Adriana Cuvalic Spent of Coffe
Adriana Cuvalic Spent of Coffe
Czech Republic
a r t i c l e i n f o a b s t r a c t
Article history: Spent coffee grounds (SCGs) arise as waste products through the production of instant cof-
Received 19 December 2017 fee and coffee brewing. This work reviews the composition of SCGs, the methods used for
Received in revised form 5 May 2018 the isolation of individual compounds present in SCGs, the ways of utilizing SCGs presented
Accepted 14 May 2018 in the literature so far, including use of SCGs’ bioactive compounds, carbohydrates, oil frac-
Available online 22 May 2018 tion, as well as SCGs as the whole composite without treatment or with some physical and
chemical modifications. However, this work mainly focuses on biotechnological processing
Keywords: of SCG hydrolysates and the reason why the fermentable sugars present in SCG hydrolysates
Biorefinery cannot support sufficiently the growth of bacteria or yeasts. The reason is basically the pres-
Biotechnology ence of toxic co-contaminants, which have antibacterial properties. One suggestion for how
Detoxification to lower the presence of such co-contaminants in SCG hydrolysates is pre-extraction of them
Food or the inclusion of a detoxification step. This review suggests that the fractionation of SCGs
Polyhydroxyalkanoates and detoxification of SCG hydrolysates might contribute to increased multiple utilization of
Spent coffee grounds this waste in many industrial sectors.
© 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2. Composition of SCG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.1. Oil fraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
2.2. Crude fiber and additional components. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .106
2.3. Valorization of spent coffee grounds without any fractionation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
3. Fractionation, extraction and valorization of SCGs’ components . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.1. Characterization, isolation, and application of minor biologically active constituents present in SCGs . . . . . . . . . . . 108
3.2. Valorization of coffee oil fractions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
3.3. Valorization of carbohydrates. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .109
3.4. Inhibitors of microbial growth and their elimination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
∗
Corresponding author:
E-mail address: [email protected] (A. Kovalcik).
https://doi.org/10.1016/j.fbp.2018.05.002
0960-3085/© 2018 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Food and Bioproducts Processing 1 1 0 ( 2 0 1 8 ) 104–119 105
1. Introduction hand may enhance the efficiency of the biotechnological processes, and
on the other hand the various isolated compounds may be secondarily
Coffee ranks as the second most valuable commodity in the world after used as value-added byproducts. The concept of fractionation of SCGs
petroleum and its derivatives (Tucker, 2011). Coffee beans originate follows the idea of a bio-refinery and fulfills the principles of a circular
from the coffee fruit and serve for the preparation of a popular bever- economy.
age. In 2015 coffee consumption worldwide reached approx. 9.1 billion
kilograms (International Coffee Organization, 2016). However, the treat-
ment and processing of coffee cherries, together with the milling of 2. Composition of SCG
dried beans, the roasting of green coffee beans and coffee brewing,
produce each year a large volume of biowaste, which contributes to Coffee spent grounds are natural composites, the composition
environmental pollution. The production of instant coffee and coffee of which depends on the type of coffee beans, the roast-
brewing generates worldwide approx. 6 million tons of spent coffee ing conditions and extraction process. The composition of
grounds (SCG) per year (Getachew and Chun, 2017). Recently, many
SCGs includes (1) an oil fraction (7.9–26.4%), (2) crude fiber
studies have focused on investigating SCGs’ composition and their sec-
(19.7–22.1%), and (3) different components such as alkaloids,
ondary applications. SCGs contain polysaccharides, oligosaccharides,
proteins, etc. (Corrêa et al., 2014; Acevedo et al., 2013).
lipids, aliphatic acids, amino acids, proteins, alkaloids (e.g., caffeine,
trigonelline) and phenolics, minerals, lignin, melanoidins and volatile
compounds (Mussatto et al. 2011; Pujol et al., 2013; Campos-Vega et al.,
2.1. Oil fraction
2015). Due to their composition, SCGs possess functional properties
such as water holding capacity (WHC ∼ 5.7 g water/g dry SCGs), oil hold-
ing capacity (OHC ∼ 5.2 g oil/g dry SCGs), emulsifing activity (54.7%), The oil derived from SCGs has the mild special coffee odor
emulsion stability (92.4%) and antioxidant potential (DPPH antioxi- and has an orange or chocolate brown color. The amounts
dant activity ∼20.0 mol TE/g dry SCGs) (Ballesteros et al., 2014). Along of lipids extractable from SCGs depend on the brewing and
with their functional properties, SCGs have been applied as adsorbers extraction method. Many polar solvents such as isopropanol,
(Castro et al., 2011) and as fillers and additives for polymer compos- ethanol, and acetone and nonpolar organic solvents such as
ites (Baek et al., 2013; Garcia-Garcia et al., 2015; Machado et al., 2010; hexane, n-pentane, toluene, chloroform, and petroleum ether
Moustafa et al., 2017a, 2017b; Wu et al., 2016; Zarrinbakhsh et al., 2016). have been tested for oil extraction. Extraction with polar sol-
Due to their high nutritional value, SCGs have been tested also as a
vents gave lower oil yields than extraction with non-polar
supplement in animal feed. However, it should be noted that pheno-
organic solvents such as hexane. The reason for this might
lic compounds and caffeine are unpalatable above a concentration of
be the competitive formation of fatty acids and carbohydrate
2.5% (Fuller, 2004; Janissen and Huynh, 2018). Among society today it is
popular to use SCGs as soil fertilizers (addition of minerals) in order to degradation products during extraction with polar solvents as
stimulate plant growth (Cruz et al., 2014b; Liu and Price, 2011; Ribeiro reported by Al-Hamamre et al. (2012), who gained an oil yield
et al., 2017). However, just as for animals, caffeine and phenolics are of 15.3% with an acid value of 7.3 mgKOH /g when the dried
toxic for plants and soil microorganisms. Gomes et al. (2013) reported SCGs were extracted with hexane for 30 min in the Soxhlet
that the composting of SCGs, before their application as fertilizer, extractor. The enhancing of the extraction time into hours and
reduced their toxicity to plants probably due to the reduced amounts of the application of a high liquid-to-solid ratio (250 mL of hex-
the phytotoxic compounds in SCGs. Recently, many works have pointed ane/2 g of SCG) facilitated obtaining even 26.4% of oil (Acevedo
out that the fractionation of SCGs may enlarge their applicability.
