새로운 Sulfonamide 유도체의 합성과 Acetolactate Synthase(ALS) 저해

신정휴,최정도,채종근,이재섭 한국농화학회 1998 Applied Biological Chemistry (Appl Biol Chem) Vol.41 No.1

Triazolopyrimidine sulfonanilide (TP) derivative is one of excellent herbicide compounds. We have synthesized three classes of a new sulfonamide derivative (TPP) as Acetolactate synthase (ALS) inhibitors, in which the benzene ring in TP skeleton was converted to substituted pyrimidyl ring and examined their inhibitory activities on barley for ALS. I_(50) values of the inhibitors ranged from 0.005 to 2 mM. Comparing the I_(50) value of each class of TPP derivatives, the substituents in pyrimidine and triazolopyrimidine ring were found to affect the degree of ALS inhibition. TPP with substituted methyl group in pyrimidine ring showed higher inhibitory activity than that with methoxy group, while the substitution of the cyclopentano group in triazolopyrimidine ring gave very large inhibitory activity than that of methyl group. The present study established that variation of the electron density by substitution at heterocyclic ring is a very important factor for ALS inhibition, but showed no dependence on steric effect by substituents.

Study on Relative Stability of Geometrically Constrained Cyclopropylcarbinyl Cation by $^{19}$F-NMR Spectroscopy

신정휴,윤보현,Jung Hyu Shin,Bo Hyeon Yoon Korean Chemical Society 1985 대한화학회지 Vol.29 No.3

고정된 사이크로 프로판환을 가진 양이온계에서 구조적 변화에 따른 상대적 안정도를 불소 19-핵자기공명분광기로 분석 검토했다. 이를 위해 8-파라-불화벤젠트리사이크로 옥탄 양이온과 9-파라불화벤젠 트리사이크로 노난 및 10-파라불화벤젠 트리사이크로데칸 양이온을 해당알코올과 불화황산과의 반응에서 얻었다. 풀루오르 19-NMR 스펙트럼에서 얻어진 결론은 사이크로프로판환이 양이온 탄소의 궤도와 ${\sigma}$ 컨쥬게이션을 위해 대칭적이며 바이섹트 구조의 유지가 하전의 안정화에 매우 중요한 요인인 반면, 사이크로 프로판기의 면과 양하전을 띈 탄소와 연결되는 결합각도(${\theta}$)의 변화는 하전의 안정화에 영향이 없음을 보여주었다. The relative stability as a function of geometry in rigid cyclopropylcarbinyl cations was examined by $^{19}$F-nmr spectroscopy. 8-p-Fluorophenyl-tricyclo[3.3.1.0$^{2,7}$]octane-8-yl-(I), 9-p-fluorophenyl-tricyclo[3.3.1.0$^{2,8}$]nonane-9-yl (II), and 10-p-fluorophenyl-tricyclo[4.3.1.0$^{2,9}$]decane-10-yl cation(Ⅲ) were prepared from the corresponding carbinols in FSO$_3$H-SO$_2$ClF solution at -120$^{\circ}C$. $^{19}$F-nmr data indicate that the symmetrical bisected geometry of cyclopropane ring for ${\sigma}$-conjugation is a very impotant factor in charge delocalization. However, varied orientation of the bond angle ${\theta}$ within the bisected conformation does not affect the charge delocalization into the cyclopropane ring.

Study on Structure of 9-Barbaralyl Cation by 1$^{13}C$ NMR Chemical Shift

신정휴,안양수,Jung-Hyu Shin,Yang-Soo Ahn Korean Chemical Society 1987 대한화학회지 Vol.31 No.2

