Concentration profiles of cocaine, pyrolytic methyl ecgonidine and thirteen metabolites in human blood and urine: determination by gas chromatography-mass spectrometry

When cocaine is smoked, a pyrolytic product, methyl ecgonidine (anhydroecgonine methyl ester), is also consumed with the cocaine. The amount of methyl ecgonidine formed depends on the pyrolytic conditions and composition of the illicit cocaine. This procedure describes detection of cocaine and 10 metabolites--cocaethylene, nor-cocaine, nor-cocaethylene, methyl ecgonine, ethyl ecgonine, benzoylecgonine, nor-benzoylecgonine, m-hydroxybenzoylecgonine, p-hydroxybenzoylecgonine and ecgonine--in blood and urine. In addition, the detection of pyrolytic methyl ecgonidine and three metabolites--ecgonidine (anhydroecgonine), ethyl ecgonidine (anhydroecgonine ethyl ester) and nor-ecgonidine (nor-anhydroecgonine)--are included. The newly described metabolites, ethyl ecgonidine and nor-ecgonidine, were synthesized and characterized by gas chromatography-mass spectrometry (GC-MS). All 15 compounds were extracted from 3 mL of blood or urine by solid-phase extraction and identified by a GC-MS method. The overall recoveries were 49% for methyl ecgonine, 35% for ethyl ecgonine, 29% for ecgonine and more than 83% for all other drugs. The limits of detection were between 0.5 and 4.0 ng/mL except for ecgonine, which was 16 ng/mL. Linearity for each analyte was established and in all cases correlation coefficients were 0.9985-1.0000. The procedure was applied to examine the concentration profiles of analytes of interest in post-mortem (PM) blood and urine, and in urine collected from living individuals (LV). These specimens previously were shown to be positive for the cocaine metabolite, benzoylecgonine. Ecgonidine, the major metabolite of methyl ecgonidine, was present in 77% of PM and 88% of the LV specimens, indicating smoking as the major route of cocaine administration. The new pyrolytic metabolites, ethyl ecgonidine and nor-ecgonidine, were present in smaller amounts. The urine concentrations of nor-ecgonidine were 0-163 ng/mL in LV and 0-75 ng/mL in PM specimens. Ethyl ecgonidine was found only in PM urine at concentrations 0-39 ng/mL. Ethanol-related cocaine metabolites, ethyl ecgonine or cocaethylene, were present in 69% of PM and 53% of cocaine-positive LV specimens, implying alcohol consumption with cocaine use. The four major metabolites of cocaine--benzoylecgonine, ecgonine, nor-benzoylecgonine and methyl ecgonine--constituted approximately 88 and 97% of all metabolites in PM and LV specimens, respectively. The concentrations of nor-cocaine and nor-cocaethylene were consistently the lowest of all cocaine metabolites. At benzoylecgonine concentrations below 100 ng/mL, ecgonine was present at the highest concentrations. In 20 urine specimens, benzoylecgonine and ecgonine median concentrations (range) were 54 (0-47) and 418 ng/mL (95-684), respectively. Therefore, detection of ecgonine is advantageous when benzoylecgonine concentrations are below 100 ng/mL.     

气相色谱/质谱法测定熏肉中的多环芳烃

建立了熏肉中多环芳烃的气相色谱/质谱(GC/MS)测定方法。样品经正己烷-丙酮(体积比为1∶1)超声波提取、氧化铝柱净化后,用GC/MS分离测定。优化了25种多环芳烃(PAHs)化合物的分离测定条件。结果 25种PAHs回收率范围为48.5%-106.5%;日内(n=7)相对标准偏差为3.75%-7.95%。方法具有灵敏度高、准确度好、能同时分离测定20余种多环芳烃化合物的优点,适合于熏肉中多环芳烃化合物的分析测定。     

