**3. Results and discussion**

The ethnobotanical research reports 37 plant species belonging to 35 genera and 28 families used for curing various diseases by the Baiga tribes in the Amarkantak region. The representing plants are mostly used to cure various diseases viz. menstrual disorder, piles, sore throat, respiratory disorder, haematuria, miscarriage, jaundice, fever, insanity, leucorrhoea, bleeding during pregnancy, spermatorrhea, infertility in women, abortifacient, Motiabind, scorpion bite, wounds of animals, stomach disorder, intestinal worms, diabetes, leukoderma, rheumatism, scabies, wart and easy delivery. The presence of such a large number of medicinal plants indicates that the area has a very rich diversity of medicinal plant species and is a site for different indigenous knowledge. The present ethno-medicinal information provided in this paper, is compared with well-known Indian medicinal literature [12–14]. The result of the present study continues to play a vital role in the healthcare system of the tribal people and paves the way for the development and discovery of new drugs.

## **Acknowledgements**

The author is grateful to the Baiga tribal people, who have shared unreservedly valuable information in the field during to study area.

## **Conflict of interest**

The author declares no conflict of interest.

*Medicinal Plants and Traditional Practices of Baiga Tribe in Amarkantak Region of Eastern… DOI: http://dx.doi.org/10.5772/intechopen.97697*


**Contents**

Reprinted from: *Antioxidants* **2022**, *11*, 1944, doi:10.3390/antiox11101944 .............. **149**

#### **Paul. J. Jacobs, Daniel W. Hart, Hana N. Merchant, Cornelia Voigt and Nigel C. Bennett** The Evolution and Ecology of Oxidative and Antioxidant Status: A Comparative Approach in African Mole-Rats Reprinted from: *Antioxidants* **2023**, *12*, 1486, doi:10.3390/antiox12081486 .............. **175**

### *Editorial* **Redox Metabolism in Ecophysiology and Evolution**

**Daniel C. Moreira 1,\*, Tania Zenteno-Savín 2 and Marcelo Hermes-Lima 3**

Aerobic organisms have developed a complex system of endogenous antioxidants to manage the reactivity of oxygen and its byproducts. This interplay between reactive oxygen/nitrogen species (RONS) and defensive mechanisms has profound implications, extending well beyond mere interactions of attack and defense. Redox metabolism, encompassing non-radical redox metabolites (e.g., hydrogen peroxide and glutathione), redox-sensitive transcription factors (e.g., Nrf2 and FOXOs), and redox-sensitive proteins (e.g., thioredoxins and peroxiredoxins), forms a network of signaling pathways with extensive effects on various processes in aerobic organisms, spanning from circadian rhythms to the regulation of lifespan.

Oxidative stress, stemming from an imbalance between RONS production and cellular antioxidant capacity, is now recognized as a pivotal determinant of the life history of organisms. Environmental stressors have the potential to disrupt the equilibrium of redox reactions, eliciting compensatory adaptive responses. Modulations in redox metabolism have been documented in a wide range of species, spanning various phylogenetic groups and exposed to diverse environmental stressors such as fluctuations in temperature, changes in water availability, shifts in oxygen levels, exposure to UV radiation, pollutants, and more.

This Special Issue is dedicated to investigating the responses of redox metabolism in organisms experiencing alterations in individual or combined environmental factors, whether of biotic or abiotic origin. Comprehending these responses to stress inducers is critical for unraveling the role of oxidative stress in the survival and fitness of organisms. By examining how organisms confront the challenges posed by these changing factors, valuable insights can be gained into the interplay between redox metabolism and the overall health of ecosystems. This research not only enhances our comprehension of the underlying mechanisms but also illuminates potential strategies for mitigating the repercussions of environmental changes on biodiversity and ecological stability.

Arango et al. [1] investigated possible physiological costs associated with olive ridley sea turtles' nesting behavior, either solitary or in "arribadas" (mass aggregations). The study examined metabolic differences between the nesting modes and found that arribada nesters were larger and had higher thyroid hormone levels. Moreover, turtles that presented arribada behavior had metabolic pathways related to phospholipid and amino acid metabolism, as well as catabolic processes, upregulated compared with those reproducing solitarily. However, arribada nesters exhibited higher levels of oxidative damage in terms of lipid peroxidation and protein oxidation, suggesting a trade-off between fitness benefits and oxidative stress associated with arribada nesting.

Cassier-Chauvat et al. [2] examined the significance of the glutathione (GSH) system in defending cells against various stressors across phylogenetically diverse organisms. They underscored the crucial roles of glutathione-dependent systems in maintaining redox balance, detoxifying harmful substances, and regulating iron metabolism. The study delved into multiple pathways, including GSH synthesis, degradation, recycling, conjugation,

#### **Citation:** Moreira, D.C.;

Zenteno-Savín, T.; Hermes-Lima, M. Redox Metabolism in Ecophysiology and Evolution. *Antioxidants* **2023**, *12*, 1769. https://doi.org/10.3390/ antiox12091769

Received: 10 September 2023 Accepted: 13 September 2023 Published: 16 September 2023

**Copyright:** © 2023 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https:// creativecommons.org/licenses/by/ 4.0/).

glutathionylation/deglutathionylation, and iron–sulfur cluster [Fe-S] synthesis and repair. The authors ultimately suggested that cyanobacteria, regarded as the originators of the GSH system, are the ideal model organisms for further research into its components.

Cubillos et al. [3] investigated the impact of experimental radiation exposure on the burrowing behavior and oxidative damage in *Anthopleura hermaphroditica*, an intertidal anemone. They exposed adults and juveniles to different radiation treatments, including photosynthetically active radiation (PAR), ultraviolet A radiation (UVA), and ultraviolet B radiation (UVB), both with and without sediment. Animals were exposed either to PAR alone, PAR + UVA, or PAR + UVA + UVB. The results showed that exposure to PAR + UVA + UVB radiation led to faster burrowing responses in both adults and juveniles compared to PAR alone. Juveniles had higher basal levels of oxidative stress markers (protein carbonyl and malondialdehyde) than those in adults. Exposure to PAR + UVA + UVB further increased oxidative damage to protein and lipids in juveniles, regardless of the presence or not of sediment. However, the presence of sediment protected adults against various radiation treatments. The research found that *A. hermaphroditica* burrows into sediment as a behavioral response to UVR radiation, indicating their evasion of UVB radiation and UVR-induced oxidative stress.

Ferreira-Cravo et al. [4] explored the role of glutathione (GSH) in managing redox homeostasis during anoxia and reoxygenation in *Helix aspersa*, a model for anoxia tolerance. The researchers depleted the total GSH pool inhibiting GSH synthesis with L-buthionine-(S, R)-sulfoximine (BSO) and subjected snails to anoxia. BSO alone led to GSH depletion but no other significant changes in antioxidants and oxidative stress markers, while anoxia triggered an increase in glutathione peroxidase (GPX) activity. However, GSH depletion before anoxia raised the GSSG/tGSH ratio during anoxia, indicating a disrupted redox balance. Therefore, GSH depletion does not directly induce oxidative stress in snails but impairs their ability to manage oxidative challenges during anoxia. The study indicates the importance of GSH in countering oxidative challenges during hypoxia and reoxygenation in land snails.

Jacobs et al. [5] investigated the impact of aridification on wild common mole rats and their oxidative status along an aridity gradient. Liver oxidative status showed no significant change with aridity levels. However, aridity did affect the total antioxidant capacity (TAC) and oxidative stress index (OSI) of the kidney, with the most arid habitats showing the highest TAC. These findings were interpreted in the context of the kidney's role in water balance and retention. The authors conclude that social common mole rats in arid environments prioritize and protect their kidneys with higher antioxidants, mitigating the impact of aridification on oxidative stress. Nevertheless, more research is needed to further explore the effects of aridity on mammalian oxidative ecology, particularly in the context of climate change.

