E‐MALDI: optimized conditions during electrowetting‐enhanced drop drying for MALDI‐MS

We recently showed that electrowetting‐enhanced sample preparation for MALDI‐MS (eMALDI) can increase the intensity of the MALDI signal by 2–25 times compared with conventional drop drying by concentrating all the dried sample in a single spot rather than leaving behind a heterogeneous coffee‐stain pattern. Here, we demonstrate that the eMALDI signal enhancement can be further increased to more than 100 times by systematically optimizing the electrowetting actuation frequency and amplitude. This enables 30 times signal increase for a peptide standard. Simultaneously, drop drying times can be reduced approximately five times by increasing the actuation voltage and/or decreasing the initial drop volume. Copyright © 2017 John Wiley & Sons, Ltd.     

Obtaining Bioactive Compounds from the Coffee Husk (Coffea arabica L.) Using Different Extraction Methods

Coffee husks (Coffea arabica L.) are characterized by exhibiting secondary metabolites such as phenolic compounds, which can be used as raw material for obtaining bioactive compounds of interest in food. The objective of this study is to evaluate different methods for obtaining the raw material and extracting solutions of bioactive compounds from coffee husks. Water bath and ultrasound-assisted extraction methods were used, using water (100%) or ethanol (100%) or a mixture of both (1:1) as extracting solutions and the form of the raw material was in natura and dehydrated. The extracts were evaluated by their antioxidant potential using DPPH radicals, ABTS, and iron reduction (ferric reducing antioxidant power (FRAP)), and later total phenolic compounds, total flavonoids, and condensed tannins were quantified the phenolic majority compounds were identified. It was verified that the mixture of water and ethanol (1:1) showed better extraction capacity of the compounds with antioxidant activity and that both conventional (water bath) or unconventional (ultrasound) methods showed satisfactory results. Finally, a satisfactory amount of bioactive compounds was observed in evaluating the chemical composition (total phenolic compounds, total flavonoids, condensed tannins, as well as the analysis of the phenolic profile) of these extracts. Corroborating with the results of the antioxidant activities, the best extracting solution was generally the water and ethanol mixture (1:1) using a dehydrated husk and water bath as the best method, presenting higher levels of the bioactive compounds in question, with an emphasis on chlorogenic acid. Thus, it can be concluded that the use of coffee husk as raw material to obtain extracts of bioactive compounds is promising. Last, the conventional method (water bath) and the water and ethanol mixture (1:1) stood out among the methods and extracting solutions used for the dehydrated coffee husk.     

NIRS and Aquaphotomics Trace Robusta-to-Arabica Ratio in Liquid Coffee Blends

Coffee is both a vastly consumed beverage and a chemically complex matrix. For a long time, an arduous chemical analysis was necessary to resolve coffee authentication issues. Despite their demonstrated efficacy, such techniques tend to rely on reference methods or resort to elaborate extraction steps. Near infrared spectroscopy (NIRS) and the aquaphotomics approach, on the other hand, reportedly offer a rapid, reliable, and holistic compositional overview of varying analytes but with little focus on low concentration mixtures of Robusta-to-Arabica coffee. Our study aimed for a comparative assessment of ground coffee adulteration using NIRS and liquid coffee adulteration using the aquaphotomics approach. The aim was to demonstrate the potential of monitoring ground and liquid coffee quality as they are commercially the most available coffee forms. Chemometrics spectra analysis proved capable of distinguishing between the studied samples and efficiently estimating the added Robusta concentrations. An accuracy of 100% was obtained for the varietal discrimination of pure Arabica and Robusta, both in ground and liquid form. Robusta-to-Arabica ratio was predicted with R²CV values of 0.99 and 0.9 in ground and liquid form respectively. Aquagrams results accentuated the peculiarities of the two coffee varieties and their respective blends by designating different water conformations depending on the coffee variety and assigning a particular water absorption spectral pattern (WASP) depending on the blending ratio. Marked spectral features attributed to high hydrogen bonded water characterized Arabica-rich coffee, while those with the higher Robusta content showed an abundance of free water structures. Collectively, the obtained results ascertain the adequacy of NIRS and aquaphotomics as promising alternative tools for the authentication of liquid coffee that can correlate the water-related fingerprint to the Robusta-to-Arabica ratio.     

