多重吸附同步净化-气相色谱-质谱法测定干性样品中丁烯氟虫腈的残留量

建立了干性样品中丁烯氟虫腈残留量的多重吸附同步净化(MASP)-气相色谱-质谱检测方法。前处理以1%乙酸-乙腈提取样品,应用MASP法对样品同时进行提取、盐析和净化,并利用气相色谱-质谱仪在选择离子扫描(SIM)模式下进行检测,以基质匹配标准溶液外标法定量。结果表明:丁烯氟虫腈在2~100 μg/L范围内线性关系良好,相关系数(r²)不小于0.999;在2~10 μg/kg添加水平范围内,丁烯氟虫腈的平均回收率为92.2%~97.5%,相对标准偏差(RSD, n=6)为2.69%~5.21%;方法检出限(S/N=3)为2 μg/kg;定量限(S/N=10)为6 μg/kg。本方法操作简便、快速、准确,可用于干性样品中丁烯氟虫腈的日常检测。同时,对丁烯氟虫腈的裂解机理进行了探讨。     

改进QuChERS-气质联用法测定蔬菜中氟虫腈和丁烯氟虫腈残留量

建立了蔬菜中氟虫腈和丁烯氟虫腈残留量的同时检测方法。样品以1%乙酸-乙腈为提取剂,应用改进的QuChERS方法对样品提取液进行净化,并利用气质联用在选择离子扫描(SIM)模式下进行检测,以基质匹配标准溶液外标法定量。结果表明:在2～10μg/kg添加水平范围内,氟虫腈和丁烯氟虫腈的平均回收率分别为99.8%～120.5%和96.4%～124.9%;相对标准偏差(RSD,n=6)分别为1.8%～11%和2.1%～7.4%;两者的方法检出限(LOD)均为2μg/kg;定量限(LOQ)均为6μg/kg。     

固相萃取/液质联用测定竹笋中丁烯氟虫腈农药残留研究

建立了高效液相色谱-串联质谱(HPLC-MS/MS)测定竹笋中丁烯氟虫腈残留的分析方法。样品采用乙腈提取,经PSA固相萃取小柱净化后,采用Waters Atlantis T3色谱柱(2.1 mm×150 mm×5μm),以含5mmol/L乙酸铵的0.1%甲酸水溶液和乙腈为流动相梯度洗脱,电喷雾离子源负离子模式多反应监测(MRM)模式定性分析,以氟虫腈为内标物质内标法消除基质效应定量测定丁烯氟虫腈。该方法在5.0～100.0μg/L范围内具有良好的线性关系,相关系数大于0.994 8;4、8、32μg/kg 3个加标水平下的平均回收率为76%～103%,相对标准偏差(RSDs)为3.2%～9.9%;方法的检出限(信噪比S/N=3)和定量下限(S/N=10)分别为0.21μg/kg和0.69μg/kg。该方法较气相色谱法和气相色谱质谱联用法具有更高的准确性和灵敏度,且更加简单快速,可满足竹笋中丁烯氟虫腈农药残留的检测要求。     

生物农药微胶囊壁材料研究

用原位聚合法对生物农药阿维菌素进行包囊,然后制备微胶囊制剂,并对用于该制剂的两种高分子囊壁材料-三聚氰胺甲醛树脂和脲醛树脂的性能进行了研究。结果表明,两种树脂皆为较好的生物农药用微胶囊缓释剂型的囊壁材料,其制备工艺简单,具有良好的稳定性、粒径大小与分布、悬浮性、缓释性等,包封率均达80％以上。其中三聚氰胺甲醛树脂悬浮性较脲醛树脂更好,缓释性更持久。     

Gaussian 09软件在电子圆二色谱教学中的应用

利用Gaussian 09软件优化并计算了手性农药R-丁烯氟虫腈和S-丁烯氟虫腈的电子圆二色谱,讨论了其在立体化学(电子圆二色谱)教学中的具体应用,帮助学生对手性分子的三维空间结构、电子圆二色谱的理解及归属等方面有更加感性的认识,使教学内容形象生动,提高了学生的学习兴趣及积极性。     

