Secondary Metabolites
Aroma
Aroma
The jasmine odour scents the morning air,
The busy bees are ransacking the flowers;-
This is the first reward of all our care.
May Heaven protect us now from the thunder-showers
To dash the blossom, leaving branches bare-
Marring our hopes; may better luck be ours,
And weather neither over-dry nor wet,
But softly moist, to make the blossom set!
The relationship between the passage above and the quality of roasted coffee may only be immediately clear to a small number of individuals within the coffee community. This is because topics like the one we are about to discuss are often seen as too abstract for research. However, understanding the relationship between the scent of a coffee blossom and the aroma in roasted coffee is no more abstract than grasping how a person's childhood experiences can shape their adult behaviour [1]. While other scientific fields readily accept these relationships, some within the coffee science community fail to recognize the importance of understanding them and are often hesitant to explore such links. This reluctance means that this field of research remains rich with opportunities for further exploration, growth and as an emerging area of study and innovation. Allow me to convince you of its potential.
[1] The cognitive biases and multi-sensory experiences encountered during cupping serve as a great example of this concept. Your past experiences shape your perceptions, such as associating colours with specific flavours or defining the taste of a banana. However, it's important to remember that not everyone shares the same experiences or associations. Despite this, cultural and regional backgrounds often lead to similar cognitive imprints. For instance, if you grew up in North America and only had artificially ripened tropical fruit, your perception of a banana's taste may differ substantially from someone who has only consumed naturally ripened bananas. They might even inquire about the specific variety you're referring to, underscoring how divergent these experiences have been.
The delightful scent of jasmine that fragrances the coffee fields as they blossom are a part of a group of compounds known as secondary plant metabolites. We will primarily concern ourselves with those that are volatile. Secondary metabolites do not contribute to the essential functions of the plant, e.g. photosynthesis, respiration or cell division amongst others (Bhatla, 2018). Instead secondary metabolites play critical roles in a (coffee) plant’s reproductive success and overall longevity by,
Attracting bees to pollinate coffee flowers, resulting in the conception of our beloved coffee cherries.
Enticing animals to disperse the seeds of ripe coffee cherries.
Protecting coffee seeds, beans, from insects and pathogens [2].
Secondary metabolites, for instance monoterpenes, which attract us with their scent, are toxic to a variety of organisms, including certain insects, microbes and even humans at the right dose [3]. This is likely why these compounds are naturally engineered to be volatile, allowing them to escape quickly from the plant’s tissue without causing it harm, as they are often also phytotoxic – toxic to the plant.
Despite these inherent roles, plants, including coffee cherries, do not need to be in a constant state of alert, trying to entice bees to pollinate their flowers or disseminate their seeds. Instead, research suggests that plants can regulate the production and release of these compounds in response to both living (organisms) and non-living (environmental) stressors. The impact of climate stress will be briefly discussed in a later section, exploring how its potential to uniquely influence cup characteristics may be contributing to the concept of terroir within the coffee industry.
Regulating the production of these secondary metabolites is key as trying to attract herbivores or birds to spread coffee seeds while the cherries are green would be nonsensical, as the beans have yet to mature to a point where they can survive on their own, away from the plant. Hence, recent findings () indicating that these compounds are produced and stored during the ripening of the fruit’s mesocarp, align with their biological role [4]. In other words as the coffee cherry matures its need for self-defence and ability to attract animals to disseminate its grain grows, enabling it to gain its independence.
[2] Actually these compounds don’t only protect the fruit, but also the leaves, roots and other anatomical structures of the plant. These compounds work somewhat like our immune system.
If you are wondering whether this means these compounds are toxic, the truth is that every molecule is at the right dose.
[3] The dose makes the poison.
[4] This should not be confused with cafestol and kahweol, which are non-volatile diterpenes occasionally esterified to fatty acids – known to be bitter. These compounds are formed and accumulated in the perisperm (maternal tissue) before the perisperm is transformation into the endosperm later in cherry development (Filipe et al., 2015). The cherry in both of these phases would still appear unripe, i.e., green. Therefore, what we are discussing happens after this stage.
The storage strategy of these toxic volatile compounds is quite clever and aligns with the biological processes we know occur during fruit ripening. As the plant hormone ethylene orchestrates the transformation of the complex carbohydrates, within the mesocarp, into sugars, boosting the fruit's Brix value, some of these sugar molecules are being tethered to the volatile secondary metabolites being simultaneously synthesized [5] - this is sometimes seen as a decrease in the compounds’ emission during ripening as they are no longer volatile. The new molecules formed are known as "bound volatiles" or "glycosidically bound volatiles (GBV)" in scientific literature [6].
Adding a sugar molecule serves as an anchor, keeping the volatile secondary metabolite in the plant's tissue, similar to how one would secure a helium balloon to prevent it from floating away. This process also reduces the molecules' phytotoxicity, as GBVs are not considered harmful to the plants. Although these compounds are no longer volatile and do not impact the aroma, they still have the potential to influence the taste of green coffee.
