• Bulletin of the Korean Chemical Society
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• 제15권12호
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• pp.1064-1069
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• 1994

Chlorobis(isoprene)rhodium(Ⅰ) (3), prepared by olefin-exchange reaction of chlorobis(cyclooctene)rhodium dimer (2) with isoprene, reacted with benzaldimine 4 to give iminoacylrhodium(Ⅲ) ${\eta}^3$-1,2-dimethylallyl complex 6. Ligand-promoted reductive elimination of 6 by pyridine and P(OMe)$_3$ produced ${\beta},{\gamma}$-unsaturated ketimine 8, which was readily hydrolyzed to give ${\beta},{\gamma}$-unsaturated ketone 9. Other methyl branched dienes such as 2,3-dimethylbutadiene, 3-methyl-1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 3-methyl-1,4-pentadiene and 2-methyl-1,4-pentadiene, were applied the synthesis of ${\beta},{\gamma}$-unsaturated ketones. In case of 2,4-dimethyl-1,3-pentadiene, only ${\gamma},{\delta}$ -unsaturated ketone 25, 1,2-addition product, was obtained, may be due to the mono-olefin coordination.

• Bulletin of the Korean Chemical Society
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• 제19권12호
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• pp.1355-1359
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• 1998

The treatment of 1,1-bis(phenylthio)-2,2,3,3,3-pentafluoropropylbenzene (1) with 2 equiv. of phenyllithium in THF at -78 ℃ resulted in the formation of isomeric mixture (70: 30) of trifluoromethylated 1,2-diphenylvinyl sulfide 2 in 87% yield. The further oxidation of 2 with m-chloroperbenzoic acid in methylene chloride afforded isomeric mixture (70:30) of trifluoromethylated 1,2-diphenylvinyl sulfone 3 in 87% yield. When 3 was reacted with carbon nucleophiles such as methyllithium, n-butyllithium, phenyllithium and lithium octylide, the corresponding addition-elimination adducts 4, 5, 6 and 7 were obtained in moderate to good yields. The reaction of 3 with 4 equiv. of tributyltin hydride in benzene at reflux temperature provided isomeric mixture (90 : 10) of trifluoromethylated 1,2-diphenylvinyl stannane 8 in 41% yield. The reaction of 8 with methyllithium in the presence of trimethylsilyl chloride gave isomeric mixtures (90: 10) of trifluoromethylated 1,2-diphenylvinyl silane 9 in 88% yield. Finally, the treatment of 8 with Br2 and 12 resulted in the formation of isomeric mixtures (90: 10) of trifluoromethylated 1,2-diphenylvinyl bromide 10 and iodide 11 in 72% and 90% yields, respectively.

• Bulletin of the Korean Chemical Society
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• 제20권5호
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• pp.573-576
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• 1999

The rate constants and kinetic solvent isotope effects (KSIE, KMeOH/kMeOD) for solvolyses of para-substituted phenylchloroformates in CH3OH, CH3OD, H2O, D2O, 50% D2O-CH3OD were determined at 15.0 and 25.0℃ using conductometric method. Kinetic solvent isotope effects for the solvolyses of para-substituted phenyl chloroformates were 2.39-2.51, 2.21-2.28, and 1.67-1.69 for methanol, 50% aqueous methanol, and water, respectively. The slopes of Hammett plot for solvolysis of para-substituted phenyl chloroformates in methanol, 50% aqueous methanol, and water were 1.49, 1.17 and 0.89, respectively. The Hammett type plot of KSIE, log (KSIE) versus p, can be a useful mechanistic tool for solvolytic reactions. The slopes of such straight lines for para-substituted phenyl chloroformates are almost zero in methanol, 50% aqueous methanol, and water. It was shown that the reaction proceeds via an associative SN2 and/or general base catalysis addition-elimination (SAN) mechanism based on activation parameters, Hammett p values, and slopes of Hammett type plot of KS-IE.

• Clinical and Experimental Pediatrics
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• 제64권11호
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• pp.543-551
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• 2021

The human microbiome, which consists of a collective cluster of commensal, symbiotic, and pathogenic microorganisms living in the human body, plays a key role in host health and immunity. The human nasal cavity harbors commensal bacteria that suppress the colonization of opportunistic pathogens. However, dysbiosis of the nasal microbial community is associated with many diseases, such as acute respiratory infections including otitis media, sinusitis and bronchitis and allergic respiratory diseases including asthma. The nasopharyngeal acquisition of pneumococcus, which exists as a pathobiont in the nasal cavity, is the initial step in virtually all pneumococcal diseases. Although the factors influencing nasal colonization and elimination are not fully understood, the adhesion of opportunistic pathogens to nasopharyngeal mucosa receptors and the eliciting of immune responses in the host are implicated in addition to bacterial microbiota properties and colonization resistance dynamics. Probiotics or synbiotic interventions may show promising and effective roles in the adjunctive treatment of dysbiosis; however, more studies are needed to characterize how these interventions can be applied in clinical practice in the future.

