Chemical properties of ergosta-4, , (14), -tetraen--one (1) were investigated. Though 1 is rather stable to acids or bases, it reacts easily with two moleculres of oxygen on irradiation with UV light to give , -epidioxy-14α-hydroperoxyergosta-4, , -trien--one (2), which is transformed successively to , ;, -diepoxy-14α-hydroperoxyergosta-4, -dien--one () and 14α-hydroperoxy--hydroxyergosta-4, , -triene-, -dione (4) under these reaction conditions.

抄録全体を表示

We screened the differentiation-inducing activities of 39 mushroom extracts from Akita prefecture, Japan, on the mouse osteoblastic cell line, MCT-1. Sixteen phosphate buffered saline (PBS), boiled PBS, 14 ethanol and 12 methanol extracts induced alkaline phosphatase (ALP) activities, an indicator of MCT-1 cell differentiation. The enzyme activities were markedly induced by extracts of Tricholoma auratum, and we isolated the active compound from methanol extracts of this mushroom. Physical data for the isolated active compound were identical to those for (,24R)-ergosta-,-diene-,5α,-triol (1). 1 induced ALP activities of MCT-1 cells and promoted cell proliferation. To investigate the relationships between the chemical structure and differentiation-inducing activity of the compound, ALP-inducing activities of MCT-1 cells by 1, ergosterol (2), ergocalciferol (), cholesta-,5α,-triol (4), -dehydrocholesterol (5) and cholecalciferol () were tested. The enzyme activities of MCT-1 cells were increased .0-fold by 10 μM 1 and 2.4-fold by 10 μM 4. However, 2, , 5 and did not induce MCT-1 cell ALP activity at 0.1—10 μM. These results suggested that the OH groups at C-5 and/or C- of 1 and 4 played an important role in their differentiation-inducing activities on MCT-1 cells. Furthermore, 1 suppressed induction of MCT-1 cell apoptosis by serum starvation.

抄録全体を表示

Two new partially saturated tricyclic ring systems, , a, , , , 10, 10a, 11-octahydro-11-oxodibenz [, ] oxepins (a and ), and -thiepins (4a and 4) were synthesized. Compounds 4a and 4 were desulfurized to give a pair of isomeric 2-methylbenzoylcyclohexanes (10a and 10). Deuterated 4a and 4 (11a and 11) were prepared starting from butadiene- (12). The stereochemical features of a (trans), (cis), 4a (trans) and 4 (cis) are compared with those of 10a, 10, 11a and 11 on the basis of proton nuclear magnetic resonance data.

抄録全体を表示

11-Amino-, a, , , , 10, 10a, 11-octahydrodibebenzo[, ]thiepines (a-d) and -oxepines (a-d) were synthesized by the Leuckart reaction of , a, , , , 10, 10a, 11-octahydro-11-oxodibenzo[, ]thiepines (1a, )and -oxepines (2a, ) followed by hydrolysis of the reaction products 4a-d and 5a-d, respectively. The four diastereomers, cis(a-H, 10a-H)-cis(10a-H, 11-H) a and a, cis(a-H, 10a-H)-trans(10a-H, 11-H) and , trans(a-H, 10a-H)-trans(10a-H, 11a-H)c and c, and trans(a-H, 10a-H)-cis(10a-H, 11-H) d and d, were isolated and their configurations and conformations were elucidated by chemical methods together with ¹H-nuclear magnetic resonance spectroscopic and X-ray crystallographic analyses.

抄録全体を表示

Brassinolide analogues, (R, 23R, 24R)-2α, , , 23-tetrahydroxy--homo--oxa-5α-ergostan--one (24-epibrassinolide) (10) and (S, 23S, 24R)-2α, , , 23-tetrahydroxy--homo--oxa-5α-ergostan--one (), were synthesized from brassicasterol (a) in five steps and with ca. 20% overall yield. The key steps are the direct formation of (, 24R)-, 5-cyclo-5α-ergost--en--one (4) from brassicasterol mesylate (), the acid-catalyzed rearrangement of 4 to (, 24R)-5α-ergosta-2, -dien--one (), and the Baeyer-Villiger oxidation of the tetrahydroxy 5α-ergostan--ones and .

