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21.
The bound site of Mo atoms and its local structure in a Mo/HY catalyst have been determined by detailed analysis of extended X-ray absorption fine structure (EXAFS). Molybdenum was introduced in the supercage of HY zeolite by cycles of saturated adsorption of Mo(CO)6 at room temperature and subsequent thermal decomposition at 573 K. Two Mo atoms per supercage were immobilized in each CVD-thermal treatment cycle. The Mo loading increased linearly with the cycles up to three cycles at saturation, where six Mo atoms were supported. Temperature-programmed decomposition of the adsorbed Mo(CO)6 was also characterized by GC, QMS, and FT-IR, respectively. The EXAFS analysis including multiple scattering based on theoretical calculations revealed that Mo bound with two oxygen atoms connects to Al, where one of the two oxygen atoms had been associated with a proton. The bound site is called the S(III)' site. The zeolite framework was significantly distorted by the introduction of low-valent Mo, resulting in isolation of the [MoO2Al] unit from the surrounding zeolite framework due to a quasi-disruption of Si-O bonds adjacent to the unit. In the mild oxidation of the low-valent Mo/HY sample two Mo=O bonds were newly formed and the position of Mo was displaced by 0.06 nm so that the distortion of zeolite framework around the Al atom was relieved. The structures were also supported by DFT calculations. This study is the first example that the position of metal cation in zeolite was determined unambiguously by the EXAFS analysis. 相似文献
22.
Because Nitrosomonas europaea contains ammonia-oxidizing enzyme, nitrite reductase, and nitrous oxide reductase, the conversion of ammonia to dinitrogen
was tried with different reaction conditions. In aerobic reaction conditions, ammonium was converted to nitrite (NO
2
−
), while under oxygen-limiting or oxygen-free conditions, NO
2
−
-N formed from ammonia oxidation by N. europaea was reduced to N2O and dinitrogen with 22% conversion. During denitrification, optimal pH for the production of N2O and dinitrogen was found to be 7.0–8.0. Dinitrogen was not produced in acidic pH<7.0. A low partial oxygen pressure as well
as oxygen-free conditions are favorable for high production of dinitrogen. 相似文献
23.
Allylation of carbonucleophiles with allylic carbamates under neutral conditions has been studied. The C-allylation of carbonucleophile is competitive with the N-allylation of amines, and the structure of amines is crucial for the selectivity. Bulky secondary amines gave the best results. Also a new method of protection-deprotection of amines as carbamates has been developed. Smooth deprotection is possible by the palladium-catalyzed reaction of allyl carbamates with formic acid. This method is particulary useful for primary amines, including optically active amino acids. 相似文献
24.
Takeshi Satake Yasunobu Onishi Masahiko Iyoda Masazumi Nakagawa 《Tetrahedron letters》1979,20(34):3171-3172
Tri-t-butylcarboxybisdehydro[14]annulene was converted by the Curtius reaction into unstable aminoannulene, which could be characterized as N-acetyl derivative. The pKa-value of the aminoannulene reflects aromatic nature of the annulene nucleus. 相似文献
25.
M. Nakagawa S. Kato H. Fukazawa Y. Hasegawa J. Miyazawa T. Hino 《Tetrahedron letters》1985,26(48):5871-5874
Oxytryptophans 3, which are readily obtained by dye-sensitized photooxygenation of tryptophan followed by acid treatment, undergo a facile N,N′-transacylation to give the 3-(2-aminophenyl)-2-pyrrolidones 4 in the absence of oxygen, whereas in the presence of oxygen 3a was oxidized to kynurenine. 相似文献
26.
Dehydrroxy-trans-resorcylide () was synthesized by efficient intramolecular alkylation of the protected cyanohydrin. The butadiene telomer obtained by the palladium catalyzed reaction of butadiene with acetic acid was used as a suitable block of the carbocycle. 相似文献
27.
Angiotensin I‐converting enzyme (ACE) inhibitory peptide was isolated from the hen ovotransferrin hydrolysate using chymotryptic hydrolysis by two steps of reverse‐phase high‐performance liquid chromatography. The amino sequence of this novel peptide was identified as Lys‐Val‐Arg‐Glu‐Gly‐Thr‐Thr‐Tyr that inhibited ACE activity in vitro in a concentration‐dependent manner with an effective concentration (IC50) of 102.8 μM. Also, this inhibition was identified as noncompetitive using the Lineweaver‐Burk plot. Moreover, the antihypertensive action of this novel peptide was investigated by an intravenous injection into spontaneously hypertensive rats (SHR). A dose‐dependent reduction of systolic blood pressure by this peptide was observed after 40 min of treatment and it decreased the blood pressure markedly at the maximal dose (1 nmol/mL/kg). The maximal blood pressure lowering activity of this peptide was calculated as 163% of captopril (10 pmol/mL/kg) that was used as positive control. In conclusion, the obtained data suggests that Lys‐Val‐Arg‐Glu‐Gly‐Thr‐Thr‐Tyr has an ability to inhibit ACE activity and decrease the systolic blood pressure in hypertensive animals. 相似文献
28.
Drying dissipative structural patterns formed in the course of drying colloidal crystals of silica spheres (110 nm in diameter)
in water, methyl alcohol, ethyl alcohol, 1-propyl alcohol, diethyl ether, and in the mixtures of ethyl alcohol with the other
solvents above have been studied on a cover glass. The macroscopic broad rings were formed in the outside edges of the dried
film for all the solvents examined. Furthermore, much distinct broad rings appeared in the inner area when the solvents were
ethyl alcohol, methyl alcohol, and their mixtures. Profiles of the thickness of the dried films were sensitive to the organic
solvents and explained well with changes in the surface tensions, boiling points, and viscosities of the solvents. The macroscopic
and microscopic spoke-like crack patterns formed. The drying area (or the drying time) increased (or decreased) as the surface
tension of the solvent decreased. However, the absolute values of these drying parameters are determined also by the boiling
points of the solvents. Importance of the fundamental properties of the solvents is supported in addition to the characteristics
of colloidal particles in the drying dissipative pattern formation. 相似文献
29.
30.
A concise route to (-)-kainic acid from enantiopure (+)-cis-4-carbobenzoxyamino-2-cyclopentenol has been devised by employing concurrent Chugaev syn-elimination and intramolecular ene reaction as the key step. 相似文献