• Bulletin of the Korean Chemical Society
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• 제16권3호
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• pp.252-256
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• 1995

Semiempirical MO calculations using the PM3 method are performed on the reactions of acetate esters with substituted phenolate anions. The mechanistic change from rate-limiting formation to breakdown of the anionic intermediate is shown to occur in the gas-phase, especially for meta-nitrophenyl acetate. However the mechanistic change-over takes place at a lower basicity ($pK_0$) of the anion nucleophile than found for the corresponding formate. This lowering of $pK_0$ has been ascribed to the electron donating effect of the methyl group in the acetate. For the reactions involving rate-limiting breakdown of the intermediate, the large Bronsted coefficients, ${\beta}_X({\beta}_{nuc})$, are expected in general, but the magnitude increases to a larger value and the pK0 is lowered accordingly, when an electron-donating nonleaving group, like $CH_3$, is present. This type of nonleaving group effect provides a necessary condition for the carbonyl addition-elimination mechanism with rate-limiting breakdown of the intermediate.

• Bulletin of the Korean Chemical Society
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• 제14권2호
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• pp.287-291
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• 1993

Catalytic iminohydroacylation has been achieved by the reaction of aldimine 1 and 1,5-hexadiene (2a) with Wilkinson's complex as catalyst. Compounds 7a, 8a and 9a were obtained as final product after hydrolysis of the resulting iminohydroacylation products 4a, 5a and 6a. Depending on the reactant ratio (2/1), the ratio of products were changed dramatically : As the 2/1 ratio was increased, 7a is the major product after hydrolysis while 8a is the major with an 1/1 ratio of 2/1. The mechanism of the formation of 5a is determined by the reaction of 1 and 2b under the identical reaction conditions. Considering that 5a may not be formed from the hydroiminoacylation of 14a since 5b cannot be formed from that of conjugate diene 14b generated from isomerization of 2b, 5a must be formed from the reaction of 4a and 10 by addition-elimination mechanism.

• Journal of Microbiology and Biotechnology
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• 제18권5호
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• pp.983-989
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• 2008

Human insulin is a hormone well-known to regulate the blood glucose level. Recombinant preproinsulin, a precursor of authentic insulin, is typically produced in E. coli as an inactive inclusion body, the solubilization of which needs the addition of reducing agents such as $\beta$-mercaptoethanol. To make authentic insulin, recombinant preproinsulin is modified enzymatically by trypsin and carboxypeptidase B. The effects of $\beta$-mercaptoethanol on the formation of human insulin derivatives were investigated in the enzymatic modification by using commercially available human proinsulin as a substrate. Addition of 1 mM $\beta$-mercaptoethanol induced the formation of various insulin derivatives. Among them, the second major one, impurity 3, was found to be identical to the insulin B chain fragment from $Phe_1$ to $Glu_{21}$. Minimization of the formation of insulin derivatives and concomitant improvement of the production yield of human insulin were achieved by the addition of hydrogen peroxide. Hydrogen peroxide bound with $\beta$-mercaptoethanol and thereby reduced the negative effects of $\beta$-mercaptoethanol considerably. Elimination of the impurity 3 and other derivatives by the addition of over 10 mM hydrogen peroxide in the presence of $\beta$-mercaptoethanolled to a 1.3-fold increase in the recovery efficiency of insulin, compared with those for the case without hydrogen peroxide. The positive effects of hydrogen peroxide were also confirmed with recombinant human preproinsulin expressed in recombinant E. coli as an inclusion body.

