Modified chitin and chitosan with different ionic liquids and solubility in solvents.
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IntechOpen Book Series will also publish a program of research-driven Thematic Edited Volumes that focus on specific areas and allow for a more in-depth overview of a particular subject.
\\n\\nIntechOpen Book Series will be launching regularly to offer our authors and editors exciting opportunities to publish their research Open Access. We will begin by relaunching some of our existing Book Series in this innovative book format, and will expand in 2022 into rapidly growing research fields that are driving and advancing society.
\\n\\nLaunching 2021
\\n\\nArtificial Intelligence, ISSN 2633-1403
\\n\\nVeterinary Medicine and Science, ISSN 2632-0517
\\n\\nBiochemistry, ISSN 2632-0983
\\n\\nBiomedical Engineering, ISSN 2631-5343
\\n\\nInfectious Diseases, ISSN 2631-6188
\\n\\nPhysiology (Coming Soon)
\\n\\nDentistry (Coming Soon)
\\n\\nWe invite you to explore our IntechOpen Book Series, find the right publishing program for you and reach your desired audience in record time.
\\n\\nNote: Edited in October 2021
\\n"}]',published:!0,mainMedia:{caption:"",originalUrl:"/media/original/132"}},components:[{type:"htmlEditorComponent",content:'With the desire to make book publishing more relevant for the digital age and offer innovative Open Access publishing options, we are thrilled to announce the launch of our new publishing format: IntechOpen Book Series.
\n\nDesigned to cover fast-moving research fields in rapidly expanding areas, our Book Series feature a Topic structure allowing us to present the most relevant sub-disciplines. Book Series are headed by Series Editors, and a team of Topic Editors supported by international Editorial Board members. Topics are always open for submissions, with an Annual Volume published each calendar year.
\n\nAfter a robust peer-review process, accepted works are published quickly, thanks to Online First, ensuring research is made available to the scientific community without delay.
\n\nOur innovative Book Series format brings you:
\n\nIntechOpen Book Series will also publish a program of research-driven Thematic Edited Volumes that focus on specific areas and allow for a more in-depth overview of a particular subject.
\n\nIntechOpen Book Series will be launching regularly to offer our authors and editors exciting opportunities to publish their research Open Access. We will begin by relaunching some of our existing Book Series in this innovative book format, and will expand in 2022 into rapidly growing research fields that are driving and advancing society.
\n\nLaunching 2021
\n\nArtificial Intelligence, ISSN 2633-1403
\n\nVeterinary Medicine and Science, ISSN 2632-0517
\n\nBiochemistry, ISSN 2632-0983
\n\nBiomedical Engineering, ISSN 2631-5343
\n\nInfectious Diseases, ISSN 2631-6188
\n\nPhysiology (Coming Soon)
\n\nDentistry (Coming Soon)
\n\nWe invite you to explore our IntechOpen Book Series, find the right publishing program for you and reach your desired audience in record time.
\n\nNote: Edited in October 2021
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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"314",title:"Regenerative Medicine and Tissue Engineering",subtitle:"Cells and Biomaterials",isOpenForSubmission:!1,hash:"bb67e80e480c86bb8315458012d65686",slug:"regenerative-medicine-and-tissue-engineering-cells-and-biomaterials",bookSignature:"Daniel Eberli",coverURL:"https://cdn.intechopen.com/books/images_new/314.jpg",editedByType:"Edited by",editors:[{id:"6495",title:"Dr.",name:"Daniel",surname:"Eberli",slug:"daniel-eberli",fullName:"Daniel Eberli"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"57",title:"Physics and Applications of Graphene",subtitle:"Experiments",isOpenForSubmission:!1,hash:"0e6622a71cf4f02f45bfdd5691e1189a",slug:"physics-and-applications-of-graphene-experiments",bookSignature:"Sergey Mikhailov",coverURL:"https://cdn.intechopen.com/books/images_new/57.jpg",editedByType:"Edited by",editors:[{id:"16042",title:"Dr.",name:"Sergey",surname:"Mikhailov",slug:"sergey-mikhailov",fullName:"Sergey Mikhailov"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"57402",title:"Solubility of Chitin: Solvents, Solution Behaviors and Their Related Mechanisms",doi:"10.5772/intechopen.71385",slug:"solubility-of-chitin-solvents-solution-behaviors-and-their-related-mechanisms",body:'\nChitin is a polysaccharide consisting of glycosidic bonds in linear or branched fashion between two adjacent monosaccharides, 2-(acetylamino)-2-deoxy-d-glucose. In general, monosaccharides undergo a polycondensation reaction to link more than 20 units of oligosaccharides by glycosidic linkages. Most polysaccharides show the degree of average polymerization (number average DP) around 200–3000 while longer polysaccharide (like cellulose) exhibits DP around 7000–15,000. The presence of acetyl, amino and hydroxyl groups in the polysaccharide chain, due to the generation of hydrogen bonds (inter and intramolecular) makes the chitin highly aggregated. Therefore, it is insoluble in all regular solvents such as water, organic solvents, mild acidic or basic solution, etc. Chitin insolubility affects the scaling up of the processes for the production of chitin-based products. The first study on solubility determination of chitin was done by Austin who tested chitin in different solvents [1]. It was a well-organized evaluation of chitin solubility in different types of solvents such as dichloroacetic (DCA) and trichoroacetic (TCA) acids in presence or absence of alcohol, etc. Later on, many studies were conducted with the same intention by many other scientists and chitin solubility was verified in many solvents such as dimethylacetamide (DMA)/LiCl mixture [2], CaBr2·H2O saturated methanol [3], hexafluoroisopropyl alcohol and hexafluoraceton [4], lithium thiocyanate [5], phosphoric acid [6] and N-methyl-2-pyrrolidone [7], etc. Although dissolution of chitin is possible by these solvents many of them are toxic, scarcely degradable, corrosive, or mutagenic. Therefore, the choice of an appropriate solvent for chitin and chitosan solubilization is important and primary issue for lab scale research and scaling up for industrial practices. The acetyl groups in chitin can be removed by deacetylation to convert insoluble chitin into a more soluble compound, namely chitosan (this name is given to chitin with at least 50% degree of deacetylation, DD). Therefore, this chapter will deal with the deacetylation process and the changes in molecular orientations and bonds after the deacetylation reaction. Moreover, the chapter will revise technical details regarding different aspects of solution behavior of chitin and chitosan. The parameters influencing solubility and their action mechanisms, theoretical discussions and recent relevant research findings on chitin and chitosan will be found in this chapter. Finally, modification of polysaccharides and their enhanced solubility will be discussed.