et al., 2013). Combination of n-hexane with isopropanol (50:50)
Namely, phenolic extractives isolated from SCGs can be used as antiox-
was also reported to be beneficial for extraction of a higher
idants (Mussatto et al., 2012a; Xu et al., 2015; Zuorro and Lavecchia,
amount of oil (Haile, 2014). Besides solvent extraction, also
2013), anti-inflammatory additives (Lopez-Barrera et al., 2016), derma-
tological anti-melanogenesis agents (Huang et al., 2016), and metal
extraction with supercritical CO2 can be used, which brings
scavengers (Liu et al., 2015; Serrano-Gomez et al., 2015; Tokimoto et al., certain advantages such as chemical inertness, no solvent
2005). Their oil fraction has been applied for the production of bio- residue, etc. (Ahangari and Sargolzaei, 2013; Couto et al., 2009;
fuels (Caetano et al., 2014; Haile, 2014; Kwon et al., 2013; Liu et al., de Melo et al., 2014). The composition of oil extracted from
2017; Park et al., 2016; Vardon et al., 2013), asphalt binder rejuvena- SCGs slightly differs from that of extracted from raw coffee
tors (Jalkh et al., 2017) and polyhydroxyalkanoates (Obruca et al., 2014b; beans, but generally coffee oil contains around 75% triacyl-
Cruz et al., 2014a). Carbohydrates present in SCGs are valuable car- glycerols, 14% terpene esters, 5% partial acylglycerols, 1% free
bon sources for biotechnological production of polyhydroxyalkanoates fatty acids, 1.5% free sterols, 1% sterol esters and 1% polar
(Obruca et al., 2015a, 2014a, 2014b), carotenoids (Petrik et al., 2014),
lipids (Nikolova-Damyanova et al., 1999). In addition to lipids,
and bioethanol (Kwon et al., 2013). Based on the current literature, it
coffee also contains volatile organic compounds such as ter-
is clear that the use of spent coffee grounds in “white biotechnology”
penes and terpenoids, which show antimicrobial activity (Di
is no gimmick, but the available amounts of SCGs are huge and novel
ways for creating value for them are needed. It is expected that new Pasqua et al., 2007). Moreover, diterpenes, namely kahweol
and improved biotechnological processes will bring an opportunity for (Arabica), cafestol and 16-O-methylcafestol (Robusta) possess
increased valuable utilization of SCG. Biotechnological processing of an anti-carcinogenic activity (Acevedo et al., 2013; Cavin et al.,
SCGs is usually based on the conversion of hemicelluloses and par- 2002). The antibacterial activity of coffee oil may be linked also
tially cellulose into fermentable sugars. However, this biotechnological with its content of free fatty acids (Knapp and Melly, 1986;
usage concept requires selective separation of carbohydrates by hydrol- McGaw et al., 2002). Huang et al. (2016) reported that the coffee
ysis, which deliberate also other components, e.g., phenolics, with a oil extracted from SCGs by supercritical extraction effectively
toxic influence on microorganisms. The concentration of the sugars
suppressed melanogenesis in B16F10 murine melanoma cells.
gained and deliberated inhibitors depends mainly on the conditions
The bioactive compounds present in coffee oil can be isolated
of hydrolysis (Obruca et al., 2015b). Therefore, this review includes
through various methods such as a solid-liquid extraction, a
the availability and sensitivity of various microorganisms utilizing fer-
mentable sugars derived from different lignocellulosic hydrolysates,
supercritical extraction, and direct saponification and the par-
including SCG hydrolysates, and offers a list of detoxification methods. ticular extraction method applied influences the composition
In addition, this review shows that isolation of bioactive compounds, of the extracted oil (Acevedo et al., 2013; Andrade et al., 2012;
which are toxic to biotechnologically relevant microorganisms, on one Akguen et al., 2014).
106 Food and Bioproducts Processing 1 1 0 ( 2 0 1 8 ) 104–119
2.2. Crude fiber and additional components perature) (Andrade et al., 2012; Pujol et al., 2013; Severini et al.,
2017; Xu et al., 2015; Zuorro and Lavecchia, 2013).
Crude fiber is the lignocellulosic fraction composed of Among the additional essential components present in
cellulose, hemicelluloses, and lignin, which are mutually SCGs are caffeine (0.4 mg/g) (Lopez-Barrera et al., 2016), pro-
interwoven. Compared to other lignocellulosic materials, teins (10% of SCGs on a dry weight basis), amino acids
SCGs contain only a relatively small amount of cellulose (about (Clarke, 2012), melanoidins, and minerals. Caffeine is a
10 wt%) and a high content of hemicelluloses (30–40 wt%). methylxanthine alkaloid, which stimulates the central ner-
Cellulose consists of between several hundred and over ten vous system. Amino acids and proteins are involved in
thousand d-anhydroglucose units, with three hydroxyl groups the formation of the flavor and color of brewed coffee
each, and joined by 1,4--d-glycosidic linkages at the C1 and (Homma, 2008; Clarke, 2012). Melanoidins are high-molecular-
C4 position. Cellulose molecules aggregate to microfibrils and weight brown-colored pigments formed through Maillard
form highly ordered (crystalline) or less ordered (amorphous) reaction during the roasting process (Moreira et al., 2012).
regions. The crystalline regions of cellulose impart stiffness Melanoidins contribute to the antioxidant, antimicrobial,
and the amorphous areas provide softness and flexibility and anti-cariogenic, anti-inflammatory, antiglycative and anti-
enable water absorption. hypertensive effects of brewed coffee. Moreira et al. (2012)
Hemicelluloses present in SCGs are mannans and arabino- reported that melanoidins can inhibit matrix metallopro-
galactans (Bradbury and Halliday, 1990; Campos-Vega et al., teases and they can modulate the bacterial population in the
2015; Tian et al., 2017). Mannans are composed of repeat- colon. Even SCG water extracts have been suggested as poten-
ing units of a mannose linked by -1,4-glycosidic linkages. tial new bioactive functional food ingredients due to their
Three types of arabinogalactans exist in SCGs, but predom- antimutagenic and antimicrobial activities against e.g. gram-
inant are arabino-3,6-galactans, which are covalently bound positive bacteria (Staphylococcus aureus, Listeria monocytogenes)
to proteins (Bradbury and Halliday, 1990). Hemicelluloses, due and yeast (Candida albicans) (Monente et al., 2015). In addition
to their amorphous structure and hydrophilic nature, have to organic compounds, SCGs contain a large variety of min-
a high mechanical sensitivity against water and are effort- erals such as K, Mg, P, Ca, Na, Fe, Mn, and Cu. The total ash
lessly hydrolysable compared to lignin and cellulose (Rowell, concentration ranges from 0.82 to 2.08 g per 100 g of dried SCGs
2012; Youssefian et al., 2017). The hemicellulose fraction of (Cruz et al., 2012).
