Biogenic amines (BAs) are a group of substances that are formed from amino acids by decarboxylation or amination and transamination of aldehydes and ketones. They may have either an aliphatic, aromatic, or heterocyclic structure. Their quantity determines their effects and optimum amounts are essential for physiological functions, but excess BAs causes various toxic effects throughout the human body. In our study, to rapidly determine 14 BAs (histamine, tyramine, dopamine, tryptamine, serotonin, putrescine, spermine, spermidine, octopamine, benzylamine, 1-Phenylethanamine, cadaverine, 2-Phenethylamine, and agmatine) in real fish samples, an ultra-performance liquid chromatography–tandem mass spectrometry method was established. The fish sample was extracted by acetonitrile with 0.1% formic acid and stable biogenic amine derivatives could be obtained by benzoyl chloride derivatization with a shorter reaction time. The method showed good linearity with a linear range of 3–4 orders of magnitude and regression coefficients ranging from 0.9961 to 0.9999. The calculated LODs ranged from 0.1 to 20 nM and the LOQs ranged from 0.3 to 60 nM. Satisfactory recovery was obtained from 84.6% to 119.3%. The proposed method was employed to determine the concentration levels of biogenic amine derivatives in different fish. The results indicated that this method was suitable for the analysis of biogenic amines.

Progesterone functions as an endocrine-disrupting compound. Imitating endogenous hormones disrupt the animals’ hormone levels. The potential hazard of progesterone in milk cannot be neglected. Thus, research has focused on establishing an efficient and convenient pretreatment and analytical approach. In this study, a metal-organic framework (MOF) material UiO-67 was prepared, which possessed a large specific surface area and excellent stability. It was employed to enrich and purify trace progesterones in a complex milk matrix as a filler to integrate the solid phase extraction column. An approach based on MOF was developed using ultra-high performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS). This approach could simultaneously determine seven kinds of progesterone residues in milk. The element spectra of UiO-67 were first measured and analyzed using X-ray photoelectron spectroscopy. The chemical interaction between UiO-67 and progesterone was proved by comparing the changes in binding energy and relative contents of functional groups, and the adsorption efficiency of 1 mg/L and 5 mg/L progesterones by UiO-67 was studied. The adsorption efficiencies of UiO-67 for 1 mg/L and 5 mg/L progesterones were 99.73%-99.95% and 88.87%-99.23%, respectively, according to the results. It proved the efficient adsorption of UiO-67 to progesterones and ensured that subsequent studies went smoothly. Furthermore, key parameters, such as the amount of sorbent, elution solvent type, and pH value, were examined and optimized to obtain optimal extraction recovery of the progesterones. Spiked concentrations of 50 μg/L were employed for extraction optimization. All experiments were performed three times. It also evaluated the matrix effect on mass spectrum signal of the progesterones. The optimized results showed that the seven progesterones could be satisfactorily recovered when the amount of adsorbent was 40 mg, pH value of the sample solution was 5, and elution solution was 5-mL acetone. Additionally, the matrix effect of progesterone in the milk sample was 0.99. The limits of detection (LODs) ranged from 0.06 to 0.30 μg/L, and limits of quantification (LOQs) ranged from 0.19 to 1.0 μg/L, respectively. At various concentration levels of progesterones in milk, the recoveries were 87.10%-105.58%, with relative standard deviations of 2.66%-9.64%. Most importantly, the approach was successfully employed to determine progesterone levels in milk samples, with results in good agreement with the standard SN/T 1980-2007. The proposed approach had the advantages of high sensitivity and satisfactory accuracy compared with the reported pretreatment and detection approaches of progesterone in milk. Satisfactory experimental results can be obtained without the calibration by isotope inner standard. Meanwhile, considering the excellent performance of MOF materials in reducing matrix interference in complex samples, such the application of materials offers a new approach. It can be employed to enrich and detect hazards in a complex matrix in the future.

Tetrodotoxin (TTX) is a kind of low-molecular-weight non-protein neurotoxin. It is one of the most potent neurotoxins found in nature, and it is found in puffer fish and various marine biota. The low sensitivity of previous analytical methods limited their application in puffer fish organ samples. This study established a method for the accurate and fast determination of TTX by reversed ultra-performance liquid chromatography coupled with proton-enhanced electron spray ionization–tandem mass spectrometry. The method yields good peak shapes, high sensitivity and low coeluted interferences. The method was successfully applied to determine TTX in puffer fish tissue samples of about 0.2 g.

快速准确的治疗药物监测对于临床上确保患者用药有效性及安全性至关重要,同时也能够确定患者用药依从性,制定个性化给药方案。该文以两支疏水性略有差异的反相分离柱Supersil ODS2和SinoChrom ODS-BP,及强阳离子交换捕集柱Supersil SCX构建了基于集成化的多柱二维液相色谱系统。通过二维色谱接口,以pH 3.0的磷酸缓冲液调整第一维分离后的洗脱液组成,降低有机相含量并维持pH,改善了中心切割模式下样品转移和捕集的效率。利用该多柱二维液相色谱系统发展了血清中氨磺必利的二维液相色谱检测方法,血清样品经过高氯酸和甲醇混合液沉淀蛋白质并离心后直接300 μL大体积进样,以乙腈/磷酸缓冲液(25 mmol/L, pH 3.0)(20/80, v/v)作为第一维分离流动相,磷酸缓冲液(25 mmol/L, pH 3.0)作为捕集过程的稀释流动相,乙腈/磷酸缓冲液(25 mmol/L, pH 7.0)(25/75, v/v)作为第二维分离流动相,12 min内即可完成分析。方法在10~200 ng/mL的范围内线性相关性良好(r=0.9998)。样品在50 ng/mL和100 ng/mL两个加标浓度下的回收率稳定,在73.7%~76.8%之间。方法的检出限为7.28 ng/mL,定量限为24.27 ng/mL,能够满足《神经精神药理学治疗药物检测共识指南》中推荐的药物监控范围要求。由于该系统日常使用及维护成本较低,且能够实现自动化分析,故该方法适合在临床上用于治疗药物监测研究。