电喷雾-离子迁移谱法快速筛查保健酒饮料中3种壮阳类药物

目的建立电喷雾-离子迁移谱(ESI-IMS)快速筛查保健酒饮料中违法添加西地那非、硫代艾地那非和伐地那非3种壮阳类违禁药物的方法。方法样品经乙腈超声提取,稀释定容后直接测定。以ESI作为电离源,空气作为迁移气体,在正离子模式进行检测,基质外标法定量。结果西地那非、伐地那非、硫代艾地那非分别在1.25~12.50、2.00~20.00、1.00~10.00 mg/L范围内线性关系良好,相关系数(r)均大于0.99,3种违禁药物的检测限分别为0.50、0.80、0.40 mg/L。平均回收率为93.33%~121.17%,相对标准偏差(RSD)为2.65%~10.00%,实际样品检测与气相色谱-质谱联用法确证结果一致。结论该方法快速简便,结果准确可靠,适用于保健酒饮料中非法添加西地那非、硫代艾地那非和伐地那非3种壮阳类违禁药物的快速筛查。     

表面增强拉曼光谱法快速测定保健酒中西地那非

目的 建立金核银壳结构纳米颗粒(Au@Ag NPs)的表面增强拉曼光谱法(surface-enhanced Raman scattering, SERS)快速检测保健酒中非法添加物西地那非的分析方法。方法 制备3种纳米粒子Ag、Au、Au@Ag NPs为SERS基底, 比较3种基底的增强效果。样品前处理基于溶剂萃取法, 利用二氯甲烷对保健酒中的西地那非进行简单提取, 通过调节体系pH值, 得到最佳提取率和SERS增强效果。结果 Au@Ag NPs的SERS增强效应优于Au NPs和Ag NPs; 用0.1 mol/L氢氧化钾调节溶液pH值可有效提高二氯甲烷的提取效果, 再用0.1 mol/L稀盐酸溶解挥发后残留物, 使得西地那非在pH调节后更有利于吸附在Au@Ag NPs表面, 获得更强的SERS信号。西地那非的检出限为0.5 mg/L, 在0.5~10 mg/L浓度范围内线性关系较好, 相关系数(r2)为0.9472, 回收率为86.0%~95.8%之间, 相对标准偏差(relative standard deviation, RSD)为3.6%~5.9%。 结论 SERS技术灵敏度高、特异性强, 可用于快速检测保健酒中的西地那非, 为快速筛查大量样品提供新方法。     

HPLC法快速筛查保健酒中那非药物及质谱确证

建立高效液相色谱法(high performance liquid chromatography,HPLC)快速筛查保健酒中14种那非违禁药物的分析方法,并采用液相色谱-串联质谱法对可疑那非类药物残留的阳性保健酒进行确证。结果表明:在0.5μg/mL～50.0μg/mL范围内,14种那非类药物质量浓度与其峰面积呈现良好的线性关系,相关系数r~2在0.999 1～0.999 9之间;方法检出限在0.06μg/mL～0.24μg/mL,方法定量限在0.20μg/mL～0.80μg/mL;平均回收率在94.1%～101.4%,RSD在1.1%～3.7%。     

表面增强拉曼光谱法定性定量检测保健食品中非法添加物西地那非

建立表面增强拉曼光谱法定性定量检测保健食品中非法添加药物西地那非。利用拉曼光谱的特异性进行西地那非定性检测;用三聚氰胺作为内标物进行西地那非定量检测,以西地那非特征峰1 234 cm~(-1)与三聚氰胺特征峰707 cm~(-1)的峰高比为纵坐标,西地那非质量浓度为横坐标进行线性回归拟合,结果表明西地那非质量浓度在0～50 mg/L范围呈现良好的线性关系,R~2=0.996 9。定性检测限为0.05 mg/L,定量检测限为5 mg/L。其固体、液体样品加标回收率分别为85.6%～92.6%、98.7%～105.2%,相对标准偏差分别为4.14%、3.25%。采用本方法对实际样品进行检测,其结果与高效液相色谱-质谱法测量结果基本一致。本方法准确、灵敏、快速,可用于保健品中非法添加西地那非类药物的定性定量检测。     