SCGs can be extracted by means of superheated water extrac-
tion and used for various high-end applications, especially in 2.3. Valorization of spent coffee grounds without any
pharmaceuticals such as pre-biotic substances (Passos et al., fractionation
2014).
Lignin is a further polymer coupled with cellulose and The first viable way of valorizing SCGs that was announced
hemicellulose and acts as a stabilizer against mechanical was to apply it as a dietary additive for animal feed. Unfor-
and other internal/external biological stresses (Koshijima and tunately, non-modified SCGs suffer from a high content of
Watanabe, 2013). The portion of lignin found in green cof- phenolics and caffeine, which limits their digestibility (Cherry,
fee beans is about 3 wt% (Maia et al., 2013). However, some 1974; Sikka et al., 1985). The second, widespread use of SCGs is
works reported that the concentration of total lignin in SCGs their application as a composting additive in organic farming
was around 19.8–29.8% (Pujol et al., 2013; Kwon et al., 2013). (Ribeiro et al., 2017) due to the presence of minerals (Cruz et al.,
The differences may have been due to the different origin 2012; Cruz et al., 2014b; Ribeiro et al., 2017). Another notable
of the coffee beans used as well as the treatment applied. utilization of SCGs is their direct use as a fuel. The heating
Lignin is a three-dimensional amorphous natural polymer value of SCGs determined in a small boiler system (around
consisting of phenylpropane units with carbonyl, hydroxyl, 18.8 MJ/kg) can be compared to other agro-industrial residues
and methoxyl substitutions and it contributes to the high or softwoods (Kang et al., 2017). Kim et al. (2017) reported that
calorific value of SCGs (Limousy et al., 2013). For biotechnolog- a hydrothermal carbonization of SCGs produced biochar with
ical use of SCGs it is important to deliberate polysaccharides a content of 73.4% carbon and with a calorific value of approx.
and break them into fermentable sugars, usually through the 26–27 MJ/kg. Similarly, Vardon et al. (2013) applied slow pyroly-
hydrolysis process (chemical and enzymatic hydrolysis). It is sis to generate bio-oil and biochar from SCGs and reported an
worth noting that SCG hydrolysates, depending on the hydrol- elevated energy density of 31 MJ/kg. The option of producing
ysis process applied, contain a mixture of fermentable sugars biogas from SCGs has been tested by Girotto et al. (2017).
along with other admixtures such as phenolics, proteins and Besides the caloric value, SCGs have a unique microporous
melanoidins. The amount of phenolic compounds in SCGs has structure with a high surface area of about 300–1000 m2 /g and
been determined to be in the range of 4.6–9.9 mg/g of SCGs metal-chelating activity. Therefore, SCGs have been success-
or 16 to 173.3 GAE/g of SCGs (Acevedo et al., 2013; Lopez- fully applied for the adsorption of phenols and heavy metals
Barrera et al., 2016; Mussatto et al., 2012a). Table 1 shows (Castro et al., 2011; Davila-Guzman et al., 2013; Liu et al., 2015).
phenolics detected in SCG. Phenolics can be extracted from Davila-Guzman et al. (2013) reported a 3-fold higher copper
SCGs by using polar or intermediately polar solvents, such ion adsorption capacity of SCGs compared to the adsorption
as ethanol or methanol mixed with deionized water. SCGs capacity of activated carbon. The ion-exchange of copper ions
phenolics are bioactive agents with an appreciable radical- with calcium and hydrogen ions has been connected with
scavenging, oxygen radical absorbance capacity, antitumor, the presence of carboxyl and hydroxyl groups (Davila-Guzman
anti-inflammatory, and anti-allergenic properties (Acevedo et al., 2013). Similarly, Liu et al. (2015) confirmed a connec-
et al., 2013; Lopez-Barrera et al., 2016; Monente et al., 2015; tion between the occurrences of oxygen functional groups in
Murthy and Naidu, 2012; Panusa et al., 2013; Ramalakshmi SCGs with metal sorption. Furthermore, the active element
et al., 2009). The amount of phenolics extracted depends on important for the metal-chelating activity of SCGs has been
the extraction method applied and the extraction conditions identified as the melanoidin-like polymer formed through the
(solvent type, SCGs solid/solvent ratio, exposure time and tem- roasting process due to the decomposition and polymeriza-
Food and Bioproducts Processing 1 1 0 ( 2 0 1 8 ) 104–119 107
Chlorogenic acid 0.3–41.3 Andrade et al. (2012) 1.8–5.6 Lopez-Barrera et al. (2016)
Catechin, Epicatechin 0.3 Andrade et al. (2012) 0.3–0.6 Lopez-Barrera et al. (2016)
Caffeic acid 0.1 Andrade et al. (2012) 0.03–0.07 Lopez-Barrera et al. (2016)
Gallic acid 14.3 Andrade et al. (2012) 1.3–2.5 Lopez-Barrera et al. (2016)
nd — not determined.
tion of sugars, amino acids, and phenolics (Takenaka et al., with a high specific surface area of 1945.7 m2 /g. Moreover,
2005). Various modifications have been applied to enhance SCGs have also been examined as a cheap filler for polymers.
the adsorption ability of SCGs. Dai et al. (2016) increased However, non-modified SCGs is interfacially incompatible
the adsorption capacity of SCGs for nitrobenzene by alkaline with hydrophobic polymers and their use as a filler for poly-
modification. Serrano-Gomez et al. (2015) modified SCGs by mers requires physical and chemical modification. Wu et al.
