苯乙烯-二乙烯苯-甲基丙烯酸聚合物微球的制备及其固相萃取性能

以苯乙烯、二乙烯苯和甲基丙烯酸为原料,聚乙烯醇为分散剂,过氧化苯甲酰为引发剂,采用悬浮聚合法制备了具有亲脂和弱阳离子交换性能的球形固相萃取填料,并确定了最佳的聚合反应条件。采用红外光谱和扫描电子显微镜表征了聚合物结构和微球的形貌,通过氮气吸附法测定了填料的比表面积和孔径分布。以氰草津、西玛津、阿特拉津和特丁津4种三嗪类除草剂为目标化合物,通过固相萃取-液相色谱联用技术,考察了样品溶液的酸度、过柱流量及洗脱剂的体积对萃取回收率的影响,确定了最佳固相萃取条件。测定了制备的固相萃取填料的吸附容量和小柱的穿透体积。氰草津、西玛津、阿特拉津和特丁津的检出限分别为0.26,0.63,0.42,0.31μg·L-1。     

分子印迹固相萃取-高效液相色谱法同时检测烟叶中磺酰脲类农药残留

以氯磺隆（CS）为模板分子,甲基丙烯酸为功能单体,三羟甲基丙烷三甲基丙烯酸酯为交联剂,在二氯甲烷氛围中,经沉淀聚合制备氯磺隆分子印迹聚合物（CS-MIP）微球。将该聚合物微球作为填料制得分子印迹固相萃取柱用于样品前处理,建立了分子印迹固相萃取-高效液相色谱（MIP-SPE-HPLC）同时检测烟叶中6种磺酰脲类除草剂残留的分析方法。针对氯磺隆、甲磺隆、苄嘧磺隆、苯磺隆、胺苯磺隆和烟嘧磺隆6种磺酰脲类除草剂,在烟叶中加标0.50~50 μg/g,经氯磺隆分子印迹固相萃取柱（CS-MIP-SPE）净化和富集,高效液相色谱（HPLC）检测,其平均回收率为77.60%~102.05%,相对标准偏差为0.16%~7.07%,检出限为0.08~0.46 μg/g。将MIP-SPE-HPLC方法用于实际农药残留检测,结果表明可同时满足烟叶中多种磺酰脲类除草剂残留量的检测要求。     

聚苯乙烯磺酸钠/氧化锆固相萃取填料的制备及其在农药残留萃取分析中的应用

采用聚合诱导胶体凝聚法(PICA)制备了ZrO2微球,用钛酸酯偶联剂对微球表面进行改性,再以苯乙烯、二乙烯基苯、苯乙烯磺酸钠,在引发剂偶氮二异丁腈(AIBN)作用下与ZrO2微球表面双键进行聚合,制备了聚苯乙烯磺酸钠/氧化锆固相萃取填料。采用FT-IR、SEM/EDS及N2吸附脱附等手段表征了合成材料的组成与结构。将固相萃取与高效液相色谱联用,测定了除草剂莠去津、异丙甲草胺和二甲戊乐灵。实验结果表明:莠去津、异丙甲草胺和二甲戊乐灵萃取的色谱峰面积与浓度的线性关系良好,相关系数(R2)分别为0.9965,0.9918,0.9934,检出限分别为0.0053,0.0042,0.0084 mg/L。     

聚合物包覆二氧化锆液相色谱固定相的制备与评价

在溶液体系中通过自由基引发长链碳烯-1、二乙烯苯和乙烯基二氧化锆交联聚合反应得到聚长链碳烯-苯乙烯包覆二氧化锆固定相.考察了这种交联聚合物包覆柱填料的色谱性能和化学稳定性,并用这种填料分离了稠环芳烃和碱性化合物.     

