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The effect of top blowing and bottom blowing conditions on spitting behavior was investigated by water model experiments and numerical calculation. The results of the water model experiment showed that reducing the jet velocity by using a larger nozzle diameter was effective for reducing spitting. The numerical calculation indicated that interference between the top blown gas jet and the bottom blowing plume increases the gas velocity at the rim of the cavity, causing heavier spitting. A new index using the geometrical locations of the neighboring cavity and plume was proposed. The spitting rate decreased under conditions with lower interference by avoiding interaction between the top blown gas jet and the bottom blowing plume. The energy distribution in the blowing process was discussed based on a water model experiment using bath mixing time, bath vibration, and the spitting rate. The energy for spitting was explained convincingly by the difference between the energy input and the energy of bath vibration, cavity formation, and bath mixing. The results implied lower interference of the top and bottom gas resulted in lower energy for spitting generation.

Theranostic probes provide both therapeutic and diagnostic imaging capabilities in one molecule and show significant promise for use in magnetic resonance imaging (MRI) examinations. The present study describes for the first time the synthesis and utility of nitroxide-based contrast agents exhibiting a nonsteroidal anti-inflammatory drug effect. The target theranostic probes were prepared by connecting the carboxyl group of ibuprofen or ketoprofen to the hydroxyl group of 3-hydroxymethyl-2,2,5,5-tetramethylprrolidine-1-oxyl by a condensation reaction in the presence of dicyclohexylcarbodiimide and 4-dimethylaminopyridine in dichloromethane. MRI of mouse heads after administration of either synthesized theranostic probe indicated that the probes enter the brain by passing through the blood-brain barrier (BBB), resulting in T1 contrast enhancement in mouse brain. This enhancement persisted for the duration of the half-life of about 40 min, which is longer than that obtained by most of pyrrolidine nitroxide molecules. The therapeutic capacities of these theranostic probes were examined using a lipopolysaccharide (LPS)-induced brain inflammation model. The production of nitric oxide, an inflammation marker in septic mouse brain induced by LPS, was remarkably inhibited by the addition of either synthesized probe, indicating that they also act as anti-inflammatory drugs. The present results indicate that nitroxide-based theranostic probes act as both BBB-permeable redox-sensitive contrast agents and as an anti-inflammatory drug in septic mouse brain. Copyright © 2016 John Wiley & Sons, Ltd.

Because many people visit zoos, prevention of zoonoses is important from the standpoint of public health. This study examined the prevalence of Chlamydia among zoo animals in Japan by PCR and characterized these bacteria by performing phylogenetic analyses of the sequences of the variable domain (VD) 2 and VD4 regions of the ompA gene, which encodes the Chlamydia major outer membrane protein. Fecal samples were collected from 1150 zoo animals in five zoos and examined for Chlamydia DNA. Chlamydia psittaci DNA was found in 3.9% of mammals, 7.2% of birds and 8.1% of reptiles. The prevalence of Chlamydia pneumoniae DNA was significantly higher in reptiles (5.8%) than in mammals (0.3%) and birds (0.3%). Phylogenetic analysis of the ompA VD2 region from 18 samples showed that nine were in three different clusters containing C. psittaci strains, six were in a cluster containing C. pneumoniae strains and three each formed a distinct branch. Furthermore, phylogenetic analysis of the ompA VD4 region showed that C. pneumoniae DNAs from reptiles were close to those from human patients. The C. pneumoniae DNAs from the European glass lizard, Emerald tree boa, and Panther chameleon were classified in clusters that were distinct from other strains, suggesting that these reptiles had each been infected with a specific C. pneumoniae genotype. This study showed that diverse Chlamydia strains have been prevalent among a variety of zoo animals.

In order to devise a better forensic test for diatoms, the DNA binding ability of the diatom frustule constructing by silica, in the presence of chaotropic ions were utilized. It was proved that the diatoms were able to be captured via λDNA using silica-coated magnetic beads (Mag beads), followed by isolation and purification from the Mag beads as a solid phase by substituting the chaotropic agent with ultrapure water. Five cases of drowning, three in freshwater and two in seawater, were applied to the present method and similar results as the usual diatom test were obtained. Specimens of lung and other organs were rendered clearly visible, with elimination of foreign impurities. The present method appears applicable for detection of diatoms indirectly using PCR amplification of bound DNA or directly staining of the DNA.

Fatty acids in our daily diet are broadly classified into cis and trans fatty acids (TFAs). TFAs are formed during the manufacturing process of hydrogenated vegetable oils such as margarine. Modern diets such as deep-fried products, frozen foods, and packaged snacks commonly include large quantities of margarine containing TFAs. Although an increased report in the effects of the diet containing TFAs on a risk factor of metabolic syndrome, diabetes mellitus, and coronary heart disease has been observed in the recent years, influence on intestinal inflammation remains unknown. This review describes pro-inflammatory effects of TFAs in our diary diet on various systemic disorders and also discusses a possible role of TFAs on gut inflammation.

