• 제목/요약/키워드: chemical ionization

검색결과 409건 처리시간 0.024초

Alkylation and Allylation of Lithium Arylborates Factors Affecting the Di/Mono Substitution Ratio$^\dag$

  • 이호성;송양섭;이동두
    • Bulletin of the Korean Chemical Society
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    • 제8권5호
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    • pp.424-425
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    • 1987
  • Alkylation and allylation of arylborates give mono(ipso) and/or di(ortho and ipso) substitution products. Those factors which promote polarization or ionization of alkylating agents favor di substitution. The ${\sigma}$-type(ipso) substitution reaction of arylborates involves direct interaction of the carbon-boron bonds rather than predissociation of arylborates into aryllithiums and boranes.

전기 분무 이온화를 이용한 단백질 질량분석용 마이크로 유체 소자의 제작 및 실험 (Sheathless electrospray ionization with integrated metal emitter on microfluidic device)

  • 김민수;주황수;이국녕;김병기;김용권
    • 대한전기학회:학술대회논문집
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    • 대한전기학회 2004년도 하계학술대회 논문집 C
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    • pp.2102-2104
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    • 2004
  • In this study, sheathless electrospray from PDMS/glass microchips with conducting metal emitter tip is described. A chip-based capillary electrophoresis/mass spectrometry (CE/MS) system has advantages of the CE separation and on-line electrospray detection of peptide solution. We have fabricated a new electrospray ionization(ESI) device composed of the metal emitter tip and CE separation channel monolithically in a glass microchip. The separation channel and metal emitter tip are fabricated using a glass wet etching and gold electro plating process, respectively. The fabricated micro electrospray chip was tested by spraying peptide sample for mass spectrometric analysis. Singlely-charged peak and doublely-charged peak of peptide were detected and further MS/MS fragmentation was performed in each peak. Direct comparisons with conventional glass or fused silica emitters showed very similar performance with respect to signal strength and stability.

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Rapid Detection of Trace 1,4-Dichlorobenzene Using Laser Mass Spectrometry

  • Ding, Lei;Ma, Jing;Zheng, Haiyang;Fang, Li;Zhang, Weijun;Kim, Duk-Hyeon;Cha, Hyung-Ki
    • Bulletin of the Korean Chemical Society
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    • 제27권9호
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    • pp.1393-1396
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    • 2006
  • The 1+1 two-photon Resonant Enhanced Multiphoton Ionization (REMPI) spectra of 1,4-dichlorobenzene was obtained from 240 nm through to 250 nm on a laser mass spectrometer. Special care was taken to build up a heatable sample inlet system suitable for detecting a trace semi-volatile organic compound and reducing the memory effort on the inner wall of the inlet system. The detection limits of 1,4-dichlorobenzene in ppbV/V concentration range at certain wavelengths are presented.

Matrix-Assisted Variable Wavelength Laser Desorption Ionization of Peptides; Influence of the Matrix Absorption Coefficient on Expansion Cooling

  • Ahn, Sung-Hee;Bae, Yong-Jin;Kim, Myung-Soo
    • Bulletin of the Korean Chemical Society
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    • 제33권9호
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    • pp.2955-2960
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    • 2012
  • Product ion yields in the in- and post-source decays of three peptide ions, $[Y_5X+H]^+$ (X = Y (tyrosine), K (lysine), and R (arginine)), generated by matrix-assisted laser desorption ionization (MALDI) were measured at six wavelengths, 307, 317, 327, 337, 347, and 357 nm, using ${\alpha}$-cyano-4-hydroxycinnamic acid (CHCA) and 2,5-dihydroxybenzoic acid (DHB) as the matrices. The temperatures of the early and late plumes generated by MALDI were estimated via kinetic analysis of the product ion yield data. For both matrices, the temperature drop (${\Delta}T$), i.e. the difference in the temperature between the early and late plumes, displayed negative correlation with the absorption coefficient. This was in agreement with the previous reasoning that deeper laser penetration and larger amount of material ablation arising from smaller absorption coefficient would result in larger extent of expansion cooling. The results support the postulation of the expansion cooling occurring in the plume presented previously.

MALDI Mass Spectrometric Analysis of Nonderivatized Steroids Using Cyclodextrin-supported 2,5-Dihydroxybenzoic Acid as Matrix

  • Son, Jeongjin;Cha, Sangwon
    • Bulletin of the Korean Chemical Society
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    • 제35권5호
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    • pp.1409-1412
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    • 2014
  • Sex hormones are important metabolites in vertebrates' development and reproduction. For rapid screening sex hormones, matrix-assisted laser desorption/ionization (MALDI) mass spectrometry (MS) is one of the promising analytical platforms, but MALDI MS faces many challenges in detecting steroids such as low ionization efficiency and matrix background interference. One potential strategy to overcome matrix interference in the low m/z region is using a cyclodextrin (CD)-supported matrix for steroid analysis since CD-supported matrixes are known to effectively suppress matrix-related ion signals. In this study, we aimed to find the optimal CD-supported matrix for the analysis of the nonderivatized sex steroids. Our results showed that the ${\alpha}CD$-supported 2,5-dihydroxybenzoic acid (DHB) matrix efficiently ionized all three major classes of sex hormones, estrogens, androgens, and progestagens, with low or no matrix background and also with high sensitivity. In addition, the ${\alpha}CD$-supported DHB matrix mainly generated molecular ions or protonated ions of sex hormones, and this enabled us to obtain information-rich tandem mass spectra which potentially lead to unambiguous identification of steroid species from complex metabolite mixtures.

