• Title/Summary/Keyword: Base substitution

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Origin of the α-Effect in Nucleophilic Substitution Reactions of Y-Substituted Phenyl Benzoates with Butane-2,3-dione Monoximate and Z-Substituted Phenoxides: Ground-State Destabilization vs. Transition-State Stabilization

  • Kim, Mi-Sun;Min, Se-Won;Seo, Jin-A;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • v.30 no.12
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    • pp.2913-2917
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    • 2009
  • Second-order rate constants (k$_{Nu–}$) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-i) with butane-2,3-dione monoximate ($Ox^-\;an\;\alpha$-nucleophile) and Z-substituted phenoxides in 80 mol% H$_2$O/20 mol% DMSO at 25.0${\pm}$0.1$^{\circ}C$. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for reactions of 1a-h with Ox$^–$ exhibit many scattered points. In contrast, the Yukawa-Tsuno plot results in a good linear correlation with ${\rho}_Y$ = 2.20 and r = 0.45, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS). A stepwise mechanism with expulsion of the leaving-group being the RDS has been excluded, since Y-substituted phenoxides are less basic and better nucleofuges than Ox$^–$. Thus, the reactions have been concluded to proceed through a concerted mechanism. Ox$^–$ is over 10$^2$ times more reactive than its reference nucleophile, 4-chlorophenoxide (4-ClPhO$^–$). One might suggest that stabilization of the transition-state (TS) through intramolecular general acid/base catalysis is responsible for the ${\alpha}$-effect since such general acid/base catalysis is not possible for the corresponding reactions with 4-ClPhO$^–$. However, destabilization of the ground-state (GS) of Ox$^–$ has been concluded to be mainly responsible for the ${\alpha}$-effect found in this study on the basis of the fact that the magnitude of the ${\alpha}$-effect is independent of the nature of the substituent Y.

Development of High Corrosion Resistant $Mo_2NiB_2$ Boride Base Cermets for Plastic Injection Molding Machine Parts

  • Hirata, Kourou;Iwanaga, Kengo;Yamasaki, Yuji;Takagi, Ken-ichi
    • Proceedings of the Korean Powder Metallurgy Institute Conference
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    • 2006.09a
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    • pp.111-112
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    • 2006
  • Injection molding of corrosive super engineering plastics and engineering plastics with various fillers is conducted under severe conditions and causes corrosion and wear problems. We have developed $Mo_2NiB_2$ boride base cermets, which have excellent corrosion-and wear-resistances, and tried to apply them into plastic molding machine parts. In this paper, the effects of V substitution for Cr on the mechanical properties, corrosion resistance and microstructure of Ni-5.0B-51.0Mo-(17.5-X)Cr-XV (mass%) model cermets were investigated. Both transverse rupture strength (TRS) and hardness increased monotonically with increasing V content and reached 2.94GPa and $87.2R_A$ at 10.0%V, respectively. The improvements of TRS and hardness were attributed to microstructural refinement.

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Genetic Analysis of Ancient Human Bones Excavated in Sacheon Nuk-do and Gyeongsan Yimdang-dong, Korea (경산 임당동 및 사천 늑도 출토 인골의 유전자 분석)

  • Seo, Min-Seok;Lee, Kyu-Shik
    • 보존과학연구
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    • s.25
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    • pp.47-74
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    • 2004
  • We investigated the nucleotide substitution and insertion polymorphism of the hypervariable region Ⅰ and Ⅱ in mt DNA by sequencing ancient DNA from 51 ancient bones and teeth excavated at Nuk-do and Yimdang-dong in Korea. It revealed 35 sequence types from the ancient Korean. Of these, different sequences were 34 sequences. There were 19 and 38 base substitutions in HVI and HVⅡ, respectively. Some substitutions were characteristic of East Asian populations as compared with data reported on Caucacianpopulations,16051, 16150, 16172, 16223 in region I and 73, 263 in region II were noted as polymorphic sites, respectively. These were distributed evenly along the control region, though the frequency of each site was variable. Nucleotide substitution rather than insertion and deletion was the prevalent pattern of variation. Insertion of cytosine between312 and 315 in region HVⅡ were detected up to 98% in 51 ancient bone samples. This sequence data represents a phylogenetic tree using NTI DNA Suite computer program. The phylogenetic tree showed that mt DNA sequences of Nuk-do bones were relative to west Siberian and Indonesian. The usefulness of mt DNA sequencing in ancient Korean population excavated atarchaeological sites is based on biological and historical evidence for origin and migration of ancient Korean.