气体爆轰波在声学吸收壁下游的再加强过程

实验研究了爆轰波在声学吸收段下游发生的再恢复过程。利用声学吸收段首先将一个稳定的爆轰波衰减,于是产生一个非稳定爆轰波,速度降为 45% ~60?J。该非稳定爆轰波传出声学吸收段后再次加强,并在距声学吸收段出口端一定距离处突然发展成超驱动爆轰。实验利用烟迹技术捕捉了爆轰波从发生衰减到再次加强的全过程,获得了爆轰波再加强距离随初压变化的实验规律。由此,本文建立了再加强段内加速传播火焰的理论模型,称为激波 -爆燃波复合态,并解释了火焰加速和超驱动爆轰形成的机理。     

加速溶剂萃取和凝胶渗透色谱净化GC–MS法测定烟熏腊肉中16种多环芳烃

采用ASE萃取、GPC净化和浓缩,建立GC–MS法快速检测烟熏腊肉中16种多环芳烃(PAHs)的分析方法。将烟熏腊肉与硅藻土充分混合后,放到萃取池中加速溶剂萃取,在优化仪器条件下测定,16种PAHs的线性范围为0.1~4 ng/m L,线性相关系数r为0.985 3~0.999 9。方法检出限在0.172~0.233μg/kg之间,加标回收率为60.3%~93.2%,测定结果的相对标准偏差为4.06%~11.60%(n=6)。该方法检测快速,准确度高,重现性好,适合于烟熏腊肉中16种PAHs的同时测定。     

Study on the influences of ultrasound on the flavor profile of unsmoked bacon and its underlying metabolic mechanism by using HS-GC-IMS

For exploring the influence of ultrasound on the flavor characteristic of unsmoked bacon, sensory evaluation combined with E-nose and headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS) were performed to analyze the overall flavor profile and specific volatile flavor compounds (VFCs), respectively. Furthermore, the metabolic pathway of VFCs affected by ultrasound was also investigated. Results demonstrated that ultrasound improved the flavor characteristic of unsmoked bacon by raising the levels of nonanal, heptanal, octanal, 3-methylbutanal n-hexyl acetate and n-propyl acetate. Enzymatic oxidation was found to be an important metabolic pathway responsible for the development of flavor characteristic after ultrasound treatment, which could be attributed to the increased activities of lipases and lipoxygenase and the higher concentration of polyunsaturated free fatty acids. The increased level of lipid oxidation after ultrasound treatment was also confirmed by thiobarbituric acid reactive substances. Consequently, ultrasound is an effective approach to enhance the flavor characteristic of unsmoked bacon.     

在线固相萃取/高效液相色谱法检测熏烤鱼及熏烤肉制品中的多环芳烃

基于在线净化富集技术,建立了熏烤鱼和熏烤肉制品中15种欧盟优控多环芳烃的在线固相萃取/高效液相色谱-紫外/荧光(Online-SPE/HPLC-UV/FLD)检测方法。对提取溶剂和流动相进行优化,样品采用乙腈-丙酮(6∶4)匀浆处理,超声提取后,在线固相萃取柱Chrom Spher Pi(80 mm×3 mm)净化富集,反相C18PAH专用柱(250 mm×4.6 mm i.d.,5μm)分离,水、乙腈和异丙醇梯度洗脱,紫外和荧光检测器检测。结果表明,15种多环芳烃在相应的浓度范围内线性良好(r20.999);检出限为0.03~8.33μg/kg;熏烤鱼的回收率为67.4%~107.2%,相对标准偏差(RSD)为0.2%~7.7%;熏烤肉的回收率为71.8%~110.5%,RSD为0.8%~8.9%。经FAPAS质控样品验证,所测化合物种类和浓度范围均满足要求。     

