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Roasted coffee oil (RCO) is rich in volatile organic compounds (VOCs), but the VOCs’ volatility and the presence of unsaturated fatty acids make RCO unstable. The microencapsulation process can extend RCO properties by transforming the liquid RCO into stable powders for further application in coffee brews to better result in-cup. In this work, a central composite rotational design was used to study the effect of the emulsification process and discuss the effect of added microcapsules to instant coffees on the time-resolved release of VOCs upon reconstitutions. Capsules were produced by complex coacervation loaded with RCO, and ultrasound-assisted (US) emulsification was used to obtain stable coffee oil–loaded emulsions. VOC release was monitored by proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF–MS). High encapsulation efficiency (EE) (> 80%) was obtained even at a high load (100%) of RCO. EE was only affected by US power while particle mean size (D43) was strongly affected by US power and the RCO concentration. The presence of microcapsules affected the VOC release from the moment of reconstitution. The microcapsules accelerated the VOC release in soluble coffee, while in instant cappuccino, an opposite effect was observed. A zero-order model described well the mechanism of VOC release during the first 300 s. The diffusional exponent values of the Korsmeyer–Peppas equation explained a zero-order transport during the first seconds of release (burst effect) and a non-Fickian release mechanism when the release slowed down. Such findings shed new light on the development of instant coffees in order to improve their sensorial properties.

This work evaluated the use of roasted coffee oil (RCO) and the effects of ultrasound (US)-assisted emulsification on RCO-in-water emulsion properties, the changes in the composition of volatile organic compounds (VOCs) of roasted coffee aroma during US and microencapsulation by spray drying, and VOCs release profile upon instant coffee reconstitution. VOCs were determined by gas chromatography-mass spectrometry, and the release profile was monitored in real-time by Proton Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF–MS). US was found to be effective in producing stable submicron emulsions (≤ 2.0 µm) that resulted in high encapsulation efficiency (> 90%) of the microparticles. Significant changes were detected in VOC composition throughout the microencapsulation process. The addition of microparticles loaded with RCO in instant coffee did not change the VOCs release profile during the brew preparation but was effective in increasing coffee aroma.

Infrared-photoacoustic spectroscopy (IR-PAS) and partial least squares (PLS) were tested as a rapid alternative to conventional methods to evaluate the proportion of coffee defects in roasted and ground coffees. Multiproduct multivariate calibration models were obtained from spectra of healthy beans of Coffea canephora and C. arabica (Arabica) and blends composed of defective and healthy beans of Arabica in different proportions. The blends, named selections, contained sour, black, broken, whole beans, skin, and coffee woods. Six models were built using roasted and ground coffee samples. The model was optimized through outlier evaluation, and the parameters of merit such as accuracy, sensitivity, limits of detection and quantification, the inverse of analytical sensitivity, linearity, and adjustment were computed. The models presented predictive capacity and high sensitivity in determining defects, all being predicted with suitable correlation coefficients (ranging from 0.7176 to 0.8080) and presenting adequate performance. The parameters of merit displayed promising results, and the prediction models developed for %defects can be safely used as an alternative to the reference method. Furthermore, the new method is fast, efficient, and suitable for in-line application in quality control industrial coffee processing.

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We report, on the successful addition of spray-dried microparticles containing roasted coffee oil, to soluble coffee (SC) and instant cappuccino (IC), to increase and tailor aroma release. Using PTR-ToF-MS (Proton Transfer Reaction Time-of-Flight Mass Spectrometry), five parameters were defined from time series intensity for each VOC, to compare the performance of different products: total area under the curve (AUC), area under the curve of burst (AUC-burst), maximum signal intensity, final intensity (5 min), and ratio AUC-burst/AUC. Microparticles with higher loads of roasted coffee oil were effective in increasing aroma intensity in SC while, for IC, all loads of microparticles improved aroma intensity. Volatility drove the VOC release in SC, and volatility and polarity for IC. Most compounds reached maximum headspace concentration in < 16 s upon start of reconstitution. These results open new perspectives for the development of instant coffee products and demonstrate their unique aroma release characteristics.

This study examined the influence of consumer behavior on furan, 2-methylfuran, 3-methylfuran, 2,5-dimethylfuran and 2,3-dimethylfuran exposure in coffee. Coffees brewed using a filter, fully automatic, capsule machine or reconstituted instant coffee were found to have a significant different cup concentrations of furan derivatives. Coffee brewed with the fully automatic machine contained the highest furan and furan derivative concentrations (99.05 µg/L furan, 263.91 µg/L 2-methylfuran, 13.15 µg/L 3-methylfuran and 8.44 µg/L 2,5-dimethylfuran) whereas soluble coffee did not contain detectable levels, thereby contributing least to a consumer’s dietary exposure. Furan and furan derivative concentrations were found to decrease significantly upon cooling, reducing consumer exposure by 8.0–17.2 % on average once the coffee reached drinking temperature 55–60 °C, in ceramic cups. Serving coffee in a ceramic or disposable cup were found to influence the cooling dynamics of the coffee but did not statistically influence the consumers exposure at a given temperature.

Chemical analyses and sensory evaluation are the most applied methods for quality control of roasted and ground coffee (RG). However, faster alternatives would be highly valuable. Here, we applied infrared-photoacoustic spectroscopy (FTIR-PAS) on RG powder. Mixtures of specific defective beans were blended with healthy (defect-free) Coffea arabica and Coffea canephora bases in specific ratios, forming different classes of blends. Principal Component Analysis allowed predicting the amount/fraction and nature of the defects in blends while partial Least Squares Discriminant Analysis revealed similarities between blends (=samples). A successful predictive model was obtained using six classes of blends. The model could classify 100% of the samples into four classes. The specificities were higher than 0.9. Application of FTIR-PAS on RG coffee to characterize and classify blends has shown to be an accurate, easy, quick and “green” alternative to current methods.

On-line analysis of coffee roasting was performed using ion mobility spectrometry–mass spectrometry (IMS–MS) with corona discharge ionization. This is the first time that formation of volatile organic compounds (VOCs) during coffee roasting was monitored not only in positive but also in negative ion mode, and not only with mass spectrometry, but also with ion mobility spectrometry. The temporal evolution of more than 150 VOCs was monitored during the roasting of Brazilian Coffea arabica. Mass-selective ion mobility spectrometry allowed a separation of isobaric and isomeric compounds. In positive ion mode, isomers of alkyl pyrazines were found to exhibit distinct time-intensity profiles during roasting, providing a unique insight into the complex chemistry of this important class of aroma active compounds. Negative ion mode gave access to species poorly detectable by other on-line methods, such as acids. In this study, the release of fatty acids during coffee roasting was investigated in detail. These increase early on in the roasting process followed by a decrease at the same time as other VOCs start to be formed.

When the SARS-CoV-2 pandemic started,[1] science came to the immediate attention of the broad public. People and politicians were hanging on every word of medical doctors, virologists, molecular biologists, data scientists and many others in the hope of finding other protective measures than those used for centuries such as basic hygiene, distance, or quarantine. Here, at the Institute of Chemistry and Biotechnology at the Zurich University of Applied Sciences (ZHAW) we were also willing to provide scientific solutions to overcome the pandemic. Together with our partners from industry, we contributed to the development of a Swiss vaccine, are working on filters for active ventilated full protective suits and are developing tests to show the efficacy and safety of an active antiviral textile that allows controlled virus inactivation through an electrochemical reaction by applying a small current.

Introduction Coffee is a widely consumed beverage containing antioxidant active compounds. During roasting the phytochemical composition of the coffee bean changes dramatically and highly polymeric substances are produced. Besides chlorogenic acids that are already present in green coffee beans, melanoidins show antioxidant capacity as well. Objective To employ post-column derivatisation by coupling high performance size exclusion chromatography (HPSEC) to an antioxidant assay to investigate the effect of roasting on the properties of antioxidant active compounds in coffee brews. Methodology We have investigated the antioxidant capacity of Coffea arabica (Arabica) and C. canephora (Robusta) beans that were roasted over the full spectrum of roast conditions (four roasting speeds to three roast degrees) by comparing the results from HPSEC coupled on-line to the ABTS assay with those from two batch assays, Folin Ciocalteu (FC) and oxygen radical absorbance capacity (ORAC) assay. Results The antioxidant capacity showed a general decrease towards slower and darker roasted coffee for all three assays, indicative of heat degradation of active compounds. Hence, low molecular weight (LMW) compounds such as chlorogenic acids (CGAs) decreased progressively already from relatively mild roasting conditions. In contrast, high molecular weight (HMW) compounds (e.g. melanoidins) increased from light to dark roast degrees with lowering magnitude towards slower roasting profiles. Conclusion By coupling HPSEC on-line to the ABTS assay we were able to separately quantify the contribution of HMW and LMW compounds to the total antioxidant capacity, increasing our understanding of the roast process. © 2016 The Authors. Phytochemical Analysis Published by John Wiley & Sons Ltd.

An oxygen scavenger based on a catalytic system with palladium (CSP) was recently developed to remove oxygen in food packagings. Although the CSP worked with various types of food, with some foods, an inhibition of the CSP was observed. Because such catalytic systems are susceptible to poisoning by sulfur-containing compounds, the aim of this study was to understand the inactivation of palladium-based catalysts in presence of foods containing volatile sulfur compounds (VSCs). To achieve this, the oxygen scavenging activity (OSA) of the CSP was evaluated in presence of selected food products. Afterwards, VSCs mainly present in these foods were exposed to the CSP, and the influence on the OSA was evaluated. Finally, headspace analysis was performed with the diluted VSCs and with the packaged food products using proton transfer reaction time-of-flight mass spectrometry. It was found that the catalytic activity of the CSP was inhibited when VSCs were present in the headspace in concentrations ranging between 10.8–36.0 ppbv (dimethyl sulfide, DMS), 1.2–7.2 ppbv (dimethyl disulfide), 0.7–0.9 ppbv (dimethyl trisulfide), 2.1–5.8 ppbv (methional) and 4.6–24.5 ppbv (furfuryl thiol). It was concluded that in packaged roast beef and cheese, DMS may be the compound mainly responsible for the inactivation of the CSP. In packagings containing ham, the key compounds were hydrogen sulfide and methanethiol; in peanuts, it was methanethiol; and in par-baked buns, an accumulation of methional, DMS, butanethiol and methionol. When potato chips were packaged, it was demonstrated that when VSCs are present in low concentrations, oxygen can still be scavenged at a reduced OSA.

