Supramolecular Zn(II)-Dipicolylamine-Azobenzene-Aminocyclodextrin-ATP Complex: Design and ATP Recognition in Water

Cyclodextrins (CyDs) are water-soluble host molecules possessing a nanosized hydrophobic cavity. In the realm of molecular recognition, this cavity is used not only as a recognition site but also as a reaction medium, where a hydrophobic sensor recognizes a guest molecule. Based on the latter concept, we have designed a novel supramolecular sensing system composed of Zn(II)-dipicolylamine metal complex-based azobenzene (1-Zn) and 3A-amino-3A-deoxy-(2AS,3AS)-γ-cyclodextrin (3-NH₂-γ-CyD) for sensing adenosine-5′-triphosphate (ATP). 1-Zn showed redshifts in the UV-Vis spectra and induced circular dichroism (ICD) only when both ATP and 3-NH₂-γ-CyD were present. Calculations of equilibrium constants indicated that the amino group of 3-NH₂-γ-CyD was involved in the formation of supramolecular 1-Zn/3-NH₂-γ-CyD/ATP. The Job plot of the ICD spectral response revealed that the stoichiometry of 1-Zn/3-NH₂-γ-CyD/ATP was 2:1:1. The pH effect was examined and 1-Zn/3-NH₂-γ-CyD/ATP was most stable in the neutral condition. The NOESY spectrum suggested the localization of 1-Zn in the 3-NH₂-γ-CyD cavity. Based on the obtained results, the metal coordination interaction of 1-Zn and the electrostatic interaction of 3-NH₂-γ-CyD were found to take place for ATP recognition. The “reaction medium approach” enabled us to develop a supramolecular sensing system that undergoes multi-point interactions in water. This study is the first step in the design of a selective sensing system based on a good understanding of supramolecular structures.     

Thermodynamic Regularities in Perovskite and K2NiF4 Compounds

It has been found that the enthalpy of formation of perovskite compounds, Δ_fH° (ABO₃, B = transition metais), from binary oxides can be well characterized in terms the tolerance factor, t≡(r_A+ r_o)√2 (r_B+ r_o), where r_A and r_B are the radii of A-site ions with 12-coordination and B-site ions with 6-coordination, respectively, and Δ_fH°=−168 + 270(1 − t) kJ·mol⁻¹ for A^IB^VO₃, Δ_fH°=−125 + 1000(1 − t) kJ·mol⁻¹ for A^IIB^IVO₃, and Δ_fH°=− 90 + 720(1 − t) kJ·mol⁻¹ for A^IIIB^IIIO₃. Although the thermodynamic data of K₂NiF₄ compounds are not extensive, a similar regularity can be found when use is made of the radii of A-site ions with 9-coordination for the K₂NiF₄ compounds. These correlations will be quite useful in predicting.     

Polymorphic behavior of gondoic acid and phase behavior of its binary mixtures with asclepic acid and oleic acid

Molecular properties of polymorphic forms of gondoic acid [cis-C_20:1Δ11ω9 (GOA)] have been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), optical microscopy, and Raman scattering, in comparison to those of six principal unsaturated fatty acids: oleic acid [cis-C_18:1Δ9ω9 (OA)], erucic acid [cis-C_22:1Δ13ω9 (ERA)], petroselinic acid [cis-C_18:1Δ6ω12 (PSA)], asclepic acid [cis-C_18:1Δ11ω7 (APA)], palmitoleic acid [cis-C_16:1Δ9ω7 (POA)], and elaidic acid [trans-C_18:1Δ9ω9 (ELA)]. In addition, phase behavior of binary mixtures of GOA and APA and OA was examined by XRD and DSC. The polymorphic structures of GOA are quite similar to those of APA, ERA, POA, and partly to OA. In particular, DSC and Raman scattering studies have shown that gondoic acid exhibits conformational disordering on heating at the ω-chain, a chain segment between the double bond and CH₃ group, as a transition from all-trans (γ form) to gauche-rich (α form) conformations. A miscible mixing phase was observed in the mixture of GOA and APA, yet eutectic phases were observed in the GOA and OA mixtures. This is a remarkable contrast because the binary mixture systems of varying combinations of cis-unsaturated fatty acids examined so far exhibited either eutectic nature or molecular compound formation. It is expected that specific molecular interactions between GOA and APA that originate from the equivalence of the length of the Δ-chain, the chain segment between the cis-double bond and COOH group, and also from the presence of the γ-α order-disorder transformation would be operating to form the miscible mixing phase.     

A pre-heating vaporization technology of coal-water-slurry for the gasification process

A pre-heating vaporization technology of coal water slurry, CWS, was developed to increase the efficiency of coal gasification with the reduction of oxygen consumption. A CWS pre-heating experimental unit having a capacity of 2.0 tons-coal/day was manufactured. After the CWS was heated to 573 K at about 10 MPa, water in CWS was continuously vaporized in a tube of which the diameter increased gradually (2–10 mm I.D.), and dry coal particles with steam were atomized and fed to a vessel. No aggregation of coal particles was observed in the atomized samples. The temperature and the pressure distributions of the fluid were calculated with empirical heat transfer and pressure drop correlations. The calculated results well corresponded to the experimental data measured in some test points. Using the calculation model, a large scale apparatus of 100 tons-coal/day was designed using KNO₃ + NaNO₂ + NaNO₃ molten salt as a heating medium.     