盐酸克伦特罗快速检测胶体金试纸的研制

为建立快速检测猪尿等样品中盐酸克伦特罗（CL）的胶体金免疫层析方法,用柠檬酸三钠还原氯金酸制备了胶体金,将其标记抗CL单克隆抗体,制备了金标抗体;以CL-人血清白蛋白（HSA）为包被抗原、羊抗鼠IgG为质控线二抗,制成胶体金试纸。优化了胶体金颗粒粒径、标记抗体用量和pH值等各项参数,最终确定胶体金粒径为15 nm、每毫升胶体金溶液中添加20 ?g抗体、胶体金溶液pH值为7.4、金标抗体稀释液为添加0.1 %牛血清白蛋白（BSA）的0.05 mol/L磷酸盐缓冲液（pH 7.4）、金标抗体喷涂量为50 ?L/cm2、CL-HSA和羊抗鼠IgG的包被浓度分别0.5 mg/mL和2 mg/mL。研制的CL胶体金试纸检测限为3 ng/mL,与莱克多巴胺、沙丁胺醇等六种?-兴奋剂类药物无交叉反应。对42份猪尿样品的检测结果与市售酶联免疫（ELISA）试剂盒的符合率为100 %。试纸无需仪器辅助,操作简便,可在5 min内完成,适用于对CL残留进行现场检测。     

食品中-种新型PDE-5抑制剂的快速筛查和定量测定

摘要：目的对食品中发现的一种非法添加的新型PDE-5抑制剂进行结构解析并建立定量测定方法。方法采用高效液相色谱-二极管阵列检测器法（HPLC-DAD）发现了一种未知的新型伐地那非类似物,采用超高效液相色谱-四级杆-静电场轨道阱质谱（UPLC-Q-Exactive Orbitrap-MS）对其结构进行质谱解析,并依据解析的化学结构购买对照品,确定该物质为O-丙基伐地那非。采用超高效液相色谱-三重四极杆质谱(UPLC-MS/MS)建立典型食品中O-丙基伐地那非的定量测定方法。结果O-丙基伐地那非在0.5025~50.25ng/mL质量浓度范围内线性关系良好,相关系数（r）为0.9998,方法检出限为0.025mg/kg,方法的定量限为0.05mg/kg,在咖啡、压片糖果、保健酒基质中3个水平加样回收率分别为92.5%、86.3％、98.6%,RSD均小于4.6％。采用该方法对市场监管部门送检的93批样品进行测定,结果其中17批检出O-丙基伐地那非,其含量为28.3~359mg/kg。结论所建立的方法快速、灵敏、准确,可用于O-丙基伐地那非的筛查和定量。研究思路可给其他非法添加未知物的鉴定提供参考。     

高效液相色谱-串联质谱检测保健酒中非法添加物艾地那非

目的：采用高效液相色谱-串联质谱（high performance liquid chromatography-tandem mass spectrometry,HPLC-MS/MS）法,建立保健酒中非法添加物艾地那非的检测方法。方法：使用Agilent RRDH Eclipse-plus C18色谱柱（2.1 mm×100 mm,1.8 μm）,以0.1%甲酸-乙腈溶液为流动相A、0.1%乙酸-20 mmol/L乙酸铵溶液为流动相B进行梯度洗脱。通过HPLC-MS/MS系统中全扫描模式对艾地那非进行定性分析,多反应监测模式对艾地那非进行定量分析。结果：该方法线性r2大于0.99,精密度相对标准偏差小于3%,不同质量浓度样品平均回收率为97.31%～100.66%,检出限为0.6 ng/mL,定量限为1.6 ng/mL。结论：此方法测定准确、灵敏度高、分离度高,可用于保健酒中非法添加物艾地那非的筛选和检测。     

超高效液相色谱-串联质谱同时测定露酒中11种那非物质

建立了一种使用超高效液相色谱仪和三重四极杆质谱仪联用同时检测露酒中11种那非类物质残留量的测试方法。样品经处理后,用超高效液相色谱在7 min内完成分离,三重四极杆质谱仪进行定量分析。对11种那非的线性、精密度、检出限(LOD)、定量限(LOQ)进行了验证。西地那非、那红地那非、红地那非、伐地那非、羟基豪莫西地那非、豪莫西地那非、氨基他达那非、他达那非、硫代艾地那非、伪伐地那非、那莫西地在1 μg/L~20 μg/L内线性良好,相关系数均大于0.999;用浓度为4 μg/L的混合标准溶液进行了重现性实验,实验结果表明连续6次进样保留时间和峰面积相对标准偏差分别在0~0.17%和2%~6%之间,检测方法重现性良好;在露酒中添加标液,回收率80%~115%。     

