Vinyl Polymerization by Metal Complexes. XXXIII. Polymerization of Acrylonitrile Initiated by Triazole-Copper(II) Complex in Dimethylsulfoxide Solution

Polymerization of acrylonitrile initiated by triazole-copper(II) complexes was studied in dimethylsulfoxide solution. It was found that the polymerization proceeds by a free radical mechanism; however, the complexes can hardly homopolymerize methyl methacrylate and styrene. Ability of the complexes to initiate polymerization seems to depend on the substituents of triazole, the sort of solvents, and the counterions of copper(n) salts. From the data of visible spectroscopy and the spin trapping, the initiation mechanism was discussed in terms of reduction of copper(II) followed by forming active species.     

Effects of Bis(aromatic) Pendants on Recognition of Nucleobase Thymine by Zn2+ -1,4,7,10-tetraazacyclododecane (Zn2+ -cyclen)

We have previously shown that the nucleobase thymine binding to Zn²⁺ -cyclen (cyclen=1,4,7,10-tetraazacyclododecane) complex became stronger by appending acridine, naphthalene, or quinoline rings to the cyclen. Amongst these, the pendant bis((1-naphthyl)methyl) or bis((4-quinolyl)methyl) groups yielded the most effective thymine-recognizing Zn²⁺ -cyclen complexes [J. Am. Chem. Soc., 121 (1999) 5426]. The present study was undertaken to find causes of the bis(aromatic) ring effect by X-ray crystal structure analysis and NMR studies. The crystal structure of the Zn²⁺ -bis((1-naphthyl)methyl)-cyclen complex with a deprotonated 1-methylthymine (1-MeT) failed to show the anticipated evidence for the double ~ - ~ stacking interactions between the two naphthalenes and the Zn 2+ -bound 1-MeT m (1-MeT m =N(3')-deprotonated 1-MeT). Crystal data: formula C₃₆ H₄₇ N₇ O₇ Zn, M r =755.19, monoclinic, space group P2₁/ c (No. 14), a =15.438(2) Å, b =14.093(3) Å, c =16.726(2) Å, g =90.53(1) V =3638.7(8) Å 3 Z =4, R =0.035, R _w =0.049. However, the ¹H NMR studies of Zn²⁼ -bis((4-quinolyl)methyl)-cyclen with 1-MeT in varying H₂O/CH₃ CN solution showed increasing upfield shifts of Me(5') and H(6') of the Zn²⁺ -bound 1-MeT in more aqueous media, indicating that the double intercalation with the two quinolines became more significant in more protic environments. We conclude that the double ~ - ~ stacking effect accounts for the enhanced recognition of thymine base by the appended bis((1-naphthyl)methyl) or bis((4-quinolinyl)methyl) groups.     

Excess enthalpies of binary mixtures of butylamines + propanols at 298.15 K

The molar excess enthalpies of eight systems of butylamines + propanols were determined at 298.15 K using a twin-microcalorimeter. All excess enthalpies were exothermic and large. An equilibrium constant K ₁ expressed in terms of mole fractions and standard thermodynamic properties of formation (Δ_f H, Δ_f G, Δ_f S) of 1:1 complex were evaluated by ideal mixtures of monomeric molecules and their associated complexes. Concentration dependence of the FT-Raman spectrum showed systematic changes of bands. Spectroscopic considerations based on this and ab initio calculations on molecules were performed at the Mp2/6-311G(d,p) level of theory. Interaction energies between butylamine and propanol were calculated by the supermolecular and NBO methods. The results were discussed with previous results to clarify the steric and positional effect of the amino and hydroxyl group.     

Small-Angle Neutron Scattering Study on Aggregation of 1-Alkyl-3-methylimidazolium Based Ionic Liquids in Aqueous Solution

Aggregation structures of 1-alkyl-3-methylimidazolium based ionic liquids (ILs) in aqueous solution were investigated by small-angle neutron scattering (SANS) from the viewpoint of alkyl chain length, n, and anions (Cl^?, Br^? and trifluoromethanesulfonate, $ {\text{CF}}_{3} {\text{SO}}_{3}^{ - } $ ). In [C₄mIm⁺]-based IL systems, no noticeable SANS intensity was observed for all of the systems examined here, although aqueous [C₄mIm⁺][ $ {\text{BF}}_{4}^{ - } $ ] solutions show a significant SANS profile originating from concentration fluctuations in the solution (Almasy et al. J Phys Chem B 112:2382–2387, 2008). This suggests that [C₄mIm⁺][Cl^?], [C₄mIm⁺][Br^?] and [C₄mIm⁺][ $ {\text{CF}}_{3} {\text{SO}}_{3}^{ - } $ ] homogeneously mix with water, unlike the [C₄mIm⁺][ $ {\text{BF}}_{4}^{ - } $ ] system, due to preferential hydration of the ions. In the case of the C _n mIm cations with longer alkyl chain lengths (n = 8 and 12), SANS profiles were clearly observed in the aqueous solutions at IL concentrations of C _IL > 230 and 20.0 mmol·dm^?3, respectively. For aqueous [C₈mIm⁺][Br^?] solutions, the asymptotic behavior of the scattering function varied largely from I(q) ~ q ^?2 to ~q ^?4 with increasing C _IL, indicating that the solution changes from an inhomogeneous mixing state to a nano-scale micelle state. Aqueous [C₁₂mIm⁺][Br^?] solutions show a typical SANS profile for micelle formation in solution. It was found from a model-fitting analysis that the structure of the [C₁₂mIm⁺][Br^?] micelle is ellipsoidal, not spherical, in solutions over the C _IL range examined here.     

