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ITC). eptimatly share plished atts a y 5 Teshenaimecareneete seater: ES CHEWIEALEDUCATION he pubsacsorgichemeduc Valorization of Sour Milk to Form Bioplastics: Friend or Foe? ‘Mark T. Jefferson, Connor Rutter, Katherine Fraine, Gabriel V. B. Borges, Gabriela M. de Souza Santos, Frederico A. P. Schoene, and Glenn A. Hurst* here 1. Chem, Educ 2020, 97, 1073-1076 Oo Read Online ACCESS! tat Mevies aoe |‘ rile Recormendetons | @ Supporting Information ABSTRACT: A demonstration was developed to inteoduce students to waste ‘valorization in order to form bioplasic. Waste valorization isthe process of reusing, recycling, or composting, from waste, wefil products or sources of| ‘nergy. In this demonstration, waste valorization is introduced by converting sour milk into a biophstic via the addition of lemon juice upon heating. Utlising lemon juice to perform the acidification ofers a greener procedure than the tational formaldehyde (used commercially to make galaith) and enhances the transferability in emote locations suchas the Amszon Rainforest in comparison to vinegar. Students can establish connections to relevant United Nations Sustinable Development Goals (UN SDGs) by adopting a systems thinking approach. However, through this sis noteworthy that this process also used (particulary inthe Indian subcontinent) to make paneer a farmer cheese. While this also enables students to make a link to additional UN 'SDGs pertaining to “zero hunger’ there i an ethical discussion to be ad as to ‘whether such a proces thats utilized to feed malnourished citizens should be used to make a decorative bioplasic. As such, despite this demonstration being transferrable, nsteuctors may consider crefilly whether to tlie this resource and fo, to use this 38 an ‘opportunity to teach the importance of ethics in science. KEYWORDS: High School/Introductory Chemisty, Plymer Chemistry, Hands-On Learning/Manipulaties, Green Chemisty, Material Science, Public Understandig/ Outreach, Systoms Thinking Sustainability sical Balance INTRODUCTION ven the highly significant global issues surrounding plastic pollution owing to the fact that plastics are eilderved and hence take thousands of years to biodegrade, there is significant demand for the production of geen and sustainable alternatives. Such plastic subsitution would contbute toward Addresing the United Nations Sastanable Development Goals (UN SDGS), eich ss to address global challenges suchas those relating to poverty, inequity, climate and environmental dlgedation, prospery and peas and fsice.Biopates are plastics that ace derived from renewable biomass soures and ‘fer an alemative to ther oilderved counterparts As such, for the next generation of scientists, engineers, and policy nmakers to addess such global challenges, lowing “us to itamion toward a moore stn soy, education in the production of bioplstis is paramount. This subject matter is Blk aligned withthe incresed emphasis from the American Chemical Society (ACS) to enhance teaching in polymers and materials chemistry.” ‘There are come examples in the btenture of biphasic being incorporated its eure to ince at the naedaar level where students have the opportunity to complete a series sf core founditioal experiments in preparation for a sodent- directed project in this area.* Another example from Hudson tnd collegues outlines an activity to valence waste lobster rcs Publications © smsroreheniateaicen we shells (in the form of chitin) to produce plastic objects Indeed, educational resources which simultaneously offer opportunities to teach waste valorization allow students to see how to achieve a whole systems thinking “closed-loop” manufacturing of products with all input materials fully utlized. In doing so, instructors can align such resources with the UN SDGs, specifically Goal 12, which aims to reduce the environmental impact of wastes and improve utilization and management within the context of circular economy pundples = In 1893, Auguste Trilla discovered the means to insoubilze casein, one of two proteins (together with whey) from milk, by immersion in formaldehyde. In doing so, a galalith bioplastic can_be formed through facilitating cross-links between neighboring casein molecules, which has found application in the. production of buttons, pen barrels, knitting needles, buckles, and more. However, despite being cheap, gallth could not be molded, leading to its demise by commercial end ‘users in the 1940s in the UK (though production continued in Received: August 12,2019 Revised: January 15, 2020 Published: February 18, 2020 Journal of Chemical Education Brasil until the 1960s). Despite this to this day, glalith is used 4s part of outreach demonstrations to show the formation of a bioplstic. However, this is far fom a “green ioplastic” given that, according to. the Global Harmonized System of Classiation and Labeling of Chemicals (GHS), foem- aldehyde is suspected of causing genetic defects (41); 5 may fause cancer (H380) and causes damage to organs (css) (1570). As such, this 6 highly unsuitable for educational use at any level GREEN ALTERNATIVE TO GALALITH FOR DEMONSTRATIONS. A reported alternative for making bioplastics from milk isto substitute formaldehyde with an acid such as vinegat.