The hot-water extraction process used to make an espresso coffee is affected by a large number of factors. A proper understanding of how these factors impact the profile of the final cup is important to the quality of an espresso coffee. This work examines the effect of water temperature and pressure on the extraction kinetics of volatile organic compounds (VOCs) in coffee. This was achieved by on-line monitoring of the volatiles directly from the coffee flow, using proton-transfer-reaction time-of-flight mass-spectrometry (PTR-ToF-MS). Using hierarchical cluster analysis (HCA), tentatively identified compounds were grouped into 5 families according to their time–intensity profiles. VOCs grouped into each family had similar physicochemical properties while polarity was found to be one of the main forces driving VOC extraction kinetics. The effect of pressure was studied by extracting espresso coffees at 7, 9 and 11 bar. A pressure of 11 bar resulted in an increased extraction of volatiles over the entire extraction time (25 s). To study the effect of temperature, espresso coffees were extracted at 82, 92 and 96 °C. An increase in temperature produced a significant increase in the extraction of VOCs, especially during the last part of the extraction. The effect of temperature on extractability was more pronounced for the less polar compounds.

Numerous projects and industrial and academic collaborations benefit from state-of-the-art facilities and expertise in analytical chemistry available at the Swiss Universities of Applied Sciences. This review summarizes areas of expertise in analytical sciences at the University of Applied Sciences and Arts Northwestern Switzerland (FHNW), the University of Applied Sciences and Arts Western Switzerland (HES-SO), and the Zurich University of Applied Sciences (ZHAW). We briefly discuss selected projects in different fields of analytical sciences

Oxygen scavenging film based on a catalytic system with palladium (CSP) was used to prevent lipid oxidation in linseed oil. Linseed oil was packaged under normal (NA) or modified atmosphere with 2 vol% oxygen (MA) with or without the CSP and stored at 45 °C for 6 months in darkness. To evaluate the evolution of primary and secondary oxidation products, conjugated dienes/trienes, peroxide and para-anisidine values were measured. Additionally, volatile oxidation products in the headspace were analyzed. While a significantly higher level of oxidation products was measured in linseed oil stored under NA compared to MA without CSP, thresholds indicating good quality oil based on the peroxide value (15 milliequivalents O2/g oil) and the para-anisidine value (2 absorbance units/g oil) were exceeded under both packaging conditions. In packages with the CSP, however, removal of headspace oxygen kept oxidation parameters below these thresholds, indicating good quality oil over the whole storage period.

Coffee is a relatively young caffeinated beverage, known in Western Europe since the 17th century. Initially consumed in Europe by the aristocracy, coffee has developed into one of the world's most popular beverages. The unique aroma is without doubt one of the key drivers for its rise in consumption. Over the past two decades, research on coffee aroma has mostly focused on two areas. (1) Identification and quantification of aroma relevant volatile compounds. This led to the publication of lists of sensory relevant (impact/key) compounds, together with their chemical and sensory properties. (2) Elucidation of the formation and degradation mechanisms of coffee aroma compound. After a period of consolidation of all these insights, the focus is shifting to new areas: (i) time-resolved studies of coffee aroma formation, release and degradation; (ii) study of different types of interactions and the development of an increasingly holistic approach to aroma perception; (iii) prediction of sensory profiles from instrumental data.

Coffee has been determined as the dominant source of furan within an adult’s diet. This study investigates the influence of coffee condiment use and stirring on the retention of furan. Three condiment lipid compositions were investigated, 0%, 3.5% and 35%, and kept at either 4 °C, 20 °C or 70 °C before addition to a freshly brewed cup of filter coffee which was subsequently mechanically stirred at three intensities, not stirred and moderately or heavily stirred. While five furans were monitored, furan, 2-methylfuran, 3-methylfuran, 2,5-dimethylfuran and 2,3-dimethylfuran, only two were quantifiable: furan and 2-methylfuran. Increasing condiment lipid concentration significantly increased retention of furan and 2-methylfuran, whereas stirring the coffee significantly increased furan release. A condiment temperature of 70 °C was found to significantly increase furan release.

The aim of this project was to develop a general concept to assess the laboratory experiments in the instrumental analysis laboratory, at the Institute of Chemistry and Biological Chemistry (ICBC) at the Zurich University of Applied Sciences (ZHAW), in terms of their sustainability and, where possible, to improve the sustainability rating of the laboratory experiments. Hence, the primary objective was to implement an empirical assessment methodology, including the “Sustainability Code” that was composed of four parts and a “Sustainability Load Index”. During the spring semester 2015, 105 different experimental projects were performed in the ICBC’s analytical chemistry practical course. These were carried out on 18 different instrumental workspaces, encompassing 12 different analytical methodologies. For the development of the first and second parts of the Sustainability Code, information concerning the chemical substances (in any state- solid, liquid or gas) used and the energy consumption of the apparatus was recorded. The third and fourth parts contain (approximate) information on the use of consumables and the sustainability of the method with reference to the apparatus used. The Load Index (LI) consists of an aggregation (summary) of the direct causality indicators ‘substances’ and ‘energy’ into a single figure. The experiments were classified on a 3-level Load Index Scale into ‘ideal’ analysis methods (LI> 20), ‘sustainable’ methods of analysis (LI 20-200), and analysis methods ‘with potential for optimization’ (LI