环境样品中阿特拉津的检测方法研究进展

综述了2011~2015年内环境样品中阿特拉津残留量分析方法的研究进展,包括液液萃取、固相萃取、固相微萃取、液相微萃取、超声提取、微波辅助萃取等分离方法和气相色谱-质谱、液相色谱-质谱、生物技术等检测方法,以及上述分析方法的应用情况,并对阿特拉津的检测方法的前景进行了展望(引用文献46篇)。     

气相色谱-质谱法同时测定植物源食品中7种农药的残留量

研究了用气相色谱-质谱法检测草莓和小麦中西玛津、阿特拉津、甲草胺、乙草胺、扑草净、禾草克和哒螨酮的残留量,样品经乙酸乙酯提取,Florisil固相萃取小柱净化,气相色谱-质谱法进行检测,各组分回收率为76．08％-108．1％,测定结果的相对标准偏差为3．9％～10．2％（n=6）。     

弱酸型聚合物微球固相萃取填料的制备及水中杀虫剂的测定

本文制备了聚合物基质弱酸型阳离子交换固相萃取填料,以甲基丙烯酸和苯乙烯为原料,二乙烯基苯为交联剂,聚乙烯醇为分散剂,过氧化苯甲酰为引发剂,采用悬浮聚合法制备了具有亲脂和弱阳离子交换性能的球形固相萃取填料,并对其结构和形貌进行了表征。以该聚合物微球作为填料制备固相萃取小柱,萃取水中联硝氯酚、硫双二氯酚、吡喹酮和丙硫苯咪唑4种杀虫剂,乙腈为洗脱剂,洗脱液采用液相色谱分析。分别考察了样品的p H值和流速、洗脱剂的体积和流速对萃取回收率的影响,确定了最佳固相萃取条件。选择了最佳色谱分析条件。结果表明,该聚合物微球单分散性好,自制固相萃取小柱对水中4种杀虫剂的吸附性能好,与HPLC联用测定结果重现性好,联硝氯酚、硫双二氯酚、吡喹酮和丙硫苯咪唑的最低检测限分别为0.26μg·L-1、0.31μg·L-1、0.42和0.63μg·L-1。     

新型混合固定相的制备与性能评价

通过共聚交联方法将长链碳烯-苯乙烯包覆到锆胶表面上, 得到聚合物包覆固定相, 再对该填料进行磺化引入离子官能团到聚合物表面, 得到混合型固定相. 用扫描电镜和红外光谱对这些填料进行了表征, 考察了混合型固定相的毛细管电色谱性能, 并用该填料分离了苯甲酸和苯胺等化合物.     

碳十八键合锆胶固定相的制备与色谱性能评价

用诱导聚合胶体凝聚法（PICA）制得的二氧化锆微球与碳十八三乙氧基硅烷反应制备了碳十八键合锆胶固定相（ODZ），评价了该柱填料的色谱性能，并用此固定相分离了中性和碱性化合物。     

表面接枝亲水性聚合物刷磁性微球的制备及其对蜂蜜中四环素类抗生素残留的磁分散固相萃取

采用电子转移活化再生催化剂原子转移自由基聚合法（ARGET-ATRP）在磁性微球（MMs）表面连续接枝了聚碱类聚合物和聚乙二醇刷。首先将MMs包覆硅胶,接枝氨基,然后在其表面接枝溴引发剂,最后在MMs表面进行聚合,制备了亲水性聚合物刷磁性微球（HMMs）。通过透射电镜、傅里叶变换红外光谱对HMMs进行表征,并研究了HMMs对蛋白质的吸附性能。结果表明,合成的HMMs粒径较为均一,分散性良好并且具有良好的抗蛋白质吸附性能。利用制备的HMMs,采用磁分散固相萃取（MDSPE）-高效液相色谱法（HPLC）测定了蜂蜜中四环素类抗生素（TCs）残留。TCs的平均回收率为85.8%~94.5%,方法的检出限和定量限分别为1.92~2.56 μg/kg和6.40~8.53 μg/kg。该方法成功地用于蜂蜜中TCs残留的快速分离富集。     

