Interaction between anionic polyelectrolytes and anion exchange membranes and change in membrane properties

Electrodialytic transport properties of anion exchange membranes were measured after formation of anionic polyelectrolyte layers on the membrane surfaces: relative transport number of various anions to chloride ions, current efficiency and apparent diffusion coefficients of neutral molecules. The anionic polyelectrolyte layers were formed by immersing the membrane into an aqueous solution of polycondensation product of sodium naphthalene sulfonate and formaldehyde or polystyrene sulfonic acid.

The change in the relative transport number between anions was remarkable in the anion exchange membrane with high ion exchange capacity by forming the layer. Results were: the relative transport number of sulfate ions to chloride ions decreased and those of nitrate ions to chloride ions, fluoride ions to chloride ions and bromide ions to chloride ions increased compared with the corresponding membrane. Although the apparent diffusion coefficient of neutral molecules suggested clogging of the membrane pores by the polyelectrolyte, anions with higher hydrated ionic diameter were able to permeate through the membrane easily. This means that difference of electrostatic repulsion force against two anions is effective on the change in the relative transport number of anions.     

Rapid fermentation of beer using an immobilized yeast multistage bioreactor

The characteristics of yeast sulfite metabolism in a multistage bioreactor system for beer fermentation were investigated. No sulfite was produced in the continuous stirred-tank reactor (CSTR). However, large amounts were produced in the packed-bed reactor (PBR). Production of sulfite in the PBR seems to be inevitable when it is operated continuously. In order to control the sulfite level in the young beer, the yeast needs to be reactivated into the growth phase. One possible strategy to achieve this is to aerate and periodically remove yeast clogged in the reactor once every 6–7 months before the sulfite level exceeds a given concentration (e.g., 20 mg/L). It was confirmed that sulfite production is closely related to the growth condition of the yeast and is therefore important to consider in the control strategy for sulfite when using the immobilized yeast reactor for beer production.     

Highly enantioselective synthesis of silahelicenes using Ir-catalyzed [2+2+2] cycloaddition

Silahelicenes, which contain two silole moieties in a helically chiral structure, were synthesized by a chiral Ir-catalyzed intermolecular [2+2+2] cycloaddition of tetraynes with diynes along with a Ni-mediated intramolecular [2+2+2] cycloaddition. The photophysical properties of the obtained highly enantiomerically enriched silahelicenes (up to 93% ee) were also measured.     

Novel Asymmetric and Stereospecific Aziridination of Alkenes with a Chiral Nitridomanganese Complex

The addition of pyridine N -oxide is necessary to obtain high enantioselectivities in the asymmetric aziridination of styrene derivatives through transfer of a nitrogen atom from chiral, toluenesulfonic anhydride activated nitridomanganese complex 1 [Eq. (a)]. Remarkably, high stereospecificity was observed in all the aziridinations of trans- and cis-1,2-disubstituted alkenes. R¹=H, Me, nPr, iPr; R²=H, Me; Ts=p-toluenesulfonyl.     

Synthesis and structural, electronic, and optical properties of oligo(thienylfuran)s in comparison with oligothiophenes and oligofurans

[structure: see text] Alternate thiophene/furan oligomers having four and six heterocycles, i.e., oligo(thienylfuran) dimer and trimer 2 (n = 4 and 6), were newly synthesized by repetitive Stille coupling reactions. The structural, electronic, and optical properties of these oligomers were investigated by X-ray crystallography (for n = 4), cyclic voltammetry (CV), UV-vis and fluorescence spectroscopy, and DFT calculations, and the results were compared with those of corresponding oligothiophenes (1) and oligofurans (3). The inter-ring torsional energy profiles calculated for bithiophene 1 (n = 2), thienylfuran 2 (n = 2), and bifuran 3 (n = 2) at the B3LYP/6-31G(d) level indicated that the most stable conformers of 2 (n = 2) and 3 (n = 2) are fully coplanar with transoid structure while that of 1 (n = 2) is twisted with a dihedral angle of 158 degrees . In accord with this, X-ray crystallographic analysis of 2 (n = 4) revealed that the pi-conjugated system is nearly planar with the inter-ring C=C-C=C dihedral angles between the thiophene and furan rings of 173.6(7) degrees , -177.0(7) degrees , and 172.6(6) degrees . In the packing structure, these nearly planar molecules are arranged in a herringbone pattern. The CV on a series of oligo(thienylfuran)s 2 showed irreversible oxidation peaks at +0.90, +0.42, and +0.29 V vs Fc/Fc(+) for n = 2, 4, and 6, which were 0.15-0.18 V lower than those for corresponding oligothiophenes 1 and were closer to those for oligofurans 3. On the other hand, the UV-vis spectra of 2 showed the longest wavelength absorption to be almost identical with those of the corresponding 1, and more bathochromically shifted than those of the corresponding 3. The results of CV and UV-vis measurements were supported by DFT calculations (B3LYP/ 6-311+G(2d,p)//B3LYP/6-31G(d)). Thus, oligo(thienylfuran)s 2 have HOMOs which are higher than those of oligothiophenes 1 and close to those of 3, and HOMO-LUMO gaps which are close to those of 1 and smaller than those of 3. In fluorescence spectra, the quantum yield of 2 increased with elongation of the pi-system (n = 2 (3.5%), 4 (19%), 6 (24%)).     

Multipoint recognition of catecholamines by hydrindacene-based receptors accompanied by the complexation-induced conformational switching

The molecular recognition of catecholamines by hydrindacene-based receptors 1 and 2, as well as the durene-based receptor 3, and the guest-induced conformational changes are reported. These receptors selectively bind adrenaline and dopamine salts through the guests' ammonium group and 3-hydroxyl group on the aromatic ring. In the case of adrenaline, an additional hydrogen bond with a benzylic hydroxyl group is formed. In 2 % CD3CN/CDCl3, the association constants are of the order of 10(4) M(-1), which is much larger than with guests without the 3-hydroxyl groups (10(3) M(-1)). The two amide groups of receptor 1 can rotate freely around the C(aromatic)--C(amide) bond, whereas the tert-amide in 2 changes between two stable conformations at a slow enough rate to allow detection by (1)H NMR spectroscopy. In the absence of a guest molecule, the syn-conformer is less stable than the anti-conformer. On complex formation with adrenaline, the syn-conformer becomes dominant due to an intramolecular dipole-reversal effect in addition to multipoint hydrogen bonding.