C-O-bond cleavage of esters with a naphthyl group in the higher triplet excited state during two-color two-laser flash photolysis

A C-O-bond cleavage of esters having a naphthyl group, NpCO-OR and RCO-ONp (Np=alpha- and beta-naphthyl ((alpha)Np and (beta)Np, respectively), R=Ph and Me), was found during the two-color two-laser flash photolysis in acetonitrile. The C-O-bond cleavage occurred when NpCO-OR and RCO-ONp were excited to the singlet excited states (S1). On the other hand, no reaction occurred from the lowest triplet excited states (T1). When NpCO-OR(T1) and RCO-ONp(T1) were excited to the higher triplet excited states (Tn) using the second laser during the two-color two-laser flash photolysis, the C-O-bond cleavage occurred. The C-O-bond cleavage quantum yield (Phi) was estimated from the plots of the T1-state esters disappeared within a laser flash versus the second laser intensities. The C-O-bond cleavage in (beta)NpCO-OPh(Tn) occurred more efficiently than in (alpha)NpCO-OPh(Tn) and that in PhCO-O(beta)Np(Tn) occurred more efficiently than in PhCO-O(alpha)Np(Tn). The Phi value for ester with Ph and beta-Np groups was larger than that for ester with Ph and alpha-Np groups. The Phi value for MeCO-O(alpha)Np(Tn) was similar to those for PhCO-ONp(Tn), while that for MeCO-O(beta)Np(Tn) was much smaller than those for PhCO-ONp(Tn) and MeCO-O(alpha)Np(Tn). On the other hand, no C-O-bond cleavage was observed in NpCO-OMe(Tn). The Phi value depended on the characters of the groups (Np, Ph, and Me) on the ester. Whether R is Ph or Me with or without pi electron, respectively, is important for the C-O-bond cleavage. In other words, electronic delocalization of the T(n) state including Np and ester groups is necessary for the occurrence of the C-O-bond cleavage in NpCO-OR(Tn) and RCO-ONp(Tn).     

波导侧壁起伏对聚酰亚胺波导光学梳状滤波器串扰特性的影响及其改善方法

提出了一种结构模型来分析由工艺引起的波导侧壁起伏对于聚合物波导光学梳状滤波器的滤波特性的影响。含氟聚酰亚胺高分子聚合物制备多级马赫一曾德尔串联型光学梳状滤波器件的工作参量为中心波长1550nm,波长间隔为0．8nm,40通道的波长交错分离。模拟计算：表明,对由高分子聚合物材料制备的多级马赫-曾德尔串联型光学梳状滤波器件,其主要影响是增大了信道之间的串扰,中心波长1550nm处的信道串扰由理想情况下的-40dB降为-12dB,极大地影响了器件的性能。在此基础上,提出一种改善光学梳状滤波器串扰性能的新结构,该结构由多级马赫-曾德尔耦合器和微环共振滤波器串接构成,40个通道的串扰改善为-0dB以下。     

Proposition of Single Molecular Orientation Determination Using polarization Controlled Beam by Liquid Crystal Spatial Light Modulators

We have proposed a method to control the three-dimensional electric field in the focus of an optical microscope using two non-twisted liquid crystal spatial light modulators, and to detect the molecular orientation of a single molecule. The three-dimensional electric field is generated by focusing the beam with two dimensional spatial distribution of polarization. The possibility of detection of three-dimensional single molecular orientation was shown by numerical calculations. © 2005 The Optical Society of Japan     

Behavior strategies,mixed strategies and perfect recall

When perfect recall is not satisfied, the informational contents of mixed and behavior strategies differ and are more than what the information partition describes. First, we consider two kinds of additional information strategies may carry, and show that such information leads to theperfect recall refinement of a given information partition. This does not, however, imply that the strategies compensate fully for the lack of perfect recall. We give a necessary and sufficient condition on an information partition, calledA-loss, for the informational content of mixed strategies to fully compensate for the lack of perfect recall. The informational content of behavior strategies never fully compensates.     

Preferential Alignment of Hydroxyapatite Crystallites in Nanocomposites with Chemically Disintegrated Silk Fibroin

Hydroxyapatite (HAp) nanocrystals were prepared at room temperature by a coprecipitation method from Ca(OH)₂ and H₃PO₄, in the presence of chemically disintegrated silk fibroin (SF). Adsorbed amounts of cations on SF and crystallinity of HAp in the composite were increased by the chemical disintegration of SF higher order structure. Preferential alignment of c-axis of HAp crystallites along the longitudinal direction of ca. 150nm SF fibril was observed. These changes due to disintegration of SF were discussed in terms of the chemical interaction between HAp and SF. The resulted composite with preferential alignment of HAp nanocrystals is a good candidate as a starting material for bone substitutes.     

Synthesis of well‐defined polymers end‐functionalized with crosslinkable aziridine groups by living anionic polymerization

Well‐defined end‐functionalized polystyrene, poly(α‐methylstyrene), and polyisoprene with polymerizable aziridine groups were synthesized by the termination reactions of the anionic living polymers of styrene, α‐methylstyrene, and isoprene with 1‐[2‐(4‐chlorobutoxy)ethyl]aziridine in tetrahydrofuran at ?78 °C. The resulting polymers possessed the predicted molecular weights and narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight < 1.1) as well as aziridine terminal moieties. The cationic ring‐opening polymerization of the ω‐monofunctionalized polystyrene having an aziridinyl group with Et₃OBF₄ gave the polymacromonomer, whereas the α,ω‐difunctional polystyrene underwent crosslinking reactions to afford an insoluble gel. Crosslinking products were similarly obtained by the reaction of the α,ω‐diaziridinyl polystyrene with poly(acrylic acid)‐co‐poly(butyl acrylate). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4126–4135, 2005     

Structures of xestospongin A,B,C and D,novel vasodilativecompounds from marine sponge, xestospongiaexigua

Xestospongin A,B,C and D represent a new class of macrocyclic 1-oxaquinolizidines, have been isolated from Australian sponge $\text{Xestospongia}$$\text{exigua}$. The structure of xestospongin C has been determined by X-ray analysis.