Direct Infusion Electrospray Ionization Mass Research Articles

Chemical profile of compounds in irrigated arabica coffee by ESI-MS

The use of irrigation in coffee aims productivity increase and better quality of the final product. The impacts of irrigation in productivity and quality are impressive. In this study, ten different varieties of Coffea arabica L., were cultivated with irrigation and no irrigation regimes and these samples were analyzed by direct infusion electrospray ionization mass spectrometry (ESI-MS), in positive mode. The constituents identified were choline; trigonelline; sucrose; βN-arachinoyl-5-hidroxytryptamide; βN-behenoyl-5-hidroxytryptamide; palmitoyl-linoleoyl (PL); dilinoleoyl (LL); dipalmitoyl-linoleoyl (PPL); palmitoyl-dilinoleoyl (PLL) and three new compounds reported in coffee – triacylglycerol (TG 54:6), phosphoethanolamine (PE 40:7) and 1-hexadecyl-2-dodecanoyl-glycero-3-phosphate It was possible to efficiently sort the groups of irrigated and non-irrigated using PLS-DA to obtain all the minimum requirements for evaluation of efficiency of the rating model. Sucrose and the ion m/z 431 (not identified) suffered a negative influence of irrigation. The trigonelline, and the ion m/z 723 (not identified) were influenced positively by irrigation. The cup test showed that the coffees cultivated in not-irrigated regime had slightly larger cupping notes that the ones cultivated under irrigation, probably because they presented higher sucrose content.

Lipid Marker ESI-MS Method for Quantification of Adulteration in Almond-Based Vegetable Beverage

ABSTRACT Almond-based beverages are valued for their functionalities. However, cases of adulteration are found in the literature aiming to reduce costs. In this study, almond (LA) and peanut (LP)-based beverages were used as investigational controls in commercial products analyzed by gas chromatography and direct infusion electrospray ionization mass spectrometry (ESI-MS) combined with principal component analysis (PCA). Thus, characteristic fatty acids were identified in plant-based beverages. The ESI-MS method combined with PCA indicated individualities regarding the disposition of triacylglycerol (TAG) composition, as higher intensities of TAG were found as a lipid marker at m/z 919 [TAG+NH4]+ of ions formed by arachidic (20:0), 8/heptadecenoic (17:1n-9) and oleic (18:1n-9) fatty acids in LP. The technique demonstrated efficiency in the detection of fraud due to its sensitivity, identifying peanut content in three almond-based commercial beverages (4.4–11.58%). This study highlights the importance of robust analytical methods to the authenticity and quality of food products.

A Complementary Multitechnique Approach to Assess the Bias in Molecular Weight Determination of Lignin by Derivatization-Free Gel Permeation Chromatography.

The growing interest in lignin valorization in the past decades calls for analytical techniques for lignin characterization, ranging from wet chemistry techniques to highly sophisticated chromatographic and spectroscopic methods. One of the key parameters to consider is the molecular weight profile of lignin, which is routinely determined by size-exclusion chromatography; however, this is by no means straightforward and is prone to being hampered by considerable errors. Our study expands the fundamental understanding of the bias-inducing mechanisms in gel permeation chromatography (GPC), the magnitude of error originating from using polystyrene standards for mass calibration, and an evaluation of the effects of the solvent and type of lignin on the observed bias. The developed partial least-squares (PLS) regression model for lignin-related monomers revealed that lignin is prone to association mainly via hydrogen bonding. This hypothesis was supported by functional group-based analysis of the bias as well as pulse field gradient (pfg) diffusion NMR spectroscopy of model compounds in THF-d8. Furthermore, although the lack of standards hindered drawing conclusions based on functionalities, direct infusion electrospray ionization mass spectrometry indicated that the relative bias decreases considerably for higher molecular weight species. The results from pfg-diffusion NMR spectroscopy on whole lignin samples were comparable when the same solvents were used in both experiments; in addition, the comparison between results obtained by pfg-diffusion NMR in different solvents gives some additional insights into the aggregation.

Study of metalation of thioredoxin by gold(I) therapeutic compounds using combined liquid chromatography/capillary electrophoresis with inductively coupled plasma/electrospray MS/MS detection.