Liquid–air partition coefficients (Henry's law constants, HLCs) of eight flavour compounds (volatile organic compounds, VOCs) were determined in water, over a temperature range of 4 °C to 85 °C. The HLCs were derived by using nitrogen to strip a dilute solution of a VOC and then determining the decrease in concentration of the VOC in real-time in the stripped gas using proton-transfer-reaction time-of-flight mass-spectrometry (PTR-ToF-MS). This approach provided HLCs of improved accuracy (small 95% standard deviation) over a large temperature range, especially for low volatility VOCs (HLC > 2 mol/(m 3 Pa)). The outstanding features of this approach are: (i) it is applicable for VOCs over a large range of volatility; (ii) it can be used over a wide temperature range (4 °C to 85 °C); (iii) it is automated (high-throughput); (iv) it does not require calibration or knowledge of the initial concentration of the analyte; and (v) the experimental temperature can be controlled very precisely (Δ T better than ±0.1 °C). The eight flavour compounds analysed in water were: (E)-β-damascenone, 2,3-butanedione, 2-ethyl-3,5-dimethylpyrazine, 2-methylfuran, 3-methylbutanal, acetaldehyde, ethyl-3-methyl butanoate and guaiacol. Based on the measured HLCs at five fixed temperatures (4 °C, 25 °C, 45 °C, 65 °C and 85 °C), accurate non-linear analytical expressions for the temperature dependence of HLCs were derived, which were then used to calculate thermodynamic constants.

During the roasting of coffee, thermally driven chemical reactions lead to the formation of gases, of which a large fraction is carbon dioxide (CO2). Part of these gases is released during roasting while part is retained inside the porous structure of the roasted beans and is steadily released during storage or more abruptly during grinding and extraction. The release of CO2 during the various phases from roasting to consumption is linked to many important properties and characteristics of coffee. It is an indicator for freshness, plays an important role in shelf life and in packaging, impacts the extraction process, is involved in crema formation, and may affect the sensory profile in the cup. Indeed, and in view of the multiple roles it plays, CO2 is a much underappreciated and little examined molecule in coffee. Here, we introduce an accurate, quantitative, and time-resolved method to measure the release kinetics of gases from whole beans and ground coffee using a gravimetric approach. Samples were placed in a container with a fitted capillary to allow gases to escape. The time-resolved release of gases was measured via the weight loss of the container filled with coffee. Long-term stability was achieved using a customized design of a semimicro balance, including periodic and automatic zero value measurements and calibration procedures. The novel gravimetric methodology was applied to a range of coffee samples: (i) whole Arabica beans and (ii) ground Arabica and Robusta, roasted to different roast degrees and at different speeds (roast air temperatures). Modeling the degassing rates allowed structural and mechanistic interpretation of the degassing process.

Coffees from different origins were roasted to different roast degrees and along varying time temperature roasting profiles. The formation of volatile organic compounds (VOCs) during roasting was analyzed on-line by proton-transfer-reaction time-of-flight mass-spectrometry (PTR-ToF-MS). Coffee samples were Coffea arabica from Colombia, Guatemala (Antigua La Ceiba), Ethiopia (Yirga Cheffe, Djimmah) and Coffea canephora var. robusta from Indonesia (Malangsari). The roasting profiles ranged from high temperature short time (HTST) to low temperature long time (LTLT) roasting, and from medium to dark roast degree. The release dynamics of the on-line monitored VOCs differed for the different coffees and showed a strong modulation with the time–temperature roasting profile. While for Guatemalan coffee the formation of VOCs started relatively early in the roasting process, the VOC formation started much later in the case of Yirga Cheffe and Malangsari. Off-line analysis of the coffee brew augmented the measurements. These included headspace solid phase micro extraction gas chromatography mass spectrometry (HS SPME GC/MS), content of total solids, chlorogenic acids, caffeine, total polyphenols (Folin Ciocalteu), organic acids (ion chromatography), titratable acidity and pH. Some general trends, irrespective of the coffee origin, were observed, such as an increase in pH when going from an HTST to an LTLT profile or from a medium to dark roast degree. Furthermore, a decrease of total headspace intensity was observed from an HTST to an LTLT roasting profile. In general, the changes of the time temperature roasting profiles and/or the roast degree influenced the intensity of the respective coffee constituents as well as their relative composition differently for different coffee origins.

Resonance-enhanced multiphoton ionisation time-of-flight mass spectrometry (REMPI-TOFMS) enables the fast and sensitive on-line monitoring of volatile organic compounds (VOC) formed during coffee roasting. On the one hand, REMPI-TOFMS was applied to monitor roasting gases of an industrial roaster (1500 kg/h capacity), with the aim of determining the roast degree in real-time from the transient chemical signature of VOCs. On the other hand, a previously developed μ-probe sampling device was used to analyse roasting gases from individual coffee beans. The aim was to explore fundamental processes at the individual bean level and link these to phenomena at the batch level. The pioneering single-bean experiments were conducted in two configurations: (1) VOCs formed inside a bean were sampled in situ, i.e. via a drilled μ-hole, from the interior, using a μ-probe (inside). (2) VOCs were sampled on-line in close vicinity of a single coffee bean's surface (outside). The focus was on VOCs originating from hydrolysis and pyrolytic degradation of chlorogenic acids, like feruloyl quinic acid and caffeoyl quinic acid. The single bean experiments revealed interesting phenomena. First, differences in time–intensity profiles between inside versus outside (time shift of maximum) were observed and tentatively linked to the permeability of the bean's cell walls material. Second, sharp bursts of some VOCs were observed, while others did exhibit smooth release curves. It is believed that these reflect a direct observation of bean popping during roasting. Finally, discrimination between Coffea arabica and Coffea canephora was demonstrated based on high-mass volatile markers, exclusively present in spectra of Coffea arabica. Copyright © 2013 John Wiley & Sons, Ltd.