Malagoli et al. [6] reviewed the critical role of reactive oxygen species (ROS) in mollusks' physiological functions and their relevance in both environmental adaptation and immune responses. The authors focused on highly invasive mollusks (e.g., *Mytilus galloprovincialis*, *Dreissena polymorpha*, *Achatina fulica*, and *Pomacea canaliculata*) and their ability to manage ROS production during challenging conditions. The review emphasizes that the capacity to maintain redox homeostasis under oxidative pressure can be advantageous when facing environmental and immunological challenges, potentially making it a trait associated with invasiveness.

Ramirez et al. [7] investigated the effect of lipoic acid, a mitochondrial coenzyme that can act as an antioxidant or pro-oxidant, on energy metabolism and redox balance. Using *Artemia* sp. nauplii as a model organism, the authors found that lipoic acid treatment positively influenced the activity of the electron transport system, particularly at higher concentrations and longer exposure times. Additionally, lipoic acid promoted glucose catabolism, decreased ROS production, and influenced protein levels and total ammoniacal nitrogen production under specific conditions.

Yang et al. [8] investigated the response of *Cherax destructor*, a freshwater crustacean, to different temperatures. After 8 weeks of exposure to 30 ◦C, 25 ◦C, 20 ◦C, 15 ◦C, or 10 ◦C, levels of components of the glutathione redox system (GSH, GSSG, GST, and GR) and transcript levels of proteins that respond to temperature stress (heat-shock proteins and cold shock-domain proteins) were quantified in the hepatopancreas. With a focus on the effect of low temperatures, the study showed that growth indicators such as weight gain and length gain decreased at lower temperatures. Exposure to 10 ◦C also decreased GST activity and GSSG/GSH ratio, while increasing GSH levels in hepatopancreas when compared with animals maintained at 25 ◦C. Different temperatures modulated the expression of temperature stress-responsive proteins, among which HSP60, HSP70, and CSP were upregulated at 10 ◦C. Transcriptome sequencing identified differentially expressed genes related to endocrine disorders, glucose metabolism, antioxidant defense, and immune responses. The findings suggest that low temperature inhibited basal metabolism and immune ability but increased redox buffering capacity and temperature–stress response in the crayfish.

Zhang et al. [9] focused on the effects of mercury (as HgCl2) toxicity on *Procambarus clarkii*, a type of crayfish commonly found in aquatic environments worldwide. The study examined the acute impact of Hg on various aspects, including biochemical responses, histopathology, hepatopancreatic transcriptome, and intestinal microbiome. Hg exposure led to significant changes in redox metabolism markers, including increases in malondialdehyde (MDA) content and a general trend of decreasing antioxidant levels. Structural damage was observed in the hepatopancreas and intestines. RNA-seq identified differentially expressed genes (DEGs) mainly associated with redox metabolism, ion transport, drug metabolism, immune response, and apoptosis. The study also showed that Hg exposure altered the composition of the intestinal microbiome. The findings provide insights into the mechanisms of Hg-induced toxicity in aquatic crustaceans at various levels, including tissue, cellular, molecular, and microbial levels.

Jacobs et al. [10] explored several factors that could be associated with redox balance and oxidative stress, such as phylogeny, social behavior, captivity, environmental aridity, resting metabolic rate (RMR), and maximum lifespan potential (MLSP).

The authors found that higher levels of oxidative markers in plasma are associated with higher MLSP by comparing several species of African naked mole rats. Such association was more evident in social species than in solitary species. Additionally, oxidative stress marker levels decrease with a higher aridity index, and wild-caught mole rats show higher antioxidant levels. The concept of hormesis, which involves a biphasic response to stimuli, is proposed as a potential mechanism contributing to longevity in certain members of the Bathyergidae family.

These studies provide further evidence of the role of oxidative stress as a key factor in the life history of living organisms. Changes in RONS production and antioxidant defenses in response to different biotic and abiotic factors (individually and/or combined) contribute to regulating signaling pathways that dictate whether an aerobic species will survive. Studies such as that of Jacobs et al. [5] highlight the role of combined responses at biochemical, physiologic, behavioral, and/or population levels in responding to those factors. Further, the studies included in this Special Issue suggest compensatory adaptive responses may modulate redox metabolism in phylogenetically diverse species. Closer analyses of these results will provide clues to understanding the evolution of antioxidant defense systems, the underlying mechanisms, the subtle connections of the redox metabolism with other vital systems, such as the immune system, and its participation in shaping existent biodiversity. Results from studies of redox metabolism with a comparative focus can provide clues towards dealing with environmental and climate change, provide viable solutions for the conservation of species, and maintain the balance between environmental, animal, and human health in a sustainable manner.

**Author Contributions:** The authors included in this study have each made significant and integral intellectual contributions to the article. Furthermore, all authors have provided their approval for the publication of this work. All authors have read and agreed to the published version of the manuscript.

**Conflicts of Interest:** The authors declare no conflict of interest.

#### **References**

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**3. Results and discussion**

#### **3.1 Overview**

*Intellectual Property Rights - Patent*

advances in ethanol production.

**2. Material and method**

Taking into account this theoretical basis and considering the raw materials that are suitable for ethanol production, as well as the three modalities of the technological trajectory of ethanol production, we conclude that ethanol produced from sugarcane is currently the bioenergy production with the highest yield per unit and higher total energy balance, when we consider the proportion of energy in the final product (ethanol and mechanical energy, thermal and electric) and the fossil energy needed for its production. Besides, sugarcane ethanol offers the possibility of two technology trajectories that are almost consecutive (first- and second-

In this context and in the light of the current technological scenario, this chapter develops an innovative approach to the production of ethanol that comes from sugarcane, combining concepts of patent heuristics with studies of technology trajectories, dependence and paradigms [1]. The study uses technology prospection techniques with analyses of "Breakthrough Inventions," also applying "Forward citations" for an analysis of future technology affinity. Finally, it seeks to obtain a consolidated profile

The piece is divided into three sections: methodology, results and final conclusions. Results and discussions are, in their turn, subdivided into five subsections: general panorama, breakthrough inventions—geographic and current owner distribution analysis, breakthrough inventions—technology analysis, breakthrough inventions—forward citation analysis and recent innovations and technological

The methodology is based on the study of patent citation and is divided into two stages. In the first stage, patent documents were retrieved with bibliometric analysis carried out through the PatSeer® commercial patent database. It uses keywords such as: alcohol, bioalcohol, ethanol, bioethanol, saccharum, sugarcane, "sugar cane," bagasse, cellulose, biomass, lignocellulose and molasses. In the title and summary fields, it used the extend family filter. The study made use of Boolean operators "OR," "AND" and words truncated with asterisk (\*). We covered the period between 2000 and 2018, according to the priority date. All the retrieved documents were classified according to the keywords in the title, summary and claim fields, which resulted in the following categories: (i) pretreatment with acid and enzymatic hydrolysis, (ii) fermentation with yeast, bacteria or non-yeast fungus, (iii) distillation and (iv) sugarcane.

The second step was the data analysis per se, composed by:

highlighting quoted documents (>5);

(individual and non-self-citation));

(1) Evolution over time of patent documents according to priority year,

(2) Analysis of patent documents (heavily cited > 5) in different types of citations: patent literature—PL (backward and forward), non-patent literature—NPL (references), family size and documents made available. Calculation of self-citations (difference between forward citations

(3) Calculation of the patent index citation of "breakthrough inventions"

(CPR: citation patent ratio) [2, 3] according to the priority origin country: CPR = %of a variable"s patents forward citation in the breakthrough inventions \_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_\_ %of all patents in the breakthrough inventions (1)

generation productions with the use of sugar cane juice and bagasse).

to forward the technology trajectory of sugarcane-based ethanol production.

**14**

As highlighted in the methodology section, the technology focus of the study is the production of ethanol from sugarcane in its various first-generation (ethanol) and second-generation (bioethanol) modalities. The search strategy used retrieved 223 patent documents in the 2000–2018 period according to the year of priority. Out of those 301 have more than five forward citations by patent family. An expressive range of data on first-generation (ethanol) and secondgeneration (bioethanol) production were observed positively that when stimulated and directed, there is a growing interest in the patent protection of the intellectual assets (in the form of patent depositories) coming from research and industrial developments (**Figure 1**).

