HPLC法同时测定石蒜中加兰他敏和石蒜碱

建立了高效液相色谱同时测定石蒜中加兰他敏和石蒜碱含量的方法。 采用phenomenex-C18色谱柱,以乙腈(A)-0.1%TFA水溶液(B)为流动相梯度洗脱,检测波长289 nm。 结果表明,加兰他敏和石蒜碱均在0.5～10 mg/L(r=0.9999)呈现良好的线性关系,最低检测限(S/N=3)分别为0.09和0.15 mg/L,平均加样回收率分别为99.53%和96.82%。 该方法简单、快速、准确,适合于石蒜中加兰他敏和石蒜碱的测定。     

Determination of galanthamine in Bulbus Lycoridis Radiatae by coupling capillary electrophoresis with end‐column electrochemiluminescence detection

A novel method for the determination of galanthamine (GAL) in Bulbus Lycoridis Radiatae has been developed based on coupling CE with an end‐column tris(2,2′‐bipyridyl)ruthenium(II) electrochemiluminescence (ECL). Parameters affecting CE separation and ECL detection were investigated and optimized. Baseline separation of GAL from other components in the Bulbus Lycoridis Radiatae sample was achieved with an 18 mmol/L phosphate running buffer at pH 9.0. Under the optimized conditions: 12 kV CE‐separation voltage, ECL detection potential at 1.25 V with 5 mmol/L and 50 mmol/L phosphate buffer at pH 7.5 in the detection reservoir, the linear range of GAL concentration was from 0.8 ng/mL to 2 μg/mL, whereas the detection limit was 0.25 ng/mL (S/N=3). The proposed method was successfully demonstrated for the determination of GAL in Bulbus Lycoridis Radiatae.     

高效液相色谱法测定石蒜中加兰他敏、力可拉敏及石蒜碱3种生物碱

以石蒜鳞茎为材料,建立了石蒜生物碱的反相高效液相色谱(HPLC)分析方法。探讨了流动相中乙腈含量、三乙胺含量、pH值、流速等对生物碱分离的影响,结果表明在ZORBAX ODS-C18(150 mm×4.6mm,5μm)反相色谱柱上,以0.9%三乙胺水溶液(pH 8.0)-乙腈-甲醇为流动相,梯度洗脱,流速为1mL/min,检测波长为234 nm时,石蒜样品可有效分离出14种石蒜生物碱,分离度良好。加兰他敏、力可拉敏和石蒜碱的检出限分别为3.375、0.475、0.495 mg/L,平均加标回收率均为98%。运用此法测定了石蒜不同部位中3种生物碱的含量,结果表明石蒜不同部位的3种生物碱含量差异较大,叶子中的含量最高;同一部位中,石蒜碱的含量最高,力可拉敏次之,加兰他敏最低。     

Capillary electrophoresis with electrochemiluminescence detection for the simultaneous determination of cisatracurium besylate and its degradation products in pharmaceutical preparations

Capillary electrophoresis with electrochemiluminescence detection for the simultaneous analysis of cisatracurium besylate and its degradation products (laudanosine, quaternary monoacrylate) in pharmaceutical preparation was developed and fully validated. The significant parameters that influence capillary electrophoresis separation and electrochemiluminescence detection were optimized. The total analysis time of the analytes was 15 min. The linearities of the method were 0.1～40.0 μg/mL for cisatracurium besylate and 0.04～8.00 μg/mL for laudanosine, with correlation coefficients (r) of 0.999 and 0.998, respectively. The detection limits (S/N = 3) were 83.0 ng/mL for cisatracurium besylate and 32.0 ng/mL for laudanosine. The intraday relative standard deviations of the analytes were <3.0%, and the interday relative standard deviations were <8.0%. The developed method was cost‐effective, sensitive, fast, and resource‐saving, which was suitable for the ingredient analysis in pharmaceutical preparation.     