How to Identify Roast Defects in Coffee Beans Based on the Volatile Compound Profile

The aim of this study was to detect and identify the volatile compounds in coffee that was obtained in defect roast processes versus standard roasting and to determine the type and strength of the correlations between the roast defects and the volatile compound profile in roasted coffee beans. In order to achieve this goal, the process of coffee bean roasting was set to produce an underdeveloped coffee defect, an overdeveloped coffee defect, and defectless coffee. The “Typica” variety of Arabica coffee beans was used in this study. The study material originated from a plantation that is located at an altitude of 1400–2000 m a.s.l. in Huehuetenango Department, Guatemala. The analyses were carried out with the use of gas chromatography/mass spectrometry (GC–MS) and an electronic nose. This study revealed a correlation between the identified groups of volatile compounds and the following coffee roasting parameters: the time to the first crack, the drying time, and the mean temperatures of the coffee beans and the heating air. The electronic nose helped to identify the roast defects.     

The Effect of Brewing Process Parameters on Antioxidant Activity and Caffeine Content in Infusions of Roasted and Unroasted Arabica Coffee Beans Originated from Different Countries

Coffee is one of the most often consumed beverages almost all over the world. The multiplicity of beans, as well as the methods and parameters used to brew, encourages the optimization of the brewing process. The study aimed to analyze the effect of roasting beans, the brewing technique, and its parameters (time and water temperature) on antioxidant activity (determined using several in vitro methods), total polyphenols, flavonoids, and caffeine content. The infusions of unroasted and roasted Arabica beans from Brazil, Colombia, India, Peru, and Rwanda were analyzed. In general, infusions prepared from roasted beans had higher antioxidant activity and the content of above-mentioned compounds. The hot brew method was used to obtain infusions with a higher antioxidant activity, while the cold brew with higher caffeine content. The phenolic compound content in infusions prepared using both techniques depended on the roasting process. Moreover, the bean’s origin, roasting process, and brewing technique had a significant effect on the tested properties, in contrary to brewing time and water temperature (below and above 90 °C), which had less impact. The results confirm the importance of coffee brewing optimization.     

Anti-Platelet Aggregation and Anti-Cyclooxygenase Activities for a Range of Coffee Extracts (Coffea arabica)

Coffee is rich in caffeine (CF), chlorogenic acid (CGA) and phenolics. Differing types of coffee beverages and brewing procedures may result in differences in total phenolic contents (TPC) and biological activities. Inflammation and increases of platelet activation and aggregation can lead to thrombosis. We focused on determining the chemical composition, antioxidant activity and inhibitory effects on agonist-induced platelet aggregation and cyclooxygenase (COX) of coffee beverages in relation to their preparation method. We prepared instant coffee and brewed coffee beverages using drip, espresso, and boiling techniques. Coffee extracts were assayed for their CF and CGA contents using HPLC, TPC using colorimetry, platelet aggregation with an aggregometer, and COX activity using ELISA. The findings have shown all coffee extracts, except the decaffeinated types, contained nearly equal amounts of CF, CGA, and TPC. Inhibitory effects of coffee extracts on platelet aggregation differed depending on the activation pathways induced by different agonists. All espresso, drip and boiled coffee extracts caused dose dependent inhibition of platelet aggregation induced by ADP, collagen, epinephrine, and arachidonic acid (ARA). The most marked inhibition was seen at low doses of collagen or ARA. Espresso and drip extracts inhibited collagen-induced platelet aggregation more than purified caffeine or CGA. Espresso, boiled and drip coffee extracts were also a more potent inhibitors of COX-1 and COX-2 than purified caffeine or CGA. We conclude that inhibition of platelet aggregation and COX-1 and COX-2 may contribute to anti-platelet and anti-inflammatory effects of espresso and drip coffee extracts.     