\nPolysaccharides mimic protein and amino acids structure consisting of special conformation of secondary, tertiary and quaternary architectural structures. Chitin is arranged as crystalline microfibrils clustered with six-stranded helixes of a protein structure. Polymerization of the monosaccharides, β-(1-4)-2-acetamido-2-deoxy-β-d-glucosamine units exhibit three different polymorphism (α, β and γ sheets) whereas the N-acetyl glycosyl moiety is a common crystallographic unit in all [2]. Electron diffraction studies reveal a highly crystalline nature of chitin in the α and β conformation. The α-conformation is one of the most abundant allomorphs in which the unit polymer chains are arranged in an antiparallel fashion whereas the adjacent chains are always in the opposite direction [3]. In β, less frequent in nature sheet all chains are in the same direction and parallel, γ conformation is a variant of the α arrangement in which two parallel, adjacent and unidirectional chains are arranged with one opposite directional chain (Figure 1). Both α and β conformations maintain a strong network dominated by intra-chain hydrogen bonds between the groups of C═O⋯NH and C═O⋯OH within a distance of 0.47 nm. In α-chitin conformation, additional inter-chain hydrogen bonds bind the hydroxymethyl groups while this type of interaction is not observed in the β conformation. Thus, β-chitin conformation is more prone to intra-crystalline swelling than α-chitin conformation. Different structural arrangement of α-chitin and β-chitin provide the reason why water, alcohol and amines are able to get access to the β conformation by swelling with and without disrupting the chain arrangement and crystalline structure [4]. For example, the swelling of β sheets in concentrated acidic solution of HNO3 or HCl solution exhibits a permanent transformation into α-chitin conformation. In this case, a partial dissolution occurs driven by hydrolysis induced by the acid treatment. The recrystallization process of the smaller hydrolyzed chain starts on the un-hydrolyzed chitin sheets, which are called “epitaxy”. Therefore, no single crystal growth is observed during the recrystallization and new α-chitin conformation crystals are observed. The transformation β→α indicates that the α-chitin sheet is thermodynamically stable and stability is achieved only via recrystallization [3]. The α-chitin sheets are not swelled by water and alcohol while aliphatic diamine or highly basic solutions can diffuse into the crystalline structure to promote the formation of chain complexes. The parameter value of inter-chain expansion is same as β-sheet around 0.7 nm. Therefore, a simple processing of β-chitin with 20% NaOH results into the conversion of α to β-conformations.
\nStructure of different chitin conformations (α, β and γ-chitin domain conformation).
Chitin polysaccharides contain functional amino groups in its backbone to provide positively charged polysaccharide upon solubilization. The amount of reactive amino groups can be increased by increasing deacetylation which is quantified by the degree of deacetylation (%DD). Chitin is the only positively charged polysaccharide among all other naturally occurred biopolymers which allows a wide range of biological applications. There are two main groups in the chitin structure influences the functionality of chitin: (i) amino groups and (ii) hydroxyl groups (Figure 1). The amino sites might react with aldehyde and ketone groups for the Schiff Bases formation and influence solubility. In addition, two hydroxyl groups in chitin structure provide excellent pathways for modification and functionalization in view of an increase of solubility. Those hydroxyl groups involve in the O-acetylation, O-alkylation, H-bonds formation, etc. [5]. Also, the amino groups are responsible for the short-range primary and secondary electrostatic interaction while the second one involves the formation of hydrogen bonds. Moreover, the available unhydrolysed acetyl groups in chitin molecules form hydrophobic bonds in the solution and get aggregated [6].
\nChitins may have different acetylation depending on the sources such as fungi, insects, crustaceans or molluscs. Due to its crystalline structure with strong hydrogen bonds and cohesive forces, highly aggregated three-dimensional network is developed which leads to insolubility in conventional solvents. Pure chitin contains around 90% N-acetyl groups in its backbone and some deacetylation reactions take place due to the extraction process of chitin from the natural sources. There are two monomer units present in the chitin structure in different fraction: (i) 2-acetamino-2-deoxy-d-glucopyronase (N-acetyl-d-glucosamine) and (ii) 2-amino-2-deoxy-d-glucopyronase (N-amino-d-glucosamine). The first one, 2-acetamino-2-deoxy-d-glucopyronase, displays insolubility due to the strong hydrogen bonds between the acetyl groups of the same or adjacent chitin chains. Hydrogen bonds network builds a three-dimensional crystalline matrix by sequencing the following bonds ─NH⋯O═C and ─OH⋯O═C. The other unit, N-amino-d-glucosamine shows a distinct property such as hydrophilic nature and positively charged in acidic solution. The domination of the hydrophilic character with a high amount of N-amino-d-glucosamine unit in the chitin backbone can be determined by degrees of deacetylation (DD). The DD is determined from the ratio of N-amino-d-glucosamine to N-acetyl-d-glucosamine while the degree of acetylation (DA) represents the deduction from 100 (i.e. 100—DD). When DD is between 60 and 90% a new chemical entity “Chitosan” is baptized which is soluble in organic acids such as acetic acid. Alternatively, the structure with a DD value less than 60% is regarded as chitin and insoluble in acidic solutions. Chitin is treated with alkali solution (NaOH) for deacetylation to occur. The type of deacetylation process provides a different distribution of acetyl groups in the chitin backbone: micro-block and random. The micro-block domain chitosan is easily susceptible to aggregation along the extended series of acetyl units which leads to a complete insolubility in the majority of the common solvents. In the case of high DA > 60% or DD < 40%, chitosan is very prone to association and aggregation while chitin with low DA = 1.5% or DD = 98.5 did not show any aggregation [7]. Simina and coworkers reported the aggregation behavior for a wide range of DD at pH 4.5 and determined the hydrodynamic radius at DD – 98.5, 63 and 31%. For very high DD (>75%), protonated charge condensation occurs in the chitosan solution due to large charge density which leads to electrostatic repulsion and high solubility. As a result, single size distribution of chitin molecules was observed with an average diameter of 40 nm at DD 98.5% [7]. When the DD was moderated (75–50%), an additional size distribution of 300 nm (an average diameter) with the previous size distribution (40 nm) was displayed which indicated the aggregated form of chitin. The circumstance asserted that the hydrophilic chitin exhibited a transition of hydrophilic character to the hydrophobic nature due to the rise of hydrogen bonds contributed by the acetyl groups or decrease of DD value. Further decrease of DD (<50%) influenced the hydrophobic nature of the polymer chains and three different size distributions were achieved including two previous size distribution. The aggregation and agglomeration of chitin chains increased the size distribution to micrometer sized (average diameter). It indicated the development of complete hydrophobic bonds influenced by higher amount of acetyl groups than the higher DD (>50%). Chitin structure at low DD (<50%) contains the largest amount of N-acetyl-d-glucosamine units and exhibits distinct domains of crystallinity. Therefore, the fraction of N-acetyl-d-glucosamine units has high influence on the solubility and solution property.
