Catalytic specificity exhibited by p-sulfonatocalix[n]arenes in the methanolysis of N-acetyl-l-amino acids

Specific acid catalysis of p-sulfonatocalix[n]arenes (n = 4, Calix-S4; n = 6, Calix-S6; n = 8, Calix-S8) was observed in the alcoholysis of N-acetyl-l-amino acids in methanol. The methanolysis rates of basic amino acid substrates (His, Lys, and Arg) were markedly enhanced in the presence of Calix-Sn, as compared with rates observed with p-hydroxybenzenesulfonic acid (pHBS), which is a noncyclic analogue of Calix-Sn. This catalytic effect of Calix-Sn was not observed for the methanolysis of Phe, Tyr, and Trp substrates. On the other hand, (1)H NMR experiments following the effect of Calix-Sn on N-acetyl-l-amino acid substrates in CD(3)OD showed that the spectrum of a mixture of the His substrate with Calix-Sn was significantly different from the combined spectra of the respective compounds. These changes in spectra support the formation of an inclusion complex of Calix-Sn with basic amino acids. Furthermore, it was obvious that methanolysis of the His substrate catalyzed by Calix-S4 and Calix-S6 obeyed Michaelis-Menten kinetics. These results indicate that the catalytic activity of Calix-Sn originates from its forming a complex with specific substrates (basic amino acids), similar to enzymatic reactions.     

Supramolecular chirogenesis in zinc porphyrins: interaction with bidentate ligands,formation of tweezer structures,and the origin of enhanced optical activity

The complexation behavior, binding properties, and spectral parameters of supramolecular chirality induction in the achiral host molecule, syn (face-to-face conformation) ethane-bridged bis(zinc porphyrin), upon interaction with chiral bidentate guests (diamines and amino alcohols) have been studied by means of UV-vis, CD, fluorescence, (1)H NMR, and ESI MS techniques. It was found that the guest structure plays a decisive role in the chirogenesis pathway. The majority of bidentate ligands (except those geometrically unsuitable) exhibit two major equilibria steps: the first guest ligation leading to formation of the 1:1 host-guest tweezer structure (K(1)) and the second guest molecule ligation (K(2)) forming the anti bis-ligated species (1:2). The second ligation is much weaker (K(1) > K(2)) due to the optimal geometry and stability of the 1:1 tweezer complex. The enhanced conformational stability of the tweezer complex ensures an efficient chirality transfer from the chiral guest to the achiral host, consequently inducing a remarkably high optical activity in the bis-porphyrin.     

Concentration dependences of dielectric properties at 105 Hz and 106 Hz for aqueous solutions of hydroxypropyl cellulose

The concentration dependences of dielectric properties measured at 10⁵ Hz and 10⁶ Hz are reported for aqueous solutions of hydroxypropyl cellulose. Phase behaviour of the solutions was also observed with a polarizing optical microscope. For solutions with concentrations well above 40 wt %, polydomain textures, including the banded texture, were observed after a prehistory of deformation. No significant discontinuous changes in the dielectric constant, ε_r′, and loss factor, ε_r″, were found at the concentrations around the onset of the isotropic–cholesteric phase transition and in the biphasic region. In contrast, the steeper changes in ε_r′ and ε_r″ were found at the critical concentration for the fully developed cholesteric phase transition with the polydomain textures.     

Visco-elastic properties of reentrant nematic liquid crystalline mixtures

The visco-elastic properties for binary mixtures of 4-n -hexyloxy-4′-cyanobiphenyl (6OCB) and 4-n-octyloxy-4′-cyanobiphenyl (8OCB) are investigated in detail by a light scattering technique. The mixtures exhibit a reentrant nematic (RN) phase between the smectic A (SmA) and crystal phases in the range 22.0–29.5 wt % of 6OCB. The viscosity and the elastic constant increase with cooling in both the nematic and reentrant nematic phases. It is also found that the mixtures exhibit anomalously large values of viscosity and elastic constant near the phase transition, i.e. a pretransitional phenomenon can be observed. The activation energy for viscosity is smaller in the RN phase than in the ordinary nematic phase appearing at higher temperatures, while the normalized elastic constant (defined as the ratio of the elastic constant to the square of the dielectric anisotropy) is larger. Moreover, the visco-elastic behaviour depends on the specific time during which the sample has been kept in the SmA phase. These results confirm that the SmA phase has a strong influence on the formation of molecular aggregates, which plays an important role in the reentrant phenomenon of these systems.     

