Analysis of aromatic amines by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence derivatization reagent, has been developed for the analysis of aromatic amines. Taking five monocyclic aromatic amines (o-toluidine, aniline, 3,4-dimethylaniline, N-ethyl-p-toluidine, and p-phenylenediamine) as testing compounds, derivatization conditions such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration have been investigated. By a one-step procedure, CEOC reacts readily with the aromatic amines to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. This derivatization reaction could be finished within 20 min even at room temperature. The peak shapes of the derivatized aromatic amines can be improved greatly without any addition of competition amines into the mobile phase. Furthermore, this method can offer excellent quantitative precision with high tolerance of the matrix of samples. (C) 2003 Elsevier B.V. All rights reserved.

Determination of peptides and amino acids from wool and beer with sensitive fluorescent reagent 2-(9-carbazole)-ethyl chloroformate by reverse phase high-performance liquid chromotography and liquid chromotography mass spectrometry

A new method for the sensitive determination of amino acids and peptides using the tagging reagent 2-(9-carbazole)-ethyl chloroformate (CEOC) with fluorescence (FL) detection has been developed. Identification of derivatives was carried out by liquid chromotography mass spectrometry. The chromophore in the 2-(9-fluorenyl)-ethyl chloroformate (FMOC) reagent was replaced by carbazole, which resulted in a sensitive fluorescence lerivatizing agent CEOC. CEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. Studies on derivatization demonstrate excellent derivative yields over the pH range 8.8-10.0. Maximal yields close to 100% are observed with three- to fourfold molar reagent excess. Derivatives exhibit strong fluorescence and allow direct injection of the reaction mixture with no significant disturbance from the major fluorescent reagent degradation by-products, such as 2(9-carbazole)-ethanol and bis-(2-(9-carbazole)-ethyl) carbonate. In addition, the detection responses for CEOC derivatives are compared to those obtained with FMOC. The ratios AC(CEOC)/AC(FMOC) = 1.00-1.82 for fluorescence (FL) response and AC'(CEOC)/AC'(FMOC) = 1.00-1.21 for ultraviolet (UV) response are observed (here, AC and AC' are, respectively, FL and UV F response). Separation of the derivatized peptides and amino acids has been optimized on a Hypersil BDS C18 column. Excellent linear responses are observed. This method was used successfully to analyze protein hydrolysates from wool and from direct-derivatized beer. (C) 2003 Elsevier Science (USA). All rights reserved.

4,7-(氯磺酸基苯基)-1,10-菲啰啉-2,9-二羧酸-铕标记甲胎蛋白抗体

在合成BCPDA基础上 ,对甲胎蛋白抗体与BCPDA连接及与铕离子螯合条件进行了研究。BCPDA与甲胎蛋白抗体反应后 ,分离纯化最佳淋洗液为pH9.1的0.1mol/L碳酸盐缓冲溶液 ,BCPDA用量为甲胎蛋白抗体量 (mol)的120～160倍;反应时间为30min。讨论了Eu3+ BCPDA AFP抗体螯合物的荧光光谱 ,最佳温育时间为60min,体系pH值为7.8的Tris HCl溶液。当Eu3+ 浓度为10-6mol/L时,BCPDA的检出限为4.3×10-11mol/L。

A highly reduced polyoxoanion with phosphorus-centered alternate layers of Mo/V oxides, [(PMo2Mo6V4O40)-Mo-V-V-VI-O-IV((VO)-O-IV)(2)](9-)

An unusual polyoxometalate [H2N(C2H4)(2)NH2](4)(H3O)[(PMO2Mo6V4O40)-Mo-V-V-VI-O-IV((VO)-O-IV)(2)].H2O is hydrothermally synthesized and characterized by IR, UV-VIS, elemental analyses, X-ray photoelectron spectrum, ESR, TG and Single crystal X-ray diffraction. The title compound crystallizes in the orthorhombic space group Pbca with a = 15-227(5), b = 19.491(4), c = 18.737(3) Angstrom, V = 5123(2) Angstrom(3), Z = 4, and R-1 (wR(2)) = 0.0726(0.1416). The compound contains an unusual highly reduced pseudo-Keggin type polyoxoanion and exhibits an interesting phosphorus-centered alternate arrangement of layers of molybdenum and vanadium oxides.