Phlebosclerotic colitis is a rare and recently known disease entity and its etiology is still to be elucidated. Some phlebosclerotic colitis cases are difficult to distinguish from collagenous colitis because of the similarity of pathological findings. In all Japanese case reports of phlebosclerotic colitis in which an association with the use of Chinese herbal medicine is suspected, sansisi (gardenia fruit) was included, suggesting pathogenesis of this disease. We report a case of phlebosclerotic colitis that wasdifficult to be distinguished from collagenous colitis, and an association with the use of Chinese herbal medicine was suspected as the cause of the disease.

Condensation of 2-hydroxyacetophenone with benzaldehyde in the presence of 70% perchloric acid in ethyl orthoformate gave the corresponding 4-ethoxyflavylium perchlorate, which was treated with aqueous ammonia or methylamine solution to afford 1,6,7,8-substituted 2-(3′,4′-substituted-phenyl)-4-quinolone in fair to good yield.

3-[3,3-Dimethyl- and 3-hydroxy-3-methyl-2,4-dihydroxy-5-(4-hydroxycinnamoyl)-6-oxo-1,4-cyclohexadienyl]- 3-(4-hydroxyphenyl)propanoic acid were synthesized as model compounds of safflomin C. Their spectra closely resembled that of safflomin C.

Precursor of Carthamin was isolated from the flowers of Carthamin tinctorius L. (Safflower) and its structure was characterized as 1 on the basis of spectroscopic analysis and by comparing its properties with those of synthetic model compound.

2,4,6-Trihydroxy-, 2,4,6-trihydroxy-5-methyl-, and 2,4,5,6-tetrahydroxy-substituted 3-(3-phenylpropionyl)benzaldehydes were efficiently synthesized. The first two compounds showed bactericidal activity for Pseudoperonospora cubersis .

Safflower yellow B, one of the yellow coloring components of safflower (Carthamus tinctorius L.), was transformed to red carthamin and safflomin-A in cultured safflower cells. This result suggests that carthamin and other yellow coloring matters are biogenetically derived from safflower yellow B in the florets of safflower.

(+)- and (−)-Model compounds of a carthamin were synthesized. The absolute configuration of carthamin was deduced to be S, S by means of CD spectroscopy and X-ray analysis.

Bis-glycosylation of 3,5-dibenzyloxyphenol with 2,3,4,6- tetra -O- benzyl-α- d -glucopyranosyl fluoride in a two-step sequence produced the bis-glucosylated product, 3,5- dibenzyloxy -2,6- bis -(2,3,4,6- tetra -O- benzyl-β- d -glucopyranosyl)phenol . Subsequent hydrogenolytic debenzylation and acetylation gave the undeca-O-acetyl derivative, which, when subjected to a Friedel-Crafts acylation with borontrifluoride-acetic acid, gave the 4-C-acetyl target compound, 1-[3,5- bis -(2,3,4,6- tetra -O- acetyl-β- d -glucopyranosyl)-2,4,6-trihydroxyphenyl]ethanone .

2′- O -Acetyl C -glycosylic compounds ( C -glycosides) were prepared via regioselective acetyl transfer from aglycons to sugar moieties with silica gel in the presence of unprotected primary and secondary hydroxyl groups.

Condensation of 2-hydroxyacetophenone with benzaldehyde in the presence of 70% perchloric acid in ethyl orthoformate gave the corresponding 4-ethoxyflavylium perchlorate, which was treated with aqueous ammonia or methylamine solution to afford 1,6,7,8-substituted 2-(3′,4′-substituted-phenyl)-4-quinolone in fair to good yield.

A flavanone, in which a hydroxyl group at the 5-position was protected with a methyl group, converted to the corresponding 5-methoxy-2-phenyl-4-quinolone via flavylium salt under mild conditions. Flavanone-O-rhamnoglucoside, naringin, was also converted to 5-methoxy-2-phenyl-4-quinolon-7-O-rhamnoglucoside in the same way in an overall 25% yield.

The syntheses of orientin, parkinsonin A, isoswertiajaponin, and parkinsonin B, which are 8- C -β- d -glucopyranosyl-3′,4′,5,7-tetrahydroxyflavone, 5-methyl orientin, 7-methyl orientin, and 5,7-dimethyl orientin, respectively, are reported herein. The C -glucosyl phloroacetophenone derivatives were obtained via a regio- and stereoselective O→C glycosyl rearrangement. Aldol condensation of the C -glucosyl phloroacetophenone derivatives with 3,4-bisbenzyloxybenzaldehyde afforded the corresponding C -glucosylchalcones. Construction of the flavone system by reaction with I 2 –Me 2 SO, followed by the elimination of the 5-benzyl protecting group in the flavone structure, yielded an orientin derivative and a isoswertiajaponin derivative. Methylation of the orientin derivatives with dimethyl sulfate afforded the parkinsonin A derivative, the isoswertiajaponin derivative, and the parkinsonin B derivative. Finally, hydrogenolysis of these C -glucosylflavone derivatives led to the four 8- C -glucosylflavones. The NMR spectra of these C -glucosylflavones showed a duplication of signals corresponding to a major rotamer, along with a minor one. Based on NOESY experiments in Me 2 SO at ambient temperature, they adopted conformations in which the H-2′′and H-4′′ protons in the glucose moiety were oriented toward the B-ring in the flavone structure.

