γ radiolysis of neat 2-phenylheptamethyltrisilane as a model of polysilastyrene

2-Phenylheptamethyltrisilane as a model compound of polysilastyrene was irradiated at a high dose (1440 kGy) of γ-rays without any additive. The trisilane was found to be resistant to γ-rays, while it gave small amounts of Me₆Si₂, Me₃SiSiMe₂Ph, Me₃SiH, Me₃SiSiHMePh and (Me₃Si)₂ SiMeC₆H₄SiMe₃. These products can be interpreted as being due to a chain contraction of the trisilane with the extrusion of methylphenylsilylene, a methyl migration with the extrusion of dimethylsilylene, a scission of an Si–Si bond due to an attack by hydrogen atoms, and a substitution of a hydrogen atom on the phenyl group by a trimethylsilyl radical. The same reactions, except the chain contraction, are observed in the cases of pentamethylphenyldisilane and 1,2-diphenyltetramethyldisilane. On the basis of the data obtained, the chemical behavior of polysilastyrene during the irradiation is discussed.     

Molecular assembly of C2-symmetric Bis-(2S)-2-methyldodecanoylamides of alpha,omega-alkylidenediamines into coiled coil and twisted ribbon aggregates

A series of 10 didodecanoylamides of alpha,omega-alkylidenediamines bridged by a straight carbon chain varying in length from 0 to 9 carbons was examined as possible gelator molecules of organic liquids to gain information on the relationships between the spacial arrangement of two amide groups in a molecule and their effects on the microscopic structures of the gel. The structural characteristics of these amides are parallel and antiparallel arrangements of two amide carbonyl groups, which depend on the even and odd numbers of a bridging zigzag carbon chain. The linear alkyl chain moieties and a center carbon chain of diamides intermolecularly interact with each other within the van der Waals contact. Two amide moieties of an even number carbon chain diamide intermolecularly interact with each other by using two pairs of hydrogen bonds with two other molecules in a plane, which formed ribbonlike self-complementarily assembled aggregates. On the other hand, a diamide of an odd number carbon chain forms four independent hydrogen bonds with four other molecules not in a plane, which assembled into woven aggregates. Asymmetric introduction of a methyl group at the alpha-position of the amide groups successfully twists the two side chain van der Waals cores of the chiral diamides in the fixed direction, giving helically twisted ribbon and coiled coil aggregates. The helically twisted ribbon and coiled coil aggregates of these chiral diamides were directly observed by CD, SEM, and TEM, providing a basis for the design of a sophisticated small molecular gelator of a tailor-made shape.     

Furan derivatives. Part 13 . Synthesis of thiopyrano[4,3,2-cd]benzofuran

Thiopyrano[4,3,2-cd]benzofuran 9 possessing benzofuran and methylenethiopyran structures in the molecule was synthesized starting from 1-chloro-4-methoxy-2-nitrobenzene 11. Some reactions (formylation, protonation and catalytic hydrogenation) on 9 were examined. The 2-position of 9 was highly reactive toward electrophilic reagents and the furan ring was readily reduced by catalytic hydrogenation with palladium-charcoal. Thiopyrano[4,3,2-cd]benzofuran 9 has both properties of methylenethiopyran and benzofuran.     

Photocyclization reactions. Part 4 . Synthesis of naphtho[1,8-bc]-furans and cyclohepta[cd]benzofurans using photocyclization of Ethyl 2-(8-Oxo-5,6,7,8-tetrahydro-1-naphthyloxy)acetates and ethyl 2-(5-Oxo-6,7,8,9-tetrahydro-5H-benzocyclohepten-4-yloxy)acetates

Photocyclization reactions were carried out on ethyl 2-(8-oxo-5,6,7,8-tetrahydro-1-naphthyloxy)acetates 1a-e and ethyl 2-(5-oxo-6,7,8,9-tetrahydro-5H-benzocyclohepten-4-yloxy)acetates 2a-e in acetonitrile. Irradiation of 1a-e gave naphtho[1,8-bc]furanols 3a-e and naphtho[1,8-bc]furans 4a-e in 33–83% yields and ethyl acrylates 5b-d were produced in 3–25% yields during irradiation of 1b-d . On the other hand, 2a-e afforded cyclohepta[ad|benzofuranols 6a-e and cyclohepta[ad]benzofurans 7a-e in 44–87% yields. Ethyl acrylates 8b-d were also produced in 7–43% yields from irradiation of 2b-d . Substituent effects on photocyclization and reaction pathways are discussed.     

Tube domain and an orbit of a complex triangular group

Let w be a complex symmetric matrix of order r, and Δ ₁(w), . . . , Δ _r (w) the principal minors of w. If w belongs to the Siegel right half-space, then it is known that Re (Δ _k (w)/Δ _k-1(w)) > 0 for k = 1, . . . , r. In this paper we study this property in three directions. First we show that this holds for general symmetric right half-spaces. Second we present a series of non-symmetric right half-spaces with this property. We note that case-by-case verifications up to dimension 10 tell us that there is only one such irreducible non-symmetric tube domain. The proof of the property reduces to two lemmas. One is entirely generalized to non-symmetric cases as we prove in this paper. This is the third direction. As a byproduct of our study, we show that the basic relative invariants associated to a homogeneous regular open convex cone Ω studied earlier by the first author are characterized as the irreducible factors of the determinant of right multiplication operators in the complexification of the clan associated to Ω.     

Optical Chirality Induced in Evaporated Poly(diacetylene) Film by Circularly Polarized Light

Summary: 10,12-tricosadiynoic acid films were deposited on glass substrate by vacuum evaporation proceess at substrate temperatures of 273 K and 313 K, and then photopolymerized using left- and right- circularly polarized light (CPL). The resulting prepared poly(diacetylene) films changed from blue phase to red phase successfully by sample annealing at 353 K for 10 min, and the absorption spectra well reflected the red phase. Surface morphology change was not observed by anneling at 353 K. Furthermore, the CD spectra revealed that the chirality induced by CPL at 313 K was stronger that at 273 K.     

Visualizing of skin chromophore concentrations by use of RGB images

A method is proposed for visualizing simply the concentrations of melanin, oxygenated blood, and deoxygenated blood in skin tissue using digital RGB images. The total blood concentration and oxygen saturation can also be reconstructed. Monte Carlo simulation of light transport specifies a relation between the chromophore concentrations and Commission Internationale de l'Eclairage XYZ, which are compatible with the common RGB working space. Experiments with a tissuelike agar gel phantom demonstrated the possibility of the method. In vivo imaging of a human hand during forearm occlusion demonstrated the ability of the method to evaluate hemodynamics of skin tissue.