Growth of NaBi（WO4）2 Dendrite and Mechanism

The solid-liquid interface motion of NaBi（WO4）2 （NBWO） melt crystal growth is observed in an in situ system, in which the whole processes of interface transition from fiat interface and cellular to dendrite are visualized. The spacing of the dendrite under smaller temperature gradient turns out to be larger than that under larger temperature gradient, which is found to be sensitive to the temperature distribution. The mechanism of dendrite growth of NBWO is studied based on the model of the growth units of anion coordination polyhedra. The { 001} face has two apex links, so it shows higher stability and has high growth rate and forms the arm of dendrite, whereas the {010} face has only one apex link, and thus shows relative slower growth rate and firstly forms the branches.     

Theoretical and experimental investigation of the linear optical response of YBa2Cu4O8 The relevance of LDA calculations

We report results of ellipsometric measurements of the dielectric tensor of YBa₂Cu₄O₈ as well as calculations employing density functional theory in the local density approximation (LDA). For the computation of the one-electron eigenvalues and states the linear-muffin-tin-orbital method (LMTO) was used. Measured and calculated results show good agreement. In particular, the calculation predicts different band structures for YBa₂Cu₃O₇ and YBa₂Cu₄O₈ in the vicinity of the Fermi energy which lead to significant differences in the optical spectra. One such difference is a region of small ε₂ in the near infrared which is a fingerprint of the high (relative to the top of the highest fully occupied band) Fermi energy as compared to the situation in YBa₂Cu₃O₇. Our experimental results confirm the theoretical findings.     

In Situ Observation of Skeletal Shape Transition during BaB2O4 Crystal Growth in High-Temperature Solution

The transition from a fiat solid-liquid interface to a skeletal shape during BaB2O4 （BBO） single crystal growth in Li2B4O7 flux is observed in real time by an optical high-temperature in-situ observation system. The movement of crystal step is also investigated. The observation results demonstrate that the steps propagate along and parallel to the fiat interface when the crystal size is small. Nevertheless, they will ‘bend＇ close to the face centre if the crystal size becomes greater. Atomic force microscopy reveals that more deposition places near the face centre give rise to the bending of advancing steps and thus the formation of a vicinal interface structure. Measurements of step velocity show that the velocity keeps nearly constant at different moments for one specific step, whereas the step on a newly formed layer advanced faster than that on a previously formed one when the crystal size is larger than 210μm or so. Thus interracial morphological instability occurs and a skeletal interface is obtained.     

Rod–coil block copolymers: An iterative synthetic approach via living free-radical procedures

A modular approach has been developed for the synthesis of rod–coil block copolymers involving the initial preparation of a macroinitiator based on the rod block followed by the growth of the coil segment with living free-radical procedures. The key feature of this strategy is the utilization of an alkoxyamine group from the beginning of the synthesis, which serves as a solubilizing group and ensures that each rod block contains a single initiating fragment. Using this approach permits block copolymers based on insoluble biphenyl ester oligomers to be conveniently prepared with coil segments that range from styrenes to acrylates to 1,3-dienes. The tendency of the rod segments to crystallize is strongly dependent on the weight fraction of the rod segment and the chemical nature of the coil segment. Rod–coil molecules containing at least 25–35 wt % polystyrene or poly(n-butyl acrylate) coil segments show a two-dimensional hexagonal arrangement of rod aggregates, as characterized by transmission electron microscopy and small-angle X-ray scattering. Polyisoprene block copolymers exhibit a lamellar microstructure with short rigid domains in which the rod units lie in an interdigitated smectic C arrangement. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3640–3656, 2003     

TDPAC studies of Hf doped YBCO

Time differential perturbed angular correlation measurements of the 133–482 keVγ-γ cascade of¹⁸¹Ta in Hf-doped YBa₂Cu₃O_7−x are presented. The¹⁸¹Hf precurser nuclei are incorporated into the sample by thermal neutron irradiation. Two quadrupole interaction frequencies are observed in the as-irradiated sample:v _Q1=161±10 MHz with intensityf ₁=75%, asymmetry parameterη ₁=0.32 and damping parameter Λ₁=0.42, andv _Q2=1108±40 MHz withf ₂=25%,η ₂=0.62, and Λ₂=0.60. On annealing the sample in air at various temperaturesT _a and quenching to room temperature,f ₁ remained nearly constant forT _a<600°C andv _Q1 for all annealing temperatures indicating that these are insensitive to oxygen stoichiometry. This frequency is interpreted to be due to¹⁸¹Hf substitutingY sites. BeyondT _a=600°C,f ₁ increased and reached a constant value of 90% forT _a=800°C. The value ofv _Q2 showed a slight variation between 1086 and 1160 MHz, whilef ₂ remained nearly constant at 25% forT _a<600°C. This component is identified to be due to¹⁸¹Hf substituting Cu 1 sites in the Cu-O chains of YBCO. Above 600°Cv _Q2 decreased and reached a value of 808 MHz beyond 750°C.     

