Syntheses and characterization of 16‐arm star and star diblock copolymer and AB8 9‐miktoarm star copolymer via NMRP and ROP from dendritic multifunctional macroinitiators

A dendritic macroinitiator having 16 TEMPO‐based alkoxyamines, Star‐16 , was prepared by the reaction of a dendritic macroinitiator having eight TEMPO‐based alkoxyamines, [G‐3]‐OH , with 4,4′‐bis(chlorocarbonyl)biphenyl. The nitroxide‐mediated radical polymerization (NMRP) of styrene (St) from Star‐16 gave 16‐arm star polymers with PDI of 1.19–1.47, and NMPR of 4‐vinylpyridine from the 16‐arm star polymer gave 16‐arm star diblock copolymers with PDI of 1.30–1.43. The ring‐opening polymerization of ε‐caprolactone from [G‐3]‐OH and the subsequent NMRP of St gave AB₈ 9‐miktoarm star copolymers with PDI of 1.30–1.38. The benzyl ether linkages of the 16‐arm star polymers and the AB₈ 9‐miktoarm star copolymers were cleaved by treating with Me₃SiI, and the resultant poly(St) arms were investigated by size exclusion chromatography (SEC). The SEC results showed PDIs of 1.23–1.28 and 1.18–1.22 for the star polymers and miktoarm stars copolymers, respectively, showing that they have well‐controlled poly(St) arms. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1159–1169, 2007.     

α-Phenylselenenylation of zirconium or aluminum enolates

Zirconium or aluminum O-enolates undergo selenenylation with PhSeBr to give α-(phenylselenenyl) ketones in good to excellent yield.     

On/off spin-crossover phenomenon and control of the transition temperature in assembled Iron(II) complexes

The present study reveals the on/off of spin-crossover (SCO) phenomenon in assembled Fe(II) complexes bridged by bis(pyridyl) type ligand. Whether SCO phenomenon occurs or not in assembled Fe(II) complexes bridged by bis(pyridyl) type ligand is determined by local structure around iron atom. SCO phenomenon occurs when the coordinating pyridines facing to each other across the iron atom are propeller type, while the phenomenon does not occur when they are parallel type or distorted propeller type. DFT calculation explained that, in the shortening of Fe-pyridine bonds when changing from high-spin state to low-spin state, the pyridines of propeller type can approach the iron atom with smaller steric hindrance than those of parallel and distorted propeller type complexes. The local structure is controlled by introducing methyl substituent and introducing π-system, changing SCO phenomenon. And the transition temperature of SCO is also controlled in assembled complexes bridged by 1,2-bis(4-pyridyl)ethane by mixing anionic ligand.     

Rearrangement of Langmuir-Blodgett stearic acid films and band assignments in deuterated stearic acid monolayers

Band assignments in the C-D stretching region of straight chain hydrocarbon species are derived from the spectra of stearic acid monolayers on gold. The fatty acid molecules reorient with respect to the metal surface as the films age. Correlating the changes in the IR spectra of both the undeuterated and deuterated acids allows one to identify the vibrational modes of the latter based on the accepted assignments of the former. The CD₂ asymmetric and symmetric stretches are observed at 2194 and 2086 cm^–1, respectively. Bands at 2212 and 2221 cm^–1 are attributed to asymmetric in-plane and out-of-plane CD₃ stretches. Assignments of several other features in this region are given while one band remains unassigned.     

Syntheses of 12‐arm star polymers and star diblock copolymers by nitroxide‐mediated radical polymerization using dendritic dodecafunctional macroinitiators

Dendritic multifunctional macroinitiators having 12 TEMPO‐based alkoxyamines were prepared by the reaction of a benzyl alcohol having 4 TEMPO‐based alkoxyamines with 1,3,5‐tris[(4‐chlorocarbonyl)phenyl]benzene and 1,3,5‐tris(4‐isocyanatophenyl)benzene. Using the dodecafunctional macroinitiators, TEMPO‐mediated radical polymerizations of styrene (St) were carried out at 120 °C, and 12‐arm star polymers ( star‐12 ) with narrow polydispersities of M_w/M_n = 1.06–1.26 were obtained. To evaluate the livingness for the TEMPO‐mediated radical polymerizations of St, hydrolysis of the ester bonds of the 12‐arm star polymers and subsequent SEC measurements were carried out. Furthermore, using star‐12 as the macroinitiator, TEMPO‐mediated radical polymerization of 4‐vinylpyridine (4‐VP) was carried out, and well‐defined poly(St)‐b‐poly(4‐VP) 12‐arm star diblock copolymers with M_w/M_n = 1.18–1.19 were obtained. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3689–3700, 2005     

Deformation of a submanifold in a Euclidean space with fixed gauss image: II

Deformation of an m-dimensional submanifold immersed in a Euclidean n-space is studied when the Gauss image does not move pointwise. The present paper is the third one and contains deformations where the tensor of deformation satisfies some differential equations, normal deformations and deformations of totally-real submanifolds in a complex space.     

Observation of population inversions in a freely expanding helium plasma

Population inversion on He I is experimentally investigated in a recombining helium plasma. Experimental results confirm that population inversions for n = 3–4 and 3–5 levels of the He I singlet system are larger than for the triplet system. The difference between the two systems is discussed by using rate equations.