HPLC法测定脂质体松萝酸中松萝酸的含量

建立了HPLC测定脂质体松萝酸中药物松萝酸的方法。以Kromasil C18反相色谱柱(250 mmⅹ4.6 mm,5μm)为分离柱,流动相组成为V(甲醇)∶V(磷酸盐缓冲液(pH 5.0))=7∶3,流速1 mL/min,紫外检测,波长284 nm。松萝酸在10~50μg/mL的范围内有很好的线性关系(r=0.9994)。加样回收率为100.1%±0.6%,RSD为0.54%±0.07%。本方法适用于脂质体松萝酸中药物松萝酸的测定。     

Detection of L‐phenylalanine using molecularly imprinted solid‐phase extraction and flow injection electrochemiluminescence

A novel flow injection electrochemiluminescence method combined with molecularly imprinted solid‐phase extraction was developed for the determination of L ‐phenylalanine, in which was used as the luminophor and indium tin oxide glass was modified as the working electrode. Molecularly imprinted polymers, synthesized by self‐assembly with functional monomer and crossing linker, were used for the selective extraction of L ‐phenylalanine. In order to overcome the drawbacks of traditional electrochemiluminescence cells such as high IR drop, high over‐potential and so on, a novel electrochemiluminescence cell was developed. The enhanced electrochemiluminescence intensity was linearly related with the concentration of L ‐phenylalanine in the range from 1.0×10^?7 to 5.0×10^?5 g/mL with a detection limit of 2.59×10^?8 g/mL. The relative standard deviation for the determination of 1.0×10^?6 g/mL L ‐phenylalanine was 1.2% (n=11). The method showed higher sensitivity and good repeatability, and was successfully applied for the determination of L ‐phenylalanine in egg white, chicken and serum samples. A possible mechanism for the enhanced electrochemiluminescence response on indium tin oxide glass is proposed.     

Determination of chlorobenzenes in pure,tap, and sea water by static headspace gas chromatography‐electron capture detection

A simple, efficient, solvent‐free, and commercial readily available approach for determination of 11 chlorobenzenes (CBs) in water samples using the static headspace (HS) sampling and gas chromatography‐electron capture detector has been described. The proposed static HS sampling method was initially optimized and the optimum experimental conditions found were 10 mL water sample containing 20% (w/v) sodium chloride placed in a 20 mL vial and stirred at 70°C for 30 min. The linearity of the method ranged from 0.16 to 8.0 μg/L for dichlorobenzene isomers, 0.0176～0.88 μg/L for trichlorobenzene isomers, 0.004～0.2 μg/L for tetrachlorobenzene isomers, and from 0.001 to 0.05 μg/L for pentachlorobenzene and hexachlorobenzene, with correlation coefficients ranging between 0.9992 and 0.9999. The limits of detection were in the low μg/L level, ranging between 0.0002 and 0.04 μg/L. The relative recoveries of spiked CBs with external calibration or standard addition method at different concentration levels in pure, tap, and sea water samples were 83～116%, 89～108%, and 93～112%, respectively, and with relative standard deviations of 1.9～6.3%, 1.6～5.4%, and 2.5～5.7% (n = 5), respectively. It is concluded that this method can be successfully applied for the determination of CBs in pure, tap, and sea water samples.     

高效液相色谱-荧光分析法同时测定人体尿液中黄蝶呤与异黄蝶呤

建立了高效液相色谱-荧光法同时测定癌症病人尿液中黄蝶呤及异黄蝶呤的新方法。选择荧光检测波长λex=345nm,λem=420nm。以磷酸盐缓冲溶液(pH=7.5)-甲醇(体积比为98∶2)为流动相,流速1.0mL/min,黄蝶呤与异黄蝶呤含量分别在0.0013～0.945μg/mL及0.00017～0.118μg/mL范围内与色谱峰面积呈良好的线性关系,线性相关系数分别为0.9999和0.9996,检出限分别为0.5ng/mL和0.05ng/mL,加标平均回收率在86.2%～107.5%之间。方法应用于癌症病人尿样分析,取得了较好的结果。     

