Adsorption of dicarboxylates on nano-sized gibbsite particles: effects of ligand structure on bonding mechanisms

The adsorption of the dicarboxylates o-phthalate, maleate, fumarate, malonate, and oxalate (representing ligands with the general composition ⁻O₂C---C_n---CO₂⁻; n=0, 1, or 2) on gibbsite were studied by means of quantitative batch adsorption experiments and attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The interpretations of ATR-FTIR spectra were aided by comparison with IR spectra of solution species and by results from theoretical frequency calculations. The main objectives of the study were to identify the molecular level bonding mechanisms of the dicarboxylates to gibbsite, and to investigate how these were influenced by the composition and structure of the ligands. Carboxylates with n=2 formed predominantly outer sphere complexes, whereas the importance of inner sphere complexes progressively increased for n=1 and 0. The inner sphere structures were identified as mononuclear chelates with one oxygen from each carboxylate group bonded to Al(III) at the surface. This showed the importance of chelate ring structure for the formation of inner sphere surface complexes, with stabilities of the complexes increasing in the order seven-membered ring less than six-membered ring less than five-membered ring. For ligands with n=2 only small variations in surface speciation were observed as a function of steric factors; irrespective of the relative positions of the carboxylate groups and bulkiness of the ligands outer sphere bonding is the dominating adsorption mode. Adsorption experiments were also conducted with gibbsite particles exhibiting differences in shape and surface roughness. These experiments showed that inner sphere complexes were favored on the less well-developed and more irregular gibbsite particles.     

A new cytotoxic limonoid from Odontadenia macrantha from the Suriname rainforest

Bioassay‐guided fractionation of the methanol extract of Odontadenia macrantha afforded a new limonoid, odontadenin A (1) and two known triterpenoids, lupeol (2) and α‐amyrin (3). The structure of 1 was established on the basis of 1D and 2D NMR and high‐resolution fast atom bombardment mass spectrometric data. The new compound was found to possess moderate cytotoxicity against A2780, the ovarian cancer cell line. Copyright © 2003 John Wiley & Sons, Ltd.     

Synthesis and characterization of wholly aromatic poly(azomethine)s containing donor–acceptor triphenylamine moieties

N‐(4‐nitrophenyl)‐4′,4″‐bisformyl‐diphenylamine was synthesized from N‐(4‐nitrophenyl)‐diphenylamine by the Vilsmeier‐Haack reaction. Soluble aromatic poly(azomethine)s (PAMs) were prepared by the solution polycondensation of N‐(4‐nitrophenyl)‐4′,4″‐bisformyl‐diphenylamine and aromatic diamine in N‐methyl‐2‐pyrrolidone (NMP) at room temperature under reduced pressure. All the PAMs are highly soluble in various organic solvents, such as N,N‐dimethylacetamide (DMAc), chloroform (CHCl₃), and tetrahydrofuran (THF). Differential scanning calorimetry (DSC) indicated that these PAMs had glass‐transition temperatures (T_gs) in the range of 170–230 °C, and a 10% weight‐loss temperatures in excess of 490 °C with char yield at 800 °C in nitrogen higher than 60%. These PAMs in NMP solution showed UV‐Vis charge‐transfer (CT) absorption at 405–421 nm and photoluminescence peaks around 462–466 nm with fluorescence quantum efficiency (Φ_F) 0.10–0.99%. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of these PAMs can be determined from cyclic voltammograms as 4.86–5.43 and 3.31–3.34 eV, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4921–4932, 2007     

Structure–electrical property study of anisotropic polyaniline films

The relationships of the structure and electrical properties of anisotropic HCl‐doped polyaniline (PANI) films cast from N,N′‐dimethylpropylene urea (DMPU) solutions and stretched to different draw ratios were studied. The anisotropic structure of the stretched PANI films was examined by X‐ray diffraction, near‐infrared wave‐guide coupling, and polarized infrared measurements. The PANI emeraldine base (EB) films cast from DMPU solutions had a single‐phase noncrystalline structure, and stretching of the films did not cause crystallization to occur. The transition moment angles of two weakly absorbing infrared bands were determined, and the Hermans' orientation functions for the PANI EB films were calculated. The PANI films were then doped with HCl, and the electrical properties were determined by impedance spectroscopy. With a specially designed test fixture, the in‐plane and through‐plane impedance was obtained. The conductivity along the stretch direction increased with orientation. The in‐plane conductivity was significantly higher than the through‐plane conductivity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 823–841, 2003     

Structure induced by irradiation of femtosecond laser pulse in dyed polymeric materials

