The increasing need for rapid, in situ, and robust tissue profiling approaches in the context of intraoperative diagnostics has led to the development of a large number of ambient ionization-based surface sampling strategies. This paper compares the performances of a diathermic knife and a CO2 laser handpiece, both clinically approved, coupled to a rapid evaporative ionization mass spectrometry (REIMS) source for quasi-instantaneous tissue classification. Several fresh meat samples (muscle, liver, bone, bone marrow, cartilage, skin, fat) were obtained from different animals. Overall, the laser produced cleaner cuts and more reproducible and higher spectral quality signals when compared with the diathermic knife (CV laser = 9–12%, CV diathermic = 14–23%). The molecular profiles were subsequently entered into a database and PCA/LDA classification/prediction models were built to assess if the data generated with one sampling modality can be employed to classify the data generated with the other handpiece. We demonstrate that the correct classification rate of the models increases (+ 25%) with the introduction of a model based on peak lists that are tissue-specific and common to the two handpieces, compared with considering solely the whole molecular profile. This renders it possible to use a unique and universal database for quasi-instantaneous tissue recognition which would provide similar classification results independent of the handpiece used. Furthermore, the laser was able to generate aerosols rich in lipids from hard tissues such as bone, bone marrow, and cartilage. Combined, these results demonstrate that REIMS is a valuable and versatile tool for instantaneous identification/classification of hard tissue and coupling to different aerosol-generating handpieces expands its field of application. Graphical abstract Electronic supplementary materialThe online version of this article (10.1007/s00216-019-02148-8) contains supplementary material, which is available to authorized users.

A new, fast and simple analytical method that is able to identify and quantify simultaneously 17 steroid hormones and metabolites (pregnenolone, 17-OH-pregnenolone, progesterone, 17-OH-progesterone, androsterone, androstenedione, dehydroepiandrosterone, dehydroepiandrosterone sulfate, testosterone, cortisol, corticosterone, aldosterone, 11-deoxycortisol, 11-deoxycorticosterone, dihydrotestosterone, estrone and estradiol) has been developed in equine serum using the ultra-high-performance liquid chromatography-tandem mass spectrometry technique. A total of 400 µl of sample was deproteinized with 1000 µl of acetonitrile, evaporated, restored with 50 µl of a solution of 25% methanol and injected in ultra-high-performance liquid chromatography-tandem mass spectrometry triple quadrupole. The recovery percentage obtained by spiking the matrix at two different concentrations with a standard mixture of steroid hormones was in all cases higher than 85.60% and with the percentage of coefficient of variation lower than 8.37%. The range of the correlation coefficients of the calibration curves of the analyzed compounds was 0.9922-0.9986, and the limits of detection and limits of quantification were in the range of 0.002-2 and 0.0055-5.5 ng ml , respectively. The detected limit of quantification for testosterone (i.e. 50 pg ml ) is twofold lower with respect to its threshold admitted in geldings plasma (100 pg ml free testosterone). The high sensitivity and the quantitative aspect of the method permitted to detect most of the steroids in equine serum. Once validated, the method was used to quantify 17 steroid hormones in mare, stallion and gelding serum samples. The main steroids detected were corticosterone (range 37.25-51.26 ng ml ) and cortisol (range 32.57-52.24 ng ml ), followed by 17-OH-pregnenolone, dihydrotestosterone and pregnenolone. Copyright © 2016 John Wiley & Sons, Ltd.

This paper reports matrix-assisted laser desorption/ionization mass spectrometry imaging to investigate systematic effects of a lentil extract treatment to lower cholesterol levels. For this purpose, mass spectrometry imaging was used to spatially investigate modifications in the lipid composition and cholesterol levels in the brain, liver, and intestines as well as bile acids in the liver and intestine of rats treated with lentil extract. Neither the lipid composition nor cholesterol levels in the brain samples were found to be significantly different between the treated and not-treated animal groups. The hypercholesterolemic livers showed signs of steatosis (lipid marker PG 36:4), but no modifications in bile acid, cholesterol, and lipid composition. We found significant differences (AUC > 0.75) in the intestines regarding bile acid and lipid composition after treatment with the lentil extract. The treated rats showed a decreased reabsorption (increased excretion) of ursodeoxycholic acid, deoxycholic acid, and chenodeoxycholic acid and an increased deconjugation of taurine-conjugated bile acids (taurochenodeoxycholic acid, taurodeoxycholic acid, taurocholic acid, and 3-keto-taurocholic acid). This indicates that the lentil extract lowers the total cholesterol level in two synergic ways: (i) it increases the excretion of bile acids; hence, new bile acids are produced in the liver from serum cholesterol and (ii) the prebiotic effect leads to free taurine which upregulates the de novo synthesis of bile acid from cholesterol while activating LDL receptors. We demonstrate here that mass spectrometry imaging is a valuable tool for a better understanding of the effects of treatments such as for the synergistic cholesterol-lowering effect of the lentil extract. Electronic supplementary materialThe online version of this article (10.1007/s13361-019-02265-9) contains supplementary material, which is available to authorized users.