高效液相色谱-串联质谱联用测定富含淀粉食品中丙烯酰胺

以甲基阿烯酰胺作为内标物，用高效液相色谱／串联质谱（HPLC／MS／MS）法测定食品中的丙烯酰胺。均质后的食品样品，加入正己烷经液-液分配去除脂肪，用蒸馏水提取丙烯酰胺，Carrez试剂净化提取样品，净化液经离心后过0．45μm微孔滤膜，采用HPLC／MS／MS电喷雾电离（ESI），阳离子，多反应监测（MRM）模式检测，外标法定量。方法的线性范围为2～500μg／L，线性相关系数为0．9997，检出限为2μg／kg；高中低3个水平的加标回收率分别为99．4％、99．6％和98．4％；相对标准偏差（RSD）均小于7．8％。     

高效液相色谱/串联质谱法测定奶粉中的硝基呋喃代谢物

用高效液相色谱／串联质谱（LC—MS／MS）法同时测定奶粉中呋喃唑酮、呋喃它酮、呋喃西林和呋喃妥因的代谢物。盐酸水解奶粉中蛋白结合的代谢物，同时加入2-硝基苯甲醛（2-NBA），37℃过夜衍生化。加入硫酸锌，调pH值至7．0后，再加入亚铁氰化钾去除蛋白。后用乙酸乙酯提取，正己烷净化，分析物采用电喷雾电离正离子（ESI＋）、多反应监测（MRM）模式检测，内标法定量。在添加浓度0．5—2μg/kg范围内，内标法回收率为89．5％～110．3％；相对标准偏差（RSD）小于11，3％。5-马啉代甲基-3-氨基-2-恶唑酮（5-methylmorpholino-3-amino-2-oxazolidinone，AMOZ）、3-氨基-2-恶唑酮（3-amino-2-oxazolidinone，AOZ）方法检出限为0．05μg／kg，氨基脲（semicarbazide，SEM）、1-氨基-乙内酰胺（1-amino—hydantoin，AHD）为0．1μg/kg。     

固相萃取高效液相色谱-质谱法测定动物组织中硝基呋喃代谢产物

研究了对动物组织中4种硝基呋喃类代谢产物AOZ、AMOZ、SEM和AHD的自动固相萃取HPLC-MS分析方法，分别以2-氯苯甲醛和2-硝基苯甲醛作为衍生化试剂，分别用AMOZ-d5、AOZ-d4作内标，用ENSPE柱进行提取，以乙腈-0．1％甲酸为流动相，采用梯度洗脱，可在15min内将4种代谢产物完全分离并进行测定。回收率为85％-90％；检出限可达0．5μg／kg。采用两种衍生化方法可获得较多的定性确证信息。采用本方法研究了硝基呋喃在鸡饲养过程中的残留规律。     

同位素稀释气相色谱串联质谱法测定海产品中的苯并（α）芘的残留量

采用同位素稀释法结合固相萃取净化,建立了海产品中苯并（α）芘残留的气相色谱串联质谱（6C—MS／MS）检测方法。样品经乙腈一丙酮（体积比6：4）溶液提取,硅胶固相萃取净化,苯并（μ）芘用GC—MS／MS测定,同位素D12-苯并芘内标法定量。方法的平均回收率为93％-98％,相对标准偏差为6.2％～12．2％（n=6）,定量限为0．2μg／kg。用该方法测定FAPAS烟熏鱼有证标准样品,测定值与标准值一致。     

反相高效液相色谱／质谱法同时测定鸡肉中5种喹诺酮药物残留

采用反相高效液相色谱／四级杆串联质谱（RP-HPLC／MS／MS）同时测定鸡肉中的5种喹诺酮药物（quinolones，QNs）。均质后的鸡肉样品采用磷酸盐缓冲溶液和乙腈的混和溶液提取。提取液经正己烷液-液分配（LLP）去除脂肪后，用C18固相萃取（SPE）柱净化，氨化甲醇洗脱，洗脱液用氮气吹干，流动相定容后，分析物采用LC／MS／MS电喷雾电离（ESI），正离子，多反应监测（MRM）模式检测，外标法定量。在添加浓度2．5～10μg/kg范围内，5种QNs的回收率在79．8％～95．1％之间；相对标准偏差（RSD）均小于11．7％。环丙沙星、丹诺沙星、恩诺沙星检出限（LOD）为0．5μg／kg，沙托沙星为1．0μg／kg，氟甲喹为0．1μg／kg。     

