The study of galactomannans with different molecular weights and their ability to form microparticles suitable for pulmonary delivery.

The influence of locust bean gum (LBG) galactomannans (GMs) molecular weight (Mw) to assemble microparticulate systems was evaluated, and carriers for deep lung delivery were developed. A commercial batch of LBG with a mannose/galactose (M/G) ratio of 2.4 (batch 1) was used to study the influence of different microwave partial acid hydrolysis conditions on carbohydrate composition, glycosidic linkages, and aqueous solutions viscosity. The microwave treatment did not affect the composition, presenting 4-Man (36-42 %), 4,6-Man (27-35 %), and T-Gal (24-25 %) as the main glycosidic linkages. Depolymerization led to a viscosity reduction (≤0.005 Pa·s) with no major impact on polysaccharide debranching. The structural composition of the LBG galactomannans were further elucidated with sequence-specific proteins using carbohydrate microarray technologies. A second batch of LBG (M/G 3.3) was used to study the impact of GMs with different Mw on microparticle assembling, characteristics, and insulin release kinetics. The low-Mw GMs microparticles led to a faster release (20 min) than the higher-Mw (40 min) ones, impacting the release kinetics. All microparticles exhibited a safety profile to cells of the respiratory tract. However, only the higher-Mw GMs allowed the assembly of microparticles with sizes suitable for this type of administration.

Quality Characteristics of Raspberry Fruits from Dormancy Plants and Their Feasibility as Food Ingredients.

The raspberry (Rubus idaeus L.) is a soft red fruit consumed worldwide due to its bitter-sweet taste and phenolics-associated health benefits. During plant dormancy, raspberry fruits are discarded. However, this work hypothesised that these fruits have the chemical quality to be valorised, which would mitigate their waste if adequately stabilised. This can be achieved by drying. The Pacific Deluxe and Versailles varieties were dried by freeze- and convective-drying (30 °C and 40 °C). The freeze-dried fruits preserved their colour, drupelets structure, and phenolic content. Convective-drying promoted a significant fruit darkening, which was more evident at 30 °C due to the longer drying process, and a loss of drupelets structure. Both temperatures promoted a similar decrease in phenolic content, as determined by HPLC, although the ABTS●+ antioxidant activity at 40 °C was lower (IC50 = 9 compared to 13 µg AAE/mg dry weight). To incorporate dried raspberries into muffin formulations, while keeping their red colour, it was necessary to change the raising agent from sodium bicarbonate to baker's yeast. Sensory analysis by a non-trained panel revealed good acceptance, showing that fresh or dried raspberry fruits from dormancy had suitable characteristics for use as food ingredients.

Mycotoxins' Prevalence in Food Industry By-Products: A Systematic Review.

The recovery of biomolecules from food industry by-products is of major relevance for a circular economy strategy. However, by-products' contamination with mycotoxins represents a drawback for their reliable valorization for food and feed, hampering their application range, especially as food ingredients. Mycotoxin contamination occurs even in dried matrices. There is a need for the implantation of monitoring programs, even for by-products used as animal feed, since very high levels can be reached. This systematic review aims to identify the food by-products that have been studied from 2000 until 2022 (22 years) concerning mycotoxins' contamination, distribution, and prevalence in those by-products. PRISMA ("Preferred Reporting Items for Systematic Reviews and MetaAnalyses") protocol was performed via two databases (PubMed and SCOPUS) to summarize the research findings. After the screening and selection process, the full texts of eligible articles (32 studies) were evaluated, and data from 16 studies were considered. A total of 6 by-products were assessed concerning mycotoxin content; these include distiller dried grain with solubles, brewer's spent grain, brewer's spent yeast, cocoa shell, grape pomace, and sugar beet pulp. Frequent mycotoxins in these by-products are AFB1, OTA, FBs, DON, and ZEA. The high prevalence of contaminated samples, which surpasses the limits established for human consumption, thus limiting their valorization as ingredients in the food industry. Co-contamination is frequent, which can cause synergistic interactions and amplify their toxicity.

Polysaccharide-Based Carriers for Pulmonary Insulin Delivery: The Potential of Coffee as an Unconventional Source.