mixing with ammonium nitrate and urea by using an aqueous (2016) reported an improved interfacial compatibility of defat-
solution combustion process at 800 ◦ C and prepared material ted SCGs with polypropylene (PP) compared to non-treated
with a surface area of 390.8 m2 /g. An adsorbent thus prepared SCGs with PP. Garcia-Garcia et al. (2015) improved the mechan-
showed a sorption capacity of 17.3 mg/g and 23.25 mg/g for ical performance of a PP/SCGs composite by hydrophobization
cobalt and cadmium adsorption, respectively (Serrano-Gomez of SCGs with palmitoyl chloride. Thiagamani et al. (2017)
et al., 2015). Ramasahayam et al. (2015a, 2015b) applied a modified SCGs by alkali treatment and used them as a rein-
microwave-assisted technique for the synthesis of phospho- forcement for cellulose films. Baek et al. (2013) improved
rous, nitrogen co-doped carbon from SCGs and ammonium the interfacial compatibility between poly(lactic acid), SCGs
polyphosphate. The synthesized product was a highly porous and bamboo flour with the addition of an isocyanate cou-
material with a surface area ranging from 506.9 m2 /g to pling agent. Moustafa et al. (2017a) noted that the addition
999.6 m2 /g. SCGs have also been suggested as a material of poly(ethylene glycol) improved the homogeneity and dis-
suitable for the production of electrode material used for persion of SCGs in poly(butylene adipate-co-terephthalate)
long-term practical fuel cells and supercapacitors. Wang et al. (PBAT). Moustafa et al. (2017b) further showed that torrefied
(2016a) enlarged the surface area of SCGs to 1622 m2 /g by KOH SCG powder is much more compatible with PBAT compared to
activation. KOH-activated SCGs treated with polyvinylidene conventional SCG powder. SCGs were found to be an additive
chloride enabled preparing an electrode with a specific capac- material also for construction materials. Muñoz Velasco et al.
itance of 175 F/g at 1 A/g and 475 F/g at 0.1 A/g. Similarly, Yun (2016) presented the preparation of bricks with reduced ther-
et al. (2015) modified SCGs using KOH and a carbonization pro- mal conductivity due to the addition of SCGs. Kua et al. (2017)
cess and fabricated hierarchically porous carbon nanosheets prepared green construction material based on SCGs, fly ash
108 Food and Bioproducts Processing 1 1 0 ( 2 0 1 8 ) 104–119
Table 2 – Extraction of different phenolic materials from SCGs (GAE — gallic acid equivalents; CGA — chlorogenic acid).
Method Solvent Type of SCGs Extractives Yield of extracts Source
Direct saponification 50% KOH in 95% ethanol Dried SCGs Diterpenes 2.14 mg kahweol/g Acevedo et al. (2013)
4.67 mg cafestol/g
Successive Ethanol:water (50:50) Dried SCGs Phenolics 273.34 mg GAE/g Acevedo et al. (2013)
extraction in Soxhlet Defatted SCGs 255.61 mg GAE/g
extractor Isopropanol:water (60:40) Dried SCGs Phenolics 11.7% (w/w) Murthy and Naidu
(2012)
Dichloromethane Dried SCGs Not specified 19.67% (w/w) Pujol et al. (2013)
Ethanol Dried SCGs Not specified 5.36% (w/w) Pujol et al. (2013)
Water Dried SCGs Not specified 1.30% (w/w) Pujol et al. (2013)
Liquid-solid Ethanol:water (60:40) Dried SCGs Phenolics 11.83–28.26 mg GAE/g Panusa et al. (2013)
extraction at CGA 30.2–51.6 mg CGA eq/g Burniol-Figols et al.
60–70 ◦ C (2016)
Water Dried SCGs Phenolics 6.33–19.62 mg GAE/g Panusa et al. (2013)
Subcritical water Water Dried SCGs Phenolics 47.25 mg GAE/g Xu et al. (2015)
extraction 26.64 mg GAE/g Mayanga-Torres
et al. (2017)
Defatted SCGs 55.31 mg GAE/g Mayanga-Torres
et al. (2017)
Autohydrolysis in Water Dried SCGs Phenolics 28.26 mg GAE/g Ballesteros et al.
cylindrical stainless (2017b)
steel reactor at
200 ◦ C
Ultrasound-assisted Methanol:water (50:50) Dried SCGs Phenolics 22.32–24.32 mg GAE/g Severini et al. (2017)
extraction
Hydrothermal Water Dried SCGs Phenolics 32.92 mg GAE/g Conde and Mussatto
treatment in (2016)
autoclave at 120 ◦ C
(a waste product of coal combustion in power plants), and slag lics and extractives can be kept direct in extraction solution or
(waste generated from iron-ore refineries). in dried form, while the storage stability of dried compounds
can be prolonged by an encapsulation process (Ballesteros
et al., 2017a).
3. Fractionation, extraction and
valorization of SCGs’ components 3.2. Valorization of coffee oil fractions
3.1. Characterization, isolation, and application of As was already mentioned, the major lipid classes found in
minor biologically active constituents present in SCGs SCGs are triglycerides, diterpene alcohol esters and fatty acids
(Ratnayake et al., 1993). Coffee oil has numerous desirable
Among the compounds with various degrees of bioactivity characteristics such as high antioxidant status, presence of
that are present in SCGs, mainly diterpene alcohol esters UVB protectors, etc. which make this fraction very attrac-
and phenolics can be mentioned. The yield of bioactive com- tive for direct applications in cosmetics. Ribeiro et al. (2013)
pounds extracted from SCGs depends on the coffee species, tested coffee oil extracted from SCGs by means of super-
storage conditions, and the extraction method, but usually critical extraction as an additive for cosmetic formulations
polar or intermediately polar solvents are used (see Table 2). with improved skin sebum and hydration properties. Coffee
Diterpene alcohol esters occur in the form of free molecules oil isolated from SCGs was also suggested as an inexpensive
or non-aromatic glycosylated precursors and can be iso- component for the preparation of sunscreen fraction (Marto
lated from the lipid fraction of SCGs. Among the most et al., 2016). Similarly, Choi et al. (2016) reported the protec-
investigated are kahweol and cafestol with anti-carcinogenic, tive activity of the oil and ethanol fractions derived from SCGs
anti-inflammatory, antioxidant and UVB protection proper- against harmful effects of ultraviolet irradiation. In addition
ties (Cavin et al., 2002). Direct saponification was found to to the high-value applications, oil extracted from SCGs has
be an effective method for extraction of kahweol and cafestol also been considered for low-end applications such as asphalt
(Acevedo et al., 2013; Dias et al., 2009). binder rejuvenators (Jalkh et al., 2016; Jalkh et al., 2017).
