High resolution mass spectral data from the analysis of copper chlorophylls and copper chlorophyll degradation products in bright green table olives

This publication reports high resolution mass spectral data for copper chlorophyll and copper chlorophyll degradation products extracted from bright green table olives. These data support analyte identifications made in “Quantitation of copper chlorophylls in green table olives by ultra-high-performance liquid chromatography with inductively coupled plasma isotope dilution mass spectrometry” in the Journal of Chromatography A (Petigara Harp et al., 2020 [1]). Table olive pigments, divided into lipophilic and hydrophilic fractions by liquid-liquid repartition, were separated by ultra-high-performance liquid chromatography and detected by visible wavelength absorbance and high resolution mass spectrometry, using an Orbitrap HF with positive electrospray ionization. Full-scan mass spectra were acquired to assign pigment chemical formulae. Fragment-rich higher-energy collisional dissociation tandem mass spectra were acquired to facilitate structural assignments. Extracted ion chromatograms, full-scan, and tandem mass spectra obtained from representative lipophilic and hydrophilic green table olive extracts are presented in Figures 1-6. Annotated mass spectra comparing experimental and calculated isotope distributions, .raw mass spectral data files, and experimental details linking .raw data files to annotated spectra are provided as Supplementary Material. Spectra extracted from these native data files can be added to mass spectral libraries for use in other studies. Access to native data files uniquely enables rigorous data examination (e.g., molecular ion isotopic distribution, effective mass resolution, presence of overlapping ion series) and use in ways that are not possible when spectra are otherwise reported in simple tables listing mono-isotopic peaks and mass errors. Mass spectra reported here can be used to design multiple-reaction monitoring methods to detect these bright green pigments in agricultural food commodities and finished products.

Chlorin Copper chlorophylls a b s t r a c t This publication reports high resolution mass spectral data for copper chlorophyll and copper chlorophyll degradation products extracted from bright green table olives. These data support analyte identifications made in "Quantitation of copper chlorophylls in green table olives by ultra-highperformance liquid chromatography with inductively coupled plasma isotope dilution mass spectrometry" in the Journal of Chromatography A (Petigara Harp et al. , 2020 [1] ). Table olive pigments, divided into lipophilic and hydrophilic fractions by liquid-liquid repartition, were separated by ultra-highperformance liquid chromatography and detected by visible wavelength absorbance and high resolution mass spectrometry, using an Orbitrap HF with positive electrospray ionization. Full-scan mass spectra were acquired to assign pigment chemical formulae. Fragment-rich higher-energy collisional dissociation tandem mass spectra were acquired to facilitate structural assignments. Extracted ion chromatograms, full-scan, and tandem mass spectra obtained from representative lipophilic and hydrophilic green table olive extracts are presented in Figures 1-6. Annotated mass spectra comparing experimental and calculated isotope distributions, .raw mass spectral data files, and experimental details linking .raw data files to annotated spectra are provided as Supplementary Material. Spectra extracted from these native data files can be added to mass spectral libraries for use in other studies. Access to native data files uniquely enables rigorous data examination ( e.g. , molecular ion isotopic distribution, effective mass resolution, presence of overlapping ion series) and use in ways that are not possible when spectra are otherwise reported in simple tables listing mono-isotopic peaks and mass errors. Mass spectra reported here can be used to design multiple-reaction monitoring methods to detect these bright green pigments in agricultural food commodities and finished products.
Published Positive ionization electrospray UHPLC-MS1 and MS2 spectra were acquired. Mass resolving power settings ranged from 60,0 0 0-120,0 0 0 in MS1 studies. HCD spectra were acquired using different collision energies (10-130), mass resolving power settings (30,0 0 0-60,0 0 0), and parent molecular ion isolation widths (0.4 and 1.0 m/z ). Individual .raw files and the Supplemental Material .xlsx file provide MS parameter details. Description of data collection UHPLC-MS1 and MS2 spectra were respectively acquired to assign chemical formulae and propose structures for copper chlorophylls and copper chlorophyll degradation products detected in lipophilic and hydrophilic bright green

Value of the data
• MS1 data support the assignment of molecular formulae to copper chlorophylls and copper chlorophyll degradation products at < 3 ppm mass error and provide free access to electrospray ionization spectra acquired at high (120,0 0 0) resolving power • Fragment-rich MS2 data support proposed structural assignments for commercially unavailable compounds and provide some of the first electrospray positive ionization HCD spectra for copper chlorophylls and copper chlorophyll degradation products • Raw mass spectrum data files enable chemists to independently evaluate, interpret, and include them in spectral libraries • Data can be further used to design multiple reaction monitoring MS experiments for the targeted detection of green pigments in table olives and other food products • Dataset may also be of use in geochemical studies of copper chlorophylls, chlorophyllins, chlorins, and related metallo-porphyrins