It is worth highlighting again that, on industrial levels, ethanol is considered to be a very relevant biofuel for producer countries, and which can be obtained from various primary and secondary (lignocellulosic biomass types) sources, such as:

i.through the hydrolysis of starch of cereal grains (corn, sorghum, wheat, triticale, rye, malted barley, rice);

#### **Figure 1.**

*Distribution over time of patent documents related to the production of sugarcane ethanol, highlighting 301 highly cited documents. Period: 2000–2018. N = 2023. Source: Compiled by the authors, PatSeer® database.*

The global ethanol production from various raw materials has grown year on year, mainly because of its usability as a fuel (or supplementary fuel), and also thanks to its availability from renewable sources as a result of incentives and social and environmentally friendly credentials. This growth in the global ethanol production noticeable from **Figure 2** takes place independently from the struggle between the use of its primary raw materials (grains and sugarcane juices/extracts, sorghum and saccharin beetroot) and food production for the global population.

From an economic point of view, when we compare **Figures 1** and **2**, we perceive a noticeable alignment of evolutions over time given that the patent system, as it reflects the advances of investments in R&D, reveals the bias that paired the economic development of a nation to its technological development thus highlighting the strong maintenance of interests in the technologies in question. It also important to emphasize that patent data analysis aids significantly to understand technology tendencies as well as forecast future technology perspectives.

This way, with a focus on studies of future technology perspectives, we applied here the analysis of "patent citation" (PC). The methodological effort made here is in line with what many researchers across the globe have been doing for decades, using methodologies based on "patent citation analysis." This methodology has gained traction and has been developed and adapted to increase access to valuable information among companies, researchers, research centers, universities and countries. The information contained in patent documents reveals the extent and conduction of applied technical research. Therefore, the use of this tool (patents) makes it possible to show that information available in those patent documents overcomes all barriers and can be used for the expansion

**17**

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation*

No documents 2023 301 (14.9%) No. of extended family members 5128 811 (15.8%)

No. of references 1612 642 (39.8%)

No. of backward citation 5585 1780 (31.9%) No. of forward citations (individual) 6807 5280 (77.7%) No. of non self citations (forward citation) 5054 3954 (78.2%) Auto-citation 1753 1326 (21.8%) Granted 685 137 (20%) Average year 2011.4 2008.1

**Document quality indicators retrieved Total Most highly cited (>5) (Percentage of total)**

of the technique and technology development. Therefore, "patent citation analysis" reveals the creation and propagation of information, as well as promotes its applicability in various technical fields which will be able to originate/spawn new

**Figure 1** also shows the evolution of highly cited patent documents based on retrieved data (orange bars), whose extraction can be observed in **Table 1**, which shows a summary of the main quality indicators of the retrieved documents, comparing the total number of retrieved documents in comparison with the most cited ones. We can see that around 78% of the individual forward citations concentrate in 15% of retrieved documents, denoting a high concentration around specific technology nuclei, while 25.1% of individual forward citations also refer to self-citations

Another very relevant information from **Table 1** refers to the relation between the values of "patent literature" (PL) and "non-patent literature" (NPL). According to Demet et al. [7], this relation (PL/NPL) infers a state of industrial maturity hoped to be reached. In other words, values below the first inferior quarter (>25%) suggest a favorable state for innovation and the commercialization of products/ processes of a given technology sector. Therefore, it is possible to conclude there are well-established maturity nuclei in detriment of the possibility of the existence of nuclei that are not mature yet. A better definition of these maturity nuclei was set

out by "breakthrough inventions" study of "patent citations" [8].

**3.2 Breakthrough inventions: geographic and current owner distribution**

technology sector of first- and second-generation ethanol production.

According to Yan et al. [9], "breakthrough inventions" can be understood as inventions that aspire to or serve as technology bases for the creation of subsequent inventions. They are inventions that are a relevant source of competitive edge and can be part of a viable strategy to boost a company" capacity to generate innovative inventions. They can help meeting the challenge to create radical/disruptive inventions through the recombination of non-redundant knowledge, mainly by using patent publications of industrial competitors' patent publications. In this case, the

*DOI: http://dx.doi.org/10.5772/intechopen.88428*

*Source: Compiled by the authors, PatSeer® database.*

*Main quality indicators of retrieved documents.*

NPL—non patent literature:

PL—patent literature:

technologies [4–6].

**Table 1.**

of patent documents.

**analysis**

**Figure 2.** *World ethanol production. Source: KNect365 Energy, 2019.*

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation DOI: http://dx.doi.org/10.5772/intechopen.88428*

#### **Table 1.**

*Intellectual Property Rights - Patent*

ii.tubers (potatoes);

charin sorghum; (c) saccharin beetroot;

and (III) non-yeast fungus; finally;

biodiesel and bioethanol.

iii.through direct use of molasses sugar and juice from: (a) sugarcane; (b) sac-

iv.through the breakdown and decomposing of the lignocellulosic structure of biomass materials, followed by processes of saccharification and fermentation, which can happen through intervention with: (I) yeast; (II) bacteria

v.by implementation of algae crops, with the potential of a co-production of

The global ethanol production from various raw materials has grown year on year, mainly because of its usability as a fuel (or supplementary fuel), and also thanks to its availability from renewable sources as a result of incentives and social and environmentally friendly credentials. This growth in the global ethanol production noticeable from **Figure 2** takes place independently from the struggle between the use of its primary raw materials (grains and sugarcane juices/extracts, sorghum and saccharin beetroot) and food production for the global population. From an economic point of view, when we compare **Figures 1** and **2**, we perceive a noticeable alignment of evolutions over time given that the patent system, as it reflects the advances of investments in R&D, reveals the bias that paired the economic development of a nation to its technological development thus highlighting the strong maintenance of interests in the technologies in question. It also important to emphasize that patent data analysis aids significantly to understand technology tendencies as well as forecast future technology perspectives. This way, with a focus on studies of future technology perspectives, we applied here the analysis of "patent citation" (PC). The methodological effort made here is in line with what many researchers across the globe have been doing for decades, using methodologies based on "patent citation analysis." This methodology has gained traction and has been developed and adapted to increase access to valuable information among companies, researchers, research centers, universities and countries. The information contained in patent documents reveals the extent and conduction of applied technical research. Therefore, the use of this tool (patents) makes it possible to show that information available in those patent documents overcomes all barriers and can be used for the expansion

**16**

**Figure 2.**

*World ethanol production. Source: KNect365 Energy, 2019.*

*Main quality indicators of retrieved documents.*

of the technique and technology development. Therefore, "patent citation analysis" reveals the creation and propagation of information, as well as promotes its applicability in various technical fields which will be able to originate/spawn new technologies [4–6].

**Figure 1** also shows the evolution of highly cited patent documents based on retrieved data (orange bars), whose extraction can be observed in **Table 1**, which shows a summary of the main quality indicators of the retrieved documents, comparing the total number of retrieved documents in comparison with the most cited ones.

We can see that around 78% of the individual forward citations concentrate in 15% of retrieved documents, denoting a high concentration around specific technology nuclei, while 25.1% of individual forward citations also refer to self-citations of patent documents.

Another very relevant information from **Table 1** refers to the relation between the values of "patent literature" (PL) and "non-patent literature" (NPL). According to Demet et al. [7], this relation (PL/NPL) infers a state of industrial maturity hoped to be reached. In other words, values below the first inferior quarter (>25%) suggest a favorable state for innovation and the commercialization of products/ processes of a given technology sector. Therefore, it is possible to conclude there are well-established maturity nuclei in detriment of the possibility of the existence of nuclei that are not mature yet. A better definition of these maturity nuclei was set out by "breakthrough inventions" study of "patent citations" [8].

