Li Fan, Cui Hua, Zhang Dingwen, Li Huilai, Guo Wei, Jin Lanlan, Hu Shenghong
State Key Laboratory of Biogeology and Environmental Geology, School of Earth Sciences, China University of Geosciences, Wuhan, 430074, People's Republic of China.
Department of Clinical Laboratory, Renmin Hospital of Wuhan University, Wuhan, 430060, People's Republic of China.
Anal Bioanal Chem. 2023 Oct;415(24):6051-6061. doi: 10.1007/s00216-023-04878-2. Epub 2023 Aug 5.
A novel method for direct high-throughput analysis of multi-elements in cerebrospinal fluid (CSF) samples by laser ablation inductively coupled plasma mass spectrometry with an aerosol local extraction cryogenic ablation cell (ALEC-LA-ICP-MS) was developed. Microliter-level CSF samples were frozen by a designed cryogenic ablation cell and directly analyzed by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) without time-consuming pretreatment. Compared with the precision obtained at room temperature (20℃), that obtained at low temperature (- 25℃) was significantly improved; the RSDs were reduced from 8.3% (Zn) to 32.6% (Mn) to 2.2% (Pb) to 6.5% (Mn) with six times parallel determination. To meet the analytical requirement of the micro-volume CSF samples, the laminar flow aerosol local extraction strategy was adopted to improve the transmission efficiency of aerosols, and the signal intensity was increased by four times compared with the standard commercial ablation cell. The standard solution with 0.4% bovine serum albumin (BSA) matrix was used as matrix-match external standard, and Rh was added into the samples as internal standard. The limits of detection (LODs) ranged from 0.17 μg·L (Mn) to 8.67 μg·L (Mg). Standard addition recovery experiments and the determination of CRM serum L-1 and L-2 were carried out to validate the accuracy of the method; all results indicated there were excellent accuracy and precision in the proposed method. The matrix-scanning function in the GeoLas software combined with the microwell plate realizes the high-throughput automatic analysis. Twenty-four CSF samples from different patients were determined; the results showed that there might be a correlation between the metal elements in CSF and the diseases, which means that the proposed method has potential in the diagnosis of neurological diseases.
开发了一种通过激光烧蚀电感耦合等离子体质谱联用气溶胶局部萃取低温烧蚀池（ALEC-LA-ICP-MS）对脑脊液（CSF）样本中的多元素进行直接高通量分析的新方法。微升级别的脑脊液样本通过设计的低温烧蚀池冷冻，无需耗时的预处理，直接用激光烧蚀电感耦合等离子体质谱（LA-ICP-MS）进行分析。与在室温（20℃）下获得的精密度相比，低温（-25℃）下获得的精密度显著提高；通过六次平行测定，相对标准偏差（RSD）从8.3%（锌）降至32.6%（锰），再降至2.2%（铅），最后降至6.5%（锰）。为满足微量脑脊液样本的分析要求，采用层流气溶胶局部萃取策略提高气溶胶的传输效率，与标准商用烧蚀池相比，信号强度提高了四倍。使用含0.4%牛血清白蛋白（BSA）基质的标准溶液作为基质匹配外标，并向样本中添加铑作为内标。检测限（LOD）范围为0.17μg·L（锰）至8.67μg·L（镁）。进行了标准加入回收实验以及CRM血清L-1和L-2的测定以验证该方法的准确性；所有结果表明所提出的方法具有出色的准确性和精密度。GeoLas软件中的基质扫描功能与微孔板相结合实现了高通量自动分析。对来自不同患者的24份脑脊液样本进行了测定；结果表明脑脊液中的金属元素与疾病之间可能存在相关性，这意味着所提出的方法在神经疾病诊断方面具有潜力。