\nThe aggregation behavior of chitosan is strongly influenced by the pH of the solvent medium. In general, chitosan molecules are more or less ionized up to pH 6.0, and the ionization increases as the pH moves to low values. Therefore, the amino groups of chitin chains (low DA) at a particular pH (<6.0) capture H+ solution ions and exhibited positive surface charge which can be determined by zeta potential value. The charged amino groups resist the aggregation of chitosan in the solution, but when the DA value increases from zero to higher value the aggregation starts to dominate over the coulombic repulsion forces of the charged groups. The pH at which the net charge of a chitosan solution prevents aggregation is called critical pH. Therefore, the aggregation behavior of chitosan can be divided into two distinct types—closed and open type aggregation based on pH values. The closed type aggregation is observed at very low pH when the radius of gyration becomes constant and insensitive to chitosan concentration. This indicates that chitosan is completely protonated and the solubilized chitosan molecules maintain stable aggregation. This phenomenon can be related to the classical Rayleigh theory in all charged species fragmented into smaller charged species beyond a certain critical point of net charge. On the other hand, open type aggregation takes place when aggregation and association forces overcome the repulsive effect at pH higher than the critical pH. The radius of gyration increases with the incorporation of more chitosan molecules in the solution system. In addition, the high pH value (>6.0) also raises the number of deprotonated species in the solution and aggregation moves to agglomeration due to the generation of hydrogen bonds involving the neutralized NH2 groups of chitosan chains [8]. Moreover, the hydrolytic cleavage occurs when chitin is treated by strong acid such as highly concentrated acetic acid or HCl by involving the glycosidic bond (Figure 2: hydrolytic degradation). The detail mechanism has been discussed in Section 4.1.
\nMechanism of hylytic and non-hydrolytic degradation by organic acid (FA).
Apart from the degree of deacetylation and pH, molecular weight influences the conformational changes and solubility of chitosan. Chitosan solubility increases with the decrease of molecular weight [9]. The solubilization process of chitosan, as it happens for functionalized polymers, involves different types of chemical and physical interactions such as hydrogen bonds, hydrophobic interactions, van der Waals forces, etc. The effect of DA on the solubility of chitosan has already been discussed in previous section in which the hydrogen bonds involving acetyl groups played a dominant role. When DA value is lower than 50%, the protonated amino groups dominate the electrostatic repulsions between chitin chain and the hydrogen bonds collapse. As a result, chitin with low DA (<50%) become soluble at acidic pH. Chitin with low DA is fully ionized at pH 3.0 while deprotonation reaches to the highest value at pH 6.0 and precipitate occurs. Therefore, a transition between dissolved and undissolved chitin is mainly controlled by the medium pH and the degree of deacetylation or number of amino groups present in the chitin structure. The formation of hydrogen bonds and the impact of hydrophobic interaction on the chain aggregation are observed even though chitin molecules are fully deacetylated [6]. Therefore, deprotonation, β→α phase transition and precipitation represents the scheme for the formulation of α-chitin by aggregation. Chitosan at high molecular weight (MW 300 kDa) exhibit the α-chitin crystalline structure upon aggregation. Aggregation determines a conformational entropy loss due to the arrangement of the molecular chains in a regular crystalline array [10]. The release of water compensates the loss of entropy during chain aggregation resulting in an overall decrease of Gibbs free energy, which is a thermodynamic criterion for a process to be spontaneous. However, the circumstance changes for chitosan oligomers of low MW (2.43 kDa). In this case, the aggregation is not favored due to the formation of shorter chains which reduce the hydrogen bonds formation between macromolecules and lack of amino groups for the formation of intermolecular hydrogen bonds. As a result, the pH for the transition between dissolved and undissolved chitosan in aqueous medium shifted to pH 8.0 from pH 6.0. Therefore, the soluble and insoluble transition of chitosan occurs when the MW (weight average) range exists in the range of 3.82–4.67 kDa. The transition moves to complete solubility when the MW decreases to the monomer scale at below 3.28 kDa because no intermolecular hydrogen bond leads to chitosan aggregation and solubilization is observed at neutral pH [9].
\nIonic strength is a measure of the total concentration of ions present in a solution. In general, charged particles exhibit a net electrostatic effect up to a distance in the solution which is indicated as Debye screening length (
where the parameter
Chitosan or modified chitin is readily soluble in dilute acidic medium below its pKa (pH = 6.5) while chitin is insoluble in organic and regular solvents. The amino groups in chitosan backbone enhance ionization at low pH by forming chit-NH3+ and increase the solubility of the polysaccharide while at higher pH value (>pH 6.0), it precipitates. Therefore, the solubility of chitin can be increased by converting to chitosan (by deacetylation reaction) which depends on the pKa value and also on the DD. The ability of acidic media to protonate chitosan mainly controls the ionization and solubility of the polyelectrolytes. Chitosan exhibits solubility in acid media (1%) such as acetic acid, formic acid [13], l-glutamic acid, lactic acid, succinic acid [14], etc. Tsao and coworkers proposed a mechanism for depolymerization of chitosan in acetic acid. The process involves two main pathways by chain scission, that is, (i) the depolymerization of glycosidic linkage by hydrolysis and (ii) the deacetylation of the
Chitin liquefaction is one of the simple processes in which chitin is transformed into small soluble molecules. Formic acid (FA) can be used as liquefaction agent for chitin. Moreover, due to high vapor pressure FA can be evaporated without leaving any residue. Three different types of products are formed after the liquefaction of chitin, that is, (i) N-acetyl glucosamine having formate functional groups (NAGF), (ii) dehydrated N-acetyl glucosamine (DH) and (iii) 5-(formyloxymethyl)furfural (FMF). The total yield in this process was achieved around 16.1% in which the highest fraction of yield was found at 10.5% for N-acetyl glucosamine having formate functional groups. In addition, the dehydrated products are achieved around 3.6% while the FMF fractions are significantly lower around 2.0%. The yield of these end products depends on the time and temperature of the liquefaction process. For example, the total yield is increased to 60% (i.e. NAGF 32.7%, DH 11.3% and FMF 16.0%) when the temperature is raised to 100°C and keeping other parameters constant. In contrast, the total yields of 28% (i.e. NAGF 12.7%, DH 11.1% and FMF 4.7%) and 57.8% (i.e. NAGF 13.2%, DH 10.0% and FMF 34.6%) are achieved after only increasing the reaction times (from 12 h) to 24 and 168 h, respectively. [16]. The breakage of glycosidic linkages does not occur in the presence of strong acidic solution, due to insufficient amount of water in the reaction. Therefore, the first step of the reaction pathway follows the generation of monomers and oligomers in the form of soluble chitin by the modification of hydroxyl groups and followed by non-hydrolytic cleavage. As the water concentration increases and reaction proceeds, the depolymerization kinetics increases with the higher supply of water leading to hydrolysis and liquefaction reaction
