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Sustain. Chem., Volume 3, Issue 3 (September 2022) – 9 articles

Cover Story (view full-size image): Sodium cyanide (NaCN), a hygroscopic white crystalline or granular powder, was first industrially produced through the Castner process. NaCN is currently manufactured exclusively by the neutralisation or wet process, which involves the reaction of sodium hydroxide (NaOH) and liquid or gaseous hydrogen cyanide (HCN). Since all of the HCN that is used is solely produced from unsustainable processes, namely the Andrussow process, methane–ammonia process, Shawinigan process, or Sohio process, it is crucial to find alternative routes to reduce the global energy and environmental problems associated with the use of hydrocarbons during the production of HCN. For this reason, since HCN is known to occur naturally in plants, a green wet production method was developed to prepare NaCN (green NaCN) from cassava leaves, devoid of any plant contaminants. View this paper
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15 pages, 769 KiB  
Perspective
Alternative Products Selling Sustainability? A Brazilian Case Study on Materials and Processes to Produce Plant-Based Hamburger Patties
by Vânia G. Zuin, Evelyn Araripe, Karine Zanotti, Aylon M. Stahl and Caroindes J. C. Gomes
Sustain. Chem. 2022, 3(3), 415-429; https://doi.org/10.3390/suschem3030026 - 08 Sep 2022
Cited by 3 | Viewed by 3050
Abstract
Plant-based protein-production and consumption have been booming recently, requiring novel, greener sources and processes that can make a real contribution to sustainability. Alternatives offered as patties can be found all over the world, promising less environmental and health risks compared to animal-based protein. [...] Read more.
Plant-based protein-production and consumption have been booming recently, requiring novel, greener sources and processes that can make a real contribution to sustainability. Alternatives offered as patties can be found all over the world, promising less environmental and health risks compared to animal-based protein. In this context, a case study on soy-based patties from Brazil is presented, pointing out sustainable aspects of this value chain, from farm to fork, whilst presenting a theoretical discussion on consumer behavior. The implications of extensive land use for soy monoculture and aspects of the soy patty industrial processes, such as use of hexane, lack of information on labels, excess ingredients, and inconclusive data on food additives (such as methylcellulose), as well as integration of these concepts to design new undergraduate Chemistry curricula, are analyzed. Heavy processing in plants to achieve the taste, texture and appearance of meat increases the environmental footprint of vegetarian diets containing these items, disrupting the idea of sustainability that these products come with. Although meat production has a significant environmental impact, plant-based patties demonstrate that less impactful meat substitutes can also have environmental, social and health risks. Full article
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11 pages, 1839 KiB  
Article
Computational Investigation of a NASICON-Type Solid Electrolyte Material LiGe2(PO4)3
by Navaratnarajah Kuganathan, Kobiny Antony Rex and Poobalasuntharam Iyngaran
Sustain. Chem. 2022, 3(3), 404-414; https://doi.org/10.3390/suschem3030025 - 07 Sep 2022
Cited by 2 | Viewed by 1786
Abstract
Phosphate-based electrolyte materials are of great interest in the field of Li-ion batteries due to their rigid structural integrity. LiGe2(PO4)3 is a NASICON-type phosphate material with high thermal and electrochemical stability. Computational simulation techniques were employed to study [...] Read more.