### **3.2 Breakthrough inventions: geographic and current owner distribution analysis**

According to Yan et al. [9], "breakthrough inventions" can be understood as inventions that aspire to or serve as technology bases for the creation of subsequent inventions. They are inventions that are a relevant source of competitive edge and can be part of a viable strategy to boost a company" capacity to generate innovative inventions. They can help meeting the challenge to create radical/disruptive inventions through the recombination of non-redundant knowledge, mainly by using patent publications of industrial competitors' patent publications. In this case, the technology sector of first- and second-generation ethanol production.

Kerr [10] used "breakthrough inventions" to identify important areas for future research in the area. Similarly, Egli et al. [11] used "breakthrough inventions" to identify and induce applied technologies to climate change mitigation. This way, in this paper we used such studies as reference in the investigation of the efforts and technology maturity, patenting growth and the influence of patents in the technology development of first- and second-generation ethanol production. This way, this work presents "breakthrough inventions" through "patent citations" with an analysis of the main technology clusters within the ethanol production sector and its temporal and spatial migrations.

Before we continue with the present analysis, it important to understand the relevance of the study on geographic distribution and the owners of technologies in "breakthrough inventions." Therefore, the analysis of components of geographical distribution and the ownership of inventions is key as it provides information on the flow of knowledge of the analyzed technology [4]. For that matter, we drew from Kaki's study on citations performances ratio (CPR). CPR comes from a comparative study based on the presence of highly cited patents in a given patent database, a specific timeline and category. The values whose ratio are bigger than the unit (CPR > 1) indicate a good performance. According to Narin and Olivastro" study [12], any patent document cited 06 (six) or more times can be considered as very relevant for the "patent citation analysis." They can also be considered "breakthrough inventions."

In this sense, **Table 2** sums up the main indicators of patent quality according to the country of origin of the priority request. The importance of analyzing this parameter is to understand which countries dominate the technology. Only the USA, China and Japan have CPR numbers above 1, which are considered good. Other countries did not obtain a good performance during analysis.

When we analyze **Table 2**, we can see a strong performance by the United States as the conductor of technology within the analyzed setting. Therefore, even if it does not have its ethanol matrix focused on sugarcane crops, the United States present a relevant patent achievement in terms of "breakthrough inventions". This suggests technology leadership in related areas when a sugarcane matrix is used. Also relevant is the fact that the United States are the biggest ethanol producers in the world, followed by Brazil, EU, China and Canada (**Figure 3**) while the largest sugarcane producer are Brazil, India, China, Thailand and Pakistan [13].

**19**

technologies herein studied.

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation*

Following the same logic, we can see that China plays an important role in the "breakthrough inventions" analyzed scenario, that is, it appears as one of the five global ethanol powers, as well as one of the five countries with the highest number of innovative inventions. We should highlight here that the Chinese government is planning the implementation of a policy of an E10 ethanol addition to gasoline across its territory by 2020. This will be very important for countries like the United States and Brazil, whose CPR of the latter is only 0.02. Such piece of information about Brazil (CPR = 0.02) may suggest a strong dependence and even propensity to the technology "colonization" in specific sub-sectors and the existence of "Patent

*Global ethanol production by country of 2018 (country; million gallons; share of global production). Source:*

Regarding the profile of the main holders of "breakthrough inventions" retrieved during the CPR analysis, **Table 3** shows the importance of Chinese companies. This is a very important piece of information for this analysis of technology trajectory because it enables a clear visualization of the steps taken by companies and Chinese university research centers toward control and technology indepen-

Although the companies listed in **Table 3** show low CPR (<0.5), an indicator they produce little impact with the dissemination of their technologies, their respective values often surpass by several times the CPR of countries like Germany

Also relevant is the fact that the number of "breakthrough inventions" documents retrieved from these companies and Chinese universities present low statistical dispersion (average standard deviation = 1.88). This, however, suggests something positive. These figures can indicate a cohesive movement of technology ascension for the sector, cluster or grouping formation. We must also call attention to the high number of documents made available by these actors, except for Toshiba Corp, Institute of Process Engineering, and the Chinese Academy of Sciences, who until the time when the analysis was made did not have patents issued for the

The analysis of **Table 3** also reveals the absence of actors from other countries. For example, the presence of actors such as the United States and Japan merely indicates them to be countries with a considerable number of "breakthrough inventions" documents. However, it can be concluded there is great dispersion of patent document ownership, which in its turn suggests an open and competitive market, without business clusters. Regarding the technology aspect of ethanol production,

dence of methods of first- and second-generation ethanol production.

(2.8×); Russia (12.5×); Brazil (25×); and France (25×).

*DOI: http://dx.doi.org/10.5772/intechopen.88428*

Pools" [14, 15] and "Patent Trolls" [16, 17].

*RFA analysis of public and private data source.*

**Figure 3.**

#### **Table 2.**

*Country of origin profile analysis of "breakthrough inventions."*

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation DOI: http://dx.doi.org/10.5772/intechopen.88428*

**Figure 3.**

*Intellectual Property Rights - Patent*

its temporal and spatial migrations.

**Priority country No. of**

*Source: compiled by the authors, PatSeer database.*

*Country of origin profile analysis of "breakthrough inventions."*

**records**

Kerr [10] used "breakthrough inventions" to identify important areas for future research in the area. Similarly, Egli et al. [11] used "breakthrough inventions" to identify and induce applied technologies to climate change mitigation. This way, in this paper we used such studies as reference in the investigation of the efforts and technology maturity, patenting growth and the influence of patents in the technology development of first- and second-generation ethanol production. This way, this work presents "breakthrough inventions" through "patent citations" with an analysis of the main technology clusters within the ethanol production sector and

Before we continue with the present analysis, it important to understand the relevance of the study on geographic distribution and the owners of technologies in "breakthrough inventions." Therefore, the analysis of components of geographical distribution and the ownership of inventions is key as it provides information on the flow of knowledge of the analyzed technology [4]. For that matter, we drew from Kaki's study on citations performances ratio (CPR). CPR comes from a comparative study based on the presence of highly cited patents in a given patent database, a specific timeline and category. The values whose ratio are bigger than the unit (CPR > 1) indicate a good performance. According to Narin and Olivastro" study [12], any patent document cited 06 (six) or more times can be considered as very relevant for the "patent citation analysis." They can also be considered "breakthrough inventions." In this sense, **Table 2** sums up the main indicators of patent quality according to the country of origin of the priority request. The importance of analyzing this parameter is to understand which countries dominate the technology. Only the USA, China and Japan have CPR numbers above 1, which are considered good.

Other countries did not obtain a good performance during analysis.

sugarcane producer are Brazil, India, China, Thailand and Pakistan [13].

United States 61 8.35 42.6 61.7 China 172 6.21 50.6 23.7 Japan 52 2.53 32.7 8.6 Germany 5 0.18 0.0 2.2 Korea 4 0.11 50.0 1.5 Czech Republic 2 0.06 50.0 0.9 Russian Federation 2 0.04 0.0 0.6 Brazil 1 0.02 100 0.5 France 1 0.02 100 0.2 United Kingdom 1 0.02 100 0.1 Total 301 45.2% 100%

When we analyze **Table 2**, we can see a strong performance by the United States as the conductor of technology within the analyzed setting. Therefore, even if it does not have its ethanol matrix focused on sugarcane crops, the United States present a relevant patent achievement in terms of "breakthrough inventions". This suggests technology leadership in related areas when a sugarcane matrix is used. Also relevant is the fact that the United States are the biggest ethanol producers in the world, followed by Brazil, EU, China and Canada (**Figure 3**) while the largest

> **CPR % granted of the priority country**

**% of extended family members**

**18**

**Table 2.**

*Global ethanol production by country of 2018 (country; million gallons; share of global production). Source: RFA analysis of public and private data source.*

Following the same logic, we can see that China plays an important role in the "breakthrough inventions" analyzed scenario, that is, it appears as one of the five global ethanol powers, as well as one of the five countries with the highest number of innovative inventions. We should highlight here that the Chinese government is planning the implementation of a policy of an E10 ethanol addition to gasoline across its territory by 2020. This will be very important for countries like the United States and Brazil, whose CPR of the latter is only 0.02. Such piece of information about Brazil (CPR = 0.02) may suggest a strong dependence and even propensity to the technology "colonization" in specific sub-sectors and the existence of "Patent Pools" [14, 15] and "Patent Trolls" [16, 17].

