• 제목/요약/키워드: base substitution rate

검색결과 26건 처리시간 0.134초

Aminolysis of Benzyl 2-Pyridyl Thionocarbonate and t-Butyl 2-Pyridyl Thionocarbonate: Effects of Nonleaving Groups on Reactivity and Reaction Mechanism

  • Kim, Min-Young;Lee, Jae-In;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제34권4호
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    • pp.1115-1119
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    • 2013
  • A kinetic study is reported for nucleophilic substitution reactions of benzyl 2-pyridyl thionocarbonate (5b) and t-butyl 2-pyridyl thionocarbonate (6b) with a series of alicyclic secondary amines in $H_2O$ at $25.0^{\circ}C$. General-base catalysis, which has often been reported to occur for aminolysis of esters possessing a C=S electrophilic center, is absent for the reactions of 5b and 6b. The Br${\o}$nsted-type plots for the reactions of 5b and 6b are linear with ${\beta}_{nuc}$ = 0.29 and 0.43, respectively, indicating that the reactions of 5b proceed through a stepwise mechanism with formation of a zwitterionic tetrahedral intermediate ($T^{\pm}$) being the rate-determining step while those of 6b proceed through a concerted mechanism. The reactivity of 5b and 6b is similar to that of their oxygen analogues (i.e., benzyl 2-pyridyl carbonate 5a and t-butyl 2-pyridyl carbonate 6a, respectively), indicating that the effect of modification of the electrophilic center from C=O to C=S (i.e., from 5a to 5b and from 6a to 6b) on reactivity is insignificant. In contrast, 6b is much less reactive than 5b, indicating that the replacement of the $PhCH_2$ in 5b by the t-Bu in 6b results in a significant decrease in reactivity as well as a change in the reaction mechanism (i.e., from a stepwise mechanism to a concerted pathway). It has been concluded that the contrasting reactivity and reaction mechanism for the reactions of 5b and 6b are not due to the electronic effects of $PhCH_2$ and t-Bu but are caused by the large steric hindrance exerted by the bulky t-Bu in 6b.

스피로벤조피란을 포함하는 셀룰로오스 유도체의 광변색 특성 (Photochromic Properties of Cellulose Derivatives Having Spirobenzopyran Group)

  • ;김은경;이명훈
    • 폴리머
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    • 제29권1호
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    • pp.25-31
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    • 2005
  • 6-(파라헥실페닐)카보닐 스피로벤조피란(6-(p-hexyloxyphenyl)carbonyl spirobenzopyran, COSP)기를 포함하는 새로운 초산 셀룰로오스 유도체(CA-COSP)를 초산 셀룰로오스의 에테르화 반응에 의해 합성하고 이들의 물리적 특성과 광변색 특성을 조사하였다. COSP 치환도는 $^1H$-NMR과 UV 분광학적으로 확인한 결과 반응조건에 따라 셀룰로오스 내 잔류 수산기에 대하여 0.87~45.5%가 됨을 알 수 있었다. 얻어진 CA-COSP의 자외선 분광학 실험 결과 이 고분자는 자외선에 의해 메로시아닌(merocyanine) 구조로 변화하면서 무색에서 푸른색으로 변색하고, 가시광선 또는 열에 의해 다시 투명한 스피로피란(spiropyran)으로 돌아오는 가역적인 색변화가 일어남을 알 수 있었다. 색변화는 용액에서의 경우가 필름보다 빠른 특성을 보여주었으며, 극성용매 중에서는 메로시아닌의 안정성이 더 높아져서 스피로피란으로의 역반응이 더 느리게 일어남을 확인하였다. COSP를 CA-COSP에 혼합할 경우의 상용성을 COSP를 초산 셀룰로오스에 혼합할 경우와 비교하였다. 그 결과 순수한 초산 셀룰로오스의 경우 0.9 wt% 이상 혼합하면 상분리가 관찰되었으나, CA-COSP의 경우에는 48%까지 COSP를 혼합하여도 상분리가 관찰되지 않았다.