Non-invasive routes for insulin delivery are emerging as alternatives to currently painful subcutaneous injections. For pulmonary delivery, formulations may be in powdered particle form, using carriers such as polysaccharides to stabilise the active principle. Roasted coffee beans and spent coffee grounds (SCG) are rich in polysaccharides, namely galactomannans and arabinogalactans. In this work, the polysaccharides were obtained from roasted coffee and SCG for the preparation of insulin-loaded microparticles. The galactomannan and arabinogalactan-rich fractions of coffee beverages were purified by ultrafiltration and separated by graded ethanol precipitations at 50% and 75%, respectively. For SCG, galactomannan-rich and arabinogalactan-rich fractions were recovered by microwave-assisted extraction at 150 °C and at 180 °C, followed by ultrafiltration. Each extract was spray-dried with insulin 10% (w/w). All microparticles had a raisin-like morphology and average diameters of 1-5 µm, which are appropriate for pulmonary delivery. Galactomannan-based microparticles, independently of their source, released insulin in a gradual manner, while arabinogalactan-based ones presented a burst release. The microparticles were seen to be non-cytotoxic for cells representative of the lung, specifically lung epithelial cells (A549) and macrophages (Raw 264.7) up to 1 mg/mL. This work shows how coffee can be a sustainable source of polysaccharide carriers for insulin delivery via the pulmonary route.

Polysaccharide-based formulations as potential carriers for pulmonary delivery - A review of their properties and fates.

Polysaccharides can be elite carriers for therapeutic molecules due to their versatility and low probability to trigger toxicity and immunogenic responses. Local and systemic therapies can be achieved through particle pulmonary delivery, a promising non-invasive alternative. Successful pulmonary delivery requires particles with appropriate flowability to reach alveoli and avoid premature clearance mechanisms. Polysaccharides can form micro-, nano-in-micro-, and large porous particles, aerogels, and hydrogels. Herein, the characteristics of polysaccharides used in drug formulations for pulmonary delivery are reviewed, providing insights into structure-function relationships. Charged polysaccharides can confer mucoadhesion, whereas the ability for specific sugar recognition may confer targeting capacity for alveolar macrophages. The method of particle preparation must be chosen considering the properties of the components and the delivery device to be utilized. The fate of polysaccharide-based carriers is dependent on enzyme-triggered hydrolytic and/or oxidative mechanisms, allowing their complete degradation and elimination through urine or reutilization of released monosaccharides.

Bioactive Properties of Instant Chicory Melanoidins and Their Relevance as Health Promoting Food Ingredients.

Instant chicory is a caffeine-free brew worldwide consumed as a coffee substitute. Like coffee grounds processing, chicory roots suffer a roasting process, which may lead to the formation of high-molecular weight nitrogen-brown compounds, the melanoidins. It is hypothesized that similarly to coffee, chicory melanoidins have health promoting potential. In this work, the chemical composition and biological activity of chicory high molecular weight material (HMWM) was evaluated. The chicory HMWM is composed by 28.9% (w/w) of carbohydrates, mainly fructose-rich polysaccharides (18.7% w/w) and 5.7% (w/w) of protein, distinct from coffee. The phenolic compounds constituent of the HMWM were mainly present in glycosidically linked and condensed structures (0.9 g/100 g and 5.8 g/100 g), showing in vitro ABTS•+ scavenging (IC50 = 0.28 mg/mL) and ferric ion reducing capacity (ca. 11 µg Fe2+ eq/mg). Chicory HMWM revealed to be effective against Gram-positive bacteria, mainly Staphylococcus aureus and Bacillus cereus, although not so efficient as coffee. It also showed potential to inhibit α-glucosidase activity (15% of inhibition), higher than coffee HMWM, approaching acarbose activity that is used in type 2 diabetes mellitus treatment. Thus, chicory melanoidins, when used as a food ingredient, may contribute to an antioxidant diet and to prevent diabetes, while increasing the protective effects against pathogenic bacteria.

Insights on Single-Dose Espresso Coffee Capsules' Volatile Profile: From Ground Powder Volatiles to Prediction of Espresso Brew Aroma Properties.

