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.     

Studies on applications of lypolytic enzymes in detergency II. Evaluation of adaptability of various kinds of lipases in practical laundry conditions

Journal of the American Oil Chemists' Society - Kinetic parameter of hydrolysis, degree of hydrolysis, pH and temperature characteristics and positional specificity of hydrolysis of seven kinds...     

The short-term effect of a smoking prevention program for the upper graders of elementary schools--the results of intervention study for two years with quasi-experimental design

The purpose of this study was to evaluate the short-term effect of a smoking prevention program for Japanese elementary school-children in the fifth and sixth grades. The program was developed with concepts found in the Know Your Body Program and the conclusions of a National Cancer Institute-convened Expert Advisory Panel, and focused on teaching about the short-term effects of smoking and on resistance to social pressures to smoke. The study was conducted with a quasi-experimental design. An intervention group (52 boys and 54 girls) received three sessions for both the fifth grade in 1992 and the sixth grade in 1993. Moreover, the intervention group received a pre-test before the first session and a post-test after the third session in each grade. A comparison group (102 boys and 91 girls) received the same tests at the same time as the intervention group, but did not receive any program on smoking prevention. The short-term effect of the program were evaluated using the results of the pre-test in the fifth grade and of the post-test in the sixth grade in both groups. The results were as follows: 1) Remarkable short-term effects of the intervention were seen in respect to awareness of the importance of not smoking in girls, and also in the knowledge of the short-term effects of smoking in both sexes. 2) The intervention was not effective with respect to intention to smoke at the age of 20 and self-efficacy of refusing to smoke in both sexes. 3) The short-term effects were not clear in the smoking behavior in both sexes because the rates of ever smokers and of monthly smokers were almost the same for two years between the intervention group and the comparison group. 4) The smoking behaviors of children, their parents and their best friends had little influence on the results of the post-test in the sixth grade.     

The propeptide of subtilisin BPN'' as a temporary inhibitor and effect of an amino acid replacement on its inhibitory activity

PURPOSE: To determine the potential benefits of applying laparoscopic techniques for the intraabdominal insertion of aortofemoral grafts and to compare results with those of conventional surgery. METHODS: Having previously demonstrated the feasibility of a totally laparoscopic aortofemoral bypass technique using carbon dioxide peritoneal insufflation in a porcine model, we now report our first human experience with this laparoscopic technique in a 49-year-old man. RESULTS: The patient's postoperative course was marked by his minimal requirements for analgesia, early ambulation, and discharge from the hospital in the morning of the third postoperative day. CONCLUSIONS: The benefits of a laparoscopic approach to aortobifemoral bypass grafting in terms of financial savings and earlier rehabilitation in this patient was significant. This less-invasive procedure warrants further investigation.     

Multi-step precipitation separation system using mixture of thermosensitive polymers

Summary Multi-step precipitation separation system was developed by using aqueous mixtures of some thermosensitive polymers. The following three polymers were used here; poly(N-n-propylacrylamide), poly(N-isopropylacrylamide), and poly(N-isopropylmethacrylamide). A mixture of the three polymers showed three endothermic peaks, and the peak top temperatures were almost consistent with that of the each polymer solution. The polymers were purified by thermal precipitation to obtain fractions which can respond in narrow temperature ranges prior to use. In the case of the precipitation separation of two polymers mixtures, purities of the obtained precipitate and supernatant fractions became high comparing with the case in which the unpurified polymers were used. Parts of the polymers which were not the precipitation targets were also precipitated by the separation procedures. This was caused not only by insolubilization of the non-targeted polymers due to their phase transitions but also by their non-specific entanglement with the targeted polymers. The purities of the fractions also improved when the difference of the phase transition temperature between two polymers was large enough to avoid the coprecipitation. In the case of the precipitation separation of mixtures of the three polymers, purities of each fraction also improved when the purified polymers were used.     

Effects of amino acid replacements around the reactive site of chicken ovomucoid domain 3 on the inhibitory activity toward chymotrypsin and trypsin

We have previously shown that replacing the P1-site residue(Ala) of chicken ovomucoid domain 3 (OMCHI3) with a Met or Lysresults in the acquisition of inhibitory activity toward chymotrypsinor trypsin, respectively. However, the inhibitory activitiesthus induced are not strong. In the present study, we introducedadditional amino acid replacements around the reactive siteto try to make the P1-site mutants more effective inhibitorsof chymotrypsin or trypsin. The amino acid replacement AspTyrat the P2' site of OMCHI3(P1Met) resulted in conversion to a35000-fold more effective inhibitor of chymotrypsin with aninhibitor constant (K_i) of 1.17x10^–11 M. The K_i valueof OMCHI3(P1Met, P2'Ala) indicated that the effect on the interactionwith chymotrypsin of removing a negative charge from the P2'site was greater than that of introducing an aromatic ring.Similarly, enhanced inhibition of trypsin was observed whenthe AspTyr replacement was introduced into the P2' site of OMCHI3(P1Lys).Two additional replacements, AspAla at the P4 site and ArgAlaat the P3' site, made the mutant a more effective inhibitorof trypsin with a K_i value of 1.44x10^–9 M. By contrast,ArgAla replacement at the P3' site of OMCHI3(P1Met, P2'Tyr)resulted in a greatly reduced inhibition of chymotrypsin, andAspAla replacement at the P4 site produced only a small changewhen compared with a natural variant of OMCHI3. These resultsclearly indicate that not only the P1-site residue but alsothe characteristics, particularly the electrostatic properties,of the amino acid residues around the reactive site of the proteaseinhibitor determine the strength of its interactions with proteases.Furthermore, amino acids with different characteristics arerequired around the reactive site for strong inhibition of chymotrypsinand trypsin.     

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.     

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.     

Analysis of PD-generated SF/sub 6/ decomposition gases adsorbed on carbon nanotubes

Chemical byproducts analysis has been recognized as a powerful diagnosis method for SF₆ gas-insulated switchgear (GIS). The authors have previously demonstrated that a carbon nanotube (CNT) gas sensor could detect partial discharge (PD) generated in SF₆ gas. However, PD-generated decomposition gas species, which were responsible for the CNT gas sensor response, have not been identified yet. In this paper, two kinds of experiments were conducted in order to identify the responsible decomposition gas species. At first, the decomposition gas molecules adsorbed on CNTs were analyzed by Fourier transformation infrared (FTIR) spectroscopy. FTIR absorbance was observed around 735 cm^-1 after CNTs were exposed to PD generated in SF₆. In the second experiment, the CNT gas sensor responses to typical SF₆ decomposition products (HF and SF₄) were examined. The CNT gas sensor responded to these gases in the same way as to PD generated in SF₆. SF₄ response was larger than HF response. Based on these results, SF ₄ and SOF₂ emerged as candidates for the responsible decomposition gases. Electrochemical interactions between adsorbed gas molecules and CNT were discussed based on theoretical predictions of molecular orbital calculations. The calculation results suggested that both of SOF₂ and SF₄ could increase the CNT gas sensor conductance