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Resistivity Analysis of Model Block for Using of Structure Grounding Electrode (구조체접지극 활용을 위한 모형블록의 저항률 분석)

  • Kim, Sung-Sam;Jeong, Man-Gil;Choi, Jong-Kyu;Koh, Hee-Seog
    • Journal of the Korean Institute of Illuminating and Electrical Installation Engineers
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    • v.21 no.2
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    • pp.40-45
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    • 2007
  • This study analyzed the resistivity characteristic of model block to make the good use of structure grounding and substitution grounding electrode base of building. After making the model block of mortar and concrete block, it measured resistivity in hydrous condition and dry condition and compared with the blocks that is mixed earth resistance lowering agent to decrease resistivity. The resistance value of block accepted much influence by block resistivity. When the block resistivity was same or similar value, the value of soil resistivity has occurred as different as the value of grounding resistance.

The Base Sequence of ITS and Genetic Variation in Sarcodon Aspratus (능이버섯의 ITS염기서열과 유전적 변이)

  • Kim Jong Bong
    • Journal of Life Science
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    • v.14 no.6 s.67
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    • pp.963-966
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    • 2004
  • The sequence of ITS (partial 16S ribosomal DNA, complete ITS1, 5.8S ribosomal DNA and ITS2, and partial 28S ribosomal DNA) was analysed by PCR and autosequencing in Sarcodon aspratus. The ITS lenght of S. aspratus was 716 base pair. As this sequence compared with other reports on S. aspratus (ace No AF335110), the sequence variation based on nucleotide deletion and substitution was $1.8\%$. This nucleotide variation rate in same species was very higher than in other species. Also, the sequence varitation rates between this S. aspratus and S. imbricatus, and S. squamus were $8\%\;and\;10\%$, respectively. This results suggested that the high sequence variation of S. aspratus might be caused specific host and inhabitat environment which limited gene flow.

Mutagenicity of Pesticides in the Salmonella System (Salmonella System에 있어서의 농약의 돌연변이 유발성)

  • 백형석;변우현;전문진;이세영
    • Microbiology and Biotechnology Letters
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    • v.5 no.4
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    • pp.159-165
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    • 1977
  • 20 pesticides induding 11 insecticides, 5 herbicides and 4 fungicides have been tested for mutagenic activity in the Salmonella microsome system. It was found that Captan showed strong mutagenic activity directly in TA 1535, TA 100 and TA 98 strains, indicating that it induces both base substitution and frame shift mutation. With microsomal activation system, mutagenicity of Captan was slightly decreased. Micut, Dimethoate and Triforine revealed slight mutagenicity in TA100 without microsmal enzyme activtion.

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Functional Analysis of the Residues C770 and G771 of E. coli 16S rRNA Implicated in Forming the Intersubunit Bridge B2c of the Ribosome

  • Kim, Hong-Man;Yeom, Ji-Hyun;Ha, Hye-Jung;Kim, Jong-Myung;Lee, Kang-Seok
    • Journal of Microbiology and Biotechnology
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    • v.17 no.7
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    • pp.1204-1207
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    • 2007
  • Structural analyses have shown that nucleotides at the positions 770 and 771 of Escherichia coli 16S rRNA are implicated in forming one of highly conserved intersubunit bridges of the ribosome, B2c. To examine a functional role of these residues, base substitutions were introduced at these positions and mutant ribosomes were analyzed for their protein synthesis ability using a specialized ribosome system. The results showed requirement of a pyrimidine at the position 770 for ribosome function regardless of the nucleotide identity at the position 771. Sucrose gradient profiles of ribosomes revealed that the loss of protein-synthesis ability of mutant ribosome bearing a base substitution from C to G at the position 770 stems from its inability to form 70S ribosomes. These findings indicate involvement of nucleotide at the position 770, not 771, in ribosomal subunit association and provide a useful rRNA mutation that can be used as a target to investigate the physical interaction between 16S and 23S rRNA.

Morphology and Sequence Analysis of Nuclear 18S rDNA from the Summer Strain of Porphyra suborbiculata (Rhodophyta) in Korea (여름철 서식 한국산 홍조류 둥근돌김 (Porphyra suborbiculata)의 형태 및 18S rDNA 염기서열 분석)

  • JIN Long-Guo;KIM Myung-Sook;CHOI Jae-Suk;CHO Ji-Young;JIN Hyung-Joo;HONG Yong-Ki
    • Korean Journal of Fisheries and Aquatic Sciences
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    • v.33 no.6
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    • pp.489-495
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    • 2000
  • The 185 ribosomal RNA gene (185 rDNA) of the marine alga Porphyra sp. 723 (Bangiales, Rhodophyta) was amplified using the polymerase chain reaction and its sequence was analysed. The Porphyra species was a summer strain collected on rocks in upper intertidal zone at Ikidae, Pusan on 23rd July 1999. The fronds were $1{\~}5 cm$ long, monostromatic, and orbicular or ovate shaped, They had spinulate processes at margin of the frond, Comparison of this 185 rDNA sequence with the other Forphyra species indicates that Porphyra sp. 723 has the same 185 rDNA sequence derived from Porphyra suborbiculata (NCBI access number; AB 013180) except one base pair substitution in 2327 base pairs.