한국인의 대장암 세포주에서 p53 돌연변이의 발견과 발현에 관한 연구 (Study on the expression and detection of the p53 mutation in Korean colon cancer cell lines)

  • 정지연;오상진
    • IMMUNE NETWORK
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    • 제1권2호
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    • pp.151-161
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    • 2001
  • Background: Inactivation in p53 tumor suppressor gene through a point mutation and deletion is one of the most frequent genetic changes found in human cancer, with 50% of an incidence. This high rate of mutation mostly suggests that the gene plays a central role in the development of cancer and the mutations detected so far were found in exons 5 to 8. Mutation of p53 locus produced accumulation of abnormal p53 protein, and negative regulation of cell proliferation and transcriptional activation as a suppressor of transformation were lost. In addition, inhibition of its normal cellular function of wild-type by mutant is an important step in tumorigenesis. Method: 4 colon cancer cell lines (SNU C1, C2A, C4, C5) were examined for mutation in exons 5 to 8 of the p53 tumor suppressor gene by PCR-SSCP analysis and expression pattern by western blotting and immunoprecipitation. p53-mediated transactivation ability were examined by CAT assay and base substitution of p53 in SNU C2A cell were detected by DNA sequencing. Results: 1) SNU C2A cell and SNU C5 cell were detected mobility shifts each in exon 5 and exon 7 of p53 gene by the PCR-SSCP method, implicating being of p53 mutation. 2) 3 colon cancer cell lines (SNU C1, SNU C2A, SNU C5) expressed wild type and mutant type p53 protein. 3) In northern blot experiment, SNU C2A and SNU C5 cell expressed high level of p53 mRNA. 4) Results of p53-mediated transactivation in colon cancer cell lines by CAT assay represented only SNU C2A cell has transcriptional activity. 5) DNA sequencing in SNU C2A cell showed missense mutation in codon 179 of one allele, histidine to arginine and wild type p53 in the other allele. Conclusion: Colon cancer cell lines showed correlation with mutation in p53 gene and accumulation of abnormal p53 protein. Colon cancer cell SNU C2A retained p53-mediated transactivation as heterozygous p53 with one mutant allele in 179 codon and the other wild-type allele.

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축산물(畜産物) 수요(需要)의 장기여측(長期予測)에 관(關)한 연구(硏究) (A Study on the Long Term Demand Estimation for the Livestock Products)

  • 김철호
    • 농업과학연구
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    • 제10권2호
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    • pp.393-405
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    • 1983
  • The demand for livestock and poultry products including beef, pork, chicken, egg and milk whose income elasticities are relatively higher than other staple foods, has been increased significantly during the past two decades in response to the remarkable increase in per capita GNP. This trend will be continued during the fifth and the sixth five year economic development plan period beginning with 1982. The annual GNP growth rate will be 7.5% on the average during the next 10 years. It is greatly needed to estimate the demand for beef, pork, chicken egg and milk and to study the feasibilities of domestic production of livestock products for the formulation of adequate policies in order to equate the consumption and the production during the 1980s. So this study reviewed the possible changes in the food consumption patterns during the 1980s, estimated the demand for beef, pork, chicken, egg and milk by using empirical demand functions and finally made suggestions for the formulation of long term price stabilization policies for each livestock, poultry and dairy products through the equilibrium of the quantity of demand for and supply of the products. There are many factors affecting the demand for meats, but this study considered own price, prices of supplements and substitutes and per capita income as the independent variables in the demand equations. It was found that it's own price and income were most significantly affecting factors among others and the degree of substitution effects were remarkably different among the products. According to the meat demand derived in this study, per capita consumption of beef, pork and chicken in the base year 1982 was 11.2kg for total meat, 2.5kg beef, 6.0kg pork and 2.5kg chicken, 106 pieces egg, 15.1kg milk respectively, while those in 1991 were 19.3kg for total meat, 4.8kg beef, 9.6kg pork, 4.9kg chicken, 133pieces egg and 44.1kg milk. It is also predicted through this study that, when the level of production costs be maintained, the domestic production of pork and chicken will meet the demand for them during the fifth and sixth five year economic plan period. However, there will be chronic shortage of beef supply during the coming years. The annual import requirement will be 30,000tons to 40,000tons during the period. In order to stabilize the domestic livestock and poultry and dairy products market, the government should introduce measures to curb the increase in beef consumption by encouraging the consumption of pork and chicken. For this, the livestock production policy measures should be concentrated on : 1) the improvement of infrastructures of beef production by introducing advanced feeding and management technology, subsidies for the establishment of facilities and price support programs for farmers : 2) the development of dairy beef : 3) the reinforcement of the forecast systems for pork and chicken production and consumption.

