A rapid derivative spectrophotometric method for simultaneous determination of naphazoline and antazoline in eye drops

A zero-crossing first-derivative spectrophotometric method is applied for the simultaneous determination of naphazoline hydrochloride and antazoline phosphate in eye drops. The measurements were carried out at wavelengths of 225 and 252 nm for naphazoline hydrochloride and antazoline phosphate, respectively. The method was found to be linear (r2>0.999) in the range of 0.2-1 microg/ml for naphazoline hydrochloride in the presence of 5 microg/ml antazoline phosphate at 225 nm. The same linear correlation (r2>0.999) was obtained in the range of 1-10 microg/ml of antazoline phosphate in the presence of 0.5 microg/ml of naphazoline hydrochloride at 252 nm. The limit of determination was 0.2 microg/ml and 1 microg/ml for naphazoline hydrochloride and antazoline phosphate, respectively. The method was successfully used for simultaneous analysis of naphazoline hydrochloride and antazoline phosphate in eye drops without any interference from excipients and prior separation before analysis.     

Simultaneous determination of sildenafil, vardenafil and tadalafil as forbidden components in natural dietary supplements for male sexual potency by high-performance liquid chromatography-electrospray ionization mass spectrometry

A high-performance liquid chromatographic method coupled with ultraviolet detection and electrospray ionization mass spectrometry (HPLC-UV-ESI-MS) was developed for simultaneous determination of banned additives-sildenafil, vardenafil and tadalafil in dietary supplements for male sexual potency. The separation was achieved on a C18 column with acetonitrile and aqueous solution (20 mmol ammonium acetate, 0.2% formic acid) as mobile phase at a flow rate of I ml/min with a linear gradient program. UV detection was at 292 nm. Identification of drugs was accomplished using ESI-MS. Good linearity between response (peak area) and concentration was found over a concentration range of 0.8-80 microg/ml for sildenafil; 2.25-225 microg/ml for vardenafil; and 1.1-110 microg/ml for tadalafil, with regression coefficient is better than 0.999. The recovery of the method ranged from 93.3 to 106.1%, and the relative standard deviation varied from 2.0 to 5.6% (n = 6). The method has been successfully applied to the analysis of practical samples of natural dietary supplements.     

Determination of chlorprothixene and amitryptyline hydrochlorides by UV-derivative spectrophotometry and UV-solid-phase spectrophotometry

Two methods for spectrophotometric determination of chlorprothixene and amitryptyline hydrochlorides were proposed. One of them is based on spectral analysis of their derivative spectra. The measurement of the value at 316.0 nm of first derivative was used for construction of calibration graph for chlorprothixene. The Beer law was obeyed in the concentration range 0.5-50.0 microg ml(-1). The amplitude of the second derivative at 261.4 nm was used for determination of amitryptyline in the range 0.5-75.0 microg ml(-1). The second proposed method is utilized the use of solid sorbent for simultaneous preconcentration and assay of studied compounds. For this purpose the filtration gel Sephadex G100 was applied. The elaborated solid-phase spectrophotometric method was used for determination of chlorprothixene at 268.0 nm in the range 2.5-75.0 microg ml(-1) and amitryptyline at 238.0 nm in the concentration range 10.0-75.0 microg ml(-1).     

高效液相色谱法同时测定化妆品中的10种合成着色剂

建立了高效液相色谱同时测定化妆品中颜料橙5、酸性黄36、颜料红53、酸性紫49、罗丹明B、溶剂蓝35、苏丹红Ⅱ、苏丹红Ⅳ、分散黄3和颜料红57等10种合成着色剂的方法。用四氢呋喃(THF)、二甲基亚砜(DMSO)和甲醇对样品进行分步超声辅助萃取、离心净化后,在Eclipse XDB-C₁₈(150 mm×4.6 mm, 5 μm)色谱柱上分离。用乙腈-0.02 mol/L乙酸铵溶液(用乙酸调pH至4.60)作为流动相进行梯度洗脱,二极管阵列检测器(DAD)检测。在0.5~20.0 mg/L范围内,10种着色剂的峰面积与质量浓度呈线性关系,相关系数(r)大于0.999;定量限(LOQ)为10~20 mg/kg。在3个添加水平的回收率均在92.9%~108.8%之间,相对标准偏差(RSD)为0.5%~6.1%(n=6)。该方法简便、快速、灵敏,适合油状、粉状和膏状化妆品中禁限用着色剂的定量检测。     

