Study of alkyl chain length dependent characteristics of imidazolium based ionic liquids [CnMIM]+[TFSA]− by Brillouin and dielectric loss spectroscopy

This study examined the acoustic phonon mode of ionic liquids consisting of 1-alkyl-3-methyl-imidazolium family (C_nMIM) cations with n values ranging from 2 to 10 and bis(trifluoromethylsulfonyl)amide (TFSA) anion in the temperature range from 300 K to 100 K. [C_nMIM]⁺[TFSA]^? showed depolarized (VH) components of Brillouin peaks at temperatures below the glass transition temperature when n is larger than 4. On the other hand, in the case of ionic liquids with different anions, such as [C₄MIM]⁺[BF₄]^?, [C₄MIM]⁺[PF₆]^? and [C₈MIM]⁺[BF₄]^?, the VH component of Brillouin peaks was not observed in the temperature range investigated. The dielectric loss spectra showed that the temperature dependence of alkyl chain domain relaxation of all ionic liquids followed the Arrhenius law and showed an increase in activation energy at the temperature where the VH component of Brillouin peak appeared. These results suggest that the observed depolarized component of Brillouin peak might originate from uniquely induced polarization in the 2nd domain composed of head groups of cations and anions.     

Stereospecific construction of a trans-1,4-diphosphacyclohexane skeleton

trans-1,4-Diphosphacyclohexanes were successfully synthesized by the stereospecific intramolecular coupling reaction of the optically active bisphosphine. This is a new route for the construction of the trans-1,4-diphosphacyclohexane skeleton. A cis isomer was also prepared along with the trans isomer from a mixture of rac- and meso-bisphosphines. The coordinated boranes were easily removed to afford the corresponding 1,4-diphosphacyclohexanes.     

Biodegradable nanogels prepared by self-assembly of poly(L-lactide)-grafted dextran: entrapment and release of proteins

We showed previously that poly(L-lactide)-grafted dextran could form biodegradable nanogels in water. In this paper, various properties of Dex-g-PLLA nanogels were compared with Dex-Chol (dextran-cholesterol conjugate) nanogels to investigate the effects of hydrophobic units. Dex-g-PLLA nanogels exhibited significantly lower CAC and higher colloidal stability, indicating a strong tendency to form nanogels. We prepared lysozyme-loaded Dex-g-PLLA nanogels, and they exhibited a sustained release of lysozyme for 1 week without denaturation in PBS at 37 degrees C. The Dex-g-PLLA nanogels therefore have great potential as a delivery vehicle for therapeutic protein.     

First acid dissociation at an aqueous H2SO4 interface with sum frequency generation spectroscopy

The vibrational sum frequency generation (SFG) spectra of the air-liquid interface of H2SO4-H2O solutions over a wide range of concentrations are measured in the SO stretching region (1000-1300 cm(-1)). The analogy of the concentration dependence of Raman and SFG is indicative of a nearly identical behavior of the first acid dissociation at the air-liquid interface as in the bulk.     

Structural change of 1-butyl-3-methylimidazolium tetrafluoroborate + water mixtures studied by infrared vibrational spectroscopy

Mixtures of ionic liquid (IL, 1-butyl-3-methylimidazolium tetrafluoroborate, [BMIM][BF4]) and water with varying concentrations were studied by attenuated total reflection infrared absorption and Raman spectroscopy. Changes in the peak intensities and peak positions of CHx (x = 1, 2, 3) vibration modes of the cation of the IL and OH vibration modes of the water molecules were investigated. Peaks from normal-mode stretch vibrations of CH bonds belonging to the imidazolium ring of the cation did not change their positions, while those from the terminal methyl group of the butyl chain blueshifted by approximately 10 cm-1 with the addition of water. On the other hand, change in the spectral shape in the OH stretch vibration region shows hydrogen-bonding network of water molecules breaking down rapidly as the IL is added. Trends in the change of the peak positions and the peak intensities suggested qualitative change of the intermolecular structure in the [BMIM][BF4] + H2O mixture at 32 +/- 2 and 45 +/- 2 mol/L of water concentration.     

Biological properties of opioid peptides replacing Tyr at position 1 by 2,6-dimethyl-Tyr.

