1st Edition

The Handbook of Polyhydroxyalkanoates, Three Volume Set

Edited By Martin Koller
    1416 Pages 231 B/W Illustrations
    by CRC Press

    1416 Pages 231 B/W Illustrations
    by CRC Press

    The Handbook of Polyhydroxyalkanoates (PHA) focusses on and addresses varying facets of PHA biosynthesis and processing, spread across three volumes. The first volume discusses feedstock aspects, enzymology, metabolism and genetic engineering of PHA biosynthesis. It addresses better understanding the mechanisms of PHA biosynthesis in scientific terms and profiting from this understanding in order to enhance PHA biosynthesis in bio-technological terms and in terms of PHA microstructure. It further discusses making PHA competitive for outperforming established petrol-based plastics on industrial scale and obstacles for market penetration of PHA.

    This second volume focusses on thermodynamic and mathematical considerations of PHA biosynthesis, bioengineering aspects regarding bioreactor design and downstream processing for PHA recovery from microbial biomass. It covers microbial mixed culture processes and includes a strong industry-focused section with chapters on the economics of PHA production, industrial-scale PHA production from sucrose, next generation industrial biotechnology approaches for PHA production based on novel robust production strains, and holistic techno-economic and sustainability considerations on PHA manufacturing.

    Third volume is on the production of functionalized PHA bio-polyesters, the post-synthetic modification of PHA, processing and additive manufacturing of PHA, development and properties of PHA-based (bio)composites and blends, the market potential of PHA and follow-up materials, different bulk- and niche applications of PHA, and the fate and use of spent PHA items. Divided into fourteen chapters, it describes functionalized PHA and PHA modification, processing and their application including degradation of spent PHA-based products and fate of these bio-polyesters during compositing and other disposal strategies.

    Aimed at professionals and graduate students in Polymer (plastic) industry, wastewater treatment plants, food industry, biodiesel industry, this set:

    • