FT‐IR and Isotherm Study on Anion Adsorption onto Novel Chelating Fibers

A new chelating fiber, poly(acrylo‐amidino diethylenediamine), was synthesized based on polyacrylonitrile fibers in diethylenetriamine with the aid of AlCl₃. Complex formation with CrO₄^2– was strongly pH‐dependent, as complexes formed only in the presence of NH₃⁺ and NH₂⁺. In the medium pH region, both ionic and hydrogen bonds were formed between poly(acrylo‐amidino diethylenediamine) and the chromate ion, as was confirmed by means of FT‐IR spectroscopy.     

Study on syntheses of phosphates and transition‐metal complexes on viscose rayon felt for flame retardancy

High‐performance materials for flameproofing, phosphates (polyphosphate and ammonium phosphate) were synthesized on viscose rayon felt. This surface reaction has the advantage of a nonblooming effect and an application in thermosetting plastics. Metal complexes have the effect of reducing the amount of smoke. Therefore, in the second step, transition‐metal complexes were synthesized on the viscose rayon ammonium phosphate felt. This article focuses on the surface modification of phosphates and metal complexes on viscose rayon. All reactions were confirmed by attenuated total reflectance Fourier transform infrared and time‐of‐flight secondary ion mass spectrometry. As the concentrations of phosphoric acid and urea increased, the peak intensities of ammonium ion groups and phosphate groups greatly increased. The thermal properties of the synthesized materials were studied with thermogravimetric analysis and oxygen index testing. On the basis of the experimental results, the synthesized flame‐retardancy materials showed excellent physicochemical and thermal effects and flame retardancy. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2815–2823, 2000     

Microstructure effect in the coupling reactions of polymeric organolithium compounds using chlorosilanes

The most important variable affecting the yield in the coupling reactions of polymeric organolithium compounds with chlorosilane compounds has been investigated through size-exclusion chromatographic (SEC) analysis. The coupling reaction of poly(styryl)lithium with dichlorodimethylsilane as a silane-coupling agent provided 44 wt % of the coupling yield. The coupling yield, depending on the chain end reactivity of active polymers, was not greatly affected. The addition of a Lewis base such as N,N,N′,N′-tetramethylethylenediamine (TMEDA) even after complete polymerization of the dienes in hydrocarbon seems to affect the coupling reaction, resulting in decreasing the yield. The 1,2- or 3,4-enchain contents in the polydiene backbones affected the reduction of the linking efficiency in the coupling of the poly(dienyl)lithiums with chlorosilanes as the linking agent. The linking yields of the active polymers including over 75 mol % of 1,2- or 3,4-enchainment on the polydiene segment were below 20 wt %. The linking yields exhibited a dependence not only on the steric requirement of the chain end, but also the microstructure of the polydiene segment. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1743–1753, 1998     

Simultaneous measurement of refractive index and thickness with a convergent beam

A new approach to the simultaneous measurement of refractive index and thickness based on the focus shifts of a convergent beam intercepted by a test plate is proposed. By using ray optics, a defined focus shift can be derived as a function of the refractive index and thickness as well as the angular position of the test plate with respect to the optical axis. From a pair of focus shifts obtained at two different angular positions, it is shown that the desired measurands can be simultaneously determined without prior knowledge of either parameter. A simulation result for the proposed concept based on graphically solving the equations of their respective focus shifts is presented.     

Synthesis of alkaloid-like compounds via the bridging Ritter reaction

Abstract  

Alkaloid-like compounds containing a benzo[c]azepine core structure were successfully prepared in three steps from 5H-dibenzo[a,d]cyclohepten-5-ol via the bridging Ritter reaction. Biological studies of these compounds revealed that some of them are AChE inhibitors and antimalarial agents.     

Pseudopolymorphic Clathrate Structures Formed by an Alicyclic Dialcohol Inclusion Host

Dialcohol host 2,7-dimethyltricyclo[4.3.1.0^3,8]undecane-syn-2,syn-7-diol 1 can form either ellipsoidal clathrate or helical tubulate inclusion compounds where only dispersion forces operate between the hosts and guests. The former (tetragonal space group I4₁/acd), built from two interpenetrating sublattices containing both diol enantiomers, encloses the guests in rugby ball-shaped cavities. The latter (trigonal space group P3₁21 or P3₂21), containing only one diol enantiomer, traps the guests within parallel tubes. Which inclusion type is produced is determined by the guest size and shape and, hence, control is possible over these structures. At room temperature, cyclohexane gives the tetragonal structure, but fluorocyclohexane yields the trigonal structure. Chloroform produces both pseudopolymorphs: the tetragonal form at higher and the trigonal form at lower temperatures. Powder and single-crystal structural X-ray data are reported for these clathrate compounds.     