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SPSS 프로그램을 이용한 중년여성의 스트레스 대처, 가족응집력이 행복감에 미치는 영향 - K시와 Y시에 거주하는 중년여성을 중심으로 - (The Effects of Stress Management and Family Cohesion on Middle-aged Women's Happiness Utilizing the SPSS Program - Focusing on middle-aged women living in Cities K and Y -)

  • 신소정;고재욱
    • 한국정보전자통신기술학회논문지
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    • 제11권2호
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    • pp.137-143
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    • 2018
  • 본 연구는 중년여성의 스트레스 대체와 가족응집력이 행복감과의 관계와 미치는 영향에 대하여 분석하고자하였다. 연구대상은 K시와 Y시에 거주하는 40세에서 60세 이하의 중년여성 322명을 대상으로 실시하였다. 분석방법은 SPSS 18.0과 통계프로그램을 이용하여, 빈도분석, 신뢰도분석, 위계적 회귀분석을 실시하였다. 연구결과 첫째, 연령은 40세 49세가 59.3%, 기혼이 82.7%(267명), 학력은 고졸 이하가 63.2%(204명), 종교는 77.6%(250명)로 높게 나타났다. 둘째, 스트레스 대처, 가족응집력, 행복감 순으로 나타났다. 셋째, 스트레스 대처, 가족 응집력 및 행복감의 관계는 모두 정(+)의 관계로 나타났다. 넷째, 중년여성의 행복감에 가족응집력은 영향을 미치지 않는 것으로 나타났다. 반면 스트레스 대처가 가장 큰 영향력을 미치는 것으로 설명량은 28.2% 나타났다. 본 연구의 시사점은 중년여성의 행복한 삶의 질 함양을 위한 사회복지실천에 기초자료가 될 것으로 사료된다.

Carcinogenicity and mutagenicity of heterocyclic amines in transgenic models

  • Ryu D.Y.
    • 한국독성학회:학술대회논문집
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    • 한국독성학회 2000년도 국제심포지움 및 추계학술대회
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    • pp.45-67
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    • 2000
  • 2-Amino-3,8-dimethylimidazo[4,5-f]quinoxaline (MeIQx) is a mutagenic and carcinogenic heterocyclic amino found in cooked meat. The in vivo mutagenicity and hepatocarcinogenicity of MeIQx were examined in mice harboring the lacZ mutation reporter gene ($Muta^{TM}$ Mice) and bitransgenic mice over-expressing the c-myc oncogene. C57B1/$\lambda$lacZ and bitransgenic c-myc (albumin promoter)/$\lambda$lacZ mice were bred and weaned onto an AIN-76 based diet containing $0.06\%$ (w/w) MeIQx or onto control diet. After 30 weeks on diet, only male bitransgenic mice on MeIQx developed hepatocellular carcinoma ($100\%$ incidence) indicating that there was synergism between c-myc over-expression and MeIQx. By 40 weeks, hepatic tumor incidence was $100\%$ ($17\%$) and $44\%$ ($0\%$) in male c-myc/$\lambda$lacZ and C57B1/$\lambda$lacZ mice given MeIQx (or control) diet, respectively, indicating that either MeIQx or c-myc over-expression alone eventually induced hepatic tumors. At either time point, mutant frequency in the lacZ gene was at least 40-fold higher in MeIQx-treated mice than in control mice of either strain. These findings suggest that MeIQx-induced hepatocarcinogenesis is associated with MeIQx-induced mutations. Elevated mutant frequency in MeIQx-treated mice also occurred concomitant with the formation of MeIQx-guanine adducts as detected by the $^{32}P$-postlabeling assay. Irrespective of strain or diet, sequence analysis of the lacZ mutants from male mouse liver showed that the principal sequence alteration was a single guanine-base substitution. Adenine mutations, however, were detected only in animals on control diet. MeIQx-fed mice harboring the c-myc oncogene showed a l.4-2.6-fold higher mutant frequency in the lacZ gene than mice not carrying the transgene. Although there was a trend toward higher adduct levels in c-myc mice, MeIQx-DNA adduct levels were not significantly different between c-myc/$\lambda$lacZ and C57B1/$\lambda$lacZ mice after 30 weeks on diet. Thus, it appeared that factors in addition to MeIQx-DNA adduct levels, such as the enhance rate of proliferation associated with c-myc over-expression, may have accounted for a higher mutant frequency in c-myc mice. In the control diet groups, the lacZ mutant frequency was significantly higher in c-myc/$\lambda$lacZ mice than in 057B1/$\lambda$1acZ mice. The findings are consistent with the notion that c-myc over-expression is associated with an increase in mutagenesis. The mechanism for the synergistic effects of c-myc over-expression on MeIQx hepatocarcinogenicity appears to involve an enhancement of MeIQx-induced mutations.

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