BaCe_(0.8)Ln_(0.2)O_(2.9)(Ln=Gd,Sm,Eu)固体电解质的低温制备及其燃料电池性质

利用溶胶 凝胶法低温合成了BaCe0 .8Ln0 .2 O2 .9(Ln =Gd ,Sm ,Eu)固体电解质 ,X射线粉末衍射表明 90 0℃即形成正交钙钛矿结构 ,较高温固相反应合成温度降低了约 6 0 0℃ .测定了样品的阻抗谱和电导率 ,研究了其导电机理 ,溶胶 凝胶法合成可减小或消除固体电解质的晶界电阻 ,80 0℃时BaCe0 .8Gd0 .2 O2 .9的σ =7.87× 10 -2S·cm-1,以它为电解质的氢氧燃料电池开路电压接近 1V ,最大输出功率密度为 30mW·cm-2 .

CE determination of 2-(9-carbazole)ethyl chloroformate-labeled oligopeptides

A pre-column derivatization method for sensitive determination of oligopeptides, using the tagging reagent 2-(9-carbazole)ethyl chloroformate (CEOC-Cl) followed by capillary electrophoresis (CE) with diode-array detection, has been developed. Maximum yield close to 100% were observed when a three to fourfold molar excess of reagent was used at pH 9.0-10.0. Excess reagent was extracted with n-hexane-ethyl acetate 9:1-10:1 (v/v); this enabled direct analysis using CE with no significant disturbance from the major fluorescent reagent degradation by-products. The effects on the results of buffer pH and of SDS and organic modifier concentrations were examined. Good baseline resolution in the separation of five CEOC-peptides was achieved with a 48.5-cm total length (effective length 40 cm) 50-mu m inner diameter capillary column.

Analysis of phenols by high-performance liquid chromatography with pre-column derivatization by 2-(9-carbazole)-ethyl-chloroformate

2-(9-Carbazole)-ethyl-chloroformate (CEOC), a novel pre-column fluorescence labeling reagent, has been synthesized and applied for the derivatization of phenols. Taken phenol, p-chlorophenol, 2,5-dimethylphenol, 2,4-dichlorophenol and 1,4-dihydroxybenzene as testing standards, the effects of derivatization conditions, such as pH of borate buffer, reaction time and fluorescent tagging reagent concentration, have been systematically studied. Under the optimized conditions, CEOC reacts readily with the phenols to form stable derivatives with excitation and emission wavelengths, respectively, at 293 and 360 nm. The single step derivatization reaction could be finished within 20 min even at room temperature. Such a method has been successfully applied to the analysis of phenols in printing ink by high-performance liquid chromatography. (c) 2005 Elsevier B.V. All rights reserved.

Pre-column derivatization of amines with 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate followed by LC-fluorescence and LC-APCI-MS

A pre-column derivatization method for the sensitive determination of amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl chloroformate (BCIC-Cl) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives is carried out by high performance liquid chromatography/atmospheric pressure chemical ionization (LC-APCl-MS-MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent is replaced by 1,2-benzo-3,4-dihydrocarbazole-9-isopropyl functional group, which results in a sensitive fluorescence derivatizing reagent BCIC-Cl. BCIC-Cl can easily and quickly label amines. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography and show an intense protonated molecular ion corresponding m/z [MH](+) under APCl in positive-ion mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 260 corresponding to the cleavage of CH2-OCO bond. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3 to 4-fold molar reagent excess. In addition, the detection responses for BCIC derivatives are compared with those obtained using CEOC and FMOC as derivatization reagents. The ratios of l(BCIC)/l(CEOC) and l(BCIC)/l(FMOC) are, respectively, 1.23-3.14 and 1.25-3.08 for fluorescent (FL) responses (here, l is relative fluorescence intensity). Separation of the derivatized amines had been optimized on reversed-phase Eclipse XDB-C-8 column. Detection limits are calculated from 1.0 pmol injection, at a signal-to-noise ratio of 3, are 10.6-37.8 fmol. The mean interday accuracy ranges from 94 to 105% for fluorescence detection with the largest mean %CV < 7.5. The mean interday precision for all standards is < 6.0% of the expected concentration. Excellent linear responses are observed with coefficients of > 0.9997.