液相色谱-串联质谱法测定抗疲劳类保健食品中非法添加的西地那非含量的不确定度评定

目的对液相色谱-串联质谱法(liquid chromatography-tandem mass spectrometry,LC-MS/MS)测定抗疲劳类保健食品中非法添加的西地那非含量的不确定度进行评定。方法根据JJF1059.1—2012《测量不确定度评定与表示》、JJF 1135—2005《化学分析测量不确定度评定》,采用液相色谱-串联质谱法测定抗疲劳类保健食品中西地那非残留量,对测定方法中的关键环节进行分析,对各不确定度分量进行识别和量化,计算出合成不确定度和扩展不确定度。结果当西地那非含量为0.927μg/g, k=2(置信水平95%)时,扩展不确定度为0.06μg/g,测试结果表示为(0.927±0.06)μg/g。结论本方法为液相色谱-串联质谱法测定抗疲劳类保健食品中非法添加的西地那非含量的不确定度提供了参考依据。     

UPLC-MS/MS法同时快速测定保健食品中7种非法添加药物

目的：建立同时快速测定保健食品中阿伐那非、米罗那非、乌地那非、西地那非、他达拉非、沙格列汀和西布曲明等7种非法添加药物的超高效液相色谱-串联质谱检测方法。方法：试样前处理采用乙腈为提取溶剂,经超声处理,Waters ACQUITY UPLC?BEH C₁₈(100 mm×2.1 mm,1.7μm)色谱柱分离,以水(含0.1%甲酸)-乙腈(含0.1%甲酸)为流动相梯度洗脱,流速0.3 mL·min^-1,柱温30℃,进样量2μL。质谱采用电喷雾离子源,以正离子多反应监测模式进行定性和定量分析。结果：7种非法添加药物在本方法色谱和质谱条件下8 min内能得到快速分离,在10～500 ng·mL^-1线性关系良好,相关系数R为0.997 1～0.999 2,检出限为0.002 5 mg·kg^-1。结论：本方法前处理过程简单快速,选择性强,灵敏度高,能够快速、准确地同时对保健食品中非法添加的阿伐那非、米罗那非、乌地那非、西地那非、他达拉非、沙格列汀和西布曲明进行定性及定量测定。     

LC-ESI-MS/MS analysis of phosphodiesterase-5 inhibitors and their analogues in foods and dietary supplements in Korea

A number of 188 food and dietary supplement samples were collected from 2009 to the first half of 2013 in Korean online and offline stores. A method to identify phosphodiesterase-5 (PDE-5) inhibitors and their analogues using liquid chromatography-electrospray ionisation-mass spectrometry/mass spectrometry (LC-ESI-MS/MS) was validated. Limit of detection and limit of quantitation of liquid-type and solid-type negative samples ranged from 0.05 to 3.33 ng/mL or ng/g and from 0.15 to 10.00 ng/mL or ng/g, respectively. Recoveries ranged from 83% to 112%. Nineteen PDE-5 inhibitors and their analogues were detected, with tadalafil group compounds being the most frequently observed (53.0%), followed by the sildenafil group (42.5%). Tadalafil concentrations ranged from 0.08 to 138.69 mg/g. Compounds were most frequently detected in capsules (in 40 of 80 adulterated samples). To protect public health and food safety, appropriate monitoring of PDE-5 inhibitors and their analogues in foods and dietary supplements is recommended.     

游离SO2、溶解氧浓度对葡萄酒颜色及花色苷含量的影响

目的：探索不同浓度溶解氧与游离SO₂对赤霞珠干红葡萄酒在陈酿中的颜色及相关参数的影响。方法：以新疆吐鲁番鄯善县新葡王酒庄赤霞珠干红葡萄酒为酿制试材,在葡萄酒陈酿过程中通过添加不同浓度的游离SO₂与溶解氧,观察其对葡萄酒色度、色调和花色苷含量等指标的影响。结果：溶解氧与游离SO₂浓度较低时葡萄酒呈鲜艳的酒红色,充氧量为2 mg/(L·30 d)时可促进葡萄酒中花色素苷、单宁适度聚合,改善葡萄酒品质;游离SO₂质量浓度为15~30 mg/L时对葡萄酒的色调值影响不大,但对色度影响较为明显,超过30 mg/L时会使葡萄的酒颜色逐渐显橙色。结论：赤霞珠干红葡萄酒陈酿的适宜游离SO₂质量浓度为25 mg/L,充氧量为2 mg/(L·30 d)。     