Molecular imprinting of bisphenol A and alkylphenols using amylose as a host matrix

A novel molecularly imprinted polymer has been created by a radical polymerisation of acryloylamylose in the presence of a template.     

Theory of ferromagnetism in Ca(1-x)La(x)B(6)

Novel ferromagnetism in Ca(1-x)La(x)B(6) is studied in terms of the Ginzburg-Landau theory for excitonic-order parameters, taking into account symmetry of the wave functions. We found that the minima of the free energy break both inversion and time-reversal symmetries, while the product of these two remains preserved. This explains various novelties of the ferromagnetism and predicts a number of magnetic properties, including the magnetoelectric effect, which can be tested experimentally.     

Crying and Behavioral Characteristics in Premature Infants

The aims of this study were to analyze 1) whether there was the relationship between the neonatal behavioral characteristics and amount of crying in premature infants at term age, and 2) what kind of difference between infants with high levels of crying and cry less on neonatal behavioral characteristics using the Neonatal Behavioral Assessment Scale (NBAS). The study participants consisted of 69 healthy low birth-weight infants who were admitted to the NICU at the Nagasaki University Hospital, Nagasaki, Japan. This study analyzed the relationship between NBAS scores measured neonatal behavioral performance and crying at term age. This study results indicate that there was significant statistical negative correlation between the amount of total daily crying and Habituation, Range of state, Regulation of state, and Autonomic stability cluster scores and some individual items scores (Response decrement to light, Response decrement to tactile of foot, Alert responsiveness, Examiner persistence, Motor maturity, Irritability, General irritability, Cuddliness, Consolability, Self-quieting activity, and State regulation). The high levels crying group also showed higher responsivity than less crying group in the items of Peak of excitement, Rapidity of build-up, Irritability and General irritability. In conclusion, neonatal behavioral characteristics such as poor inhibit discrete stimuli while asleep, hyper-responsivity and poor state regulation abilities were risk factors of high levels of crying.     

Hole transport in polymers of (N-ethylcarbazol-3-yl) methyl acrylate and methacrylate

(N-Ethylcarbazol-3-yl)methyl acrylate and methacrylate were polymerized anionically and radically. Anionically-polymerized polyacrylate using ethylmagnesium chloride-benzalacetophenone as catalyst is an isotactic rich polymer with 85% isotactic dyad. All polymers except anionically polymerized polymethacrylate showed good film forming property. Hole drift mobilities measured by the time-of-flight method at room temperature and at 5 × 10⁵ V/cm are in the following order: isotactic polyacrylate (1.0 × 10^-5 cm²/V s) > atactic polyacrylate (1.8 × 10^-6 cm²/V s) > atactic polymethacrylate (1.2 × 10^-6 cm²/V s) at 5 × 10⁵ V/cm. These results are discussed in terms of the hopping model between localized sites.     

Surface properties of styrene–ethylene oxide block copolymers

Hydrophobic–hydrophilic block copolymers were prepared by “living” anionic polymerization. They consist of polystyrene and poly(ethylene oxide) blocks, and are soluble in water. Their interfacial properties were investigated, employing aqueous solutions. The block copolymers lowered the surface tension of water in analogy with the low molecular weight surfactants such as sodium lauryl sulfate and heptaethylene oxide n-dodecyl ether. Their aqueous solutions exhibited solubilization properties differing from those of polyethylene glycol. Therefore, it is thought that the polystyrene blocks produce solubilization phenomena. In samples of the same styrene content, the precipitation temperature of a high molecular weight copolymer in water was lower than that of a low molecular weight copolymer at the same concentration in the same solvent. The surface tension and precipitation temperature of aqueous solutions seem to be influenced by molecular weight and composition.