Many inorganic acids, bases and salts are used for the dissolution of chitin and chitosan. The extensive decomposition and deacetylation of chitin can be obtained by alkali treatment, which increases the solubility in water of the regenerated chitin. The alkali chitin solution is prepared by using 10 times more alkali than chitin. The precipitation of chitin occurs by pouring the solution into acetone followed by neutralization with HCl [17]. The obtained precipitates are insoluble in water, but after 104 h of reaction the alkali treatment allows to reach the aqueous solubility. The enhanced solubility was due to the cleavage of chitin chain and led to the destruction of the crystalline structure of chitin. A prolonged treatment with NaOH also increases the degree of deacetylation up to 90% while 50% and more deacetylated chitin is dissolved in water. Einbu and coworkers analyzed the random degradation of chitin in 2.77 M NaOH and observed random coil conformation of chitin chains regardless of molecular weight [18]. Depolymerization, deacetylation and stability of chitin solution can be enhanced when urea is added to the alkali medium. Hu et al. dissolved chitosan in a mixture continuing 8 wt% NaOH and 4 wt% urea at the temperature of −20°C and stirred for 36 h. Chitin solubilization was not possible below 4 wt% NaOH and solution instability arises upon increasing the alkali solution above 12% NaOH. The addition of 2–8% urea in the 6–10% NaOH increases the solubility and stability of depolymerized chitin fragments in the solution. The explanations behind the achieved solubility and stability is the destruction of inter- and intramolecular hydrogen bonds and the role of urea is to limit aggregation leading to the stability of the solution [19]. The entire process of chitin solubilization is also dependent on the freezing temperature of chitin in a particular mixture of solvent. For example, the chitin solution in 8 wt% NaOH and 4 wt% urea exhibits the freezing point at −19°C. The presence of more than 4 wt% NaOH enables water molecules to get access into the chitin chain matrix; water is expanded and separated from the NaOH molecules at temperature below freezing point. The volume expansion of the chitin matrix upon freezing-induced stretch and collapses of the hydrogen bonds, which brought to depolymerization and solubilization of chitin chains (Figure 3). In contrast, the extent of chitin deacetylation in the alkali solution was greater than the same process in presence of urea. The DA value reduced from 94 to 84% after 480 h storage in the mixture of 8 wt% NaOH and 4 wt% urea indicating that urea stabilized the chitin solution and stopped the deacetylation process. Another similar study was carried out by Fang and coworkers who described the insight mechanism of dissolution property of chitin in NaOH-urea mixture [20]. The combined system (NaOH/urea) was quite suitable to prepare a chitin solution at −30°C. The hydrated NaOH captured the chitin chains by hydrogen bonds and formed complexes while urea clusters surrounded outside the complexes as a shell-like structure. The chitin chains were separated by the hydrated NaOH and urea disrupting the inter- and intramolecular hydrogen bonding network and displayed a complete dissolution. The solution was sensitive to temperature and concentration and formed an extended wormlike structure confirmed by TEM, AFM and DLS analysis [21]. Gong and coworkers have already reported a study recently with KOH and KOH-urea as a solvent for chitin dissolution. The chitin solubility was around 80% in the aqueous KOH solution (8.4–25 wt%) and the dissolution power of bases was in the order KOH > NaOH > LiOH at −30°C. Importantly, the degree of acetylation decreased only 12.5% after the treatment with KOH and storage at 4°C for 15 days. Urea did not exhibit any significant effect for enhancing the solvent capability of KOH [21]. Moreover, chitin solubility was also observed in a mixture of 5% LiCl and N,N-dimethylacetamide (DMA). The solution obtained from the mixture solubilized only 2 wt% chitin at 120°C and produced a gel, but 3 wt% chitin was dissolved when lithium thiocyanate was used as a solvent at 100°C [22]. Also, the recovery of the product in a strong acidic environment is quite difficult and expensive. For example, the hydrolysis of chitin/chitosan or depolymerization by 12.07 M inorganic acid (HCl) at 40°C for 28 h does not produce any N-deacetylated moiety [23]. Therefore, use of nitrous acid is a cheaper alternative for chitosan depolymerization by the cleavage of glycosidic bonds but the stoichiometry of the reaction depends on the amount of acidic solution. Water soluble chitosan oligosaccharides and highly deacetylated chitosan oligosaccharides were synthesized using nitrous acid [24]. The depolymerization process was carried out by adding sodium nitrite (NaNO2) to the chitosan solution (2% acetic acid) and keeping the solution for 3 h at pH 7.0, then the excess water in the reaction was evaporated at 50°C. The fractionation and extraction were carried out by methanol and filtrated for separation. The depolymerization started with the deamination of the 2-amino-2-deoxy-β-d-glucopyranose (GlcNH2) units and produced a new reducing sugar of 2,5-anhydro-d-mannose (M-units). The M-units did not exhibit any interconversion between anomers of the reducing sugar. The aldehyde groups of the M-unit were quite reductive to amino groups by avoiding any intramolecular hemiacetal formation
Hydrolysis by NaOH.
Hydrolysis by NaNO2.
Strong organic and inorganic acids, strong alkali solution or other inorganic solvents such as LiCl-tertiary solvent, CaCl2-MetOH system possess some disadvantages like corrosiveness, volatility, toxicity and so on. Moreover, inappropriate segmentation of chains, unstable yields occur during the hydrolysis or depolymerization in those solvents. As a suitable alternative, ionic liquids (ILs) are considered as green solvents due to their non-volatility, excellent solvation power, wide temperature ranges in the liquid phase, strong polarity and stability of end products. 1-butyl-3-methylimidazolium chloride (BminCl) is an ionic liquid (IL) which gives a swelled state of 5 wt% chitin after treatment at 130°C for 5 h [3]. The swelling of chitin in the IL, [BminCl] occurs due to the strong coordination of the Cl− ions and partially break the hydrogen bonds of chitin chains. The complete solubility of chitin is only possible when a stronger coordinating anion than Cl− ion will destroy the entire hydrogen bonds network (─NH⋯O═C and ─OH⋯O═C) produced by
Chitin/chitosan | \nSolvent | \nReferences | \n
---|---|---|
Acetylated chitin | \nDimethyl sulfoxide (DMSO) | \n[30] | \n
Chitin-graft-polystyrene | \nDimethyl sulfoxide (DMSO) | \n[31] | \n
Monomethyl-modified chitosan | \nWater | \n[32] | \n
O-alkylated chitosan | \nChloroform, ethanol, water and acetic acid | \n[33] | \n
Chitosan-graft-polycaprolactone | \nDimethylformamide (DMF), DMSO, ethanol and toluene | \n[34] | \n
Modified chitin and chitosan with different ionic liquids and solubility in solvents.
