超高效液相色谱-串联质谱法测定洗发水中14种防脱育发类药物的含量

提出了超高效液相色谱-串联质谱法测定洗发水中西咪替丁、米诺地尔、美拉酮宁、香草酸甲酯、酮康唑、比马前列素、非那雄胺、塞替匹仑、尼鲁米特、氟罗地尔、螺内酯、氟他胺、拉坦前列素、度他雄胺等14种防脱育发类药物含量的方法。样品经水溶解、乙腈提取后,用氨基固相萃取柱净化。以Waters Accquity UPLC BEH C18色谱柱为固定相,以乙腈-含0.1%(体积分数)甲酸的2 mmol·L^(-1)乙酸铵溶液为流动相体系进行梯度洗脱;分离后的14种目标物经电喷雾离子源正、负离子模式扫描,多反应监测模式检测。结果表明:14种目标物的质量浓度在1.0~50.0μg·L^(-1)内与对应的峰面积呈线性关系,检出限(3S/N)为0.05~3.0μg·kg^(-1);对空白样品进行3个浓度水平的加标回收试验,回收率为83.6%~99.0%,测定值的相对标准偏差(n=6)为5.6%~15%;方法用于10个洗发水样品分析,一个样品中检出米诺地尔、西咪替丁、塞替匹仑、酮康唑、尼鲁米特、氟罗地尔,另一个样品中检出美拉酮宁,检出量为0.4~47.8μg·kg^(-1)。

QuEChERS-气相色谱-质谱联用法测定育发类化妆品中的斑蝥素

目的 建立QuEChER孓气相色谱质谱法测定育发类化妆品中斑蝥素的分析方法。方法用丙酮溶解样品，超声、离心后取上清液，加人分散固相萃取吸附剂（PSA粉末、GCB粉末和无水硫酸镁）净化，冷冻离心后取上清液浓缩，供气相色谱-质谱分析。结果斑蝥索在浓度0．1～2．5／μg／mL范围线性良好（r2=0．999 5），在0．1～2．5 μg／g添加水平回收率为86．0％～92．8％，相对标准偏差（RSD）为5．2％～7．3％；检出限（LOD）为0．02／μg／g，定量限（LGQ）为0．08／μg／g。结论该方法能有效去除育发类化妆品中的复杂基质，灵敏度高，定性、定量准确，可满足测定基质复杂的育发类化妆品中斑蝥素检测的需要。

高效液相色谱/二极管阵列检测法快速测定育发类化妆品中8种违禁药物

建立了一种简单、快速同时测定育发类化妆品中8种违禁药物的分析方法。样品经甲醇提取后采用HLB固相萃取小柱净化,甲醇复溶后用Agilent Poroshell 120 Bonus-RP色谱柱分离,以10 mmol/L乙酸铵-甲醇作为流动相进行梯度洗脱,二极管阵列检测器进行检测,可同时对米诺地尔、雌三醇、螺内酯、坎利酮、雌酮、雌二醇、己烯雌酚、黄体酮8种违禁药物进行定性和定量分析。在优化实验条件下,8种药物在0.5～100 mg/L范围内线性关系良好,空白育发类化妆品在5.0、10.0、50.0 mg/kg 3个加标水平下的回收率为80%～96%,相对标准偏差为3.7%～8.9%。方法的定量下限(S/N=10)除螺内酯和黄体酮为2.0 mg/kg外,其余均为5.0 mg/kg。该方法简单、快速、准确,可满足育发类化妆品中8种违禁药物的检测要求。

HPLC测定中草药育发类化妆品中非法添加的米诺地尔

目的建立检测中草药育发类化妆品中非法添加米诺地尔的方法。方法采用高效液相色谱（HPLC）梯度洗脱法。色谱柱：Shimadzu Shim-packVP—ODS柱（150mm×4．6mm，4．6um），柱温35℃。流动相A：甲醇，B：水良好线性关系，户0．9999；高、中、低3个水平平均回收率分别为101．7％（RSD=2．5％），96．9％（RSD=I-3％，流速1．0mL／min，检测波长231nm。结果0．201-50．360gg／mL范围内，米诺地尔浓度与峰面积呈）和96．6％（RSD=I_3％）。结论该方法准确可靠，专属性强。

HPLC-MS/MS法测定育发类化妆品中22种禁用物质

建立了高效液相色谱-串联质谱(HPLC-MS/MS)同时测定育发类化妆品中22种禁用物质的分析方法。样品经饱和氯化钠分散后,采用乙腈超声提取,梯度洗脱,多反应监测扫描方式测定,基质匹配标准曲线进行定量分析。结果显示,22种禁用物质在相应的质量浓度范围内成良好的线性关系,相关系数(r)均在0.995以上,检出限(LODs)为4.9~49.7 ng/g,两种基质中的平均回收率为80.7%~110.3%,相对标准偏差(RSD,n=6)均小于15%。本方法简便、灵敏、准确,可用于育发类化妆品中非法添加22种禁用物质的定性及定量测定。

