液相色谱-串联质谱法同时测定化妆品中18种磺胺类相关化合物残留

为建立化妆品中18种磺胺类相关化合物的LC-MS/MS测定法,将样品用丙酮提取,经SPE固相萃取柱净化富集,在C18色谱柱（4.6mm×50mm×2.7μm）上以甲醇-0.1%（体积分数）甲酸水溶液为流动相梯度洗脱,在ESI正离子MRM模式下检测。结果发现：18种化合物在10-800ng/mL的质量浓度范围内线性关系良好,加标回收率为78.6%-97.2%,检出限为25μg/kg。     

高效液相色谱法同时测定猪血中的5种磺胺类药物残留

建立了高效液相色谱法同时测定猪血中磺胺间甲氧嘧啶（SMM）、磺胺地索辛（SDM）、磺胺二甲嘧啶（SM2）、磺胺甲恶唑（SMZ）、磺胺喹恶啉（SQ）这5种磺胺药物残留方法。猪血样品经过乙腈提取,蒸干后,用2.00 mL去离子水定容。采用Waters Symmetry C18色谱柱,用磷酸（0.017 moL/L）-乙腈作为流动相进行分离。这5种磺胺类药物的检出限为：0.02~0.05 mg/kg,线性范围为：0.1~20μg/mL,平均回收率为：75.6%~102.4%,相对标准偏差为：3.2%~7.6%。     

超高效液相色谱-串联质谱法测定化妆品中27种磺胺类药物

建立超高效液相色谱-串联质谱法（UPLC-MS/MS）测定化妆品中27种非法添加磺胺类药物的分析方法。样品经甲醇提取,用Thermo Hypersil GOLD(100×2.1 mm,1.9μm)色谱柱分离,以0.1%(V/V)乙酸水溶液-0.1%(V/V)乙酸乙腈溶液为流动相梯度洗脱,在电喷雾正、负离子模式下以多反应监测（MRM）方式对化妆品中的27种磺胺类药物进行定性定量测定。27种待测组分在各自的质量浓度范围内线性关系良好,相关系数均大于0.99,在3个不同添加水平下,平均回收率为79.3%～112.2%,RSD为1.4%～13.1%(n=6),方法的检出限（S/N≥3）和定量限（S/N≥10）分别为2.3～97.6μg/kg和7.7～322.0μg/kg。该方法简单快速,灵敏可靠,适用于化妆品中27种磺胺类药物的同时定性定量筛查分析。     

UPLC-MS/MS法测定不同基质祛痘化妆品中17种磺胺类药物

建立同时测定不同基质祛痘化妆品中17种磺胺类药物含量的超高效液相色谱-串联三重四极杆质谱法（UPLC-MS/MS）。样品经50%甲醇水溶液超声提取后，用Waters ACQUITY UPLC?BEH C18色谱柱（100 mm×2.1 mm,1.7μm），以不同体积分数的甲醇和0.1%（体积分数）甲酸水溶液的混合液为流动相进行梯度洗脱分离。质谱分析中采用电喷雾离子源和正离子多反应监测模式检测，外标法定量。结果显示样品基质效应较小，可不予考虑。17种磺胺类药物在质量浓度为0.5～100 ng/mL范围内与其对应的响应值呈线性关系，相关系数均大于0.999，检出限为0.002～0.028μg/g，定量限为0.006～0.094μg/g。按标准物质加入法进行回收试验，添加含量为0.25～2.5μg/g时，回收率为97.5%～118.3%，相对标准偏差为0.74%～6.37%。按此方法分析了10批市售祛痘化妆品，均未检出17种磺胺类药物成分。     

高效液相色谱串联质谱法同时测定猪肉中9种磺胺类药物残留

建立了高效液相色谱串联质谱法同时测定猪肉中9种磺胺类药物的方法,能够有效地检测食品中的磺胺类药物残留,为食品安全筛查提供技术支持。2 g猪肉样品,用乙腈提取2次后,旋转蒸发仪减压蒸干,加入2 m L乙腈水溶液(50∶50,V/V)溶解残渣,正己烷去脂后,样品溶液用超高效液相色谱分离,电喷雾串联四级杆质谱检测,外标法定量。结果表明,9种磺胺类药物的线性范围为1～100μg/kg,线性相关系数r均大于0. 999,方法检出限为0. 15～0. 97μg/kg,3个水平添加范围内的平均回收率为67. 2%～98. 4%,相对标准偏差为0. 5%～7. 8%。该方法重现性好,灵敏度高,能够有效地检测猪肉中的磺胺类药物残留。     