Enzymatic hydrolysis is a green process to achieve chitosan excellent solubility in water by producing chitooligosaccharides (COS). The process does not require extreme conditions (very low pH or high concentration of acids) and the tuning of molecular weight, and DD of final product can be achieved by avoiding any unwanted yield. Chitinase, chitosanase are specific enzymes and many other nonspecific enzymes such as glycanases, proteases, lipase are isolated from many biological sources. Unlike acid hydrolysis, enzymatic hydrolysis affects both the depolymerization and deacetylation of chitin or chitosan through the catalytic activities, which mainly depends on the molecular structure of chitinase (enzyme). Chitinase contains four catalytic domains in its structure, that is, (i) signal sequence, (ii) catalytic domain, (iii) serine/threonine region which can accept O-glucosylation and (iv) C-terminal chitin-binding domain [41]. The depolymerization occurs in the similar style of classical acid-base catalytic reaction (Figure 3: hydrolytic cleavage) followed by retention (two steps) or inversion (one step) reaction. In the retention mechanism, firstly, the acidic residues release protons, cleavage of glycosidic bonds and subsequently positively charged oxocarbonium ions intermediates are produced. Then, secondly, the intermediates are stabilized with the help of intermediate covalent bonds (glycosal-enzyme) but the subsequent reaction with the water molecules leads to the retention of anomeric configuration again. However, the inversion mechanism involves negative-charged residue, carbonium intermediate and water molecules at a time for the degradation of chain and inversion of the anomeric configuration. Moreover, the deacetylation of chitin molecules takes place by deacetylase treatment. The chitin deacetylase enzyme isolates from
Enzyme | \nWater soluble modified chitosan | \nReferences | \n
---|---|---|
Lysozyme | \nChitooligosaccharides (COS) | \n[35, 36] | \n
Papain | \n||
Cellulase | \n||
Low MW chitosan (3–6 kDa) | \n[37] | \n|
Chitosanase and β-d-glucosaminidase | \nd-glucosamine | \n[38] | \n
Chitin deacetylases | \nChitin and chitosan oligomers | \n[39] | \n
Carbohydrases from Myceliophthora sp | \nLow MW chitosan (4–28 kDa with 85% DD) | \n[40] | \n
List of enzymes for the hydrolysis of polysaccharide (chitin, chitosan).
Modification of molecular structure can enhance the solubility of chitosan in water. Phosphorylated chitosan, quaternized chitosan derivatives and carboxymethyl chitosan can be solubilized in different solvents at ambient conditions (Table 3). The solubility trend of chitin based on the modification of the molecular structure has been clearly displayed in Figure 5.
\nModified chitosan | \nSolubility in | \nReferences | \n
---|---|---|
N-methylene phosphonic chitosan | \nWater, HCl, acetic acid | \n[43] | \n
Chitosan diethyl phosphate | \nDiluted organic or mineral acid | \n[44] | \n
α-Galactosyl-chitosan conjugates | \nWater | \n[45] | \n
Chitosan-dendrimer hybrid | \nWater | \n[46] | \n
N-phenmethyl-N,N-dimethyl chitosan (PDCS) N-(1-pyridylmethyl-2-ylmethyl)-N,N-dimethyl chitosan N-(1-pyridylmethyl-3-ylmethyl)-N,N-dimethyl chitosan N-(1-pyridylmethyl-4-ylmethyl)-N,N-dimethyl chitosan | \n0.1–1.6 mg/ml in water | \n[47] | \n
N-[(2-hydroxy-3trimethylammonium)propyl]chitosan chloride (HTACC) | \nWater | \n[48] | \n
O-carboxymethyl chitosan sodium | \nN-methylmorpholine-N-oxide (NMMO) | \n[49] | \n
N,N-dicarboxymethyl chitosan | \nWater | \n[50] | \n
N,O-carboxymethyl chitosan | \nWater | \n\n |
Photosensitive chitosan with benzene group | \nBenzene and toluene | \n[5, 51] | \n
Dibutyryl chitin | \nDMF, DMSO, dimethylacetamide (DMAc) and ethanol | \n[52] | \n
Modified chitosan and solubility in different solvents.
Trend of solubility and intermolecular hydrogen bond between acetyl groups.
Chitin and chitosan have shown a big potential in pharmaceuticals, biomedical, agricultural sectors as well as food and textiles industry. Despite the myriad of opportunities, chitin and chitosan poor solubility in the most common solvents is a greatly limitation for scaling up the process from lab to industrial level. High viscosity of chitin and chitosan solution is another drawback with great impact of processing operations and equipment requirements. Even though chitin is sparingly soluble in strong acidic solution, corrosive and hazardous solvents should not be practiced to meet up regulatory compliances concerning chemical safety management. In conclusion, much works is still required to exploit the opportunities of this futuristic material which can contribute to economically feasible industrial growth.
\nThe project work has been funded by EU under the framework of Erasmus Mundus Program in Sustainable Management and Design for Textile (SMDTex).
\nIn December 2019, the European Commission (EC) unveiled a plan to become the first climate-neutral organization worldwide by 2050. The so-called European Green Deal [1] is a roadmap for setting the sustainability and well-being of citizens at the center of policymaking and then turning climate and environmental challenges into opportunities across all policy areas. As it was created, the EU Green Deal is a commitment with sustainable development and a fundamental part of the EC strategy to undertake the United Nations (UN) 2030 Agenda for Sustainable Development [2]. The 17 Sustainable Development Goals (SDGs) involve the three dimensions of sustainability (economic, social, and environmental) and require all the stakeholders to act in a global collaborative partnership. Such goals aim to achieve no poverty and hunger, to grant access to health services, to improve infrastructures, to reduce inequality, to fight climate change, to protect marine ecosystems, or to promote alliances between different actors to improve people’s lives, among others.
Emerging technologies like the Internet of Things (IoT), 3D/4D printing, augmented reality/mixed reality/virtual reality (AR/MR/VR), cyber-physical systems (CPSs), robotics, novel human-machine interfaces (HMI), artificial intelligence (AI), big data techniques, machine learning (ML), deep learning (DL), 5G/6G connectivity, and new computing paradigms, when oriented toward SDGs, will bring a wide range of disruptive solutions in multiple fields. Nonetheless, the mentioned technologies will create ever-increasing complex systems in terms of heterogeneity, autonomy, interoperability, and scalability that will also come with additional cybersecurity risks and threats of malicious attacks.
Distributed ledger technology (DLT) represents nowadays an evolution toward the so-called Web 3.0, the Internet of Value. This new era of the Internet will include a collaborative economy among peers with crowdsourcing data sharing systems [3, 4]. A blockchain is a specific type of DLT that involves timestamped blocks of transactions linked in a chain by cryptographic hashes. Blockchain presents a decentralized architecture that provides benefits in terms of security, privacy, non-repudiation, integrity, accountability, transparency, robustness, and authentication. Moreover, it provides a high operational efficiency and eliminates the need for centralized parties and/or intermediaries. In fact, the World Economic Forum (WEF) forecasts that, by 2027, 10% of the global gross domestic product (GDP) will likely be stored on DLTs [5].
In this context, blockchain and other DLTs can enable global partnerships for open innovation and cyber-resilient applications compliant with the aims of the EU Green Deal and the UN SDGs. Thus, the contribution of this chapter is to provide a global overview of blockchain as an enabler for sustainability and open innovation. In addition, its aim is also to make the different involved stakeholders to rethink global development challenges to create cyber-resilient, decentralized, and high-impact sustainable developments.
The rest of the chapter is organized as follows. Section 2 overviews the basic concepts of blockchain. Sections 3 and 4 summarize the main principles of blockchain for sustainability and open innovation. Section 5 presents some relevant use cases of blockchain-based applications toward each of the SDGs. Section 6 summarizes the key main benefits of blockchain for SDGs and their main open challenges. Finally, Section 7 is devoted to conclusions.