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DNA Sequence Analysis of 1-Nitropyrene-4,5-Oxide and 1-Nitropyrene-9,10-Oxide Induced Mutations in the hprt Gene of Chinese Hamster Ovary Cells

  • Kim, Hyun-Jo;Kim, Tae-Ho;Lee, Sun-Young;Lee, Dong-Hoon;Kim, Sang-In;Pfeifer, Gerd P.;Kim, Seog K.;Lee, Chong-Soon
    • Molecules and Cells
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    • v.19 no.1
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    • pp.114-123
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    • 2005
  • Nitropyrene, the predominant nitropolycyclic hydrocarbon found in diesel exhaust, is a mutagenic and tumorigenic environmental pollutant that requires metabolic activation via nitroreduction and ring oxidation. In order to determine the role of ring oxidation in the mutagenicity of 1-nitropyrene, its oxidative metabolites, 1-nitropyrene 4,5-oxide and 1-nitropyrene 9,10-oxide, were synthesized and their mutation spectra were determined in the coding region of hprt gene of CHO cells by a PCR amplification of reverse-transcribed hprt mRNA, followed by a DNA sequence analysis. A comparison of the two metabolites for mutation frequencies showed that 1-nitropyrene 9,10-oxide was 2-times higher than 1-nitropyrene 4,5-oxide. The mutation spectrum for 1-nitropyrene 4,5-oxide was base substitutions (33/49), one base deletions (11/49) and exon deletions (5/49). In the case of 1-nitropyrene 9,10-oxide, base substitutions (27/50), one base deletions (15/50), and exon deletions (8/50) were observed. Base substitutions were distributed randomly throughout the hprt gene. The majority of the base substitutions in mutant from 1-nitropyrene 4,5-oxide treated cells were $A{\rightarrow}G$ transition (15/33) and $G{\rightarrow}A$ transition (8/33). The predominant base substitution, $A{\rightarrow}G$ transition (11/27) and $G{\rightarrow}A$ transition (8/27), were also observed in mutant from 1-nitropyrene 9,10-oxide treated cells. The mutation at the site of adenine and guanine was consistent with the previous results, where the sites of DNA adduct formed by these compounds were predominant at the sites of purines. A comparison of the mutational patterns between 1-nitropyrene 4,5-oxide and 1-nitropyrene 9,10-oxide showed that there were no significant differences in the overall mutational spectrum. These results indicate that each oxidative metabolite exhibits an equal contribution to the mutagenicity of 1-nitropyrene, and ring oxidation of 1-nitropyrene is an important metabolic pathway to the formation of significant lethal DNA lesions.

Characteristic Signature Extraction using the Base Distribution Substitution Comparison (염기분포와 대치 비교를 이용한 염기서열 집단의 고유 시그너쳐 추출)

  • Hwang, Gyeong-Sun;Lee, Hye-Ri;Lee, Geon-Myeong;Kim, Seong-Su;Lee, Chan-Hui;Lee, Seong-Deok;Yun, Hyeong-U
    • Proceedings of the Korean Institute of Intelligent Systems Conference
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    • 2007.11a
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    • pp.419-422
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    • 2007
  • 유전자 변이가 쉽게 일어나는 바이러스 등은 변이 계통에 따라 집단을 형성하게 된다. 이러한 집단들에 대한 분석은 해당 바이러스 집단에 대한 추적, 백신 및 치료약 개발에서 필수적이다. 어떤 집단의 염기 서열의 특성을 효과적으로 표현하는 패턴을 시그너쳐라 하며, 이러한 시그너쳐는 특정 염기서열 집단의 고유한 특성을 나타내면서 다른 집단과 구별되는 정보를 포함하는 것이 바람직하다. 이 논문에서는 가능한 후보 시그너쳐들을 염기분포를 이용하여 생성해가면서, 시그너쳐 해당부위의 염기를 상대 서열집단의 공통 서열의 염기로 변환하여 집단간의 상대거리를 측정함으로써, 후보 시그너쳐에 의한 집단의 고유성질 표현능력과 집단간 차별화 능력을 고려하여 시그너쳐를 추출하는 방법을 제안한다.

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