Coffee is a relatively young beverage that has only been known about since the 17th century. Initially consumed by the aristocracy, coffee has developed since the early 20th century into one of the world’s most popular beverages and is now part of our daily routine and lifestyle. It also represents a major source of income for many coffee-producing countries and is a significant business sector in consumer countries. The triumph of this beverage may have been driven by various factors, but there is no doubt that its unique flavor is the prime reason for its amazing success. Here we will review current knowledge on the aroma of coffee from a chemical and analytical perspective and outline future trends. It is believed that most coffee aroma compounds have already been identified and quantified. Yet little is understood about how these aroma compounds are generated from green coffee precursors during roasting. A true definition of the aroma of freshly roasted and/or brewed coffee is very elusive and some aroma compounds start to degrade the moment they form. Furthermore, research on interindividual differences in the sensation and perception of coffee aromas is still in its infancy. After reviewing our current knowledge on coffee aroma compounds, we will outline recent developments in time-resolved analysis in three fields: 1. Aroma formation during roasting 2. Aroma extraction during espresso preparation and 3. In-mouth release during consumption. Finally, we will address predictive models for sensory profiles derived from instrumental measurements – possibly the holy grail of aroma sciences.

Coffees and teas are beverages that are both exceptionally rich in antioxidant molecules, and are also both associated with beneficial health effects. Thus although the quality characteristics of these beverages are conventionally assessed on the basis of their sensory properties, their antioxidant contents represent an additional and increasingly valued attribute of quality based on their contributions to healthy diets. Both beverages are prepared by hot water extraction of a pure plant-derived product, and thus their compositions can potentially change quite rapidly as a result of oxidation in contact with air. Oxidative processes often proceed via free radical intermediates, and sometimes also result in the formation of stable radical end-products; thus EPR spectroscopy is a convenient technique for investigating some of the various free radical reactions that occur in these beverages. This paper reviews progress that has been made in elucidating free radical processes that occur during the preparation and storage of coffees and teas, and the results are discussed in terms of quality criteria of the beverages.

Introduction Coffee is a widely consumed beverage containing antioxidant active compounds. During roasting the phytochemical composition of the coffee bean changes dramatically and highly polymeric substances are produced. Besides chlorogenic acids that are already present in green coffee beans, melanoidins show antioxidant capacity as well. Objective To employ post‐column derivatisation by coupling high performance size exclusion chromatography (HPSEC) to an antioxidant assay to investigate the effect of roasting on the properties of antioxidant active compounds in coffee brews. Methodology We have investigated the antioxidant capacity of Coffea arabica (Arabica) and C. canephora (Robusta) beans that were roasted over the full spectrum of roast conditions (four roasting speeds to three roast degrees) by comparing the results from HPSEC coupled on‐line to the ABTS assay with those from two batch assays, Folin Ciocalteu (FC) and oxygen radical absorbance capacity (ORAC) assay. Results The antioxidant capacity showed a general decrease towards slower and darker roasted coffee for all three assays, indicative of heat degradation of active compounds. Hence, low molecular weight (LMW) compounds such as chlorogenic acids (CGAs) decreased progressively already from relatively mild roasting conditions. In contrast, high molecular weight (HMW) compounds (e.g. melanoidins) increased from light to dark roast degrees with lowering magnitude towards slower roasting profiles. Conclusion By coupling HPSEC on‐line to the ABTS assay we were able to separately quantify the contribution of HMW and LMW compounds to the total antioxidant capacity, increasing our understanding of the roast process. © 2016 The Authors. Phytochemical Analysis Published by John Wiley & Sons Ltd., The composition of green coffee beans is complex, yet roasting adds to this complexity by producing highly polymeric melanoidins. Next to chlorogenic acids melanoidins also show antioxidant capacity, which was measured with batch assays as well as by on‐line coupling to size exclusion chromatography to investigate the roasting effect on the formation and/or degradation of high and low molecular weight compounds. Adding chromatography enabled us to separately quantify antioxidant activity of high and low molecular weight compounds to increase our understanding of the roasting process.

