药物中盐酸异丙嗪的微流控芯片非接触电导法快速检测

建立了微流控芯片非接触式电导法快速测定药物中盐酸异丙嗪含量的分析方法.研究了缓冲液、添加剂、分离电压和进样时间等因素对检测的影响,以20 mmol·L-1 MES-20 mmol·L-1 His 的缓冲液为分离介质,分离电压为2.2 kV时可实现较好的分离检测.在优化实验条件下,盐酸异丙嗪的线性范围为100 ～1 000 mg·L-1;检出限(S/N=3)为10 mg·L-1;线性方程为Y＝-502+4.99×103X,相关系数r=0.995 6;0.1 g·L-1盐酸异丙嗪的RSD为2.1%(n＝5);3批药品的加标回收率为96% ～101%,RSD为1.7% ～3.0%.该方法简便、快速、灵敏度高,可以用于盐酸异丙嗪药物的质量控制.     

毛细管电泳-电化学检测法测定饲料中的磺胺类药物

采用毛细管电泳-电化学检测法(CE-ED),对饲料中的6种磺胺类药物磺胺脒、磺胺二甲嘧啶、磺胺甲嘧啶、磺胺二甲氧嘧啶、磺胺嘧啶、磺胺甲恶唑进行了分离和测定。分别考察了工作电极电位、运行缓冲液的pH和浓度、分离电压和进样时间等实验参数对实验结果的影响。在优化的实验条件下,以直径300μm的碳圆盘电极为工作电极,检测电位为0.95 V(vs.SCE),在30 mmol/L硼砂-KH2PO4(pH7.6)的运行缓冲溶液中,6个分析物能够在16 min内实现很好的基线分离,被测物浓度与峰电流在3个数量级呈良好的线性,检出限(S/N=3)范围0.08～0.20μg/mL。该方法已应用于实际样品的分析。     

反相高效液相色谱法同时测定青蟹组织中磺胺嘧啶和甲氧苄啶残留

本文在比较检测波长以及不同提取方法的基础上,优化了测定拟穴青蟹血淋巴、肌肉、鳃和肝胰腺等组织中磺胺嘧啶和甲氧苄啶含量的反相高效液相色谱法(RPHPLC)。采用Aglient Zorbax SB-C18柱(150×4.6mm,5μm),以乙腈和0.01mol·L~(-1)乙酸铵(乙酸调节pH为3.80)为流动相,柱温35℃;紫外检测波长245nm;进样量10μL,流速1.0mL·min-1。磺胺嘧啶在0.05~10μg·mL~(-1)范围内线性关系良好,相关系数R2=0.9999。甲氧苄啶在0.05~10μg·mL~(-1)范围内线性关系良好,相关系数R2=0.9999。采用乙腈提取青蟹血淋巴、肌肉、肝胰腺和鳃组织中磺胺嘧啶和甲氧苄啶,加标回收率分别为82.26%~95.23%、81.52%~98.59%,日内精密度分别为1.77%~2.53%、1.75%~4.09%,日间精密度分别为2.27%~3.30%、1.95%~4.82%;定量限分别为0.05μg·mL~(-1)、0.05μg·g-1。该方法操作简单,重现性好,药峰无干扰,适用于青蟹样品中磺胺嘧啶和甲氧苄啶含量的同时分析测定。     

碳纳米管修饰电极离子色谱电化学法测定盐酸麻黄碱

采用阴离子交换分离,碳纳米管修饰电极安培检测离子色谱电化学法测定盐酸麻黄碱.在优化条件下,用碳酸钠溶液和甲醇溶液混合溶液为淋洗液,用碳纳米管修饰玻碳电极,在0.8 V电位处进行直流安培检测.结果发现在碳纳米管修饰玻碳电极后盐酸麻黄碱的电流响应值比未修饰前大大增加,方法的灵敏度比未修饰电极提高了10倍,用未修饰电极测定的检出限为2.4 μg·L-1,用修饰电极测定的检出限为0.2 μg·L-1,样品加标回收率为103.6%..     

