As a fundamental study on dibenzothiepins, reaction of 11-phenyl-6, 11-dihydrodibenzo [, ] thiepin-11-ol (10) or 11-chloro-11-phenyl-6, 11-dihydrodibenzo [, ] thiepin (14) with triphenylmethyl cation or was examined under various conditions. 11-Phenyl-6, 11-dihydrodibenzo [, ] thiepin-11-ylium salt (8) was isolated as a black powder (perchlorate) and a green powder (hexachloroantimonate), but BF₄ salt was obtained only as a solution. Treatment of the hexachloroantimonate with excess of was found to result in a novel dehydrocyclization reaction to give selectively , 13-dihydrofluoreno [1, a, -, d] [2]-benzothiepin-13-ylium hexachloroantimonate (19). Some discussions were made on the mechanism of the formation of 19.

抄録全体を表示

This paper outlines a mathematical description of the stress dilatancy behaviour of granular materials which accounts for stress level and void ratio dependencies. The consideration of these aspects has important implications in the modelling of granular material behaviour. In fact, granular material mechanical response is largely dominated by the evolution of dilatancy, fabric and void ratio histories. The starting point in this study is the well established Rowe's theory which is revisited and ultimately modified by introducing a factor linked to governing state parameters in order to describe the complete behaviour of granular materials during deformation. Numerical simulations of triaxial tests on granular materials at different void ratios and stress levels are herein presented to illustrate the model.

抄録全体を表示

The phase diagrams of the Ni-Mo- and Ni-W- ternary systems in the region of less than 50mol% were constructed by thermodynamic calculation, based on the data obtained by thermodynamic measurement of the related materials. We found three ternary eutectic points and three or two ternary peritecto-eutectic points as follows:
:L (1365K, 71.mol%Ni-6.mol%Mo-.mol%)=(Ni)++
:L (1355K, 62.mol%Ni-2.mol%Mo-30.mol%)=++
:L (1445K, 42.mol%Ni-30.6mol%Mo-10.mol%)=(Ni)+NiMo+
P₁:L (1812K, 34.mol%Ni-42.mol%Mo-.8mol%)+MoB=+
P₂:L (1633K, 42.mol%Ni-40.4mol%Mo-17.mol%)+Mo=+
:L (1812K, 53.mol%Ni-33.7mol%Mo-12.8mol%)+Mo=NiMo+
:L (1622K, 51.mol%Ni-31.6mol%W-17.4mol%)=(Ni)+W+
:L (1260K, 71.mol%Ni-7.mol%W-.mol%)=(Ni)++
:L (1291K, 65.4mol%Ni-4.8mol%W-29.8mol%)=++
P₁:L (2115K, 23.8mol%Ni-43.1mol%W-33.1mol%)+WB=+
P₂:L (1657K, 48.mol%Ni-33.1mol%W-18.mol%)+=W+
The calculated phase diagrams are expected to be useful for the development of new Ni-based heat-, corrosion- or wear-resistance alloys.

抄録全体を表示

This study aimed to determine the prevalence of fecal carriage of extended spectrum β-lactamase (ESBL) and/or plasmidic AmpC β-lactamase (pAmpC) producing Escherichia coli among dogs (n=428) in Turkey. Polymerase chain reaction (PCR) and sequencing were used to characterize genes encoding β-lactamase and plasmid mediated quinolone resistance (PMQR). Antimicrobial susceptibility testing and PCRs for virulence genes and phylogenetic groups were also performed. Cefotaxime resistant

. coli isolates were detected in 95 (.2%) of the swab samples. Sequencing analysis results showed occurrence of various β-lactamase genes: bla_CTX-M-15 (62), blaTEM-

1b

(42), bla_CMY-2 (

22

), blaCTX-M-

3

(16), bla_CTX-M-1 (15), bla_OXA-1 (

9

) and bla_SHV-12 (

3

) alone or in combination. The most frequently encountered phylogenetic group was group A₁ (35.8%), followed by group D₂ (

22

.1%),

B

1 (15.8%), D₁ (

9

.

5

%),

A₀

(7.4%),

B2₂

(

5

.

3

%) and

B2₃

(4.2%), respectively. PMQR genes, aac(6’)-Ib-cr, qnrS1 and qnrB10 were detected in 25.

3

, 10.

5

and 1.1% of the isolates, respectively. While all isolates were susceptible to imipenem and amikacin, resistance rates to non-β-lactam antibiotics ranged from 20.