Suppression of the Methyl Radical Loss from Acetone Cation within (CH3COCH3)n{CH3COCH3}+ Clusters

  • Lee, Yong-Hoon;Oh, Myoung-Kyu;Choi, Sung-Chul;Ko, Do-Kyeong;Lee, Jong-Min
    • Bulletin of the Korean Chemical Society
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    • 제29권8호
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    • pp.1519-1524
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    • 2008
  • We have investigated the photophysics of the acetone radical cation in the vacuum ultraviolet energy region by multiphoton ionization combined with time-of-flight mass spectrometry in a cluster beam. We have found that the loss of methyl radical from the acetone radical cations is remarkably suppressed at 10.5 eV when they are solvated by a few neutral acetone molecules. The cluster ion mass spectra obtained by nanosecond and picosecond laser pulses reveal that there are intermolecular processes, occurring in several tens of picoseconds, which are responsible for the survival of the acetone cations in clusters. This remarkable solvation effect on the yield of the methyl radical loss from the acetone cation can be rationalized by the intracluster vibrational energy redistribution and the self-catalyzed enolization which compete with the methyl radical loss process.

Discrimination of Bacillus anthracis Spores by Direct in-situ Analysis of Matrix-Assisted Laser Desorption/Ionization Time-Of-Flight Mass Spectrometry

  • Jeong, Young-Su;Lee, Jonghee;Kim, Seong-Joo
    • Bulletin of the Korean Chemical Society
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    • 제34권9호
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    • pp.2635-2639
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    • 2013
  • The rapid and accurate identification of biological agents is a critical step in the case of bio-terror and biological warfare attacks. Recently, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry has been widely used for the identification of microorganisms. In this study, we describe a method for the rapid and accurate discrimination of Bacillus anthracis spores using MALDI-TOF MS. Our direct in-situ analysis of MALDI-TOF MS does not involve subsequent high-resolution mass analyses and sample preparation steps. This method allowed the detection of species-specific biomarkers from each Bacillus spores. Especially, B. anthracis spores had specific biomarker peaks at 2503, 3089, 3376, 6684, 6698, 6753, and 6840 m/z. Cluster and PCA analyses of the mass spectra of Bacillus spores revealed distinctively separated clusters and within-groups similarity. Therefore, we believe that this method is effective in the real-time identification of biological warfare agents such as B. anthracis as well as other microorganisms in the field.

기체 크로마토그래프-질량분석법을 이용한 뇨중 비스테로이드성 소염진통제 (NSAIDs)의 동시 분석법 (Simultaneous Analysis of Several Non-Steroidal Anti-Inflammatory Drugs in Urine by Gas Chromatograph/Negative Chemical Ionization-Mass Spectrometry)

  • 명승운;박준호;김명수;조현우
    • 분석과학
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    • 제12권6호
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    • pp.571-576
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    • 1999
  • 소변 시료에서 비스테로이드성 소염진통제 (Non-Steroidal Anti-Inflammatory Drugs)인 Fenamates 부류의 6종에 대해서 pentafluoropropionyl 유도체화 반응을 통하여 Gas Chromatograph/Negative Chemical Ionization-Mass Spectrometer에 감응도가 높은 유도체를 만들었다. 6종의 소염 진통제 약물에 대하여 반응성이 좋은 유도체화 반응 조건과 크로마토그래피 조건을 설정하였으며 이들 약물은 동시에 분석 가능하였고 검출한계가 4-25 pg/mL 이어서 경마 경기에서 자주 사용되고 있는 NSAIDs의 미량 성분에 대한 검출 및 법과학에서의 응용이 가능하다.

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이온화를 고려한 Arcjet 추력기의 화학 평형 유동 및 성능해석 (Chemical Equilibrium Flow and Performance Analysis of the Arcjet Thruster with Ionization Effects)

  • 신재렬;오세종;최정열
    • 한국추진공학회:학술대회논문집
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    • 한국추진공학회 2005년도 제25회 추계학술대회논문집
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    • pp.132-135
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    • 2005
  • 하이드라진을 추진제로 쓰는 아크젯 추력기 내의 열화학적 유동장을 전산유체를 이용해 해석하였다. Ohm가열 및 Lorentz힘을 고려하기 위하여 Maxwell 방정식과 연계된 RANS 방정식을 이용하였으며, 매우 빠른 반응 및 광학적으로 두꺼운 매질을 가정하여 이온화와 열복사를 해석에 포함하였다. 해석의 결과는 아크젯 추력기 내부 유동의 열-물리적 이해와 더불어 0.6 kW 가열에 의하여 하였을 때 추력과 비추력이 각각 20%와 70%가 향상됨을 보여주었다.

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Electronic Photodepletion Spectroscopy of Dibenzo-18-crown-6 with a Potassium Ion

  • Kim, Hwan-Jin;Shin, Won-Jik;Choi, Chang-Min;Lee, Jun-Ho;Kim, Nam-Joon
    • Bulletin of the Korean Chemical Society
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    • 제29권10호
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    • pp.1973-1976
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    • 2008
  • Electronic photodepletion spectrum of dibenzo-18-crown-6 with a potassium ion ($K^+$-DB18C6) was obtained in the gas phase using electrospray ionization and quadrupole ion-trap reflectron time-of-flight mass spectrometry. The spectrum exhibited rather a broad absorption band at 36350 $cm^{-1}$, which was tentatively assigned as the origin of the S1 band. The photodepletion spectrum of $Cs^+$-DB18C6 was also obtained to elaborate the effects of metal cations on electronic and geometric structures of metal cation-DB18C6 complexes. We found that the S1 band of $Cs^+$-DB18C6 was red-shifted by 180 $cm^{-1}$ from that of $K^+$-DB18C6. With the results of quantum theoretical calculations using the density functional theory, we suggested that the red-shift arose mainly from weaker binding of $Cs^+$ to DB18C6 than that of K+, which resulted from a larger size of $Cs^+$ than that of the cavity in DB18C6.