Eucaglobulin, A New Complex of Gallotannin and Monoterpene from Eucalyptus globulus

EucalyPtusgl0bulusLabill.(Myrtaceae)isakindofmedicinalplantwidelydistributedintheYunnanpr0vinceofChina.ItSleaves,rootSandffoitShavebeenusedastraditionalremediesforthetreatmentofinfluenza,dysentery,enteritis,rheumatalgiaandbleeding.BesidesvolatileterpenoidconstituentSintheessential0iloftheleavesandfruits,theoccurrenceofanumber0fphloroglucinol-sesquiterpene-or-m0n0terpene-c0upledcomPoundsnamedmacrocarpals'andeugl0bals'intheleavesandbudshasbeenrepofted.Inordertostudythechendcalandbioactivecon…     

Polymerization of acrylamide initiated by peroxomonosulphate and metal ion catalysis

The kinetics of polymerization of acrylamide initiated by potassium peroxomonosulphate, in the presence and absence of Ag⁺, were studied. Rates of polymerization and oxone disappearance were followed. From the rate law for the polymerization, a mechanism has been proposed.     

Ion-Bearing Propellers: Alkali Metal Complexes of Tris(2-alkoxyphenyl)amine Ionophores

NMR spectroscopic studies reveal that binding of Na(+) by tris(2-methoxyphenyl)amine (3) brings two of these tripod ethers together about the metal ion; the related double-tripod-ether ionophore 1,2-bis[2-(bis(2-methoxyphenyl)amino)phenoxy]ethane (4), in which two triarylamines are covalently attached, binds LiI, LiBPh(4), NaI, NaBPh(4), and KB(4-ClPh)(4). Dynamic NMR puts lower limits on binding free energies of 4 for Na(+) (71.8 kJ mol(-)(1)) and K(+) (66.8 kJ mol(-)(1)) ions. X-ray studies of 3(2).NaBPh(4), 4.NaBPh(4), 4.NaB(4-ClPh)(4), and 4.KB(4-ClPh)(4).CH(3)NO(2) show eight-coordinate M(+) ions bound between crystallographically independent, homochiral triarylamine tripod ethers in structures reminiscent of alkali metal [2.2.2] cryptates. Complexes crystallize as follows: 3(2).NaBPh(4), monoclinic, P2(1)/c, Z = 4, a = 10.701(3) ?, b = 37.593(3) ?, c = 13.774(2) ?, and beta = 98.24(2) degrees; 4.NaBPh(4), triclinic, P&onemacr;, Z = 2, a = 12.157(1) ?, b = 14.811(1) ?, c = 15.860(2) ?, alpha = 105.400(8) degrees, beta = 91.594(9) degrees, and gamma = 95.354(8) degrees; 4.NaB(4-ClPh)(4), monoclinic, P2(1)/n, Z = 4, a = 13.652(5) ?, b = 18.75(1) ?, c = 22.805(5) ?, and beta = 92.21(5) degrees; 4.KB(4-ClPh)(4).CH(3)NO(2), monoclinic, Pn, Z = 2, a = 13.663(4) ?, b = 12.228(3) ?, c = 18.712(8) ?, and beta = 91.45(3) degrees. They show variable N-M-N angles; 3(2).NaBPh(4) is surprisingly bent ( angleN-Na-N = 154.5 degrees ), while the 4.M(+) complexes are normal: nearly linear for Na(+) ( angleN-Na-N = 178.6, 178.1 degrees ) and again bent with the larger K(+) ( angleN-K-N = 164.5 degrees ). Finally, free 4 is structurally similar to 3; it crystallizes in the triclinic space group P&onemacr;, with Z = 2, a = 8.068(1) ?, b = 14.599(2) ?, c = 16.475(3) ?, alpha = 115.43(1) degrees, beta = 92.51(1) degrees, and gamma = 90.40(1) degrees.     

In situ UV-visible spectroelectrochemical studies on the copolymerization of diphenylamine with ortho-methoxy aniline

UV-visible spectroelectrochemical studies on copolymerization of diphenylamine (DPA) with ortho-methoxy aniline (OMA) were carried out for different feed ratios of DPA and OMA using indium tin oxide (ITO)-coated glass as working electrode. The UV-visible spectra show clear dependencies on the molar feed composition of DPA or OMA used in electropolymerization. Derivative cyclic voltabsorptogram (DCVA) was deduced at the wavelengths corresponding to the absorption by the intermediate species and used to confirm the intermediates generated during the electropolymerization. The composition of DPA and OMA in the copolymer for the copolymers synthesized with different molar feed ratios of DPA and OMA was determined by UV-visible spectroscopy. Reactivity ratios of DPA and OMA were deduced by using Fineman-Ross and Kelen-Tudos methods and correlated with spectroelectrochemical results.