磷酸、膦酸酯类农药的质谱裂解规律研究

在对23种磷酸、膦酸酯类农药及其氧化物的质谱数据进行归纳整理的基础上,明确了这类农药质谱裂解规律。结果表明:电子轰击离子化条件下,磷酸、膦酸酯类农药分子极易裂解,且分子离子峰较弱。发现C_2H_6O_3P~+(m/z109)是其最具代表性的特征碎片离子。磷酸酯类农药裂解规律是二甲氧基磷酸酯P-0键易发生a断裂,生成m/z 109特征碎片离子。二乙氧基磷酸酯易脱去中性碎片C_2H_4,形成m/z81的特征离子。R'含有烯烃结构,易产生m/z127的特征碎片离子。膦酸酯类农药裂解规律与磷酸酯类似,特征性弱,膦键容易发生a断裂。选定了磷酸、膦酸酯类农药在质谱分析中常见的碎片离子,为农药残留筛查、确证分析提供参考。     

Computed Tomography and Magnetic Resonance Imaging of an Epidermoid Cyst in a Foot of a Horse

An 18-year-old Quarter Horse mare was evaluated because of moderate left forelimb lameness of 4 weeks’ duration. The clinical evaluation and diagnostic perineural analgesia localized the lameness to the distal portion of the left forelimb. There was swelling on the dorsal and lateral aspect of the coronary band. Radiography, ultrasound, magnetic resonance imaging, and computed tomography of the foot revealed circumscribed well-capsulated soft tissue mass causing a focal deformation of the dorsolateral border of the middle phalanx. The treatment aimed to remove the mass surgically and stabilized the interphalangeal joint, but the owner elected human euthanasia before treatment attempt. Histopathology diagnosis was an epidermoid cyst, which was characterized by multilayers of keratin surrounded by stratified squamous epithelium. Although rare, an epidermoid cyst should be considered as a differential diagnosis for space-occupying mass in horses’ foot that develops chronic lameness after trauma. This report describes the multimodality appearance of the epidermoid cyst.     

A systematic approach to determine the impact of elevated CO2 levels on the chemical composition of wheat (Triticum aestivum)

Two wheat genetic lines (responsive and non-responsive to elevated CO₂) grown under ambient and free-air CO₂ enrichment (FACE) conditions were compared using fuzzy chromatography mass spectrometry (FCMS) metabolite fingerprinting. A more comprehensive survey of the changes in their chemical composition was made on selected samples using ultra-high-performance liquid chromatography (UHPLC) metabolomic profiling with high resolution accurate mass/tandem mass spectrometry (HRAM/MSⁿ). Principal component analysis (PCA) of the metabolite fingerprints showed four clusters for the two genetic lines (responsive and non-responsive) and the two CO₂ levels (ambient and elevated) in score plots. Metabolite profiling of representative samples for each of the four clusters identified 25 and 16 compounds from negative and positive data, respectively, including amino acids, saccharides, phenolic acids, flavonoids, and lipids. Loading plots demonstrated that some saccharides and lipids were responsible for discriminating between not only two genetic lines but also two CO₂ levels. Analysis of free amino acids (not bound) showed a clear pattern of reduced concentration for both lines with elevated CO₂. After acid hydrolysis, the responsive line 6 (41% increase in yield) showed the same pattern observed for free amino acids, but the non-responsive line 5 (6% increase in yield) showed different trends in concentrations of amino acids with elevated CO₂.     

Effects of germination and kilning on the phenolic compounds and nutritional properties of quinoa (Chenopodium quinoa) and kiwicha (Amaranthus caudatus)

Quinoa (Chenopodium quinoa) and kiwicha (Amaranthus caudatus) are nutritious pseudocereals that originate from the Andean region. The aim of this research was to study the effect of germination and the subsequent kilning on the phenolic compounds and proximate composition in selected Peruvian varieties of quinoa (“Chullpi”) and kiwicha (“Oscar Blanco”). The germination process was carried out for 24, 48 and 72 h at 22 °C, and the kilning was performed with samples germinated for 72 h by drying the seeds at 90 °C for 5 min. Both processes increased the protein content of the samples. However, lipid content was reduced during germination. On the other hand, germination and kilning clearly increased the concentration of total phenolic compounds in both quinoa and kiwicha. Germination for 72 h either with or without kilning process resulted in a significant (p < 0.05) increase in the total content of phenolics compared to untreated materials, which was especially due to coumaric acid and a kaempferol tri-glycoside in quinoa and caffeoylquinic acid in kiwicha. Based on the results, germination and kilning may improve the nutritional quality of the Andean grains, encouraging the usage of the processed grains as ingredients in functional products for people with special gluten-free or vegetarian diets.     

超高效液相色谱-串联质谱法测定牛奶和奶粉中五种苯并咪唑类药物

为建立牛奶及奶粉中5种苯并咪唑类药物(阿苯达唑、芬苯达唑、奥芬达唑、噻苯达唑、苯硫氨酯)简便、准确的分析检测方法,以固相萃取为净化手段,采用Acquity UPLC^® BEH C₁₈(100 mm×2.1 mm,1.7 μm)色谱柱进行分离,电喷雾离子源(ESI⁺),多反应监测(MRM)模式检测。结果表明,5种苯并咪唑类药物在1~500 μg·L^-1范围内呈线性相关,相关系数(r)均大于0.996,加标平均回收率介于91.7%~97.8%之间,相对标准偏差(RSD)在1.4%~6.5%之间,基质效应均小于15%。5种药物的检出限均在0.1~3 μg·kg^-1范围内,定量限均在0.5~10 μg·kg^-1范围内。该方法操作简单、快速且灵敏度高,重现性好,能够用于牛奶及奶粉5种苯并咪唑类药物的同时测定。     