发酵乳杆菌RC4对咸肉亚硝酸盐含量及挥发性风味物质的影响

为降低咸肉中亚硝酸盐含量, 将具有高效降解亚硝酸盐的发酵乳杆菌RC4应用于咸肉制作中, 研究其对咸肉亚硝酸盐含量、品质和风味的影响. 通过单因素实验及正交实验, 对添加发酵乳杆菌RC4的实验组咸肉制作工艺进行优化, 比较接菌组和未接菌发酵对照组在感官评分、亚硝酸盐含量、pH、色差、水分、硫代巴比妥值及挥发性风味成分的差异. 结果表明: 实验组咸肉亚硝酸盐含量降解显著, 降解率为78.60%; 实验组咸肉的最佳发酵条件为接种2.0%(μL·mL^-1)的发酵乳杆菌RC4菌液, 18℃发酵10d. 与对照组相比, 实验组咸肉pH降低; 色差及水分含量与对照组差异不显著(P＞0.05); TBA值的变化量明显小于对照组(P＜0.05). 在鉴定出的87种挥发性物质中, 庚醛为RC4发酵产生, 苯甲醛等的含量显著高于对照组, 而这几种醛均为特征风味化合物. 由此可知, 在咸肉制备工艺中, 添加发酵乳杆菌RC4能显著降低咸肉的亚硝酸盐含量, 提高咸肉保质期, 增加其特征风味化合物含量.     

Possibility of Campylobacter jejuni inactivation in smoked salmon by high-pressure treatment

The sterile samples of cold-smoked salmon were placed in polyamide–polyethylene pouches and inoculated with three-strain composite of Campylobacter jejuni (inoculum ca 10⁷ CFU g^?1). The inoculated samples were sealed under vacuum and subjected to 200, 300 and 400 MPa of hydrostatic pressure for 0, 5, 10 and 15 min. The number of surviving C. jejuni per gram was determined by the 10-fold dilution method followed by plating on Karmali agar. D ₁₀ values were calculated. This work has shown that for reducing C. jejuni in cold-smoked salmon by 6 log units, the application of 200 MPa for 64.26 min or 300 MPa for 17.10 min or 400 MPa for less than 5 min is needed. Applying such parameters of high-pressure processing should not change significantly the organoleptic properties of the product.     

Thermal stability, texture, liquid holding capacity and colour of smoked salmon on retail level

Retail samples of vacuum-packed sliced cold smoked salmon were investigated for changes in texture, colour and expressible moisture approximately 1 week before expiry date and on the best before date. For comparison, retail samples of gravelax were also investigated. To gather information on alteration in protein caused by processing and refrigerated storage, DSC measurements were performed at the same samples and furthermore on hot smoked salmon and frozen raw material, Salmo salar. Texture parameters varied markedly between the retail samples; however, almost no clear tendencies were observable with increased refrigerated storage time while expressible moisture raised. Colour also differed considerably between the samples. Gravelax behaved almost comparable to cold smoked salmon. DSC curves taken from cold smoked salmon and gravelax were almost comparable and demonstrated that muscle proteins being largely denatured by the influence of salt and cold smoking temperature compared to the raw material.     

近红外光谱定量检测腌腊肉制品品质的研究

以中国传统腌腊肉为对象,研究用近红外光谱分析技术快速准确检测肉制品品质的可行性。腊肉是富含脂肪的肉制品,其酸价是目前国标中必须检测的品质指标,它可以反映腊肉在加工储藏过程中脂肪氧化酸败的情况, 对腊肉的品质尤为重要。腊肉样品经过简单的粉碎后在BRUKER傅里叶变换近红外光谱仪上扫描,获得其近红外光谱参照国标法测定酸价和水分含量,采用附加散射校正光谱预处理方法,建立了腊肉酸价和水分含量的PLS回归模型。酸价模型预测集中样品的预测值与标准值的相关系数r2为0.98,预测标准差RMSECV为0.25;水分含量模型预测集中样品的预测值与标准值的r2为0.90,RMSECV为0.02。成对t检验统计结果表明近红外光谱分析技术可以用于腊肉制品品质的快速检测。