Development of a sensitive fluorescent derivatization reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) and its application for determination of amino acids from seeds and bryophyte plants using high-performance liquid chromatography with fluorescence detection and identification with electrospray ionization mass spectrometry

A pre-column derivatization method for the sensitive determination of amino acids and peptides using the tagging reagent 1,2-benzo-3,4dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by high-performance liquid chromatography with fluorescence detection has been developed. Identification of derivatives was carried out by liquid chromatography/electrospray ionization mass spectrometry (LC/ESI-MS/MS). The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent BCEOC. BCEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. The derivatives showed an intense protonated molecular ion corresponding m/z (M + H)(+) under electrospray ionization (ESI) positive-ion mode with an exception being Tyr detected at negative mode. The collision-induced dissociation of protonated molecular ion formed a product at m/z 246.2 corresponding to the cleavage of C-O bond of BCEOC molecule. Studies on derivatization demonstrate excellent derivative yields over the pH 9.0-10.0. Maximal yields close to 100% are observed with a 3-4-fold molar reagent excess. Derivatives exhibit strong fluorescence and extracted detzvatization solution with n-hexane/ethyl acetate (10:1, v/v) allows for the direct injection with no significant interference from the major fluorescent reagent degradation by-products, such as 1,2-benzo-3,4-dihydrocarbazole-9-ethanol (BDC-OH) (a major by-product), mono- 1,2-benzo-3,4-dihydrocarbazole-9-ethyl carbonate (BCEOC-OH) and bis-(1,2-benzo-3,4-dihydrocarbazole-9-ethyl) carbonate (BCEOC)(2). In addition, the detection responses for BCEOC derivatives are compared to those obtained with previously synthesized 2-(9-carbazole)-ethyl chloroformate (CEOC) in our laboratory. The ratios AC(BCEOC)/AC(CEOC) = 2.05-6.51 for fluorescence responses are observed (here, AC is relative fluorescence response). Separation of the derivatized peptides and amino acids had been optimized on Hypersil BDS C-18 column. Detection limits were calculated from 1.0 pmol injection at a signal-to-noise ratio of 3, and were 6.3 (Lys)-177.6 (His) fmol. The mean interday accuracy ranged from 92 to 106% for fluorescence detection with mean %CV < 7.5. The mean interday precision for all standards was < 10% of the expected concentration. Excellent linear responses were observed with coefficients of > 0.9999. Good compositional data could be obtained from the analysis of derivatized protein hydrolysates containing as little as 50.5 ng of sample. Therefore, the facile BCEOC derivatization coupled with mass spectrometry allowed the development of a highly sensitive and specific method for the quantitative analysis of trace levels of amino acids and peptides from biological and natural environmental samples. (c) 2005 Elsevier B.V. All rights reserved.

Judd-Ofelt analysis of spectra and experimental evaluation of laser performance of Tm3+ doped Lu2SiO5 crystal

This paper reports that the TM3+:Lu2SiO5 (Tm:LSO) crystal is grown by Czochralski technique. The room-temperature absorption spectra of Tm:LSO crystal are measured on a b-cut sample with 4 at.% thulium. According to the obtained Judd-Ofelt intensity parameters Omega(2)=9.3155 x 10(-20) cm(2), Omega(4)=8.4103 x 10(-20) cm(2), Omega(6)=1.5908 x 10(-20) cm(2), the fluorescence lifetime is calculated to be 2.03 ms for F-3(4) -> H-3(6) transition, and the integrated emission cross section is 5.81 x 10(-18) cm(2). Room-temperature laser action near 2 mu m under diode pumping is experimentally evaluated in Tm:LSO. An optical-optical conversion efficiency of 9.1% and a slope efficiency of 16.2% are obtained with continuous-wave maximum output power of 0.67 W. The emission wavelengths of Tm:LSO laser are centred around 2.06 mu m with spectral bandwidth of similar to 13.6 nm.

中国鲤科鱼类染色体组型的研究——Ⅸ.鳊亚科9种鱼和鲴亚科1种鱼的染色体组型

<正> 我们曾报道过分布于湖北省的鳊、鲴亚科鱼类的核型。本文继续报道采自四川和广东省的鳊、鲴亚科另10种鱼的核型考察结果。材料和方法四川半(歺又鱼)由于采集困难,仅分析了一尾雄鱼。其余9种鱼均分析了3—5尾,包括雌雄两种性别(表1)。染色体标本的制备采用体外短期培养肾细胞制片法(采自四川的鱼),或肾细胞直接制片法(采自广东的鱼)。根据我们实验室以前的工作,两种方法的核型分析结果基本上一致。每种鱼计数60—170个细胞确定其2n数。染色体分组按Levan氏的标准,核型分析方法和臂数计算均同以前的报道。核型图

