Solvent effects on the crystal photochromism of 4,4′-methylenebis{(<Emphasis Type="Italic">N</Emphasis>-3,5-di-<Emphasis Type="Italic">tert</Emphasis>-butylsalicylidene)-2,6-dimethylaniline}

4,4′-methylenebis{N-(3,5-di-tert-butylsalicylidene)-2,6-dimethylaniline} formed a definite acetone-inclusion crystal by recrystallization with acetone. Through crystal-to-crystal solvent exchange of the crystal, various types of crystals were obtained. All resulting crystals exhibited photochromism. Rate constants of thermal fading of photochromes were found to depend on the number of solvent molecules included in the crystal unit. The thermal stability of photochrome is discussed in connection with molecular mobility in the crystal lattice.     

Scaling form of zero-field-cooled and field-cooled susceptibility in superparamagnet

The scaling form of the normalized ZFC and FC susceptibility of superparamagnets (SPMs) is presented as a function of the normalized temperature y(=k_BT/K_u〈V〉), normalized magnetic field h (=H/H_K), and the width σ of the log-normal distribution of the volumes of nanoparticles, based on the superparamagnetic blocking model with no interaction between the nanoparticles. Here 〈V〉 is the average volume, K_u is the anisotropy energy, and H_K is the anisotropy field. Main features of the experimental results reported in many SPMs can be well explained in terms of the present model. The normalized FC susceptibility monotonically increases as the normalized temperature y decreases. The normalized ZFC susceptibility exhibits a peak at the normalized blocking temperature y_b(=k_BT_b/K_u〈V〉), forming the y_b vs h diagram. For large , y_b starts to increase with increasing h, showing a peak at h=h_b, and decreases with further increasing h. The maximum of y_b at h=h_b is due to the nonlinearity of the Langevin function. For small σ, y_b monotonically decreases with increasing h. The derivative of the normalized FC magnetization with respect to h shows a peak at h=0 for small y. This is closely related to the pinched form of M_FC vs H curve around H=0 observed in SPMs.     

Structure and rheology of wormlike micelles

In a semi-dilute aqueous solution under certain conditions, surfactant molecules will self assemble to form wormlike micelles. The micelles are dynamic in structure since they can break and reform, providing an additional mode of relaxation. The viscoelastic properties of the wormlike micelles can be predicted using simple theological models. For many surfactant solutions the mechanical data can be related to the optical data by the stress-optical rule. From the viscoelastic data it is possible to estimate the breaking time of the micelle. The techniques of birefringence and small angle light scattering are used to study the microstructure of a surfactant solution under simple shear and extensional flow. The sample under investigation is a solution of cetyltrimethylammonium bromide and sodium salicylate in water, with a salt to surfactant ratio of 7.7. Below a critical shear rate, the birefringence increases linearly with shear rate and the stress-optical rule is valid. The SALS patterns reveal distinctive butterfly patterns indicating that scattering is a result of concentration fluctuations that moderately couple to the flow. However, above a critical shear rate the birefringence plateaus and the stress-optical rule is no longer valid. SALS patterns show both a bright streak and a butterfly pattern. The bright streak is caused by elongated structures aligned in the direction of the flow. The oriented structures occur when the characteristic time of flow is faster than the breaking time of the micelles.Dedicated to Prof. Dr. J. Meissner on the occasion of his retirement from the chair of Polymer Physics at the Eidgenössische Technische Hochschule (ETH) Zürich, Switzerland     

Synthesis and characterizations of meso-disubstituted asymmetric porphycenes

A post-synthetic method has been developed to synthesize novel asymmetric porphycenes bearing two different substituents on the meso-positions. Nitration of 9-acetoxy-2,7,12,17-tetra-n-propylporphycene with AgNO₃ in CH₃COOH/CH₂Cl₂ occurs regioselectively at the 19-position of the macrocycle to give 9-acetoxy-19-nitro-2,7,12,17-tetra-n-propylporphycene (3a) which was readily converted to 9-acetoxy-19-amino-2,7,12,17-tetra-n-propylporphycene (4a) by the reduction with SnCl₂ in pyridine.     