气相色谱-质谱联用对菠菜中丁烯氟虫腈残留的检测

建立了固相萃取(SPE)/气相色谱-质谱(GC-MS)测定菠菜中丁烯氟虫腈残留量的分析方法.利用乙腈提取,提取液依次过无水硫酸钠、氯化钠和PSA固相萃取柱后采用GC-MS进行检测,选择定量离子m/z 403,选择定性离子m/z 421、55、213、371.6次重复测定峰面积的相对标准偏差小于10%;定量下限为0.05 mg/kg,检出限为0.01 mg/kg,在0.05 ～100 mg/kg范围内具有良好的线性关系,为丁烯氟虫腈的检测和判断提供了方法.     

气相色谱–质谱法测定鲜蛋中氟虫腈及其代谢物

建立鲜蛋中氟虫腈及其代谢物氟甲腈、氟虫腈砜、氟虫腈亚砜残留量的气相色谱–质谱检测方法。样品采用乙腈提取,用QuECHERS萃取包和氨基固相萃取柱净化,外标法定量。氟虫腈、氟甲腈、氟虫腈砜、氟虫腈亚砜的质量浓度在0.01～0.20μg/mL范围内与色谱峰面积呈良好的线性关系,线性相关系数均在0.999以上,方法检出限为0.002 mg/kg。样品的加标回收率为90.8%～104.5%,测定结果的相对标准偏差小于10%(n=6)。该方法具有较好的灵敏度、准确性和重复性,适用于鲜蛋中氟虫腈及其代谢物氟甲腈、氟虫腈砜、氟虫腈亚砜残留量的测定。     

甲胺基阿维菌素苯甲酸盐微胶囊的制备与表征

以三聚氰胺-甲醛树脂为壁材,采用原位聚合法制备了甲胺基阿维菌素苯甲酸盐微胶囊,研究了三聚氰胺与甲醛的质量比、芯壁比、乳化剂、搅拌速度与时间、pH值、温度等因素对微胶囊形成的影响,对制备的微胶囊进行了表征,测定了甲维盐微胶囊化前后的光解率。结果表明,三聚氰胺与甲醛质量比为1∶2、芯材与壁材质量比为3∶2、以质量分数1%羟乙基纤维素(HEC)为乳化剂、在1000r/min搅拌速度下、pH=5.0和50℃保温2h可制备出形貌较好、平均粒径4.4μm的甲维盐微胶囊。红外光谱分析证明,甲维盐已完全被包覆在微胶囊中。紫外分光光度法测定其缓释性能良好。光解实验表明,微胶囊化可有效降低甲维盐原药的光解。     

磁性微胶囊的制备及其药物缓控释性能

用乳液-凝胶法制备了磁性壳聚糖/海藻酸钠微胶囊. 在壳聚糖/海藻酸钠微胶囊中掺入Fe3O4磁性中空球, 使微胶囊具有磁靶向性能. 以头孢拉定作为模型药物研究了载药磁性微胶囊的载药量、包封率及药物缓控释性能等. 结果表明, 提高头孢拉定的初始浓度可以提高载药量, 却不利于提高药物的包封率. 所制备的微胶囊在各种缓冲溶液中长时间内具有显著的缓释效果, 并具有pH 刺激响应释放的性能, 即在模拟胃液中的药物释放率大大降低, 而在模拟体液和肠液中的释放时间大大延长, 可达50 h以上. 另外, 在外加磁场作用下, 微胶囊表现出良好的磁定向运动性能, 为磁靶向药物输送提供基础.     