Synthesis and lyotropic liquid crystal properties of chiral helical polycarbodiimides

Chiral helical polymers have been expected to exhibit optical activity with a significantly large optical rotation power. In this paper polymethylphenylethylcarbodiimides (Poly-PhEMCDI) with helical structure were synthesized by the insertion polymerization of a corresponding chiral monomeric carbodiimide initiated by a copper complex. The circular dichroism spectra and optical rotation power induced by the ordered rigid main chain helical structure of polycarbodiimides, in solution and as cast films, were studied. Polycarbodiimides have a rigid rod helical structure and form lyotropic liquid crystal (LLC) in organic solvents such as dichloromethane (DCM), chloroform and THF. The LLC phase was studied using polarizing optical microscopy and X-ray diffraction. A chiral nematic phase was formed in DCM and chloroform in the concentration range 20–36%. Spherulites were formed in more concentrated solution. The formation of a LLC phase in polycarbodiimides organic solutions makes it possible to align the polymer helical chain to form an ordered film for electro-optical applications.     

Chiral Photoresponsive Tetrathiazoles That Provide Snapshots of Folding States

Herein, we designed chiral photoresponsive tetra(2‐phenylthiazole)s, which induce a diastereoselective 6π‐electrocyclization reaction in a helically folded structure to freeze the conformational interconversions. The folding conformation with one helical turn of tetra(2‐phenylthiazole)s was supported by multiple intramolecular noncovalent interactions including vicinal S???N interheteroatom interactions and CH–π and π–π stacking interactions between nonadjacent units, as found in X‐ray crystal structures as well as quantum chemical calculations. The introduction of a chiral group at both ends of tetra(2‐phenylthiazole) dictates the preferential folding into a one‐handed helix conformation by the simultaneous operation of S???O and multiple CH–π interactions that involve the chiral end groups. Since the tetra(2‐phenylthiazole)s possess two equivalent photoreactive 6π‐electron systems and the folded conformation is suitable for photoinduced electrocyclization reaction, they undergo a photocyclization reaction in a stereoselective manner to memorize the chirality of the helix in a resulting diastereomeric closed form.     

Improvement of TiO2/Dye/Electrolyte Interface Conditions by Positional Change of Alkyl Chains in Modified Panchromatic Ru Complex Dyes

A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation.     

Complexation of hydrazine with native cellulose in water and toluene

Adsorption–complexation of cellulose by hydrazine solutions in water and toluene was studied for native cellulose of varied crystallinity. Penetration of hydrazine into cellulose takes place more readily in hydrazine solution of higher concentration and with cellulose of lower crystallinity, but the equilibrium uptake was nearly independent of crystallinity. Complexation from toluene solution takes place at lower hydrazine concentration in toluene than in water, presumably because of the difference in hydrazine–solvent interaction. The adsorption isotherm of hydrazine in water is likely to be sigmoid, implying a cooperative sorption mechanism. It can presumably be ascribed to the disordered structure in the course of complexation.     

Enzymatic Hydrolysis-Responsive Supramolecular Hydrogels Composed of Maltose-Coupled Amphiphilic Ureas

Maltose is a ubiquitous disaccharide produced by the hydrolysis of starch. Amphiphilic ureas bearing hydrophilic maltose moiety were synthesized via the following three steps: I) construction of urea derivatives by the condensation of 4-nitrophenyl isocyanate and alkylamines, II) reduction of the nitro group by hydrogenation, and III) an aminoglycosylation reaction of the amino group and the unprotected maltose. These amphiphilic ureas functioned as low molecular weight hydrogelators, and the mixtures of the amphipathic ureas and water formed supramolecular hydrogels. The gelation ability largely depended on the chain length of the alkyl group of the amphiphilic urea; amphipathic urea having a decyl group had the highest gelation ability (minimum gelation concentration=0.4 mM). The physical properties of the supramolecular hydrogels were evaluated by measuring their thermal stability and dynamic viscoelasticity. These supramolecular hydrogels underwent gel-to-sol phase transition upon the addition of α-glucosidase as a result of the α-glucosidase-catalyzed hydrolysis of the maltose moiety of the amphipathic urea.