A real-time automated process control tool for coffee roasting is presented to consistently and accurately achieve a targeted roast degree. It is based on the online monitoring of volatile organic compounds (VOC) in the off-gas of a drum roaster by proton transfer reaction time-of-flight mass spectrometry at a high time (1Hz) and mass resolution (5,500m/Δm at full width at half-maximum) and high sensitivity (better than parts per billion by volume). Forty-two roasting experiments were performed with the drum roaster being operated either on a low, medium or high hot-air inlet temperature (= energy input) and the coffee (Arabica from Antigua, Guatemala) being roasted to low, medium or dark roast degrees. A principal component analysis (PCA) discriminated, for each one of the three hot-air inlet temperatures, the roast degree with a resolution of better than ±1 Colorette. The 3D space of the three first principal components was defined based on 23 mass spectral profiles of VOCs and their roast degree at the end point of roasting. This provided a very detailed picture of the evolution of the roasting process and allowed establishment of a predictive model that projects the online-monitored VOC profile of the roaster off-gas in real time onto the PCA space defined by the calibration process and, ultimately, to control the coffee roasting process so as to achieve a target roast degree and a consistent roasting. Figure Online monitoring of coffee roasting by real-time analysis of the roaster off-gas using PTR-ToF-MS. In a first phase, 42 calibration experiments were conducted at three different roasting temperatures and to three final roast degrees, to generate the 3D space defined by the three first principle components PC1, PC2 and PC3. Inverted triangles mark the dark roast degree, square medium and circle light, respectively. The hot-air inlet temperature is marked as follows: high (black), medium (grey), low (white). The different hot-air inlet temperatures and roast degrees are clearly separated. In a second phase, an online monitored PTR-ToF-MS spectrum of a roasting process was projected onto the 3D space, allowing following in real-time the roasting process and halting the roasting with a precision better that ± 1 Colorette roast degree

In the past decade, we have witnessed rapid development of direct-injection mass spectrometric (DIMS) technologies that combine ever-improving mass and time resolution with high sensitivity and robustness. Here, we review some of the most significant DIMS technologies, which have been applied to rapid monitoring and quantification of volatile organic compounds (VOCs) and biogenic VOCS (BVOCs). They include MS-e-noses, atmospheric-pressure chemical ionization (APCI), proton-transfer-reaction mass spectrometry (PTR-MS), and selected ion-flow-tube mass spectrometry (SIFT-MS). DIMS-based MS-e-noses provide the possibility to screen large sample sets and may yield rich analytical information. APCI is a widespread ionization method and pioneered DIMS in environmental and flavor-release applications. SIFT-MS and PTR-MS allow better control of precursor-ion generation and hence of the ionization process. SIFT-MS puts the focus on control of the ionization process, while PTR-MS does so on sensitivity. Most (B)VOCs of interest can be efficiently detected and often identified by DIMS, thanks also to the possibility of switching between different precursor ions and the recent realization of time-of-flight-based equipments. Finally, we give selected examples of applications for each of the key technologies, including research in food-quality control (MS-e-nose), flavor release (APCI), environmental sciences (PTR-MS) and health sciences (SIFT-MS).

The formation of acrylamide was measured in real time during thermal treatment (120-170 degrees C) of potato as well as in Maillard model systems composed of asparagine and reducing sugars, such as fructose and glucose. This was achieved by on-line monitoring of acrylamide released into the headspace of the samples using proton transfer reaction mass spectrometry (PTR-MS). Unambiguous identification of acrylamide by PTR-MS was accomplished by gas chromatography coupled simultaneously to electron-impact MS and PTR-MS. The PTR-MS ion signal at m/z 72 was shown to be exclusively due to protonated acrylamide obtained without fragmentation. In model Maillard systems, the formation of acrylamide from asparagine was favored with increasing temperature and preferably in the presence of fructose. Maximum signal intensities in the headspace were obtained after approximately 2 min at 170 degrees C, whereas 6-7 min was required at 150 degrees C. Similarly, the level of acrylamide released into the headspace during thermal treatment of potato was positively correlated to temperature.

The goal of this study was to better understand the correspondence between sensory perception and in-nose compound concentration. Five aroma compounds at three different concentrations increasing by factors of 4 were added to four matrixes (water, skim milk, 2.7% fat milk, and 3.8% fat milk). These were evaluated by nosespace analysis with detection by proton transfer reaction mass spectrometry (PTR-MS), using five panellists. These same panellists evaluated the perceived intensity of each compound in the matrixes at the three concentrations. PTR-MS quantification found that the percent released from an aqueous solution swallowed immediately was between 0.1 and 0.6%, depending on the compound. The nosespace and sensory results showed the expected effect of fat on release, where lipophilic compounds showed reductions in release as fat content increases. The effect is less than that observed in headspace studies. A general correlation between nosespace concentration and sensory intensity ratings was found. However, examples of perceptual masking were found where higher fat milks showed reductions in aroma compound intensity ratings, even if the nosespace concentrations were the same.

We report on the in vivo breath-by-breath analysis of volatiles released in the mouth during eating of ripe and unripe banana. The air exhaled through the nose, nosespace (NS), is directly introduced into a proton transfer reaction mass spectrometer and the time-intensity profiles of a series of volatiles are monitored on-line. These include isopentyl and isobutyl acetate, two characteristic odour compounds of ripe banana, and 2E-hexenal and hexanal, compounds typical of unripe banana. Comparing the NS with the headspace (HS) profile, two differences are outlined. First, NS concentrations of some compounds are increased, compared to the HS, while others are decreased. This indicates that the in-mouth situation has characteristics of its own—mastication, mixing/dilution with saliva, temperature and pH—which modify the aroma relative to an HS aroma. Second, we discuss the temporal evolution of the NS. While 2E-hexenal and hexanal steadily increase in the NS during mastication of unripe banana, no such evolution is observed in volatile organic compounds (VOCs) while eating ripe banana. Furthermore, ripe banana shows high VOC concentrations in the swallow breath in contrast to unripe banana.