Phosphate-based electrolyte materials are of great interest in the field of Li-ion batteries due to their rigid structural integrity. LiGe2(PO4)3 is a NASICON-type phosphate material with high thermal and electrochemical stability. Computational simulation techniques were employed to study the defects, diffusion, and dopant properties of LiGe2(PO4)3. Furthermore, the reaction energies for the formation of LiGe2(PO4)3 and the incorporation energies for the insertion of additional Li into this material were calculated. The calculations revealed that the Li Frenkel is the lowest-energy defect. The second most favorable defect is the Ge-P anti-site defect cluster. A low Li migration energy of 0.44 eV implies high Li ionic conductivity. The most favorable isovalent dopants on the Li and Ge sites are Na and Si, respectively. The formation of Li interstitials and oxygen vacancies can be facilitated through the doping of Ga on the Ge site. The doping of Ga slightly enhances the Li ionic conductivity. Li incorporation (up to four Li) is thermodynamically feasible. Full article
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28 pages, 2977 KiB  
Review
Progress toward Circularity of Polyester and Cotton Textiles
by Siyan Wang and Sonja Salmon
Sustain. Chem. 2022, 3(3), 376-403; https://doi.org/10.3390/suschem3030024 - 05 Sep 2022
Cited by 20 | Viewed by 7609
Abstract
Millions of tons of textile waste are landfilled or incinerated in the world every year due to insufficient recycle value streams and the complex composition of textile end products. The goal of this review is to highlight pathways for simplifying and separating textile [...] Read more.
Millions of tons of textile waste are landfilled or incinerated in the world every year due to insufficient recycle value streams and the complex composition of textile end products. The goal of this review is to highlight pathways for simplifying and separating textile wastes into valuable raw material streams that will promote their recovery and conversion to useful products. The discussion focuses on advances in sorting, separation, decolorization and conversion of polyester and cotton, the two most common textile fibers. Sorting processes are gaining automation using spectroscopic methods that detect chemical composition differences between materials to divide them into categories. Separation, through dissolving or degrading, makes it possible to deconstruct blended textiles and purify polymers, monomers and co-products. Waste cotton can produce high quality regenerated cellulose fibers, cellulose nanocrystals (CNCs) or biofuels. Waste polyester can produce colored yarns or can be chemically converted to its starting monomers for the recreation of virgin polymer as a complete closed loop. The current strategies for decolorization are presented. Life cycle assessment (LCA) studies found that recycling polyester/cotton blended fabrics for subsequent uses is more sustainable than incineration, and research on producing biomass-based poly-ester also offers feasible avenues for improving textile sustainability and promoting circular processing. Full article
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18 pages, 2081 KiB  
Article
Human Cytotoxicity, Hemolytic Activity, Anti-Inflammatory Activity and Aqueous Solubility of Ibuprofen-Based Ionic Liquids
by Joana C. Bastos, Nicole S. M. Vieira, Maria Manuela Gaspar, Ana B. Pereiro and João M. M. Araújo
Sustain. Chem. 2022, 3(3), 358-375; https://doi.org/10.3390/suschem3030023 - 13 Aug 2022
Cited by 6 | Viewed by 2664
Abstract
Ionic liquids (ILs) are a potential solution to the general problem of low solubility, polymorphism and low bioavailability of active pharmaceutical ingredients (APIs). In this work, we report on the synthesis of three pharmaceutically active ILs (API-ILs) based on ibuprofen, one of the [...] Read more.
