• Mass Spectrometry Letters
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• 제4권4호
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• pp.79-82
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• 2013

Various types of alkaloids observed in several herbal medicines were analyzed by electrospray ionization tandem mass spectrometry in positive ion mode. In the present study, MS/MS spectralpatterns were investigated for eight-types of alkaloids (aporpine, protoberberine, tetrahydroprotoberberine, benzylisoquinoline, protopine, phthalide, morpine, and bisbenzylisoquinoline). For aporpine- and protoberberine-type alkaloids, main fragmentations occurred at substituted groups on rigid ring structures, not showing ring fusion. Interesting fragmentations due to iminolization and retro-Diels-Alder (RDA) reaction were observed in MS/MS spectra of protopine- and tetrahydroprotobereberine-type alkaloids. Also, several types of fragmentations such as inductive cleavage and ${\alpha}$-cleavage, or bond cleavage between two ring structures were observed depending on their structural characteristics. These fragmentation patterns are expected to allow instant classification of the specific alkaloid type in various MS/MS spectra of alkaloids.

• Journal of Microbiology and Biotechnology
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• 제8권3호
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• pp.264-269
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• 1998

Commamonas acidovorans SMN4 showed wide growth substrate spectra for various aromatic hydrocarbons. Strain SMN4 was able to grow on biphenyl producing a meta-cleavage compound, yellow 2-hydroxy-6-oxophenylhexa-2,4-dienoic acid with a spray of 2,3-dihydroxybiphenyl, while it also grew on catechol, developing yellow 2- hydroxymucoic semialdehyde with a spray of 100 mM catechol. Thus these results indicate that two-ring structures of biphenyl were cleaved by meta-mode in upper and lower pathways. Strain SMN4 metabolized various substituted biphenyl compounds and xylene to the corresponding benzoate derivatives through oxidation of the ring structures. It was clearly shown that biphenyl can be a common inducer in the oxidation of biphenyl and 2,3-dihydroxybiphenyl. Various compounds were examined for their suitability to serve as substrates for indole oxidation, indicating that biphenyl, benzoate, and succinate are quite good inducers of indigo production due to the activity of biphenyl dioxygenase. This results suggest that indigo formation is by means of the combined activities of biphenyl dioxygenase and tryptophanase.

• Bulletin of the Korean Chemical Society
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• 제10권1호
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• pp.15-19
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• 1989

Mass spectral fragmentations of some s-triazine herbicides have been investigated using tandem mass spectrometry. Major pathways driven by the side chains have been confirmed. However, most of the previously proposed pathways which were thought to be characteristic of the ring have been found unlikely. A class of ring cleavage reactions characteristic of s-triazine rings with alkylamino side chains has been found and the mechanism has been proposed. In addition, tandem mass spectrometry has been utilized to differentiate tautomeric structures and to analyze the fragmentation reactions occurring from the mixture of isobaric ions.

• Bulletin of the Korean Chemical Society
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• 제18권4호
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• pp.390-394
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• 1997

Nucleophilic substitution reactions of 2-thiopheneethyl benzenesulfonates (2-TEB) and 3-thiopheneethyl benzenesulfonates (3-TEB) with anilines and N,N-dimethylanilines (DMA) are investigated in acetonitrile at 60.0 ℃. The cross-interaction constants ρxz determined for the reactions with anilines are large negative (- 0.50) which are comparable to those for the similar predominantly frontside-attack SN2 reactions of 1-phenylethyl (1-PEB), 2-phenylethyl (2-PEB) and cumyl benzenesulfonates. A large negative ρxz value (- 0.4∼- 0.8) is considered to provide a mechanistic criterion for the frontside-attack SN2 mechanism with a four-center transition state. In agreement with this proposal the kinetic isotope effects, kH/kD, involving deuterated aniline nucleophiles are all greater than one reflecting partial N-H(D) bond cleavage in the transition state. The MO theoretical reactant structures of 1-PEB, 2-PEB and 2-TEB based on the PM3 calculation show that the benzene ring blocks the backside nucleophile approach to the reaction center carbon (Cα) enforcing the frontside-attack SN2 mechanism.

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1253-1257
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• 2011

The surface structures, adsorption conditions, and thermal desorption behaviors of cyclopentanethiol (CPT) self-assembled monolayers (SAMs) on Au(111) were investigated by scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and thermal desorption spectroscopy (TDS). STM imaging revealed that although the adsorption of CPT on Au(111) at room temperature generates disordered SAMs, CPT molecules at $50^{\circ}C$ formed well-ordered SAMs with a $(2{\surd}3{\times}{\surd}5)R41^{\circ}$ packing structure. XPS measurements showed that CPT SAMs at room temperature were formed via chemical reactions between the sulfur atoms and gold surfaces. TDS measurements showed two dominant TD peaks for the decomposed fragments ($C_5H_9^+$, m/e = 69) generated via C-S bond cleavage and the parent molecular species ($C_5H_9SH^+$, m/e = 102) derived from a recombination of the chemisorbed thiolates and hydrogen atoms near 440 K. Interestingly, dimerization of sulfur atoms in n-alkanethiol SAMs usually occurs during thermal desorption and the same reaction did not happen for CPT SAMs, which may be due to the steric hindrance of cyclic rings of the CPT molecules. In this study, we demonstrated that the alicyclic ring of organic thiols strongly affected the surface structure and thermal desorption behavior of SAMs, thus providing a good method for controlling chemical and physical properties of organic thiol SAMs.