高效液相色谱串联质谱法同时测定猪肉中9种磺胺类药物残留

建立了高效液相色谱串联质谱法同时测定猪肉中9种磺胺类药物的方法,能够有效地检测食品中的磺胺类药物残留,为食品安全筛查提供技术支持。2 g猪肉样品,用乙腈提取2次后,旋转蒸发仪减压蒸干,加入2 m L乙腈水溶液(50∶50,V/V)溶解残渣,正己烷去脂后,样品溶液用超高效液相色谱分离,电喷雾串联四级杆质谱检测,外标法定量。结果表明,9种磺胺类药物的线性范围为1～100μg/kg,线性相关系数r均大于0. 999,方法检出限为0. 15～0. 97μg/kg,3个水平添加范围内的平均回收率为67. 2%～98. 4%,相对标准偏差为0. 5%～7. 8%。该方法重现性好,灵敏度高,能够有效地检测猪肉中的磺胺类药物残留。     

液质联用技术的应用与发展

液相色谱/质谱(LC/MS)正在快速发展,它是液相色谱仪的首选工具。液相色谱-质谱(LC-MS/MS)是一种使用液相色谱(或HPLC)和质谱法的技术。它是一种分析化学技术,它结合了液相色谱的物理分离能力和质谱分析的质量分析能力。(LC-MS/MS)通常用于实验室,用于药物和生物样品的定性和定量分析。LC-MS现已成功应用于许多领域的常规分析,包括治疗药物监测(TDM)、临床和法医毒理学和二维(2-D)连字技术。     

超高效液相色谱-串联质谱法测定海螵蛸中9种磺胺类药物残留量

采用超高效液相色谱-串联三重四极杆质谱法(UPLC-MS/MS)定性和定量测定,建立动物源性中药海螵蛸中9种磺胺类药物残留的检测方法。干燥样品加EDTA溶液复原,以乙腈作为提取溶剂,使用萃取盐盐析分层,以增强型脂质去除分散固相萃取(EMR-Lipid dSPE)净化,以ACQUITY BEH C18柱(2.1 mm×100 mm, 1.7μm)为分离色谱柱进行分离分析,以动态多反应监测模式(d-MRM)进行检测,外标法定量。9种磺胺类药物在0～30 ng/mL范围内呈良好的线性关系,相关系数(R~2)均大于0.997 3,方法检出限和定量限分别在0.013 6～0.128 3μg/kg和0.045 5～0.432 6μg/kg之间,各加标水平的回收率在63.3%～91.9%之间,相对标准偏差为1.7%～5.7%。方法简单、快速、准确,适合于中药海螵蛸中9种磺胺类药物残留的快速筛查。     

贵州省不同产区茶叶中7种农药的基质效应评价

选取7种农药和4大类65个茶叶基质,考察在QuEChERS前处理条件下采用液相色谱-串联质谱（LC-MS/MS）技术的基质效应行为。结果显示,在LC-MS/MS检测中,7种农药产生的基质效应以基质抑制为主,且不同农药在不同茶叶中的基质效应差异较大。乙酰甲胺磷和氧乐果主要表现为强基质抑制效应,噻虫嗪主要表现为弱基质抑制效应,啶虫脒、克百威、苯醚甲环唑和辛硫磷主要表现为弱基质效应。茶叶的种类会对不同农药产生不同程度基质效应影响。因此,在检测茶叶中农药残留时,应根据农药的基质效应行为强弱,选取合适的前处理和定量方法。     

液质联用技术在药品质量分析中的应用进展

药品是一类特殊的商品，具有预防治疗疾病和引起不良反应两方面的特点，当下药品种类繁多，市面上的药品鱼目混杂，开展药品质量分析，有效地对药品实行监督抽检、对制药流程、体内代谢、违法添加等行为进行动态管控显得尤为重要。伴随着新技术的研发，液相色谱质谱联用技术(LC-MS/MS)因具有分析速度快、分离效能高、高特异性和高灵敏度等特点被广泛地应用到新药研发、药品复杂成分鉴定和代谢产物分析等领域。文章从介绍LC-MS/MS的基本原理入手，依次介绍了LC-MS/MS技术在药品含量测定、中药活性成分分析、药品有关物质分析、农药残留检测、非法添加物质分析、药物代谢动力学和药物代谢组学七个方面的研究进展，分析LC-MS/MS技术在各方面的优势特点和不足，并预测其未来的研究发展方向，文章可以为药品检测和研发人员选择合适的检测手段提供参考，也可以为药品监管部门提供技术和理论支持。     

RRLC—MS—MS对海水养殖水体中磺胺类残留量的检测

建立了快速高分离液相色谱-色谱串联质谱法同时测定海水养殖水体中16种磺胺类抗菌素的方法。水样经固相萃取小柱富集、洗脱、浓缩后用液相色谱串联质谱仪测定,采用多反应监测模式进行测定,内标法定量。方法的检出限在0.467-1.88 ng/L之间,加标回收率在80.1%114%之间,相对标准偏差（RSD）0.731%-8.79%;适用于海水养殖水体中磺胺类残留的定量检测。     