在线固相萃取-超高效液相色谱-串联质谱法快速测定地表水中超痕量阿特拉津

建立了在线固相萃取-超高效液相色谱-串联质谱（on line SPE-UPLC-MS/MS）测定地表水中超痕量阿特拉津的方法。样品经滤膜过滤,HLB Direct Connect HP在线固相萃取小柱富集纯化,甲醇溶液洗脱,以Acquity BEH 130为分析柱,串联质谱进行检测,外标法定量。阿特拉津在1.0~5000 ng/L范围内线性关系良好,相关系数（r）为0.9989;该方法检出限为0.2 ng/L,阿特拉津的回收率为83.0%~105.1%,相对标准偏差为1.6%~5.3%（n=7）,满足超痕量分析测试的要求。该法灵敏度高,分析速度快,对于保障水环境安全、及时提供污染信息、有效应对环境应急突发事件具有十分重要的意义。     

Ultra-pressure liquid chromatography-electrospray tandem mass spectrometry for multiresidue determination of pesticides in water

A multiresidue analysis method has been developed for the determination of pesticides in water by ultra-performance liquid chromatography (UPLC) combined with tandem mass spectrometry (MS/MS). The selected pesticides represent a broad range of polarity and volatility [benzoylcyclohexanedione (mesotrione and sulcotrione); chloroacetamide (acetochlor, alachlor, dimethenamide, and metolachlor); phenoxyacetic acid (2,4-D and MCPA); phenoxypropionic (dichloprop and mecoprop); phenylurea (chlortoluron, diuron, isoproturon, linuron, and metoxuron); sulfonylurea (foramsulfuron, iodosulfuron, and nicolsulfuron); triazine (atrazine, cyanazine, desethylatrazine (DEA), desisopropylatrazine (DIA), simazine, and terbutylazine)]. The analytes were extracted using solid-phase extraction (SPE). The separation was carried out on an acquity UPLC BEH C18 column (1.7 microm, 50 mm x 1 mm ID) using a gradient elution profile and mobile phase consisting of 0.1% formic acid in water and acetonitrile. The pesticides were detected with a tandem mass spectrometer after being ionised positively or negatively (depending on the molecule) using an electrospray ionisation (ESI) source. To achieve the suitable extraction conditions for sample preparation, several parameters affecting the efficiency of SPE such as the nature of the sorbent and the eluent, extractant volume and pH were studied. The best recovery was obtained by the extraction with an Oasis HLB cartridge and 3 mL of a solution of acetonitrile/dichloromethane (1:1, v/v) at pH 2. The average recoveries of the pesticides in different samples ranged from 82 to 109%. The weight least squares (WLS) linear regression was used to calculate the limits of detection and quantification (LOD and LOQ) because the dispersion was heteroskedastic. All the pesticides could be correctly quantified at a concentration level of 50 ng L(-1) and most of them could be detected at a concentration inferior or equal to 8 ng L(-1). Efficiency and robustness of this method were evaluated by the analysis of several samples of real natural water.     

新型毛细管内固相萃取-气相色谱法检测纺织品中烷基酚类物质

建立了毛细管内固相萃取(SPE)-气相色谱(GC)检测纺织品中壬基酚和辛基酚含量的分析方法。通过比较4种性质不同固相萃取剂的萃取效果,筛选出对烷基酚(APs)类物质萃取效果最佳的固相萃取剂,将其作为填充物质制作毛细管内固相萃取柱,将毛细管内固相萃取法与气相色谱联用进行分析检测。最佳固相萃取剂为Abselut NEXUS,毛细管内固相萃取最佳条件为:1.2 μL甲醇和1.2 μL超纯水活化,1.2 μL甲醇洗脱,上样速率是0.4 μL/min。该法在较低浓度范围内呈现良好的线性相关性,对烷基酚的富集倍数约为100倍,对辛基酚和壬基酚的检出限分别为3.7 μg/L和4.5 μg/L,加标回收率分别为85.6%~98.2%和83.8%~95.7%,结果表明,此法能够简捷、迅速、有效地检测出纺织品中残留的烷基酚类物质。     