以L-Cys-GNPs为手性选择剂对异丙肾上腺素的毛细管电泳分析

本文采用柠檬酸钠还原法合成了纳米金,并以L-半胱氨酸对其进行表面修饰,得到络合物L-Cys-GNPs。然后以该络合物为手性选择剂,采用毛细管区带电泳法对盐酸异丙肾上腺素进行手性拆分。对络合物浓度、缓冲液的浓度、pH值、运行电压等方面进行考察和优化。结果表明,当L-半胱氨酸的络合浓度为2.61×10~(-3)mmol·L~(-1)时,以15mmol·L~(-1)磷酸盐缓冲液(pH=7.0)为运行缓冲液、运行电压20kV、分离柱温25℃、进样量0.5Psi×5s以及214nm的检测波长下,盐酸异丙肾上腺素达到了基线分离,在7min内分离度达到10.49。     

Ti基电极上光化学沉积Hg用于吸附溶出伏安法测定磺胺嘧啶

该研究发现采用紫外光照射钛电极表面氧化钛层能够光催化还原Hg2+生成Hg微粒,在Ti基电极上光化学沉积Hg比电化学沉积Hg对磺胺嘧啶具有更强的吸附作用,基于光化学沉积Hg/Ti电极建立了一种吸附溶出伏安法测定磺胺嘧啶的方法.详细考察了溶液pH值、吸附富集时间、溶出起始电位、扫描速率等对测定的影响.结果表明,在pH 2.0 的B-R缓冲溶液中,磺胺嘧啶在0.48 V左右处产生1个灵敏的氧化峰,其峰电流与磺胺嘧啶的浓度在1.2×10-8～1×10-6 mol/L范围内呈良好的线性关系(r=0.997 2),检出限达4.35 nmol/L.     

电活化玻碳电极差分脉冲溶出伏安法测定磺胺嘧啶

采用线性循环溶出伏安法和差分脉冲溶出伏安法对磺胺嘧啶在电活化玻碳电极上的电化学行为进行了研究。玻碳电极在PBS溶液中(pH 7.0),用恒电位法在1.7 V阳极氧化400 s,在B-R缓冲溶液中,磺胺嘧啶在1.02V(vs.Ag/AgCl)处有一良好的氧化峰,在0.02～0.25 V/s范围内,其氧化峰电流与扫描速率呈良好线性关系,表明电极过程为受吸附控制的不可逆过程。差分脉冲溶出伏安法的氧化峰电流(Ipa)与磺胺嘧啶浓度1×10-6～1×10-4mol/L范围内呈良好的线性关系(r=0.9977),检出限为8.7×10-7mol/L(S/N=3)。方法已用于分析磺胺嘧啶片剂的分析。     

电堆积柱上富集-高效毛细管电泳法测定药品中盐酸麻黄碱和盐酸伪麻黄碱的含量

应用电堆积柱上富集-高效毛细管电泳法测定了6种药品中盐酸麻黄碱和盐酸伪麻黄碱含量。试验选择了以下分析条件:①检测波长205 nm;②内标物为间苯二酚;③运行液为pH9.2的40 mmol·L-1硼砂缓冲溶液;④分离电压20 kV;⑤进样时间10 s;⑥分离温度25℃。麻黄碱及伪麻黄碱质量浓度在1~400 mg·L-1之间与相应的相对峰面积值(即被测物与内标物的峰面积之比)呈线性关系。方法的检出限(3S/N)为0.35 mg·L-1(麻黄碱)和0.29 mg·L-1(伪麻黄碱)。以2种药品作基体加入标准溶液做回收试验,测得平均回收率依次为101.1%及103.6%。     

分子印迹化学发光传感器在线检测牛肉与鸡肉组织中残留的磺胺嘧啶

以分子印迹作为识别体,制成高灵敏度和高选择性的化学发光传感器在线检测牛肉与鸡肉组织中残留的磺胺嘧啶。磺胺嘧啶作为靶分子,通过悬浮聚合制备了1～10μm的分子印迹聚合物。将分子印迹聚合物装入聚四氟乙烯管中,作为固相萃取柱,并联在八通阀上,用于在线选择吸附磺胺嘧啶。在最佳条件下,测得磺胺嘧啶线性范围7.0×10–9～9.0×10–7g/mL,方法的检出限为(3σ)2×10–10g/mL,11次平行测定3.0×10–8g/mL的磺胺嘧啶溶液的化学发光强度相对标准偏差为3.4%。方法能够用于检测肉类产品中残留的磺胺嘧啶。     

高效液相色谱-串联质谱测定熟肉制品中磺胺嘧啶和氯霉素药物残留

建立了一种应用高效液相色谱-串联质谱法(HPLC-MS/MS)同时检测熟肉制品中磺胺嘧啶和氯霉素药物残留的方法。样品经乙腈多次提取,正己烷去脂,采用乙酸铵-乙腈体系为流动相,梯度洗脱分离,电喷雾多反应监测模式同时质谱检测。磺胺嘧啶和氯霉素分别在5～500μg/kg和0.1～10μg/kg的线性范围内线性相关系数(R2)均大于0.999,其检出限分别为5μg/kg和0.1μg/kg。磺胺嘧啶和氯霉素在熟肉制品中的回收率分别为78.6%～94.4%和68.7%～86.3%。     

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.