高效液相色谱-电喷雾串联质谱法快速分离鉴定纺织品中的9种致癌染料

采用高效液相色谱-电喷雾串联四极杆质谱(HPLC-ESI-MS/MS)在选择反应监测(SRM)模式下分离鉴定纺织品中禁用的9种致癌染料。用甲醇超声同时提取天然纤维和化学纤维上的染料,以5 mmol/L乙酸铵和乙腈为流动相在C18柱上于前段洗脱酸性红26、直接蓝6、直接黑38和直接红28(采用电喷雾质谱负离子模式检测),于后段洗脱碱性红9、碱性紫14、分散蓝1、分散橙11和分散黄3(采用电喷雾质谱正离子模式检测),实现了对不同种类纤维织品中分属4类性质不同染料的一次提取和一次分析检测。通过比较试样与标样的色谱保留时间和质谱图中子离子的相对丰度比,可准确鉴别纺织品中的致癌染料。     

超高效液相色谱电喷雾串联四极杆质谱法检测豆制品中12种禁用工业染料

建立了超高效液相色谱-电喷雾串联四极杆质谱(UPLC-MS/MS)同时检测豆制品中12种橙黄色工业染料(碱性橙2、碱性橙21、碱性橙22、苏丹黄、苏丹橙G、二乙基黄、碱性嫩黄O、溶剂黄124、酸性橙Ⅱ、酸性间胺黄、酸性黄11和茜素黄R)的分析方法。样品经酸化乙腈提取;提取液于-20℃冷冻2 h后离心,可有效去除豆制品中的脂质类干扰物;梯度洗脱条件下经ACQUITY UPLCBEH C18柱(1.7μm,2.1 mm×100 mm)分离后采用多离子反应监测模式(MRM)检测,4种工业染料(酸性橙Ⅱ、酸性间胺黄、酸性黄11和茜素黄R)使用负离子模式,以乙腈-0.1%氨水为流动相,其余8种采用正离子模式检测,流动相为乙腈-0.1%甲酸水。结果表明:豆制品中12种工业染料的定量下限(LOQ)为0.2~10.0μg/kg,3个加标水平的回收率为76.2%~122.0%,相对标准偏差为1.1%~7.4%,各项指标满足食品中痕量污染物检测的需要。该方法操作简便、灵敏度高,实现了12种禁用橙黄色染料的同时提取和净化,适合于豆制品中非法添加工业染料的筛查、确证。     

高效液相色谱法同时测定染发剂中8种合成染料

使用甲醇对样品进行超声提取,以乙腈-0.02 mol/L乙酸铵溶液为流动相,采用XB-C18色谱柱分离,二极管阵列检测器检测,外标法定量,建立了同时测定染发剂中8种合成染料的高效液相色谱分析方法。HC红3号、分散黑9、HC黄2号、分散紫1及HC橙1号的检测波长设为240 nm,HC黄4号设为410nm,HC蓝7号为450 nm,HC红1号为270 nm。8种染料在0.5~100.0μg/m L范围内具有良好线性,相关系数(r2)均不小于0.999 3。HC红3号、HC黄4号、HC橙1号和分散紫1的检出限均为0.70 mg/kg,分散黑9、HC黄2号、HC蓝7号和HC红1号的检出限分别为2.50,0.60,0.35,0.50 mg/kg。样品的平均回收率为85.4%~99.8%,相对标准偏差(n=6)为1.1%~3.6%。方法的精密度、准确度、回收率和基质效应均符合染发剂样品测定的要求,用于实际样品测定,结果满意。该方法快速简便、定量准确,能满足染发剂中8种合成染料含量的分析检测要求。     

化妆品中2种限用呫吨染料的高效液相色谱检测

建立了化妆品种中2种限用呫吨染料酸性黄73和溶剂橙16的高效液相色谱/二极管阵列检测器检测方法。在ODS C18反相色谱柱上,流动相为0.1 mol/L乙酸铵-甲醇-乙腈(体积比为65:17.5:17.5)等度洗脱,检测波长为492 nm,柱温35℃,流速1.0 mL/min。以保留时间定性,外标法定量。在5～500μg/mL范围内,酸性黄73和溶剂橙16的质量浓度与各自相应的峰面积呈现良好的线性关系,仪器检出限均为0.5μg/mL。样品前处理方法采用甲醇作溶剂超声提取,酸性黄73和溶剂橙16的加标回收率分别在91.2%～106.2%和93.2%～101.5%范围内。     

