Mass spectrometric identification of multihydroxy phenolic compounds in Tibetan herbal medicines

A highly selective and accurate method based on derivatization with dansyl chloride coupled with liquid chromatography-mass spectrometry has been developed for identification of natural pharmacologically active phenolic compounds in extracts of Lomatogonium rotatum plants (Tibetan herbal medicine) obtained by solid-phase extraction. The number of hydroxyl groups on the dansylated phenols was estimated by LC-MS-MS analysis in positive-ion mode. Dansyl derivatization of the compounds introduced basic secondary nitrogen into the phenolic core structures and this was readily ionized when acidic HPLC mobile phases were used. MS fragmentation of the derivatives generated intense protonated molecular ions of m/z [MH](+) (phenol aglycones were transformed into the corresponding free phenols by cleavage of an aglycone bond). Collision-induced dissociation of the protonated molecule generated characteristic product ions of m/z 234 and 171 corresponding to the protonated 5-(dimethylamino)naphthalene sulfoxide and 5 -(dimethylamino) naphthalene moieties, respectively. Selected reaction monitoring based on the m/z [MH](+) to 234 and 171 transitions was highly specific for these phenolic compounds. Characteristic ions with m/z values of [MH - 234](+), [MH 2 x 234](+), and [MH - 3 x 234](+) were of great importance for estimation of the presence of multihydroxyl groups on the phenolic backbone.

Analysis of saturated free fatty acids from pollen by HPLC with fluorescence detection

A sensitive method for the determination of free fatty acids using 2-(2-(anthracen-10-yl)-1H-naphtho[2,3-dimidazol-1-yl) ethyl-p-toluenesuIfonate (ANITS) as tagging reagent with fluorescence detection has been developed. ANITS could easily and quickly label fatty acids in the presence of the K2CO3 catalyst at 90 degrees C for 40 min in N,N-dimethylformamide solvent. From the extracts of rape bee pollen samples, 20 free fatty acids were sensitively determined. Fatty acid derivatives were separated on a reversed-phase Eclipse XDB-C8 column by HPLC in conjunction with gradient elution. The corresponding derivatives were identified by post-column APCI/MS in positive-ion detection mode. ANITS-fatty acid derivatives gave an intense molecular ion peak at mlz [M+H](+); with MS/MS analysis, the collision-induced dissociation spectra of m/z [M+H](+) produced the specific fragment ions at mlz [M-345](+) and mlz 345.0 (here, m/z 345 is the core structural moiety of the ANITS molecule). The fluorescence excitation and emission wavelengths of the derivatives were lambda(ex) = 250 nm and lambda(em) = 512 nm, respectively. Linear correlation coefficients for all fatty acid derivatives are > 0.9999. Detection limits, at a signal-to-noise ratio of 3 : 1, are 24.76-98.79 fmol for the labeled fatty acids.

Enhancement of atmospheric pressure chemical ionization for the determination of free and glycine-conjugated bile acids in human serum

A highly sensitive and accurate method based on the precolumn derivatization of bile acids (BA) with a high ionization efficiency labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl-benzenesulfonate (BDEBS) coupled with LC/MS has been developed. After derivatization, BA molecules introduced a weak basic nitrogen atom into the molecular core structure that was readily ionized in commonly used acidic HPLC mobile phases. Derivatives were sufficiently stable to be efficiently analyzed by atmospheric pressure chemical ionization (APCI)-MS/MS in positive-ion mode. The MS/MS spectra of BA derivatives showed an intense protonated molecular ion at m/z [M + H](+). The collision-induced dissociation of the molecular ion produced fragment ions at [MH - H2O](+), [MH - 2H(2)O](+), [MH - 3H(2)O](+). The characteristic fragment ions were at m/z 320.8, 262.8, and 243.7 corresponding to a cleavage of N - CO, O - CO, and C - OCC, respectively, and bonds of derivatized molecules. The selected reaction monitoring, based on the m/z [M + H]+ -> [MH - H2O](+), [MH - H2O](+), [MH - 2H(2)O](+), [MH-3H(2)O](+), 320.8, 262.8, and 243.7 transitions, was highly specific for the BA derivatives. The LODs for APCI in a positive-ion mode, at an S/N of 5, were 44.36-153.6 fmol. The validation results showed high accuracy in the range of 93-107% and the mean interday precision for all standards was < 15% at broad linear dynamic ranges (0.0244-25nmol/mL). Good linear responses were observed with coefficients of > 0.9935 in APCI/MS detection. Therefore, the facile BDEBS derivatization coupled with mass spectrometric analysis allowed the development of a highly sensitive and specific method for the quantitation of trace levels of the free and glycine-conjugated BA from human serum samples.

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.