Single-dose coffee capsules have revolutionized the coffee market, fueling espresso coffee popularity and offering access to a wide selection of coffee blends. Nevertheless, scarce information related to coffee powder and brew's combined volatile characterization is available. In this study, it is hypothesized that coffee brew aroma characteristics can be predicted based on coffee powder's volatile composition. For this, headspace solid-phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry detection (GC × GC-ToFMS) was used. The data were combined via chemometric tools to characterize in depth the volatile composition of eight blends of capsule-coffee powder and respective espresso brews, simulating the consumer's perception. A total of 390 volatile compounds were putatively identified, 100 reported for the first time in roasted coffee or brews. Although the same chemical families were determined among the coffee powders and espresso brews, a different volatile profile was determined for each matrix. The Pearson correlation of coffee powders and respective brews allowed to identify 15 volatile compounds, mainly terpenic and esters recognized by their pleasant notes, with a strong relationship between the amounts present in both matrices. These compounds can be key markers to predict the volatile aroma potential of an espresso brew when analyzing the coffee powder.

HS-SPME Gas Chromatography Approach for Underivatized Acrylamide Determination in Biscuits.

Acrylamide (AA) is a food contaminant in thermally processed products that is object of tight control. A simple and easy-to-apply methodology for routine monitoring of AA levels in food products could allow producers to be players in the control of their own products. In this work, a simple methodology for AA quantification without derivatization was developed for biscuits, for which the benchmark levels recommended by EFSA are 350 µg/kg, and 150 µg/kg for biscuits for infants and young children. Headspace-solid phase microextraction (HS-SPME) was used in 120 mL screwed-cap vials with a carboxen/polydimetylsiloxane fiber, 4 g of biscuits, and 10 mL of water during 15 min at room temperature under stirring. The addition of 30 mL of propanol under stirring during 15 min at room temperature and 15 min at 60 °C was used to promote AA transfer to the headspace. The fiber exposure was 45 min. A gas chromatography-mass spectrometry analysis allowed to obtain an external calibration curve at m/z 71, with linearity R2 > 0.99 and precision RSD < 9%. The detection and quantification limits were 27.4 µg/kg and 91.5 µg/kg, respectively. The methodology was successfully used in biscuits with lower AA amount, where mitigation strategies (asparaginase or pectate) were applied.

Microwave hydrodiffusion and gravity as a sustainable alternative approach for an efficient apple pomace drying.

Apple pomace valuation has been impaired by its high perishability and absence of fast drying approaches demanded by industry. This work aimed to assess the feasibility of Microwave Hydrodiffusion and Gravity (MHG) process applied for apple pomace drying using discrete delivery powers (300-900 W) and comparison with hot-air drying (40-100 °C). To dry 0.4 kg of apple pomace (81% moisture), hot-air drying required 3.6-9.9 h with estimated water evaporation flux of 1.0-3.5 mL/min. For MHG, which processed 1.2 kg, these corresponded to 1.0-2.6 h and 5.1-13.9 mL/min. Furthermore, MHG allowed water recovery containing part of apple pomace phenolic compounds and carbohydrates. The dried pomace was stable for 2 years, after which phenolic compounds and polysaccharides were still recoverable by hot water extractions. These results pave the way for MHG to be used for apple pomace and other by-products preservation, boosting their conversion into valuable co-product for valuation of its components.

Coffee By-Products and Their Suitability for Developing Active Food Packaging Materials.

The coffee industry generates a wide variety of by-products derived from green coffee processing (pulp, mucilage, parchment, and husk) and roasting (silverskin and spent coffee grounds). All these fractions are simply discarded, despite their high potential value. Given their polysaccharide-rich composition, along with a significant number of other active biomolecules, coffee by-products are being considered for use in the production of plastics, in line with the notion of the circular economy. This review highlights the chemical composition of coffee by-products and their fractionation, evaluating their potential for use either as polymeric matrices or additives for developing plastic materials. Coffee by-product-derived molecules can confer antioxidant and antimicrobial activities upon plastic materials, as well as surface hydrophobicity, gas impermeability, and increased mechanical resistance, suitable for the development of active food packaging. Overall, this review aims to identify sustainable and eco-friendly strategies for valorizing coffee by-products while offering suitable raw materials for biodegradable plastic formulations, emphasizing their application in the food packaging sector.