The analysis of the zero-order and the second derivative spectra of retinol acetate, tocopherol acetate and coenzyme Q10 and estimation of their analytical usefulness for their simultaneous determination in synthetic mixtures and pharmaceuticals

The aim of the present work was to develop a simple and rapid method of retinol acetate, tocopherol acetate and coenzyme Q(10) determination in pharmaceuticals without involving any preparation operations like separation or masking. The values of second derivative amplitude at 212 nm for tocopherol, 351 nm for retinol and 222 nm for coenzyme were used for construction of calibration graphs. Beer's law is obeyed in the concentration range 0.5-20, 0.5-7.5 and 0.5-30 microg ml(-1) for retinol acetate, tocopherol acetate and coenzyme, respectively. The elaborated procedures were successfully applied to the simultaneous determination of studied compounds in their binary synthetic mixtures and in commercial preparations with high reliability and repeatability. Spectral properties of retinol acetate allows to determine its contents in ternary mixture which includes Vitamin E and coenzyme Q(10).     

GC-MS法测定氧化型染发剂中的苯二胺

建立了气相色谱-质谱同时测定氧化型染发剂中邻苯二胺、间苯二胺和对苯二胺的方法。以乙酸乙酯提取氧化型染发剂中苯二胺,用气相色谱-质谱方法进行定性和定量分析。该方法对氧化型染发剂中的3种苯二胺的检出限为20 mg/kg,线性范围为0.2~10 mg/L,线性相关系数为0.999 2~0.999 9。方法的回收率为75%~110%,满足氧化型染发剂中3种苯二胺检测的需要。     

高效液相色谱-串联质谱法测定化妆品中的欧前胡素和异欧前胡素

建立了化妆品中欧前胡素和异欧前胡素的高效液相色谱-串联质谱(HPLC-MS/MS)测定与确证方法。样品经甲醇提取,以C18柱为分离柱,10 mmol/L乙酸铵/甲醇溶液-5 mmol/L乙酸铵水溶液(80:20, v/v)为流动相分离,采用电喷雾串联四极杆质谱进行检测。欧前胡素和异欧前胡素在0.25～20 μg/L内线性良好(相关系数大于0.999);方法定量限(LOQ)为0.50 mg/kg。在0.50～10.0 mg/kg内,欧前胡素和异欧前胡素的回收率范围分别为82.2%～105%和80.0%～103%,相对标准偏差分别为2.7%～4.9%和1.8%～4.6%。该方法能够满足化妆品中欧前胡素和异欧前胡素检测的需要。     

微波辅助萃取-气相色谱法测定茶叶中的有机磷农药

建立了微波辅助萃取–气相色谱法测定茶叶中甲胺磷、乐果、毒死蜱、水胺硫磷、三唑磷5种有机磷农药残留量的分析方法。样品用乙酸乙酯微波辅助提取,提取液经分散固相萃取法(DSPE)净化,用气相色谱配FPD检测器测定,外标法定量。结果表明农药混合标准溶液在0.01～0.5μg/mL范围内线性良好(r>0.999),方法的检出限为0.005～0.01 mg/L,在0.05,0.125,0.5μg/mL 3个水平添加平均回收率为63.3%～99.9%,测定结果的相对标准偏差为5.1%～8.2%(n=6)。该方法适合于茶叶中多种有机磷农药残留量的同时检测。     

顶空气相色谱法测定氟尼辛葡甲胺原料药中有机溶剂残留量

建立了氟尼辛葡甲胺原料药中乙酸乙酯、甲醇、异丙醇、乙醇和乙腈有机溶剂残留量的顶空气相色谱分析方法。以HP-FFAP色谱柱(30 m×0.32 mm×1.0 μm)为分离柱,火焰离子化检测器检测,外标法定量,并考察了顶空平衡温度、平衡时间等对残留有机溶剂测定的影响。实验结果表明,在顶空平衡温度为90 ℃、平衡时间为30 min条件下获得较好的定量结果。乙酸乙酯、甲醇、异丙醇、乙醇和乙腈的线性范围分别为0.40～7.93 mg/L (r=0.9998)、7.32～146.48 mg/L (r=0.9996)、4.53～90.61 mg/L (r=0.9999)、3.62～72.32 mg/L (r=0.9998)和2.31～46.24 mg/L (r=0.9996);平均回收率范围为95.96%～100.31%,精密度(以相对标准偏差计,n=6)为1.97%～3.28%;检出限分别为0.08、0.9、0.2、0.4和0.3 mg/L。利用该方法对实际样品氟尼辛葡甲胺原料药中有机溶剂残留量进行了检测。结果表明,该样品中含有异丙醇和乙醇,其含量分别为177.44 μg/g与69.32 μg/g。本方法快速、灵敏、准确,适用于氟尼辛葡甲胺原料药中残留溶剂的检测。     