The reactivity of thioredoxin (Trx1) with the Au(I) drug auranofin (AF) and two therapeutic N-heterocyclic carbene (NHC)2-Au(I) complexes (bis [1-methyl-3-acridineimidazolin-2-ylidene]gold(I) tetrafluoroborate (Au3BC) and [1,3-diethyl-4,5-bis(4methoxyphenyl)imidazol-2-ylidene]gold(I) (Au4BC)) was investigated. Direct infusion (DI) electrospray ionization (ESI) mass spectrometry (MS) allowed information on the structure, stoichiometry, and kinetics of formation of Trx-Au adducts. The fragmentation of the formed adducts in the gas phase gave insights into the exact Au binding site within the protein, demonstrating the preference for Trx1 Cys32 or Cys35 of AF or the (NHC)2-Au(I) complex Au3BC, respectively. Reversed-phase HPLC suffered from the difficulty of elution of gold compounds, did not preserve the formed metal-protein adducts, and favored the loss of ligands (phosphine or NHC) from Au(I). These limitations were eliminated by capillary electrophoresis (CE) which enabled the separation of the gold compounds, Trx1, and the formed adducts. The ICP-MS/MS detection allowed the simultaneous quantitative monitoring of the gold and sulfur isotopes and the determination of the metallation extent of the protein. The hyphenation of the mentioned techniques was used for the analysis of Trx1-Au adducts for the first time.

Mass spectrometry molecular fingerprinting of mineral and synthetic lubricant oils.

The molecular composition of lubricating oils has a strong impact on how automotive engines function, but the techniques used to monitor the quality parameters of these oils only inspect their gross physical-chemical properties such as viscosity, color, and bulk spectroscopy profiles; hence, bad-quality, adulterated, or counterfeit oils are hard to detect. Herein, we investigated the ability of direct infusion electrospray ionization mass spectrometry (ESI-MS) to provide simple, rapid but characteristic fingerprint profiles for such oils of the mineral and synthetic types. After a simple aqueous extraction, ESI-MS analyses, particularly in the positive ion mode, did indeed show characteristic molecular markers with unique profiles, which were confirmed and more clearly visualized by partial least squares-discriminant analysis (PLS-DA). Nuclear magnetic resonance and Fourier transform infrared-attenuated total reflection spectroscopy were also tested for the bulk samples but showed nearly identical spectra, thus failing to reveal their distinct molecular composition and to differentiate the oil samples. To simulate adulteration, mixtures of mineral and synthetic oils were also analyzed by ESI(+)-MS, and additions as low as 1% of mineral oil to synthetic oil could be detected. The technique therefore offers a simple and fast but powerful tool to monitor the molecular composition of lubricant oils, particularly vias their more polar constituents.

Simplex centroid mixture design, DI-ESI-MS, and chemometric analysis-guided isolation of parinarioidin C from bark of Brosimum parinarioides (Moraceae)

Brosimum parinarioides , a plant species native to the Amazonian region, is used in folk medicine for the treatment of several diseases. However, knowledge regarding its phytochemical content is scarce. In order to investigate the phytochemical composition of B. parinarioides , an integrative approach based on simplex-centroid design, direct infusion electrospray ionization mass spectrometry (DI-ESI-MS), and chemometric analysis was adopted. According to simplex-centroid design, dichloromethane (DCM), ethyl acetate (AcOEt), and ethanol-based (EtOH) extracts were prepared and analyzed using DI-ESI-MS, and their chemical profile was submitted to principal component analysis (PCA) and hierarchical cluster analysis (HCA). The AcOEt extract from the bark was obtained on a large scale and subjected to chromatographic separation. The multivariate analysis indicated the formation of three groups and highlighted isoliquiritigenin ( 1 ), licoagrochalcone A ( 2 ), caffeic acid glucoside ( 3 ), epicatechin-glycoside ( 4) , caffeic acid ( 5 ), and one unknown compound, as being responsible for the segregation of these groups. Thus, the new compound was isolated and characterized using 1D and 2D nuclear magnetic resonance spectroscopy (NMR) and high-resolution mass spectrometry (HR-MS) as parinarioidin C ( 10 ). In addition, parinarioidin A ( 6 ), parinarioidin B ( 7 ), 3- O -caffeoylquinic acid ( 8 ), and kanzonol C ( 9 ) were tentatively identified based on manual interpretation of MS/MS spectra. Overall, the integrative approach proposed in the study provided a simple and effective model to dereplicate known compounds and guide the isolation of a new compound from a native amazon species, thus improving the knowledge regarding the phytochemical content of B. parinarioides . • One new compound was isolated from Brosimum parinarioides. • Nine phenolic compounds were identified based on the MS/MS data. • This study provided an effective model to guide the isolation of new natural products.

