Heat capacity of a five-coordinated iron(III) complex,chlorobis(N,N-dimethyldithiocarbamato) iron(III), between 0.4 and 300 k: New finding of a magnetic phase transition

The heat capacity of the title complex, Fe[S₂CN(CH₃)₂]₂Cl, has been measured between 0.4 and 300 K. A λ -type phase transition with a small shoulder arising from magnetic ordering was found at (0.609 ± 0.005) K. The character of the ordered phase has been suggested to be ferromagnetic on the basis of comparison between the methyl- and ethyl-homologues. The magnetic hyperfine structure of the Mössbauer spectra and the line broadening due to electronic relaxation effects at 1.2 K hitherto reported are concluded to result from a critical slowing-down when the magnetic transition temperature is approached from the high-temperature side. A Schottky-type anomaly arising from the zero-field splitting of a single ferric ion was observed around 2 K. The excess entropy beyond the lattice contribution at low temperatures amounts to (14.05 ±0.27) J K^?1mol^?1, which cannot be accounted for solely by the magnetic entropy of Rln 4 (= 11.53 JK^?1mol^?1) for the intermediate spin of $\text{S =}\text{3}\text{2}$. Two possibilities concerning additional conntribution have been discussed; one is a mixing of spin species of $\text{S =}\text{5}\text{2}$ and the other is a tunnel-splitting of the rotational levels of four methyl-constituents. The present study cannot give a definite conclusion as to the existence of dimeric units suggested from Mössbauer spectroscopy.     

Krein space representation and Lorentz groups of analytic Hilbert modules

This paper aims to introduce some new ideas into the study of submodules in Hilbert spaces of analytic functions. The effort is laid out in the Hardy space over the bidisk H~2(D~2). A closed subspace M in H~2(D~2) is called a submodule if ziM ? M(i = 1, 2). An associated integral operator(defect operator) CM captures much information about M. Using a Kre??n space indefinite metric on the range of CM, this paper gives a representation of M. Then it studies the group(called Lorentz group) of isometric self-maps of M with respect to the indefinite metric, and in finite rank case shows that the Lorentz group is a complete invariant for congruence relation. Furthermore, the Lorentz group contains an interesting abelian subgroup(called little Lorentz group) which turns out to be a finer invariant for M.     

Algebra of Screening Operators for the Deformed W n Algebra

We construct a family of intertwining operators (screening operators) between various Fock space modules over the deformed W _n algebra. They are given as integrals involving a product of screening currents and elliptic theta functions. We derive a set of quadratic relations among the screening operators, and use them to construct a Felder-type complex in the case of the deformed W ₃ algebra. Received: 3 March 1997 / Accepted: 20 May 1997     

Thermal Stability of Oxidized Single‐Walled Carbon Nanotubes: Competitive Elimination and Decomposition Reaction Depending on the Degree of Functionalization

The thermal stability of oxidized single‐walled carbon nanotubes (SWNTs) with various degrees of oxidation was investigated. The oxidized SWNTs exhibited lower absorption and radial breathing mode (RBM) peaks and a higher intensity ratio of the D band to the G band (D/G) in their absorption and Raman spectra than those of the pristine SWNTs. After the thermal treatment, the D/G ratio of the oxidized SWNTs almost recovered its original intensity, regardless of the degree of oxidation. The absorption, photoluminescence (PL), and RBM peaks could not recover their original intensities when the oxidation degree was high. The results indicate that the elimination and decomposition reactions proceeded competitively depending on the degree of oxidation. In addition, a new PL peak was observed in the near‐infrared region, and the PL peak intensity increased with the subsequent thermal treatment. The theoretical calculations provided an insight into the possible pathways for the decomposition of oxidized SWNTs, showing that the O₂ elimination and CO/CO₂ evolution proceed competitively during thermal treatment.     