• Mass Spectrometry Letters
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• 제4권2호
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• pp.30-33
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• 2013

Chalcones are naturally occurring, biologically active molecules generating interest from a wide range of research applications including synthetic methodology development, biological activity investigation and studying fragmentation patterns. In this article, a series of chalcones has been synthesized and their fragmentation behavior was studied using modern ambient ionization technique Direct Analysis in Real Time (DART). DART ion source connected with an ion trap mass spectrometer was used for the fragmentation of various substituted chalcones. The chalcones were introduced to the DART source using a glass capillary without sample preparation step. All the chalcones showed prominent molecular ion peaks $[M]^{{\cdot}+}$ corresponding to the structures. Multistage mass spectral data $MS^n$ ($MS^2$ and $MS^3$) were collected for all the chalcones studied. The chalcones with substitutions at 3, 4 or 5 positions gave product ion peaks with the loss of a phenyl radical ($Ph^{\cdot}$) by radical initiated ${\alpha}$-cleavage, while substitution at 2 position of chalcone in the A-ring gave a product ion peak with the loss of substituted styryl radical (PhCH = $CH^{\cdot}$). In case of the chalcones with the substituent at 4 positions in A and B rings gave both types of fragmentation patterns. In conclusion, chalcones can be easily characterized using modern DART interface in very short time and efficiently without any cumbersome sample pretreatment.

• 한국산림과학회지
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• 제16권1호
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• pp.33-62
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• 1972