Data Description
High resolution full scan (MS1) and higher-energy collisional dissociation tandem (HCD-MS2) mass spectra were acquired using an Orbitrap HF spectrometer to assign chemical formulae and structures to lipophilic copper chlorophylls and hydrophilic copper chlorophyll degradation products extracted from bright green table olives. These data support chemical formulae assignments made for pigment analytes in reference [1] . UHPLC separation of copper chlorophylls extracted from a bright green table olive sample using Cu isotope inductively coupled plasma (Cu ICP) MS, optical absorbance, and positive electrospray ionization MS1 detection is presented in Figure 1 . MS1 and HCD-MS2 spectra acquired at retention times corresponding to lipophilic analyte peaks in Fig. 1 . are respectively presented in Figs. 2-3 . Similarly to Fig. 1 , Fig. 4 presents the UHPLC separation of copper chlorophyll degradation products extracted from a bright green table olive sample. Figs. 5-6 respectively present MS1 and HCD-MS2 spectra acquired at retention times corresponding to hydrophilic analytes in Fig. 4 . Annotated MS1 spectra, annotated HCD-MS2 spectra, and raw mass spectral data files are provided as Supplementary Material. Also, experimental details related to raw data files and further details linking raw data files to both Figs. 1-6 and annotated spectra are provided in the Supplementary Material. Experimental MS1 spectra are annotated by presentation with calculated spectra for co-detected even and odd-electron molecular ions. References are provided for specialists that seek details regarding fragmentation mechanisms and the interpretation of metallo-chlorin mass spectra that are important to this work. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16]

UHPLC-UV-Vis analyses of table olive extracts
Lipophilic and hydrophilic table olive extracts prepared as described in reference [1] were analyzed using a Waters Acquity UPLC system (Waters Corp, Milford, MA) equipped with an Acquity PDA e λ detector and Ascentis Express C18 (2.1 × 150 mm, 2 μm, Millipore Sigma, Bellefonte, PA) column. All chromatograms were acquired from 30 0-80 0 nm at 0.35 mL/min, but different gradients and injection volumes were used for each type of extract.
Lipophilic extracts were separated with an elution gradient of (A) 0.1% acetic acid in methanol and (B) 50:50 acetonitrile/acetone as follows: from 0-100 % B in 25 min, hold for 5 min at 100% B, from 100-0 % B in 0.1 min, and 10 min of re-equilibration. The injection volume was 5 μL and the elution temperature was 27 °C.

UHPLC-HRMS1 and higher-energy collision dissociation MS2 analyses
The UHPLC-PDA system was connected to a QExactive HF Orbitrap mass spectrometer (Ther-moFisher Scientific, Bremen, Germany). Positive ESI MS1 and HCD spectra were acquired at mass resolving powers varying from 30 to 240k. Heated ionization source parameters were tuned via post-column infusion (125 μL/min) of sodium copper chlorophyllin in 50:50:0.1 acetonitrile/water/trifluoroacetic acid to: V s 4 kV; capillary 300 °C; probe heater 438 °C; S-lens 55; sheath gas 53; and auxiliary gas 38. External mass calibration provided a mass error tolerance of < 3 ppm. MS1 and HCD spectra were acquired during the post-column infusion (120 μL/min) of 0.1% formic acid in 50:50 acetonitrile/water for lipophilic extract and 1% acetic acid in 50:50 acetonitrile/water for hydrophilic extract. HCD spectra were obtained using N 2 collision gas, stepped normalized collision energy (30-45) with a data-dependent or parallel reaction monitoring method, and variable parent molecular ion isolation width (0.4 or 1.0 m/z ). Detailed instrument parameters are provided as Supplementary Material and within individual .raw data files. A variety of instrumental parameter ( e.g. , resolution, collision energy) ranges and data acquisition techniques ( e.g. , MS1 only, top 10 MS2, and unscheduled and scheduled MS2) were used. In one case, the green table olive lipophilic extract UPLC peak eluting at 12.3 min (Cu 15 2 -Me-phytyl-isorhodin g5) was hand collected and reanalysed via direct infusion (10 μL/min) for

Conflict of Interest
The authors declare no competing financial interests or personal relationships which have, or could be perceived to have, influenced the work reported in this article.

Supplementary materials
Supplementary material associated with this article can be found, in the online version, at doi: 10.1016/j.dib.2020.105548 .