卤化物基质中3m~(2+)离子光谱性质的研究

3m~(2+)离子在红区和红外区可以产生4f~6组态内的f-f跃迁锐线发射和d-f跃迁宽带发射。在某些基质中，这两种跃迁形式可以同时存在。由于d-f跃迁是原于宇称允许的跃迁，所以其发射强度要比4f~n组态内的f-f跃迁强得多。这可以保证对泵浦的有效吸收，提高光泵效率。而4f~n组态内部的f-f跃迁可以实现激光振荡，有利于提高储能降低阈值。所以研究3m~(2+)离子的光谱性质及其影响因素对于寻找和设计新的激光和发光材料有着重要意义。近年来，低价稀大离子的价态问题一直是人们力求探讨的问题，3m~(2+)离子具有极强的还原性和不稳定性，因此关于它的价态研究更具有特殊的意义。本论文采用了几种较简单的方法合成了三十种掺杂3m~(2+)离子的磷光体，分别经x－射线。荧光光谱等实验证实。其中有二十种未见过文献报道。在BaMgF_4:3m~(2+)等十七种体等中研究了基质格位的对称性，对于3m~(2+)离子f－f跃迁性质的影响。如果3m~(2+)离子占据其质中有反演对称中心的点群位置，只有f－f磁偶极跃迁是可能的。这时，~5Do→~7F_1发射线最强。如果3m~(2+)离子占据基质中无反演对称中心的点群位置，f－f磁偶极跃迁和受迫电偶极跃迁都是可能的，这时~5Do→~7Fo发射线最强。在KMgF_3:3m~(2+)等四种体系中研究了电荷补偿效应对3m~(2+)离子f－f跃迁性质的影响。如果3m~(2+)离子取代基质中的一价阳离子，电荷补偿效应使3m~(2+)离子的局部对称性降低，结果f－f跃迁发射线增多。在NaMgF_4:3m~(2+)体系中研究了基质晶体构形变化对3m~(2+)离子f－f跃进性质的影响。NaMgF_3:3m~(2+)由立方相变为正多相时，3m~(2+)离子的点对称性降低，结果出现了~5Do→~7F_3、~5Do→~7F_4两组新线。讨论了晶场强度和化学键性质对于3m~(2+)离子跃迁形式的影响。在有小半径或高正电荷阳离子作为中间阳离子的复合氟化物体系中，3m~(2+)离子周围的晶场变弱，3m－F的共价性降低，结果不能产生d-f跃宽带发射，只能产生f－f跃迁锐线发射。在某些共价性较强的碱金属卤化物和碱S金属卤化物基质中，3m~(2+)离子受到较强的共价作用，这种作用产生主影响，结果能够产生3m~(2+)离子的d-f跃迁宽带发射。在KxNo_1-xMgF_3:3m~(2+)、KMgF_3-xClx:3m~(2+)、KMgF_(2.9)*0.1:3m~(2+) (X=F、Cl、Br、I)三种体系中研究了基质组成变化对3m~(2+)离子f－f跃迁发射强度的影响。在形成化合物或固熔体的条件下，基质组成变化如果导致了3m~(2+)离子对称性降低，3m~(2+)离子的f－f跃迁发射就增强。和阳离子组成的变化相比，阳离子变化对3m~(2+)离子f－f跃迁发射强度影响更大。和正交体等相比，立方体系中基质组成变化对3m~(2+)离子f－f跃迁发射强度的影响更大。在BaCl_2:3m~(2+)等六种体系中讨论了激活剂浓度变化对3m~(2+)离子发射强度的影响。3m~(2+)离子浓度萃取的临界值一般在0.02mol左右，在临界浓度为，随激活剂浓度的增加，3m~(2+)离子的发射强度增大。研究了高温分解3mF_3法制备KMgF_3:3m~(2+)过程中3m(III)→3m(II)的价态转变。由于基质反应的存在，产生了某些局部化学因素，有利于3mF_3的分解，实现了3m(III)→3m(II)的价态转化。在某些复合氟化物和碱S金属氟卤化体系中研究了基质结构因素对于3m~(2+)离子价态的影响。得出了稳定3m~(2+)离子的基质条件为：①基质中含有半径接近3m~(2+)离子的一价或二价阳离子② 复合基质的形成速度要快。找出了KMgF_3、NaMgF_3、BaClF、BaBrF等四种特别能够稳定3m~(2+)离子的基质。在MLnFs(M=Ca Sr Ba Ln=La Crd)考定了几种合成方法对于3m(III)→3m(II)价态转化的影响，其中3m粉还原法为最佳方法。