Ionic liquids (ILs) are a potential solution to the general problem of low solubility, polymorphism and low bioavailability of active pharmaceutical ingredients (APIs). In this work, we report on the synthesis of three pharmaceutically active ILs (API-ILs) based on ibuprofen, one of the most commonly available over-the-counter nonsteroidal anti-inflammatory drugs (NSAIDs), with imidazolium cations ([C2C1Im][Ibu] and [C2(OH)C1Im][Ibu]) and a cholinium cation ([N1112(OH)][Ibu]). An upgrade to the aqueous solubility (water and biological simulated fluids) for the ibuprofen-based ILs relative to the ibuprofen’s neutral and salt form (sodium ibuprofen) was verified. The cytotoxic profiles of the synthesized API-ILs were characterized using two human cells lines, Caco-2 colon carcinoma cells and HepG-2 hepatocellular carcinoma cells, up to ibuprofen’s maximum plasma concentration (Cmax) without impairing their cytotoxicity response. Additionally, the EC50 in the Caco-2 cell line revealed similar results for both parent APIs and API-ILs. The biocompatibility of the ibuprofen-based ILs was also evaluated through a hemolytic activity assay, and the results showed that all the ILs were hemocompatible at concentrations higher than the ibuprofen Cmax. Moreover, the anti-inflammatory properties of the API-ILs were assessed through the inhibition of bovine serum albumin (BSA) denaturation and inhibition of cyclooxygenases (COX-1 and COX-2). The results showed that [C2C1Im][Ibu], [C2(OH)C1Im][Ibu] and [N1112(OH)][Ibu] maintained their anti-inflammatory response to ibuprofen, with improved selectivity towards COX-2, allowing the development of safer NSAIDs and the recognition of new avenues for selective COX-2 inhibitors in cancer chemotherapy and neurological diseases such as Alzheimer’s and Parkinson’s. Full article
(This article belongs to the Special Issue Alternative Solvents for Green Chemistry)
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13 pages, 2054 KiB  
Article
Production of Bio-Oil from De-Oiled Karanja (Pongamia pinnata L.) Seed Press Cake via Pyrolysis: Kinetics and Evaluation of Anthill as the Catalyst
by Jan Nisar, Salman Waris, Afzal Shah, Farooq Anwar, Ghulam Ali, Ali Ahmad and Faisal Muhammad
Sustain. Chem. 2022, 3(3), 345-357; https://doi.org/10.3390/suschem3030022 - 27 Jul 2022
Cited by 15 | Viewed by 2193
Abstract
In this study, bio-oil was produced from the pyrolysis of de-oiled karanja seed press cake in the presence of abandoned anthill as the catalyst. The anthill was characterised by SEM, EDX, XRF, XRD and surface area and pore size analysis. The pyrolysis experiments [...] Read more.
In this study, bio-oil was produced from the pyrolysis of de-oiled karanja seed press cake in the presence of abandoned anthill as the catalyst. The anthill was characterised by SEM, EDX, XRF, XRD and surface area and pore size analysis. The pyrolysis experiments were carried out in an indigenously made furnace in a nitrogen atmosphere from 310 to 400 °C. The pyrolysis oil was collected at an optimised temperature and analysed through gas chromatography–mass spectrometry (GC-MS). The compounds identified via GC-MS of non-catalytic bio-oil were in the range of C5 to C19, and compounds identified from catalytic bio-oil were in the range of C2–C63. Furthermore, thermogravimetric analysis of the karanja seed press cake without and with anthill was carried out in a nitrogen atmosphere with temperature programme rates of 3, 12, 20 and 30 °C·min−1. Kinetic parameters were determined by applying the Kissinger equation. The activation energy (Ea) values for hemicelluloses, cellulose and lignin were obtained as 99.7 ± 0.4, 182.9 ± 0.5 and 199.5 ± 0.7 kJ·mol−1 without catalyst; and with catalyst, the Ea were lowered to 74.8 ± 0.2, 83.1 ± 0.4 and 108.0 ± 0.5 kJ·mol−1, respectively. From the results, it was concluded that the catalyst played a key role in lowering the activation energy for the pyrolysis reaction and enhanced the quality of the bio-oil obtained as well. Full article
(This article belongs to the Collection Heterogeneous Catalysts Applied in Sustainable Chemistry)
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11 pages, 677 KiB  
Article
Impact of Solvent Type on Total Phenol and Flavonoid Content and Sun Protection Factor of Crude Cashew Nutshell Liquid
by Kadango Zombe, James Nyirenda, Agape Lumai and Hellen Phiri
Sustain. Chem. 2022, 3(3), 334-344; https://doi.org/10.3390/suschem3030021 - 06 Jul 2022
Cited by 7 | Viewed by 2579
Abstract
Cashew nutshell liquid (CNSL) is a cheap source of natural phenolic compounds that have numerous applications. These phenolic compounds have chemical structures with chromophores similar to those found in synthetic chemical UV-filters, which are present in commercial sunscreen products (SSPs). Thus, this study [...] Read more.