A blockchain is a secured distributed ledger whose data are shared among peers [6, 7, 8, 9]. In some blockchains like Bitcoin, decentralized miners validate every transaction (by following a consensus protocol), which allows them to solve the Byzantine Generals Problem (i.e., a situation where different parties must agree on a strategy and some of them may be corrupt, disseminate false information, or have intention to deceive). In the case of cryptocurrencies, the problem to be solved is called the double-spend problem: it must be guaranteed that the exchanged digital cash was not spent previously [6].
There are four main types of blockchains depending on who can access the stored data (private or public blockchains) and who can manage such data (permissionless or permissioned blockchains). Since a blockchain can store any kind of digital information, it could be the future of all secure transactions. Moreover, blockchain enables smart contracts, which consist of self-sufficient decentralized code that is executed autonomously according to a business logic. Furthermore, some blockchain platforms can also run decentralized applications, which are commonly called DApps [10].
Another important concept is the so-called decentralized autonomous organization (DAO), which can operate without requiring management hierarchy or a centralized authority [11]. The first DAO was launched in 2016 and raised $150 million worth of Ether (ETH) in 27 days. Nevertheless, DAOs are still very immature from the legal and security standpoints (e.g., a DAO attack due to code bugs led to a more than $50 million (ETH) theft in June 2016). Since 2016, a number of DAO initiatives have arisen (e.g., Steemit). In addition, the proliferation of DAOs is linked to the concept of decentralized autonomous society (DAS), in which citizens may be able to establish self-enforcing trade agreements without relying on centralized institutions of power and control.
It must be noted that a blockchain is not suited for every SDG-oriented application, which must fulfill the following main requirements:
Trustworthy transactions are needed, but traditional databases do not cover the application needs.
Data need to be updated by more than one stakeholder.
There is a lack of trust among the entities that will update the data.
The updaters are not willing to give the control of the database to a third party, and the involvement of intermediaries wants to be avoided when possible.
A database could be used, but it is likely to be attacked (e.g., denial-of-service (DoS) attacks) or censored.
Data redundancy in multiple distributed computers is needed.
Additional requirements could be involved, so several researchers have proposed more detailed decision frameworks about the use of blockchain [6, 12, 13].
It is worth mentioning that a detailed description of the different blockchain design aspects is out of the scope of this chapter, but the reader can find additional insights on the following recent works [4, 6, 8, 13].
Sustainability is related to the effect that current actions will have upon the future. Such an effect can take many forms that vary depending on their nature, like the utilization of natural resources as a part of production processes, the waste management processes, the effects of competition among corporations in the same market, the enrichment of the community by creating employment, the produced pollution, the outbreak of a pandemic, or the relation with regulators. For example, if natural resources run out, then they may be no longer available (i.e., raw materials). Thus, the way in which economic, social, and environmental resources are efficiently managed is a key issue for long-term sustainability.
Recently, the EU has progressed significantly toward sustainability through the three main approaches [14]:
Corporate social responsibility (CSR)/responsible business conduct (RBC) and new business models
Business and human rights and the protection of human rights in general
Sustainability and the implementation of the UN 2030 Agenda for Sustainable Development
The definition of CSR and RBC is related with ethical behavior and particularly with the relationship between a corporation and its stakeholders within a societal context, integrating social, environmental, and economic concerns into its business processes [14]. CSR/RBC can also be seen as actions under SDG 8 (decent work and economic growth).
In 2011, the UN Human Rights Council endorsed 31 Guiding Principles on Business and Human Rights (UNGPs) [14]. This approach came up as a sort of response to the perceived failure of CSR/RBC in terms of law binding and state oversight.
Recently, given the clear relationship between the three approaches (CSR/RBC, UNGPs, and the SDGs), the EC has adopted a holistic and practical approach toward sustainability irrespective of its name (i.e., CSR, RBC, business and human rights, SDG) while at the same time recognizing the target goal between the different agendas.
Within this context, blockchain is able to bring advantages toward sustainability in four main aspects: cybersecurity, accountability, transparency, and traceability:
The importance of external traceability has been enhanced by globalization, the free movement of people and the global expansion of complex supply chain structures, combining networks of actors from multiple sectors (business, public, non-profit, and informal) in multiple locations.
Open innovation, where innovative knowledge and ideas flow freely internally and externally to an organization, has become an important factor to enable sustainability [20]. To address SDGs, the EU recognizes the need for strengthening the impact of research and innovation and the use of coordinated approaches to ensure knowledge exchanges at an EU level [15]. These coordinated approaches will involve stakeholders with inter- and transdisciplinary points of view and the ability to manage jointly these development processes (SDG 17, partnerships for the goals) [21]. Although the current literature in open innovation details theoretical frameworks to guide solution development [20, 22], this development implies novel governance models that create thriving and diverse ecosystems where solutions are conceived, designed, experimented, implemented, supplied to the market, scaled up, and adopted. In that sense, one of the latest paradigms is called Open Innovation 2.0 (OI2) [23], a quadruple helix model where science, policy, industry, and society collaborate to achieve greater aims than a single entity.
Open innovation is uncertain and involves a high risk [20]. However, the lack of trust is today a major concern that withholds the cooperation and involvement of stakeholders in open innovation processes [24], especially for small- and medium-sized enterprises (SMEs). This need for orchestrating multiple stakeholders in a trusted and reliable way matches perfectly with the distributed nature of blockchain [20], which also provides the following main benefits:
Stronger intellectual property (IP) protection. It includes responsible open-source licensing, processes of idea claiming [25], IP registries (e.g., trade secrets, patents, and trademarks), record keeping, licensing, and non-disclosure agreements (NDAs). In addition, profits (e.g., patent royalties and revenue on creative work) can be paid automatically according to predetermined agreements.
Accurate collaboration between stakeholders modeled through smart contracts. Content can be shared among the stakeholders using smart contracts. Such smart contracts may deal with timestamping any IP disclosure or creation and automate corrective actions when unauthorized IP usage, IP infringements, and disclosure happen, acting as signed NDAs [25]. Furthermore, incentivized and rewarding mechanisms can be established (e.g., GlucoCoins to promote a global knowledge of diabetes [26]).
Open data. It means the availability of data to all the stakeholders with a high degree of privacy (i.e., sovereignty and data ownership) and data protection.
Regulatory compliance. It involves back-office processes mostly burdensome and inefficient to report to regulatory bodies. It also enables new open governance models.
Currently there are few examples of academic research on the use of blockchain for SDGs. For instance, the authors of [16] review recent academic and commercial “blockchain for good” applications in supply chain, innovations in governance, sharing economy, and financial inclusion. This section provides some relevant use cases of blockchain-based applications toward each of the SDGs. Such use cases are summarized in Figure 1.
Blockchain4SDGs: main blockchain use cases for SDGs.
