CRYSTAL AND MOLECULAR STRUCTURES AND MS ANALYSE OF beta-CARBOXYLETHYL (OR alpha-METHYLETHYL) GERMANIUM TRICHLORIDES

This paper reports the results of the crystal and molecular structures, CI-MS and FAB-MS analyse of Cl3GeCH2CH2COOH and Cl3GeCH(CH3)CH2COOH. The characters and active parts of these molecules are also discussed

Determination of multiple trace elements in seawater using chelation ion chromatography and ICP-MS

An off-line chelation system combined with ICP-MS technique was developed for the quantitative determination of trace elements in seawater, namely V, Co, Ni, Cu, Zn, Mo, Cd, Pb, U and rare earth elements(REEs). The system was built based on an ion chromatography equipped with MetPac((R)) CC-I chelation columns which had a strong selective chelation to these target elements within a pH range 5.2-5.6. Acidified seawater samples and NH4Ac(2 mol/L) were blended to meet suitable pH before being injected into the chelation column, thus target elements were retained while alkali and alkaline metals were excluded. Then chelated elements were eluted by HNO3 (1 mol/L) and samples were collected for ICP-MS analysis. Varying the ratio of input( gen. 200 mL) to output( gen. 5 mL), the target elements which were concentrated as 40 times as their concentrations were far beyond instrumental quantification limits. At last, a certificated seawater CASS-4 was introduced and our detected values were in good agreement with those certified values.

GC-MS法测定藏木香栽培品种挥发油的化学成分

[目的]基于气相色谱-质谱（GC-MS）法测定藏木香栽培品种挥发油的化学成分。[方法]采用水蒸气蒸馏法从藏木香栽培品种中提取挥发油,并用GC-MS联用仪对其挥发油的化学成分进行研究。[结果]分离并确认了37种成分,其主要成分是桉叶油二烯5,11（13）-内酯-8,12,异-榄香烯,异-喇叭烯,桉叶油二烯4,11（13）-内酯-8,12。[结论]分析获得的主要化学成分及其功效为藏木香这一天然药用植物资源的人工规范化栽培和进一步综合开发利用提供了科学依据。

藏药帕朱胶囊超临界CO_2萃取成分的GC-MS分析

目的：分析治疗胃病常用的藏成药帕朱胶囊（寒水石,诃子,石榴子,胡椒,荜拔等）的主要化学成分。方法：采用超临界CO_2萃取方法提取帕朱胶囊的可溶性成分,并用气相色谱-质谱联用法对提取部位进行化学成分分析,峰面积归一化法计算各组分的相对含量。结果：共分离鉴定了22种化合物,主要成分含量为胡椒碱44.2%、亚油酸21.1%、甲基-甲撑基奥-异丙烯内酯10.5%、棕榈酸4.8%和γ-羟基-榄香烯酸内酯3.5%等。结论：藏药帕朱胶囊的主要化学成分为胡椒碱和亚油酸,两者含量共占全部提取物的65.3%

藏药材石榴籽超临界CO_2萃取成分的GC-MS分析

目的：用新方法提取藏药材石榴籽油,并对其进行化学成分分析,为石榴籽的药理研究和应用提供实验依据。方法：采用超临界CO_2萃取方法提取石榴籽的可溶性成分,并用气相色谱-质谱联用法对提取部位进行化学成分分析,峰面积归一化法计算各组分的相对含量。结果：共分离鉴定了10种化合物,主要成分含量为亚油酸40.0%、油酸22.7%、棕榈酸17.5%、硬脂酸9.0%及共轭亚油酸5.7%。结论：藏药材石榴籽的主要化学成分为亚油酸和油酸,两者含量共占全部提取物的62.7%。

藏药蕨麻油脂化合物的GC-MS分析

蕨麻,藏医谓之卓老沙曾,原植物为蔷薇科委陵菜属鹅绒委陵菜Potentilla anserine L.,为多年生草本.在高海拔地区蕨麻根的中下部形成块根,在温暖低平地区不形成膨大的块根[1].蕨麻全草入药,收敛止血,止咳利痰,治各种出血及下痢.块根入药,有健脾益胃、生津止渴、益气补血功效;治脾虚、腹泻、产后贫血、营养不良等症[2].

