The analysis of small sample volumes, such as biofluids, tissues, and cells, has become increasingly popular over the past few years. In this paper, we introduce a sample-preparation tool that is suitable for such analysis, namely, a solid-phase microextraction (SPME) minitip featuring a tip apex (1 mm) that is coated with biocompatible polyacrylonitrile (PAN) and N-vinylpyrrolidone-co-divinylbenzene, also known as HLB particles. HLB particles are suitable for extracting a wide range of compounds with varying polarities, and the proposed SPME minitips were successfully used for the targeted (MS/MS) quantitation of polar, semi-polar, and nonpolar drugs of abuse (DoAs) in 1 µL of blood via offline nanoelectrospray ionization (nESI). Low limits of detection (LOD) and quantification (LOQ) were obtained for most of the targeted analytes (i.e. LODs between 0.5 and 2.5 ng mL⁻¹). In addition, untargeted metabolomic profiling was performed on a single caviar egg (diameter ≤2.9 mm), with analysis being conducted via liquid chromatography high-resolution mass spectrometry (LC/HRMS). Clear chromatographic peaks were obtained despite the small size of the caviar eggs and the dilution introduced by LC. Multidimensional statistical analysis (PCA & PLS-DA) showed that the SPME minitips were able to successfully discriminate between samples, and the compounds that were tentatively identified corresponded with those expected to be found in fish. These findings highlight the importance of using suitable materials for pre-concentrating probe-sampling approaches, as they can provide analysts with sensitive instrumental response, particularly when studying the chemical profiles of small organisms

在过去几年中，对小样本量（例如生物流体，组织和细胞）的分析已变得越来越流行。在本文中，我们介绍了一种适用于此类分析的样品制备工具，即固相微萃取（SPME）微型吸头，其特征是尖端（1毫米），并涂有生物相容性聚丙烯腈（PAN）和N-乙烯基吡咯烷酮-co-二乙烯基苯，也称为HLB颗粒。HLB颗粒适用于提取各种极性不同的化合物，建议的SPME minitips成功用于1 µL极性，半极性和非极性滥用药物（DoAs）的目标（MS / MS）定量分析通过离线纳米电喷雾电离（nESI）采集血液。对于大多数目标分析物（例如，低检出限（LOD）和定量限（LOQ））^-1）。另外，对单个鱼子酱蛋（直径≤2.9mm）进行了非目标代谢组学分析，并通过液相色谱高分辨率质谱法（LC / HRMS）进行了分析。尽管鱼子酱蛋尺寸较小，并且LC引入了稀释液，但仍获得了清晰的色谱峰。多维统计分析（PCA＆PLS-DA）表明，SPME minitips能够成功地区分样品，初步鉴定出的化合物与预期在鱼类中发现的化合物相对应。这些发现凸显了使用合适的材料进行预浓缩探针采样方法的重要性，因为它们可以为分析人员提供敏感的仪器响应，尤其是在研究小型生物的化学特征时