液相色谱-串联质谱法对动物源性食品中14种苯二氮革类药物及其代谢物残留量的同时检测

建立了液相色谱-串联质谱（LC—MS／MS）同时检测动物源性食品中14种苯二氮革类药物及其代谢物残留量的测定方法。在pH5．2乙酸铵缓冲溶液中药物残留经酶解后,用氨水调节pH值大于9．5。溶液经乙酸乙酯-异丙醇（体积比5：1）提取和阳离子交换柱（MCX）净化,并用多反应监测技术所确定的定性离子对检测物进行定性和同位素内标法定量。方法的定量下限为1．0μg／kg,线性范围为1．0～20．0μg/L,各基质的加标平均回收率为64％～117％,相对标准偏差为3．6％～12．3％。     

高效液相色谱-电喷雾三级四极杆质谱测定鸡肉组织中氯霉素残留的研究

建立了鸡肉组织中氯霉素残留的液相色谱-电喷雾质谱联用(LC—ESI—MS—MS)测定法。采用微量化前处理方法,省去固相萃取步骤,以m／z321．0为母离子,m／z152．1、257．0和194．1为子离子,采用多反应监测(MRM)负离子模式对鸡肉组织中的氯霉素残留进行检测、方法的检出限为0．010μg／kg(S／N≥3),定量下限为0．10μg／kg,线性范围为0．100～1．00μg／L,加标回收率为74．3％～84．0％,相对标准偏差(n=6)为7．9％～12．7％。该法具有操作简便、有机试剂消耗量少、测定周期短等优点。     

高效液相色谱-串联质谱法测定鸡组织中的喹烯酮标示残留物

采用液相色谱-串联质谱（HPLC—MS／MS）法测定鸡组织（肌肉、肝、肾）中喹烯酮标示残留物3-甲基喹噁啉-2-羧酸的含量。组织匀浆样品经碱水解、液液萃取，采用HPLC—MS／MS电喷雾电离（ESI），正离子模式，多反应监测（MRM），以喹噁啉-2-羧酸为内标进行定量。检出限为5μg／kg。     

固相萃取-气相色谱-质谱法测定猪组织中沙丁胺醇残留量

建立了动物组织中沙丁胺醇残留量固相萃取-气相色谱-质谱分析方法。动物组织样品经过葡萄糖醛甙酶酶解后调节pH至9．5，然后用异丙醇／乙酸乙酯混合溶剂液液分配去除杂质，旋转浓缩后用乙酸铵缓冲溶液溶解经SCX固相萃取（SPE）柱净化，洗脱液经氮气吹干后用双三甲基硅基三氟乙酰氨（BSTFA）衍生，采用选择离子模式（86、350、369、440）进行测定，外标法定量。检出限为0．10μg/kg。在添加浓度0．5～5．0μg/kg范围内，平均添加回收率在66．4％～82．4％，相对标准偏差（批内）（CV）在3．5％～5．9％之间；批间（CV）在2．2％～4．8％之间。衍生物的峰面积与样品浓度在0．002～0．50mg／L范围内呈良好的线性关系，线性回归系数大于0．999。     

气相色谱-质谱法测定肝脏组织中盐酸克伦特罗和盐酸菜克多巴胺

建立了同时测定动物肝组织中盐酸克伦特罗和盐酸莱克多巴胺残留量的固相萃取-气相色谱-质谱分析方法。动物肝组织样品在碱化的条件下用乙酸乙酯和异丙醇混合溶剂提取，提取液浓缩后用乙酸乙酯溶解，然后再用稀盐酸反萃取去除脂肪，调pH值后经SCX固相萃取（SPE）柱净化，洗脱液经氮气吹干后经双三甲基硅基三氟乙酰氨（BSTFA）衍生，采用选择离子模式（盐酸克伦特罗：86、212、262、277，盐酸莱克多巴胺：163、192、234、250）进行测定，外标法定量。盐酸克伦特罗和盐酸莱克多巴胺的检出限分别为0．30和1．00μg／kg。盐酸克伦特罗添加浓度在1．0～5．0μg／kg范围内，添加回收率为77．4％～88．3％；相对标准偏差（RSD）为3．1％～5．1％；盐酸莱克多巴胺添加浓度在4．0～20．0μg／kg，添加回收率为69．8％～82．1％；相对标准偏差（RSD）为3．5％～4．9％；衍生物的峰面积与被测物浓度分别在0．003～1．00mg／L和0．012～4．00mg／L范围内呈良好的线性关系，线性回归系数均大于0．999。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.