Determination of megestrol acetate and cyproterone acetate in serum of patients with advanced breast cancer by high-performance liquid chromatography

A reversed-phase high-performance liquid chromatographic method with ultraviolet detection of megestrol acetate and cyproterone acetate in human sera is described. The proposed assay is linear up to 1400 ng/ml (r = 0.999) and has a detection limit of 5 ng/ml. Recoveries of both compounds in spiked sera were ca. 95%; inter-assay coefficients of variation were 4.0 and 3.1% and intra-assay values were 1.3 and 1.4%, respectively. For validation of the method we also developed a gas chromatographic-mass spectrometric method for both steroids. The results obtained by the two methods showed good correlation: for megestrol acetate r = 0.98, n = 31, p less than 0.0001, and for cyproterone acetate r = 0.94, n = 0, p less than 0.0001. Large inter-individual differences in the serum concentrations of both substances were found in groups of patients with metastatic breast cancer receiving the same oral load of either steroid.     

超高效液相色谱法测定美白、祛痘化妆品中4种禁用激素

建立了超高效液相色谱同时测定美白、祛痘化妆品中4种糖皮质激素氢化可的松、曲安奈德醋酸酯、氯倍他索丙酸酯、倍他米松双丙酸酯的方法。样品采用甲醇涡旋超声提取,色谱柱采用Waters ACQUITY UPLC BEH C18柱(100 mm×2.1 mm,1.7μm),流动相为乙腈–水溶液,梯度洗脱,流量为0.5 m L/min,用PDA检测器检测,检测波长为240 nm。方法检出限以3倍空白噪音计,氢化可的松、曲安奈德醋酸酯、氯倍他索丙酸酯、倍他米松双丙酸酯的检出浓度分别为0.12,0.18,0.30,0.30 mg/kg。在质量浓度为1.0~40.0 mg/L时,标准工作曲线相关系数r0.999 8,4种激素的回收率为85.3%~102.8%,测定结果的相对标准偏差为2.1%~5.0%(n=6)。该方法前处理简单,分离效果好,且灵敏度高,速度快,能满足美白、祛痘化妆品中4中糖皮质激素的检测需要。     

反相高效液相色谱法同时测定墨旱莲中的蟛蜞菊内酯和异去甲基蟛蜞菊内酯

建立了同时测定墨旱莲中香豆草醚类成分蟛蜞菊内酯和异去甲基蟛蜞菊内酯含量的高效液相色谱法。采用Kromasil C18柱(250 mm×4.6 mm, 5 μm),流动相为甲醇-0.5%醋酸水溶液(体积比为55∶45),流速为1.0 mL/min,检测波长为351 nm,柱温为30 ℃,进样量为20 μL。在上述条件下测得的异去甲基蟛蜞菊内酯和蟛蜞菊内酯的质量浓度分别在1.6~32.0 mg/L和5.6~112.0 mg/L时与色谱峰面积之间的线性关系良好,二者高、中、低浓度条件下的平均加标回收率分别为97.5%～ 98.2%和99.0%～ 100.2%。该方法简便、快速、准确,可作为墨旱莲质量控制的一个有效方法。     

Simultaneous determination of zirconium and molybdenum by first-derivative spectrophotometry.

A first-derivative spectrophotometric method for the simultaneous determination of Zr and Mo with Alizarin Red S is described. Measurements were made at the zero-crossing wavelengths at 490.5 nm for Zr and 446.0 nm for Mo. The calibration graphs were linear at 0.5-20 and 0.5-13.0 microg ml(-1) for Zr and Mo, respectively. The possible interfering effects of various ions were studied. Only iron was interfered in this system. The validity of the method was examined by using some mixtures of Mo and Zr. The method was applied in different matrix in both presence and absence of some foreign metal ions.     