To understand the effect of the replacement of Tyr residue at position 1 in opioid peptides by 2,6-dimethyl-Tyr (Dmt) on the biological property, chiral (D or L) Dmt1 analogs of Leu-enkephalin (Enk) and Tyr-D-Arg-Phe-beta Ala-NH2 (YRFB) were synthesized and their enzymatic stabilities, in vitro bioactivities and receptor binding affinities compared with those of parent peptides. [L-Dmt1]Enk (1) exhibited 4-fold higher stability against aminopeptidase-M and possessed dramatically increased activities in guinea pig ilium (GPI) (187-fold) and mouse vas deferens (MVD) (131-fold) assays, and in rat brain receptor binding assays (356-fold at mu receptor and 46-fold at delta receptor) as compared to Enk. [L-Dmt1]YRFB (3) also exhibited increased activities in GPI (46-fold) and MVD (177-fold) assays, and in the binding assays (69-fold at mu receptro and 341-fold at delta receptor) as compared to the parent peptide. [D-Dmt1]Enk (2) and [D-Dmt1]YRFB (4) exhibited activities with diminished or lesser potency than the parent peptide in all assays. These results indicate that there is a tendency for mu affinity to be enhanced more than delta affinity with introduction of L-Dmt into delta ligand peptide (Enk), and for delta affinity to be enhanced more than mu affinity in case of mu ligand peptide (YRFB), resulting in reduced receptor selectivities at the receptors.     

Stereoregulation in cationic polymerization by designed Lewis acids. II. Effects of alkyl vinyl ether structure

Stereoregulation in the cationic polymerization of various alkyl vinyl ethers was investigated with bis[(2,6‐diisopropyl)phenoxy]titanium dichloride ( 1 ; catalyst) in conjunction with the HCl adduct of isobutyl vinyl ether as an initiator in n‐hexane at −78 °C. The tacticities depended on the substituents of the monomers. Isobutyl and isopropyl vinyl ethers gave highly isotactic polymers (mm = 83%), whereas tert‐butyl and n‐butyl vinyl ethers resulted in lower isotactic contents (mm ∼ 50%) similar to those for TiCl₄, a conventional Lewis acid, thus indicating that the steric bulkiness of the substituents was not the critical factor in stereoregulation. A statistical analysis revealed that the high isospecificity was achieved not by the chain end but by the catalyst 1 or the counteranion derived therefrom. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1060–1066, 2001     

Synthesis and enzymatic hydrolysis of lactic acid–depsipeptide copolymers with functionalized pendant groups

Since poly(lactic acid) is the biodegradable polyester having low immunogenicity and good biocompatibility, it is utilized as a medical material. However, poly(lactic acid) is a water-insoluble crystalline polymer having no reactive side-chain group. Thus, the use of poly(lactic acid) is limited. To modify the properties of poly(lactic acid) and to introduce the functionalized pendant groups to poly(lactic acid), we synthesized two kinds of lactic acid-depsipeptide copolymers with reactive pendant groups, namely poly[LA-(Glc-Lys)] and poly[LA-(Glc-Asp)]. This was done through ring-opening copolymerizations of L-lactide with the corresponding protected cyclodepsipeptides, cyclo[Glc-Lys(Z)] and cyclo[Glc-Asp(OBzl)], and subsequent deprotection of benzyloxycarbonyl and benzyl groups, respectively. By changing the mole fraction of the corresponding depsipeptide units, the solubility, thermal transition and degradation behavior of the modified poly(lactic acid) could be varied. © 1997 John Wiley & Sons, Inc.     

Excitation and emission spectra of polyethylene terephthalate and polyethylene 2,6‐naphthalate films

With excitation by the light of the wavelengths longer than 320 nm, fluorescence spectra of polyethylene terephthalate (PET) films had somewhat different shapes from those excited below 300 nm through the intrinsic absorption of PET molecules. Also, in the measurements taken with a polarizer in front of the receiving monochoromator but none before the sample, the intensity ratio of parallel (to the draw axis of the film) and perpendicular components of the emission spectra was different if excited above 320 nm or below 300 nm. Discussion was made about the first step of pumping photon energy at the wavelengths above 320 nm. Fluorescence spectra of polyethylene 2,6‐naphthalate films showed a mirror image of their absorption spectra, consisting of one broad band having the same polarization as their absorption spectra. Their fluorescence occurred from the lowest excited level, conforming to the Kasha law. Copyright © 1999 John Wiley & Sons, Ltd.