Centerband‐only analysis of rotor‐unsynchronized spin echo for measurement of lipid 31P chemical shift anisotropy

Structural diversity and molecular flexibility of phospholipids are essential for biological membranes to play key roles in numerous cellular processes. Uncovering the behavior of individual lipids in membrane dynamics is crucial for understanding the molecular mechanisms underlying biological functions of cell membranes. In this paper, we introduce a simple method to investigate dynamics of lipid molecules in multi‐component systems by measuring the ³¹P chemical shift anisotropy (CSA) under magic angle spinning (MAS) conditions. For achieving both signal separation and CSA determination, we utilized a centerband‐only analysis of rotor‐unsynchronized spin echo (COARSE). This analysis is based on the curve fitting of periodic modulation of centerband intensity along the interpulse delay time in rotor‐unsynchronized spin‐echo experiments. The utility of COARSE was examined by using phospholipid vesicles, a three‐component lipid raft model system, and archaeal purple membranes. We found that the apparent advantages of this method are high resolution and high sensitivity given by the moderate MAS speed and the one‐dimensional acquisition with short spin‐echo delays. COARSE provides an alternative method for CSA measurement that is effective in the investigation of lipid polymorphologies. Copyright © 2015 John Wiley & Sons, Ltd.     

Star‐shaped cyclopolymers: A new category of star polymer with rigid cyclized arms prepared by controlled cationic cyclopolymerization and subsequent microgel formation of divinyl ethers

The combination of living/controlled cationic cyclopolymerization and crosslinking polymerization of bifunctional vinyl ethers (divinyl ethers) was applied to the synthesis of core‐crosslinked star‐shaped polymers with rigid cyclized arms. Cyclopolymerization of 4,4‐bis(vinyloxymethyl)cyclohexene ( 1 ), a divinyl ether with a cyclohexene group, was investigated with the hydrogen chloride/zinc chloride (HCl/ZnCl₂) initiating system in toluene at 0 °C. The reaction proceeded quantitatively to give soluble poly( 1 )s in organic solvents. The content of the unreacted vinyl groups in the produced polymers was less than ～3 mol%, and therefore, the degree of cyclization of the polymers was determined to be ～97%. The number‐average molecular weight (M_n) of the polymers increased in direct proportion to monomer conversion and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture, indicating that living cyclopolymerization of 1 occurred. The chain linking reactions among the formed living cyclopolymers with 1,4‐bis(vinyloxy)cyclohexane ( 3 ) as a crosslinker in toluene at 0 °C produced core‐crosslinked star‐shaped cyclopoly( 1 )s [star‐poly( 1 )s] in high yield (100%). Dihydroxylation of the cyclohexene double bonds of star‐poly( 1 ) gave hydrophilic water‐soluble star‐shaped polymers with rigid arm structure [star‐poly( 1 )‐OH] with thermo‐responsive function in water. T_gs of star‐poly( 1 ) and star‐poly( 1 )‐OH were 135 °C and 216 °C, respectively; these values are very high as vinyl ether‐based star‐shaped polymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1094–1102     

Synthesis of poly(vinyl ether)‐based,ABA triblock‐type thermoplastic elastomers with functionalized soft segments and their gas permeability

The ABA‐type triblock copolymers consisting of poly(2‐adamantyl vinyl ether) [poly(2‐AdVE)] as outer hard segments and poly(6‐acetoxyhexyl vinyl ether) [poly(AcHVE)], poly(6‐hydroxyhexyl vinyl ether) [poly(HHVE)], or poly(2‐(2‐methoxyethoxy)ethyl vinyl ether) [poly(MOEOVE)] as inner soft segments were synthesized by sequential living cationic polymerization. Despite the presence of polar functional groups such as ester, hydroxyl, and oxyethylene units in their soft segments, the block copolymers formed elastomeric films. The thermal and mechanical properties and morphology of the block copolymers showed that the two polymer segments of these triblock copolymers were segregated into microphase‐separated structure. Effect of the functional groups in the soft segments on gas permeability was investigated as one of the characteristics of the new functional thermoplastic elastomers composed solely of poly(vinyl ether) backbones. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1114–1124     

Calorimetric study of the cubic mesogen,ACBC(16)

The heat capacity of the cubic mesogen ACBC(16) was measured between 16 and 500?K by adiabatic calorimetry. As well as the known condensed phases, a new crystalline phase was found to undergo a glass transition at around 165?K. Phase transitions between crystal, SmC, cubic, and isotropic liquid phases took place at 399.16, 431.15, and 474.30?K, respectively. As in the case of ANBC, a broad hump was observed in the heat capacity of the isotropic liquid phase. The first order nature of the SmC–cubic phase transition was confirmed for the first time by the observation of supercooling of the cubic phase. The broad hump in the isotropic liquid phase was shown to extend to a low temperature side if the isotropic liquid was supercooled, suggesting that the event occurring at the hump is not directly related to the cubic–isotropic liquid phase transition.