靛蓝胭脂红-溴酸钾体系催化光度法测定微量碘

研究了在室温及0．4mol/L H2SO4介质中碘离子对KBrO3氧化靛蓝胭脂红褪色反应的催化作用,建立了一种测定微量碘的新方法。碘离子浓度在0．20－2．0μg/mL范围内与△A呈线性关系,检测限为0．14μg/mL。多数常见离子无干扰。可用于海带中微量碘的测定。     

The structure of chuin,a new coumarin from the roots of Seseli tschuense

Conclusions 1. The polarographic behavior of galanthamine, lycorine, pancratine, hordenine, and dl-narwedine on a support of 0.01 N (C₂H₅)₄NOH has been studied.2. A chromatopolarographic method for determining the amount of galanthamine in a chloroform extract from plant raw material has been developed.Khimiya Prirodnykh Soedinenii, Vol. 6, No. 4, pp. 450–453, 1970     

甲基绿-高碘酸钾系统催化动力学光度法测定痕量铱(Ⅳ)

基于以H3PO4为反应介质,用HAc-NaAc(1+8)(pH5.7)作缓冲溶液,在沸水浴中加热条件下,痕量铱(Ⅳ)能灵敏地催化高碘酸钾氧化甲基绿的褪色反应,建立了一种测定痕量铱(Ⅳ)的新催化光度法。研究了反应的最佳条件。催化反应吸光度A与非催化反应吸光度A0的差值ΔA与铱(Ⅳ)的质量浓度ρ在0～2.0μg/25mL范围内呈良好的线性关系。检出限为2.97×10-10g/mL。对1μg/25mL铱(Ⅳ)测定的相对标准偏差为1.7%(n=11)。测定了动力学参数。该催化反应对铱(Ⅳ)为一级反应,总反应为准一级反应。反应的表观速率常数为4.613×10-4/s,表观活化能为40.56kJ/mol。该方法用于分子筛样品和活性炭中痕量铱(Ⅳ)的测定,回收率97.9%～104.4%。     

蛋白质-钼(Ⅵ)-邻苯二酚紫-OP显色体系的研究及应用

建立了一种测定蛋白质的蛋白质－钼（Ⅵ）-邻苯二酚紫－OP显色体系光度法,蛋白质含量在0－50.0μg/mL范围内符合比尔定律。方法已应用于尿液、血清和豆浆中总蛋白测定,加标回收率90％－108％,相对标准偏差1．8％－3．0％（n=5),检出限4．0μg/mL。     

异硫氰酸荧光素-人血清白蛋白标记物化学发光反应的研究

采用反相流动注射分析方法,研究了异硫氰酸荧光素（FITC）－人血清白蛋白（HSA）标记物的化学发光性能和反应的最佳条件,建立了化学发光测定人血清白蛋白的新方法。体系的化学发光强度与人血清白蛋白的含量在0．08－16μg/mL内呈线性关系,方法的检出限为0．04μg/mL。讨论了蛋白质标记物化学发光性增强的原因。     

钯(II)-柠檬黄-离子液体三元络合体系的共振瑞利散射光谱及其分析应用研究

在pH 2.0～6.0的BR缓冲溶液中, Pd(II)与柠檬黄(TTZ)形成的络离子与溴化1-十六烷基-3-甲基咪唑([C₁₆mim]Br)离子液体发生作用形成离子缔合物, 引起溶液共振瑞利散射(RRS)显著增强, 并产生新的RRS光谱, 其最大RRS峰位于458 nm. 在0.043～0.860 μg/mL范围内散射强度(ΔI)与柠檬黄的浓度成正比. 该方法简单灵敏, 对柠檬黄的检出限(3σ/K)为5.5 ng/mL (n＝11). 建立了一种简便、快速测定柠檬黄的新方法, 并成功用于饮料样中柠檬黄含量的测定.     