Regarding the profile of the main holders of "breakthrough inventions" retrieved during the CPR analysis, **Table 3** shows the importance of Chinese companies. This is a very important piece of information for this analysis of technology trajectory because it enables a clear visualization of the steps taken by companies and Chinese university research centers toward control and technology independence of methods of first- and second-generation ethanol production.

Although the companies listed in **Table 3** show low CPR (<0.5), an indicator they produce little impact with the dissemination of their technologies, their respective values often surpass by several times the CPR of countries like Germany (2.8×); Russia (12.5×); Brazil (25×); and France (25×).

Also relevant is the fact that the number of "breakthrough inventions" documents retrieved from these companies and Chinese universities present low statistical dispersion (average standard deviation = 1.88). This, however, suggests something positive. These figures can indicate a cohesive movement of technology ascension for the sector, cluster or grouping formation. We must also call attention to the high number of documents made available by these actors, except for Toshiba Corp, Institute of Process Engineering, and the Chinese Academy of Sciences, who until the time when the analysis was made did not have patents issued for the technologies herein studied.

The analysis of **Table 3** also reveals the absence of actors from other countries. For example, the presence of actors such as the United States and Japan merely indicates them to be countries with a considerable number of "breakthrough inventions" documents. However, it can be concluded there is great dispersion of patent document ownership, which in its turn suggests an open and competitive market, without business clusters. Regarding the technology aspect of ethanol production,

**Table 3.**

**21**

**Table**

**Figure 4.**

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation*

**3** reveals to readers that the great intellectual effort by Chinese companies is in areas such as: (i) pretreatment of raw materials (hydrolysis); (ii) fermentation;

China Petrochem Corp (Sinopec) appears as an exception to the block composed

relationship between actors and technology areas in each category. Therefore, it is possible to verify a certain level of non-binding cohesion among the analyzed actors, there being no sharing of technology in those supposed partnerships.

*Relationship network among the 10 main holders of technologies associated to the production of ethanol, "breakthrough inventions" and biomass categories (sugarcane), pretreatment (acid hydrolysis and enzymatic hydrolysis), fermentation (yeast, bacterium and yeast-free fungus) and distillation. N = 301. Source: Elaborated*

by all the other actors. The data suggests low adhesion by that company to the cluster formed by other companies and universities. There seems to be no apparent

In the case of technology associated to the production of ethanol, the "break

through inventions" and the analysis of biomass (sugarcane) analysis, pretreatment (acid hydrolysis and enzymatic hydrolysis), fermentation (yeast, bacterium and yeast-free fungus), post-treatment (distillation) indicates possible dispersion.

In 2016, the United Nations Conference on Trade and Development (UNCTAD)

[18] launched a report where they laid out the main distinctions between first and second generation renewable fuels, based on their raw materials' features (**Table 4**). Therefore, **Table 4** shows that first generation biofuels are made from

seeds, cereals and sugar types (from extracts and juices) while second genera

tion biofuels are produced from the pretreatment of cellulosic and lignocellulosic biomass, such as: carbonaceous materials of renewable vegetable sources (wood,

In order to comply with the time-based interval adopted in this paper, it is necessary to highlight that the conversion of lignocellulosic biomass materials into

**4**, created from 301 "breakthrough inventions"

**3** analysis, showing a

and, (iii) post-treatment (distillation); in that order.

documents-corroborates previous understandings of **Table**

link between them and no effort of interaction among them.

**3.3 Breakthrough inventions: technology analysis**

bagasse, straw, barks, grass, etc.).

From that point of view, **Figure**

*by the authors, PatSeer® database.*

*DOI: http://dx.doi.org/10.5772/intechopen.88428*

*Analysis of the profile of the main patent holders of "breakthrough inventions".*

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation DOI: http://dx.doi.org/10.5772/intechopen.88428*

#### **Figure 4.**

*Intellectual Property Rights - Patent*

**Distillation**

**20**

**Current owner**

China petroleum

9

0.27

9

1

3

3

4

5

0

4

& chem-sinopec

Univ tsinghua Tsukishima kikai

7

0.32

2

0

2

2

1

0

0

0

Co Ltd

Univ tianjin Toshiba corp Oji holding corp

Inst process Eng

4

0.13

0

0

0

1

2

0

0

3

Cas

Hitachi group

Cofco Ltd Dalian chem

3 *N = 301. Source: Compiled by the authors, PatSeer® database.*

**Table 3.**

*Analysis of the profile of the main patent holders of "breakthrough inventions".*

0.08

3

0

0

0

0

0

0

0

physics inst

3 3

0.10

3

0

2

3

3

3

0

0

0.10

1

0

0

0

0

0

0

1

5

0.20

4

0

0

0

1

0

0

2

5

0.12

0

0

0

1

2

0

0

0

7

0.29

5

2

0

1

4

1

1

5

8

0.32

8

4

3

3

4

3

1

4

**No.**

**CPR**

**No.**

**Sugarcane**

**Biomass**

**Acid**

**Enzymatic**

**Yeast**

**Bacterium**

**Fungus**

**without**

**yeast**

**hydrolysis**

**hydrolysis**

**Pretreatment**

**Fermentation**

**granted**

**records**

*Relationship network among the 10 main holders of technologies associated to the production of ethanol, "breakthrough inventions" and biomass categories (sugarcane), pretreatment (acid hydrolysis and enzymatic hydrolysis), fermentation (yeast, bacterium and yeast-free fungus) and distillation. N = 301. Source: Elaborated by the authors, PatSeer® database.*

**Table 3** reveals to readers that the great intellectual effort by Chinese companies is in areas such as: (i) pretreatment of raw materials (hydrolysis); (ii) fermentation; and, (iii) post-treatment (distillation); in that order.

From that point of view, **Figure 4**, created from 301 "breakthrough inventions" documents-corroborates previous understandings of **Table 3** analysis, showing a relationship between actors and technology areas in each category. Therefore, it is possible to verify a certain level of non-binding cohesion among the analyzed actors, there being no sharing of technology in those supposed partnerships.

China Petrochem Corp (Sinopec) appears as an exception to the block composed by all the other actors. The data suggests low adhesion by that company to the cluster formed by other companies and universities. There seems to be no apparent link between them and no effort of interaction among them.

In the case of technology associated to the production of ethanol, the "breakthrough inventions" and the analysis of biomass (sugarcane) analysis, pretreatment (acid hydrolysis and enzymatic hydrolysis), fermentation (yeast, bacterium and yeast-free fungus), post-treatment (distillation) indicates possible dispersion.

#### **3.3 Breakthrough inventions: technology analysis**

In 2016, the United Nations Conference on Trade and Development (UNCTAD) [18] launched a report where they laid out the main distinctions between first and second generation renewable fuels, based on their raw materials' features (**Table 4**). Therefore, **Table 4** shows that first generation biofuels are made from seeds, cereals and sugar types (from extracts and juices) while second generation biofuels are produced from the pretreatment of cellulosic and lignocellulosic biomass, such as: carbonaceous materials of renewable vegetable sources (wood, bagasse, straw, barks, grass, etc.).

In order to comply with the time-based interval adopted in this paper, it is necessary to highlight that the conversion of lignocellulosic biomass materials into

#### **Table 4.**

*Differences between the production of first- and second-generation biofuel according to raw materials.*

biofuel was already viable in the mid-2000s and, on an industrial level, biofuels derived from this process involving enzymatic stages were not a common practice nor were they produced in great volumes for the market before the year 2005 [19]. Besides, it is possible to notice a significant change in the alcohol (ethanol) production from 2005 onwards (see **Figure 2**), the year when the Kyoto protocol was signed by most ethanol-producing countries and regions. At first, China and the United States did not agree to sign the protocol. However, after discussions that lasted more than half a decade, those countries ratified the protocol and started a global pact aimed at mitigating the production of greenhouse gases, in 2011 [20].