• 한국산학기술학회논문지
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• 제17권3호
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• pp.450-456
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• 2016

케이블에 인가되는 신호로 의사잡음 수열을 사용하여 인가신호와 반사신호의 시간 상관 분석을 실시하여 케이블 고장을 검출하는 STDR (sequence time domain reflectometry)은 노이즈 환경에 강하고, 단선, 합선을 포함한 간헐적 고장의 검출이 가능한 것으로 알려져 있다. 하지만 고장 위치의 거리가 멀거나 경미한 고장의 경우 반사신호의 감쇄가 크고 상관계수가 작아지게 되어, 케이블 고장 판별이 어렵거나 측정 거리 오차가 커진다. 또한 위상과 피크치 검출에 의한 고장 탐지 자동화가 어렵게 된다. 따라서 본 논문에서는 기존의 STDR의 고장 검출 성능을 향상시키기 위해 케이블에 인가되는 인가신호의 상관계수의 최댓값을 검출하고, 다음으로 인가신호를 제거하여 반사신호의 상관계수의 최댓값을 검출하는 알고리즘을 제안하였다. 제안된 방법은 저압 전력 케이블에서의 고장 검출 실험을 통해 성능을 입증하였다. 그 결과 제안된 방법은 신호가 감쇄되더라도 전통적인 STDR보다 고장 여부의 정확한 구분과 위치의 추적이 가능하였다. 또한 기준신호 제거와 상관계수의 정규화를 통해 위상과 최대값 검출 방법을 사용함으로써 자동 고장 판별과 거리 계산에 오류가 발생하지 않았다.

• 대한화장품학회지
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• 제30권4호
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• pp.491-497
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• 2004

일련의 Alkyl-3,4-dihydroxybenzoate (A)와 N-Alkyl-3,4-dihydroxybenzamide (B) 유도체들의 치환기($R_l$ 및 $R_2$) 변화에 따른 멜라닌생성 저해활성 관계들을 HQSAR 방법으로 분석하였다. 멜라닌생성 저해활성에 관하여 유도된 HQSAR 모델은 매우 양호한 예측성(cross-validated $r^2_{cv.},\;q^2=0.674)$과 적합성(non-cross-validated, $r^2_{ncv}=0.936)$을 나타내었다. 멜라닌생성 저해활성과 가수분해 반응성은 공히, (A)가 (B)보다 컸으며(A$R_l$-치환기가 $R_2$-치환기보다 저해활성에 의존적인 경향을 나타내었다$(R_l>R_2)$. 또한, 경계분자궤도(FMO) 이론에 따라 가수분해 반응은 (A), (B)의 LUMO와 물분자의 HOMO 사이에 강한 상호작용으로 orbital-control 반응인 친핵성 첨가-제거반응$(Ad_{N-E})$이 주로 일어나는 것을 알 수 있었다.

• 대한한의학원전학회지
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• 제21권1호
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• pp.111-122
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• 2008

At the book I of "The Golden Mirror of Medicine[醫宗金鑑] The Elimination and Supplement about Famous Prescription Comments[刪補名醫方論]", 22 prescriptions are recorded. At the first part of the book, it mainly described about the prescriptions of invigorating Gi[補氣], which is followed by the prescriptions on enriching blood and nourishing vital essence fluid[補陰血], and the prescriptions on strengthening Gihyeol[補氣血] and tranquilization[安神] are described at the last part of the book. At the current review, the 8 prescriptions of strengthening Gihyeol[補氣血] and tranquilization[安神] of the last part of the book I will be translated, and compared with the similar related comments in the book of "The Famous Prescription Comments on Ancient and Modern Times[古今名醫方論]" to review about the characteristics of formula, prescriptions notes and the relationship of these contents. In terms of formula, the order of prescriptions to strengthen Gihyeol[補氣血] could be listed from the indirectly strengthening prescriptions to the directly strengthening prescriptions. In addition, the list of prescriptions will be sequenced by following the order of weak strengthening prescriptions to the strong strengthening prescriptions. The order of tranquilization prescription must be ordered for the symptoms showing mild psychological symptoms to severe symptoms in terms of severity of symptom, and will be ordered from the prescriptions highly dependent on invigorating Gi[補氣] to the prescriptionless dependent on invigorating Gi[補氣]. In the way of controlling Premier Fire[相火], these prescriptions are ordered from the prescriptions that use indirect methods to the prescriptions that use direct methods Characteristics of the prescription notes could be mentioned that the herbs of invigorating Gi(補氣) is pivotal in strengthening Gihyeol[補氣血] and the sour flavor and pungent flavor acted as negative and positive[陰陽的] when sour flavor and pungent flavor are used to enrich liver, and that sweet flavor could easily indigested to cause abdominal distension. When comparing with the content of "The Famous Prescription Comments on Ancient and Modern Times[古今名醫方論]", it mostly adopted the content as it is, but differentiation of the formula and addition of 2 new prescriptions with their explanation in the middle of the book could be considered to be creative aspect that helped the convenience of readers.