Inhibitory Effects of Red Wine on Lipid Oxidation in Fish Oil Emulsion and Angiogenesis in Zebrafish Embryo

The capabilities of red wine against lipid oxidation and angiogenesis were evaluated by using a fish oil emulsion system and an in vivo zebrafish embryos model, respectively. The red wine contained 12 different antioxidant phenolics which levels were led by anthocyanins (140.46 mg/L), catechin (55.08 mg/L), and gallic acid (46.76 mg/L). The diversity of the phenolics in red wine was greater than the tea, coffee, or white wine selected as a peer control in this study. The total phenolics concentration of red wine was 305.53 mg/L, although the levels of tea, coffee, and white wine were 85.59, 76.85, and 26.57 mg/L, respectively. The activity of red wine in scavenging DPPH (2,2‐diphenyl‐1‐picrylhydrazyl) free radicals was approximately 4 times higher than the tea and 8 times than the coffee or white wine. The red wine showed the highest capability in preventing long chain PUFA oxidation in the fish oil emulsion. Because of the outstanding antioxidant activity of red wine, the red wine dried extract was used to monitor its inhibitory effect against angiogenesis by using transgenic zebrafish embryos (Tg[fli1:egfp]^y1) with fluorescent blood vessels. After incubated in 100 μg/mL of the extract solution for 26 h pf, each of the embryos had a lower number of intersegmental vessel than the control embryo. The inhibition rate of red wine extract against growing of angiogenic blood vessel reached 100%.     

分光光度法测定葡萄酒中瓜氨酸含量

目的：建立分光光度法定量检测葡萄酒中瓜氨酸含量的方法。方法：依据费伦反应原理,采用分光光度法测定葡萄酒中瓜氨酸含量。结果：建立方法的最佳参数为混合酸中硫酸添加量350mL/L、磷酸添加量200mL/L、三氯化铁质量浓度为50mg/L、反应液在100℃的沸水浴中保持5min,暗处室温放置冷却,用分光光度计在波长530nm 处测其吸光度。方法的检出限5μg/L,检测葡萄酒样品方法相对标准偏差为2.4%～3.2%,回收率为96.9%～106.6%。结论：此方法简便、快速、准确可靠,适合用于葡萄酒样品中瓜氨酸含量的定量检测。     

A novel approach to simultaneous screening and confirmation of regulated pharmaceutical compounds in dietary supplements by LC/MS/MS with an information-dependent acquisition method

The commercial success of synthetic phosphodiesterase-5 (PDE-5) inhibitors (viz. sildenafil, vardenafil and tadalafil) for erectile dysfunction (ED) has led to their widespread use as adulterants in dietary supplements (DSs). Reports on adulteration by ED drugs or their analogues in DSs suggest they may cause a serious threat to human health. The problem is becoming more complex as hidden and structurally modified analogues are continuously being reported. To analyse known drugs and their analogues, three commonly used PDE-5 inhibitors, naturally existing icariin and yohimbin, and their 19 analogues were analyzed in this study. They were identified using ion-spray liquid chromatography/tandem mass spectrometry (LC/MS/MS) using multiple reaction monitoring (MRM). This MRM procedure gave a limit of detection of less than 0.02?ng?ml^?1 for the 24 compounds, selectivity of fragmentation using MRM for 2.5?–?8.5?min in a single run and peak height repeatability of coefficient of variation of 3.9?–?31.8%. An IDA method using the MRM scans to detect the presence of known analytes was set up and added to a built-in library for screening for PDE-5 inhibitors. These MRM experiments were used to trigger product ion scans using a hybrid quadrupole-linear ion trap instrument. The product ion scan was compared and confirmed by a library search of MS/MS spectra acquired from a reference standard. To search for new analogues of PDE-5 inhibitors, a precursor ion scan of an expected ion m/z 283, which was one of the mass fragments from the analogues of sildenafil or vardenafil, was performed and fragmentation of the precursor ion, by combining a precursor ion scan with automatic confirmation using EPI spectra, was acquired. Of the 37 DSs tested, two were eventually found to be adulterated with yohimbin and vardenafil, respectively. The approach proposed in this study would be valuable in characterizing chemical constituents of drug residues and their analogues with identical chemical substructures from complex natural and synthetic sources in DSs using an information-dependent acquisition-enhanced product ion (IDA–EPI) scan.     