快速筛查中草药育发类产品中非法添加米诺地尔的研究

目的建立了一种快速筛查中草药育发类产品中违法添加化学物质米诺地尔的方法,同时建立其液相色谱确证方法。方法采用试管法快速筛查样品中所含米诺地尔,采用液相色谱法对米诺地尔进行定性定量分析。结果 38批次产品中6批次检出米诺地尔。快筛方法的检出限为3.12 mg/mL,液相色谱法测得米诺地尔在0.201~50.360μg/mL时,色谱峰面积与分析浓度呈良好线性关系,检出限（S/N=3）和定量限（S/N=10）分别为0.05μg/mL和0.17μg/mL。加标高、中、低3个浓度水平的回收率分别为101.7%、96.9%和96.6%,RSD分别为2.5%、1.3%和1.3%。结论所建立的快筛方法简便快捷、灵敏度高,液相色谱法专属性强,重现性好,可作为该类产品是否添加米诺地尔的检测方法。

育发类化妆品中甾体激素含量的不确定度评价

对育发类化妆品中非法添加4种甾体激素的含量测定过程进行不确定度的评价。依据JJF1059.1-2012《测量不确定度评定与表示》,建立数学模型,考察测定过程中不确定度的来源,计算合成标准不确定度和扩展不确定度。结果表明,标准品称量、标准系列溶液的配制、进样精密度及样品回收率是分析过程中引入不确定度的主要因素。该方法对于提高育发类化妆品非法添加甾体激素含量测定的准确度具有指导性意义。

育发类化妆品中斑蝥素的含量测定

建立用乙酸乙酯作为萃取剂的育发类化妆品中斑蝥素的含量气相测定方法。以乙酸乙酯为萃取剂,利用漩涡振荡器振摇提取,离心分离,气相色谱测定斑蝥素含量。结果表明：斑蝥素在0.0005~0.0031mg/ml之间线性关系良好,r=0.9960,回收率为96.0%,RSD为1.3%（n=6）。该方法操作准确、简单、分离好,安全可以作为育发类化妆品中斑蝥素含量的测定。

2002年健美、美乳、育发、烫发类化妆品监督抽检结果

根据《卫生部关于印发2002年国家卫生监督抽检工作计划的通知》(卫法监发[2002]3号)要求,2002年第三季度,卫生部在全国组织了对健美、美乳、育发、烫发类化妆品的监督抽检工作,抽检工作依据《国家卫生监督抽检规定》和卫生部《化妆品卫生规范》实施和评价。

基于社会网络分析法的国产中药育发类化妆品的现状分析

目的分析中国1999—2019年已上市的中药育发类化妆品的现状,为相关特殊类化妆品的研发提供思路。方法通过检索国家药品监督管理局数据库已公布的国产育发类化妆品,汇总产品注册及其配方组成信息,统计含中药提取物的批准产品数量、申报年份、地域、产品剂型等信息,对配方中中药的性味归经等信息进行整理,并结合Bibexcel分析软件对中药的主要配伍关系进行抽取和整理,采用Ucinet 6.0软件中NetDraw构建可视化网络。结果检索得知近21年间中国注册含中药的育发类特殊用途化妆品423个(占全部育发类化妆品的56.63%)。2012年为注册高峰(13.5%),注册数量受国家政策的影响。产品注册地区分布于全国26个省市,以广东为主(48.70%)。剂型以液体制剂为主,洗发水(38.53%)、育发液(32.62%)两类占比最高,但近年开始出现了按摩膏、喷剂等新类型产品。国产中药育发类化妆品共涉及中药154种,其中侧柏叶(286次)、何首乌(257次)等5味中药频次超过百次,补气及补血药的累积使用频次较高(463次),凉血止血药(321次)次之;性温、味甘、归肝经中药占多数。产品多数由2~4种药材构成小复方(占比45.30%),最常见配伍为侧柏叶-何首乌(共现频次184次),另外侧柏叶、何首乌、当归、人参等高频药材的相互配伍共现频次高,配伍较为丰富化。结论中药育发类化妆品市场广阔,国家监管日趋规范化,剂型将日渐丰富化。中药在国产育发类化妆品中应用广泛,未来将重视化妆品中中药新配方的挖掘及配伍优化,尤其应注重中医药理论的指导,完善功效评价体系,明确中药化学成分并重视其作用机制的探讨。