HPLC-APCI-MS法分析测定白刺籽油中游离脂肪酸

利用荧光衍生试剂1,2-苯并-3,4-二氢咔唑-9-乙基对甲苯磺酸酯(BDETS)作为脂肪酸柱前衍生化试剂,采用梯度洗脱在Eclipse XDB-C_8色谱柱上对游离脂肪酸(FFA)(油酸、亚油酸、软脂酸和硬脂酸)衍生物进行分离.利用柱后在线的串联质谱以大气压化学电离源(APCI)正离子模式实现了各组分的质谱定性.荧光检测的激发和发射波长分别为λ_(ex)=333 nm,λ_(em)=390 nm.脂肪酸的线性回归系数大于0.9990,检出限为3.38～6.59 nmol/L.建立的方法具有良好的重现性.利用此方法对超临界CO_2提取的唐古特白刺籽油中几种游离脂肪酸进行了分析.结果表明白刺籽油中含有大量的游离不饱和脂肪酸.

3种绿绒蒿挥发油化学成分的GC-MS分析

目的 分析全缘叶绿绒蒿、五脉绿绒蒿和多刺绿绒蒿挥发油的化学成分.方法 采用水蒸气蒸馏法获得挥发油,经GC-MS技术结合计算机检索对其化学成分进行分离和鉴定,用色谱峰面积归一化法计算各组峰的相对含量.结果 从全缘叶绿绒蒿、五脉绿绒蒿和多刺绿绒蒿的挥发油中分别鉴定了25,42和53个化合物,占其各自总量的80.76%,73.34%和76.10%.结论 3种绿绒蒿挥发油化学成分存在一定程度的差异,但其主要成分都为酯类物质

唐古特白刺籽油的超临界CO_2流体萃取及GC／MS分析

利用超临界CO_2萃取唐古特白刺籽油，并对籽油进行了GC／MS分析。实验确定的最佳超临界CO_2流体萃取条件是:萃取温度45℃，萃取压力20 MPa，CO_2流量为35-40 kg／h，萃取时间120min，在此条件下白刺籽油的萃取率为15.11％。利用GC／MS对白刺籽油分析，发现其不饱和脂肪酸的相对含量高达93.37％。比较了超临界CO_2萃取白刺籽油油样和石油醚萃取白刺籽油油样的理化性质，发现超临界CO_2流体萃取的籽油质量优于传统溶剂萃取的籽油。

LC-DAD-ESI-MS Characterization of Carbohydrates Using a New Labeling Reagent

A novel labeling reagent 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP) coupling to liquid chromatography with electrospray ionization mass spectrometry for the detection of carbohydrates from the derivatized rape bee pollen samples is reported. Carbohydrates are derivatized to their bis-NMP-labeled derivatives. Derivatives showed an intense protonated molecular ion at m/z [M+H](+) in positive-ion detection mode. The mass-to-charge ratios of characteristic fragment ions at m/z 473.0 could be used for the accurately qualitative analysis of carbohydrates. This characteristic fragment ion is from the cleavage of C2-C3 bond in carbohydrate chain giving the specific fragment ions at m/z [MH-CmH2m+1Om-H2O](+) for pentose, hexose and glyceraldehydes and at m/z [MH-CmH2m-1Om+1-H2O](+) for alduronic acids such as galacturonic acid and glucuronic acid (m = n - 2, n is carbon number of carbohydrate). No interferences for all aliphatic and aromatic aldehydes presented in natural environmental samples were observed due to the highly specific parent mass-to-charge ratio and the characteristic fragment ions. The method, in conjunction with a gradient elution, offered a baseline resolution of carbohydrate derivatives on a reversed-phase Hypersil ODS-2 column. The carbohydrates such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose and fucose can successfully be detected.

