Interplay of the main chain, chiral side chains, and solvent in conformational transitions: poly([(R)-3,7-dimethyloctyl]-[(S)-3-methylpentyl]silylene).

Light scattering, sedimentation equilibrium, viscosity, circular dichroism (CD), and UV absorption (UV) measurements were made on dilute solutions of poly([(R)-3,7-dimethyloctyl]-[(S)-3-methylpentyl]silylene)(PRS) as functions of molecular weight. From light scattering and viscosity data, PRS is found to be a very stiff polymer of persistence length q as large as 103 nm at 25 degrees C, essentially a 7(3) helix found in the solid state; q increases only gradually with lowering temperature between -15 and 25 degrees C. The CD data show that PRS undergoes a conformational transition around 3 degrees C in isooctane (transition temperature T(c)). The CD signal is largely positive at low temperatures, passes through zero at T(c), and becomes largely negative at higher temperatures; T(c) is independent of sample's chain length N. This is a highly cooperative helix (M)-to-helix (P) transition depending remarkably on N, as PRS is substantially rodlike. The CD data are converted to the fraction f(P) of P helix as a function of N and analyzed successfully by a statistical mechanical theory based on a helix reversal model, where a polymer chain consists of M and P helices intervened by helix reversals, with the result that the free energy difference DeltaG(h) between P and M shows a temperature dependence similar to that of 2f(P) - 1, whereas the helix reversal energy is substantially constant at 1.2 x 10(4) J mol(-1); the latter value means that the helix reversal occurs only once in 100 Si units or less. This DeltaG(h) change and solvent dependence of T(c) are explained by a double-well potential for the rotation about Si-Si bonds, which incorporates into DeltaG(h) the solvent interactions with the helical grooves of side chains surrounding the main chain. Detailed features of UV absorption spectra at different temperature and molecular weights are also presented.     

Effect of ligand substituents in olefin polymerisation by half-sandwich titanium complexes containing monoanionic iminoimidazolidide ligands-MAO catalyst systems

Various half-sandwich titanium complexes containing iminoimidazolidide ligands, CpTiCl(2)[1,3-R(2)(CH(2)N)(2)C=N] (1a-d) [R = Ph (a), 2,6-Me(2)C(6)H(3) (b), cyclohexyl (c), (t)Bu (d)], have been employed as the catalyst precursors for ethylene polymerisation, syndiospecific styrene polymerisation, and copolymerisation of ethylene with 1-hexene in the presence of MAO cocatalyst; 1d showed the highest catalytic activity for ethylene polymerisation whereas 1b showed the highest activity for syndiospecific styrene polymerisation.     

Highly reactive “RIKEN click” probe for glycoconjugation on lysines

One pot double click strategy containing strain-promoted click-reaction followed by 6π-azaelectrocyclization (RIKEN click reaction) has worked well in the synthesis of multivalent homogeneous and heterogeneous N-glycoalbumins. We have slightly changed the structure of linker unsaturated aldehyde used in this method. As a result it can be easily synthesized from commercially available material and furthermore, the enhancement of its reactivity towards both click-reactions was observed. The data described in this Communications facilitate the usage of the double click strategy as a general method for the synthesis of a variety of neo-N-glycoproteins.     

Chiroptical generation and inversion during the mirror-symmetry-breaking aggregation of dialkylpolysilanes due to limonene chirality

We observed the emergence and inversion of chiroptical handedness in three chiroptically silent dialkylpolysilanes during aggregation in limonene-methanol-THF tersolvents.     

Remarkable Effects of External Magnetic Field on Circularly Polarized Luminescence of EuIII(hfa)3 with Phosphine Chirality

Herein, magnetic circularly polarized luminescence (CPL) (MCPL) spectroscopy was conducted to analyze an Eu^III(hfa)₃ complex with three chiral P^III-ligands. Resultantly, (R)-chirality luminophores with S-up orientation and (S)-chirality luminophores with N-up orientation were observed to possess symmetrical mirror image spectra, i. e., they were enantiomers. Similarly, the (R)-chirality luminophores with N-up orientation and the (S)-chirality luminophores with S-up orientation were also enantiomers. Contrarily, (R)-S-up and (S)-S-up were diastereomers and did not possess a mirror-image relationship. Likewise, (R)-N-up and (S)-N-up were diastereomers. The J-dependency of g_MCPL and g_CPL datasets suggested that the N-up/S-up external magnetic field, with the aid of chiral P^III-ligands, increased the g_MCPL values by two- to sixteen-fold and modulated the g_MCPL signs at J=1–4. Additionally, the origins of the nonideal mirror-symmetric CPL and MCPL spectral characteristics of Eu^III(hfa)₃ with three chiral P^III-ligands were discussed in terms of parity (space-inversion, P)-symmetry, time-reversal (T)-symmetry, and PT-symmetry laws.     