高效液相色谱-电喷雾串联质谱法测定水产品中14种喹诺酮类与磺胺类药物残留

建立了高效液相色谱-电喷雾串联质谱法测定水产品中恩诺沙星、环丙沙星、双氟沙星、沙拉沙星、氟甲喹、喹酸、磺胺嘧啶、磺胺甲唑、磺胺喹啉、磺胺甲基嘧啶、磺胺二甲氧嘧啶、磺胺二甲基嘧啶、磺胺间二甲氧嘧啶、甲氧苄胺嘧啶共14种常用喹诺酮类与磺胺类兽药的残留检测方法。样品制备后,采用1%乙酸-乙腈提取液提取,用正己烷净化处理后,采用LC/MS/MS电喷雾电离(ESI),多反应监测(MRM)正离子模式检测,外标法定量。在0～100μg/kg范围内14种兽药的线性相关系数均>0.99。在添加浓度5～50μg/kg范围内,14种药物的回收率在70.0%～110%,相对标准偏差(RSD)均在12%以内。方法的检出限为0.1～0.5μg/kg。     

Further improvement of broad specificity hapten recognition with protein engineering

Sulfa-antibiotics (sulfonamides) are widely used in veterinarymedicine. Meat and milk from treated animals can be contaminatedwith sulfa residues. Current sulfonamide assays are unfit forscreening of food, because they are either too laborious, insensitiveor specific for a few sulfa compounds only. An immunoassay fordetection of all sulfas in a single reaction would be usefulfor screening. Previously we have improved the broad specificitysulfa binding of antibody 27G3 with random mutagenesis and phagedisplay. In order to improve the properties of this antibodyfurther, mutants from the previous study were recombined andmore mutations introduced. These new libraries were enrichedwith phage display and several different mutant antibodies wereisolated. The cross-reaction profile of the best mutant wasbetter than that of the wild-type antibody and the mutants ofthe previous study: it was capable of binding 10 of the tested13 sulfonamides within a narrow concentration range and alsobound the rest of the sulfas 5- to 11-fold better than the mutantsof the previous study.     

Electrogenerated chemiluminescence in mechanistic investigations of electroorganic reactions—V. cathodic cleavage of aromatic sulfonyl compounds

The cathodic cleavage of some aromatic sulfochlorides Ia–Ie, sulfonic ethers IIa-IIr, sulfonamides IIIa–IIIe and sulfones IVa–IVc was studied by way of electrogenerated chemiluminescence in presence of some suitable aromatic hydrocarbons at the dropping mercury electrode or at a platinum disc electrode in a 1:1 acetonitrile/toluene mixture or in DMF. The luminescence intensity with the sulfochlorides is much stronger than with the sulfonic ethers. With the sulfonamides an emission could only be observed, if the N-atom was substituted by electron withdrawing groups, and with the sulfones no luminescence is generated. The results are discussed in terms of the reduction potentials of intermediate radicals ArSO₂, ArO, and Ar-N·-R and with respect to the kinetics of the homogeneous catalysis of the cleavage by the hydrocarbon redox system.     

Chromatographic separations enabling the structural characterisation of heavy petroleum residues

Two petroleum residues from European crudes have been fractionated using solvent (heptane) separation and column chromatography. The residues and the separated fractions have been characterised by size exclusion chromatography (SEC) and by UV-fluorescence spectroscopy (UV-F). Matrix assisted laser desorption/ionisation-mass spectrometry of the whole residues and the heptane insoluble fractions indicated that the bulk of the residues covered the mass range m/z 300-2000, while the heptane insolubles (1-2% of the whole) contained material in the mass range from about m/z 300 to 10?000. The upper mass ranges indicated by SEC using polystyrene standards were higher; the earliest eluting material from both distillation residues eluted at times corresponding to polystyrene standards of MMs above 1.85 million u. Possible reasons for the different observations are given. Data from UV-F suggests that the heptane solubility separation method was the most successful for the separation of the largest molecular mass and also probably the most polar materials in these residues. However, all three fractionation methods produced similar trends, showing greater polarity of the fractions to correlate with increasing molecular mass. The shift of maximum intensity of fluorescence towards longer wavelengths (in UV-fluorescence) with increasing molecular size, as indicated by SEC, strongly suggests that the fluorescing molecules are large rather than aggregates of small molecules. Differences in comparison with American petroleum residues can be observed.     