Role of Coffee Caffeine and Chlorogenic Acids Adsorption to Polysaccharides with Impact on Brew Immunomodulation Effects.

Coffee brews have High Molecular Weight (HMW) compounds with described immunostimulatory activity, namely polysaccharides and melanoidins. Melanoidins are formed during roasting and are modified during brews technological processing. In addition, brews have Low Molecular Weight (LMW) compounds, namely free chlorogenic acids and caffeine, with well-known anti-inflammatory properties. However, this study shows that both espresso and instant coffee brews did not present immunostimulatory neither anti-inflammatory in vitro activities. It is possible that the simultaneous existence of compounds with antagonistic effects can mitigate their individual effects. To test this hypothesis, an ultrafiltration separation process was applied, studying the behavior of coffee brews' HMW on retention of LMW compounds. Several ultrafiltration sequential cycles were required to separate retentates from LMW compounds, suggesting their retention. This effect was higher in instant coffee, attributed to its initial higher carbohydrate content when compared to espresso. Separation of HMW and LMW compounds boosted their immunostimulatory (6.2-7.8 µM nitrites) and anti-inflammatory (LPS induced nitrite production decrease by 36-31%) in vitro activities, respectively. As coffee anti-inflammatory compounds are expected to be first absorbed during digestion, a potential in vivo fractionation of LMW and HMW compounds can promote health relevant effects after coffee intake.

Gentianose: Purification and structural determination of an unknown oligosaccharide in grape seeds.

Grape seeds are among the main constituents of grape pomace, ranging between 20% and 30% of the wet matrix; however, their oligosaccharide composition has not been studied. This paper describes the purification and the identification of low molecular weight oligosaccharides contained in an EtOH/water extract of grape seeds. A sequential two-step purification by size exclusion chromatography was carried out to fractionate compounds according to molecular weights. Chemical characterization of the combined fractions was performed by Magnetic Resonance Spectroscopy and Gas Chromatography-Mass Spectrometry analyses. The separation process gave two fractions abundant in sucrose and glucose. A third fraction containing trisaccharides was acetylated allowing the purification of the main trisaccharide. The structure elucidation of the acetylated product made it possible to identify gentianose, a predominant carbohydrate reserve found in the storage roots of perennial Gentiana lutea. Grape seeds are wine industry by-products and the obtained results suggest the importance of their recovery.

Carbohydrates as targeting compounds to produce infusions resembling espresso coffee brews using quality by design approach.

All coffee brews are prepared with roasted coffee and water, giving origin to espresso, instant, or filtered coffee, exhibiting distinct physicochemical properties, depending on the extraction conditions. The different relative content of compounds in the brews modulates coffee body, aroma, and colour. In this study it was hypothesized that a coffee infusion allows to obtain extracts that resemble espresso coffee (EC) physicochemical properties. Carbohydrates (content and composition) were the target compounds as they are organoleptically important for EC due to their association to foam stability and viscosity. The freeze-drying of the extracts allowed better dissolution properties than spray-drying. Instant coffee powders were obtained with chemical overall composition resembling espresso, although with lower lipids content. The extracts were able to produce the characteristic foam through CO2 injection or salts addition. Their redissolution at espresso concentration allowed a viscosity, foamability and volatile profile representative of an espresso coffee, opening new exploitation possibilities.

Blanching impact on pigments, glucosinolates, and phenolics of dehydrated broccoli by-products.