Access to credit and financial services (e.g., microfinance) is one of the most commonly known mechanisms to reduce poverty. For instance, crowdsourcing and crowdlending platforms can also ease financial inclusion. Blockchain can help to increase the efficiency, traceability, and transparency of these financial processes [27]. Moreover, micro-transactions and automatic funding through forecast-based financing [28] can be implemented jointly with smart contracts and big data analytics. Such models can provide more efficient funding, since no additional intermediaries are required and some procedures can be substantially simplified.
According to [29], 206.4 million people of 81 countries needed humanitarian assistance in 2018. For instance, only 6 of such countries represent 80.6 million people in need. Such a humanitarian assistance from governments and private donors reached US $28.9 billion in 2018. Nevertheless, a substantial percentage of the assistance was and is today lost due to fraud and corruption. Blockchain can be applied to provide tracking of the funds and to reduce cyberattacks. The authors of [28] highlight the need for ethical guidelines (i.e., privacy, intentional design choices, and humanitarian principles) and a common evaluation framework of the solutions, especially as DLT developments are still in their early stages.
In 2017, the World Food Programme (WFP) [30] developed a proof of concept (PoC) in Sindh (Pakistan) named Building Blocks to evaluate blockchain for authentication and registration of transactions without financial intermediaries. Refugees have restrictions to open bank accounts and limited choices regarding the access and spending of their cash assistance. Building Blocks was also deployed with the aid of a biometric authentication system (i.e., iris scanning identification at checkout) in two refugee camps in Jordan to improve security and to ease cash transfers and the purchase of goods.
Sustainable food production systems along their life cycle can be guaranteed with the traceability properties of blockchain (e.g., avoid malpractice and guarantee food security).
In Yue et al. [31], the authors propose a decentralized solution that enables healthcare intelligence that allows patients to control their data without compromising privacy or security.
In addition, blockchain can be used for managing data more efficiently during public health diseases. For instance, with the current rapid spread of the coronavirus disease (COVID-19) pandemic, a blockchain-based monitoring and traceability system can help to automatically identify unsafe areas by using geographic information and provide real-time information about patients (e.g., temperature, symptoms, and social distancing) for further analysis. As a result, it may keep communities from further infections and ensure (or even certify) that some locations (e.g., workplaces) are safe areas. For the implementation of such an application, cybersecurity and privacy (i.e., pseudo-anonymization) will be key issues for a successful deployment. Disease control may also depend on the ability of organizations (e.g., centers of disease control, state and local agencies, journalists, governments, hospitals, scientists) to collaborate in an effective and efficient manner. It must also be noted that richer countries are better prepared than poorer countries to identify a virus outbreak, to face infection with public health contingency plans, and to minimize the socioeconomical impact.
The authors of [32] have thoroughly reviewed the utilization of emerging technologies like blockchain, IoT, and fog and edge computing for improving education. Examples of applications include record verification [33], the management of digital copyright information [34], or the design and evaluation of novel learning approaches [35, 36, 37].
For instance, Sony Global Education [38] is an educational platform that uses Hyperledger Fabric to guarantee the authenticity of the student transcripts. Another commercial example is Learning Machine [39], a company that has created an open peer-to-peer infrastructure to issue digital records that can be easily shared and verified. The system is not only devoted to educational institutions: governments and companies can also issue blockchain-based records at scale, rooted in any blockchain they select.
Easier access to financial services (e.g., even informal financial networks) promotes women empowerment as well as their independence. For example, hiveonline [40] is helping women through the CARE Village Savings and Loan Association (VSLA) program to get access to credits and markets with a fact-based reputation supported by blockchain. Such a financial infrastructure reduces the cost of cross-border payments and the risk of lending.
It must be noted that blockchain implies the use of Information and Communication Technologies (ICT), which can contribute to increase access to literacy. Furthermore, the inner characteristics of blockchain remove trust issues and enable the creation of new types of governance that may create equal opportunities for women leadership.
Sustainable and efficient water management systems involve the use of sophisticated IoT architectures that optimize consumption and availability. Such architectures may be subject to security attacks (e.g., physical attacks on sensors, device cloning, data theft, DoS, jamming, or eavesdropping). Therefore, it is important to cyber-secure these systems and minimize the reliance on cloud-centered architectures that, when the server is down, may derive in the unavailability of the service. In addition, the communication between IoT devices within a decentralized architecture allows for avoiding single points of failure and enables the use of autonomous IoT transactions in a secure manner, thus guarantying tamper-proof data, visibility, and transparency in water trading [41].
The authors of [42] study blockchain-based smart grid sustainable local energy markets. These systems enable cost-efficient micro-transactions, avoid central intermediaries, and promote reliability and equality among the different involved agents.
Blockchain has the ability to promote economic growth by enabling free trade. For instance, it also has the potential to optimize global financial infrastructure in terms of asset transfer and operative costs.
In addition, it may ease new types of economic organization and governance (e.g., innovation-centered and governance-centered [43]). In Davidson et al. [43] the authors present an example of a self-governing organization for evaluating the contributions to projects on a network. When evaluating such an example, they introduce a wide range of perspectives to be considered, such as the problem of contractual enforcement, efficient institutions, governance, or even the constitutional characteristics of a nation.
The Industry 4.0 paradigm is expected to represent the next phase in the digitalization of all the sectors in the economy [8]. Supply chain traceability has been traditionally performed by wireless technologies like radio-frequency identification (RFID) [44], which can be enhanced with additional security capabilities [45]. The next step forward is the so-called smart label [46], which adds novel features like event detection, interaction, and IoT capabilities. Such IoT solutions link cyber and physical worlds while enabling tracking and monitoring of assets and processes. Thus, blockchain goes one step further, making feasible end-to-end transparency in global supply chains. Business data can be shared rapidly between the different stakeholders across a trusted network [13]. In addition, smart contracts provide lower transaction costs by avoiding the intervention of intermediaries and third parties.
Ultimately, the ambition is to achieve Sustainable Supply Chain Management (SSCM), aiming to reduce the social and environmental impacts in global supply chains [47]. It is worth mentioning that, although research suggests that the combined use of blockchain and IoT devices will add significant value in supply chain, it will also impose some additional constraints in terms of computing power and power efficiency [6].
There are a number of supply chain projects deployed worldwide. For instance, Walmart, together with IBM, has developed a blockchain-based traceability system with Hyperledger Fabric [48]. In October 2016, they started with a PoC that tracked two items that were shipped to multiple stores. Before that, when a product had an issue (e.g., a customer became ill), it could take days to identify the batch, shipment, and vendor, and it may require to throw away a lot of the product. Through blockchain, it is possible to obtain specific data and details on the “how, where, and when” of the item within its supply chain. The shared database is able to capture attributes at the level of an individual package to take informed decisions. This functionality enables Walmart today to track a product in seconds (instead of days or sometimes weeks).
Following this approach, in August 2017, IBM announced a consortium with the food sector that included Walmart, Driscoll’s, Dole, McCormick, Nestlé, Kroger, Tyson Foods, and Unilever. This consortium, named IBM Food Trust, will further explore the potential of blockchain to boost traceability along global supply chains with more products [48].