This global agreement directed, once and for all global efforts and interests in ethanol-producing technologies from lignocellulosic materials (biomass route: **Figure 5**). This way, it boosted their sustainability footprint and benefits for the

#### **Figure 5.**

*Schematic representation of the stages of second-generation ethanol production. Source: Elaborated by authors.*

**23**

**Figure 6.**

*by the authors, PatSeer® database.*

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation*

Fuel 2009 2010 2011 2012 2013 2014 2015 2016

27.71 42.36 46.52 922.62 2.522.22 4.770.26 8.538.41 8.848.82

0.00 0.04 0.08 0.08 3.82 3.82 102.21 102.21

environment and also appeased disputing parts regarding sources of raw materials to be used to produce energy in detriment of food for people, as is the case of

and take part of the emerging industry of second generation biofuels [18].

of the main routes of ethanol production (**Figure 6**).

In this sense, after 2013 the whole political debate about the implementation of second-generation fuels became a new reality of technological-industrial trajectory, while for example, ethanol coming from lignocellulosic materials (vegetable biomass and cellulosic residue) began to be produced at industrial/commercial scale (**Table 5**), representing an opportunity for a number of countries to be inserted technologically

As we can see from **Table 5**, the advanced route of ethanol production, similarly to biomass route (cellulose), gains momentum from 2013, when several new technologies started to be implemented in the industrial field. This way, using studies on clusters of the topic-based documents of "breakthrough inventions" as a departing point, a series of more detailed analysis was carried out about the technology profile

*Graphic representation of the topics in documents of patents of "breakthrough inventions". Source: Compiled*

*DOI: http://dx.doi.org/10.5772/intechopen.88428*

Advanced Ethanol

Cellulosic Sugars Ethanol

**Table 5.**

**Biofuel type and production capacity (millions of liters per year)**

*Source: Biofuels digest, 2011. Note: 2012–2016 data represents 2011 estimates.*

sugarcane in Brazil and China [21].

*Biofuel type and production capacity.*

#### **Table 5.**

*Intellectual Property Rights - Patent*

**Petroleum-gasoline substitutes**

**Petroleum-diesel substitutes**

FAEE)

*Source: UNCTAD [18].*

**Table 4.**

• Ethanol or butanol by fermentation of starches of sugars

• Biodiesel by transesterification of plant oils (FAME and

• Can be produced from various crops such as rapeseed (RME), soybeans (SME), sunflowers, coconut oil, palm oil,

jatropha, recycled cooking oil and animal fats.

• Pure plant oils (straight vegetable oil)

biofuel was already viable in the mid-2000s and, on an industrial level, biofuels derived from this process involving enzymatic stages were not a common practice nor were they produced in great volumes for the market before the year 2005 [19]. Besides, it is possible to notice a significant change in the alcohol (ethanol) production from 2005 onwards (see **Figure 2**), the year when the Kyoto protocol was signed by most ethanol-producing countries and regions. At first, China and the United States did not agree to sign the protocol. However, after discussions that lasted more than half a decade, those countries ratified the protocol and started a global pact aimed at mitigating the production of greenhouse gases, in 2011 [20]. This global agreement directed, once and for all global efforts and interests in ethanol-producing technologies from lignocellulosic materials (biomass route: **Figure 5**). This way, it boosted their sustainability footprint and benefits for the

*Schematic representation of the stages of second-generation ethanol production. Source: Elaborated by authors.*

*Differences between the production of first- and second-generation biofuel according to raw materials.*

**First-generation biofuels (from seeds, grain and sugar) Second-generation biofuels (from**

**lignocellulosic biomass, such as crop residues, woody crops or energy**

**Biochemically produced Petroleum-**

• Ethanol or butanol by enzymatic

**Thermochemically produced Petroleum-gasoline substitutes**

**Thermochemically produced Petroleum-diesel substitutes** • Fischer-Tropsch diesel

• Dimethyl ether (substitutes propane

• Fischer-Tropsch gasoline

**grasses)**

hydrolysis

• Methanol

as well) • Green diesel

• Mixed alcohols

**gasoline substitutes**

**22**

**Figure 5.**

*Biofuel type and production capacity.*

environment and also appeased disputing parts regarding sources of raw materials to be used to produce energy in detriment of food for people, as is the case of sugarcane in Brazil and China [21].

In this sense, after 2013 the whole political debate about the implementation of second-generation fuels became a new reality of technological-industrial trajectory, while for example, ethanol coming from lignocellulosic materials (vegetable biomass and cellulosic residue) began to be produced at industrial/commercial scale (**Table 5**), representing an opportunity for a number of countries to be inserted technologically and take part of the emerging industry of second generation biofuels [18].

As we can see from **Table 5**, the advanced route of ethanol production, similarly to biomass route (cellulose), gains momentum from 2013, when several new technologies started to be implemented in the industrial field. This way, using studies on clusters of the topic-based documents of "breakthrough inventions" as a departing point, a series of more detailed analysis was carried out about the technology profile of the main routes of ethanol production (**Figure 6**).

#### **Figure 6.**

*Graphic representation of the topics in documents of patents of "breakthrough inventions". Source: Compiled by the authors, PatSeer® database.*

By reading **Figure 6**, we can see that technology linked to the Ethanol Fermentation phase and pre-treatment (Alcohol Production) are the base of new technology trajectories in the production of ethanol. The image allows us to see subsections related to the conversion of cellulose into ethanol, as well as the treatments with the use of acids and enzymes for the preparation of sugars that will be consumed by microorganisms during fermentation. Regarding the raw materials the analysis in **Figure 6** comprises, it is possible to see the technological inclination toward the use of biomass material (lignocellulosic) as a pillar for the technology trajectory in the production of fuel alcohol that will continue into coming years. The greater emphasis is on the biomass material that is not consumable by humans and animals, especially the waste from the lignocellulosic base.

As a way to corroborate this timely analysis, **Table 6** shows the relation of the 10 main international classifications of patents with the biomass categories (sugarcane), pre-treatment (acid and enzymatic hydrolysis), fermentation (yeast, bacterium, yeastfree fungus) and post-treatment (distillation). We noticed the main classification is C12P (fermentation or enzyme-using processes to synthesize a desired chemical compound or composition or to separate optical isomers from a racemic mixture), with a TII higher than one (3.67), proving to be a relevant technology field for the production of ethanol. The most representative categories were related to yeast and distillation, because during the ethanol production process, both first and second generation, fermentation and distillation are crucial. However, TII for both was low (0.37).

Based on the data in **Table 6**, it must be highlighted that the classification code C12P, (Fermentation or enzyme-using processes to synthesize a desired chemical compound or composition or to separate optical isomers from a racemic mixture) was the main classification for the analysis, using a TII above one (3.67), a technology field

*N = 301. C12P: Fermentation or enzyme-using processes to synthesize a desired chemical compound or composition or to separate optical isomers from a racemic mixture; C12R: Indexing scheme associated with subclasses; C12N: Microorganisms or enzymes; compositions thereof; C07C: Acyclic or carbocyclic compounds; C02F: Treatment of water, waste water, sewage or sludge; C12M: Apparatus for enzymology or microbiology; C10L: Fuels not otherwise provided for; natural gas; synthetic natural gas obtained by processes; C08L: Compositions of macromolecular compounds; B01J: Chemical or physical processes; B01D: Separation. Source: Compiled by the authors, PatSeer® database.*

#### **Table 6.**

*List of the top 10 IPC main class with document classification according to "breakthrough inventions" patent technology process, and technical impact index–TII.*

**25**

lulase enzymes.

**Figure 7.**

suitable biocatalyst to produce ethanol.

material for use in ethanol production.

lytic enzyme and alcohol fermentation microorganism.

**3.4 Breakthrough inventions: forward citation analysis**

lulosic biomass (LB) followed by steam-explosion pre-treatment.