ICP–AES法同时测定食品包装铝箔中锌、铅、镉、砷的溶出量

建立了ICP–AES法同时测定食品包装铝箔中锌、铅、镉、砷溶出量的方法。以4%乙酸溶液浸泡样品,室温放置24 h,分析线为Zn 213.856,Pb 220.353,Cd 226.502,As 193.759 nm。Zn,Pb,Cd,As的线性范围分别为0.3~5.0,0.1~2.0,0.01~0.2,0.03~0.5 mg/L,线性方程分别为Y=23 487.27X+769.79,Y=6 713.35X+38.46,Y=30 562.52X+362.02,Y=6 448.97X+13.57;相关系数分别为0.999 9,0.999 8,0.999 9,0.999 5;检出限分别为0.009 6,0.003 7,0.000 4,0.013 9mg/L;加标回收率为96.5%~100.5%;相对标准偏差为1.38%~3.06%(n=6)。该方法简便快速,测定结果准确。     

Atmospheric pressure photoionization applied to quantitation of cyproterone acetate in human plasma

Cyproterone acetate [6-chloro-1beta,2beta-dihydro-17alpha-hydroxy- 3'H-cyclopropa(1,2)-pregna-1,4,6-triene-3,20-dione acetate] is a powerful antiandrogen used in the treatment of women suffering from disorders associated with androgenization such as hirsutism and acne. A fast, sensitive, and robustness method is developed for the determination and quantitation of cyproterone acetate in human blood plasma by liquid chromatography coupled with tandem mass spectrometry. Cyproterone acetate is extracted from 0.2 mL human plasma by liquid-liquid extraction. The method has a chromatographic run of 4.5 min, using a C18 analytical column (100- yen 2.1-mm i.d.), and the linear calibration curve over the range is linear from 1 to 500 ng/mL (r2 > 0.994). The between-run precision, based on the relative standard deviation replicate quality controls, is 96.2% (3 ng/mL), 97.5% (120 ng/mL), and 99.1% (400 ng/mL). The between-run accuracy was +/- 2.7%, 3.1%, and 4.8% for the previously mentioned concentrations, respectively. The method is employed in a bioequivalence study of two tablet formulations of cyproterone acetate (100 mg).     

高效液相色谱-串联质谱法同时测定减肥保健食品中非法添加的药物利莫那班和奥利司他

建立了一种专属、灵敏的同时测定减肥保健食品中非法添加的药物利莫那班和奥利司他的高效液相色谱-串联质谱分析方法。不同类型的减肥保健食品经加速溶剂萃取后,用甲醇和10 mmol/L乙酸铵水溶液作流动相,采用梯度洗脱方式以Waters Atlantis T3色谱柱(150 mm×2.1 mm, 3 μm)分离,以电喷雾离子源正离子检测方式进行质谱分析。实验结果表明,利莫那班和奥利司他的方法检出限为0.5 mg/kg;在0.5～100 μg/L范围内呈良好的线性关系,相关系数分别为0.9989和0.9994;在2, 5, 10 mg/kg 3个添加水平范围内的平均回收率为80.5%～102.1%;日内精密度均小于6%,日间精密度均小于8%。同时研究了这两种药物的质谱特征,推测了其质谱裂解途径。本方法灵敏度高,重现性好,可用于不同类型减肥保健食品中非法添加的奥利司他和利莫那班的检测。     

Rapid and sensitive HPLC method for the simultaneous determination of paraquat and diquat in human serum.

A rapid and sensitive HPLC method for the simultaneous determination of paraquat and diquat in human serum has been developed. After deproteinization of the serum with 10% trichloroacetic acid, the samples were separated on a reversed-phase column, and subsequently reduced to their radicals with alkaline sodium hydrosulfite solution. These radicals were monitored with a UV detector at 391 nm. This method permitted the reliable quantification of paraquat over linear ranges of 50 ng - 10 microg/ml and 100 ng - 10 microg/ml for diquat in human serum. The within- and between-day variations are lower than 2.3 and 2.2%, respectively. This technique was also utilized to determine the paraquat and diquat serum levels in a patient who had ingested herbicide (Prigrox L) containing paraquat and diquat.     