The structure of 9-barbaralyl cation was examined by Hammett-Brown plot using $^{13}C$ NMR chemical shifts. 9-Aryltricylclo$[3.3.1.0^{2,8}]$]nonan-9-yl cation (5) and 9-aryltricyclo-$[3.3.1.0^{2,8}]$nona-3,6-dien-9-yl cation (6) were prepared from the corresponding carbinols in $FSO_3H-SO_2ClF$ solution at -$120^{\circ}C$, and their chemical shifts of cation centers were measured. The slopes, ${\rho}^{C+}$ values, of the Hammett-Brown plot of (5) and (6) were -5.01 and -7.52, respectively. From these values themselves, it seemed that the double bonds participated in the delocalization of the positive charge. However, comparing ${\rho}^{C+}$ value and ${\rho}^{C_a^+}$ value in 9-barbaralyl cation (6) and those in 8,9-dehydroadamantyl cation (7), we concluded that 9-barbaralyl should be represented by the structure 4 shown in Scheme I. 9-바바라릴 양이온의 구조를 탄소-13 핵자기공명을 이용한 Hammett-Brown식을 이용해서 조사하였다. 이를 위하여 9-아릴트리시클로$[3.3.1.0^{2,8}]$노난 (5) 및 9-아릴트리시클로 $[3.3.1.0^{2,8}]$노나-3,6-디엔 (6)계 양이온을 영하 $120^{\circ}C$에서 해당 알코올과 불화황산과의 반응에서 얻었고 양하전 탄소에 대한 화학적이동이 측정되었다. 양이온 5와 6에 대한 Hammett-Brown식의 기울기, 즉 ${\rho}^{C+}$값은 각각 -5.01과 -7.52였다. 이들 값의 결과로만 보면 이중결합의 영향이 있는 것처럼 보인다. 그러나, 9-바바라릴과 8, 9데히드로아다만틸 양이온들의 ${\rho}^{C+}$와 ${\rho}^{C_a^+}$ 값들을 비교한 결과에서 9-바바라릴 양이온도 도표 1에서의 4의 구조를 가져야 된다는 결론을 얻어냈다.

한문과(漢文科) Courseware 개발(開發) : 한시(漢詩) 학습(學習)을 중심(中心)으로

신정휴 한국한자한문교육학회 1997 漢字 漢文敎育 Vol.3 No.-

漢詩의 나타난 文藝美 : 自然詩를 중심으로

申貞休 청주대학교 한문교육과 1984 淸大漢林 Vol.3 No.-

漢詩에 나타난 文藝美

申貞休 淸州大學校 漢文敎育科 1984 淸大漢林 Vol.3 No.1

Low Temperature NMR Study on p-Fluorophenylthioxanthylium Ions

안양수,신정휴,Yang-Soo Ahn,Jung-Hyu Shin Korean Chemical Society 1982 대한화학회지 Vol.26 No.3

티오크잔틸이움 이온과 안트라센이움 이온은 동리평면성의 구조를 가진다. 그러므로 이 양이온들에서 양전하 중심부의 빈 $P_z$-궤도는 융합된 벤젠고리의${\pi}$-궤도와 겹쳐진다. 이 양이온들은 Huckel의 (4n + 2)${\pi}$ 법칙에 따라 방향족성을 가진다. 방향족성의 안정화에 황원자가 기여하는 것은 티오크잔틸이움 이온과 안트라센이움 이온의 ${^19F}$핵자기 공명의 화학적 이동의 비교로 평가되었다. The thioxanthylium ion ard anthracenium ion have coplanar geometries. The empty $P_z$-orbitals of the positive centers in the cations, therefore, overlap with the ${\pi}$-orbitals of the fused benzen rings. These cations have aromatic characters, obeying Huckel's (4n + 2)${\pi}$ rule. The contribution of the sulfur atom to aromatic stabilization was estimated by comparing the ${^19F}$-nmr chemical shifts of the thioxanthylium ions and anthracenium ions.