0

% for tobramycin to 56.8% for tetracycline. The virulence genes were only detected in 34 (36.2%) of the isolates and this isolates carried single or various combination of virulence genes of iucD, papC, papE, f17a-A and eaeA. Four isolates were identified as human virulent pandemic CTX-M-15 producing

E

. coli clone O25

b

:ST131/

B

2. To the best of our knowledge, this is the first study to show fecal carriage of ESBL/pAmpC type β-lactamase producing

E

. coli isolates among dogs in Turkey.

抄録全体を表示

We compared three groups of pregnant women: placebo with normotensive women, group A which included preeclamptics, and group which comprised preeclamptics who were supplemented their diets with vitamins and . MDA increased from 6. ± 2.8 (placebo) to 8.48 ± 1.2 (A) and 8.02 ± 1.8 nmol/gHb (). NO concentrations were enhanced from 19. ± 4.2 (P) to 23.8 ± 6.4 (A) and 24.1 ± .4 μmol/L (). GSH contents were decreased from 10.42 ± 2.81 (P) to 8.02 ± 2.92 (A) and .39 ± 1.02 μmol/g Hb (), whereas GSSG concentrations increased from .98 ± .28 (P) to 1.24 ± .29 (A) and 1.08 ± .12 μmol/g Hb (). SOD activity decreased 23% in A and 14% in ; GRx decreased 27% in A and .% in ; GPx decreased 12% in A and .6% in . Catalase activity, however, increased 27% in A and 29% in as compared to control. Thus, we conclude that the use of vitamins and should be considered for the control of certain important biochemical indices during the development of preeclampsia; however, further studies are needed to develop methods for the prevention of preeclampsia in women at high risk.

抄録全体を表示

One method currently being considered for the disposal of high level radio-active waste is burial in the seabed. When a hot object is buried in soil, the temperature of the soil adjacent to the object is raised and there is transient heat flow away from the object. The rise in the temperature of the soil causes excess pore pressures to be generated and transient pore water diffusion also takes place. A finite element formulation of the coupled heat flow and consolidation problem is presented. The computer implementation of this formulation is found to compare favourably with analytical solutions based on the same physical principles.

抄録全体を表示

Various serum lipid levels (hypo-, normo- and hyper-cholesterolemic) are shown in dys-β-lipoproteinemia (-LP). Though type III hyper-LP (hypercholesterolemic dys-β-LP) is characterized by abnormal lipid composition of VLDL and elevaied level of apolipoprotein (apo ), diagnosis of normo- and hypo-cholesterolemic dys-β-LP are offenly difficult. At the present study, we established simple and sensitive methods to diagnose dys-β-LP only by measurement of serum apolipoproteins. In purpose to define new approach for diagnosis of dys-β-LP, serum apo , apo -II, apo -III and apo levels were determined by the method of single radial immunodiffusion. These apolipoproteins were analysed in subjects with dys-β-LP (n=7), hyper-LP (n=67) and normo-LP (n=41). A serum apo /apo -III ratio in dys-β-LP was 1.37±.59 (mean±SD). This value was significantly higher than the ratios among normo-LP (.45±.17), type IIa (.51±.11), type IIb (.45±.17), type IV (.45±.13) and type V (.47±.). A serum apo /apo (×100) ratio in dys-β-LP was 25.2±10.2. This value was also significantly higher than the ratios among normo-LP (4.4±1.), type IIa (4.±.), type IIb (4.7±1.), type IV (7.2±.1) and type V (15.±.). Based on these data, it is proposed that the apo /apo -III ratio of >1. was diagnostic value of type III and the apo /apo (×100) ratio of >10. was also diagnostic value of normo- and hypo-cholesterolemic dys-β-LP. As to determine serum apolipoproteins very simple by single radial immunodiffusion method, the ratios will be useful for diagnosis and detection of dys-β-LP in clinical and epidemiological studies.

