Gas chromatographic separation of wax esters based on the degree of unsaturation

The wax esters of sperm whale head oil have been characterized by gas-liquid chromatography on an APOLAR 10C column according to their carbon number and number of double bonds. The novel technique permits the direct quantitative analysis of saturated and unsaturated wax esters.     

Antioxidant for fats and oils from canary seed: Sterol and triterpene alcohol esters of caffeic acid

Several kinds of seeds used as bird feed were extracted successively with hexane, ether and methanol. In the antioxidant test with extracts, the ether extract from canary seeds showed the highest activity. The antioxidant fraction separated from it by thin layer chromatography showed excellent activity for lard and sardine oil. The effective components were identified by gas chromatography and gas chromatography-mass spectrometry of the hydrolyzed products as the esters of caffeic acid with cycloartenol, gramisterol, sitosterol and campesterol with the minor amounts of 24-methylenecycloartanol, obtusifoliol, brassicasterol and Δ7-stigmastenol.     

Potential bile acid metabolites. 24. An efficient synthesis of carboxyl-linked glucosides and their chemical properties

A facile and efficient synthesis of the carboxyl-linked glucosides of bile acids is described. Direct esterification of unprotected bile acids with 2,3,4,6-tetra-O-benzyl-d-glucopyranose in pyridine in the presence of 2-chloro-1,3,5-trinitrobenzene as a coupling agent afforded a mixture of the α- and β-anomers (ca. 1∶3) of the 1-O-acyl-d-glucoside benzyl ethers of bile acids, which was separated effectively on a C₁₈ reversedphase chromatography column (isolated yields of α- and β-anomers are 4–9% and 12–19%, respectively). Subsequent hydrogenolysis of the α- and β-acyl glucoside benzyl ethers on a 10% Pd−C catalyst in acetic acid/methanol/EtOAc (1∶2∶2, by vol) at 35°C under atmospheric pressure gave the corresponding free esters in good yields (79–89%). Chemical specificities such as facile hydrolysis and transesterification of the acyl glucosides in various solvents were also discussed.     

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.     

Adsorption and desorption properties of cationic polyethylene film gels to organic anions and their regeneration

An investigation was undertaken on the adsorption and desorption properties of 2‐(dimethylamino)ethyl methacrylate grafted polyethylene (PE‐g‐PDMAEMA) films to anionic dye anions with one to three sulfonic groups in response to pH and temperature changes. The amounts of dye anions adsorbed on the PE‐g‐PDMAEMA films passed through the maximum values at about pH 3 because of an increase in the protonation of dimethylamino groups caused by a decrease in the pH value. The amounts of adsorbed dye anions decreased below pH 3 because the ionic strength increased with the addition of HCl to adjust the initial pH values of the aqueous dye solutions. The amounts of adsorbed dye anions decreased with an increase in the number of sulfonic groups in the dye molecules at the same pH value because electrostatic repulsion was generated between free sulfonic groups of the dye anions adsorbed onto the PE‐g‐PDMAEMA films and free dye anions in the medium. A large number of dye anions adsorbed were desorbed from the PE‐g‐PDMAEMA film with initial pH values above 11.0. The cyclic processes of adsorption at pH 3.0 and desorption at pH 11.0 were repeated without considerable fatigue. The PE‐g‐PDMAEMA films showed practically regenerative adsorption and desorption behavior in response to the pH changes. In addition, when the dye‐anion‐adsorbed PE‐g‐PDMAEMA films were alternately immersed in water at two different temperatures, dye anions were desorbed in water at higher temperatures without any chemical agents because of the deprotonation of dimethylamino groups and thermosensitive contraction of grafted PDMAEMA chains. These results indicate that PE‐g‐PDMAEMA films can be applied as regenerative ion‐exchange membranes for adsorption and desorption processes of anionic compounds in response to the pH and temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 381–391, 2006     

Interplane charge dynamics in high-temperature superconductors; Charge confinement and spin gap

We have studies optical and transport properties of the prototypical high-T_c system La_2–xSr_xCuO₄ in the direction perpendicular to the CuO₂ planes (c-axis direction). In the normal state, it is found that the c-axis spectral weight is suppressed over a wide energy range. This is a demonstration of charge confinement in the real material which has been proposed theoretically by Anderson. Upon reducing temperature the low-energy spectral weight of the underdoped compound is further reduced, due perhaps to spin gap effect. The suppressed spectral weight results in completely different out-of-plane charge transport in the normal state and leads to the appearance of a superconducting plasma edge within the gap region in the superconducting state.     

Relationship of occupation to blood pressure among middle-aged Japanese men--the significance of the differences in body mass index and alcohol consumption

To clarify how and why blood pressure differs between occupations, the proportions of hypertensives, and the measures of blood pressure, body mass index (BMI) and alcohol consumption among the individuals not taking antihypertensive drugs were compared between the eight occupational categories using the data from a health check-up for 589 middle-aged Japanese males, mostly randomly selected from five areas in Japan. After adjusting for age, the relationships of occupation to the proportion of hypertensives and the mean systolic and diastolic blood pressure substantially differed among the five areas. However, after further adjustment for residence, these blood pressure levels (the proportion of hypertensives, and the mean systolic and diastolic blood pressure) were found to be higher for the "Personnel in transport and communications", the "Clerical personnel", the "Managerial and civil personnel" and the "Professional and technical personnel", whereas these values were consistently lowest in the "Service personnel". Age and residence-adjusted mean BMI was also higher for the four occupational categories with the increased blood pressure levels. According to a weighted multiple regression analysis across the eight occupations, the age and residence-adjusted mean BMI was a significant predictor of the age and residence-adjusted mean systolic and diastolic blood pressure (p = 0.068 and 0.018, respectively). These results suggest that the occupation-related changes in BMI may largely contribute to the occupation-related changes in blood pressure.     

Ergonomic Chair Design by Fusing Qualitative and Quantitative Criteria Using Interactive Genetic Algorithms

This paper emphasizes the necessity of formally bringing qualitative and quantitative criteria of ergonomic design together, and provides a novel complementary design framework with this aim. Within this framework, different design criteria are viewed as optimization objectives, and design solutions are iteratively improved through the cooperative efforts of computer and user. The framework is rooted in multiobjective optimization, genetic algorithms, and interactive user evaluation. Three different algorithms based on the framework are developed, and tested with an ergonomic chair design problem. The parallel and multiobjective approaches show promising results in fitness convergence, design diversity, and user satisfaction metrics.