Chemical Modification and Feedback Inhibition of Arabidopsis thaliana Acetolactate Synthase

홍성택,최명언,신정휴,고은희,Hong, Seong-Taek,Choi, Myung-Un,Shin, Jung-Hyu,Koh, Eun-Hie 한국응용생명화학회 1997 Applied Biological Chemistry (Appl Biol Chem) Vol.40 No.4

아라비돕시스 탈리아나의 아세토락테이트 합성 효소 (ALS)를 그 유전자를 포함하고 있는 대장균 MF 2000/pTATX로부터 부분 정제하였다. 부분 정제된 이 효소를 가지고 여러 가지 변형 화학물질들 즉, 요오드아세트산, 요오드아세타마이드, N-에틸말레이미드 (NEM), 5,5'-디티오비스(2-니트로벤조산) (DTNB), 파라염화수은벤조산 (PCMB), 그리고 페닐글리옥살 등에 대한 민감성을 조사하였다. PCMB가 가장 민감하게 저해를 했으며, DTNB와 NEM이 그 뒤를 따랐다. 이 효소의 기질인 피루브산이 요오드아세트산에 의한 활성 저해를 보호하지 못하였으므로 기질의 결합에 시스테인의 관련이 없는 것 같이 보인다. 한편, 기질이 페닐글리옥살에 의한 효소의 활성 저해를 부분적으로 보호하는 것으로 보아 기질이 아르기닌기와 상호 작용함을 암시하고 있다. 부분 정제된 효소는 발린과 이소루신에 민감하게 방해를 받았으나 루신은 그렇지 않았다. 그러나, PCMB로 변형시킨 효소는 되먹임 방해를 더 강하게 받았다. 그 외 ALS에 대한 새로운 제초제 후보인 피리미디설퍼 벤조산 유도체의 저해 효과를 검토하였다. Acetolactate synthase (ALS) was partially purified from Escherichia coli MF2000/pTATX containing Arabidopsis thaliana ALS gene. The partially purified ALS was examined for its sensitivity toward various modifying reagents such as iodoacetic acid, iodoacetamide, N-ethylmaleimide (NEM), 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB), p-chloromercuribenzoic acid (PCMB), and phenylglyoxal. It was found that PCMB inhibited the enzyme activity most strongly followed by DTNB and NEM. Since iodoacetic acid did not compete with substrate pyruvate, it appeared that cysteine is not involved in the substrate binding site. On the other hand, the substrate protected the enzyme partly from inactivation by phenylglyoxal, which might indicate interaction of arginine residue with the substrate. The partially purified enzyme was inhibited by end products, valine and isoleucine, but not by leucine. However, the ALS modified with PCMB led to potentiate the feedback inhibition of all end products. Additionally, derivatives of pyrimidyl sulfur benzoate, a candidate for a new herbicide for ALS, were examined for their inhibitory effects.

Evaluation of bio-compatibility for new bio-material in use of corneal therapies

문형호,조익준,신정휴,여형수,조영낭,박연주,김진아,장하영,강길태,최재준,박철용,이병한,최우성,현병화 한국실험동물학회 2016 한국실험동물학회 학술발표대회 논문집 Vol.2016 No.08

아라비돕시스 탈리아나 Acetolactate Synthase의 화학적 변형과 되먹임 방해

홍성택,최명언,신정휴,고은희 ( Seongtaek Hong,Myung Un Choi,Jung Hyu Shin,Eun Hie Koh ) 한국응용생명화학회 1997 Applied Biological Chemistry (Appl Biol Chem) Vol.40 No.4

Acetolactate synthase (ALS) was partially purified from Escherichia coli MF2000/pTATX containing Arabidopsis thaliana ALS gene. The partially purified ALS was examined for its sensitivity toward various modifying reagents such as iodoacetic acid, iodoacetamide, N-ethylmaleimide (NEM), 5,5`-dithiobis(2-nitrobenzoic acid) (DTNB), p-chloromercuribenzoic acid (PCMB), and phenylglyoxal. It was found that PCMB inhibited the enzyme activity most strongly followed by DTNB and NEM. Since iodoacetic acid did not compete with substrate pyruvate, it appeared that cysteine is not involved in the substrate binding site. On the other hand, the substrate protected the enzyme partly from inactivation by phenylglyoxal, which might indicate interaction of arginine residue with the substrate. The partially purified enzyme was inhibited by end products, valine and isoleucine, but not by leucine. However, the ALS modified with PCMB led to potentiate the feedback inhibition of all end products. Additionally, derivatives of pyrimidyl sulfur benzoate, a candidate for a new herbicide for ALS, were examined for their inhibitory effects.