrenaline show the characteristic fluorescence bands of Tb (III) ions which are attributed to energy transfer from ligands to Tb (III) ions.

Study on the bond covalency and bond susceptibility in NdCr1-xMxO3 (M=Mn, Fe, Co)

Bond covalency, bond susceptibility and macroscopic linear susceptibility in NdCr1-xMxO3 (M=Mn, Fe, Co, 0.0 less than or equal to x less than or equal to 1.0) are investigated by complex chemical bond theory. The results indicate the bond covalencies are insensitive to the doping level. With the increasing doping level, the macroscopic linear susceptibilities increase for M=Mn, Fe, decrease for M=Co. The valence state of Cr can be strongly influenced by the properties of the doping ions.

Synthesis, crystal structure and properties of (Z)-3-triphenylstannyl-1,1-diphenyl propenol

Five new organotin compounds were synthesized and characterized, X-ray crystal structure analysis of (Z)-3-triphenylstannyl-1,1-diphenyl propenol was performed, The crystal belongs to space group P2(1)/n. The cell parameters are: a = 1.235 7(2) nm, b = 0.987 4(2) nm, c = 2.208 1(4) nm, beta = 95.23(3)degrees, V = 2.683 0(9) nm(3), Z = 4, R = 0.027 9, R-w = 0.064 5. The tin atom of the molecule exists in a distorted tetrahedron, Z isomer of double bond is obtained.

Detection of specific noncovalent protein-fullerenols complexes by matrix-assisted laser desorption ionization mass spectrometry

Matrix-assisted laser desorption ionization (MALDI) mass spectrometry is difficult for the characterization of noncovalent complexes hitherto because of the limitations in acidic matrix, sample preparation, laser-induced polymerization and adduct formation with matrix. Under our experimental conditions, sinapinic acid is used as a matrix, the specific noncovalent interactions of protein with fullerenols were observed by MALDI mass spectrometry. Some mass spectrometric features, such as mass shifts, broad adduct peaks and stoichiometries, showed that the specific non-covalent complexes between protein and fullerenols have been formed at a ratio of 1 : 4 for hemoglobin-fullerenols or 1 : 1 for myoglobin-fullerenols. The results implied that fullereneols could be used to protect partly hemoglobin from decomposition in acidic media, and therefore, it is possible to realize the molecular weight determination of a quaternary protein by MALDI mass spectrometry via the addition of specific organic compound in the matrix.