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, 71.5mol%Ni-.0mol%Mo-.5mol%)=(Ni)++
:L (1355K, 62.5mol%Ni-2.5mol%Mo-30.5mol%)=++
:L (1445K, 42.0mol%Ni-30.mol%Mo-10.mol%)=(Ni)+NiMo+
P₁:L (1812K, 34.mol%Ni-42.mol%Mo-.mol%)+MoB=+
P₂:L (1633K, 42.mol%Ni-40.4mol%Mo-17.mol%)+Mo=+
:L (1812K, 53.5mol%Ni-33.mol%Mo-12.mol%)+Mo=NiMo+
:L (1622K, 51.0mol%Ni-31.mol%W-17.4mol%)=(Ni)+W+
:L (1260K, 71.0mol%Ni-.0mol%W-.0mol%)=(Ni)++
:L (1291K, 65.4mol%Ni-4.mol%W-29.mol%)=++
P₁:L (2115K, 23.mol%Ni-43.1mol%W-33.1mol%)+WB=+
P₂:L (1657K, 48.mol%Ni-33.1mol%W-18.0mol%)+=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

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, α -dihydroxy-5α, α-epoxy-Δ^ steroid nucleus. This was confirmed by direct comparison with the authentic sample prepared by lead tetra-acetate oxydation of cholest--ene- β, 5α, α-triol -monoacetate. Twelve new polyhydroxysterols were isolated from an Alcyonium sp. (,,), 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 to were identified as 24-methylenecholest-5-ene- β, 16β-diol--0-α-L fucoside () and its β-() and α-hydroxy () derivatives. Compound 14 was shown to be 24S-24-methylcholest-5-ene-β,25ξ,26-triol and was correlated to the known compound 15 by 5α, β-glycolation. Compound 16 was shown to be 5β, α-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 -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, 5α 25-triol--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-5-ene-β, α. 11α, 21-tetrol and novel secosteroid, 11,21-cyclo--homo-11-oxa-, 11-secoergostane-β, α, 12ξ-triol--one, respectively, by spectral analyses (H-HCOSY, HMQC, HMBC).

抄録全体を表示

Eight new sterols, 5α, -epidioxy-(, 24R)-23-methylergosta-, -dien--ol (1), , 5α, -trihydroxy-(, 24R)-23-methylergosta-, -dien--one (2), , 5α, -trihydroxy-(24S)-ergost--en--one (), , 5α, , 14α-tetrahydroxy-(, 24R)-ergosta-, -dien--one (4), (, 24R)-ergosta-, -diene-, 5α, , -tetrol (5), 5α, -epidioxy--hydroxy-(, 24R)-ergosta-, -dien--one (), 5α, -epidioxy--hydroxy-(24S)-ergost--en--one () and 5α, -epoxy-(, 24R)-ergosta-, -diene-, , 14α-triol (), have been isolated from five edible mushrooms, Lentinus edodes, Flammulina velutipes, Hypsizigus marmoreus, Pleurotus ostreatus and Pholiota nameko together with fifteen known ones (-23), of which two (16 and 17) are reported for the first time from a fungal source. The structures of these new compounds were elucidated on the basis of their spectral data.

抄録全体を表示

Six new sterols, 5α, ;, -diepoxy-(, 24R)-ergost--ene-, -diol (1), 5α, ;, -diepoxy-(, 24R)-ergost--ene-, -diol (2), 5α, -epoxy-(, 24R)-ergosta-, -diene-, -diol (), (, 24R)-23-methylergosta-, -diene-, 5α, -triol (4), (, 24R)-23-methulergosta-, -diene-, 5α, , -tetrol (5) and (24S)-ergost--ene-, 5α, , -tetrol (), have been isolated from seven mushrooms, Amanita pantherina, Amantia virgineoides, Lactarius piperatus, Lyophyllum shimeji, Tricholoma portentosum, Hypsizigus marmoreus and Lentinula edodes together with eighteen known ones (-24). The structures of these new compounds were elucidated on the basis of their spectral data.

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

Mycobacteriocin produced by human type tubercle bacilli could be demonstrated easily on eggmedium containing 0.05% tween by means of stab culture or streak plate methods, and elevenmycobacteriocin-types have been recognized on the basis of the inhibition pattern by using indicator strains of rapidly growing mycobacteria.
At present, types 1 (4.%), 2 (13%), 4 (38.5%), (2%) and 11 (14.%) showed a stablemycobacteriocin pattern, but types (.%) and (.%) were apt to show type replacement totypes 2 and 4, respectively, and strains belonging to types 5, and were few, less than 1.5%to the total. In order to perform a reproducible mycobacteriocin typing, our previous typingscheme was revised to be consisted of five groups (A-). Among 438 strains, mycobacteriocingroup C containing types 4 and was 46.1% of strains tested, group containing types 2, and was .%, group containing type 11 was 15.1%, group A containing types 1 and was5.5%, group D containing types and 10 was 4.1%, and untypable strains were no more than .% among all tested strains.
Human type tubercle bacilli classified as type 4, which consisted of more than 45% of strainstested, could be divided into three sub-types from sensitivity to M. gordonae 1324 and M. terrae 1450.
Mycobacteriocin producing strains belonging to type D: showed an extremly wide antibacterialactivity to strains of more than 90% of rapidly growing mycobacteria (42 strains), to about 40% of slow growing mycobacteria (29 strains), and even to 10 strains of Staphylococcus aureus.