育发类化妆品中三种禁用物质的高效液相色谱-串联质谱测定法

目的建立可同时测定育发类化妆品中二苯基环丙烯酮(DPCP)、地蒽酚和维A酸含量的高效液相色谱-串联三重四级杆质谱(HPLC-MS-MS)法。方法样品用甲醇超声提取10 min,采用Luna C8色谱柱(2.0 mm×100 mm,3.0μm),以流动相为0.1%甲酸甲醇-0.1%甲酸水溶液进行梯度洗脱,流速为0.3 ml/min,柱温为25℃。采用电喷雾离子源以正离子(ESI+)多反应监测模式(MRM)进行质谱监测。结果在0.2~86.7 ng/ml的线性范围内,DPCP、地蒽酚和维A酸的回归方程均呈较好的线性关系(r>0.999)。该方法的检出限为0.3~7.4 ng/g,平均回收率:液体为90.9%~98.2%,乳液为89.6%~95.9%,凝胶为91.8%~97.2%,RSD:液体为3.7%~6.2%,乳液为3.2%~6.3%,凝胶为3.6%~6.1%。结论该方法高效、快捷、准确,适用于育发类化妆品中DPCP、地蒽酚和维A酸三种物质的同时快速检测。

育发健康产品中米诺地尔的薄层色谱快筛方法研究

目的建立育发类健康产品中米诺地尔的薄层色谱快筛方法。方法液体样品可直接点样,粘稠膏状样品用少量二氯甲烷振摇提取后点样,以硅胶GF254薄层板展开,展开剂为乙酸乙酯-二氯甲烷-甲醇(6∶5∶5)。结果薄层色谱法能有效检出育发类健康产品中的米诺地尔。结论此方法操作简便、结果准确、耗材成本低,适合基层单位用于日常监督工作。

HPLC-MS/MS法同时测定育发液中的9种禁限用物质

目的:建立可同时检测育发液中斑蝥素、米诺地尔、雌三醇、雌二醇、睾酮、甲睾酮、雌酮、己烯雌酚、黄体酮9种禁限用物质的液相色谱-质谱法。方法:采用CAPCELL PAK MG C_(18)色谱柱(150 mm×2 mm,5μm)进行分离,以10 mmol·L^(-1)醋酸铵溶液(A)-乙腈(B)为流动相进行梯度洗脱(0~12 min,90%A→50%A;12~13 min,50%A→60%A;13~20 min,60%A;20~30 min,60%A→20%A;30~31 min,20%A→90%A;31~40 min,90%A),流速0.2 m L·min^(-1);使用加热电喷雾离子源,正负离子检测,采用选择反应监测扫描方式。结果:斑蝥素、米诺地尔、雌三醇、雌二醇、睾酮、甲睾酮、雌酮、己烯雌酚、黄体酮质量浓度分别在1~100、0.001~0.05、0.25~25、15~300、0.05~5、0.1~5、0.06~3、0.02~2、0.05~5μg·m L^(-1)范围内均有良好的线性关系(r≥0.998);最低检出浓度分别为1.25、0.001、0.25、15、0.05、0.1、0.08、0.02、0.05μg·g^(-1),最低定量浓度分别为5、0.005、1.25、75、0.25、0.5、0.3、0.1、0.25μg·g^(-1)。在12批育发液样品中检出2批非法添加了米诺地尔。结论:本研究建立的方法可同时定性定量检测育发液中性激素、斑蝥素与米诺地尔等9种禁限用物质。

Effects of Different Light Qualities on Activity and Gene Expression of Caspase-like Proteases in Tobacco Leaves

[Objective] The study aimed to investigate the activity and gene expression of caspase-like proteases in tobacco leaves growing under different light qualities. [Method] By covering tobacco plants with white, red, yellow, blue and purple films to obtain different light quality, the changes of chlorophyll content, activity and gene expression of caspase-like proteases in the tobacco leaves were studied. [Results] Compared with treatments of white, red and yellow film, blue and purple films delayed the decrease of chlorophyll content and senescence of tobacco leaves at the late growth stage, and relatively lowered the activity and gene expression of caspase-like proteases during growth, development and senescence periods. [Conclusion] Different light qualities exhibited various effects on the growth, development and senescence of tobacco leaves, possibly by affecting the activity and gene expression of caspase-like proteases to some extent.