橄榄醇分子印迹聚合物的制备及评价(英文)

以橄榄醇为模板分子,α-甲基丙烯酸(MAA)为功能单体,乙二醇二甲基丙烯酸酯(EDMA)为交联剂,甲苯和十二醇为溶剂,通过本体聚合法制备了橄榄醇分子印迹聚合物。利用平衡结合实验、扫描电镜(SEM)及红外光谱(FTIR)对分子印迹聚合物(MIP)进行了表征,并用该聚合物进行了加标麦麸中橄榄醇的固相萃取(SPE)研究。平衡结合实验表明MIP对模板分子具有更好的识别性。Scatchard分析表明对橄榄醇分子的吸附存在2类不同结合位点,其中高亲和力结合位点和低亲和力结合位点的解离常数分别为0.021和1.002 mmol/L,相应的最大表观结合量分别为18.74和135.9 μmol/g。在优化的固相萃取条件下,MIP固相萃取柱对加标麦麸中橄榄醇的回收率达到97.8%~98.8%,相对标准偏差为2.8%~4.2%(n=5),线性范围为0.1~100 mg/L,检出限(S/N=3)为0.062 mg/L。与非印迹聚合物(NIP)柱及市售聚苯乙烯/二乙烯基苯(PLS)柱相比,MIP柱的选择性更强,回收率更高,纯化效果更好。     

超高效液相色谱-串联质谱法快速测定地表水中联苯胺、苦味酸、甲萘威、阿特拉津和溴氰菊酯

建立了一种经简单过滤即可直接进样的超高效液相色谱-串联质谱（UPLC-MS/MS）分析方法,可快速测定地表水中联苯胺、苦味酸、甲萘威、阿特拉津和溴氰菊酯5种有机物的残留。样品经0.2 μ m针式滤头过滤除去颗粒性杂质后,进行UPLC-MS/MS分析,采用UPLC HSS T₃色谱柱,2 mmol/L乙酸铵甲醇溶液和2 mmol/L乙酸铵水溶液作为流动相进行梯度洗脱,电喷雾离子源电离,正、负离子切换多反应监测模式进行定性和定量分析。5种目标化合物分别在0.10~10.0 μ g/L或1.00~100 μ g/L范围内线性关系良好,相关系数为0.996~0.999,方法的检出限为0.01~0.22 μ g/L;高、中、低3个添加水平的回收率为81.4%~113%,相对标准偏差为0.84%~14.0%。利用该方法对杭州市部分河流和水库的地表水样品进行分析,其中阿特拉津和溴氰菊酯在部分水样中有阳性检出。结果表明,该方法简便快捷、灵敏准确,适用于地表水样品中联苯胺、苦味酸、甲萘威、阿特拉津和溴氰菊酯的快速测定。     

基于中空氧化镍纳米微球和离子液体复合膜固定血红蛋白的NaNO2生物传感器

采用微波水热法合成了一种中空氧化镍纳米微球(NiO), 然后将其与1-丁基-3-甲基-咪唑四氟硼酸盐(BMIMBF4)的复合膜用于血红蛋白(Hb)在碳糊电极上的固定, 制备了NaNO2生物传感器. 通过扫描电子显微镜、 傅里叶变换红外光谱及紫外-可见光谱等分析表明, Hb已固定于NiO和BMIMBF4的复合膜中并能保持其生物活性; 进一步通过电化学阻抗法研究了修饰电极中混合物各组分的作用. 结果表明, 在NiO和BMIMBF4的复合膜中, Hb能实现有效的直接电子转移, 且修饰后的电极对NaNO2有良好响应, 响应时间小于5 s, 检出限为4.57 μmol/L(S/N=3), 灵敏度为46.2 μA·L·mmol-1, 线性范围为10~170 μmol/L, 表观米氏常数KM为2.4 mmol/L, 该方法的重现性和电极的稳定性良好.     