Determination of Tricyclazole Content in Paddy Rice by Surface Enhanced Raman Spectroscopy

Abstract: An ultrasensitive method based on Surface enhanced Raman scattering (SERS) has been developed to determine content of a pesticide which is tricyclazole in paddy rice using sliver colloid as a substrate and pyridine as an internal standard. The peaks at 424 and 1035 cm^?1 in a SERS spectrum were selected as analytic and internal peaks, respectively, and their intensity ratio I_t/I_p was used to calculate the regression concentration of tricyclazole. The correlation between I_t/I_p and concentration showed significant linear relationship with a correlation coefficient of R²= 0.995 in a concentration range of 0.05 to 0.70 mg/L and the tricyclazole solution can be detected to be low as 0.002 mg/L by SERS. The method was applied to determine tricyclazole contents of 3 real rice samples with a standard addition method in order to eliminate interference of matrix. The errors of SERS measurements for the 3 samples were 0.0008 to 0.0246, 0.0013 to 0.0028, and 0.0129 to 0.0304 mg/kg, respectively, compared with the results obtained by high performance liquid chromatography method. This also showed a good reproducibility with low values of relative standard deviation (n= 3) for the 3 samples ranged from 3.63% to 4.64%. Practical Application: SERS is a simple, rapid, and sensitive method to detect pesticides residue in agricultural food. Our results demonstrate that coupled with silver colloid, SERS is able to rapidly determine tricyclazole residue in paddy rice, indicating that SERS can provide rapid, accurate, and reproducible results for tricyclazole determination at trace level in paddy rice.     

纸喷雾离子化质谱法快速筛查保健食品中违禁添加的磷酸二酯酶5抑制剂

目的建立纸喷雾离子化质谱(PSI-MS)法快速检测保健食品中3种非法添加的磷酸二酯酶5(PDE5)抑制剂(西地那非、伐地那非和他达拉非)的方法。方法利用PSI-MS法对样品中非法添加物进行初步定性鉴别,并通过内标法进行半定量分析。结果 24种包括胶囊、片剂、丸剂、粉末、酒剂、糖浆及口服液等剂型在内的待测市售保健品的PSI-MS检测结果与HPLC-UV检测结果基本一致。各目标物在一定范围内线性关系良好,相关系数r~2均0.99,检出限均在1.0 mg/L以下,相对标准偏差为20%~24%。结论本方法快速、准确、专属性强,适用于大批量复杂基质样品中PDE5抑制剂的快速筛查。     

QuEChERS-表面增强拉曼光谱法测定花生中黄曲霉毒素B1

目的 建立基于QuEChERS净化和表面增强拉曼光谱法(surface-enhanced Raman spectroscopy,SERS)测定花生中黄曲霉毒素B1(aflatoxin B1,AFB1)的分析方法.方法 以纳米银(nano silver,AgNPs)作为SERS活性基底,结合QuEChERS样品预处理技术...     

挤压重组糙米-刺五加茶酒的研制、品质分析及抗氧化评价

以挤压重组糙米蒸馏酒为酒基、刺五加茶汁为茶基,配以赤藓糖醇和柠檬酸制作茶酒,并采用单因素结合正交试验法优化茶酒制作工艺。结果表明,茶酒最佳制作配方为柠檬酸添加量0.14%,赤藓糖醇添加量4%,酒基与茶基的体积比0.5∶1.0,制备的茶酒色泽橙黄、晶亮透明、无沉淀和悬浮物,茶香和酒香融合协调,口感丰富,酸甜适口。酒精度为9.0%vol、总酸含量为4.23 g/L、可溶性固形物为14.18%、透光率为76.68%,总黄酮、总多酚和多糖含量分别为28.57 mg/L,287.08 mg/L和1 112.68 mg/L,特征物质紫丁香苷和异嗪皮啶含量分别为4.09 mg/L和5.86 mg/L,且对DPPH、羟基和超氧阴离子自由基的最大清除率分别为（90.39±3.32）%、（88.33±2.89）%、（80.81±3.19）%,清除能力较强。因此,该研究制备的茶酒具有较高的品质和抗氧化能力。