Comparison of activities of homogeneous Ti-based catalysts in the presence of methylaluminoxane (MAO) for synthesis of syndiotactic polystyrene by UV/visible spectroscopic study

The catalytic activities in syndiospecific polymerization of styrene in hydrocarbon using homogeneous Ti-based catalysts in the presence of methylaluminoxane (MAO) were investigated through UV/visible spectroscopic analysis. A strong UV absorption band of CpTiCl₃, itself, incipiently appeared at λ_max = 400 nm in toluene, followed by a bathochromic shift with its remarkable decrease by the addition of MAO. The absorption band intensity at λ_max = 400 nm arising from delocalization of π-electrons on the cyclopentadienyl ring decreased by methylation in the presence of MAO with regard to the mechanism for production of an active center (“cation-like”), for example, the change of the ionic nature. The intensity decrease at λ_max = 400 nm was suppressed over 2000 of the [Al]/[Ti] ratio. In the case of Ti(OC₄H₉)₄ having a σ-ligand, new and broad UV absorption bands were developed at λ_max = 340 nm and 410 nm in the presence of MAO in contrast with the CpTiCl₃/MAO system. Comparison between the relative absorption intensities at λ_max = 340 nm and 410 nm led to the determination of a maximum catalytic activity of Ti(OC₄H₉)₄ in the presence of MAO related to the polymerization yield. The maximum polymerization yield was observed with regard to the relative maximum value of the absorption intensity at λ_max = 410 nm with the [Al]/[Ti] ratio (500). From observation for polymorphism of the final products via differential scanning calorimetric analysis (DSC), the thermally unstable β-form seemed to be produced by the CpTiCl₃/MAO system independent of the MAO concentration, the Ti(OC₄H₉)₄/MAO system produced a thermally stable α-form in the low MAO concentration (up to 100 of the [Al]/[Ti] ratio), and a mixture of α- and/or β-forms over 200 of the [Al]/[Ti] ratio under our experimental conditions. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1733–1741, 1998     

In beam gamma spectroscopy of62Zn

The decay scheme of⁶²Zn has been investigated by studying the yield functions, angular distributions and coincidence relation-ships of theγ-rays emitted in the⁶³Cu(p, 2nγ) and⁶⁰Ni(α, 2nγ) reactions. Spins up to7? were assigned to the observed states. Nuclear Reactions ⁶⁰Ni(α, 2nγ)⁶²Zn,E _α=28–35 MeV and⁶³Cu(p, 2nγ)⁶²Zn,E _p = 22–31 MeV; measuredE _γ,I _γ(θ),I _γ(E _p , andI _γ,E _α-γ coincidences,⁶²Zn deduced decay scheme. Enriched target, Ge(Li) detectors.     

Extreme nonlinear optical enhancement in chalcogenide glass fibers with deep-subwavelength metallic nanowires

A nanostructured chalcogenide-metal optical fiber is proposed. This hybrid nanofiber is embedded with a periodic array of triangular-shaped deep-subwavelength metallic nanowires set up in a bowtie configuration. Our simulations show that the proposed nanostructured fiber supports a guided plasmonic mode enabling both subwavelength field confinement and extreme nonlinear light-matter interactions, much larger than a bare chalcogenide nanowire of comparable diameter. This is all achieved with less than 3% by volume of metal content.     

Regioselectivity of enzymatic and photochemical single electron transfer promoted carbon-carbon bond fragmentation reactions of tetrameric lignin model compounds

New types of tetrameric lignin model compounds, which contain the common β-O-4 and β-1 structural subunits found in natural lignins, have been prepared and carbon-carbon bond fragmentation reactions of their cation radicals, formed by photochemical (9,10-dicyanoanthracene) and enzymatic (lignin peroxidase) SET-promoted methods, have been explored. The results show that cation radical intermediates generated from the tetrameric model compounds undergo highly regioselective C-C bond cleavage in their β-1 subunits. The outcomes of these processes suggest that, independent of positive charge and odd-electron distributions, cation radicals of lignins formed by SET to excited states of sensitizers or heme-iron centers in enzymes degrade selectively through bond cleavage reactions in β-1 vs β-O-4 moieties. In addition, the findings made in the enzymatic studies demonstrate that the sterically large tetrameric lignin model compounds undergo lignin peroxidase-catalyzed cleavage via a mechanism involving preliminary formation of an enzyme-substrate complex.