Cashew nutshell liquid (CNSL) is a cheap source of natural phenolic compounds that have numerous applications. These phenolic compounds have chemical structures with chromophores similar to those found in synthetic chemical UV-filters, which are present in commercial sunscreen products (SSPs). Thus, this study investigated the impact of solvents on the yield, total phenol content (TPC), total flavonoid content (TFC), and the sun protection factor (SPF) of crude CNSL. The percent yield ranged from (30.4 ± 0.7% to 49.3 ± 3.2%); hexane recorded the lowest yield, while ethanol recorded the highest. Acetone (101.2 ± 2.5 mg GA/g), methanol (99.5 ± 0.10), and chloroform (95.4 ± 3.7 mg GAE/g), recorded the highest TPC respectively, while hexane (33.3 ± 0.7 mg QE/g) recorded the highest TFC. The SPFs ranged from (22.1 ± 1.1 to 16.4 ± 0.8), chloroform (22.1 ± 1.1), acetone (21.5 ± 1.1), and methanol (19.3 ± 1.0) again recorded the highest values respectively, while hexane (16.4 ± 0.8) recorded the lowest. Our results revealed that extracting solvents has a significant impact on the yield and SPF of CNSL. Therefore, we propose that acetone, chloroform, and methanol, either alone or as mixtures, could be the best solvents for extracting CNSL with a good TPC and SPF. Full article
(This article belongs to the Special Issue Alternative Solvents for Green Chemistry)
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22 pages, 8201 KiB  
Article
Green Synthesis of Sodium Cyanide Using Hydrogen Cyanide Extracted under Vacuum from Cassava (Manihot esculenta Crantz) Leaves
by Ilunga Monga, Vimla Paul, Sudhakar Muniyasamy and Orpah Zinyemba
Sustain. Chem. 2022, 3(3), 312-333; https://doi.org/10.3390/suschem3030020 - 05 Jul 2022
Cited by 2 | Viewed by 5464
Abstract
This study was carried out to develop a green approach to synthesising sodium cyanide (NaCN) using hydrogen cyanide (HCN) extracted from cassava (Manihot esculenta Crantz) leaves after 120 min of maceration at 30 °C and 45 min of recovery under vacuum at [...] Read more.
This study was carried out to develop a green approach to synthesising sodium cyanide (NaCN) using hydrogen cyanide (HCN) extracted from cassava (Manihot esculenta Crantz) leaves after 120 min of maceration at 30 °C and 45 min of recovery under vacuum at 35–40 °C. The CN- ion released via autolysis was reacted with the Na+ ion following vacuum extraction of the former to produce NaCN by saturating the absorbing sodium hydroxide (NaOH) solution. This specific extraction method avoided direct contact between the cassava leaves homogenate and the absorbing solution. NaCN was crystallised by drying the NaCN slurry at 100 °C in an air oven. A total of 15.70 kg of fresh cassava leaves was needed to produce 32.356 g of NaCN (green-NaCN) (% NaCN yield = 0.21%). The results of X-ray diffraction, attenuated total reflectance–Fourier transform infrared spectroscopy and scanning electron microscopy with energy-dispersive X-ray spectroscopy, show that NaCN was successfully prepared using the proposed method. These spectral techniques showed that the control and green-NaCN contained sodium carbonate impurities. The latter was quantified by the titration experiments and was found to be 0.61% and 2.29% in the control and green-NaCN, respectively. Furthermore, the titration experiments revealed that the residual NaOH content was 1.63% in control NaCN and 4.68% in green-NaCN. The aim of modifying the green synthesis route for producing NaCN from cassava, developed by the Attahdaniel research group in 2013 and 2020, was achieved. Full article
(This article belongs to the Topic Green and Sustainable Chemistry)
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12 pages, 6576 KiB  
Article
Fast and Efficient Mechanosynthesis of Aldonamides by Aminolysis of Unprotected Sugar Lactones
by Abed Bil, Bemba Abdellahi, Gwladys Pourceau and Anne Wadouachi
Sustain. Chem. 2022, 3(3), 300-311; https://doi.org/10.3390/suschem3030019 - 22 Jun 2022
Cited by 3 | Viewed by 1811
Abstract
Sugar amides, such as aldonamides, are interesting, sugar-based molecules used in various fields, from detergency to medicine. Nevertheless, their valorization, especially as alternatives to petroleum-based substances, can be slowed down by their synthetic pathway, which is generally not in accordance with green chemistry [...] Read more.