固相萃取/超高效液相色谱-串联质谱法测定化妆品中12种合成着色剂

建立了固相萃取/超高效液相色谱-串联质谱法(SPE/UPLC-MS/MS)同时测定指甲油、眼影、唇膏等化妆品中12种合成着色剂(酸性紫49、颜料红57、颜料红53∶1、酸性黄36、结晶紫、罗丹明B、分散黄3、颜料橙5、苏丹红Ⅰ、苏丹红Ⅱ、苏丹红Ⅳ和溶剂蓝35)的分析方法。样品用四氢呋喃(THF)、二甲基亚砜(DMSO)和甲醇分步超声波辅助萃取,HLB固相萃取柱净化后,在Acquity UPLC BEH-C18(2.1 mm×50mm,1.7μm)色谱柱上分离,乙腈和0.05%甲酸溶液为流动相梯度洗脱,采用多反应监测(MRM)模式进行检测,基质外标法定量。结果表明:12种着色剂在6 min内均显示较好峰形,其线性范围为0.5~800μg·L-1,相关系数均大于0.99。定量下限(LOQ,S/N10)为1.4~2 000μg·kg-1。在指甲油、眼影和唇膏中分别添加0.025~20 mg·kg-1浓度的着色剂进行加标回收实验,测定回收率为60.8%~118.0%,相对标准偏差(RSD)为2.3%~10.8%。该方法快速、简便、灵敏,适用于油状、粉状及膏状化妆品中禁限用着色剂的定量和确证分析。     

反相液相色谱法同时检测染发剂中4种合成染料的研究

应用超高效液相色谱(UPLC),建立了一套同时分析染发剂中酸性紫6B、罗丹明B、甲基紫2B、结晶紫4种染料类化合物的方法。该方法用V(乙腈):V(水)=30:70萃取染发剂中的染料类成分,定容后用作UPLC检测。经CapcellPakC18色谱柱分离,检测器波长560nm。4种染料类物质的检出限均不高于0.01μg/mL,定量限均不高于0.05μg/mL。用外标法定量,3个添加水平下,4种物质回收率在74.60%～109.15%之间,RSD(n=6)在0.67%～12%之间。方法可用于染发剂中合成染料类物质的快速检测。     

高效液相色谱-串联质谱法同时测定食品中五种黄色化工染料

采用高效液相色谱-串联质谱法(HPLC-MS/MS)建立了食品中非法添加的碱性橙、碱性嫩黄、酸性橙I、酸性橙II和酸性黄36这5种黄色工业染料的定量定性分析方法。使用Agilent ODS C18分离柱(50 mm×2.0 mm, 1.8 μm),以5 mmol/L乙酸铵水溶液(0.1%甲酸)-乙腈(3:2, v/v)为流动相,流速为0.3 mL/min。采用电喷雾离子化源,以多反应监测(MRM)方式分别在正、负离子模式下进行检测。在最佳检测条件下,得到了较宽的线性范围和较低的定量检出限。碱性橙和碱性嫩黄的线性范围均为5.0～80.0 mg/L;酸性橙I、酸性橙II及酸性黄36的线性范围均为10.0～160.0 μg/L。食品中碱性橙、碱性嫩黄、酸性橙I、酸性橙II及酸性黄36的定量限分别为20、20、40、40、40 ng/g。该方法重现性较好,保留时间和峰面积的相对标准偏差分别不大于0.50%和2.14%。本研究还测定了鸡肉、豆制品和黄鱼中添加的5种化工染料,回收率在79.8%~95.2%之间,结果令人满意。     

超临界流体色谱-紫外检测法同时测定混纺地毯中8种致敏性分散染料

建立了超临界流体色谱-紫外检测同时测定混纺地毯中分散黄1、分散黄49、分散黄9、分散橙37/76、分散红1、分散橙1、分散橙3和分散棕1共8种致敏性分散染料的分析方法。样品在70℃水浴中经甲醇超声萃取30 min后,以超临界态二氧化碳-甲醇(90∶10,v/v)为流动相,等度洗脱,在440 nm波长下检测。8种致敏性分散染料在12 min内即可实现分离,其在各自的线性范围内均具有良好的线性关系,相关系数(r~2)为0.999 2~0.999 8,方法的检出限(LOD,S/N=3)为0.05~0.10 mg/L。用该方法分析8种致敏性分散染料,其峰面积的相对标准偏差(RSD)均小于1.2%(n=5)。8种染料在实际样品中的加标回收率为95.6%~104.2%。该方法可以对混纺地毯等纺织品中8种致敏性分散染料进行检测,方法简便、快速、灵敏、选择性高、结果准确,能满足纺织品中致敏性分散染料的检测标准。     