The shipping industry can also benefit greatly from blockchain. Ocean freight and maritime transport account for over 90% of the goods shipped globally [49]. The main characteristics are high number of involved stakeholders, complex transactions (e.g., letters of credit), burdensome paperwork, and lack of transparency, traceability, and information sharing. For instance, Maersk and IBM created TradeLens, a blockchain-based solution to create a more secure and efficient global logistics and spur industry-wide innovation [50].
Additionally, several blockchain startups are also innovating in traceability. For instance, the startup Provenance [51] has created an application to engage customers in the point of sale by providing mechanisms to verify sustainability claims (i.e., no greenwashing).
As it was previously mentioned, blockchain is also able to reduce transaction costs by reducing intermediaries and thus allowing more direct payment flows. For instance, DocuSign [52] is a company that offers several applications (e.g., electronic signature, contract lifecycle management). In 2015, DocuSign collaborated with Visa in a PoC project that used a smart contract to enhance car leasing processes. In 2018, DocuSign integrated an Ethereum blockchain in their signing services. As a result, the signers of an agreement can check anytime the integrity of the contract. DocuSign is also part of the Accord Project [53], a non-profit initiative that aims to develop a technology-agnostic ecosystem with open-source tools for smart contracts.
Accurate transaction records enable the use of tools for forecasting. For instance, Augur [54] is a decentralized platform built with Ethereum smart contracts that allows users to create their own prediction markets (i.e., oracle).
Another relevant commercial solution is Storj.io [55], which is a blockchain-enabled cloud storage network where users can rent the storage space that do not use and get paid in Storj tokens or store their information on a globally distributed network.
Some startups focus on removing intermediaries from trading like OpenBazaar [56], while other companies focus on providing visibility and transparency to philanthropy [57]. Such a global foundation leverages Bitcoin and blockchain to perform and track transactions while providing an immutable record of charitable financial transactions.
In 2018, IBM was awarded a patent for its Autonomous Decentralized Peer-to-Peer Telemetry (ADEPT) environment [58]. In 2016, IBM developed jointly with Samsung a PoC using different elements of Bitcoin to create a distributed network of IoT devices. For instance, to secure transactions, it uses a mix of proof of work (PoW) and proof of stake (PoS) as consensus protocols, BitTorrent for file sharing, Telehash for messaging, and Ethereum to support smart contracts.
It is also worth mentioning that other authors focused on smart grids and supply chain management systems as substantial areas of sustainable innovation [59].
Theoretically, blockchain capabilities make the technology a catalyst for enabling a sharing economy with a democratic ownership structure (e.g., fractionally own goods by every community member) while avoiding unnecessary intermediaries. Nevertheless, authors like Novak [60] evaluate the implications of blockchain for income inequality and consider that, although it has potential to have a positive impact, it may also exacerbate current wealth concentration.
The authors of [61] propose a systematic literature review on specific blockchain use cases proposed by the research community. They remark the great concern about the infancy stage of blockchain.
Production patterns can be monitored by using supply chain traceability techniques.
Blockchain will likely play an important role on the urgent actions for improving the accountability and transparency of policies to limit global fossil fuel consumption and foster decarbonization. Hyperledger, as part of the Linux Foundation, has recently announced a new Special Interest Group (SIG) that will explore how blockchain can help to address the climate goals set out in the Paris Agreement [62].
The company Possible Future oriented one of its projects to the sustainable use of the oceans, preserving their life and restoring damaged coral reefs [63]. They created a game, named CryptoCorals, in which for each purchase of a virtual coral, another coral is planted. The project is developed, thanks to the collaboration of a non-governmental organization (NGO) partner, and blockchain is used to guarantee transparency, as it is one of the major concerns of potential users.
Blockchain can be used to register trustworthy data about the different terrestrial ecosystems.
Blockchain can help to reduce paper-based processes, minimize fraud, create inclusive institutions, and increase accountability in public services.
A good example is Delaware Blockchain Initiative [64], which was born with the aim of creating a legal framework for DLT sharing in corporations and governments. A more ambitious approach is Aragon [65], which is a startup that aims to create worldwide decentralized organizations, including employees and contractors from developing countries.
Other initiatives focus on increasing the transparency of democratic processes and on avoiding potential frauds. An example is Follow My Vote [66], which is a cost-effective online voting platform that audits ballots in real time.
To strengthen the means of collaboration between stakeholders is the key for enabling open innovation and for achieving SDGs.
The following paragraphs summarize the key main benefits that blockchain will bring to SDGs and their main open challenges.
Blockchain may provide significant operational benefits, since current information systems rely on centralized databases that operate in silos. By having a single, timestamped, immutable, and unique version of the truth, transparency and simplified audits can be guaranteed.
Furthermore, re-balancing the degree of information symmetry between stakeholders will help to achieve SDGs and will enable new forms of corporate governance and decentralized corporations. A collaborative mindset (the so-called coopetition) will be necessary to find additional ways to create value.
In terms of the maturity of the technology, there are a number of open challenges related to scalability, interoperability, standardization, or even energy consumption. The process of mining public networks, especially in the case of Bitcoin [67], requires enormous amounts of electricity. Therefore, although the underlying networks can provide sustainable applications, their footprint cannot be neglected [68].
From the cybersecurity standpoint, it is essential to provide secure applications with no single point of failure that comply with the expected degree of privacy. Nonetheless, it must be noted that blockchain can be also subject to cyberattacks [6]. The evolution of quantum computers will affect the security of public-key cryptosystems and hash functions. For instance, the authors of [9] analyze how to evolve blockchain cryptography to resist attacks based on Grover’s and Shor’s algorithms.
Blockchain can be used to develop secure peer-to-peer platforms for exchanging assets without intermediaries and in a trustworthy, sustainable, accountable, and transparent way to fulfill UN SDGs and the objectives of the EU Green Deal. Although research into blockchain has significantly increased in the last few years, there are not many academic or commercial solutions with sustainability and open innovation in mind. Moreover, most of them present solutions at very early stages of development.
Blockchain has the potential to radically change many societal sectors and to foster open innovation in all types of organizations, including supply chains, or the enforcement of governance in a completely innovative way. This overview has inherent methodological limitations due to its length and high level, so only a sample selection of some of the recent solutions is presented to give an idea of the potential of blockchain. The solutions described are not meant to be representative or generalizable. Such cases are the basics for further research, having in mind how blockchain can solve many of the current cybersecurity issues. Furthermore, open challenges were mentioned as a guidance for researchers and companies for future developments.
IoT | Internet of Things |
CPS | cyber-physical system |
CSR | corporate social responsibility |
DLT | distributed ledger technology |
DoS | denial of service |
PKI | public-key cryptography |
NGO | non-governmental organization |
PoC | proof of concept |
P2P | peer-to-peer |
PoS | proof of stake |
PoW | proof of work |
SSCM | sustainable supply chain management |
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