Sugar amides, such as aldonamides, are interesting, sugar-based molecules used in various fields, from detergency to medicine. Nevertheless, their valorization, especially as alternatives to petroleum-based substances, can be slowed down by their synthetic pathway, which is generally not in accordance with green chemistry principles, and is also not economically competitive. We propose herein a fast procedure for the synthesis of aldonamide-derived glycoconjugates with mechanochemistry. The conditions were first optimized with galactonolactone, used as a model lactone, and dodecylamine. After only 5 min of grinding of stoechiometric amounts of amine and lactone, in the presence of water used as a Liquid Assisted Grinding (LAG) agent, the corresponding galactonamide was isolated with a high yield (90%) after a simple aqueous work-up. The optimized conditions were then applied to a wide variety of amines and sugar lactones, showing the versatility of the methodology. Gluco- and ribono-lactone exhibited similarly excellent reactivity, showing that the procedure is not sugar-dependent. Furthermore, the procedure was shown to be compatible with various functional groups such as alkene, alkyne, thiol, ester and hydroxyl. Full article
(This article belongs to the Topic Green and Sustainable Chemistry)
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14 pages, 2931 KiB  
Article
Development of a Binder-Free Tetra-Metallic Oxide Electrocatalyst for Efficient Oxygen Evolution Reaction
by Muhammad Asad, Afzal Shah, Faiza Jan Iftikhar, Rafia Nimal, Jan Nisar and Muhammad Abid Zia
Sustain. Chem. 2022, 3(3), 286-299; https://doi.org/10.3390/suschem3030018 - 21 Jun 2022
Viewed by 1772
Abstract
Water splitting has emerged as a sustainable, renewable and zero-carbon-based energy source. Water undergoes hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) during electrolysis. However, among these half-cell reactions, OER is more energy demanding. Hence, the development of efficient catalysts for speeding [...] Read more.
Water splitting has emerged as a sustainable, renewable and zero-carbon-based energy source. Water undergoes hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) during electrolysis. However, among these half-cell reactions, OER is more energy demanding. Hence, the development of efficient catalysts for speeding up OER is a key for boosting up the commercial viability of electrolyzers. Typical binders like Nafion and PVDF are not preferred for designing commercial electrocatalysts as they can compromise conductivity. Thus, we have designed a novel and cost-effective binder-free tetra-metallic (Co-Cu-Zn-Fe) oxide catalyst that efficiently catalyzes OER. This catalyst was grown over the surface of Fluorine doped tin oxide (FTO) transducer by a facile potentiodynamic method. The structure and morphology of the modified electrode were characterized by X-ray diffraction (XRD), scanning electron microscopy, and energy dispersive X-ray spectroscopy. XRD analysis confirmed the deposition of CoFe2O4 and CuCo2O4 along with alloy formation of Co-Fe and Co-Cu. Similarly, EDX and SEM results show the presence of metals at the surface of FTO in accordance with the results of XRD. Linear scan voltammetry was employed for testing the performance of the catalyst towards accelerating OER in strongly alkaline medium of pH-13. The catalyst demonstrated stunning OER catalytic performance, with an overpotential of just 216 mV at 10 mA cm−2 current density. Moreover, the chronopotentiometric response revealed that the designed catalyst was stable at a potential of 1.80 V for 16 h. Thus, the designed catalyst is the first example of a highly stable, efficient, and inexpensive catalyst that catalyzes OER at the lowest overpotential. Full article
(This article belongs to the Collection Heterogeneous Catalysts Applied in Sustainable Chemistry)
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