薄层色谱扫描法同时检测豆制品中碱性橙、皂黄、柠檬黄和日落黄以及辣椒粉中酸性橙Ⅱ、丽春红2R和罗丹明B

建立了利用薄层色谱和薄层色谱扫描技术同时检测豆制品中碱性橙、皂黄、柠檬黄、日落黄4种色素和辣椒粉中酸性橙Ⅱ、丽春红2R、罗丹明B3种非食用色素的方法。豆制品经丙酮和乙醇-氨溶液提取,辣椒粉经乙醇-氨溶液提取,采用硅胶G薄层板,正丁醇-无水乙醇-1%氨水(6:2:2)为展开剂上行展开。利用双波长反射锯齿薄层扫描方式,碱性橙、皂黄、柠檬黄、日落黄采用450nm为检测波长,酸性橙Ⅱ、丽春红2R、罗丹明B采用520nm为检测波长,参比波长均为700nm。7种色素的线性范围在0.04～2.4μg之间,相关系数在0.9954～0.9994之间。碱性橙、皂黄、柠檬黄、日落黄、丽春红2R的最低检出量为0.02μg,酸性橙Ⅱ为0.08μg,罗丹明B为0.01μg。辣椒面和豆皮样品的加标回收率为74.0%～98.0%,相对标准偏差(RSD)在1.1%～4.5%之间。通过与高效液相色谱法的对比,该方法可以有效的对辣椒面和豆制品中的碱性橙等色素进行同时分析。     

液相色谱-串联质谱测定纺织品中分散黄23和分散橙149

建立了高效液相色谱法(HPLC)和液相色谱-串联质谱法(LC-MS/MS)测定纺织品中分散黄23和分散橙149含量的方法.样品上的分散染料经氯苯蒸汽完全剥离纤维,浓缩后的残留物用甲醇定容,以0.1% H3PO4(或0.1%甲酸)和乙腈为流动相,经反相色谱柱分离后,用二极管阵列检测器(DAD)在420 nm处测定,并用电喷雾串联质谱确认.分散黄23和分散橙149的定量离子对分别为m/z 303/105和m/z 459/399.分散黄23和分散橙149的检出限(S/N=3):HPLC法为2.0和1.0 mg/kg,LC-MS/MS法都为1.0 μg/kg.HPLC在0.5～250 mg/L、LC-MS/MS在0.5～200 μg/L范围内,线性相关系数都大于0.995.方法的回收率在92.1%～98.7%之间,批间RSD都小于8.0%,含有分散黄23的阳性样品重复测试的RSD也小于8.0%.     

Determination of textile dyes by means of non-aqueous capillary electrophoresis with electrochemical detection

Eight textile dye compounds including five cationic dyes, namely, basic blue 41, basic blue 9, basic green 4, basic violet 16 and basic violet 3, and three anionic dyes, acid green 25, acid red 1 and acid blue 324, were separated and detected by non-aqueous capillary electrophoresis (NACE) with electrochemical detection. Simultaneous separations of acid and basic dyes were performed using an acetonitrile-based buffer. Particular attention was paid to the determination of basic textile dyes. The optimized electrophoresis buffer for the separation of basic dyes was a solvent mixture of acetonitrile/methanol (75:25, v/v) containing 1 M acetic acid and 10 mM sodium acetate. The limits of detection for the basic dyes were in the range of 0.1–0.7 μg mL⁻¹. An appropriate solid-phase extraction procedure was developed for the pre-treatment of aqueous samples with different matrices. This analytical approach was successfully applied to various water samples including river and lake water which were spiked with textile dyes.     

杂环-双氰乙基系列分散染料的合成、表征及染色性能

以4个杂环芳香胺为重氮组分, 3个N,N-二氰乙基芳香胺为偶合组分, 经重氮化、 偶合反应合成了12个杂环-双氰乙基系列偶氮物; 采用紫外-可见吸收光谱、 红外光谱及核磁共振氢谱等对其结构进行了表征; 还考察了它们在涤纶织物、 乙酰化杉改性木粉和氰乙基化改性木粉上的染色性能. 结果表明, 12个偶氮物为目标产物, 在N,N-二甲基甲酰胺(DMF)中的最大可见吸收波长为417～621 nm, 摩尔吸光系数均大于10⁴. 这些化合物染色涤纶织物的色光分属黄色、 红色、 紫红色和蓝色系列, 并具有高水洗牢度和高日晒牢度; 染色乙酰化木粉和氰乙基木粉的色光和水洗牢度与染色涤纶织物相近. 这12个分散染料具有色谱范围广、 色泽鲜艳、 高发色强度和高牢度等特点, 可用于多种纤维的染色.     