We investigated the structures induced by an irradiation of a near‐infrared (NIR) femtosecond laser pulse in dye‐doped polymeric materials {poly(methyl methacrylate) (PMMA), thermoplastic epoxy resin (Epoxy), and a block copolymer of methyl methacrylate and ethyl acrylate‐butyl acrylate [p(MMA/EA‐BA) block copolymer]}. Dyes used were classified into two types—type 1 with absorption at 400 nm and type 2 with no absorption at 400 nm. The 400‐nm wavelength corresponds to the two‐photon absorption region by the irradiated NIR laser pulse at 800 nm. Type 1 dye‐doped PMMA and p(MMA/EA‐BA) block copolymer showed a peculiar dye additive effect for the structures induced by the line irradiation of a NIR femtosecond laser pulse. On the contrary, dye‐doped Epoxy did not exhibit a dye additive effect. The different results among PMMA, p(MMA/EA‐BA) block copolymer, and Epoxy matrix polymers are supposed to be related to the difference of electron‐acceptor properties. The mechanism of this type 1 dye‐additive‐effect phenomenon for PMMA and p(MMA/EA‐BA) block copolymer is discussed on the basis of two‐photon absorption of type 1 dye at 400 nm by the irradiation of a femtosecond laser pulse with 800 nm wavelength and the dissipation of the absorbed energy to the polymer matrix among various transition processes. Dyes with a low‐fluorescence quantum yield favored the formation of thicker grating structures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2800–2806, 2002     

Possible application of X-ray optical elements for reducing the spectral bandwidth of an X-ray SASE FEL

A new design for a single pass X-ray Self-Amplified Spontaneous Emission (SASE) FEL is proposed. The scheme consists of two undulators and an X-ray monochromator located between them. The first stage of the FEL amplifier operates in the SASE linear regime. After the exit of the first undulator the electron bunch is guided through a non-isochronous bypass and the X-ray beam enters the monochromator. The main function of the bypass is to suppress the modulation of the electron beam induced in the first undulator. This is possible because of the finite value of the natural energy spread in the beam. At the entrance to the second undulator the radiation power from the monochromator dominates significantly over the shot noise and the residual electron bunching. As a result the second stage of the FEL amplifier operates in the steady-state regime when the input signal bandwidth is small with respect to that of the FEL amplifier. Integral losses of the radiation power in the monochromator are relatively small because grazing incidence optics can be used. The proposed scheme is illustrated for the example of the 6 nm option SASE FEL at the TESLA Test Facility under construction at DESY. As shown in this paper the spectral bandwidth of such a two-stage SASE FEL (Δλ/λ 5 × 10⁻⁵) is close to the limit defined by the finite duration of the radiation pulse. The average brilliance is equal to 7 × 10²⁴ photons/(s × mrad² × mm² × 0.1% bandw.) which is by two orders of magnitude higher than the value which could be reached by the conventional SASE FEL. The monochromatization of the radiation is performed at a low level of radiation power (about 500 times less than the saturation level) which allows one to use conventional X-ray optical elements (grazing incidence grating and mirrors) for the monochromator design.     

Thickness of a silica-tethered poly(ethylene oxide) layer measured by spin labeling

EPR spectroscopy of labeled poly(ethylene oxide) (PEO) grafted on silica has been used to characterize the conformation and local dynamics of the chains. Grafted molecules of MW 2000 with grafting ratios of 0.045, 0.057, 0.126, and 0.42 molecules/nm² were in contact with benzene. The mobility of the label was compared with that observed for solution of PEO from very diluted to highly concentrated and even bulk PEO. Thus, the concentration inside the grafted layer could be evaluated and also the thickness, which evolves rather linearly with the grafting ratio. © 1995 John Wiley & Sons, Inc.     

Fluorinated,crosslinkable terpolymers based on vinylidene fluoride and bearing sulfonic acid side groups for fuel‐cell membranes

The radical terpolymerization of 8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene with vinylidene fluoride (VDF) and perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride is presented. Changing the feed compositions of these three fluorinated comonomers enabled us to obtain different random‐type poly[vinylidene fluoride‐ter‐perfluoro(4‐methyl‐3,6‐dioxaoct‐7‐ene) sulfonyl fluoride‐ter‐8‐bromo‐1H,1H,2H‐perfluorooct‐1‐ene] terpolymers containing various sulfonyl fluoride and brominated side groups. Yields higher than 70% were reached in all cases. The hydrolysis of the sulfonyl fluoride group into the ? SO₃Li function in the presence of lithium carbonate was quantitatively achieved without the content of VDF being affected, and so dehydrofluorination of the VDF base unit was avoided. These original terpolymers were then crosslinked via dangling bromine atoms in the presence of a peroxide/triallyl isocyanurate system, which produced films insoluble in organic solvents such as acetone and dimethylformamide (which totally dissolved uncured terpolymers). The acidification of ? SO₃Li into the ? SO₃H function enabled protonic membranes to be obtained. The thermal stabilities of the crosslinked materials were higher than those of the uncured terpolymers, and their electrochemical performances were investigated. According to the contents of the sulfonic acid side functions, the ion‐exchange capacities ranged from 0.6 to 1.5 mequiv of H⁺/g, whereas the water uptake and conductivities ranged from 5–26% (±11%) and from 0.5 to 6.0 mS/cm, respectively. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4566–4578, 2006     

Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007