Inclusion complex of β‐cyclodextrin with coffee chlorogenic acid: new insights from a combined crystallographic and theoretical study

This work reports the elusive structural evidence for the [4]pseudorotaxane of β‐cyclodextrin (β‐CD) with coffee chlorogenic acid (CGA), a conjugate of caffeic acid (CFA) and quinic acid (QNA). A single‐crystal X‐ray structure analysis of the inclusion complex β‐cyclodextrin–chlorogenic acid–water (2/2/17), 2C₄₂H₇₀O₃₅·2C₁₆H₁₈O₉·17H₂O, reveals that CGA threads through β‐CD and assembles via O—H…O hydrogen bonds and parallel‐displaced π–π interactions in the twofold symmetry‐related dimer yielding a [4]pseudorotaxane, which is crystallographically observed for the first time in CD inclusion complexes. The encapsulation of the aromatic ring and C=C—C(=O)O chain in the β‐CD dimeric cavity indicates that the CFA moiety plays a determinant role in complexation. This is in agreement with the DFT‐derived relative thermodynamic stabilities of the trimodal β‐CD–CGA inclusion complexes, that is, β‐CD complexed with different CGA components: C=C—C(=O)O chain > cyclohexane ring > aromatic ring. The complexation stability is further enhanced in the dimeric β‐CD–CGA complex, with the CFA moiety totally enclosed in the β‐CD dimeric cavity.     

Learning from "coffee rings": ordered structures enabled by controlled evaporative self-assembly

Research into the evaporation of solutions is not only aimed at a better understanding the physics of evaporation, but increasingly at capitalizing on the extremely simple method it offers to assemble diverse nonvolatile solutes into complex ordered structures on the submicron and longer length scales. This Review highlights recent advances in evaporative assembly of confined solutions, focusing especially on recently developed approaches that provide structures with unprecedented regularity composed of polymers, nanoparticles, and biomaterials, by controlled evaporation-driven, flow-aided self-assembly. A broad range of variables that can control the deposition are explored and the future directions of this rich field are presented.     

How to distinguish between cinnamoylshikimate esters and chlorogenic acid lactones by liquid chromatography-tandem mass spectrometry

In this study, liquid chromatography–tandem mass spectrometry (LC–MSⁿ; n = 2–3) has been used to characterize and distinguish chlorogenic acid lactones from cinnamoylshikimate esters. This is the first time when an LC–MSⁿ method has been developed to distinguish between these two isomeric classes of compounds formed in particular in food processing from chlorogenic acids at elevated temperature through loss of water. The structures of regioisomeric chlorogenic acid lactones and shikimate esters have been assigned on the basis of LC–MSⁿ patterns of fragmentation, relative hydrophobicity, and fragmentation analogy with the synthetic standards of dimethoxycinnamic, ferulic, and caffeic acid containing monoacyl chlorogenic acid lactones and shikimate esters. Copyright © 2011 John Wiley & Sons, Ltd.     

Analysis of commercial beverage products by size exclusion chromatography coupled with UV-vis absorbance detection and dynamic surface tension detection

Multidimensional analysis of instant coffee and barley beverage samples using size exclusion chromatography (SEC) combined with a dynamic surface tension detector (DSTD) and a UV-vis absorbance detector (UV) is reported. A unique finding of this study was the action of the tetrabutylammonium (TBA) cation as a modifying agent (with bromide as the counter anion) that substantially increased the surface pressure signal and sensitivity of many of the proteins in the chromatographically separated samples. The tetrabutylammonium bromide (TBAB) enhancement of the surface pressure signal was further investigated by studying the response of 12 commercial standard proteins (α-lactalbumin, β-lactoglobulin, human serum albumin (HSA), albumin from chicken egg white (OVA), bovine serum albumin (BSA), hemoglobin, α-chymotrypsinogen A, cytochrome C, myoglobin, RNase A, carbonic anhydrase, and lysozyme) in buffer performed using flow injection analysis (FIA) coupled with the DSTD with and without various concentrations of TBAB. The FIA-DSTD data show that 1 mM TBAB enhances sensitivity of HSA detection, by lowering the limit of detection (LOD) from 2 mg/mL to 0.1 mg/mL. Similarly, the LOD for BSA was reduced from 1 mg/mL to 0.2 mg/mL. These FIA-DSTD experiments allowed the detection conditions to be optimized for further SEC-UV/DSTD experiments. Thus, the SEC-UV/DSTD system has been optimized and successfully applied to the selective analysis of surface-active protein fractions in a commercial instant coffee sample and in a soluble barley sample. The complementary selectivity of using the DSTD relative to an absorbance detector is also demonstrated.