Ionic liquid reconstituted cellulose composites as solid support matrices with good transparency for biocatalytic reaction.

Disclosed are composites comprising regenerated cellulose, a first active substance, a second active substance, and a linker. Thus, microcryst. cellulose was dissolved in 1-butyl-3-methylimidazolium chloride using microwave pulse heating at 120-150°, cooled to 60° to form a super-cooled liq., 20% (based on cellulose) poly(L-lysine hydrobromide) was added therein, homogenized, cast onto a glass plate, the resulting film soaked in water for at least 24 h to leach residual from the film to give a reconstituted cellulose film, showing good transparency. [on SciFinder(R)]

Crystal and liquid crystalline polymorphism in 1-alkyl-3-methylimidazolium tetrachloropalladate(II) salts

1-Alkyl-3-methylimidazolium tetrachloropalladate(ii) salts ([C-n-mim](2)[PdCl4], n = 10, 12, 14, 16, 18) containing a single, linear alkyl-chain substituent on the cation have been synthesised and their behaviour characterised by differential scanning calorimetry, polarising optical microscopy and small-angle X-ray scattering. The salts display thermotropic polymorphism, exhibiting both crystal-crystal transitions and, for n = 14-18, the formation of a thermotropic smectic liquid crystalline phase.

Ionic liquid-reconstituted cellulose composites as solid support matrices for biocatalyst immobilization

Preparation of cellulose-polyamine composite films and beads, which provide high loading of primary amines on the surface allowing direct one-step bioconjugation of active species, is reported using an ionic liquid (IL) dissolution and regeneration process. Films and bead architectures were prepared and used as immobilization supports for laccase as a model system demonstrating the applicability of this approach. Performance of these materials, compared to commercially available products, has been assessed using millimeter-sized beads of the composites and the lipase-catalyzed transesterification of ethyl butyrate.

Rigid tetracatenar liquid crystals derived from 1,10-phenanthroline

Tetracatenar liquid crystals were obtained by substituting the 1,10-phenanthroline central core unit at the 3- and 8-positions by extended, rigid acetylene moieties, equipped at the termini with two alkoxy chains of various lengths (n = 6, 8, 10, 12, 14). The liquid crystals exhibit a rich mesomorphism including smectic C, cubic, hexagonal and rectangular columnar phases, depending on the alkoxy chain length. The corresponding rhenium(I) complexes containing the bulky [ReBr(CO)₃] fragment are not liquid-crystalline. The ligands and rhenium(I) complexes were investigated by scanning tunneling microscopy (STM). Both the ligands and the rhenium(I) complexes can be self-assembled into monolayers at the TCB–graphite and octanoic acid–graphite interfaces. The ligands and rhenium(I) complexes are luminescent.

Synthesis, thermal characterization and rheological properties of a homologous series of polymethacrylate-based side-chain liquid crystal polymers

A new homologous series of side-chain liquid crystal polymers, the poly[omega-(4-cyanoazobenzene-4'-oxy)alkyl methacrylate]s, have been prepared in which the length of the flexible alkyl spacer is varied from 3 to 12 methylene units. All the polymers exhibit liquid crystalline behaviour; specifically, crystal E, smectic A and nematic phases are observed. The glass transition temperatures decrease on increasing spacer length before reaching a limiting value at ca. 30 degrees C. The clearing temperatures exhibit an odd-even effect on varying the length and parity of the spacer. This is attributed to the change in the average shape of the side chain as the parity of the spacer is varied. This rationalization also accounts for the observed alternation in the entropy change associated with the clearing transition. A weak relaxation is observed theologically for several members of this polymer series at temperatures above their respective glass transition temperatures. This is attributed either to specific motions of the smectic layers or to 180 degrees reorientational jumps of the long axis of the mesogenic unit about the polymer backbone. (C) 1997 Elsevier Science Ltd. All rights reserved.

The Effect of Tacticity on the Conformational Properties of Poly(1-olefin sulfone)s

The effect of tacticity on the conformational properties of poly(olefin sulfone)s was studied. Tactic polymers, prepared from racemic thiirane monomers using chiral inititators were compared with atactic polymers prepared by free radical co-polymerisation of the 1-olefin with sulfur dioxide. Analysis of the XRD patterns showed that the tactic polymers formed more ordered structures in the bulk with longer layer spacings, consistent with a model in which their side chains meet at the tips in contrast with the atactic polymers whose side chains interdigitate. 13C MAS nmr experiments suggest that as tacticity increases so too does the proportion of C-S bonds in the gauche conformation, however the proportion of S-C bonds in the trans conformation falls, in contrast to a reported molecular mechanics study. Finally, DSC measurements on the polymers with longer side chains showed the presence of two endotherms on heating, illustrating definite liquid crystalline behaviour.

Molecular layering and local order in thin films of 1-alkyl-3-methylimidazolium ionic liquids using X-ray reflectivity

X-ray reflectivity measurements in air of thin films of 1-alkyl-3-methylimidazolium salts in the liquid, liquid crystalline and solid states supported on Si( 111) are described. The films show Bragg features in both liquid crystalline and solid phases, but only after an initial annealing cycle. Kiessig fringes are observed only for the 1-octadecyl-3-methyl-imidazolium hexafluorophosphate films and, following analysis using Parratt32, a bi-layer model is proposed whereby the molecules are orientated with ionic groups at both salt-air and salt-silicon interfaces.

Small-angle scattering from long-chain alkylimidazolium-based ionic liquids

This paper compares the structure of 1-alkyl-3-methylim ridazolium salts using SAXS and X-ray reflectivity. A range of anions have been investigated namely chloride, bromide, trifluoromethanesulfonate (OTf), bis(trifluoromethanesulfonyl)imide (TFI) and tetrachloropalladate(II) with cation alkyl chains ranging from n = 12-20. In general, the salts show liquid crystalline behaviour whose structure is still observed on melting into an isotropic liquid.