The phenolic compounds present in SCGs are from the Moreover, coffee oil can be converted into biodiesel through
polyphenol family of esters (caffeic acid, ferulic acid, p- direct transesterification into fatty acid methyl and ethyl
coumaric acid, chlorogenic acid) and possess antioxidant, esters (FAME) with short-chain alcohols (mainly methanol)
antibacterial, hepatoprotective, hypoglycemic, anticancer and (Abdullah and Koc, 2013). The efficiency of coffee oil’s
antiviral activity (Andrade et al., 2012; Burgos-Moroń et al., conversion into FAME corresponds with the applied transes-
2012). Further active polyphenols present in SCGs are con- terification method. The high level of free fatty acids present
densed and hydrolyzable tannins (Low et al., 2015). in oil extracted from SCGs influences the transesterification
The bioactive substances isolated from SCGs have poten- process because they tend to form significant amounts of
tial uses in the pharmaceutical, cosmetic and food industries unwanted soap byproducts during the alkali-catalyzed trans-
(Cruz et al., 2012; Huang et al., 2016). Kim et al. (2016) suggested esterification process, which promotes the formation of stable
that the high antioxidant capacity of SCG ethanol extract can emulsions. The presence of free fatty acids increases the vis-
be used for protection of raw or cooked meat. Isolated pheno- cosity of the reactant mixture and creates severe problems
Food and Bioproducts Processing 1 1 0 ( 2 0 1 8 ) 104–119 109
a
Liquid to solid ratio.
b
Yield of sugar in mg on 1 g of SCG.
during biodiesel separation from glycerol during processing, tion of coffee oil influences biomass and polymer production.
ultimately lowering the yield substantially (Al-Hamamre et al., As a decisive factor in supporting bacterial growth and PHA
2012; Sharma et al., 2008). This disadvantage may be par- production, the content of free fatty acids present in the oil
tially overcome by using acid-catalyzed transesterification, has been suggested (Obruca et al., 2014b).
but nevertheless the high free fatty acid content influences
the physical properties of the oil since it enhances the kine-
matic viscosities of the oil. The high viscosity of the oil leads 3.3. Valorization of carbohydrates
to high power consumption (Meher et al., 2006). Calixto et al.
(2011) successfully converted SCG oil to FAME in supercrit- The concentration and composition of polysaccharides in
ical methanol and CO2 with a yield of 93.4%. Similarly, an spent coffee grounds depend mainly on the natural source
increased oil conversion of 99% was reported after a two-step of coffee, fruit growing conditions, and roasting conditions
transesterification process consisting of an acid-catalyzed (Oosterveld et al., 2003). One of the biopolymers which can be
pre-treatment and alkali-catalyzed transesterification (Al- isolated from SCGs is cellulose, but its concentration is negligi-
Hamamre et al., 2012). Recently, direct transesterification ble, reaching around 5–12 wt%. Much preferable is the isolation
of SCGs without previous isolation of the oil fraction was of hemicelluloses from SCGs due to their much higher con-
reported as a method for achieving biodiesel yields of 77% tent (about 40 wt%). Galactomannans predominantly present
(Tuntiwiwattanapun et al., 2017). in SCGs have been found to have valuable applications in cos-
Finally, numerous microorganisms can utilize coffee oil metics and healthcare (Passos et al., 2014; Tian et al., 2017).
as a carbon source for the production of valuable products. Often the methodologies applied for separation of hemicellu-
In this concept, bacterial polyesters polyhydroxyalkanoates loses are dilute acid hydrolysis, subcritical water hydrolysis,
(PHA), which are considered to be a biodegradable and bio- or enzymatic hydrolysis, giving hydrolysates with a content
compatible alternative to petrochemical plastics, are the most of fermentable sugars in the range from 0.192 mg/g SCGs up
widely mentioned biotechnological product. Hence, biotech- to 521.6 mg/g SCG (Rocha et al., 2014; Wang et al., 2016b).
nological conversion of SCG oil into PHA was performed using SCG hydrolysates contain a mixture of fermentable sugars
fed-batch cultivation in a 2 L bioreactor, utilizing 20 g/L of SCG composed of mannose, galactose, glucose, arabinose, and cel-
oil as a sole carbon source employing the bacterium Cupri- lobiose (Obruca et al., 2014a). The total concentration of sugars
avidus necator H16. Such a process provided 16.7 g/L of biomass in hydrolysates corresponds with the efficiency of the hydrol-
with a 78.4% content of poly-3-hydroxybutyrate (P3HB) (Cruz ysis method applied. Issues such as the origin of SCGs (the
et al., 2014a). Similarly, Obruca et al. (2014b) applied fed-batch type of coffee, roasting, brewing), pretreatment of SCGs (pre-
cultivation of C. necator H16 by using SCG oil and reported extraction of the oil fraction and phenolics), conditions used
55.4 g/L of biomass and 89.1% of P3HB. The varying composi- for dilute acid hydrolysis and application of enzymatic post-
treatment influence the final concentration of fermentable
110 Food and Bioproducts Processing 1 1 0 ( 2 0 1 8 ) 104–119
sugars present in SCG hydrolysates (see Table 3). Dilute acid production bacteria preferring one substrate, such as glu-
hydrolysis of SCGs is often carried out under high pressure cose. Therefore, other types of sugars in hydrolysate remain
and with the addition of diluted sulfuric acid or hydrochloric unused. This problem is usually associated with pentose-rich
acid (0.5–5 wt%), at a temperature range of 95–180 ◦ C and for hydrolysates. During fed-batch cultivation, pentoses remain
1–4 h. The influence that the solvent–solid ratio used has on unused and accumulate in cultivation media, potentially
the concentration of sugars was reported to be negligible com- reaching limiting concentrations (Stülke and Hillen, 1999). The
pared to other conditions such as reaction temperature, acid advantage of SCG hydrolysates is their low pentose content.