Synthesis and Characterization of Novel Monoazo N‐Ester‐1,8‐Naphthalimide Disperse Dyestuffs

Five novel monoazo disperse dyestuffs based on N‐ester‐1,8‐naphthalimide were synthesized. Acenaphthene was nitrated, then oxidized to 4‐nitro‐1,8‐naphthalic anhydride. 4‐Nitro‐1,8‐naphthalic anhydride was reacted with methyl and ethyl glycinate in alcoholic media, followed with reduction. 4‐Amino‐N‐methyl and ethyl glycinate‐1,8‐naphthalimide were obtained. These products were diazotized and coupled with appropriate aromatic amines to give bluish‐red or violet dyestuffs. All intermediates and dyestuffs were purified and characterized by ¹H‐NMR, FTIR, DSC, UV‐VIS and Elemental Analysis. Dispersion of dyestuffs was prepared in water and applied to polyester fabrics. The dyed fabrics showed that four of the synthesized dyestuffs were suitable for coloring polyester fibers, producing deep bluish red with very good build up properties.     

Pre-resonance Raman intensity studies of TCNQ and TCNQ−

Pre-resonance Raman spectra have been obtained for TCNQ and LiTCNQ in acetonitrile solution using an Ar⁺—Kr⁺ laser and a tunable rhodamine 6G dye laser. Using the theory of Albrecht and Hutley, we have calculated frequency factors for the intensity variations for several symmetric vibrational modes of each molecule. The observed spectra for TCNQ and LiTCNQ with violet, blue, and green excitation give evidence for B-type resonance enhancement due to vibronic mixing between at least two violet and ultraviolet transitions. The Raman spectra for LiTCNQ with yellow, orange, and red excitation show A-type enhancement due to a single electronic excitation in the near infrared.     

Determination of 40 synthetic food colors in drinks and candies by high-performance liquid chromatography using a short column with photodiode array detection

Forty synthetic food colors were determined in drinks and candies by reversed-phase high-performance liquid chromatography with photodiode array detection. The following food colors were analyzed within 19 min using a short analytical column (50 mm × 4.6 mm i.d., 1.8 μm) at 50 °C with gradient elution: Ponceau 6R, Tartrazine, Fast yellow AB, Amaranth, Indigotine, Naphthol yellow S, Chrysoine, Ponceau 4R, Sunset yellow FCF, Red 10B, Orange G, Acid violet 7, Brilliant black PN, Allura red AC, Yellow 2G, Red 2G, Uranine, Fast red E, Green S, Ponceau 2R, Azorubine, Orange I, Quinoline yellow, Martius yellow, Ponceau SX, Ponceau 3R, Fast green FCF, Eosine, Brilliant blue FCF, Orange II, Orange RN, Acid blue 1, Erythrosine, Amido black 10B, Acid red 52, Patent blue V, Acid green 9, Phloxine B, Benzyl violet 4B, and Rose bengal. The recoveries of these compounds added to soft drinks and candies at 5 μg/g ranged from 76.6 to 115.0%, and relative standard deviations (R.S.D.s) were within 6.0%. The limits of detection and the limits of quantitation were 0.03 and 0.1 μg/g, respectively.     

Dielectric and thermal effects on the optical properties of natural dyes: a case study on solvated cyanin

The optical properties of the flavylium state of the cyanin dye are simulated numerically by combining Car-Parrinello molecular dynamics and linear-response time-dependent density functional theory calculations. The spectrum of the dye calculated in the gas phase is characterized by two peaks in the yellow and in the blue (green and violet), using a GGA-PBE (hybrid-B3LYP) DFT functional, which would bring about a greenish (bright orange) color incompatible with the dark purple hue observed in nature. Describing the effect of the water solvent through a polarizable continuum model does not modify qualitatively the resulting picture. An explicit simulation of both solvent and thermal effects using ab initio molecular dynamics results instead in a spectrum that is compatible with the observed coloration. This result is analyzed in terms of the spectroscopic effects of the molecular distortions induced by thermal fluctuations.     

