Innovative Uses Of Agricultural Products And Byproducts

This volume presents the latest and most promising research in obtaining novel products from the byproducts of agricultural processing and existing crops. Each chapter explores various ways that the food industry can utilize microorganisms and parts of agricultural plants that would ordinarily go to waste. Previously scattered topics have been compiled into one comprehensive collection, including research on edible foods, such as vegetable oil, as well as byproducts, such as the inedible parts of the sorghum plant. This work is a valuable resource for agricultural and plant scientists, polymer and protein chemists, as well as food processors, both established companies and entrepreneurs. Innovative Uses of Agricultural Products and Byproducts ACS Symposium Series1347 Innovative Uses of Agricultural Products and Byproducts Library of Congress Cataloging-in-Publication Data Foreword Preface Chemicals from Vegetable Oils, Fatty Derivatives, and Plant Biomass Preparation of Xylan Esters with the Use of Selected Lewis Acids Deriving Biofuels and Value-Added Co-Products from Sorghum bicolor: Prospects in Biorefinery Applications and Product Development Biosynthesis and Applications of Microbial Glycolipid Biosurfactants Roles of Green Polymer Materials in Active Packaging Synthetic Platform for Controlled Delivery of 1-MCP: An Effective Approach to the Protection of Crops and Fresh Produce Pectin-Derived Vehicle for the Controlled Delivery of Bioactives The Character of Queso Chihuahua Editors’ Biographies Indexes Indexes Author Index Subject Index Preface 1 Chemicals from Vegetable Oils, Fatty Derivatives, and Plant Biomass Introduction Figure 1. Structure of typical triglyceride present in VO. Characteristics of VOs (Structure/Properties) Different Modes of Chemical Transformation of VOs/Biomass into Functional Materials and Their Application Areas Reaction of the Carboxy Group: Transesterification Scheme 1. Different Aspects of Chemical Modification of VOs Figure 2. Transesterification of fatty esters. Hydrolysis and Preparation of Different Fatty Derivatives (Esters, Amines, Amides, and Alcohols) Figure 3. Hydrolysis and preparation of different fatty derivatives. Epoxidation of Fatty Acids/Esters and Their Applications in Diverse Fields Scheme 2. Application of Epoxidized Fatty Esters in Different Fields Preparation of Cyclic Carbonate Derivatives of VOs/Fatty Acids Figure 4. Carbonation of epoxy fatty esters and application areas of the product. Polymerization and Preparation of PNCs Metathesis Figure 5. Rupture of fatty acid bond through metathesis reaction. Hydroformylation Figure 6. Hydroformylation of triglycerides. Oxidative Cleavage Figure 7. Oxidative cleavage of oleic acid. Preparation of Nanolubricants/Nanofluids by Dispersing Different Nanoparticles in VO Derivatives Figure 8. Nanolubricant working principle. Chemical Transformation of VOs: Turning Organic Waste Materials into Valuable Chemicals by Thermal Pyrolysis Figure 9. Proposed catalytic conversions of AW, FW, woody biomass, and VO into advanced hydrocarbon fuels and renewable byproducts. Figure 10. Flow chart of pyrolysis process of biomass. Advantages of Using Biobased Materials Biodegradability Renewability Environmentally Friendly Conclusions References 2 Preparation of Xylan Esters with the Use of Selected Lewis Acids Introduction Experimental Materials Synthetic Procedures NMR Analysis Results and Discussion Acetylation of Xylan Scheme 1. Structure of unsubstituted xylan (U), xylan acetate (M and N), and xylan diacetate (B). The carbons and protons for all compounds are numbered as shown in structure U. Figure 1. 13C (top) and 1H (bottom) NMR spectra of acetylated xylan in d6-DMSO obtained through catalysis of AlCl3; Ac = acetyl, D = DMSO, w = water. The subscripts for unsubstituted xylan (U), xylan acetate (M, N), and xylan diacetate (B) refer to the carbon number as shown for structure U in Scheme 1. Reaction of Xylan with Succinic Anhydride Figure 2. 