PMID- 27382971 OWN - NLM STAT- MEDLINE DCOM- 20180116 LR - 20180116 IS - 1618-2650 (Electronic) IS - 1618-2642 (Linking) VI - 408 IP - 22 DP - 2016 Sep TI - Black phosphorus-assisted laser desorption ionization mass spectrometry for the determination of low-molecular-weight compounds in biofluids. PG - 6223-33 LID - 10.1007/s00216-016-9737-z [doi] AB - Quantitative analysis of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been a challenging task due to matrix-derived interferences in low m/z region and poor reproducibility of MS signal response. In this study, we developed an approach by applying black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix for the quantitative analysis of small molecules for the first time. Black phosphorus-assisted laser desorption/ionization mass spectrometry (BP/ALDI-MS) showed clear background and exhibited superior detection sensitivity toward quaternary ammonium compounds compared to carbon-based materials. By combining stable isotope labeling (SIL) strategy with BP/ALDI-MS (SIL-BP/ALDI-MS), a variety of analytes labeled with quaternary ammonium group were sensitively detected. Moreover, the isotope-labeled forms of analytes also served as internal standards, which broadened the analyte coverage of BP/ALDI-MS and improved the reproducibility of MS signals. Based on these advantages, a reliable method for quantitative analysis of aldehydes from complex biological samples (saliva, urine, and serum) was successfully established. Good linearities were obtained for five aldehydes in the range of 0.1-20.0 muM with correlation coefficients (R (2)) larger than 0.9928. The LODs were found to be 20 to 100 nM. Reproducibility of the method was obtained with intra-day and inter-day relative standard deviations (RSDs) less than 10.4 %, and the recoveries in saliva samples ranged from 91.4 to 117.1 %. Taken together, the proposed SIL-BP/ALDI-MS strategy has proved to be a reliable tool for quantitative analysis of aldehydes from complex samples. Graphical Abstract An approach for the determination of small molecules was developed by using black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix. FAU - He, Xiao-Mei AU - He XM AD - Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan, Hubei, 430072, China. FAU - Ding, Jun AU - Ding J AD - Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan, Hubei, 430072, China. jding@whu.edu.cn. FAU - Yu, Lei AU - Yu L AD - Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan, Hubei, 430072, China. FAU - Hussain, Dilshad AU - Hussain D AD - Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan, Hubei, 430072, China. FAU - Feng, Yu-Qi AU - Feng YQ AD - Key Laboratory of Analytical Chemistry for Biology and Medicine (Ministry of Education), Department of Chemistry, Wuhan University, Wuhan, Hubei, 430072, China. yqfeng@whu.edu.cn. LA - eng PT - Journal Article DEP - 20160706 PL - Germany TA - Anal Bioanal Chem JT - Analytical and bioanalytical chemistry JID - 101134327 RN - 0 (Aldehydes) RN - 27YLU75U4W (Phosphorus) SB - IM MH - Aldehydes/analysis/*blood/*urine MH - Humans MH - Isotope Labeling/methods MH - Limit of Detection MH - Phosphorus/*chemistry MH - Saliva/chemistry MH - Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization/*methods OTO - NOTNLM OT - Black phosphorus OT - MALDI matrix OT - Quantitative analysis OT - Quaternary ammonium compounds OT - Stable isotope labeling EDAT- 2016/07/08 06:00 MHDA- 2018/01/18 06:00 CRDT- 2016/07/08 06:00 PHST- 2016/05/26 00:00 [received] PHST- 2016/06/21 00:00 [accepted] PHST- 2016/06/15 00:00 [revised] PHST- 2016/07/08 06:00 [entrez] PHST- 2016/07/08 06:00 [pubmed] PHST- 2018/01/18 06:00 [medline] AID - 10.1007/s00216-016-9737-z [pii] AID - 10.1007/s00216-016-9737-z [doi] PST - ppublish SO - Anal Bioanal Chem. 2016 Sep;408(22):6223-33. doi: 10.1007/s00216-016-9737-z. Epub 2016 Jul 6.