Effect of molecular weight on molecular orientation and morphology of polypropylene sheets containing a β-nucleating agent

In this study, polypropylene (PP) films containing the β nucleating agent, N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide, were prepared using PP with three different molecular weights (low, medium, and high) by extrusion process with T-shaped die. The structure and morphology of the films were studied after stretching. It was found that a unique molecular orientation, in which both the c-axis and crystalline lamellae were oriented perpendicular to the flow direction, was formed in all undrawn film samples, irrespective of the molecular weights of the PP. In the PP sheets stretched in the machine direction, the low-molecular-weight sample containing the nucleating agent exhibited brittle properties owing to a lack of tie chains in the stretching direction. In contrast, cavitation was prominent in the medium (M-PP)- and high (H-PP)-molecular-weight samples. Notably, M-PP containing the nucleating agent, with a high degree of molecular orientation, promoted the formation of a large number of voids. In H-PP containing the nucleating agent, the presence of numerous tie chains inhibited cavitation, resulting in fewer voids. The experimental results demonstrated the influence of the molecular weight on the void structure, which will be useful in the field of microporous membranes.     

Factors associated with serum magnesium and vascular stiffness in maintenance hemodialysis patients

Introduction : We evaluated the associated factors of serum magnesium in patients on maintenance hemodialysis (MHD). Furthermore, we evaluated the relationship between low serum magnesium and arteriosclerosis in these patients. Methods : In 129 patients on MHD, we evaluated the blood levels of magnesium, brachial‐ankle pulse wave velocity (ba‐PWV), ankle‐brachial index (ABI), and intima‐media thickness of the common carotid artery (IMT). Findings : In MHD patients, the serum level of magnesium was significantly correlated with age, calcium, TNF‐α, albumin, and ba‐PWV but not with ABI or IMT. In the multiple regression analysis, albumin (P = 0.0001, β = 0.31) and calcium (P = 0.029, β = 0.18) were selected as significant predictors of the magnesium level in MHD patients. Furthermore, the serum level of magnesium, as well as systolic blood pressure (P = 0.0001, β = 0.32) and age (P = 0.005, β = 0.25), were selected as significant (P = 0.012, β = ?0.22) predictors of ba‐PWV in MHD patients. Discussion : In MHD patients, the serum magnesium level was associated with the serum levels of calcium and albumin. Furthermore, a low serum magnesium level in MHD patients was associated with the index of vascular stiffness.     

Dominant stress region for crack initiation at interface edge of microdot on a substrate

In order to examine the mechanics of crack initiation at the free interface edge of a microcomponent on a substrate, delamination tests are carried out for two specimen shapes of Cr microdots on a SiO₂ substrate. The microdots of the first specimen are shaped like the frustum of a round cone. The Cr microdots are successfully delaminated from the SiO₂ substrate in a brittle manner and the critical load is measured by atomic force microscopy (AFM) with a lateral loading apparatus. Stress analysis reveals that a singular stress field exists near the interface edge and the strength for the crack initiation is governed by the intensified normal stress field. The critical stress intensity parameter is evaluated as K_σC ≈ 0.24 MPa m^0.39. Similar delamination tests are conducted for microdots shaped like the frustum of an oval cone. The stress distributions at the crack initiation of this specimen shape show a higher normal stress than the first specimen shape in the region near the interface edge of about x < 40 nm, while it is lower in the region of about x > 50 nm (x: distance from the edge). This suggests a limitation of conventional fracture mechanics: namely, the crack initiation in these specimens is not uniquely governed by the intensity of the singular field. It is found that the delamination crack is initiated when the averaged stress σ_ya in the region of 90-130 nm reaches 190-270 MPa, regardless of the specimen shape. This indicates that the dominant stress region of crack initiation is roughly estimated as 90-130 nm and the criterion is given in terms of the averaged stress in the region.     

High Temperature Schottky Barrier on n-Type SrTiO3 and Its Sensitivity to Ambient Gases

Metal or oxide electrodes (Pt, Au, Ag, (La, Sr)CoO₃) were deposited on single crystals of 0.02 mol% Nb doped SrTiO₃ by pulsed laser deposition. Current-voltage and capacitance-voltage responses were measured using three-terminal electrode configuration. Under high oxygen partial pressures, clear rectification behaviors were observed. Diffusion model well explained the current vs. voltage relationship with ideality factors close to unity. The barrier height varied reversibly with oxygen partial pressure, and was almost independent of the electrode materials, which suggested that the Fermi level at the interface was pinned by the surface states. The origin of the surface states was discussed in terms of oxygen adsorption or oxidative formation of metal vacancies around the surface. Chemical interaction between the surface and oxygen and resulting cation rearrangement was concluded to play an important role from the long stabilization time on oxygen partial pressure change. The water vapor pressure dependence of the barrier height was also explained by competitive adsorption of oxygen and water.