Liquid-crystalline characteristics of cellulose derivatives: Binary and ternary mixtures of ethyl cellulose,hydroxypropyl cellulose,and acrylic acid

Phase behavior in binary and ternary mixtures of ethyl cellulose (EC), hydroxypropyl cellulose (HPC), and acrylic acid (AA) was investigated by optical techniques including polarized-light microscopy (POM), refractometry, UV absorption, and circular dichroism (CD) spectrophotometries, and laser-light scattering. Both derivatives of cellulose formed a cholesteric liquid-crystal phase in concentrated solutions in AA. EC and HPC homopolymer solutions in AA showed iridescent colors in the concentration range of 42–50 wt% and 65–80 wt%, respectively. In the 30–50 wt% HPC/AA solutions, an optical image with fingerprint-like patterns was observed between crossed polars. CD revealed that the cholesteric helical sense was right-handed in the HPC/AA mesophase, while the EC/AA mesophase formed left-handed structures. Anisotropic samples of HPC/AA and EC/AA also showed a POM image with a grid-like texture, which was much coarser in the former system compared with that in the latter. A phase diagram constructed for the ternary system EC/HPC/AA was divided into five distinct regions: (1) isotropic (I) monophase, (2) I + HPC mesophase (HLC), (3) I + HLC + EC mesophase (ELC), (4) HLC + ELC, and (5) anisotropic monophase, with the optical appearance changeable depending on polymer composition and concentration. In region 5 the anisotropic system was apparently monophasic in POM observations; however, CD and UV results indicated that the biphasic separation into the two cholesteric structures still occurred. Optical anisotropy and phase behavior were also examined for the EC/ HPC binary blends prepared from solutions and melt.     

Infrared reflection spectra of the one-dimensional ionic conductor K— and RbAl priderites

The reflection spectra of the one-dimensional ionic conductors K_1.6Al_1.6Ti_6.4O₁₆ and Rb_1.49Al_1.65Ti_6.35O_15.92 have been measured for the polarizations E ∥ c (channel direction) and E 6 c in the frequency region 60–2000 cm^-1. The spectra of these two compounds are very similar with their features and have the same number of bands. The vibrational mode frequencies are obtained from a Kramers-Kronig analysis for each polarized reflectivity spectrum. A comparison of the corresponding mode frequencies for both priderites shows that only the lowest frequency mode observed in the E 6 c spectra is strongly associated with the alkali ion, while the others are not. The effect due to the non-stoichiometry is not found in the infrared reflection spectra.     

Synthesis of homopolymers and multiblock copolymers by the living ring‐opening metathesis polymerization of norbornenes containing acetyl‐protected carbohydrates with well‐defined ruthenium and molybdenum initiators

The ring‐opening metathesis polymerization (ROMP) of norbornenes containing acetyl‐protected glucose [2,3,4,6‐tetra‐O‐acetyl‐glucos‐1‐O‐yl 5‐norbornene‐2‐carboxylate ( 1 )] and maltose [2,3,6,2′,3′,4′,6′‐hepta‐O‐acetyl‐maltos‐1‐O‐yl 5‐norbornene‐2‐carboxylate ( 2 )] was explored in the presence of Mo(N‐2,6‐ⁱPr₂C₆H₃)(CHCMe₂Ph)(O^tBu)₂ ( A ), Ru(CHPh)(Cl)₂(PCy₃)₂ ( B ; Cy = cyclohexyl), and Ru(CHPh)(Cl)₂(IMesH₂)(PCy₃) ( C ; IMesH₂ = 1,3‐dimesityl‐4,5‐dihydromidazol‐2‐ylidene). The polymerizations promoted by B and A proceeded in a living fashion with exclusive initiation efficiency, and the resultant polymers possessed number‐average molecular weights that were very close to those calculated on the basis of the monomer/initiator molar ratios and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.18) in all cases. The observed catalytic activity of B was strongly dependent on both the initial monomer concentration and the solvent employed, whereas the polymerization initiated with A was completed efficiently even at low initial monomer concentrations. The polymerization with C also took place efficiently, and even the polymerization with 1000 equiv of 1 was completed within 2 h. First‐order relationships between the propagation rates and the monomer concentrations were observed for all the polymerization runs, and the estimated rate constants at 25 °C increased in the following order: A > C > B . On the basis of these results, we concluded that ROMP with A was more suitable than ROMP with B or C for the efficient and precise preparation of polymers containing carbohydrates. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4248–4265, 2004     

Grafting of polymers onto a carbon‐fiber surface by ligand‐exchange reaction of poly(vinyl ferrocene‐co‐vinyl monomer) with polycondensed aromatic rings of the surface

To improve the surface of carbon fiber, the grafting reaction of copolymer containing vinyl ferrocene (VFE) onto a carbon‐fiber surface by a ligand‐exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of carbon fiber was investigated. The copolymer containing VFE was prepared by the radical copolymerization of VFE with vinyl monomers, such as methyl methacrylate (MMA) and styrene, using 2,2′‐azobisisobutyronitrile as an initiator. By heating the carbon fiber with poly(VFE‐co‐MMA) (number‐average molecular weight: 2.1 × 10⁴) in the presence of aluminum chloride and aluminum powder, the copolymer was grafted onto the surface. The percentage of grafting reached 46.1%. On the contrary, in the absence of aluminum chloride, no grafting of the copolymer was observed. Therefore, it is considered that the copolymer was grafted onto the carbon‐fiber surface by a ligand‐exchange reaction between ferrocene moieties of the copolymer and polycondensed aromatic rings of carbon fiber. The molar number of grafted polymer chain on the carbon‐fiber surface decreased with increasing molecular weight of poly(VFE‐co‐MMA) because the steric hindrance of grafted copolymer on the carbon‐fiber surface increases with increasing molecular weight of poly(VFE‐co‐MMA). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1868–1875, 2002