New insights into the Van Krevelen diagram: Automated molecular formula determination from HRMS for a large chemical profiling of lichen extracts.

In recent years, LC-MS has become the golden standard for metabolomic studies. Indeed, LC is relatively easy to couple with the soft electrospray ionization. As a consequence, many tools have been developed for the structural annotation of tandem mass spectra. However, it is sometimes difficult to do data-dependent acquisition (DDA), especially when developing new methods that stray from the classical LC-MS workflow. An old tool from petroleomics that has recently gained popularity in metabolomics, the Van Krevelen diagram, is adapted for an overview of the molecular diversity profile in lichens through high-resolution mass spectrometry (HRMS). A new method is benchmarked against the state-of-the-art classification tool ClassyFire using a database containing most known lichen metabolites (n ≈2,000). Four lichens known for their contrasted chemical composition were selected, and extractions with apolar, aprotic polar, and protic polar solvents were performed to cover a wide range of polarities. Extracts were analyzed with direct infusion electrospray ionization mass spectrometry (DI-ESI-MS) and atmospheric solids analysis probe mass spectrometry (ASAP-MS) techniques to be compared with the chemical composition described in the literature. The most common lichen metabolites were efficiently classified, with more than 90% of the molecules in some classes being matched with ClassyFire. Results from this method are consistent with the various extraction protocols in the present case study. This approach is a rapid and efficient tool to gain structural insight regarding lichen metabolites analyzed by HRMS without relying on DDA by LC-MS/MS analysis. It may notably be of use during the development phase of novel MS-based metabolomic approaches.

Membrane Sampling Separates Naphthenic Acids from Biogenic Dissolved Organic Matter for Direct Analysis by Mass Spectrometry.

Oil sands process waters can release toxic naphthenic acids (NAs) into aquatic environments. Analytical techniques for NAs are challenged by sample complexity and interference from naturally occurring dissolved organic matter (DOM). Herein, we report the use of a poly(dimethylsiloxane) (PDMS) polymer membrane for the on-line separation of NAs from DOM and use direct infusion electrospray ionization mass spectrometry to yield meaningful qualitative and quantitative information with minimal sample cleanup. We compare the composition of membrane-permeable species from natural waters fortified with a commercial NA mixture to those derived from weak anion exchange solid-phase extraction (SPE) using high-resolution mass spectrometry. The results show that SPE retains a wide range of carboxylic acids, including biogenic DOM, while permeation through PDMS was selective for petrogenic classically defined NAs (CnH2n+zO2). A series of model compounds (log Kow ∼1–7) were used to characterize the perm-selectivity and reveal the separation is based on hydrophobicity. This convenient sample cleanup method is selective for the O2 class of NAs and can be used prior to conventional analysis or as an on-line analytical strategy when coupled directly to mass spectrometry.

Sustainable utilization of cold‐pressed green coffee oil and its by‐products for high‐value materials

In this study, the cold-pressing extraction conditions of regular and defective green coffee beans were compared to obtain green coffee oil (GCO). The total phenolic content (TPC) in GCO, press-cake, and sediment was quantified. GCO was characterized by mass spectrometry and incorporated into carboxymethyl cellulose (CMC) films. Highest TPC was found for cake and sediment from defective beans (55.8 and 41.1 mg of GAE/g dry matter, respectively). Oil yield was increased (5.9%) using the finest particle size (<850 μm). Fatty acids, phenolic compounds, and carboxyatractyloside II were identified in GCO by Direct-Infusion Electrospray Ionization-Mass Spectrometry. Films added with 0.3 ml of GCO and lecithin (0.1 g/1.5 g CMC) exhibited greater strength (38.6 MPa) and flexibility (27.6%). Results are promising for both the production of CMC-GCO films, and high-value antioxidant from GCO and its by-products with a sustainable perspective using defective Arabica beans. Practical applications Green coffee oil (GCO) added to carboxymethyl cellulose films improved mechanical properties in the presence of lecithin. GCO by-products, cake, and sediment from defective beans showed higher content of phenolic compounds than regular beans. From a sustainable and economical perspective, cold-pressed GCO and its residues can be exploited in bio-based materials and high-value antioxidants.