Structural study of alternating copolymerization of aziridines with cyclic imide

The structures of copolymers of aziridines with cyclic imides were determined by means of infrared spectrometry, paper electrophoresis of the hydrolyzate, and NMR spectrometry. The structure of the repeating unit in the copolymer of ethylenimine with succinimide was \documentclass{article}\pagestyle{empty}\begin{document}$\rlap{--} ({\rm CH}_2 {\rm CH}_2 {\rm NHCOCH}_2 {\rm CH}_2 {\rm CONH}\rlap{--} ) $\end{document}. The endgroups of the copolymer were N-acylethylenimine ring, N-substituted succinimide ring, and primary amide group. The copolymer of ethylenimine with N-ethylsuccinimide had the repeating unit of \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm CH}_2 {\rm CH}_2 {\rm NHCOCH}_2 {\rm CH}_2 {\rm CON}({\rm C}_2 {\rm H}_5 )\rlap{--} ] $\end{document} and the endgroups of N-acylethylenimine and N-substituted succinimide ring. N-Ethylethylenimine did not copolymerize with succinimide, but in the presence of water, the reaction occurred to give an amorphous polymer. This copolymer had the repeating unit \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} [{\rm CH}_2 {\rm CH}_2 {\rm NHCOCH}_2 {\rm CH}_2 {\rm CON}({\rm C}_2 {\rm H}_5 )\rlap{--} ] $\end{document} and the endgroups were N-substituted succinimide ring and amine group but not N-acylethylenimine ring. On the basis of this structural information, the initiation reaction was discussed.     

Electrical conductivity and chemical diffusion in Perovskite-type proton conductors in H2-H2O gas mixtures

The electrical conductivities of SrZr_0.9Y_0.1O_3-δ (SZY10) and BaCe_0.95Y_0.05O_3-δ(BCY5) were measured as a function of hydrogen partial pressure P(H₂), oxygen partial pressure P(O₂), steam partial pressure P(H₂O) and temperature. Their relaxation processes were analyzed using the solution of Fick's diffusion equation to determine the chemical diffusion coefficients and surface reaction rate constants. There were the differences in chemical relaxation kinetics and the conductivity dependence on P(H₂O) between the both oxides. The chemical diffusion coefficients depend on temperature but are essentially independent of P(H₂), P(O₂) and P(H₂O). The ambipolar diffusion treatment can explain the temperature dependence of chemical diffusion coefficients quantitatively. The chemical diffusion coefficients of SZY10 is one or two order of magnitude smaller than those of BCY5 at low temperature. The sluggish conductivity relaxation in SZY10 was due to considerably small oxygen vacancy diffusion coefficients at low temperatures. The total conductivity depends on P(H₂O) in the case of SZY10, but not for BCY5. This different dependence on P(H₂O) is caused by the difference in the ratio between proton mobility and oxide-ion mobility.     

Influence of substrate on self-assembled photonic crystal

Freestanding monolayers of two-dimensional particle arrays, in which fine particles are two-dimensionally self-assembled in a highly oriented manner, was prepared to examine the influence of substrate on the transmission spectra of 2D particle array; as a result, the spectrum of the freestanding 2D particle array has less noise than that of the 2D particle array on the substrate, and besides, agree with the theoretical result particularly in the near-field discussion.     

Copolymerization with depropagation. V. Copolymerization of α-methylstyrene and methyl methacrylate between their ceiling temperatures

The variation of copolymer composition with monomer feed has been studied for the system α-methylstyrene-methyl methacrylate at 60, 114 and 147°C. The compositions predicted by the diad model of Part III of this series accurately describe the data.     

Symplectic twistor spaces

The paper describes the geometry of the bundle (M, ω) of the compatible complex structures of the tangent spaces of an (almost) symplectic manifold (M, ω), from the viewpoint of general twistor spaces [3], [9], [1]. It is shown that M has an either complex or almost Kaehler twistor space iff it has a flat symplectic connection. Applications of the twistor space to the study of the differential forms of M, and to the study of mappings : N → M, where N is a Kaehler manifold are indicated.     

Adduct between quadricyclane and (η-cyclopentadienyl)(1,2-benzenedithiolato)cobalt(III): formation and structure

The reaction of (η⁵-cyclopentadienyl)(1,2-benzenedithiolato)cobalt(III) (1) in quadricyclane (Q) at 90°C gives 1:1 adducts of 1 and Q. The main adduct (40% yield) has a unique structure, in which the 5-and 7-positions of norbornene are bonded to Co and S of 1. A mechanism of the formation of the adduct (by the use of deuterium-labeled Q), including a skeletal rearrangement of Q, is proposed.