* Given thatthe isoelectric point of casein is 4.6," and the pH of milk is 66, upon acidification of milk with vinegat, this instigates coagulation of the casein and precipitation ofa curd, which ean be extracted. Upon drying, a bioplastic can be formed Following the ACS Global ianovation imperative in Belém, Pari Bra, in 2016 to develop green chemistry experiments for remote locations,” a white paper was produced with recommendations to develop low-cost and transferable green chemistry experiments, for implementation in Brazil and developing countries.'° This served as motivation to collaboratively develop a bioplastic demonstration, using reagents that are realy avilable in communities within the Amazon Rainforest and surrounding areas while simlta- neously incorporating opportunities to show the power of waste valorization, aligning with the UN SDGs. To this end, sour skimmed mill (S10 days past expiration date) was used as the waste feedstock (given this has a higher casein content than semiskimmed and fll fat milk). Furthermore, as lemons are grown in the Amazon Rainforest, vinegar was substituted with lemon juice to complete the acidification. All reagents are totally benign with no known hazards, and the demonstration was conducted in the UK ahead of 3 (diferent) bioplastic- themed laboratory experiment as pat of a summer transitional course in chemistry for 30 students studying natural sciences according to the following steps 1. Using a measuring cylinder, measure $0 mL. of sour skimmed milk, and then, pour the milk into a 100 ml, beaker. Using a ster hot plate, heat the milk to 60 °C. Use a thermometer to check the temperature while heating the rll, continuously stirring it witha glass rod. Ifyou wish to add color to the bioplastc, add a small volume (~$ mL) of food coloring now. While the milk is heating, measure 3 ml. of lemon juice into a § mL measuring cylinder. Once the mill has reached 60 °C, remove the beaker from the hot plate and place it on a desk. ‘Add the lemon juice and sti the milk and lemon juice mixture using a glass rod for about 5 s Using a spatols, scrape out the sold from the beaker conto a paper towel. Use a paper towel to dab the white solid to help dry the surface. Do ths until as much water has been removed from the solid as possible Flatten the sold on a desk and use a plastic shape cutter to cut out the desired shape. Place the shaped bioplastic in a Petsi dish and put the Pets dish and plastic into an oven (set to 65 °C) for +b. pubs-acsorgichemedve 9, Remove the bioplastic from the oven, allow to it cool, and distribute it to the clas. A useable product can be made such as a Christmas-tree (or other) decoration if a hole is punched into the bioplastic ducing step 7 and a piece of string is looped through it and tied in a knot (Figure 1, inset). This demonstration enables ‘Volume of mon juice added / ml. Figure 1. Representative data depicting bioplastic mass variation asa function of lemon juice addition together with an inset of representative bioplastcs made with holes punched for string to be inserted for use a8 a decoration, students to identify links with the UN SDGs, specially goals 4 (quality education), 9 (industry, innovation and inf structure), 11 (sustainable cities and communities), 12 {responsible consumption and production), 13. (climate action), 14 (life below water), and 15 (life on land). A representative student comment following the demonstration and subsequent laboratory experiment was "Helped me to see ‘why we dd the experiment and why society needs to shit away from oibbased plastics.” If desired, the demonstration can be modifed to be more interactve'* by requesting for volunteers to assist the instructor in preparing additional samples where parameters such as the volume of lemon juice added is varied and investigated as a fanction of the resultant mass of the bioplastc. For example, if formulations are made with 1, 2, 3,4, and 5 ml. additions of lemon juice, the trend depicted in Figure 1 is produced showing an increase in bioplastie mass up to 3 mb followed by a decrease. The increase can be rationalized by acidification decreasing the net charge of caseins and instigating the solubilization of colloidal calcium phosphate from the casein micelles into the solution.” In doing so, micelles will be brought closer together to form dense clusters, facilitating. coagulation and formation of a bioplastc!” However, at high lemon juice addition (4~$ mL), the mass of bioplastic produced decreases because the casein moieties will have an overall postive charge (which is likely duc to amine and hydroxyl moieties acting as Lewis bases), leading to electrostati repulsion between cxscin molecules and reduced coagulation.” Indeed, student participation may be enhanced further by converting this demonstration into an activity where students physically make the bioplstic themselves with the addtional option of investigating varying the volume of lemon juice added as a function of bioplastic mass as described. Approximately 7-8 h should be made available for students to complete this with the flexbilty of being able to engage 07 ost aerator Journal of Chemical Education with alternatively taught content or take a break while the samples are in an oven, I SYSTEMS THINKING APPROACH REVEALS MORE ‘While this demonstration to vaorize sour milk using green and readily available reagents and processes nicely allows students to consider the lifecycle of materials with speciic emphasis on ‘waste valorization taking a whole systems thinking approach to designing this resource uncovered potential issues and additional learning outcomes for students Systems thinking uses cognitive frameworks, strategies, and tools to enable visualization of interconnections and relationships among ‘components