[5] Interestingly some research suggests that the carbohydrates being transformed also are used as building blocks for these secondary plant metabolites.
[6] It would be interesting to know whether the accumulation of these compounds leads to a form of feedback inhibition, as the terpene synthase genes cease to be expressed in completely ripe cherries (del Terra et al., 2013), but nonetheless are known to be responsive to environmental stressors.
For instance, researchers have identified the diterpene glycoside mozambioside [7] in green C. pseudozanguebariae and C. arabica coffee whose bitterness threshold (60 μmol/L) is more than ten times lower than that of caffeine (680 μmol/L) (Prewo et al., 1990; Lang et al., 2015). In other words, if you have one gram of mozambioside, you would need around 11.3 grams of caffeine to match the perceived bitterness, according to Lang and colleagues’ (2015) study. As mozambioside decreases [8] during roasting, the incomplete breakdown [9] of this compound may contribute to the characteristic bitter taste found in underdeveloped coffees, a roast defect. As there are few studies covering the sensory contribution of GBV’s [10], to this author’s knowledge, it is unsurprising that the connection between scientific outcome and practical application remains to be substantiated.
[7] Mozambioside may not be volatile even in the absence of the glucose molecule. This example further underscores the significant gaps in knowledge existing in these pathways.
[8] Provided that it isn’t converted into more potent bitter compounds
[9] Some of the breakdown products of mozambioside have been found to be bitter as well. Therefore, a more comprehensive study is needed to fully understand its temperature dependence degradation and its potential influence on cup quality, i.e. sensory profile.
[10] Most of the research into diterpene species encountered within coffee are interested in the molecules’ potential pharmacological properties. As mentioned in a previous article these aspects will not be discussed in my work.
Although GBVs are more abundant than their free volatile form, their full potential is unlikely to be realized through taste. Instead, these compounds can be seen as a reservoir of aroma waiting to be liberated from their glycosidic bond. The release of these aromas are already exploited in the juice and wine industry to enhance the natural aroma character of these products. Indicating that GBVs likely play a significant role in creating some of the most beloved aroma profiles in the coffee industry.
To illustrate this point, let us consider terpenes and by extension terpenoids (oxidized terpenes), a category of secondary metabolites that cannot be generated during roasting. Since these compounds do not arise from heat-induced reactions like the Maillard reaction, they must either naturally pre-exist or be produced through microbial fermentation. It is entirely possible that these processes are also interrelated, but let’s not complicate matters just yet. For the purposes of this conversation, we will focus on their natural occurrence.
Individual terpenes and terpenoids, as seen in the table, hold significant potential for imparting certain cup characteristics, and in so doing elevating cup quality. However, their influence extends beyond their individual aroma contributions, as they play a crucial role in creating a variety of delightful aroma combinations found in fruits like blueberries [11], blackcurrants, mangoes, and even potentially in vegetables like tomatoes [12] (Felipe et al., 2021, Arauez and Valpuesta, 2013). It is therefore unsurprising to consistently associate the sensory characteristics of coffee with the aroma profiles of flowers, fruits, spices and vegetables in literature, as their biochemical processes, e.g. terpene synthesis, stem from a common ancestry [13]. Despite the myriad of knowledge that we should have on these aroma mixtures, it is difficult to find their exact composition or recipe, suggesting that they are likely kept as proprietary secrets by companies [14].
[11] Blueberry has been found to be composed of a mixture of linalool and a 5-7 carbon alcohol or aldehyde at specific molar ratios (Thomas Holden Parliment, 1977). The origin of the blueberry flavour within coffee remains outstanding, so we do not know whether this information is directly applicable. However, we will see in the discussion on terroir how this association is plausible.
[12] I suspect the reminiscent tomatoey flavour I associated with Kenyan coffee originates from the secondary metabolites eugenol and guaiacol.
[13] Acetate/Mevalonate pathway in the cytosol & Pyruvate/Glyceraldehyde-3-phosphate pathway in the plastids.
[14] Knowing which compounds are associated with an aroma is insufficient to reproduce it as many flavours can contain the same ingredients. It is the relative amount that triggers the product’s sensory recognition.
If we want to produce coffee with enticing aromas, such as blueberry and blackcurrant, then we need to be alert to why these terpenes are there and do what we can to encourage their presence in the beans.
Terpenes are secondary metabolites that are naturally formed within the maternal tissue as part of the plant's defence mechanism against living and environmental stress. To be effective for defence, they have to be volatile. But to survive through to the roasted bean they need to be attached to one or more sugar molecules. So we need a balance of build-up of defence chemicals (the plant should be aware of potential threats) without the need for those chemicals to be released due to a real threat.
The Release article helps you to understand this subtle balance, so that your knowledge of your plants and their environment might allow you to more reliably add these delicious notes to your roasted beans.
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