13C (top) and 1H (bottom) NMR spectra of succinylated xylan in D2O obtained through the catalysis of AlCl3; S = succinyl, D = DMSO, W = water. The subscripts for U (unsubstituted xylan) refer to the carbon number (Scheme 1). Trends in the Acylation Reaction Conclusions Acknowledgments References 3 Deriving Biofuels and Value-Added Co-Products from Sorghum bicolor: Prospects in Biorefinery Applications and Product Development Introduction Grain Sorghum: Ethanol from Starch and Co-Products from Bran Figure 1. Simplified process schematic with product mass balance incorporating wax removal from sorghum grain followed by ethanol fermentation. Adapted with permission using data from reference 46. Copyright 2018 MDPI. Sweet Sorghum: Non-Structural Sugars from Sweet Sorghum Juice as a Carbon Source for Fermentation Lignocellulosic Sorghum: Structural Polysaccharides from Sweet Sorghum Bagasse and Biomass Sorghum Figure 2. Simplified process diagram incorporating SSJ and SSB for ethanol and xylitol production. Conclusion Acknowledgments References 4 Biosynthesis and Applications of Microbial Glycolipid Biosurfactants Introduction Sophorolipids Figure 1. Structure of generic SL molecules produced from Starmerella bombicola (17-L-[{2′-O-β-glucopyranosyl-β-D-glucopyranosyl}-oxy]-9-octadecenoic acid 6′,6′′-diacetate) in the free acid, open-chain form (A) and in the 1′,4′′ lactone form (B) and Pseudohyphozyma bogoriensis (13-[{2′-O-13-D-glucopyranosyl-8-n-glucopyranosy1}-oxy] docosanoic acid 6′,6′′-diacetate) (C). Rhamnolipids Figure 2. Generic chemical structures of mono-RLs (A, B) and di-RLs (C, D). In most instances m or n=1, 3, or 5 but can reach 7 or 9 depending on producing strain and growth conditions. Other Relevant Glycolipid Biosurfactants Figure 3. Generic chemical structures of MELs (A; typically m=8–16 carbons, n=2–12 carbons, and R1 and R2 may or may not be sites of acetylation), TLs (B; represented by trehalose-6,6′-dimycolate), and CLs (C; where R1=H or CH3, R2=H or OH, R3=H or acetyl group, R4=H or (n=2 or 4). Conclusions Acknowledgments References 5 Roles of Green Polymer Materials in Active Packaging Introduction Green Biopolymers Chitosan Pectin Polylactic Acid (PLA) Lignin Sugar Beet Pulp (SBP) Antimicrobial Packaging Systems from Biopolymers Advantages for Using Biopolymers in Antimicrobial Packaging Figure 1. Survival of total aerobic bacteria in strawberry puree at 10 °C. 50 ml of strawberry puree samples were treated with sodium benzoate (SB) and potassium sorbate (PS) film (22.5 mg PS and 37.5 mg SB), and SB/PS direct treatment containing 22.5 mg PS and 37.5 mg SB. Error bars represent the standard deviation of the mean. Reproduced with permission from reference 38. Copyright 2010 International Association for Food Protection. Figure 2. Survival of molds and yeasts in strawberry puree at 10 °C. 50 ml of strawberry puree samples were treated with SB/PS film (22.5 mg PS and 37.5 mg SB, and SB/PS direct treatment containing 22.5 mg PS and 37.5 mg SB. Error bars represent the standard deviation of the mean. Reproduced with permission from reference 38. Copyright 2010 International Association for Food Protection. Figure 3. Effect of direct and indirect addition of nisin on growth of L. monocytogenes in BHI broth at 24 °C. Pectin/PLA plus nisin film containing 10,000 IU nisin were tested in 10 ml of BHI broth (approximately 1000 IU nisin per ml of BHI broth). Error bars represent the standard deviation of the mean from three separate tests. Reproduced with permission from reference 43. Copyright 2009 International Association for Food Protection. Application of Biopolymers for Antimicrobial Coatings Application of Biopolymers for Antimicrobial Packaging Films Figure 4. Confocal fluorescence images of film surfaces. A. PLA area; B. Pectin/PLA area. Reproduced with permission from reference 28. Copyright 2007 John Wiley and Sons. Figure 5. Effect of film treatment on growth of L. monocytogenes in BHI broth at 24 °C. PLA film, PLA plus nisin film and pectin/PLA plus nisin film containing 50,000 IU nisin were tested in 50 ml of BHI broth (approximately 1000 IU nisin per ml of BHI broth). Error bars represent the standard deviation of the mean from three separate tests. Reproduced with permission from reference 43. Copyright 2009 John Wiley and Sons. Combination of Antimicrobial Packaging with Other Interventions Gaseous Antimicrobials Released from Green Polymers Protection of Antimicrobial Activity of Bioactive Compounds during Thermal Processing Figure 6. Changes in appearance of deli meat after 14 days at room temperature. A: film treated; B: Control. Figure 