CS/TPP纳米微胶囊的制备及其载药性能

利用离子凝胶法, 以三聚磷酸钠(TPP)为交联剂, 由壳聚糖(CS)制备了CS/TPP纳米微胶囊. 用红外光谱仪、扫描电镜和粒径分析仪进行了表征, 并以牛血清蛋白(BSA)作为模型药物, 考察了所制备的CS/TPP纳米微胶囊的包载和缓释性能. 结果表明, CS/TPP纳米微胶囊的红外光谱相对于CS和TPP的红外光谱发生了很大变化, 说明CS和TPP通过正负电荷吸引聚合成囊; 粒径分析表明, 离子凝胶法可以得到粒径约430 nm的均匀分散的壳聚糖纳米微胶囊, 经冷冻干燥后粒径变为300 nm左右; 微胶囊包封率最高可达79.74%, 模型药物的持续释放时间可达7 d以上.     

Iron cross-linked carboxymethyl cellulose—gelatin complex coacervate beads for sustained drug delivery

The formation and smooth recovery of ibuprofen encapsulated in microcapsules using gelatin and carboxymethyl cellulose (CMC) complex coacervation without glutaraldehyde were the objectives of this investigation. The microcapsules were recovered as ionically cross-linked beads using aqueous ferric chloride in 50 vol.% of 2-propanol. A physical mixture of CMC/gelatin (FP1) and CMC alone (FP2) beads was also prepared for comparison. The drug-entrapment efficiency of complex coacervate beads (FP3-FP5) was dependent on the drug-to-polymer ratio and was in the range of 86–92 mass %. Beads prepared with the highest ratio of the drug (FP5) exhibited the lowest entrapment. FP1 and FP2 beads exhibited an entrapment efficiency of 98.5 mass % and 91.3 mass %, respectively. Infrared spectroscopy (FTIR) revealed different functional groups in complex coacervate, physical mixture and FP2 beads. Optical and scanning electron microscopy revealed the distinct appearance and surface morphology of the various beads. The stable and crystalline nature of ibuprofen in the beads was confirmed by FTIR and differential scanning calorimetry (DSC), respectively. Ibuprofen release from FP1 and FP2 beads was very slow and unsuitable for oral delivery. The bead prepared by complex coacervation (FP5) showed a better release profile over 48 h and could be developed as a sustained drug delivery system.     

Preparation and Research of Butylene Fipronil Microencapsulation by Layer-by-Layer Polyelectrolyte Self-Assembly

This paper introduced the preparation of butylene fipronil-loaded microcapsules with oppositely charged chitosan and sodium lignosulfonate as shell materials. It summed up the performance, preparation methods of microcapsules and sketched the application status of layer-by-layer self-assembly. The whole progress of the preparation was controlled by measuring the change of the Zeta potential and the morphology of microcapsules was characterized by microscope and SEM. Entrapment efficiency and slow release performance of the microcapsule were determined as measurement index. The results of experiment showed that the surface of the microcapsules was rougher than the butylene fipronil particles. With the increasing layer number of assembly, the entrapment efficiency reduced while the slow release performance increased. After encapsulation, the photodegradation rate of butylene fipronil under the UV decreased obviously. Results showed that the condition of preparation was the best when NaCl with the concentration of 0.5 mol/L and PH of 5.0.     

Preparation and characterization of liposomes-in-alginate (LIA) for protein delivery system

This paper describes the preparation and characterization of a novel drug delivery system for protein, liposomes-in-alginate (LIA) of biodegradable polymers, which is conceived from a combination of the polymer and the lipid-based delivery systems. LIA were prepared by first entrapping bovine serum albumin (BSA), a model protein within multivesicular liposomes (MVLs) by double emulsification process, which are then encapsulated within alginate hydrogel microcapsule, with untrapped BSA which are added during preparation of MVLs. Factors impacting encapsulation efficiency of MVLs are investigated and release of protein from the microcapsules in vitro is studied. At the same time, characterization of MVLs, microcapsules encapsulated protein formulation and integrality analyse of BSA in microcapsules are also studied, with the aim of improving the entrapment efficiency and prolonging release time. It is found that encapsulation efficiency and size of MVLs are affected by the composition and fabrication parameters of LIA. The data also show LIA have high encapsulation efficiency (up to 95%), little chemical change in drug caused by the formulation process, narrow particle size distribution and spherical particle morphology. Drug release assays conducted in vitro indicates that these formulations provide sustained release of encapsulated drug over a period, about 2 weeks.     