抄録全体を表示

From the black coral Antipathies dichotoma, a sphingolipid (2S*,*,,)-2N-[tetradecanoyl]-4(),()-icosadiene-1,-diol (1) and a steroid ()-methylcholesta-5,-diene-1α,,-triol (2) were isolated. Other known compounds, ,-dihydroxy-cholest-5-ene (), (,24S),5α,-epidioxy-24-methylcholesta-,-dien--ol (4) and (,24S),5α,-epidioxy-24-methylcholesta-,(11),-trien--ol (5). The structures were established on the basis of NMR spectroscopic analysis and comparison with literature. The antibacterial activity of five compounds was evaluated.

抄録全体を表示

Four new sterols, 5α, -epoxy-(, 24R)-ergosta-(14), -diene-, -diol (1), (, 24R)-ergosta-, -diene-, 5α, , -tetrol (2), (, 24R)-ergosta-, (11), -triene-, 5α, -triol () and , 5α, -trihydroxy-(, 24R)-ergost--en--one (4), have been isolated from the fruit bodies of Grifola frondosa (FR.) S. F. GRAY (Polyporaceae)together with fourteen known ones (5-18), of which two (5 and ) are reported for the first time from a natural source. The structures of these compounds were elucidated on the basis of spectral data.

抄録全体を表示

Purpose: The purpose of this study was to determine if the optical properties of zirconia and glass–ceramic (

.max) were affected by low-temperature degradation (aging).

Methods: Experiment samples were fabricated with seven zirconia brands (n=10): Zenostar, Zirlux, Katana, Bruxzir, DD-BioZX², DD-cubeX², NexxZr; and

.max were used as a control. This resulted in a total of samples in the experiment. The L*, a* and * were measured for each sample, and then the optical properties including translucency parameter (TP), contrast ratio (CR), and opalescence parameter (OP) were calculated. The samples were aged (20, 40, 60, , 100h), and the optical properties were calculated after each interval.

Results: Most zirconia brands had lower L*, higher a*, higher

* with increased aging, which visually corresponds to darker, redder, and more yellow. Aging also increased CR, lowered TP, and lowered OP. .max was also affected by aging but still had the highest TP (23.±2.), L* (81.±.4), and lowest CR (0.41±0.05) compared to any zirconia. The Zenostar had the closest TP (24.1±0.4), and L* (90.2±0.5) values to .max before aging. However, after 100h of aging, the DD-cubeX² was least effected and had the highest TP (.2±0.) and lowest CR (0.43±0.01) compared with other zirconia samples and highest OP (11.±0.2) of all ceramic samples.

Conclusions: The optical properties of zirconia and

.max materials were affected by aging with the effects increasing with time. The magnitude of change was affected by seven brands of dental zirconia.

抄録全体を表示

N-n-ヘキシル-マレイミド (I), N-シクロヘキシル-マレイミド (II), N-ベンジル-マレイミド (III) の単独重合, 共重合をアゾビスイソブチロニトリル (IV) を開始剤としてテトラヒドロフラン中, 60℃で行った. 単独重合の初速度 (R_p) はR_p=k [I] ^2.5 [IV]

0.80

, R_p=>k [II]

2.8

[IV]

0.80

, R_p=>k [III]

2.7

[IV] ^0.54となった. kは速度定数である. 全重合の活性化エネルギー (

E

), 頻度係数 (A) は

E

=

22

.

8

kcal/mol (I),

22

.2kcal/mol (II), 24.1kcal/mol (III), A=

9

.5×10¹¹ (I),

6

.4×10¹¹ (II),

6

.

6

×10¹² (III) となった. またN-置換マレイミドとメタクリル酸メチル (V) との共重合におけるモノマー反応性比r₁, r₂およびQ,

e

値を次のように決定した. I (M₁) -V (M₂) 系でr₁=0.17, r₂=2.02, Q₁=0.56,

e₁

=1.43, II (M₁) -V (M₂) 系でr₁=0.13, r₂=2.29, Q₁=0.50,

e₁

=1.50, III (M₁) -V (M₂) 系でr₁=0.14, r₂=1.54, Q₁=0.79,

e₁

=1.63となった.