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation*

that is essential for ethanol production. Meanwhile, the other technology categories (IPCs) involved in the ethanol process have proven to be statistically with TII impacts but without major discrepancies or significant dispersion (average TII = 0.434; Average deviation = 0.163). They are hierarchically ranked in the relevance sequence that follows: (1st): Fermentation technologies (Yeast, Bacterium and Yeast-free Fungus), because both in first and second generation, fermentation is a crucial stage to obtain ethanol. (2nd) pre-treatment technologies (Acid and enzymatic hydrolysis- slight tendency toward the latter); finally (3rd) Post-treatment technologies (Distillation). This hierarchical configuration can be confirmed in **Figure 7**, which shows the relation between all networks of relationship between technology clusters. Still looking at **Figure 7A** and **B** it is possible to see strong and direct relations between the stages of the ethanol production process, especially between the pretreatment and fermentation stages, which are interrelated and form a network of weak knots. But when isolated, they are intense. We can observe that, together, such

*Networking of the top 10 IPC Main class and the categories (pre-treatment = acid hydrolysis, enzymatic hydrolysis; fermentation = yeast, bacterium, fungus without yeast; distillation), (A) and density graph of the same networking (B). Source: Compiled by the authors, PatSeer® database and VOS viewer visualization [22].*

stages make up the central technology focus of ethanol production.

"breakthrough inventions" within the context of previous analysis.

involves treating a pre-treated lignocellulosic substrate with cellulase.

In the sequence, we present some of the most highly cited patent documents of

WO2003078644-A2 (25 September 2003): Conversion of cellulose to glucose

WO2006007691-A1 (26 January 2006): Obtaining a product sugar stream from cellulosic biomass, involves hydrolyzing a neutralized cellulosic biomass with cel-

WO2006110900-A2 (19 October 2006): Production (P1) of ethanol comprising biomass with aqueous solution containing ammonia, a saccharification enzyme consortium to produce fermentable sugars, and a fermentation conditions with a

JP4522797-B2 (11 August 2010): Pre-processing of lignocellulose-containing raw

JP5233452-B2 (10 July 2013): System for saccharification and fermentation of woody biomass raw material, by adding cellulose degrading enzyme, hemicellulo-

BR200100762-A (06 November 2001): The method involves grinding lignocel-

Currently, the analysis of "Forward Citation" is often used by authors of nonpatent literature when the objective is a better understanding of patterns, for

*DOI: http://dx.doi.org/10.5772/intechopen.88428*

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation DOI: http://dx.doi.org/10.5772/intechopen.88428*

**Figure 7.**

*Intellectual Property Rights - Patent*

By reading **Figure 6**, we can see that technology linked to the Ethanol Fermentation phase and pre-treatment (Alcohol Production) are the base of new technology trajectories in the production of ethanol. The image allows us to see subsections related to the conversion of cellulose into ethanol, as well as the treatments with the use of acids and enzymes for the preparation of sugars that will be consumed by microorganisms during fermentation. Regarding the raw materials the analysis in **Figure 6** comprises, it is possible to see the technological inclination toward the use of biomass material (lignocellulosic) as a pillar for the technology trajectory in the production of fuel alcohol that will continue into coming years. The greater emphasis is on the biomass material that is not consumable by humans

As a way to corroborate this timely analysis, **Table 6** shows the relation of the 10 main international classifications of patents with the biomass categories (sugarcane), pre-treatment (acid and enzymatic hydrolysis), fermentation (yeast, bacterium, yeastfree fungus) and post-treatment (distillation). We noticed the main classification is C12P (fermentation or enzyme-using processes to synthesize a desired chemical compound or composition or to separate optical isomers from a racemic mixture), with a TII higher than one (3.67), proving to be a relevant technology field for the production of ethanol. The most representative categories were related to yeast and distillation, because during the ethanol production process, both first and second generation, fermentation and distillation are crucial. However, TII for both was low (0.37).

Based on the data in **Table 6**, it must be highlighted that the classification code C12P, (Fermentation or enzyme-using processes to synthesize a desired chemical compound or composition or to separate optical isomers from a racemic mixture) was the main classification for the analysis, using a TII above one (3.67), a technology field

> **Enzymatic hydrolysis**

C12P 1105 **3.67** 130 322 363 562 264 35 379 C12R 370 **1.23** 50 139 151 261 135 15 125 C12N 260 **0.86** 23 47 56 151 80 17 54 C07C 200 **0.66** 17 20 14 18 4 1 71 C02F 126 **0.42** 7 2 2 11 16 4 25 C12M 110 **0.37** 13 16 19 35 16 3 47 C10L 107 **0.36** 10 17 19 20 16 2 42 C08L 99 **0.33** 1 8 1 2 12 0 18 B01J 78 **0.26** 0 7 2 0 0 0 8 B01D 63 **0.21** 6 4 5 3 1 0 32 TII **0.11 0.23 0.25 0.37 0.18 0.03 0.37** *N = 301. C12P: Fermentation or enzyme-using processes to synthesize a desired chemical compound or composition or to separate optical isomers from a racemic mixture; C12R: Indexing scheme associated with subclasses; C12N: Microorganisms or enzymes; compositions thereof; C07C: Acyclic or carbocyclic compounds; C02F: Treatment of water, waste water, sewage or sludge; C12M: Apparatus for enzymology or microbiology; C10L: Fuels not otherwise provided for; natural gas; synthetic natural gas obtained by processes; C08L: Compositions of macromolecular compounds; B01J:*

*Chemical or physical processes; B01D: Separation. Source: Compiled by the authors, PatSeer® database.*

*List of the top 10 IPC main class with document classification according to "breakthrough inventions" patent*

**TII Biomass Pretreatment Fermentation Posttreatment**

**Yeast Bacterium Fungus**

**(without yeast)**

**Distillation**

and animals, especially the waste from the lignocellulosic base.

**Sugarcane Acid**

**hydrolysis**

**24**

**Table 6.**

*technology process, and technical impact index–TII.*

**IPC No. records** *Networking of the top 10 IPC Main class and the categories (pre-treatment = acid hydrolysis, enzymatic hydrolysis; fermentation = yeast, bacterium, fungus without yeast; distillation), (A) and density graph of the same networking (B). Source: Compiled by the authors, PatSeer® database and VOS viewer visualization [22].*

that is essential for ethanol production. Meanwhile, the other technology categories (IPCs) involved in the ethanol process have proven to be statistically with TII impacts but without major discrepancies or significant dispersion (average TII = 0.434; Average deviation = 0.163). They are hierarchically ranked in the relevance sequence that follows: (1st): Fermentation technologies (Yeast, Bacterium and Yeast-free Fungus), because both in first and second generation, fermentation is a crucial stage to obtain ethanol. (2nd) pre-treatment technologies (Acid and enzymatic hydrolysis- slight tendency toward the latter); finally (3rd) Post-treatment technologies (Distillation). This hierarchical configuration can be confirmed in **Figure 7**, which shows the relation between all networks of relationship between technology clusters.

Still looking at **Figure 7A** and **B** it is possible to see strong and direct relations between the stages of the ethanol production process, especially between the pretreatment and fermentation stages, which are interrelated and form a network of weak knots. But when isolated, they are intense. We can observe that, together, such stages make up the central technology focus of ethanol production.

In the sequence, we present some of the most highly cited patent documents of "breakthrough inventions" within the context of previous analysis.

WO2003078644-A2 (25 September 2003): Conversion of cellulose to glucose involves treating a pre-treated lignocellulosic substrate with cellulase.

WO2006007691-A1 (26 January 2006): Obtaining a product sugar stream from cellulosic biomass, involves hydrolyzing a neutralized cellulosic biomass with cellulase enzymes.

WO2006110900-A2 (19 October 2006): Production (P1) of ethanol comprising biomass with aqueous solution containing ammonia, a saccharification enzyme consortium to produce fermentable sugars, and a fermentation conditions with a suitable biocatalyst to produce ethanol.

JP4522797-B2 (11 August 2010): Pre-processing of lignocellulose-containing raw material for use in ethanol production.