Characterization and release behaviors of porous PCL/Eudragit RS microcapsules containing tulobuterol

In this work, porous poly(ɛ-caprolactone) (PCL)/Eudragit RS 100 (ERS-100) microcapsules containing tulobuterol base as a model drug were prepared by a solvent evaporation method and the effect of the quaternary ammonium groups of ERS-100 on the release behaviors of the microcapsules was investigated. The microcapsules prepared with PCL alone showed a stable and smooth surface, whereas porous microcapsules were formed with the addition of ERS-100. Drug loading and encapsulation efficiency of the microcapsules were slightly decreased with an increase of ERS-100 content, resulting from an increase in the porosity of the microcapsules. In an acidic release medium, PCL microcapsules showed slow drug release, whereas PCL/ERS-100 microcapsules showed a faster release rate with an increasing ERS-100 content. These behaviors are likely due to an increase in the diffusion rate of the drugs stemming from an increased hydration of the microcapsules, which results from the interaction between the carboxyl group of the release medium and the quaternary ammonium group of ERS-100.     

复凝聚法制备昆虫激素模拟物十二醇微胶囊及其释放性能

以明胶(GE)和阿拉伯胶(AG)为壁材, 通过复凝聚法将昆虫激素模拟物十二醇(C12OH)包覆在微胶囊中, 改变微胶囊壁材的浓度和交联度, 探讨了体系中C12OH的可控释放性能. 通过对壁材质量比为1及不同pH条件下的壁材凝聚率测试确定最佳复凝聚的pH为4.0; 考察了不同分散剂对微胶囊及其分散液性能的影响, 确定以Tween 20/Span 80(质量比1∶1)作为复凝聚法包覆C12OH体系的分散剂. 在壁材质量分数大于或等于3%条件下制备的微胶囊粒径大于壁材质量分数为2%的微胶囊, 胶囊的载药量和C12OH包覆率明显高于后者. 增加交联剂的用量, 壁材交联度、胶囊的载药量和C12OH包覆率都显著提高. 在相同用量的情况下, 用甲醛作交联剂时得到的微胶囊的交联度比用戊二醛作交联剂时的要低, 但其对C12OH的包覆率更高. 通过扫描电镜对微胶囊进行了分析, 认为GE与AG通过复凝聚能够将C12OH包覆在微胶囊内部. 对胶囊中C12OH在恒温恒湿条件下的释放研究结果表明, 3%与4%壁材含量下1%戊二醛交联的微胶囊和5%壁材含量下4%戊二醛交联的微胶囊中C12OH的释放行为有明显的可控性. 通过调节微胶囊的壁材含量和交联度可以达到昆虫激素可控释放的目的.     

Solid lipid nanoparticles prepared by solvent diffusion method in a nanoreactor system

In this study, water-in-oil (W/O) miniemulsion was used as nanoreactor to prepare solid lipid nanoparticles (SLN) by solvent diffusion method. n-Hexane, Tween 80 and Span 80 were used as the oil phase and surfactant combination for preparation of W/O miniemulsion, respectively. The stable miniemulsion with the particle size of 27.1 ± 7.6 nm was obtained when the composition of water/Tween 80/Span 80/n-hexane was 1 ml/18 mg/200 mg/10 ml. Clobetasol propionate (CP) was used as a model drug. The physicochemical properties of the SLN, such as particle size, zeta potential, surface morphology, drug entrapment efficiency, drug loading capacity and in vitro drug release behaviors were investigated, comparing with those of SLN prepared by conventional aqueoethod. The SLN prepared by the novel method displayed smaller particles size and higher dus solvent diffusion mrug entrapment efficiency than those of SLN prepared by the conventional method. The drug entrapment efficiency decreased with increasing of charged amount of drug, and 15.9% of drug loading was achieved as the charged amount of drug was 20%. The in vitro drug release tests indicated that the drug release rate was faster than that of SLN prepared by the conventional method, and the drug content in SLN did not affect the in vitro drug release profile.     