7. Effect of heat treatment on antimicrobial activity of pure nisin against L. monocytogenes. Physical and Mechanical Properties of Packaging Materials from Bioplymers Figure 8. Photographs of (A,C) PLA samples and (B,D) pectin/PLA composites containing 19% pectin particles (w/w): (A,B) top view and (C,D) side view with a circular shape. Reproduced with permission from reference 28. Copyright 2007 John Wiley and Sons. Figure 9. Film 0: PLA; Film 8: 4g PLA plus 60mg Lignin; Film 9: 4g PLA plus 100mg Lignin; Film 11: 4g PLA plus 100mg Chitosan; Film 12: 4g PLA plus 300mg Chitosan; Film 14: 4g PLA plus 500mg Chitosan and 100mg lignin; Film 16: 4g PLA plus 400mg lignin. Figure 10. UV–Vis absorption spectra of pure PLA film and antimicrobial PLA film. Antimicrobial PLA film contained 7.5% tributyl citrate (TBC) and 5% AIT. Reproduced with permission from reference 74. Copyright 2017 Elsevier. Acknowledgments References 6 Synthetic Platform for Controlled Delivery of 1-MCP: An Effective Approach to the Protection of Crops and Fresh Produce Introduction Hypothesis Figure 1. The structures of R,R′-B-MCP compounds. R,R′-B-MCP Compounds Mechanism of Releasing 1-MCP from an R,R′-B-MCP Compound Figure 2. Releasing mechanism of 1-MCP from R,R′-B-MCP compound. Reproduced with permission from reference 35. Copyright 2015 Elsevier. Synthesis of R,R′-B-MCP Compounds Figure 3. Synthetic scheme of R,R′-B-MCP compounds, DHMB (1), DCMB (2), and DPMB (3). Reproduced with permission from reference 35. Copyright 2015 Elsevier. Figure 4. Synthetic scheme of BPMB (4). Reproduced with permission from reference 36. Copyright 2016 Canadian Center of Science and Education. Figure 5. Synthetic scheme of BNMB (5) and BPNMB (6). Reproduced with permission from reference 17. Copyright 2017 Canadian Center of Science and Education. Analysis of R,R′-B-MCP Compounds for Controlled Delivery of 1-MCP Figure 6. Controlled release of 1-MCP from R,R′-B-MCP compounds: A) DHMB; B) DCMB; C) DPMB; D) BPMB; E) BNMB; and F) BPNMB, when in contact with water. Reproduced with permission from references (1735), and 36. Copyright 2017 Canadian Center of Science and Education, 2015 Elsevier, and 2016 Canadian Center of Science and Education. Comparative Study of Release of 1-MCP from BPMB, BNMB, and BPNMB at Different Time Intervals Figure 7. Mechanism of complete hydrolysis of R,R′-B-MCP compounds. Figure 8. Comparative release pattern of 1-MCP from BPNMB, BPMB, and BNMB when in contact with water. Reproduced with permission from reference 17. Copyright 2017 Canadian Center of Science and Education. Figure 9. Resonance structures of a) BNMB, b) BPNMB, and c) BPMB. Reproduced with permission from reference 17. Copyright 2017 Canadian Center of Science and Education. Figure 10. 1-MCP- releasing data from DCMB (1) at various temperatures. Reproduced with permission from reference 35. Copyright 2015 Elsevier. Effect of Environmental Stimuli on Releasing 1-MCP from R,R′-B-MCP Compounds Effect of Temperature on Release Rate of 1-MCP Effect of Humidity Figure 11. The effect of humidity at 22 ± 1 °C on release rate of 1-MCP from A) DCMB and B) BNMB. Reproduced with permission from reference 17. Copyright 2017 Canadian Center of Science and Education. Effect of Surface Area Figure 12. Effect of surface area on release rate of 1-MCP from A) DCMB and B) BNMB at 95% humidity. Reproduced with permission from reference 17. Copyright 2017 Canadian Center of Science and Education. Impact of Water pH Figure 13. Effect of water’s pH on release rate of 1-MCP from A) DCMB and B) BNMB. Reproduced with permission from reference 17. Copyright 2017 Canadian Center of Science and Education. Effect of Water Volume Figure 14. Effect of water volume on release rate of 1-MCP from A) DCMB and B) BNMB. Reproduced with permission from reference 17. Copyright 2017 Canadian Center of Science and Education. Evaluation of Application Effectiveness of R,R′-B-MCP Compounds Figure 15. Comparative color changes of treated and NT tomatoes in 7 days of storage: A) color changes; B) changes in L*; C) changes in a*/b* ratio; and D) changes in firmness. Figure 16. Comparative color changes of treated and NT tomatoes in an open environment for 7 days: A) color changes; B) changes in L*; C) changes in a*/b* ratio; and D) changes in firmness. Encapsulation of R,R′-B-MCP