Identification and dating of the fountain pen ink entries on documents by ion-pairing high-performance liquid chromatography

A novel approach for the identification and dating of the fountain pen ink entries on paper has been established by ion-pairing high-performance liquid chromatography (IP-HPLC). Twelve black and six red fountain inks have been collected, and their ink entries have been prepared by drawing lines on paper. The chromatographic conditions for separation of their dye components after extraction with solvents were optimized. Under the optimized conditions, the 18 fountain pen inks were differentiated individually by comparing the number of detectable main or minor dye components, and the relative peak intensities of each component. The ink entries were artificially and naturally aged, and the analysis results showed that the ink dye components were significantly decomposed when exposed to UV or fluorescent light compare to those of inks stored under natural condition. The changes of the relative peak height for the dye components were linearly related to the aging time, especially under natural aging conditions. The degradation characteristics of the dye components under different aging conditions provide scientific evidences for dating of the suspicious fountain pen ink entries on document.     

UPLC分析大鼠血浆中阿齐沙坦浓度及其初步药代动力学研究

目的 采用UPLC建立大鼠血浆中阿齐沙坦浓度的测定方法,并探究阿齐沙坦在大鼠血浆中初步药代动力学情况。方法 选用缬沙坦为内标,色谱柱Kinetex C18（100 mm×2.10 mm,1.7 μm）,紫外检测波长254 nm,流动相为水-乙腈-冰醋酸（容积比为57∶42∶1）,流速0.2 mL/min,柱温25 ℃,进样量2 μL,建立在大鼠血浆中阿齐沙坦的分析方法。在此方法的基础上,经大鼠尾部静脉注射阿齐沙坦0.5 mg/kg,测定不同时间点其血浆浓度。实验数据运用DAS 2.1软件分析,得其主要药代动力学参数。结果 大鼠血浆中阿齐沙坦的线性范围为0.05～12.5 mg/L（r=0.999 9）,定量下限为0.05 mg/L,低、中、高浓度（0.1、1.0、10.0 mg/L）的提取回收率分别为（88.6±3.2）%、（86.5±2.2）%、（85.7±1.3）%（RSD<5%）,日内、日间精密度RSD不大于10%,准确度在85%~100%范围内。通过DAS 2.1软件拟合,阿齐沙坦的分布半衰期t1/2（α）为（0.39±0.04）h,消除半衰期t1/2（β）为（4.22±0.12）h,药时曲线下面积（AUC0-t）为每小时（53.25±2.46）mg/L。结论 本实验建立的UPLC操作快速、简单,且专属性强,适用于阿齐沙坦在大鼠血浆中浓度的分析及其药代动力学的探究。     

超高效液相色谱法比较鲜川芎和川芎药材中6种成分含量

目的 采用超高效液相色谱法(ultra-high performance liquid chromatography, UPLC)比较鲜川芎和川芎药材中6种活性成分(川芎嗪、阿魏酸、洋川芎内酯I、洋川芎内酯H、洋川芎内酯A、藁本内酯)的含量差异,为该药材的产地加工提供实验依据。方法 采用75%甲醇超声提取,UPLC测定鲜川芎和川芎药材中6种活性成分,根据样品处理条件计算质量分数并进行比较。流动相为乙腈(A)-0.1%甲酸水溶液(B),梯度洗脱,流速为0.2 mL/min,检测波长为294 nm,柱温30 ℃,进样体积2 μL。结果 经检测,阿魏酸、藁本内酯、洋川芎内酯A为鲜川芎和川芎药材的共有成分,鲜川芎中未检测到洋川芎内酯I及洋川芎内酯H。鲜川芎样品中各成分的质量分数为阿魏酸0.003 9%、洋川芎内酯A 0.006 4%、藁本内酯0.54%;川芎药材中各成分的质量分数为阿魏酸0.088%、洋川芎内酯I 0.20%、洋川芎内酯H 0.031%、洋川芎内酯A 0.76%、藁本内酯 1.3%。结论 川芎药材与鲜川芎中化学成分存在差异,推测在川芎的产地加工及贮藏过程中存在成分的转化。     

超高液相色谱法测定桔梗饮片和桔梗配方颗粒中桔梗皂苷D含量

目的 采用超高效液相色谱法建立桔梗饮片及桔梗配方颗粒中桔梗皂苷D的含量测量方法,为桔梗配方颗粒的质量控制提供实验依据。 方法 采用Waters Acquity UPLC HSS T3柱（2.1 mm×50 mm,μm）,以乙腈和水为流动相,梯度洗脱,流速 0.25 mL/min,检测波长210 nm,柱温29 ℃。 结果 桔梗皂苷D进样量在0.504~2.520 μg范围内与峰面积的线性关系良好,平均加样回收率为99.89%,RSD为1.64%;桔梗饮片和桔梗配方颗粒中桔梗皂苷D的含量具有差异。 结论 本实验所建立的测定方法简便、准确、可靠,可用于桔梗饮片和桔梗配方颗粒中桔梗皂苷D含量的检测。     