UV-C辐照降解水中磺胺类药物

采用C类紫外线或称为短波紫外线（即UV-C）辐照降解水中磺胺类药物,考察了磺胺类药物种类、UV光强、磺胺类药物初始浓度、反应液pH对降解效果的影响。结果表明UV-C辐照对磺胺嘧啶、磺胺甲基嘧啶和磺胺甲恶唑的降解过程均符合拟一级反应动力学。UV-C辐照技术对磺胺甲恶唑的去除率最高,在反应液pH为7,光强为142μW/cm^2,初始浓度为0.02mmol/L条件下,辐照30 min后磺胺甲恶唑去除率达到67.80%,而磺胺嘧啶和磺胺甲基嘧啶去除率仅15%左右。通过增大紫外光强和减小初始浓度,可提高反应速率和磺胺甲恶唑去除率。反应液pH对反应效果的影响显著,酸性条件更利于UV-C辐照降解磺胺甲恶唑。     

Synthesis,Molecular Docking Analysis,and Biological Evaluations of Saccharide-Modified Sulfonamides as Carbonic Anhydrase IX Inhibitors

Based on the strategy of the “tail approach”, 15 novel saccharide-modified sulfonamides were designed and synthesised. The novel compounds were evaluated as inhibitors of three human carbonic anhydrase (CA) isoforms, namely cytoplasmic CA II, transmembrane CA IX, and XII. Most of these compounds showed good activity against CAs and high topological polar surface area (TPSA) values, which had a positive effect on the selective inhibition of transmembrane isoforms CA IX and XII. In the in vitro activity studies, compounds 16a, 16b, and 16e reduced the viability of HT-29 and MDA-MB-231 cells with a high expression of CA IX under hypoxia. The inhibitory activity of compound 16e on the human osteosarcoma cell line MG-63 with a high expression of CA IX and XII was better than that of AZM. Moreover, high concentrations of compounds 16a and 16b reversed the acidification of the tumour microenvironment. In addition, compound 16a had a certain inhibitory effect on the migration of MDA-MB-231 cells. All the above results indicate that the saccharide-modified sulfonamide has further research value for the development of CA IX inhibitors.     

Self/Co-Assembling Peptide,EAR8-II,as a Potential Carrier for a Hydrophobic Anticancer Drug Pirarubicin (THP)—Characterization and in-Vitro Delivery

A short ionic-complementary peptide, EAR8-II, was employed to encapsulate the hydrophobic anticancer drug pirarubicin (THP). EAR8-II was designed to inherit advantages from two previously introduced peptides, AAP8 and EAK16-II, in their self/co-assembly. This peptide is short, simple, and inexpensive to synthesize, while possessing a low critical assembly concentration (CAC). The choice of alanine (A) residues in the peptide sequence provides moderate hydrophobic interactions, causing a minimal degree of aggregation, compared with other more hydrophobic residues. EAR8-II is an ionic-complementary peptide, similar to EAK16-II, can self/co-assemble with hydrophobic compounds such as THP, and forms a stable fibular nanostructure in aqueous solution. Physiochemical properties and cellular activities of the EAR8-II and THP complexes were evaluated and show dependency on the peptide-to-drug ratio. The complex at the peptide-to-drug mass ratio of 5:1 provides a stable solution, uniform nanostructure, and highly effective anticancer activity against various cancer cell lines. This work forms the basis for detailed studies on EAR8-II and THP formulations in vitro and in vivo, for future development of peptide-based delivery systems for hydrophobic anticancer drugs.     

Decomposition,nitrogen and phosphorus mineralization from winter-grown cover crop residues and suitability for a smallholder farming system in South Africa

Increasing land degradation has prompted interest in conservation agriculture which includes growing cover crops. Besides providing soil cover, decaying cover crops may release substantial amounts of nutrients. Decomposition, N and P release from winter cover crops [grazing vetch (Vicia darsycarpa), forage peas (Pisum sativum) and oats (Avena sativa)] were assessed for suitability in a cropping system found in the smallholder irrigation sector of South Africa. Nitrogen and P contribution to maize growth by cover crop residues was also estimated. Decrease in mass of cover crop residues was highest in grazing vetch (7% remaining mass after 124 days) followed by forage peas (16%) and lastly oats (40%). Maximum net mineralized N and P were higher for grazing vetch (84.8 mg N/kg; 3.6 mg P/kg) than for forage peas (66.3 mg N/kg; 2.7 mg P/ha) and oats (13.7 mg N/kg; 2.8 mg P/kg). Grazing vetch and forage pea residues resulted in higher N contribution to maize stover than oat residues. Farmers may use grazing vetch for improvement of soil mineral N while oats may result in enhancement of soil organic matter and reduction land degradation because of their slow decomposition. Terminating legume cover crops a month before planting summer crops synchronizes nutrient release from winter-grown legume cover crops and uptake by summer crops.