concentration, and hydrolysis time (Go et al., 2017; Mussatto Therefore, the risk of carbon catabolite repression is limited.
et al., 2011). Go et al. (2017) presented an optimization of the Table 4 shows a list of published bacterial strains capable of
hydrolysis conditions by using the Taguchi statistical method. metabolizing the mixture of sugars present in various lignocel-
The optimized hydrolysate with a sugar content of 40 g/L lulose hydrolysates. Burkholderia cepacia (Obruca et al. 2014a),
was obtained by hydrolysis with 4% sulfuric acid, a liquid- Bacillus megaterium (Obruca et al., 2015a), and Halomonas
solid ratio of 8 mL/g, for 3 h and at 95 ◦ C (Go et al., 2017). halophila (Kovalcik et al., 2018) are PHA-accumulating strains
Concerning other hydrolysis methods, e.g. subcritical water reported to utilize the fermentable sugars present in SCGs
hydrolysis (held between 100 ◦ C and 374 ◦ C), it must be noted hydrolysates. Utilization of B. cepacia resulted in the highest
that temperatures above 150 ◦ C have a destructive effect on PHA yields and, moreover, this bacterial strain was capable
SCGs and increase the concentration of 5-HMF, furfural and of accumulating the copolymer poly(3-hydroxybutyrate-co-
organic acids (microbial inhibitors) (Mayanga-Torres et al., 3-hydroxyvalerate) [P(HB-co-HV)]. It was proposed that the
2017). Therefore, the temperature should be carefully selected levulinic acid present in the hydrolysate of spent coffee
to regulate the composition of hydrolysates. The content of grounds served as the precursor of 3-hydroxyvalerate for
fermentable sugars in SCG hydrolysate can be increased by copolymer biosynthesis by B. cepacia (Obruca et al., 2014a).
combining dilute acid hydrolysis with enzymatic digestion The hydrolysate of the carbohydrate fraction of SCGs was
(Obruca et al., 2014a; Wang et al., 2016b). Various cellulolytic recently utilized for biotechnological production of lactic acid;
and hemicellulolytic microorganisms have been applied for the highest yields were achieved employing Lactobacillus rham-
enzymatic hydrolysis of SCGs and among the most efficient nosus CCM 1825 and lactic acid titers reached 25.69 g/L, which
enzymes are mannanases (Jooste et al., 2013). Unfortunately, represented a 98% conversion rate of sugars into lactic acid
the use of enzymatic hydrolysis raises cost expenditures. (Hudeckova et al., 2018). Concerning further biotechnologi-
It is believed that the careful adjustment of process condi- cal production, the sugars present in hydrolysates of SCGs
tions may eliminate the financial disadvantages. Chiyanzy can be used for the fermentation of yeast. Various species of
et al. (2015) reported an increased efficiency of hydrolysis yeasts have been used for ethanol fermentation, but the most-
by the combination of mannanase and cellulase along with used yeast was Saccharomyces cerevisiae, probably due to its
the steam explosion pretreatment of SCGs. Furthermore, the ability to consume mono- and disaccharides (Lagunas, 1993).
effectiveness of chemical as well as enzymatic hydrolysis can Similarly, Mussatto et al. (2012b) reported that in a compari-
be enhanced by the mechanical pre-treatment of SCG mate- son of the efficiency of Saccharomyces cerevisiae, Pichia stipitis,
rial before hydrolysis (e.g., ball-milling, ultrasound) (Ravindran and Kluyveromyces fragilis to utilize SCGs acid hydrolysates,
et al., 2017; Rocha et al., 2014). the most useful yeast strains were S. cerevisiae. Kwon et al.
As it is known, lignocellulosic waste hydrolysates, includ- (2013) also fermented S. cerevisiae by using SCG hydrolysates
ing SCG hydrolysates, may serve as inexpensive renewable and reached a high content of sugars in hydrolase by applica-
carbon substrates for the production of numerous micro- tion of the combination of acid and enzyme hydrolysis from
bial products such as PHA. However, each hydrolysis method the defatted SCGs, and produced ethanol in yields of 0.46 g/g
gives a different amount of total reducing sugars present in for the hydrolysate. Pre-extraction of the oil fraction from
hydrolysate (Sampaio et al., 2013). Ballesteros et al. (2015) SCGs has been found to be an effective method for produc-
determined 39 g of sugars in 100 g SCGs extracted by alkali ing biodiesel and bioethanol, respectively (Rocha et al., 2014).
pretreatment and the composition of sugars was as follows: Recently, Burniol-Figols et al. (2016) in their work reached,
15.37 mol% of glucose, 19.93 mol% of arabinose, 4.43 mol% of through the optimization of hydrolysis conditions and the
mannose, and 60.27 mol% of galactose. Interestingly, Burniol- application of pre-extractions, up to 95.38 g/L of fermentable
Figols et al. (2016) obtained 50.1 g of sugars from 100 g of SCGs sugars in hydrolysate and produced ethanol in a concentration
treated by acid hydrolysis and determined a slightly different of 39 g/L.
composition of sugars, namely 17.5% glucose, 57% mannose, SCG hydrolysates have been found to be valuable also for
20% galactose and 5% arabinose. Next, Obruca et al. (2014a) carotenogenic yeasts such as Rhodotorula glutinis, Cystofiloba-
derived 50.1 g sugars from 150 g SCGs by acid hydrolysis and sidium capitatum, Rhodotorula mucilaginosa, and Sporobolomyces
enzymatic digestion of defatted SCGs and determined 47.1% roseus (Obruca et al., 2015a). Petrik et al. (2014) reported that the
mannose, 34.5% galactose, 7.8% glucose, 5.6% arabinose, and extraction of oil from SCGs supported to receive higher quan-
5.4% cellobiose. The composition of other lignocellulosic (LC) tity of biotechnological produced carotenoids and -carotene
hydrolysates, for example, derived from wood are very similar; (29.9 mg/L and 15.6 mg/L, respectively) compared to the non-
the difference is only in the presence of xylose. It is impor- extracted SCGs.