Rapid authenticity assessment of Brazilian palm kernel oils by mass spectrometry combined with chemometrics

Adulteration became a serious problem to food industries as it steadily spread across the globe in the past decades, affecting several food products, but especially vegetable oils. Palm kernel oil is a highly susceptible target for adulteration due to its exceptional characteristics and several applications. Hence, this study utilized gas chromatography with flame ionization detector, and direct infusion electrospray ionization mass spectrometry combined with chemometrics to assess the authenticity of seven Brazilian brands of palm kernel oil. Results indicated adulteration with at least 30% in all brands evaluated. Furthermore, presence of a different additive was verified for PKO1, PKO5, and PKO7. Thus, the association of direct infusion electrospray ionization mass spectrometry analysis with pattern recognition methods proved to be an attractive candidate for fast routine analyses to identify adulteration in industries.

Evaluation of the Adulteration of Edible and Cosmetic Sunflower Oils by GC-FID and ESI-MS

Sunflower oil has several properties that are valuable to the human skin and health; however, they are target of adulterations. In this study, in order to evaluate the authenticity of edible and cosmetics based on sunflower oils, the triacylglycerol (TAG) profiles using direct infusion electrospray ionization mass spectrometry (ESI-MS), the fatty acid (FA) composition by gas chromatography with flame ionization detection (GC-FID) and principal component analysis, of seven commercial samples were determined and the results obtained were compared with the pure sunflower and soybean oils. Of the seven brands analyzed, just one sample presented only sunflower oil in its composition; two stated in the label soybean addition; and four did not present the real composition of the product in the label. Therefore, GC-FID and ESI-MS analysis in conjunction with principal component analysis (PCA) demonstrated that they are complementary techniques and could be applied in food industries to assess the quality of vegetable oils, since results showed the need for stricter quality control for this product.

Eco-Friendly Methodology for the Formation of Aromatic Carbon-Heteroatom Bonds by Using Green Ionic Liquids.

A new sustainable method is reported for the formation of aromatic carbon-heteroatom bonds under solvent-free and mild conditions (no co-oxidant, no strong acid and no toxic reagents) by using a new type of green ionic liquid. The bromination of methoxy arenes was chosen as a model reaction. The reaction methodology is based on only using natural sodium bromine, which is transformed into an electrophilic brominating reagent within an ionic liquid, easily prepared from the melted salt FeCl3 hexahydrate. Bromination reactions with this in-situ-generated reagent gave good yields and excellent regioselectivity under simple and environmentally friendly conditions. To understand the unusual bromine polarity reversal of sodium bromine without any strong oxidant, the molecular structure of the reaction medium was characterised by Raman and direct infusion electrospray ionisation mass spectroscopy (ESI-MS). An extensive computational investigation using density functional theory methods was performed to describe a mechanism that suggests indirect oxidation of Br- through new iron adducts. The versatility of the methodology was successively applied to nitration and thiocyanation of methoxy arenes using KNO3 and KSCN in melted hexahydrated FeCl3 .

Integrative Approach Based on Simplex-Centroid Design, ESI-MS and Chemometric Analysis for Comprehensive Characterization of Phenolic Compounds from Endopleura uchi Bark

Endopleura uchi (Huber) Cuatrec. is an Amazonian medicinal plant with restricted distribution to the North Region of Brazil. Its bark is commonly used as natural medicines for the treatment of many diseases. Although widely investigated from the phytochemical viewpoint, the knowledge regarding the phenolic content remains unexplored. In order to access the phenolic composition of E. uchi bark, an integrative approach based on simplex-centroid design, direct infusion electrospray ionization mass spectrometry (ESI-MS) and chemometric analysis was adopted. In addition, the extracts were evaluated to total phenolic content and antioxidant activity. The multivariate analysis pointed to the ethanol-based extracts as the most representative for phenolic compounds, with 3,5-di-O-galloylquinic acid (2), gallic acid (4), 5-galloylquinic acid (5) and gallocatechin gallate (6) tentatively identified by MS analysis, all described for the first time in E. uchi. Besides, pure ethanol extract presented highest total phenolic content (TPC = 133.61 ± 0.3 mg GAE 100 g-1) and antioxidant activity (half maximal inhibitory concentration, IC50 = 9.32 ± 0.15). The integrative approach proposed to this work provided an effective way to assess the phenolic compounds of E. uchi bark, therefore, improving the knowledge regarding phenolic content in this Amazonian medicinal plant.