Combination of ionic liquid dispersive liquid-phase microextraction and high performance liquid chromatography for the determination of triazine herbicides in water samples

A temperature-controlled ionic liquid dispersive liquid-phase microextraction in combination with high performance liquid chromatography was developed for the enrichment and determination of triazine herbicides such as cyanazine,simazine,and atrazine in water samples.1-Octyl-3-methylimidazolium hexafluorophosphate([C8MIM][PF6]) was selected as the extraction solvent.Several experimental parameters were optimized.Under the optimal conditions,the linear range for cyanazine was in the concentration range of 0.5–80 mg/L and the linear range for simazine and atrazine was in the range of1.0–100 mg/L.The limit of detection(LOD,S/N = 3) was in the ranges of 0.05–0.06 mg/L,and the intra day and inter day precision(RSDs,n = 6) was in the ranges of 3.2%–6.6% and 4.8%–8.9%,respectively.Four real water samples were analyzed with the developed method,and the experimental results showed that the spiked recoveries were satisfactory.All these exhibited that the developed method was a valuable tool for monitoring such pollutants.     

Determination of chloro-s-triazines including didealkylatrazine using solid-phase extraction coupled with gas chromatography-mass spectrometry

Chloro-s-triazines are a class of compounds comprising atrazine, simazine, propazine, cyanazine and their chlorinated metabolites. The US Environmental Protection Agency (EPA) has determined that selected chloro-s-triazines--atrazine, simazine, propazine, deethylatrazine, deisopropylatrazine, and didealkylatrazine--have a common mode of toxicity related to endocrine disruption. In this paper, a dual-resin solid-phase extraction (SPE) gas chromatography-mass spectrometry (GC-MS) method is reported that provides for each of these chloro-s-triazines including the polar metabolite, didealkylatrazine. The method utilizes deuterated internal standards for quantitation and terbuthylazine as a recovery standard. The limit-of-detection was 0.01 microg/L for simazine, deethylatrazine, deisopropylatrazine and didealkylatrazine, and 0.02 microg/L for atrazine and propazine in surface water. Mean recoveries for 0.5 and 3.0 microg/L spikes for atrazine, simazine, propazine, deethylatrazine, deisopropylatrazine and didealkylatrazine were 94, 104, 103, 110, 108 and 102%, respectively, in surface water. The method was also validated by matrix spikes into fourteen different raw and treated natural surface waters. This method is useful for monitoring "total chloro-s-triazines" in both raw and treated drinking waters.     

左氧氟沙星印迹聚合物微球及其特异吸附研究

以甲基丙烯酸为功能单体,乙二醇二甲基丙烯酸酯为交联剂,采用沉淀聚合法制备了左氧氟沙星印迹聚合物(MIP)微球,用SEM和IR分别对微球形貌和结构进行表征,用静态吸附法和Scatchard分析考察了聚合物微球对模板及其结构类似物的吸附行为和选择性识别能力.结果表明,MIP对模板分子的吸附平衡速度快,40min即可达到吸附...     

固相萃取-高效液相色谱法测定环境水样中的三嗪类化合物

建立了固相萃取-高效液相色谱法(SPE-HPLC)测定地表水中三嗪类化合物的方法。考察了4种不同固相萃取柱对三嗪类化合物的吸附效果,最终选择ENVI-18固相萃取柱用于萃取地表水中的三嗪类化合物;系统研究了环境水样中三嗪类化合物的最佳固相萃取条件,选择洗脱溶剂为甲醇,洗脱溶剂用量5 mL,水样在萃取前不需要添加甲醇,不调节pH值。测定了方法的检测限,结果表明,扑草净、莠去津、西玛津、脱乙基莠去津、羟基化莠去津和脱异丙基莠去津的最低检测限依次为0.14 μg/L,0.12 μg/L,0.08 μg/L,0.08 μg/L,0.10 μg/L和0.18 μg/L。将该法应用于实际环境水样的分析测定,结果表明某湖水中扑草净的含量为（9.33±0.27） μg/L,某江水中莠去津和扑草净的含量分别为（5.28±0.43） μg/L和（7.12±0.54） μg/L。