Glycosylation of the nitroxyl radicals, 4-acetoxy-2,2,6,6-tetramethylpiperidin-1-oxyl (4-acetoxy-TEMPO) and 3-carbamoyl-2,2,5,5-tetramethylpyrollin-1-oxyl (3-carbamoyl-PROXYL) with peracetylglycosyl fluoride as the glycosyl donor, in the presence of boron trifluoride diethyl etherate (BF3·OEt2) and an amine base afforded the corresponding hydroxylamine-O-glycosides in 25–100% yields.

Carthamin acetate, (3S,3′S)-1-[5-(p-acetoxycinnamoyl)-3-C-(β-D-2″,3″,4″,6″-tetra-O-acetylglucopyranosyl)-3,4-dihydroxy-2,6-diketo]cyclohex-4-enylidene-1′-[5′-(p-acetoxycinnamoyl)-3′-C-(β-D-2″′,3″′,4″′, 6″′-tetra-O-acetylglucopyranosyl)-2′,3′,4′-trihydroxy-6′-keto]cyclohexa-1′,4′-dienylmethane 7a and its (3R, 3′R)-epimer 7b were synthesized via the C-glycosylation of 2-acetyl-1,3,4,5-benzenetetrol using acetobromoglucose in the presence of sodium hyride, followed by aldol condensation with p-hydroxybenzaldehyde after methyl-protection of the enolic hydroxy group, and subsequent dimerization with triethyl orthoformate after demethylation, in a total yield of 0.6%. Their absolute configurations were determined by X-ray analysis of the key intermediate 4b.

Refluxing of diacetylphloroglucinol C‐β‐D‐gluco‐, ‐galacto‐, and ‐allopyranosides in water for 1 d gave two kinds of spiroketal derivatives in total yields of 77%, 74%, and 64%, respectively. The structure and stereochemistry of the six new spiro(benzofuran‐[2H]pyran and ‐[2H]furan) derived from galactoside and alloside were verified by NMR analysis. The production ratios of the spiro derivatives were measured by HPLC analysis at regular time intervals. Since the majority of spiro(benzofuran‐[2H]furan) were produced after 8 to 12 h of refluxing and most spiro(benzofuran‐[2H]pyran) produced after 2 d of refluxing, it is assumed that formation of spirofuran and spiropyran is a kinetic‐ and thermodynamic‐controlled reaction, respectively.

A flavanone, in which a hydroxyl group at the 5-position was protected with a methyl group, converted to the corresponding 5-methoxy-2-phenyl-4-quinolone via flavylium salt under mild conditions. Flavanone-O-rhamnoglucoside, naringin, was also converted to 5-methoxy-2-phenyl-4-quinolon-7-O-rhamnoglucoside in the same way in an overall 25% yield.

Isoorientin, a 6-C-β- d -glucopyranosyl-3′,4′,5,7-tetrahydroxyflavone, was synthesized in a 15% overall yield, in ten steps, starting from the commercially available phloroacetophenone. The C-glucosyl phloroacetophenone derivative, a synthetic intermediate that contains a free hydroxyl group that is para to the glucosyl moiety, was obtained by hydrogenolysis by taking advantage of differences in the hydrogenolysis rates between a benzyl protecting group and a 2-methylbenzyl protecting group. Aldol condensation of the C-glucosyl phloroacetophenone derivative with 3,4-bis-benzyloxybenzaldehyde afforded the corresponding chalcone as a precursor of the 6-C-glucosyl flavone. Construction of the flavone system by application of I2–DMSO, followed by deprotection, yielded isoorientin.

Treatment of 3- C -β- d -galactopyranosylphloroacetophenone in hot water with a catalytic amount of p -toluenesulfonic acid afforded a spiroketal compound as the main product. The chirality of the spiro carbon of the product was R, which is the opposite of the spiroketal obtained by the conversion of 3- C -β- d -glucopyranosyl phloroacetophenone under identical conditions. The structure was determined by 1 H– 1 H COSY, 1 H– 13 C COSY, NOESY and HMBC spectroscopy.

The total synthesis of (±)-15-norsolavetivone, a key intermediate in the synthesis of oxygenated spirovetivane stress metabolites, is described.

In connection with studies of the structure of carthamin derivatives, 2,5-bis(p-methoxycinnamoyl)-1,3,4,6,7,8- and 4,5-bis(p-methoxycinnamoyl)-1,2,3,6,7,8-hexamethoxyxanthene were synthesized. The comparison of these two hexamethoxyxanthenes with carthamin derivatives is described.

The total synthesis of the title compounds, examples of the spirovetivane type of phytoalexins in the genus Solanum, by transformation of (±)-15-norsolavetivone and derivatives is described.

The participation of nonionic donor-acceptor complex [A] was suggested by the analyses of product isolated in the Friedel–Crafts reaction of m-dichlorobenzene with CH3SO2Cl in the presence of AlCl3. On the basis of these observations a new practical method of methanesulfonylation of deactivated benzenes employing methane-sulfonic anhydride and CF3SO3H was developed.