Direct infusion electrospray ionisation mass spectrometry applied in the detection of adulteration of coconut oil with palm kernel oil

ABSTRACTCoconut oil has properties that are beneficial to human health. It assists in reducing total cholesterol, triacylglycerol (TAG), phospholipids, low-density lipoprotein (LDL) cholesterol, and very low-density lipoprotein (VLDL) cholesterol in serum and tissues. So its production, and consequently consumption, have increased in recent years. However, it has been a target for intentional adulteration with lower priced oils and fats, such as soybean oil and palm kernel oil (PKO). Coconut oil (CO) and PKO have similar chemical and physical characteristics that make it difficult to verify adulteration of CO with PKO. This study demonstrates a simple, sensitive, and fast technique that uses direct infusion electrospray ionisation mass spectrometry (ESI-MS) in conjunction with principal component analysis (PCA), in order to detect CO adulterated with PKO. Among the seven commercial coconut oil samples analysed, three were adulterated with PKO. Therefore, the suggested direct infusion ESI-MS method can be used in routine analysis to guarantee the quality of coconut oil.

Rapid Evaluation of the Debromination Mechanism of Eosin in Oil Paint by Direct Analysis in Real Time and Direct Infusion-Electrospray Ionization Mass Spectrometry.

Eosin is a synthetic organic colorant prone to fading under the influence of light. On the basis of the growing interest in the understanding of the discoloration mechanism of eosin-based lakes, this study compares the ability of two ultrafast and ultrasensitive mass spectrometry techniques to detect eosin derivatives in complex matrices, such as oil media without the use of conventional separation columns or additional sample preparation protocols. Direct analysis in real time mass spectrometry (DART-MS) and direct infusion electrospray ionization mass spectrometry (DI-ESI-MS) were used to characterize the degradation pathway of eosin in oil media. The analysis protocols developed in this study are applied to discern the degradation mechanism of the lake pigment eosin (comprising the molecule per se complexed to an inorganic substrate) dispersed in linseed oil to create an oil paint. The analysis of oil paints by high resolution MS without an extraction methodology that modifies the system chemistry allowed us to identify the degradation forms without causing any additional fragmentation. Both techniques revealed the primary photodegradation pathway of eosin in linseed oil, and DI-ESI-MS provided additional information on the native conformation of the lake.

Pro-oxidant and pro-inflammatory effects of glycated albumin on cardiomyocytes

Human serum albumin (HSA) is the most abundant circulating protein in the body and presents an extensive range of biological functions. As such, it is prone to undergo post-translational modifications (PTMs). The non-enzymatic early glycation of HSA, one of the several PTMs undergone by HSA, arises from the addition of reducing sugars to amine group residues, thus modifying the structure of HSA. These changes may affect HSA functions impairing its biological activity, finally leading to cell damage.The aim of this study was to quantitate glycated-HSA (GA) levels in the plasma of heart failure (HF) patients and to evaluate the biological effects of GA on HL-1 cardiomyocytes.Plasma GA content from HF patients and healthy subjects was measured by direct infusion electrospray ionization mass spectrometry (ESI-MS). Results pointed out a significant increase of GA in HF patients with respect to the control group (p < 0.05). Additionally, after stimulation with GA, proteomic analysis of HL-1 secreted proteins showed the modulation of several proteins involved, among other processes, in the response to stress. Further, stimulated cells showed a rapid increase in ROS generation, higher mRNA levels of the inflammatory cytokine interleukin-6 (IL-6) and tumor necrosis factor alpha (TNF-α), and higher levels of the oxidative 4-HNE-protein adducts and carbonylated proteins.Our findings show that plasma GA is increased in HF patients. Further, GA exerts pro-inflammatory and pro-oxidant effects on cardiomyocytes, which suggest a causal role in the etiopathogenesis of HF.

Detection and assignment of inorganic aqueous polymers relevant to environmental nanogeoscience by direct infusion electrospray ionization mass spectrometry.