This chapter describes the measurement of free radical processes in liquid coffee samples, and their impact on the quality and stability of the beverage. Free radicals generated during the roasting process are relatively stable and located in the polymeric melanoidins, but their concentrations change in coffee solutions via O2-independent decay and O2-dependent formation processes. In addition, the chemistry of coffee solutions is strongly influenced by highly unstable free radicals, presumably hydroxyl radicals generated via Fenton reaction chemistry. These radicals react virtually indiscriminately with organic molecules by hydrogen atom extraction, and can thus initiate progressive degradation of coffee brews. Identification of stable markers of such reactions are discussed along with possible strategies for slowing the rate of alteration of liquid coffee products during storage.

A platform composed of three complementary and validated antioxidant assays is proposed for the routine and fast assessment of the antioxidant capacity of coffee brews. Firstly, a brief review of the principles underlying antioxidant measurements in foods, and the rationale behind the development of an analytical platform for measuring the antioxidant capacity of coffee is given. A range of complementary methods is described based on either hydrogen atom or electron transfer reactions. Secondly, three total antioxidant capacity (TAC) assays are recommended for the platform. Two are based on electron-transfer reactions—the Folin–Ciocalteu (FC) assay for total phenols, and the ABTS assay, which on oxidation forms the cationic chromophore, 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulphonate) (ABTS•+). The third, which is based on hydrogen-atom transfer, is the oxygen radical absorbance capacity (ORAC), in which the antioxidant and the substrate fluorescein compete for thermally generated peroxyl radicals after their formation by decomposition of 2,​2′-​azobis-​2-​amidinopropane,​dihydrochloride (AAPH). Finally, validated protocols for conducting these three assays, using flow injection analysis (FIA), are presented along with actual results to illustrate their reproducibility and robustness. The three assays are combined into an analytical platform to profile and compare the antioxidant potential of a series of roasted coffee samples. Antioxidant values obtained with the same dark-roast coffee are 2103, 710, and 5868 gallic acid equivalents (GAE) for the FC, ABTS, and ORAC assays, respectively. These numbers thus reflect the different types of chemical reaction that are performed, and illustrate the fact that assays for TAC are actually selective (and hence complementary) for specific types of antioxidant molecule.

Heat and mass transfer in individual coffee beans during roasting were simulated using computational fluid dynamics (CFD). Numerical equations for heat and mass transfer inside the coffee bean were solved using the finite volume technique in the commercial CFD code Fluent ; the software was complemented with specific user-defined functions (UDFs). To experimentally validate the numerical model, a single coffee bean was placed in a cylindrical glass tube and roasted by a hot air flow, using the identical geometrical 3D configuration and hot air flow conditions as the ones used for numerical simulations. Temperature and humidity calculations obtained with the model were compared with experimental data. The model predicts the actual process quite accurately and represents a useful approach to monitor the coffee roasting process in real time. It provides valuable information on time-resolved process variables that are otherwise difficult to obtain experimentally, but critical to a better understanding of the coffee roasting process at the individual bean level. This includes variables such as time-resolved 3D profiles of bean temperature and moisture content, and temperature profiles of the roasting air in the vicinity of the coffee bean.

During coffee roasting major changes occur in coffee bean composition. Among others dark coloured melanoidins are formed, which are high molecular weight Maillard reaction products. A new approach is presented here to monitor the influence of roasting conditions on the antioxidant capacity of melanoidins and chlorogenic acids (CGAs) in a coffee brew. Validated Folin–Ciocalteu (FC) and ABTS assays were used as on-line antioxidant assays coupled (post-column) with high performance size-exclusion chromatography (HPSEC). HPSEC enabled the separation of melanoidins from CGAs and the determination of the antioxidant capacity of each fraction, within a total elution time of 25 min. Besides the on-line assay measurements, both assays were also applied off-line with flow injection analysis (FIA). The maximum antioxidant capacity was determined to be at a light-to-medium roast degree, measured with both ABTS-FIA and FC-FIA assays as well as on-line ABTS assay. With FC on-line assay the maximum was found to be at a very light roast degree. Based on the peak areas obtained with the new coupled technique the roasting effects on the variability of melanoidin and CGA contents in coffee brews were studied. The majority of melanoidins are already formed in the early stage of the roasting process and the relative contribution of melanoidins to the total antioxidant capacity increases towards darker roasts, mainly because CGAs degrade during roasting. A new parameter, the ratio of melanoidin to CGA peak area, was introduced as a possible predictor of the roast degree.

Development of liquid coffee products of good quality with extended shelf lives is hampered by their rapid quality degradation as a result of both physical and flavor instability. One approach that is being considered for extending the shelf lives of liquid coffees is that of supplementing the beverage with a very mild and slow continuous extraction from intact roasted beans that are held within an aluminum can. This paper reports the use of electron paramagnetic resonance (EPR) spectroscopy to examine the effects of key parameters that affect the stability of liquid coffee prepared from aqueous extracts from whole roasted coffee beans, namely, the O2 content of the water and headspace during extraction and the temperature during storage. It was found that the magnitude of the free radical signal was sensitive to the O2 content of the water used for extraction and storage time and temperature, whereas the intensity of the Fe(III) (g = 4.3) signal was affected only by the O2 content of the water and the Mn signal was insensitive to the experimental parameters. The most critical factor was the O2 content of the water used for extraction, and careful control of O2 exposure at the extraction stage could be a crucial factor for generating products with resistance to oxidative processes during storage.