tant to note that the use of SCG hydrolysates, which contain
a mixture of pentoses (arabinose), hexoses (mannose, galac- 3.4. Inhibitors of microbial growth and their
tose, and glucose) and disaccharide (cellobiose) require proper elimination
selection of bacterial strains capable of utilizing this mixture of
sugars. The limiting factor in the utilization of LC hydrolysates In addition to fermentable sugars, SCG hydrolysates contain
is the existence of a regulatory mechanism known as car- also other compounds, which can be toxic to fermented bac-
bon catabolite repression. This mechanism is responsible for teria and yeasts. Fig. 1 shows a list of the co-contaminants
that are often present and recognized as inhibitors for
Table 4 – List of PHA producing strains metabolizing fermentable sugars present in lignocellulosic hydrolysates.
Strains Lignocellulosic Hydrolysis Enzymatic CDW PHA Detoxification Cultivation Source
substrate treatment (g/L) (%)
Azotobacter Coir pitch Enzymatic Yes 5.0 48.0 No Shake flask cultures Sathesh Prabu and
beijerinickii hydrolysis Murugesan (2010)
Bacillus firmus Rice straw Acid hydrolysis No 1.9 89.0 No Shake flask cultures Sindhu et al. (2013)
Bacillus megaterium Oil palm empty fruit Enzymatic Yes 24.2 51.6 No Shake flask cultures Zhang et al. (2013)
bunch hydrolysis
Bacillus mycoides Rice husk Acid hydrolysis No 47.0 14.9 No Shake flask cultures Narayanan et al.
(2014)
111
112
– Table 4 (Continued)
Strains Lignocellulosic Hydrolysis Enzymatic CDW PHA Detoxification Cultivation Source
substrate treatment (g/L) (%)
Cupriavidus necator Pulp fibre Enzymatic Yes 8.8 31.9 No Shake flask cultures Zhang et al. (2004)
hydrolysis
microbial growth. The substances which can be toxic to many microorganisms through chemical interference with
fermented bacteria are mainly: (1) phenolics and alkaloids cell maintenance functions (Maiorella et al., 1983). Furfural
(naturally present in SCG), (2) compounds formed during and hydroxymethyl–furfural influence the electron trans-
the roasting process and (3) compounds formed during port chain in the mitochondria, lower the growth rate of
thermal degradation of carbohydrates (e.g. acetic acid, fur- some microorganisms, and therefore lower their fermenta-
fural, and hydroxymethylfurfural). The decomposition of tion ability (Chung and Lee, 1985; Weigert et al., 1988). The
reducing sugars increases rapidly with the increase of the sensitivity of microorganisms capable of using lignocellulosic
hydrolysis temperature applied (Mayanga-Torres et al., 2017). hydrolysates varies. Dietrich et al. (2013) reported a significant
The reasons for the toxicity of individual co-contaminants variation in the sensitivity of several PHA-producing bacteria
in hydrolysates vary. Phenolic substances, alkaloids and such as Azohydromonas lata, Bacillus megaterium, Bacillus cereus,
melanoidins mostly inhibit the growth of microorganisms Burkholderia cepacia, Pseudomonas olevorans, Pseudomonas pseud-
(Gregorova, 2016; Parajo et al., 1997; Almeida et al., 2006; oflava and Cupriavidus necator against the presence of acetic
Daglia et al., 2007). Acetic acid inhibits fermentation of acid, levulinic acid, coumaric acid, ferulic acid, syringalde-
114 Food and Bioproducts Processing 1 1 0 ( 2 0 1 8 ) 104–119
hyde, furfural, and hydroxymethylfurfural, while B. cepacia and processes including the processing and use of spent coffee
P. pseudoflava were recognized as the most resistant bacteria grounds is highly desirable.
able to produce PHA by utilizing LC hydrolysates. One way Spent coffee grounds due to their composition have a high
to decrease the concentration of toxic co-contaminants in LC potential for reuse as a renewable source of lipids, phenolic
hydrolysates is to apply one of the detoxification methods. bioactive compounds, and carbohydrates for the production
Fig. 2 shows the main principles and detoxification methods of many value-added products. The advantage is that SCGs
used for the elimination of phenolic compounds and products do not compete with food products and they are generated in
of sugar breakdowns from LC hydrolysates. Phenolic com- volumes industrially and economically acceptable enough to
pounds can be extracted from SCGs before the hydrolysis start thinking about their secondary reuse. SCGs can be reused
(Mussatto et al., 2012a; Zuorro and Lavecchia, 2012) or their directly with only minor modifications such as composting
presence in hydrolysates can be eliminated by the applica- additives for organic farming, or as adsorption materials for
tion of post-treatment detoxification methods (Obruca et al., phenols and metal ions. Furthermore, SCGs have a relatively
2014a). An efficiency of the detoxification step on the elim- high caloric value, which can be exploited through combus-
ination of inhibitors as well as a final effect on the bacterial tion as fuel. Surface-treated SCGs or SCGs modified with
fermentation has different effectivity on the growing of bacte- additives can also be used as a filler for non-biodegradable
ria (Guo et al., 2013). One of the reasons for this may be a drop and biodegradable polymers. Although direct utilization of
in sugar concentration due to the detoxification treatment SCGs can be seen as one of the economically advantageous
(e.g. overliming, alkali treatment with NH4 OH, and adsorp- paths, the composition of SCGs enables sophisticated uses
tion by ion-exchange resins). Another reason may be induction that follow the principles of a circular economy. The raw
of osmotic stress after alkali treatments. In some cases, the SCG powder contains oil, cellulose, hemicelluloses, pheno-
extraction of potential microbial inhibitors (e.g. phenolics) is lic compounds, proteins, melanoidins, and minerals. This
more preferable than a post-hydrolysis detoxification step due work shows various possibilities for the reuse of individual
to the stable concentration of fermentable sugars (Burniol- fractions derived from SCGs employing current concepts of
Figols et al., 2016). Moreover, the pre-extracted phenolics can biorefineries and the circular economy. Fractionation of SCGs
be used as a high-value side product (Obruca et al., 2014a). is a concept bringing opportunities for secondary uses of the
Briefly, fractionation of SCGs may not only lower the amount oil fraction, diterpenes, phenolic compounds, and carbohy-
of co-contaminants in SCG hydrolysates but may also support drates as well as rest crude materials. All these compounds
the production of numerous valuable products and thus con- can be used for different applications, or they can be chemi-
tribute to the economic valorization of spent coffee grounds cally or even biotechnologically converted into other valuable
(see Fig. 3). products, such as antioxidants, biodiesel, and polymers.
