Anion recognition by 1,3-disiloxane-1,1,3,3-tetraols in organic solvents

Anion recognition by 1,3-disiloxane-1,1,3,3-tetraols has been elucidated by ¹H NMR titrations and ESI-MS in organic solvents. The association constants of the receptors for halide anions are larger than those of silanediol and 1,3-disiloxane-1,3-diol due to the cooperative hydrogen bonds by four silanol hydroxy groups of 1,3-disiloxane-1,1,3,3-tetraols.     

Unusual behavior in light scattering experiments of poly(<Emphasis Type="Italic">N</Emphasis>-vinylimidazole) prepared by precipitation polymerization

Poly(N-vinylimidazole) (PVI) was synthesized by the precipitation polymerization using 2,2’-azobis(isobutyronitrile) (AIBN; initiator) and benzene (solvent) at two different monomer/initiator ratios. The solution polymerization was also performed with the following initiator/solvent systems: AIBN/water–methanol mixture (1:1 by volume) and 4,4’-azobis(4-cyanovaleric acid)/aqueous HCl solution (pH 0.8). All the four preparations of PVI in ethanol and in 0.2 M NaCl (pH 3 with HCl) were examined by dynamic light scattering (DLS). The CONTIN analysis of DLS data for each preparation from the solution polymerization showed a unimodal distribution in both ethanol and aqueous solvents. A good agreement was obtained between the molar masses in these different solvents by static light scattering (SLS). However, the polymers from the precipitation polymerization exhibited a heterogeneous bimodal distribution in DLS under the same conditions as above, indicating that the SLS data as in reference [6] (Savin et al. Macromolecules 37:6565) cause a serious error in the understanding of solution behavior of PVI.     

RNA Aptamers That Reversibly Bind Photoresponsive Azobenzene‐Containing Peptides

Modulation of biological networks assembled by diverse interactions among biologically active molecules has provided a platform for innovative biotechnologies. Here, we report RNA aptamers that bind to a photoresponsive peptide (KRAzR; Lys‐Arg‐azobenzene‐Arg) containing azobenzene chromophore, which can change its structure by photoirradiation. Aptamers were identified after 10 cycles of an in vitro selection procedure starting with a DNA library containing a 70 nt random region. Surface plasmon resonance (SPR) analysis demonstrated that interactions between aptamers and KRAzR were fully controlled by appropriate photoirradiation to the SPR sensor chip. Upon irradiation of 360 nm on the KRAzR‐immobilized surface, the binding of each aptamer to the surface was significantly decreased. Subsequent photoirradiation of the same surface with 430 nm restored the aptamer binding to the surface. We also observed that direct photoirradiation of the aptamer–peptide complex on a gold surface actively promoted dissociation of the complex. Furthermore, a doped reselection method was applied to acquire structural and sequence information of aptamer 66. From a data analysis of the conserved region and the mutation frequency, we were able to select a plausible secondary structure among three candidates predicted by computational folding simulation.     

New Quenching Procedure for Preservation of Initial Polymer/Catalyst Particle Morphology in Ziegler–Natta Olefin Polymerization

Preservation of initial polymer/catalyst particle morphology under air, was examined using stopped‐flow Ziegler–Natta polymerization with various quenching conditions and post‐chemical treatments. The exposure of the initial particles to air caused the fast formation of cracks on the surface, finally leading to significant reformation of the particle shape, when polymerizing particles were washed with heptane at ?65 °C under N₂ or under CO₂. On the other hand, when the particles were washed with heptane containing an appropriate amount of tetrahydrofuran under CO₂, the particle morphology under air was almost completely maintained even after 1 h exposure. The present results are useful for various ex situ characterizations of unstable initial polymer/catalyst particles.

     

Synthesis and antinociceptive activity of orally active opioid peptides: improvement of oral bioavailability by esterification

To improve the oral bioavailability of a dermorphin tetrapeptide analog, N(alpha)-1-iminoethyl-Tyr-D-MetO-Phe-MebetaAla-OH (III), which has a potent analgesic activity after oral administration, various derivatives were synthesized to increase lipophilicity by esterification of the C-terminal carboxyl group and/or acylation of the phenolic hydroxyl group on Tyr1. Antinociceptive activity was evaluated after subcutaneous or oral administration using the mouse tail pressure test. As a result, increased antinociceptive activity after oral administration as well as an improved ED50(p.o.)/ED50(s.c.) ratio, which is an indicator of oral bioavailability, were found for some compounds. With regard to the improvement of bioavailability, derivatives with acylation of the phenolic hydroxyl group on Tyr1 showed better results than derivatives with esterification of the C-terminal carboxyl group. In particular, an ED50(p.o.)/ED50(s.c.) ratio equivalent to that of morphine was found for an acetylated derivative, N(alpha)-1-iminoethyl-Tyr(COMe)-D-MetO-Phe-MebetaAla-OH (7a), as well as for a methoxycarbonylated derivative, N(alpha)-1-iminoethyl-Tyr(CO2Me)-D-MetO-Phe-MebetaAla-OH (7l).     