of systems together with an examination of the ‘dynamic nature of systems and how systemslevel phenomena ‘emerge from interactions among the systems parts.”” Within ‘education, this approach can help students to addeess complex, interdisciphinary, real-world problems that are aligned with the UN SDGs" Indeed, examples have been reported ofthe use ‘of systems thinking to inform curricular change and resource development within green chemistry and sustainability.” ”* “Through taking this approach and considering transferability for international adoption of this demonstration, it is noteworthy that chhena are curds originating from the Indian subcontinent, made from cow milk by adding lemon juice and straining"* Chhena is then pressed and can be processed to make paneet, an unaged, nonmelting farmer cheese. This slemonstrates that paneer, which is created via a very similar process to the demonstration, is used as an important source of food to provide nutrition and alleviate hunger in parts of India and elsewhere. As such, this affords an additional opportunity to demonstrate to students that valorization of sour mile in this way also serves to address goal 2 ofthe UN SDGs pertaining to ending hunger, achieving food security and improved nutrition together with promoting sustainable agriculture, While this acts as an additional learning point for students it highlights serious ‘ethical implications of making biopastics from milk, which has formed the basis of outreach demonstrations'?"°"” and even processes used by industrial companies.” This therefore enables instructors to instigate an ethical discussion as to ‘whether such a process should be implemented for commercial application to prepare bioplasties when many malnourished citizens rely on converting sour milk to form pancer, an important foodstuf” Further details are available in the instructor guide as pat of the Supporting Information ‘On the other hand, while considering the entire system has ‘opened up new leaming opportunities for students, some instructors may be reticent to implement this demonstration of bioplastic formation owing to its application to make paneer. I is therefore recommended that, Further to creating learning ‘opportunities for students to use systems thinking, instructors should consider the entice system at large when evaluating ‘whether a resource/demonstation i fit for the purpose. Given the ubiquity of this demonstration (using. formaldehyde, vinegar, lemon juice, or another option), this indicates 2 wider issue in that there are not enough transferrable demonstrations /laboratory experiments on the subject of bioplastics in the literature for instructors to implement and that there should be a focus devoted to this area in the near future pubs-acsorgichemedve 07s | Denorstaton J CONCLUSIONS “This demonstration enables the widespread implementation of forming a bioplastic from sour milk, showing students how to ute waste ina prodctve fashion to create a useful product, {eg inthe form ofa decoration). Through this, students can adapt a systems thinking approach in the context of the life cycle of the sour milk Burther to showing students a potential route to bioplistis, the demonstration can be made more interactive where parameters suchas the volume of mon juice can be vased with the mass of bioplasic being monitored, This erie allows students to make a connection to relevant UN SDGs by considering the entire systems farther to applications 2 a biopasi, students can be challenged to recognize that the process demonstrated i used in the formation of paneer. This nables instructors to discuss the ethical imphations of applying this process to make a commodity biopastc in Competition with a valuable foodstull [and hence satisfying 3 different UN SDG (goal 2)]. Indeed, some instructors may Conclude that, given the later, this may not be an appropriate demonstration for bioplastic formation and perhaps seek to wie an alternative ASSOCIATED CONTENT © Supporting Information ‘The Supporting Information is available at https://pubsac ssorg/doi/10.1021 /acsjchemed 9b00754, Instructor guide (PDP, DOCX) AUTHOR INFORMATION Corresponding Author Glenn A. Hurst — Department of Chemistry and Green ‘Chemistry Centre of Excellence, Department of Chemistry, University of York, York YOIO SDD, England United Kingdom; © orci org/0000-0002-0786-312X; Emaik:glenn-hurst@yorkacuk Authors Mark T. Jefferson — Department of Chemistry, Unversity of York, York YOIO SDD, England, United Kingdon Connor Rutter ~ Department of Chemistry, University of York York YOIO SDP, England, United Kingdom Katherine Fraine — Department of Chemistry, University of York, York YOIO SDD, England, United Kingdon Gabriel V. B. Borges ~ Department of Natural Sciences, Escola SESC de Ensino Medio, $677 Rio de Janeiro, Rj, Brazit Gabriela M. de Souza Santos ~ Department of Natural Sciences, Escola SESC de Ensino Medio, $677 Ro de Jancr, Ry, Braid Frederico A. P. Schoene ~ Department of Natural Sciences, -Bcola SESC de Ensino Medio, $677 Rio de Janeiro, RJ, Brazil Complete contact information is available at: https//pubsacs.og/10.1021/aesjchemed 9600754 Notes ‘The authors declare no competing financial interest. ACKNOWLEDGMENTS ‘The authors wish to thank Jonathan Miller for assisting with preparation of the abstract graphic. Journal of Chemical Education REFERENCES (1) United Nations Sustainable Development Goals. iips// sistinaledevelopmentanrg/menu=1300 (Date Accessed: 8th January 2020). 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