This work discusses the composition of SCGs, the
extraction methods applied for the derivation of bioac-
4. Conclusions
tive compounds present in SCGs, use of bioactive com-
pounds, derivation of sugars through hydrolysis, use of SCG
Coffee is one of the most popular beverages in the world,
hydrolysates in biotechnology, and reviews the detoxifica-
and therefore a huge amount of solid waste known as spent
tion methods focused on lowering the amount of toxic
coffee grounds is perpetually generated. SCGs are a waste
co-contaminants present in SCG hydrolysates. Many different
material containing a large amount of organic and inorganic
means of SCG valorization have been considered in the litera-
compounds, and these compounds can be utilized as valu-
ture. However, published works have mainly been focused on
able byproducts in many industrial sectors. The present study
a single theme. Future investigations should pay more atten-
summarizes a few possible ways of valorization of spent coffee
tion not only to the thorough collection of SCGs but also on
grounds, a waste product of the coffee production/industry.
the fractionation of SCGs and purification of products, e.g.
Concerning the position of coffee industry on world markets
detoxification of hydrolysates. Such fractionation and purifi-
and the amount of waste produced (which is furthermore
cation may be a way to produce a much more significant scale
constantly growing), we can note that the development of
Food and Bioproducts Processing 1 1 0 ( 2 0 1 8 ) 104–119 115
of value-added products in economically acceptable and effi- Ballesteros, L.F., Teixeira, J.A., Mussatto, S.I., 2014. Chemical,
cient ways, which may be attractive not only to society but functional, and structural properties of spent coffee grounds
also industry. The current trend of recent years has aimed and coffee silverskin. Food Bioprocess. Technol. 7, 3493–3503.
Ballesteros, L.F., Cerqueira, M.A., Teixeira, J.A., Mussatto, S.I.,
at a “zero waste economy” and this trend should continue.
2015. Characterization of polysaccharides extracted from
One can expect that research focused on the investigation spent coffee grounds by alkali pretreatment. Carbohydr.
and utilization of SCGs will support activities to develop new Polym. 127, 347–354.
technologies contributing to the circular economy and avoid- Ballesteros, L.F., Ramirez, M.J., Orrego, C.E., Teixeira, J.A.,
ance or minimization of waste production. Currently, when Mussatto, S.I., 2017a. Encapsulation of antioxidant phenolic
many concerns have arisen about the consequences of deple- compounds extracted from spent coffee grounds by
tion of natural resources, the large availability of SCGs should freeze-drying and spray-drying using different coating
materials. Food Chem. 237, 623–631.
be accepted and utilized wisely as a “value-added product”. In
Ballesteros, L.F., Ramirez, M.J., Orrego, C.E., Teixeira, J.A.,
addition, as the final step, the necessity of modifying current Mussatto, S.I., 2017b. Optimization of autohydrolysis
industrial technologies and acceptance of waste materials as conditions to extract antioxidant phenolic compounds from
a valuable source of organic and inorganic substances should spent coffee grounds. J. Food Eng. 199, 1–8.
be incorporated into new scientific projects and research. Bertrand, J.L., Ramsay, B.A., Chavarie, C., 1990. Biosynthesis of
poly--hydroxyalkanoates from pentoses by Pseudomonas
pseudoflava. Appl. Environ. Microbiol. 56, 3133–3138.
Conflict of interest Bowers, T., Vaidya, A., Smith, D.A., Lloyd-Jones, G., 2014. Softwood
hydrolysate as a carbon source for polyhydroxyalkanoate
There are no conflicts to declare. production. J. Chem. Technol. Biotechnol. 89, 1030–1037.
Bradbury, A.G.W., Halliday, D.J., 1990. Chemical structures of green
coffee bean polysaccharides. J. Agric. Food Chem. 38, 389–392.
Acknowledgements Burgos-Moroń, E., Calderoń-Montan˜o, J.M., Orta, M.L., Pastor, N.,
Peŕez-Guerrero, C.N., Austin, C., Mateos, S., Loṕez-Laźaro, M.,
This work was funded through the project SoMoPro (project 2012. The coffee constituent chlorogenic acid induces cellular
DNA damage and formation of topoisomerase I- and II-DNA
No. 6SA18032). This project has received funding from the
complexes in cells. J. Agric. Food Chem. 60, 7384–7391.
European Union’s Horizon 2020 research and innovation Burniol-Figols, A., Cenian, K., Skiadas, I.V., Gavala, H.N., 2016.
programme under the Marie Skłodowska-Curie, and it is co- Integration of chlorogenic acid recovery and bioethanol
financed by the South Moravian Region under grant agreement production from spent coffee grounds. Biochem. Eng. J. 116,
No. 665860. This work was also supported by the project 54–64.
“Materials Research Centre at FCH BUT – Sustainability and Caetano, N.S., Silva, V.F.M., Melo, A.C., Martins, A.A., Mata, T.M.,
2014. Spent coffee grounds for biodiesel production and other
Development” No. LO1211 of the Ministry of Education, Youth
applications. Clean Technol. Environ. Policy 16, 1423–1430.
and Sports of the Czech Republic
Calixto, F., Fernandes, J., Couto, R., Hernandez, E.J.,
Authors confirm that the content of this work reflects only Najdanovic-Visak, V., Simoes, P.C., 2011. Synthesis of fatty
the author’s view and that the EU is not responsible for any acid methyl esters via direct transesterification with
use that may be made of the information it contains. methanol/carbon dioxide mixtures from spent coffee grounds
feedstock. Green Chem. 13, 1196–1202.
Campos-Vega, R., Loarca-Pina, G., Vergara-Castaneda, H.A.,
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