Der Nachweis organischer Farbstoffe durch Mikrosublimation. II Besonderer Teil

Zusammenfassung Folgende organische Farbstoffe, die entweder als Pulver oder auch als Ausfärbung oder als Druck vorlagen, gaben kennzeichnende Sublimate:Indischgelb G, Dianilgelb G, die Hansagelbsorten 10 G, 5 G, 5 G transparent, 3 G, G, G transparent, GGR extra, GR, 3 R, Litholechtgelb RN, Helioechtgelb 6 GL, Litholechtorange RN, Permanentrot R extra, Litholechtscharlach RN (Hansarot B), Litholechtscharlach B, Permanentrot FRL, Autolrot BL, Autolrot RLP, Brillant-Indigo BASF, Indanthrengelb G, Indanthrenbraun G, Indanthrenblau RSN, Indanthrenviolett FFBN, Indanthrengelb 7 GK, Indanthrenbrillantorange GR, Indanthrenbrillantorange RK.

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Summary The following organic dyestuffs which were present either as powders or as dyed or printed material, gave characteristic sublimates:Indian yellow G, dianil yellow G, the 10 G, 5 G, 5 G transparent, 3 G, G, G transparent, GGR extra, GR, 3 R brands of Hansa yellow, lithol-fast yellow RN, helio-fast yellow 6 GL, lithol-fast orange RN, permanent red R extra, lithol-fast scarlet RN (Hansa red B), lithol-fast scarlet B, permanent red FRL, autol red BL, autol red RLP, brilliant indigo BASF, indanthrene yellow G, indanthrene brown G, indanthren blue RSN, indanthrene violet FFBN, indanthrene yellow 7 GK, indanthrene brilliant orange GR, indanthrene brilliant orange RK.

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Résumé Les pigments organiques suivants, qui étaient à notre disposition, soit comme poudre, soit comme colorisation ou comme impression, donnèrent des sublimés caractéristiques:Indischgelb G, Dianilgelb G, les sortes de Hansagelb 10 G, 5 G, 5 G transparent, 3 G, G, G transparent, GGR extra, GR, 3 R, Litholechtgelb RN, Helioechtgelb 6 GL, Litholechtorange RN, Permanentrot R extra, Litholechtscharlach RN (Hansarot B). Litholechtscharlach B, Permanentrot FRL, Autolrot BL, Autolrot RLP, Brillant-Indigo BASF, Indanthrengelb G, Indanthrenbraun G, Indanthrenblau RSN, Indanthrenviolett FFBN, Indanthrengelb 7 GK, Indanthrenbrillantorange GR, Indanthrenbrillantorange RK.

     

3,14‐Bis(p‐nitrophenyl)‐17,17‐dipentyltetrabenzo[a,c,g,i]‐fluorene: A New Fluorophore Displaying Both Remarkable Solvatochromism and Crystalline‐Induced Emission

A series of 17,17‐dialkyl‐3,14‐diaryltetrabenzofluorenes were efficiently prepared by using Suzuki–Miyaura cross‐coupling reactions of the corresponding 3,14‐dibromo derivatives. Studies of the unique fluorescence properties of these compounds showed that they display intense blue to yellow fluorescence with high quantum yields in the solution state and blue to orange fluorescence with moderate quantum yields in the solid state. In addition, the fluorescence wavelength of the bis(p‐nitrophenyl) derivative is remarkably solvent‐dependent in a manner that correlates with the solvent polarity parameter E_T(30). The results of density function theory calculations suggest that the intramolecular charge‐transfer character of the HOMO–LUMO transition is responsible for the large solvent effect. Moreover, addition of water to a tetrahydrofuran (THF) solution of this compound leads to quenching of the yellow fluorescence owing to an increase in the solvent polarity. However, when the amount of water fraction exceeds 70 %, a new fluorescence band appears at the same orange‐red emission wavelength as that of the solid‐state fluorescence. This observation suggests the occurrence of a crystallization‐induced emission (CIE) phenomenon in highly aqueous THF.     

Determination of sulfonated azo dyes in river water samples by capillary zone electrophoresis

A method based on capillary zone electrophoresis coupled with photodiode-array detection has been developed to determine several sulfonated dyes, including a sulfonated dye (acid yellow 1), and the sulfonated azo dyes acid orange 7, acid orange 12, acid orange 52, acid red 26, acid red 27 and acid red 88. A CElect-FS75 CE column is used. The electrophoresis buffer contains a 1:5 dilution of 10 mM phosphoric acid and tetrabutylammonium hydroxide buffer (pH 11.5), and 25 mM of triethylamine, the final pH being 11.55. The detection limits for the seven dyes ranged from 0.1 to 4.53 microg/ml. Spiked river water samples (100 ml), containing different concentration levels (0.025-0.150 microg/ml) of the dyes were analyzed after acidification (pH 3) and pre-concentration in disposable SPE Oasis HLB, 1 ml cartridges.