抄録全体を表示

Melithasterols A-D (1-4), isolated from a gorgoinan coral Melithaea ocracea of Okinawa, were shown to be cholestane-, 24-methyl--dehydrocholestane-, -dehydrocholestane-, and 24-methylenecholestane-derivatives. respectively, having a common β, 7α -dihydroxy-α, 6α-epoxy-Δ^8 steroid nucleus. This was confirmed by direct comparison with the authentic sample prepared by lead tetra-acetate oxydation of cholest-6-ene- β, α, 8α-triol -monoacetate. Twelve new polyhydroxysterols were isolated from an Alcyonium sp. (7,8,), and Sclerophytum sp. (14,16,19,20,21,a,23,26,28) soft corals collected off the coasts of the Andaman and Nicobar Islands in the Indian Ocean. All the Sclerophytum sp. soft corals contained 17a or its 25-deacetyl derivative. Compounds 7 to were identified as 24-methylenecholest--ene- β, 16β-diol---α-L fucoside (7) and its 7β-(8) and 7α-hydroxy () derivatives. Compound 14 was shown to be 24S-24-methylcholest--ene-β,25ξ,26-triol and was correlated to the known compound 15 by α, 6β-glycolation. Compound 16 was shown to be β, 6α-isomer of 17, correlating to 17 by PCC oxidation followed by dehydration. Compound 19 was identified with 25-deacetyl derivative of the known compound lobosterol (19a) by hydrolysis of authentic lobosterol. Compounds 20 and 21 were shown to be 7-dehydro-(20) and -dehydro-(21) derivative of 17a and 17, respectively, by comparisons of their spectral data with reference compounds. Compounds a and 23 were 24S-methylcholestane-β, α 25-triol-6-one 25-monoacetate (a) and its 25-deacetoxyl derivative (23). Partial PCC oxidation of 17a afforded a. Compounds 26 (andamansterol) and 28 (nicobarsterol) were shown to be gorgost--ene-β, α. 11α, 21-tetrol and novel secosteroid, 11,21-cyclo--homo-11-oxa-, 11-secoergostane-β, 6α, 12ξ-triol--one, respectively, by spectral analyses (H-HCOSY, HMQC, HMBC).

抄録全体を表示

Pironetin 1 (PA-48153) is a novel unsaturated δ-lactone derivative isolated from the fermentation broths of Streptomyces species which shows immunosuppressive and plant growth regulating activities. Several total syntheses of 1 have been reported to date, but we show here a novel approach to 1 via a convergent route using our chiral building block, (1S,S,6R)--hydroxybicyclo[4.1.]heptan-2-one . We dissected pironetin at 6-7 and employed the coupling of the epoxide 16 with the dithiane 25, which would be derived from , as a key step. The THP ether of was methylated and the following reduction gave an inseparable mixture of four diastereomers 8. After etherification, removal of THP group afforded separable isomers a and in a ratio of 13 to 1. The desired major isomer a was oxidized to ketone 6. Oxidation of 6 via silyl enol ether with osmium tetroxide gave ketol 21 in quantitative yield. Reduction of cyclopropylketone moiety of 21 under Birch condition afforded a mixture of a and . The ketol moiety of a and was oxidatively cleaved with lead tetraacetate in benzene-methanol to give the single aldo-ester 23. Acetalization of 23 followed by reduction of ester group gave aldehyde 24. Introduction of 2-unit via Takai's protocol as -olefin formation followed by thioacetalization afforded the dithiane 25, as 7-14 unit of pironetin. Meanwhile, the epoxide 16 as 1-6 unit was prepared from known epoxy alcohol in 6 steps. Coupling reaction of two units, the dithiane 25 and the the epoxide 16, successfully gave the product with the whole skeleton 26 in high yield. Mercuric ion assisted hydrolysis of the thioacetal 26 gave ketol 27. Selective reduction of β-hydroxyketone 27 by Mori's method afforded and-diol 28a predominantly (91: ). Finally, desilylation and oxidation with manganese dioxide afforded pironetin 1.

抄録全体を表示

Nine isoquinoline alkaloids belonging to the protoberberine, proaporphine and bisbenzyl-isoquinoline series were isolated from Caryomene olivascens (Menispermaceae). Four compounds are new : (-)-2-norlimacine (4), (-)-caryolivine (6), (+)-1, 2-dehydro-2-norlimacusine () and N-formylstepharine (). The last one is the first N-formyl derivative to be reported in the proaporphine group. Its biogenetic origin is discussed. Structures were established on the basis of 360 MHz (FT) nuclear magnetic resonance measurements and also by chemical correlation in the case of .

抄録全体を表示

The solubility and supersolubility of L-phenylalanine in aqueous solutions is firstly reported in this work. At temperatures from 273.15 to 343.15 K, both solubility and supersolubility in water generally increase with the temperature, and the average metastable zone width is about 8.°. At the temperature of 298.15 K, the solubility remarkably decreases with an increase in the concentration of ethanol, which indicates that ethanol can be used as an antisolvent for the precipitation and crystallization of L-phenylalanine. When sodium chloride is added to the solution, the solubility of L-phenylalanine increases with the concentration of sodium chloride.

抄録全体を表示