Recommendations for reporting ion mobility mass spectrometry measurements

© 2019 The Authors. Mass Spectrometry Reviews Published by Wiley Periodicals, Inc. Here we present a guide to ion mobility mass spectrometry experiments, which covers both linear and nonlinear methods: what is measured, how the measurements are done, and how to report the results, including the uncertainties of mobility and collision cross section values. The guide aims to clarify some possibly confusing concepts, and the reporting recommendations should help researchers, authors and reviewers to contribute comprehensive reports, so that the ion mobility data can be reused more confidently. Starting from the concept of the definition of the measurand, we emphasize that (i) mobility values (K0) depend intrinsically on ion structure, the nature of the bath gas, temperature, and E/N; (ii) ion mobility does not measure molecular surfaces directly, but collision cross section (CCS) values are derived from mobility values using a physical model; (iii) methods relying on calibration are empirical (and thus may provide method-dependent results) only if the gas nature, temperature or E/N cannot match those of the primary method. Our analysis highlights the urgency of a community effort toward establishing primary standards and reference materials for ion mobility, and provides recommendations to do so. © 2019 The Authors. Mass Spectrometry Reviews Published by Wiley Periodicals, Inc

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

Proteome Profiling of Breast Cancer Biopsies Reveals a Wound Healing Signature of Cancer-Associated Fibroblasts

Breast cancer is still the most common type of cancer in women; an important role in carcinogenesis is actually attributed to cancer-associated fibroblasts. In this study, we investigated whether it is possible to assess the functional state of cancer-associated fibroblasts through tumor tissue proteome profiling. Tissue proteomics was performed on tumor-central, tumor-near, and tumor-distant biopsy sections from breast adenocarcinoma patients, which allowed us to identify 2074 proteins. Data were interpreted referring to reference proteome profiles generated from primary human mammary fibroblasts comprising 4095 proteins. These cells were analyzed in quiescent cell state as well as after in vitro treatment with TGFβ or IL-1β, stimulating wound healing or inflammatory processes, respectively. Representative for cancer cells, we investigated the mammary carcinoma cell line ZR-75-1, identifying 5212 proteins. All mass analysis data have been made fully accessible via ProteomeXchange, DOI PXD001311 and PXD001323-8. Comparison of tissue proteomics data with all of those reference profiles revealed predominance of cancer cell-derived proteins within the tumor and fibroblast-derived proteins in the tumor-distant tissue sections. Remarkably, proteins characteristic for acute inflammation were hardly identified in the tissue samples. In contrast, several proteins found by us to be induced by TGFβ in mammary fibroblasts, including fibulin-5, SLC2A1, and MUC18, were positively identified in all tissue samples, with relatively higher abundance in tumor neighboring tissue sections. These findings indicate a predominance of cancer-associated fibroblasts with wound healing activities localized around tumors

DOSY NMR, X‑ray Structural and Ion-Mobility Mass Spectrometric Studies on Electron-Deficient and Electron-Rich M₆L₄ Coordination Cages

A novel modular approach to electron-deficient and electron-rich M₆L₄ cages is presented. From the same starting compound, via a minor modulation of the synthesis route, two <i>C</i>₃-symmetric ligands <b>L1</b> and <b>L2</b> with different electronic properties are obtained in good yield. The trifluoro-triethynylbenzene-based ligand <b>L1</b> is more electron-deficient than the well-known 2,4,6-tri­(4-pyridyl)-1,3,5-triazine, while the trimethoxy-triethynylbenzene-based ligand <b>L2</b> is more electron-rich than the corresponding benzene analogue. Complexation of the ligands with cis-protected square-planar [(dppp)­Pt­(OTf)₂] or [(dppp)­Pd­(OTf)₂] corner-complexes yields two electron-deficient (<b>1a</b> and <b>1b</b>) and two electron-rich (<b>2a</b> and <b>2b</b>) M₆L₄ cages. The single crystal X-ray diffraction study of <b>1a</b> and <b>2a</b> confirms the expected octahedral shape with a ca. 2000 ų cavity and ca. 11 Å wide apertures. The crystallographically determined diameters of <b>1a</b> and <b>2a</b> are 3.7 and 3.6 nm, respectively. The hydrodynamic diameters obtained from the DOSY NMR in CDCl₃:CD₃OD (4:1), and diameters calculated from collision cross sections (CCS) acquired by ion-mobility mass spectrometry (IM-MS) were for all four cages similar. In solution, the cage structures have diameters between 3.3 to 3.6 nm, while in the gas phase the corresponding diameters varied between 3.4 to 3.6 nm. In addition to the structural information the relative stabilities of the Pt₆L₄ and Pd₆L₄ cages were studied in the gas phase by collision-induced dissociation (CID) experiments, and the photophysical properties of the ligands <b>L1</b> and <b>L2</b> and cages <b>1a</b>, <b>1b</b>, <b>2a</b>, and <b>2b</b> were studied by UV–vis and fluorescence spectroscopy

Anthracene-Tethered Ruthenium(II) Arene Complexes as Tools To Visualize the Cellular Localization of Putative Organometallic Anticancer Compounds

Anthracene derivatives of ruthenium­(II) arene compounds with 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]­decane (pta) or a sugar phosphite ligand, viz., 3,5,6-bicyclophosphite-1,2-<i>O</i>-isopropylidene-α-d-glucofuranoside, were prepared in order to evaluate their anticancer properties compared to the parent compounds and to use them as models for intracellular visualization by fluorescence microscopy. Similar IC₅₀ values were obtained in cell proliferation assays, and similar levels of uptake and accumulation were also established. The X-ray structure of [{Ru­(η⁶-C₆H₅CH₂NHCO-anthracene)­Cl₂(pta)] is also reported