快速滤过型净化法结合高效液相色谱-串联质谱同时检测人参中的5种农药残留

基于人参样品基质特点，采用快速滤过型净化法 (m-PFC) 结合高效液相色谱-串联质谱 (HPLC-MS/MS)，建立了人参中嘧菌酯、苯醚甲环唑、吡虫啉、茚虫威和噻嗪酮5种农药残留同时检测的分析方法。该方法具有较低的检出限 (0.03~0.18 μg/kg) 和定量限 (0.11~0.59 μg/kg)，其定量限较中国国家标准GB 2763—2016中规定的对人参中苯醚甲环唑和嘧菌酯的最大残留限量 (MRL) (0.5~1 mg/kg) 低3个数量级，5种农药的线性范围在1~500 μg/L之间。在2、10、50、100和300 μg/kg的添加水平下，方法的平均回收率均在76%~115%之间，相对标准偏差 (RSD) 均小于11%，回收率较好且方法稳定。与传统样品前处理方法相比，该方法具有操作简单、省时省力和灵敏度高等优点。将该方法应用于市售6份人参样品中5种农药残留的检测，结果未检出相应的农药残留。该方法为研发建立更快速、准确地检测人参中农药残留的方法提供了思路，也为后续中国国家标准修订人参中农药最大残留限量提供了参考。     

柚木石油醚抽提物成分及其对心边材颜色的影响

为探究国产柚木抽提物对心材和边材颜色差异的影响,采用3种沸程的石油醚溶液分别对国产柚木的心材与边材进行抽提处理,利用气相色谱-质谱法分析抽提液的成分和含量,并以差异较大的抽提物溶液处理柚木边材,通过色度学参数表征柚木边材的变色情况,从而验证影响柚木心材和边材颜色的主要抽提物成分。结果表明:在3种沸程的石油醚抽提液中,柚木心材抽提物在成分种类数量和含量上均显著高于边材;不同沸程的石油醚对柚木心、边材中抽提物成分有一定的影响,其中30~60℃(低沸程)和60~90℃(中沸程)石油醚抽提物成分和含量的差异较小,而90~120℃(高沸程)石油醚抽提物的含量较高,约为中、低沸程抽提物含量的2倍;柚木心材抽提液中酚类、醌类、烯烃类物质的含量较多,但这些物质在边材中含量极低;4-叔丁基-2-苯基苯酚、2-甲基蒽醌(柚木醌)、全反式三十碳六烯(角鲨烯)是柚木心、边材抽提物含量差异最明显的物质。经角鲨烯溶液处理后的柚木边材表面颜色变黄,更接近心材颜色,因此,角鲨烯是导致柚木心边材颜色差异的重要抽提物成分。     

超高效液相色谱串联质谱法对水产品中硝基呋喃代谢物的测定

建立了使用Waters UPLC Xevo TQ超高效液相色谱串联质谱仪检测水产品中4种硝基呋喃代谢物的分析方法。匀浆后的样品在酸性环境下水解,并用2-硝基苯甲醛衍生16h,经磷酸氢二钾提取,LMS固相萃取小柱净化后,在三重四极杆多反应监测模式下进行测定。方法采用同位素内标法定量,四种代谢物的检出限(LOD)均低于0.25μg·kg-1,线性范围在0.5μg·L~(-1)到10μg·L~(-1)间,相关系数大于0.99。在0.5、1.0和5μg·kg-1浓度下分别进行添加回收试验(n=5),回收率在75.2%~123.3%之间,相对标准偏差(RSD)小于9.4%。     

原子吸收光谱法检测大蒜制品中微量元素锗

[目的]研究不同大蒜制品中锗元素含量的差别。[方法]采用马弗炉灰化样品,火焰原子吸收光谱法测定以金乡紫皮蒜为原料加工而成的黑蒜、蒜蓉辣酱、脱水蒜片、蒜粉、糖醋蒜5种制品中锗的含量。[结果]试验表明,黑蒜中锗含量为1.384 mg/g,蒜蓉辣酱中锗含量为0.784 mg/g,脱水蒜片中锗含量为0.913 mg/g,蒜粉中锗含量为0.956 mg/g,糖醋蒜中锗含量为0.827 mg/g。5种蒜制品中均含有锗元素,其含量由多到少依次为黑蒜、蒜粉、脱水蒜片、糖醋蒜、蒜蓉辣酱。[结论]研究可为大蒜及大蒜制品的开发利用提供参考依据。     

分散固相萃取结合UPLC-Orbitrap MS联用测定鸡蛋中五氯苯酚残留量

建立了超高效液相色谱-静电轨道阱质谱联用测定禽蛋中五氯苯酚残留量的分析方法。取均质后的禽蛋样品经乙腈溶液提取,加入无水硫酸镁和氯化钠进行脱水和盐析,高速离心分层后,取适量乙腈层溶液经0.1%(V∶V)甲酸稀释后,用酸性氧化铝粉末进行样品净化并以10000 r/min离心取上清液,过0.22μm滤膜后上机测定。使用反相色谱柱进行分离,流动相为乙腈:0.1%甲酸=75∶25,采用等度程序进行洗脱,静电轨道阱质谱进行定性定量分析。结果表明,五氯苯酚在0.5~100μg/kg范围内线性关系良好(r>0.995),方法的最低检出限为0.2μg/kg,最低定量限为0.5μg/kg,添加回收率在74.43%~96.85%之间,批内批间变异系数CV%<10%。该方法具有较好的准确度与精密度,适用于禽蛋中五氯苯酚残留量的测定。