Mixed metal clusters of sodium and cesium with gold have been generated in a supersonic expansion from the mixed vapor phase. Their tendency towards binary cluster formation, relative thermodynamic stability, and ionization potentials have been experimentally and computationally investigated. The properties of the NaxAu clusters may be understood within an electronic shell model based on delocalized cluster orbitals, whereas the characteristics of CsxAu are indicative of substantial ionic interactions. Relativistic density functional calculations have been performed to elucidate the cluster electronic structure and to rationalize observed properties which may not be accounted for by the jellium model. The properties of these finite-size clusters are shown to be related to the known bulk intermetallic compounds sodium gold and cesium-gold (cesium aurid), respectively.

� 2016 IOP Publishing Ltd. The persistence of aroma compounds in breath after swallowing is an important attribute of the overall aroma experience during eating and drinking. It is mainly related to the coating of the oral tract with food residues and the interaction between volatile compounds and airway mucosa. We have studied the persistence of eight compounds (2,5-dimethylpyrazine, guaiacol, 4-methylguaiacol, phenylethylalcohol, ethylbutanoate, ethyloctanoate, isoamylacetate and 2-heptanone) both in-nose and in-mouth after administration of volatiles in gas phase (vapor) to five different panelists. By using volatiles in the gas phase, only the interaction with the mucosa is highlighted and the formation of a liquid coating in the oral and tracheal airway is avoided. The physicochemical properties of the compounds, mainly polarity and vapor pressure, determine the interactions of the volatiles with the airway mucosa. The use of different breathing protocols allowed the study of the differences between nasal and oral mucosa in volatile retention, with higher persistence of volatiles obtained in-mouth. Initial concentration also affected persistence, but only for compounds with high volatility and at low concentration.

The preferred fragmentation patterns of negatively charged carbon clusters, C−N have been investigated by cluster—beam impact methods using various surfaces and impact energies (Ei = 0-150 eV). Transitions from one type of cluster structure to another are inferred from the observed change in fragmentation patterns. The results are made possible by the high intact-scattering yield of C−N clusters, and by the competitiveness of fragmentation with electron emission for clusters N < 40. The main inferred structures and diagnostic fragmentation patterns are (i) chain structures (4 < N < 18), which fragment by C(0)3 loss; (ii) ring structures, N ≈ 17-32, reflected by preferential cleavage to give large neutral clusters C(0)14, and C(0)22, (iii) polycyclic or cage structures, which shatter to yield an array of small fragments; and (iv) fullerene-type structures, N > 33, for which electron emission dominates over fragmentation. These results are compared and contrasted with results obtained from other fragmentation and collisional methods.

Die Strukturbildung an Grenzflachen, deren Induktion und Charakterisierung, dadurch bewirkte Fortschritte in der heterogenen Katalyse und die Aufklarung der Struktur elektrochemischer Phasengrenzen sind Schwerpunkte dieses Trendberichts. Von hoher Aktualitat sind auch die zeitaufgeloste Untersuchung chemischer Reaktionen, die Nutzung der Dichtefunktionaltheorie fur neue quantenchemischen Methoden und die Cluster.

Among the 100 different known Coffea species, Coffea arabica L. (Arabica) and Coffea canephora Pierre (Robusta) are the only two of commercial interest. They differ in a range of agronomic, genetic, and chemical properties. Due to the significant price difference between Arabica and Robusta, there is an economic incentive to illicitly replace Arabica with Robusta. Therefore, it is crucial to have accurate methods to determine the Robusta-to-Arabica-ratio in blends. This paper presents the proof of principle of a new and fast approach to determine the Robusta fraction in a blend based on Raman spectroscopy. The oils of two references (a pure Robusta and pure Arabica coffee) and six blends thereof consisting of different Robusta and Arabica fractions were extracted using a Soxhlet system. The solutes were analyzed by means of Raman spectroscopy without further workup. Using the intensity ratio between two Raman peaks, one characteristic for kahweol and one characteristic for fatty acids, allowed determinination of the Robusta content in a given mixture. The intensity ratio is linearly dependent on the Robusta content of the compound. Above a Robusta content of 75 wt %, kahweol was not detectable. The Raman data are in agreement with results obtained from the very time-consuming multistep DIN 10777 procedures based on HPLC.

An experimental technique is investigated to separate/enrich fullerenes of metallofullerenes, exploiting differences in sublimation temperatures without the use of solvents. Fullerenes are sublimed out of the soot and deposited on a quartz rod along a temperature gradient (gradient sublimation). In a position-sensitive experiment the composition of the deposit on the rod is monitored by laser-desorption mass spectrometry. Strongly enriched regions containing specific fullerene molecules (i.e., C[sub 84] or LaC[sub 82]) are observed. Furthermore, C[sub 74], which could not be extracted from the soot by organic solvents, sublimes out of the soot. 26 refs., 6 figs.

The authors report the formation of fullerenes from graphite by sputtering and electron beam evaporation. Under conditions that differ dramatically from those in the previously known fullerene production processes, the new methods preferentially yield the soluble higher fullerenes C{sub 70}, C{sub 76}, C{sub 78}, and C{sub 84} in addition to minor amounts of C{sub 60} only. Upon passage of carbon particles formed by electron beam evaporation through an electrostatic field, fullerenes are mainly isolated from the cathode, not from the anode, which supports the formation of cationic intermediates in fullerene growth mechanisms. The variables thought to be important for fullerene production can be controlled efficiently in the new processes. 18 refs., 3 figs.