Because of high water content, the valorisation of broccoli by-products requires dehydration that can preserve bioactive compounds. Blanching pre-treatment has been reported to improve the drying rate of broccoli. As a thermal treatment, it promotes also enzyme inactivation. Therefore, in this study, the impact of pre-dehydration blanching step, freeze-drying, air-drying at 40 °C, and microwave hydrodiffusion and gravity (MHG) dehydration on the levels of pigments, glucosinolates, and phenolics, was evaluated by UHPLC-DAD-ESI/MSn. When compared to freeze-drying, a technique known to preserve compounds, a pre-blanching step increased the extractability of both pigments and phenolics, while air-drying only retained 49% of the pigments and 70% of phenolics, both without affecting glucosinolates. However, when air-drying was preceded by blanching, less than 50% of compounds were retained. On the other hand, MHG dehydration increased the phenolics extractability by 26%, particularly that of kaempferol derivatives while also retaining the amount of the glucosinolate glucoraphanin, when compared to freeze-drying. Nevertheless, only 23% of indole glucosinolates were recovered and pigments were severely reduced, with lutein accounting only for 32% and only chlorophyll b was observed in trace amounts after MHG dehydration. Therefore, to valorise broccoli by-products as ingredients, different drying technologies may be used when targeting different composition richness: freeze-drying is suitable for pigments and glucosinolates, air-drying is suitable for glucosinolates, while MHG promotes the extractability of phenolic compounds.

In Vitro Hypocholesterolemic Effect of Coffee Compounds.

(1) Background: Cholesterol bioaccessibility is an indicator of cholesterol that is available for absorption and therefore can be a measure of hypocholesterolemic potential. In this work, the effect of commercial espresso coffee and coffee extracts on cholesterol solubility are studied in an in vitro model composed by glycodeoxycholic bile salt, as a measure of its bioaccessibility. (2) Methods: Polysaccharide extracts from coffees obtained with different extraction conditions were purified by selective precipitation with ethanol, and their sugars content were characterized by GC-FID. Hexane extraction allowed us to obtain the coffee lipids. Espresso coffee samples and extracts were tested regarding their concentration dependence on the solubility of labeled 13C-4 cholesterol by bile salt micelles, using quantitative 13C NMR. (3) Results and Discussion: Espresso coffee and coffee extracts were rich in polysaccharides, mainly arabinogalactans and galactomannans. These polysaccharides decrease cholesterol solubility and, simultaneously, the bile salts' concentration. Coffee lipid extracts were also found to decrease cholesterol solubility, although not affecting bile salt concentration. (4) Conclusions: Coffee soluble fiber, composed by the arabinogalactans and galactomannans, showed to sequester bile salts from the solution, leading to a decrease in cholesterol bioaccessibility. Coffee lipids also decrease cholesterol bioaccessibility, although the mechanism of action identified is the co-solubilization in the bile salt micelles. The effect of both polysaccharides and lipids showed to be additive, representing the overall effect observed in a typical espresso coffee. The effect of polysaccharides and lipids on cholesterol bioaccessibility should be accounted on the formulation of hypocholesterolemic food ingredients.

Impact of microwave-assisted extraction on roasted coffee carbohydrates, caffeine, chlorogenic acids and coloured compounds.

Microwave-assisted extraction (MAE) allows to quickly achieve soluble compounds from solid matrices due to the promotion of temperatures higher than the solvent (atmospheric) boiling point, once a closed-vessel system is used for operating at high pressure. In this study, the feasibility of MAE for producing high yield coffee extracts with properties that allow their commercial application was tested through a quality by design approach. It was studied the influence of time of extraction (1, 5.5, 10 min), temperature (120, 150, 180 °C) and the mass-to-volume (m/V) ratio (2, 4, 6 g/60 mL) in the overall extraction yield (24-47%, w/w), carbohydrates content (18-43%, w/w), sugars composition, caffeine (4-7%, w/w), 5-caffeoylquinic acid (1-2%, w/w), colour and antioxidant activity of the extracts. FTIR analysis was used to study the resemblance of coffee extracts and commercial instant coffee. MAE allowed overall extraction yields considerably higher than the home brewing methods, mainly when performed at 180 °C, with a substantial increase in arabinogalactans (AG) extraction associated to higher temperatures. Temperature exerted a crucial role in coffee extracts differentiation, although time and m/V ratio also lead to different values in the responses. Under a circular economy concept, MAE was able to produce extracts that can be used as defined food/brew ingredients and provides a galactomannan and cellulose rich residue that can also be valued as a source of dietary fibre.

Apple Pomace Extract as a Sustainable Food Ingredient.