Spectrophotometric and spectrodensitometric determination of paracetamol and drotaverine HCl in combination

Thin-layer chromatography, first derivative, ratio spectra derivative spectrophotometry and Vierordt's method have been developed for the simultaneous determination of paracetamol and drotaverine HCl. TLC densitometric method depends on the difference in Rf values using ethyl acetate:methanol:ammonia (100:1:5 v/v/v) as a mobile phase. The spots of the two drugs were scanned at 249 and 308 nm over concentration ranges of 60-1200 microg/ml and 20-400 microg/ml with mean percentage recovery 100.11%+/-1.91 and 100.15%+/-1.87, respectively. The first derivative spectrophotometric method deals with the measurements at zero-crossing points 259 and 325 nm with mean percentage recovery 99.25%+/-1.08 and 99.45%+/-1.14, respectively. The ratio spectra first derivative technique was used at 246 and 305 nm with mean percentage recovery 99.75%+/-1.93 and 99.08%+/-1.22, respectively. Beer's law for first derivative and ratio spectra derivative methods was obeyed in the concentration range 0.8-12.8 and 0.4-6.4 microg/ml of paracetamol and drotaverine HCl, respectively. Vierordt's method was applied to over come the overlapping of paracetamol and drotaverine HCl in zero-order spectra in concentration range 2-26 and 2-40 microg/ml respectively. The suggested methods were successfully applied for the analysis of the two drugs in laboratory prepared mixtures and their pharmaceutical formulation. The validity of the methods was assessed by applying the standard addition technique. The obtained results were statistically agreed with those obtained by the reported method.     

Simultaneous determination of glucose, 1,5-anhydro-d-glucitol and related sugar alcohols in serum by high-performance liquid chromatography with benzoic acid derivatization

A new, simple and sensitive pre-column high-performance chromatographic method for the determination of diabetes marker d-glucose, 1,5-anhydro-d-glucitol and related compounds is reported. Sugars (d-glucose, d-galactose, d-mannose, sucrose and arabinose) were derivatized with benzoic acid (BA) at 80 degrees C for 60 min. l-Fucose, fructose, d-lactose, l-rhamnose, arabinose and ascorbic acid were not reacted. Sugar alcohols (xylitol, erythritol, mannitol, sorbitol myo-inositol) were also derivatized with BA at 80 degrees C for 60 min. The fluorescence derivatives were separated on a TSK amide 80 column (4.6 mm i.d. x 250 mm, 5 microm) with acetonitrile-50 mm acetate buffer (pH 5.6; 4:96, v/v) as the mobile phase. The detection wavelength of beizoic acid derivatives was lambda(ex) 275 nm and lambda(em) 315 nm. The detection limits of sugars were 10-80 microg/mL. The calibration graphs were linear up to 10 mg/mL. The relative standard deviations of 500 microg/mL sugars were 7.0-7.3%. The proposed method was compared with the enzymatic photometric glucose analysis method (Glucose B-Test II Wako). The correlation coefficient was 0.83 (n = 20) and y = 0.82x + 5.91, where y and x are concentrations in microg/mL obtained by the proposed pre-column HPLC and enzyme-photometric method, respectively. The detection limits of sugar alcohols were 100-1000 ng/mL. The calibration graphs were linear to 50 microg/mL and relative standard deviations of 10 microg/mL were 7.2-8.2%. The 1,5-AG data by the proposed method was also compared with the enzymatic photometric 1,5-AG analysis method (Rana AG 1,5-AG determination kit, Nihon Kayaku) and good correlation (r = 0.91, n = 20) was also obtained. The proposed method was applied to the simultaneous determination of d-glucose, 1,5-AG and related sugar alcohols in serum from healthy males.     

高效液相色谱法测定水产品中残留的吡喹酮

建立了一种灵敏度高、操作简单的定量分析水产品中残留的微量吡喹酮的高效液相色谱方法。样品经乙酸乙酯提取、极性硅胶柱净化后进行高效液相色谱分析,以乙腈-水(体积比为50∶50)为流动相,流速为0.9 mL/min,ZORBAX C18色谱柱分离,紫外检测波长为214 nm。在此条件下吡喹酮在0.02～20 mg/L范围内呈线性关系,相关系数为0.99998;吡喹酮的加标回收率在85%以上,检出限为10 μg/kg。