抄録全体を表示

Agaricus blazei is an important fungus for producing bioactive compounds. There are some reports of polysaccharides and steroid derivatives from the fruiting bodies of A. blazei. However, the chemical examination of the secondary metabolites of the cultured mycelia of this species has not been reported. Eight compounds, an unprecedented skeleton have been isolated from the cultured mycelia of A. blazei. The structures of the novel compounds each named blazeispirols A (1), (2), C (), D (4), (5) X(), Y () and Z () were confirmed by extensive 1D and 2D NMR spectral data and X-ray analysis. Blazeispirols A (1), (2), C (), D (4) and (5) were des-A-ergostane type compounds having spiroacetal structure as a side chain. Blazeispirols X () and Y () were determined to be (20S, S, 23R, 24S)-1 (10→) abeo-14β, :, 25-diepoxyergosta-5,,,11-tetraene-α,23-diol and (20S, S, 23R, 24S)-14β,:,25-diepoxy-,23-dihydroxyergosta-4,,11-triene-,-dione by comparison of extensive 1D and 2D NMR spectral data with that of blazeispirol A. The biosynthesis of blazeispirol A was investigated by feeding ^<13>C-labeled acetates and methionine to the growing cultures of A. blazei. The labeling patterns of 1 derived from singly and doubly ^<13>C-labeled acetates were consistent with that of ergosterol reported previously except for the A-ring and then ^<14>C-labeled ergosterol was incorporated into blazeispirol A. Taking the structures of blazeispirols Z and D into consideration, it can be assumed that blazeispirol A is biosynthesized from ergosterol by the cleavage of C-4, C-5 and C-1, C-10 bonds on retro aldol condensation and Michael reaction via such as intermediate A as shown in Fig. 4. A large number of ergostane-type steroids have been isolated from many fungi. However, blazeispirol A is the first example of a naturally occurring des-A-ergostane-type steroid including a spiroacetal structure moiety as a side chain.

抄録全体を表示

As the mortality of infant at the Joboji-machi was very high as compard with national mean value, this town was appointed as the special district for sanitaly guaidance of mothers and children in 1955.
The Preesent author conducted an examination for infants and studied on the actual sanitory condition of mothers and children in August 1955.
1) On the infantile nursing and the other items.
The results of the reseach on 295 mothers who have infants 2 months to 1 year and half aiter bjrth.
Indifference of the infant nursing .%
Nurse is grandparents 66.1%
Use of “Ejiko”= a cracel 52.0%
Days of taking bath once in .4 days
Change of underwear once in 2.2 days
Change of diaper. .4 in a day
Days of puerperium 50 days
No holiday during pregnancy 74.%
Witness of birth except doctor and midwife. 13.%
2) On the infant.
The result of the research on 297 infants from 2 months to 1 year and half after birth.
a) Illness 122 infants (41.1%)
Rachitis constitution 20.5% Harnia 16.4%
Bronchitis .% Impetigo 11.5%
) Body measurement.
Stature and weight on the birth at maternity clinic was a little higher than national mean value and it was a slight dicrease to school age from a threemonth old baby.
c) The manner of nutrition.
Breast milk WS%
Artificial feeding 1.%
Mixed feeding .%
d) The state of development.
Dentition (at a seven-month old baby of the national value.). c34.1%
Walking start (at a thirteen-month old baby of the national mean value.). c25%
Weaning start (at a seven-month old baby.). c16%
) Marriage of parents was earlier then that of the city people.
Male 23.2 . years old Female 20. 2. years old
f) Mother of the dead child were 26.% more then that of the city people.
) On the state of birth.
a) The body weight on the birth was lower that of the national meal value.
13) - The rote stillbirth was 2.5% and the birth after bleeding was 4.5%.

抄録全体を表示

The gamma-ray spectrum and the conversion-electron spectrum are measured in the decay of the Tb¹⁵² activity. The L-subshell electron lines of the 586. keV +→2₁⁺ transition are separated by the ion-free beta-ray spectrometer. The M1-2 mixing ratio, δ², and the dimensionless ratio X of 0-2 mixing of the 586. keV transition are obtained to be δ²≤0.16 and 0.034≤X≤0.038, respectively. The 2 branching ratio (2; +→0_g⁺): (2; +→2₁⁺): (2; +→0₁⁺) is determined to be 0.023 : 1.0 : 5..

抄録全体を表示