Apple pomace is a by-product of apple processing industries with low value and thus frequent disposal, although with valuable compounds. Acidified hot water extraction has been suggested as a clean, feasible, and easy approach for the recovery of polyphenols. This type of extraction allowed us to obtain 296 g of extract per kg of dry apple pomace, including 3.3 g of polyphenols and 281 g of carbohydrates. Ultrafiltration and solid-phase extraction using C18 cartridges of the hot water extract suggested that, in addition to the apple native polyphenols detected by ultra-high-pressure liquid chromatography coupled to a diode-array detector and mass spectrometry UHPLC-DAD-ESI-MSn, polyphenols could also be present as complexes with carbohydrates. For the water-soluble polyphenols, antioxidant and anti-inflammatory effects were observed by inhibiting chemically generated hydroxyl radicals (OH•) and nitrogen monoxide radicals (NO•) produced in lipopolysaccharide-stimulated macrophages. The water-soluble polyphenols, when incorporated into yogurt formulations, were not affected by fermentation and improved the antioxidant properties of the final product. This in vitro research paves the way for agro-food industries to achieve more diversified and sustainable solutions towards their main by-products.

Data on yields, sugars and glycosidic-linkage analyses of coffee arabinogalactan and galactomannan mixtures and optimization of their microwave assisted extraction from spent coffee grounds.

The data presented here are related to the research paper entitled "Structural features of spent coffee grounds water-soluble polysaccharides: towards tailor-made microwave assisted extractions" [1]. Microwave assisted extraction conditions were applied to spent coffee grounds for recovery of polysaccharides, namely arabinogalactans and galactomannans. Following an experimental design testing temperature, time, and alkali conditions as influence factors during microwave assisted extraction, this article reports the response data for the total extracted mass, sugars yield (including arabinogalactans and galactomannans total content, and mass ratio), and structural features (including degree of polymerization and degree of branching) for each set of operating conditions. In addition, it provides gas chromatography-mass spectrometry (GC-MS) chromatograms (and respective GC-MS spectra) of arabinogalactan and galactomannan mixtures with different structural features corresponding to representative microwave treatment conditions.

Structural features of spent coffee grounds water-soluble polysaccharides: Towards tailor-made microwave assisted extractions.

This work studies the microwave-assisted extraction conditions for recovery of polysaccharides from spent coffee grounds, including their effect on arabinogalactans and galactomannans polymerization and branching structural features. Temperature (140, 170, and 200 °C) has the most significant impact on total extracted mass (ηtotal soluble solids) and sugars yield (ηsugars), arabinogalactans (ηAG) and galactomannans (ηGM), and polysaccharide mass ratio (ηAG/ηGM). Time (2, 5, and 10 min) and alkali (diluted 0.1 M NaOH) treatments have less influence. Alkali treatment and shorter time (2 min) provided a protective effect against polysaccharides degradation. At 170 °C, the yield of arabinogalactans was found to be significantly higher than that of galactomannans (ηAG/ηGM >1). Increasing temperature to 200 °C leads to decrease the polymerization of polysaccharides, promoting the formation of debranched polysaccharides and oligosaccharides. This study shows that the optimum conditions for polysaccharides extraction cannot be selected only by mass yield but need to be defined according to the desired structural features for the specific applications.

Microwave assisted dehydration of broccoli by-products and simultaneous extraction of bioactive compounds.

Broccoli by-products from frozen-food industry account for 45% of the initial broccoli heads. They consist on stalks, inflorescences, and leaves, blanched and non-blanched, sharing the nutritional value and bioactive compounds of commercial broccoli heads. However, their high perishability prevents further valorisation. Therefore, in this study microwave hydrodiffusion and gravity (MHG) technology was used to dehydrate broccoli by-products and simultaneously recover the water-soluble diffused compounds for food ingredients use. The hydrodiffusion allowed to obtain a dried material with 12% moisture in 43 min when 550 g of broccoli by-products were used, preserving polysaccharides and proteins. Diffused water contained up to 317 µg/mL gallic acid equivalents of phenolic compounds, 11 mg/mL free sugars, 9 mg/mL amino acids, and 356 µg/mL glucosinolates, depending on the type of by-product used. These results show the potential of MHG technology for valorisation of broccoli by-products by its simultaneous stabilization by dehydration and extraction of bioactive compounds.