Analysis of carbohydrates in a tibetan medicine using new labeling reagent, 1-(2-naphthyl)-3-methyl-5-pyrazolone, by HPLC with DAD detection and ESI-MS identification

A new labeling reagent, 1-(2-naphthyl)-3-methyl-5-pyrazolone (NMP), coupling with liquid chromatography (LC) with electrospray ionization mass spectrometry (ESI-MS) for the detection of carbohydrates from a famous Tibetan medicine is reported. Carbohydrates were derivatized to their bis-NMP-labeled derivatives. The method, in conjunction with a gradient elution, offered a baseline resolution of carbohydrate derivatives on a reversed phase Hypersil ODS-2 column. The carbohydrates such as mannose, galacturonic acid, glucuronic acid, rhamnose, glucose, galactose, xylose, arabinose, and fucose could be successfully detected by UV and ESI-MS. Derivatives showed intense protonated molecular ion at m/z [M+H]+ in positive ion mode. The mass to charge ratios of characteristic fragment ions at m/z 473.0 could be used for the accurately qualitative identification of carbohydrates; this characteristic fragment ion was from the cleavage of C2-C3 bond in the carbohydrate chain giving the specific fragment ions at m/z [MH-CmH2m+1Om-H2O](+) for pentose, hexose, and glyceraldehydes, and at m/z [MH-CmH2m-1Om+1-H2O](+) for alduronic acids, such as galacturonic acid and glucuronic acid (m=n-2, n is carbon atom number of carbohydrate). Compared with the traditional 1-phenyl-3-methyl-5-pyrazolone (PMP) reagent, currently synthesized NMP show the advantage of higher sensitivity to carbohydrate compounds with UV and ESI-MS detection.

Analysis of primary aromatic amines using precolumn derivatization by HPLC fluorescence detection and online MS identification

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and 2-(9-acridone)-acetic acid (AAA), two novel precolumn fluorescent derivatization reagents, have been developed and compared for analysis of primary aromatic amines by high performance liquid chromatographic fluorescence detection coupled with online mass spectrometric identification. PPIA and AAA react rapidly and smoothly with the aromatic amines on the basis of a condensation reaction using 1-ethyl-3-(3dimethylaminopropyl)-carbodiimide (EDC) as dehydrating catalyst to form stable derivatives with emission wavelengths at 380 and 440 nm, respectively. Taking six primary aromatic amines (aniline, 2-methylaniline, 2-methoxyaniline, 4-methylaniline, 4-chloroaniline, and 4-bromoaniline) as testing compounds, derivatization conditions such as coupling reagent, basic catalyst, reaction temperature and time, reaction solvent, and fluorescent labeling reagent concentration have also been investigated. With the better PPIA method, chromatographic separation of derivatized aromatic amines exhibited a good baseline resolution on an RP column. At the same time, by online mass spectrometric identification with atmospheric pressure chemical ionization (APCI) source in positive ion mode, the PPIA-labeled derivatives were characterized by easy-to-interpret mass spectra due to the prominent protonated molecular ion m/z [M + H](+) and specific fragment ions (MS/MS) m/z 335 and 295. The linear range is 24.41 fmol-200.0 pmol with correlation coefficients in the range of 0.9996-0.9999, and detection limits of PPIA-labeled aromatic amines are 0.12-0.21 nmol/L (S/N = 3). Method repeatability, precision, and recovery were evaluated and the results were excellent for the efficient HPLC analysis. The most important argument, however, was the high sensitivity and ease-of-handling of the PPIA method. Preliminary experiments with wastewater samples collected from the waterspout of a paper mill and its nearby soil where pollution with aromatic amines may be expected show that the method is highly validated with little interference in the chromatogram.