JP5233452-B2 (10 July 2013): System for saccharification and fermentation of woody biomass raw material, by adding cellulose degrading enzyme, hemicellulolytic enzyme and alcohol fermentation microorganism.

BR200100762-A (06 November 2001): The method involves grinding lignocellulosic biomass (LB) followed by steam-explosion pre-treatment.

#### **3.4 Breakthrough inventions: forward citation analysis**

Currently, the analysis of "Forward Citation" is often used by authors of nonpatent literature when the objective is a better understanding of patterns, for

example, of formation of a portfolio of patent documents for a systematic analysis of the international codes of patent classification. Carpenter, Narin and Woolf [23] and Trajtenberg [8], in their respective works, managed to measure the relationship between "Forward Citation" and the future value of an invention, therefore the "Forward Citation" number that a given patent document receives, and which accumulates over time, is related to the significant technology impact of the technical content of those documents (that is, "breakthrough inventions"). That suggests that patents with a high number of citations have a relevant technology impact and contribute significantly to the advance of technology [24].

Keeping that in mind, it was necessary for the present analysis of investigation of the technology trajectory for the field of first and second generation ethanol production sector to use "Forward Citation" analysis as a "proxy" for the measurement of intangible added value that those "breakthrough inventions" documents really have. This way, under the prism adopted by this study, it was noted that: the more valuable a patented technology, the newer the incentives are created from past learnings; this way, looking at it from an economic point o view, "Forward Citation" results in the measurement of the valuing of those documents of "breakthrough inventions".

This way, the "Forward Citation" analysis of the 301 documents of "breakthrough inventions" was carried out by taking into account the codes of international classification of patents retrieved in previous analyses (**Figure 8**). From that analysis it was possible to identify: (i) 3506 patent documents in "forward citation"; and, (ii) 1524 patent documents in "backward citation"; the main classifications in the documents in (i) were: (a) C12P7 (count-1337); (b) C12P19 (count-532); (c) C07C29 (count-434); and, (d) C12M1 (count-359).

Still looking at **Figure 8**, it is possible to note that the ratio between the quantity of retrieved documents to (i) "forward citation" and (ii) "backward citation" outnumbers the unit by 2.3 times, thus indicating that the 301 "breakthrough inventions" documents analyzed in this study presented a strong impact on subsequent technology generations [25].

*Analysis of citations of breakthrough inventions. Source: Compiled by the authors, PatSeer® data.*

**27**

**Table 7.**

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation*

Moving on, the 3506 patent documents in "forward citation" were treated and filtered through extended family, resulting in 2406 original documents of patent family (no document doubling). These were equally stratified and analyzed according to technology categories and international codes of patent classification (IPC),

Analyzing **Table 7** in relation to **Figure 7A** and **B**, it is possible to see there is a prevalence of subclass C12P in detriments to other classification codes (IPC). This highlights that the technology trajectory in analysis is clearly directed to the production of second generation ethanol, through the use of cellulosic waste (biomass).

**Biomass Pretreatment Fermentation Post-**

**Yeast Bacterium Fungus**

**(without yeast)**

**Enzymatic hydrolysis**

460 56 165 192 179 59 0 95

262 38 95 133 64 29 0 41

167 24 29 33 32 12 0 45

161 21 61 72 22 11 0 10

149 22 47 63 112 47 0 31

148 18 50 33 10 6 0 10

113 8 14 19 16 6 0 23

113 11 26 29 42 12 0 39

**treatment**

**Distillation**

*DOI: http://dx.doi.org/10.5772/intechopen.88428*

which resulted in **Table 7**.

**IPC full class No.**

C12P7/10: Substrate containing cellulosic material

C12P19/14: Produced by the action of a carbohydrase

C12M1/00: Apparatus for enzymology or microbiology

C12P19/02: Monosaccharides

C12R1/865: *Saccharomyces cerevisiae*

C13K1/02: By saccharification of cellulosic materials

B09B3/00: Destroying solid waste or transforming solid waste into something useful or harmless

C12P7/08: Produced as by-product or from waste or cellulosic material substrate

*N = 2406. Source: Compiled by the authors, PatSeer® database.*

*of "breakthrough inventions" patents.*

**records**

**Sugarcane Acid**

**hydrolysis**

C12P7/06: Ethanol 362 50 61 75 147 57 0 75

C12P7/16: Butanol 114 23 39 32 25 17 0 27

*List of top 10 IPC full class with document classification according to the technology process of forward citation*

*Technological Trajectories Studies of Sugarcane Ethanol Production Using Patent Citation DOI: http://dx.doi.org/10.5772/intechopen.88428*

Moving on, the 3506 patent documents in "forward citation" were treated and filtered through extended family, resulting in 2406 original documents of patent family (no document doubling). These were equally stratified and analyzed according to technology categories and international codes of patent classification (IPC), which resulted in **Table 7**.

Analyzing **Table 7** in relation to **Figure 7A** and **B**, it is possible to see there is a prevalence of subclass C12P in detriments to other classification codes (IPC). This highlights that the technology trajectory in analysis is clearly directed to the production of second generation ethanol, through the use of cellulosic waste (biomass).

#### **Table 7.**

*List of top 10 IPC full class with document classification according to the technology process of forward citation of "breakthrough inventions" patents.*

*Intellectual Property Rights - Patent*

inventions".

example, of formation of a portfolio of patent documents for a systematic analysis of the international codes of patent classification. Carpenter, Narin and Woolf [23] and Trajtenberg [8], in their respective works, managed to measure the relationship between "Forward Citation" and the future value of an invention, therefore the "Forward Citation" number that a given patent document receives, and which accumulates over time, is related to the significant technology impact of the technical content of those documents (that is, "breakthrough inventions"). That suggests that patents with a high number of citations have a relevant technology impact and

Keeping that in mind, it was necessary for the present analysis of investigation of the technology trajectory for the field of first and second generation ethanol production sector to use "Forward Citation" analysis as a "proxy" for the measurement of intangible added value that those "breakthrough inventions" documents really have. This way, under the prism adopted by this study, it was noted that: the more valuable a patented technology, the newer the incentives are created from past learnings; this way, looking at it from an economic point o view, "Forward Citation" results in the measurement of the valuing of those documents of "breakthrough

This way, the "Forward Citation" analysis of the 301 documents of "breakthrough inventions" was carried out by taking into account the codes of international classification of patents retrieved in previous analyses (**Figure 8**). From that analysis it was possible to identify: (i) 3506 patent documents in "forward citation"; and, (ii) 1524 patent documents in "backward citation"; the main classifications in the documents in (i) were: (a) C12P7 (count-1337); (b) C12P19 (count-532); (c)

Still looking at **Figure 8**, it is possible to note that the ratio between the quantity

of retrieved documents to (i) "forward citation" and (ii) "backward citation" outnumbers the unit by 2.3 times, thus indicating that the 301 "breakthrough inventions" documents analyzed in this study presented a strong impact on subsequent

*Analysis of citations of breakthrough inventions. Source: Compiled by the authors, PatSeer® data.*

contribute significantly to the advance of technology [24].

C07C29 (count-434); and, (d) C12M1 (count-359).

technology generations [25].

**26**

**Figure 8.**

This information can be inferred by the sequenced information of the main classifications, as follows: (i) C12P7/10: Substrate containing cellulosic material; (ii) C12P7/06: Ethanol; (iii) C12P19/14: Produced by the action of a carbohydrase (set of enzymes that catalyzes 5 types of breakdown during carbohydrates into simple sugars); (iv) C12M1/00: Apparatus for enzymology or microbiology; (v) C12P19/02: Monosaccharides; (vi) C12R1/865: Saccharomyces cerevisiae; (vii) C13K1/02: By saccharification of cellulosic materials; (viii) C12P7/08: Produced as by-product or from waste or cellulosic material substrate. Besides, there is emphasis on the use of enzymes during the initial stage of pre-treatment of raw materials through enzymatic hydrolysis.

This way, it is clear that the stages of pre-treatment and fermentation are the strongest and most relevant technology nuclei for the sector in the near future.