同多酸和染料探针共振光散射法测定蛋白质

在酸性条件下,铬黑T、钼酸铵与蛋白质形成聚合物,使体系的共振光散射明显增强。据此建立了利用共振光散射技术测定总蛋白含量的新方法。在最佳条件下,体系的最大散射峰位于555nm处。共振光散射增强的程度与蛋白质的浓度呈良好的线性关系。牛血清白蛋白和人血清白蛋白的线性范围分别为0.20～10.0μg/mL和0.10～8.0μg/mL,检出限为0.050μg/mL和0.039μg/mL。方法已用于人血清样品的分析,并与考马斯亮蓝的测定结果进行了比较,两者无显著性差异。     

微波辅助提取/HPLC分析石蒜中的生物碱

石蒜科石蒜属(amaryllidaceae)植物,含有石蒜碱、力可拉敏和加兰他敏(图1)等生物碱,具有镇静、镇痛、解热、降压、抗炎、催吐、抗病毒、抗癌等作用[1]。目前石蒜生物碱的提取主要采用溶剂回流法(SRE),但SRE提取效率低、耗时、耗溶剂,而且有效成分易被破坏[2-3]。微波辅助提取法     

Determination of dopamine,epinephrine, and norepinephrine by open‐tubular capillary electrochromatography using graphene oxide molecularly imprinted polymers as the stationary phase

A novel capillary electrochromatography method was developed for the determination of dopamine (DA), epinephrine (EP), and norepinephrine (NE) by using a graphene oxide (GO) molecularly imprinted polymers (MIPs) coated capillary. In this article, GO was introduced as supporting matrix to synthesize MIPs in the presence of DA as template molecule. Then GO MIPs were used as the stationary phase in electrochromatography for the determination of DA, EP, and NE. The separation of these three analytes was achieved under the optimal conditions with a satisfactory correlation coefficients (R²) > 0.9957 in the range of 5.0–200.0 μg/mL for EP and NE, and 20.0–200.0 μg/mL for DA, respectively. The RSDs for the determination of three analytes were <6.19%, and the detection limits were 1.25 μg/mL for EP and NE, and 10.0 μg/mL for DA, respectively. Finally, this method was used for the determination of DA, EP, and NE in human serum and DA hydrochloride injection.     

双波长双指示剂-催化动力学光度法测定奶粉中的锌

研究发现在HCl介质中,痕量锌对H2O2氧化甲基紫和亚甲基蓝褪色具有强烈的催化作用,通过测量580 nm和668 nm处催化反应体系和非催化反应体系吸光度的变化,建立了双波长双指示剂催化动力学光度法测定痕量锌的新方法。在最佳实验条件下,线性范围为1.5~60μg/L,线性方程为ΔA=0.0169ρZn2+(μg/mL)+0.0019,r=0.9982,方法检出限为0.84μg/L。该方法可用于奶粉痕量锌的测定。     

毛细管电泳-电化学发光间接测定人血浆中盐酸甲氯芬酯

建立了一种毛细管电泳-电化学发光间接测定人血浆中盐酸甲氯芬酯(MFX)的新方法.在碱性条件下,三联吡啶钌在铂电极上的弱电化学发光信号可以被MFX增敏,且MFX水解后灵敏度比未水解的灵敏度提高了6倍.研究了工作电极电位、磷酸盐缓冲溶液浓度及其pH值、分离电压、进样电压和进样时间等实验参数对MFX水解产物N,N-二甲氨基乙醇测定的影响.在优化实验条件下,其浓度线性范围为0.020～50 μg/mL,检出限(3σ)为6.3 ng/mL,峰高的相对标准偏差为3.1%(10 μg/mL MFX,n=11).利用该法间接地测定了人血浆中MFX的含量,回收率为95.9%～96.9%.     

流动注射-抑制化学发光法测定银杏叶中总黄酮含量

提出了流动注射-抑制化学发光测定银杏叶中的总黄酮含量的分析方法.它是基于银杏叶中物质黄酮类具有还原性,在碱性条件下还原H_2O_2,抑制鲁米诺-H_2O_2-KIO_4体系的化学发光,其抑制程度的大小与总黄酮的含量成线性关系.方法的线性范围为1.5～30μg/mL,检出限为0.03μg/mL,相对标准偏差(RSD)为1.2%,采样频率为240次/h,回收率为101%～104%.