Inorganic polymers in aqueous solutions are being proposed as essential components in new theories concerning nonclassical nucleation and growth of nanominerals relevant to environmental nanogeosciences. The study of those complex natural processes requires multi-technique analytical approaches able to characterize the solutions and their constituents (solutes, oligomers, polymers, clusters and nanominerals) from atomic to micrometric scales. A novel analytical approach involving an electrospray ionization source (ESI) coupled to time-of-flight mass spectrometry (TOF/MS) was developed to identify inorganic polymers in aqueous solution. To this end, the presence of initial Al oligomers and their polymerization processes was studied during a nanomineral aqueous synthesis (hydrobasaluminte, Al4 SO4 (OH)10 ·12-36H2 O). Ensuring the feasibility and robustness of the methodology as well as the stability of the polymers under study (avoiding undesirable fragmentation), a meticulous study of the ESI-TOF MS working conditions was performed. Precision of the methodology was evaluated obtaining relative standard deviations below 3.3%. For the first time in the study of inorganic polymers in the earth sciences, the mass accuracy error (ppm) has been reported and the use of significant decimal figures of the m/z signal has been taken into account. Complementary to this, a four-step polymer assignment methodology and a database with the Al- and Al-SO4 2- polymers assigned were created. Several polymers have been assigned for the first time, including Al (SO4 )+ ·H2 O, Al2 O(SO4 )2+ ·H2 O, Al5 O4 (OH)5 2+ ·2H2 O, and Al3 O5 (OH)2- ·4H2 O, among others. The results obtained in the present study help create a foundation to include mass spectrometry as a routine analytical technique to study mineral formation in aqueous solution.

The Formation of Glycerol Oligomers with Two New Types of End Groups in the Presence of a Homogeneous Alkaline Catalyst.

The purpose of this work was to synthesize and characterize oligoglycerols with the chains of more than four repeating units. Those oligoglycerols may have some interesting applications, among others, as polyoxyalkylation starters. The glycerol oligomerization process was carried out during 12 h, at 230 °C, under the pressure of 0.4 bar, with the use of sodium carbonate as a homogeneous basic catalyst; various concentrations of the catalyst in the reaction medium were used. The reaction products were analyzed with the use of direct infusion electrospray ionization mass spectrometry (ESI-MS), nuclear magnetic resonance (13C NMR) and Fourier transform infrared spectroscopy (FTIR) techniques. Based on the analytical findings, the compositions of the obtained product mixtures and the structures of oligoglycerols present in individual fractions were determined. The effect of catalyst concentration on the composition of the post-reaction mixture was observed. Moreover, in addition to the conventional linear oligomers (α,α-oligoglycerols), two new types of the oligomers were for the first time detected in the post-reaction mixture: one with two hydroxyl groups and the other with a carboxylate group at the α-carbon atom.

Determination of Coconut Oil Adulteration with Soybean Oil by Direct Infusion Electrospray Ionization Mass Spectrometry

Coconut oil has several domestic uses and health benefits, which can be used in food, pharmaceuticals and cosmetics products. However, it has been the target of adulteration with lower price oils and fats, such as soybean oil. In this study, a fast, easy and simple methodology was used to detect low quantities of intentionally adulterated coconut oil with soybean oil by direct infusion electrospray ionization mass spectrometry (ESI-MS) at different levels (0, 2, 5, 10, 15, 20, 30, 50, 70 and 100%). In the oil industry, intentional adulterations usually occur with the addition of low quantities of soybean oil to coconut oil. Therefore, the suggested ESI-MS method is promising for routine analysis to guarantee the quality control of coconut oil since it is possible to detect adulteration with a minimal of 2% soybean oil addition.

Direct-infusion electrospray ionization-mass spectrometry analysis reveals atractyligenin derivatives as potential markers for green coffee postharvest discrimination

Coffee quality is strongly related to postharvest processes. Dry and wet are the most traditional and employed processes. However, more recently, the semi-dry process has been introduced and applied for producing coffees of good quality in a more environmental friendly manner compared to the wet process. In this work, green Arabica coffee cherries from two consecutive crops were submitted to the dry and semi-dry postharvest processes and their methanol:water extracts were characterized by ESI(−) FT-ICR MS followed by chemometric data analysis. Thirty-three compounds were identified in the extracts by their high-resolution and accurate m/z values and MS/MS spectra being nine of them diterpenes related to atractyligenin derivatives. The dry and semi-dry processes led to distinct extracts in which compounds such as atractyloside II, carboxyatractyloside II and carboxyatractyloside III showed the greatest contributions (p < 0.05) based on t-Student's test and PLS-DA statistical analyses. These compounds were able to discriminate the postharvest processes for coffees from two consecutive crops. These results can help to better understand the effects of the postharvest processes in the final chemical composition and coffee quality.