Aripiprazole Loaded Polymeric Biodegradable Microspheres: Formulation and In Vitro Characterization

In the present study, we attempted to prepare biodegradable microspheres of polylactic acid containing aripiprazole in order to achieve its controlled release profile suitable for parenteral administration. Biodegradable microspheres were prepared by solvent evaporation method using methylene dichloride as a solvent. The optimization of various formulation variables (e.g., stirring speed, and polymer:drug ratio, stabilizer concentration) to obtain spherical particles was also investigated. The optimized product was further characterized for various in vitro attributes, such as particle size and its distribution, encapsulation efficiency, surface properties, percentage yield, and in vitro release. Changing the ratio of polymer, stabilizers, and leaching agent (sodium chloride) affected the entrapment efficiency and release rate of aripiprazole. The release quantum was 88.41% when stirring rate was 2000 rpm and it was further increased to 94.65% when stirring speed was increased to 3000 rpm (Formulation E). Drug entrapment of microspheres was increased by increasing the concentration of PVP and maximum entrapment (62.35%) was obtained at 4% concentration of PVP (Formulation E). Spherical particles with good surface characteristics were obtained at stirring rate 3000 rpm and drug:polymer ratio 1:10.     

Performance of biodegradable microcapsules of poly(butylene succinate), poly(butylene succinate-co-adipate) and poly(butylene terephthalate-co-adipate) as drug encapsulation systems

Poly(butylene succinate) (PBSu), poly(butylene succinate-co-adipate) (PBSA) and poly(butylene terephthalate-co-adipate) (PBTA) microcapsules were prepared by the double emulsion/solvent evaporation method. The effect of polymer and poly(vinyl alcohol) (PVA) concentration on the microcapsule morphologies, drug encapsulation efficiency (EE) and drug loading (DL) of bovine serum albumin (BSA) and all-trans retinoic acid (atRA) were all investigated. As a result, the sizes of PBSu, PBSA and PBTA microcapsules were increased significantly by varying polymer concentrations from 6 to 9%. atRA was encapsulated into the microcapsules with an high level of approximately 95% EE. The highest EE and DL of BSA were observed at 1% polymer concentration in values of 60 and 37%, respectively. 4% PVA was found as the optimum concentration and resulted in 75% EE and 14% DL of BSA. The BSA release from the capsules of PBSA was the longest, with 10% release in the first day and a steady release of 17% until the end of day 28. The release of atRA from PBSu microcapsules showed a zero-order profile for 2 weeks, keeping a steady release rate during 4 weeks with a 9% cumulative release. Similarly, the PBSA microcapsules showed a prolonged and a steady release of atRA during 6 weeks with 12% release. In the case of PBTA microcapsules, after a burst release of 10% in the first day, showed a parabolic release profile of atRA during 42 days, releasing 36% of atRA.     

高效氯氰菊酯微胶囊的制备、表征及释放性能

以高效氯氰菊酯为芯材, 乙基纤维素为壁材, 采用溶剂蒸发法制备了微胶囊, 并对其理化性能进行表征, 通过单因素实验研究了工艺参数对微胶囊外观形貌、 粒径大小及分布、 包封率、 载药量和缓释性能的影响. 结果表明, 乳化剂种类和剪切时间可以显著影响微胶囊的外观形貌; 随着乳化剂用量增大, 微胶囊粒径减小, 分布变窄, 当Tween-80用量从4%增加至8%时, 微胶囊平均粒径从59.9 μm减少到29.8 μm, 跨距也从1.21减少到0.72. 随着芯壁比(质量比)减小, 微胶囊粒径和包封率均逐渐增大, 载药量逐渐减小, 当芯壁比为1:1.75时, 包封率可以达到70%以上. 微胶囊释放动力学模型符合Ritger-Peppas模型(lgQ=lgk+nlgt); 平均粒径相近而载药量不同时, 初期载药量最小的样品释放速率慢, 累积释放率低; 载药量相近而平均粒径不同时, 粒径大的样品释放速率低, 累积释放率也低.