PHYLOGENY OF THE SINIPERCINE FISHES WITH SOME TAXONOMIC NOTES

Phylogeny of the sinipercine fishes, their relationships with some fossils and their systematic position were studied in this paper. Consisting of 2 sister groups, the sinipercine fishes were grouped as 2 genera - Coreoperca and Siniperca, while the genus Coreosiniperca was unwarranted for its type being a member in Siniperca, Having many special characters, Tungtingichthys was denied as the ancestor of the sinipercine fishes, however, Siniperca wusiangensis was taken as one member in Siniperca and some fossil percoids found in Japan had close relationship with sinipercine fishes. All characters of the sinipercine fishes are not concordant with that in Serranidae or Percichthyidae which leads to the conclusion that either the sinipercine fishes are not in Percichthyidae, or the defining characters of Percichthyidae listed by Gosline (1966) are wrong. But at present, we can only put the sinipercine fishes in Percichthyidae.

Phylogenetic Relationships of Monal Pheasants Lophophorus Inferred from Sequences of Mitochondrial Cytochrome b Gene

The phylogeny of the monal pheasants (Lophophorus) and their relationships to some species of the genera Tragopan,Pucrasia and Ithaginis were studied by comparing mitochondrial cytochrome b (cyt b) nucleotide sequences.The molecular phylogenetic trees show that:①the genus Tragopan and the genus Pucrasia share a common ancestor which is the sister taxon of the ancestor of the genus Lophophorus;②the genus Lophophorus had evolved into two branches:One was the Sclaters Monal;the other included the Chinese Monal and the Himalayan Monal.Considering its molecular phylogeny,distribution patterns and morphological evidences,the genus Lophophorus might originate in the Hengduan mountains region of southwestern China.

PHYLOGENETIC RELATIONSHIPS OF THE ENDEMIC CHINESE CYPRINID FISH Pseudogyrinocheilus prochilus

Evidence is provided to support the hypothesis that the taxa Pseudogyrinocheilus, Semilabeo, and Discolabeo form a monophyly in which Semilabeo and Discolabeo are sister groups, and both together constitute the sister group of Pseudogyrinocheilus. On the basis of phylogenetic relationships of Pseudogyrinocheilus to others, it is proposed that the taxon Pseudogyrinocheilus be a valid genus. In addition, comments are made on importance of some features used in the traditional taxonomy of the subfamily Labeoninae.

Phylogenetic Relationships of the Pentatomomorpha (Hemiptera: Heteroptera) Inferred from Nuclear 18S rDNA Sequences

Sequences from a region of the nuclear ribosomal 18S rDNA gene of approximately 1 912 base pairs （bp） were used to generate a molecular phylogeny for the Pentatomomorpha based on 53 species representing 21 putative families. Phylogenetic analyses using the most parsimony method （MP）, maximum likelihood method （ML）, and neighbor joining method （NJ） showed strong support that the Pentatomomorpha lineage is a monophyly and the superfamily Aradoidea is a sister group to the remainder of the Pentatomomorpha （Trichophora）. The Trichophora could be divided into two clades ： one clade consisted of the monophyletic superfamilies Pentatomoidea and Pyrrhocoroidea; the other was mainly the polyphyletic superfamilies Lygaeoidea, Coreoidea and Idiostoloidea. The superfamilies Lygaeoidea and Coreoidea were both polyphyletic. Within Lygaeoidea, Piesmatidae was sister to Berytidae. They formed a clade locating at the basal of the Trichophora and distantly related to the other two families Lygaeidae and Rhyparochromidae. This research suggested that 18S rDNA was a proper marker to reconstruct the phylogeny of Pentatomomorpha that was accordant to morphological studies and the research of Li et al （2005）. The Pyrrhocoroidea was further divided from the Coreoidea （s./at ）. It was suggested that the Piesmatidae might be assigned as a superfamily of Pentatomomorpha rather than a family in Lygaeoidea.

Reanalysis of the phylogenetic relationships of the Pentatomomorpha(Hemiptera: Heteroptera) based on ribosomal, Hox and mitochondrial genes

Pentatomomorpha is one of the most biodiverse infraorders among the true bugs（Hemiptera： Heteroptera）. Phylogenetic relationships among the superfamilies within this infraorder have been uncertain, especially for the Eutrichophora. The previous studies were based on morphological characters, or just mitochondrial or nuclear genes, or only partial 18 S rDNA and COI. In this study, we used maximum likelihood（ML） and Bayesian inference（BI） based on massive molecular datasets（18S rDNA, 28 S rDNA, Hox and mitochondrial genes totaling 21 loci and 12,538 characters） to infer a robust phylogeny for this terrestrial group. Results strongly support the monophyly of all superfamilies; the superfamily status of Aradoidea and the following relationships：（Aradoidea ＋（Pentatomoidea ＋（Coreoidea ＋（Lygaeoidea ＋ Pyrrhocoroidea）））） in Pentatomomorpha, and（Coreoidea ＋（Lygaeoidea ＋ Pyrrhocoroidea）） in Eutrichophora. Our results suggest that sampling greater numbers of genes is an effective tool for resolving phylogenetic problems.