Determination of free fatty acids in bryophyte plants and soil by HPLC with fluorescence detection and identification by online MS

A method for the determination of long and short chain free fatty acids (FFAs), using 1-[2-(ptoluenesulfonate)-ethyll-2-phenylimidazole-[4,5-f-9,10-phenanthrene (TSPP) as labeling reagent, has been developed. Identification of FFA derivatives was carried out by HPLC-MS with atmospheric pressure chemical ionization (APCI) in positive ion mode. Gradient elution on an Agilent Eclipse XDB-C-8 column gave good separation of the derivatives. Excellent linear responses were observed and good compositional data could be obtained from as little as 200 mg of bryophyte plants and soil samples. Facile TSPP derivatization coupled with HPLC-APCI-MS analysis allowed the development of a highly sensitive method for the quantitative analysis of trace level of FFAs from biological and natural environmental samples.

Identification of phenolics and nucleoside derivatives in Gastrodia elata by HPLC-UV-MS

An HPLC-UV-MS method for simultaneous identification of predominant phenolics and minor nucleoside derivatives in Gastrodia elata was developed, which was based on their UV and MS characteristics summarized through a series of homemade reference standard experiments. Phenolics showed characteristic UV lambda(max) at 267 nm, [M + NH4](+) base peak in positive mode and [M - H](-) base peak in negative mode while nucleosides exhibited UV lambda(max) at 255 nm, [M + H](+), [M - H + 2H(2)O](-) or [M - H + CH3COOH](-). Phenolics conjugates mainly underwent the consecutive loss of gastrodin residue (- 268 U) and the combined loss of H2O and CO2 from the citric acid unit under negative MS/MS conditions whereas nucleosides simply lost the ribose (- 132 U) under positive MS/MS conditions. According to these characteristics, a special pattern under MS/MS conditions and reported compound data for G. elata in the literature, not only 15 phenolics were identified but also 6 nucleoside derivatives were identified. Among these compounds, seven phenolics and three nucleoside derivatives have not been reported yet from G. elata.

Determination of aliphatic amines from soil and wastewater of a paper mill by pre-column derivatization using HPLC and tandem mass spectrometry (HPLC-MS/MS)

A pre-column derivatization method for the sensitive determination of aliphatic amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by HPLC with fluorescence detection and APCI/NIS identification in positive-ion mode has been developed. The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by the 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent, BCEOC, that could easily and quickly label amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M + H](+) with APCI/MS in positive-ion mode. The collision induced dissociation of the protonated molecular ion formed characteristic fragment ions at m/z 264.1, m/z 246.0 and m/z 218.1, corresponding to the cleavages of CH2CH2O-CO, CH2CH2-OCO, and N-CH2CH2O bonds. Studies on derivatization conditions demonstrated that excellent derivatization yields close to 100% were observed with a 3 to 4-fold molar reagent excess in acetonitrile solvent, in the presence of borate buffer (pH 9.0) at 40 degrees C for 10 min. In addition, the detection responses for BCEOC derivatives were compared with those obtained with CEOC and FMOC as labeling reagents. The ratios I-BCEOC/I-CEOC and I-BCEOC/I-FMOC were, respectively, 1.40-2.76 and 1.36-2.92 for fluorescence responses (here, I was the relative fluorescence intensity). Separation of the amine derivatives had been optimized on an Eclipse XDB-C-8 column. Detection limits calculated from an 0.10 pmol injection, at a signal-to-noise ratio of 3, were 18.65-38.82 fmol (injection volume 10 mu L for fluorescence detection. The relative standard deviations for intraday determination (n = 6) of standard amine derivatives (50 pmol) were 0.0063-0.037% for retention times and 3.36-6.93% for peak areas. The mean intra-and inter-assay precision for all amines were <5.4% and 5.8%, respectively. The recoveries of amines ranged from 96 to 113%. Excellent linear responses were observed with correlation coefficients of >0.9994. The established method provided a simple and highly sensitive technique for the quantitative analysis of trace amounts of aliphatic amines from biological and natural environmental samples.