리기다소나무는 미국(美國)으로부터 우리나라에 도입(導入)하여 온지 60여년(餘年)의 세월이 흐르는 동안 오늘날에는 중요(重要)한 조림수종(造林樹種)으로 발전(發展)하였고 이미 국내(國內)에서는 상당량(相當量)의 목재생산(木材生産)이 이루지고 있기 때문에 합리적(合理的)인 목재이용(木材利用)을 위(爲)해서는 그 기본적(基本的)인 성질연구(性質硏究)가 필연적(必然的)으로 요청(要請)되고 있다. 따라서 본연구(本硏究)에서는 리기다소나무의 목재해부학적(木材解剖學的), 물리학적(物理學的), 기계학적성질(機械學的性質)을 구명(究明)키로 한 것이다. 본연구(本硏究)에서 사용(使用)한 공시목(供試木)은 서울대학교(大學校) 농과대학(農科大學) 부속수원연습림내(附屬水原演習林內)에 위치(位置)하고 있는 46~52년생(年生)의 리기다소나무임분(林分)에서 정상적(正常的)으로 생장(生長)한 15개림목(個林木)을 선정(選定)하였는데 5개림목(個林木)은 해부학적(解剖學的) 연구(硏究)를 위(爲)해서 1967년(年) 2월(月)에 대채(代採)하였다. 이들 시험목(試驗木)은 간(幹), 지(枝), 근(根), 초두목(梢頭木)의 성질연구(性質硏究)를 위(爲)해서 수목(樹木)의 모든 재부분(材部分)을 채취(採取)하였다. 이 연구(硏究)의 해부학적성질(解剖學的性質)에 있어서는 연륜(年輪), 수지구(樹脂溝), 방사조직(放射組織), 가도관(假導管), 방사가도관(放射假導管), 방사유세포(放射柔細胞) 및 막공등(膜孔等)의 육안적(肉眼的) 현미경적특징(顯微鏡的特徵)이 재부분(材部分)(간(幹), 지(枝), 근(根), 초두목(梢頭木))별(別)로 관찰(觀察)하고 측정(測定)하였다. 물리적(物理的) 그리고 기계적성질(機械的性質)에 있어서는 생재함수율(生材含水率), 목재비중(木材比重), 수축율(收縮率), 섬유평행방향(纖維平行方向)의 압축강도(壓縮强度), 섬유평행(纖維平行) 및 직각방향(直角方向)의 인장강도(引張强度), 경단(徑斷) 및 촉단방향(觸斷方向)의 전단강도(剪斷强度), 곡강도(曲强度), 할렬강도(割裂强度) 및 경도(硬度)에 관해서 연구(硏究)하였는데 본연구(本硏究)에서 얻은 결론(結論)은 다음과 같다. 1. 목재(木材)의 육안적성질(肉眼的性質)에 있어서 재부분간(材部分間)에 비교(比較)할수 있는 특성(特性)은 연륜(年輪)의 판명도(判明度), 연륜폭(年輪幅), 춘추재간(春秋材間)의 이행(移行), 재색등(材色等)이 가장 중요(重要)한 것이었다. 또 현미경적성질(顯微鏡的性質)에 있어서는 목재구성요소(木材構成要素)의 크기가 재부분간(材部分間)을 비교(比較)할수 있는 특징(特徵)이 되는데 가도관(假導管)의 장(長), 폭(幅), 막후(膜厚), 수지구(樹脂溝), 방사조직등(放射組織等)이 중요(重要)한 것이었다. 2. 재부분간(材部分間)에 비교(比較)된 현미경적특성(顯微鏡的特性)은 간재(幹材)와 초두목간(梢頭木間)에 비슷한 결과(結果)를 나타내었으나 근재(根材)는 촉단면상(觸斷面上)에서 다른 재부(材部)와 비교(比較)하여 일층(一層) 큰 방사조직(放射組織)이 관찰측정되었는데 단열방사조직최대(單列放射組織最大)의 것은 높이 27세포고(細胞高)($550{\mu}$)에 폭(幅)은 $35{\mu}$이었다. 그리고 방추상방사조직(紡錘狀放射組織)은 1~수개(數個)의 수평수지구(水平樹脂溝)를 내포(內包)하는 연합방사조직(連合放射組織)을 형성(形成)한다. 한편 지재(枝材)에 있어서 조직(組織)의 특징(特徵)은 간재(幹材)와 같았으나 구성요소(構成要素)의 측정치(測定値)가 다른 재부(材部)에 비(比)하여 일층(一層) 작었다. 3. 재부분간(材部分間)에 측정(測定)된 가도관(假導管)의 크기는 간재(幹材)에서 길이가 가장 길었고 지재(枝材)에서 가장 짧았다. 재부분가도관장간유의차(材部分假導管長間有意差)를 검정(檢定)한바 간재(幹材)와 근재간(根材間)에만 차이(差異)가 없었고 기타재부분간(基他材部分間)에는 모두 차이(差異)가 있었다. 가도관폭(假導管幅)은 근재부분(根材部分)이 가장 넓었고 지재부분(枝材部分)이 가장 좁았으나 재부분간(材部分間)에는 차이(差異)가 없었다. 막후(膜厚)는 근재(根材)가 가장 두꺼웠고 지재(枝材)가 가장 좁았는데 재부분간(材部分間)에는 근재(根材)와 초두목간(梢頭木間), 근재(根材)와 지재간(枝材間) 또 간재(幹材)와 지재간(枝材間)에는 차이(差異)가 있었으나 기타재부분간(基他材部分間)에는 차이(差異)가 없었다. 4. 입목(立木)의 생재함수율(生材含水率)은 초두목(梢頭木)이 가장 높았고 간재(幹材)의 심재부분(心材部分)이 가장 낮았다. 재부분별(材部分別) 함수량간유의차(含水量間有意差)를 검정(檢定)한바 초두목(梢頭木)과 기타재부분간(基他材部分間), 심재(心材)와 기타재부분간(基他材部分間)에 차이(差異)가 있었으나 근재(根材)와 지재간(枝材間) 그리고 근재(根材)와 변재간(邊材間)에는 차이(差異)가 없었다. 5. 목재(木材)의 비중(比重)은 간재(幹材)가 가장 높았고 다음은 근재(根材), 지재(枝材)의 순(順)이고 초두목(梢頭木)은 가장 낮았다. 재부분비중간유의차(材部分比重間有意差)를 검정(檢定)한바 간재(幹材)와 다른 재부분(材部分) 사이에는 뚜렷하게 차이(差異)가 있으며 근재(根材)와 지재(枝材)사이에는 차이(差異)가 없었고 초두목(梢頭木)은 제일작은 치(値)로서 유의차(有意差)가 인정(認定)된다. 6. 함수율(含水率) 14%때 재부분간(材部分間)의 섬유평행방향압축강도(纖維平行方向壓縮强度)를 비교(比較)하면 가장 높은 강도(强度)는 간재(幹材)에서 나타났고 다음은 지재(枝材), 근재(根材)의 순(順)이고 초두목(梢頭木)은 가장 낮은 강도(强度)를 나타내었다. 7. 함수율(含水率) 14%때 재부분간(材部分間)의 곡강도(曲强度)를 비교(比較)하면 지재(枝材)에서 뚜렷하게 높은 강도(强度)를 나타내었으며 다음은 간재(幹材), 지재(枝材), 근재(根材)의 순(順)이고 초두목(梢頭木)은 가장 낮은 강도(强度)를 나타내었다. 특(特)히 지재(枝材)는 간재(幹材)보다 낮은 비중(比重)을 갖이고 있었는데도 불구(不拘)하고 높은 곡강도(曲强度)를 나타내었다.