Effects of Pluronics surfactants on morphology and porosity of hematite particles produced from forced hydrolysis reaction

The shape and porosity of hematite particles, produced from a forced hydrolysis reaction of acidic FeCl₃ solution, were controlled by using Pluronics as nonionic surfactants (0–4 wt.%). Pluronics possess a nominal formula of (PEO) _x –(PPO) _y –(PEO) _x . The effect of Pluronics with low hydrophilicity (PEO contents were less than 50 mol%) was small and provided spherical particles the same as that of the system without Pluronics (control system). However, Pluronics with higher hydrophilicity (PEO contents were over 50 mol%) gave ellipsoidal hematite particles. This effect on the particle morphology was enhanced by an increase in their molecular weight. On the other hand, the Pluronics possessing an opposite nominal formula [(PPO) _x –(PEO) _y –(PPO) _x ] exhibited no effect on the particle shape; it only depressed phase transformation from ?-FeOOH to hematite. Not only the morphology but also the pore size of hematite particles was controlled from nonporous to mesoporous by using Pluronics. The N₂ adsorption experiment and t-plot curve analysis revealed that the hematite particles changed from mesoporous to microporous by an increase in the concentration of Pluronics. On the other hand, in the presence of very low amounts of Pluronics molecules (0.1 wt.%), nonporous hematite particles were produced via strong aggregation of PN particles by their hydrogen bonding between hydroxyl and PEO or PPO groups. The dynamic light scattering measurement for the system with Pluronics clarified the existence of polynuclear (PN) particles with a hydrodynamic particle diameter (D _a) of ca. 40 nm after these were aged for 6 h. The size of PN particles remained constant at ca. 40 nm during aging time of 12 h～3 days, but the scattering intensity was decreased. This decrease in the scattering intensity reveals that the number of PN particles is reduced by aggregation. The transmission electron microscope, inductively coupled plasma atomic emission spectroscopy, and total organic carbon analysis measurements employed on the systems produced for ellipsoidal particles elucidated that the formation of ellipsoidal hematite particles is attributed to the adsorption of Pluronics on the surfaces of PN and growing hematite particles.     

Biradical character of linear π-conjugated oligomer dications composed of thiophene, pyrrole, and methylthio end-capping units

Combined DFT calculations and UV-vis-NIR, ESR, and SQUID measurements revealed that the ground-state electronic structure of a linear π-conjugated oligomer dication composed of two pyrrole and six or seven thiophene rings and methylthio end-capping units is dominated by a singlet biradical character.     

Synthesis of Non-natural Xyloglucans by Polycondensation of 4,6-Dimethoxy-1,3,5-triazin-2-yl Oligosaccharide Monomers Catalyzed by Endo-β-1,4-glucanase

Summary: A cellotetraose-backboned hepta-saccharide (XXXG) (a capital X represents a glucopyranose residue that is substituted with a xylopyranose through an α-1,6 glycosidic bond, and a capital G represents a non-substituted glucopyranose residue) and a nona-saccharide (XLLG) (a capital L represents a glucopyranose residue that is substituted with a galactopyranoseβ(1-2)xylopyranose through an α-1,6 glycosidic bond) have directly been converted to the corresponding 4,6-dimethoxy-1,3,5-triazin-2-yl derivatives (DMT-β-XXXG 1 and DMT-β-XLLG 2 , respectively) by the action of 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methyl morpholinium chloride (DMT-MM). The selective nucleophilic attack of the anomeric hydroxyl group to DMT-MM has been achieved in water without using any protection of the hydroxyl groups. The resulting activated oligosaccharide derivatives ( 1 and 2 ) were found to polymerize catalyzed by an endo-β-1,4-glucanase as catalyst. The polymerization took place in a complete regio- and stereo-selective manner, affording non-natural polysaccharides having a XXXG-repeating unit and a XLLG-repeating unit, respectively, in the main chain. It is extremely difficult to construct such definite repeating structures via the conventional synthetic routes including protection-deprotection procedures.     

Synthesis and Fluorescence Properties of Thiazole-Boron Complexes Bearing a β-Ketoiminate Ligand

Novel fluorescent dyes, thiazole-boron complexes bearing β-ketoiminate ligands, have been synthesized, and their fluorescence properties were investigated. The BF(2) complexes showed a pronounced aggregation-induced emission enhancement effect because of the restriction of C-Ph intramolecular rotation. The BPh(2) complexes showed higher fluorescence quantum yields than the corresponding BF(2) complexes, both in solution and in the solid state.