基于EPC Class-1 Gen-2标准的防冲突算法与改进

针对RFID读写器识别多标签过程中出现的冲突问题,研究并实现了EPC Class-1 Gen-2标准中的防冲突算法,即时隙随机算法(SR算法),同时针对SR算法的不足提出改进算法。改进算法采用不避让冲突时隙的处理方式,降低了由时隙的随机选取所导致的标签间冲突的概率。实验结果证明,改进后的算法在通信次数和吞吐率方面均优于原算法,有效提高标签识别效率。

一种移动机器人在三维动态环境下的路径规划方法

提出一种基于遗传算法的三维动态环境下的路径规划方法,通过对机器人的运动行为进行编码,将各种约束条件融入到遗传算法当中,规划出可实际应用的避障路径,仿真研究表明该方法是简单有效的。

多机器人的改进型边界探索算法

针对多机器人探索未知环境问题,提出了改进型边界探索算法。该算法综合考虑边界角度和距离两种因素,引入分散机制,使机器人团队协同工作,避免出现拥挤,减少探索过程中的重复覆盖和路径交叉现象。基于与其他方法的实验比较结果表明,该探索方法使多机器人具有更好的团队协作能力,提高了探索效率。

室外自主移动机器人AMOR的导航技术

在非结构化环境,移动机器人行驶运动规划和自主导航是非常挑战性的问题。基于实时的动态栅格地图,提出了一个快速的而又实效的轨迹规划算法,实现机器人在室外环境的无碰撞运动导航。AMOR是自主研发的室外运动移动机器人,它在2007年欧洲C-ELROB大赛中赢得了野外自主侦察比赛的冠军。它装备了SICK的激光雷达,用来获取机器人运动前方的障碍物体信息,建立实时动态的环境地图。以A*框架为基础的改造算法,能够在众多的路径中快速地找到最佳的安全行驶路径,实现可靠的自主导航。所有的测试和比赛结果表明所提方案是可行的、有效的。

排爆作业机器人模拟训练系统研究

介绍了一种排爆机器人模拟训练系统.该系统提供了友好的人机交互界面,使操作人员可以进行各种模拟训练,并提高操作水平.重点介绍了该模拟训练系统的体系结构及关键实现技术,包括排爆机器人及其工作环境的建模方法、机器人运动学和动力学简化模型、碰撞检测和技能评定等.通过实验,证明了该模拟训练系统的可行性和有效性.

动态未知环境下基于相对坐标系的移动机器人实时运动规划

提出了一种简单、新颖的在动态未知环境下的移动机器人运动规划方法．此方法基于相对坐标系，通过传感器信息实时调整机器人的行为来实现规划．在规划过程中，机器人有两种行为：向目标运动和避碰，且避碰行为具有优先权．机器人两种行为的切换是基于加速度空问的，首先解决的是避碰问题，而向目标运动是作为避碰的反问题来考虑的．仿真研究验证了此规划方法的有效性。

基于人工协调场的多移动机器人实时协调避碰规划

为克服传统人工势场在动态未知环境下机器人避碰规划中存在的缺陷,提出人工协调场法(ACF).将场函数与机器人的风险状态相结合,给出并讨论了人工协调场的基本设计.基于人工协调场,考虑机器人的运动约束,实现了多机器人之间以及机器人与环境间的实时协调避碰,提出了一个多移动机器人无死锁实时避碰规划算法.理论分析和仿真试验证明所提方法的有效性.

智能机器人系统中局部环境特征的提取

本文基于栅格地图和滚动视窗的控制方法 ,提出了一种提取机器人局部障碍物群环境特征的数据融合新方法 .该方法在多个级别对原始数据进行不同程度的抽象和压缩 ,减少机器人内部模块之间或机器人之间、机器人与控制中心进行通讯的数据量 ,提高系统的动态性能 .同时 ,该方法对复杂环境具有良好的自适应性和实时性 .本文分别列举了仿真实验和物理实验结果 ,表明了机器人采用障碍物群的环境特征提取方法可以成功地完成躲避障碍物和路径规划的任务

基于超冗余度机械臂动力学的时间最优轨迹规划

基于超冗余度机械臂的动力学方程 ,提出了一种超冗余度机械臂同时受速度和力矩约束的时间最优轨迹规划方法 .它首先采用 B样条曲线拟合无碰撞离散路径 ,得到由伪位移参数 s表示的超冗余度机械臂连续、光滑运动路径 ,然后对动力学方程和约束方程进行数学变换 ,得到由 s表示的动力学方程和约束方程 ,最后以 s和伪速度 s· 分别作为动态规划的阶段变量和状态变量 ,对超冗余度机械臂进行时间最优轨迹规划 .仿真结果表明 ,所给出的时间最优轨迹规划算法是正确的 ,所采取的解决方法是可行的

Stabilization of Dynamic Systems for Multiple Omni-Directional Mobile Robots

本文考虑了由2个全方位移动机器人组成的混合动力学系统的协调拟镇定问题.利用机器人位置之间的向量与机器人目标之间向量的内积,设计了多步拟镇定律,该控制律能够在避碰后按指数速率运动到目标点,且在整个过程中两机器人之间的距离不小于避碰的安全距离.最后对2个全方位移动机器人进行了仿真,验证了所给方法的有效性。