生血宝颗粒中何首乌苷的含量测定

目的 测定生血宝颗粒中何首乌苷（2,3,5,4′-四羟基二苯乙烯-2-O-β-D葡萄糖苷）的含量。方法 采用高效液相色谱法,色谱柱为Agilent HC-C18(4.6 mm×250 mm×5 μm）;流动相为乙腈-水（18∶82）;流速为1.0 ml/min,检测波长为320 nm。 结果 何首乌苷进样量在3.580～114.5 μg/ml范围内与峰面积呈良好的线性关系（r=0.999 94,n=6）,RSD=1.3%;平均回收率为100.3%,RSD=1.76%。结论 高效液相色谱法简便易行,结果可靠,可有效地控制生血宝颗粒的质量。     

梯度洗脱反相高效液相色谱法测定粉萆薢与绵萆薢中薯蓣皂苷含量

目的 建立粉萆薢和绵萆薢中薯蓣皂苷含量的高效液相色谱测定方法。方法 色谱柱：Gemini C18（250 mm×4.60 mm,5 μm）;流动相：乙腈-0.1%磷酸水溶液,梯度洗脱;检测波长：203 nm;流速：0.8 ml/min;柱温：30 ℃。结果 薯蓣皂苷与其他成分分离良好,色谱峰面积与浓度呈良好的线性关系,线性范围为7.8～156.0 μg/ml（r=0.999 4）,平均回收率分别为97.99%、97.82%。结论 梯度洗脱反相高效液相色谱法准确、简便、重现性好,可用于萆薢类药材的质量评价。     

不同炮制温度和时间对炮姜中姜酮含量的影响

目的 考察不同炮制温度和时间对炮姜中姜酮含量的影响。方法 采用超高效液相色谱法对15份不同炮制温度和炮制时间的炮姜样品中姜酮含量进行测定。色谱条件：色谱柱为Acquity BEH C18（100 mm×2.1 mm,1.7 μm）;流动相为乙腈-水,梯度洗脱;流速0.3 ml/min,检测波长280 nm,柱温30 ℃。结果 姜酮进样量在0.073 2～0.366 0 μg时与峰面积呈良好的线性关系（r=0.999 8）,平均加样回收率为97.42%（RSD=2.35%）。炮姜中姜酮含量随着炮制温度和时间的变化明显,以炮制温度为200 ℃、炮制时间为6 min时样品中姜酮含量最高。结论 炮制过程中姜酮含量随着温度升高和时间延长呈现先升高后降低的趋势,所建立的超高液相色谱法简便、准确、重现性好,可用于炮姜中新生成分姜酮的测定。     

苦丁茶提取物质量分析

目的 对苦丁茶药材水提物进行质量分析。方法 以槲皮素、山柰素作为对照品,采用薄层色谱法对苦丁茶药材中黄酮类化合物进行定性鉴别;采用反相高效液相色谱法测定苦丁茶药材中槲皮素和山柰素含量。结果 薄层色谱鉴别结果表明,供试品色谱中在与对照品色谱相应的位置上,显现相同颜色的斑点。槲皮素、山柰素进样量分别在0.1～3.2 μg、0.01～0.32 μg范围内,与峰面积线性关系良好（槲皮素r1＝0.999 9;山柰素r2＝0.999 8）,槲皮素及山柰素的平均加样回收率分别为102.34%和101.24%,RSD分别为3.26%和3.15%(n＝9)。结论 薄层色谱法和反相高效液相色谱法简便、准确,重复性好,可作为苦丁茶药材水提物的质量分析方法。     

超高效液相色谱-四级杆飞行时间串联质谱快速分析复方守宫散化学成分及血中移行成分

目的 采用超高效液相色谱-四级杆飞行时间质谱(ultra-performance liquid chromatogra-phy/quadrupole time-of-flight-tandem mass spectrometry,UPLC-Q-TOF/MS)对复方守宫散中化学成分及其血中移行成分进行定性分析,为该制剂的...     

Identification of furosemide in hair in a post‐mortem case by UHPLC‐MS/MS with guidance on interpretation

Testing for drugs in hair raises several difficulties. Among them is the interpretation of the final concentration(s). In a post‐mortem case, analyses revealed the presence of furosemide (12 ng/mL) in femoral blood, although it was not part of the victim's treatment. The prosecutor requested our laboratory to undertake an additional analysis in hair to obtain information about the use of furosemide. A specific method was therefore developed and validated to identify and quantify furosemide in hair by UHPLC‐MS/MS. After decontamination of 30 mg of hair, incubation in acidic condition, extraction with ethyl acetate, the samples were analyzed by UHPLC‐MS/MS. Furosemide was found in the victim's hair at 225 pg/mg. However, it was not possible to interpret this concentration due to the absence of data in the literature. Therefore, the authors performed a controlled study in two parts. In order to establish the basis of interpretation, several volunteers were tested (four after a single 20 mg administration and twenty‐four under daily treatment). The first part indicated that a single dose is not detectable in hair using our method. The second part demonstrated concentrations ranging from 5 to 1110 pg/mg with no correlation between dosage and hair concentrations. The decedent's hair result was interpreted as repeated exposures. In the case of furosemide analysis, hair can provide information about its presence but cannot give information about dosage or frequency of use.