Compounds Within Biodegradable Polymers Figure 17. Molecular structure of C-PEG. Conclusion Acknowledgments References 7 Pectin-Derived Vehicle for the Controlled Delivery of Bioactives Nature and Structure of Pectin Figure 1. Pectin consists of linear domains (smooth areas) and branched domains (hairy areas). Figure 2. Crosslinking reaction for sugar-beet pectin. Reproduced with permission from reference 6. Copyright 2003 Elsevier. Pectin Formulations for Oral Drug Delivery Device Designed Based on the Characters of the Gastrointestinal Tract (GIT) Preparation of a Pectin, Ca2+, and Zein Delivery Vehicle Figure 3. Autofluorescence images of pectin and Ca2+ (left) and pectin, Ca2+, and zein (right) beads. Measured at 425 and 475 nm (ex. and em.) on a fluorescence stereomicroscope (Leica MZ FLIII, Leica Microsystem, Easton, PA, USA) with a field width of 1.0 mm. Reproduced with permission from reference 12. Copyright 2007 Springer. Figure 4. Protease susceptibility examination: two types of pectin, Ca2+, and zein hydrogel beads (zein content in total mass: 17% (black triangles) and 6% (red circles)) were incubated in a pepsin solution at pH 3.5 and 37 °C either with increasing protease concentrations at a fixed time period or with a fixed protease concentration for various time periods. Figure 5. Swelling measurement of drug-free, pectin-based hydrogel beads in solutions with different pHs at ambient temperature.. No obvious changes in bead size could be recorded for pectin, Ca2+, and zein hydrogel beads at pH 7.4 (gray; sample code VI) and over all solutions at pH 3.5. A pH-dependent swelling behavior can be clearly seen for pectin and Ca2+ beads (Sample Code I; pH 3.5 red, pH 5.0 green, and pH 7.4 blue). Application of Pectin, Ca2+, and Zein for Colon-Specific Delivery of Active Protein P40 Produced by Lactobacillus rhamnosus GG (LGG) Figure 6. Cumulative release of BSA from pectin and Ca2+ (left; sample code I) and pectin, Ca2+, and zein hydrogel beads (right; sample code) at 37 °C. The release media were changed in the sequence of a 0.01 M KH2PO4 and citrate buffer (stomach colored orange; pH 3.5, 2 h), Sorensen’s buffer (small intestine colored green; pH 7.4, 4 h), and 0.05 M phosphate-citrate buffer containing pectinex 3XL, 120 FDU/mL (large intestine colored blue; pH 5.0, 8 h). The incorporated BSA is mainly released from pectin, Ca2+, and zein beads at the colon site, where pectin was degraded. Figure 7. Illustration of in vivo experimental design. p40 protection (A) and treatment (B) of a DSS-induced colon injury on WT (C) and Ewegfrwa2 (D) mutant mice were examined by measuring the injury and inflammation of colon tissue (E, healthy tissue; F, diseased tissue) and the change in colon length (G). Conclusions Acknowledgments References 8 The Character of Queso Chihuahua Background of Queso Chihuahua (QC) Figure 1. Commercial Mexican QC made from RM (left) or PM (right). Photo courtesy of Diane Van Hekken. Food Safety Manufacture Figure 2. Manufacturing details for QC. Reproduced with permission from 13. Copyright 2008 John Wiley & Sons. Composition and pH Textural and Rheological Properties Figure 3. PCA plot of rheological properties and composition (moisture, fat, and protein) of fresh QC made with RM (brands A-J, solid rectangle) or PM (brands L-Q, dash circles). Data from reference 14. Figure 4. Comparison of torsion data (shear stress and strain at failure) for QC cheese (black symbols) to other popular styles of cheese, either fresh (squares) or at ages when typically sold (circles). Data from references (1422), and 27. Functional Properties Figure 5. Images of fresh RM (panels a and c)and PM (panels b and d) Mexican QC after heating at 232 °C for 5 min (panels a and b) or 130 °C for 75 min (panels c and d). Reproduced with permission from reference 28. Copyright 2011 Elsevier. Sensory Characterization Figure 6. Radar graph of key flavors and aromas in fresh (two-week old) QC made from RM (grey triangles, solid line) or PM (white squares, dashed line). Descriptors with * were not present in all brands of RM cheese while ** indicated they were not present in all brands of PM cheese. Data from reference 29. Microflora of QC Conclusions Acknowledgments References Editors’ Biographies Michael H. Tunick LinShu Liu Indexes Author Index Subject Index A B C M Q S V X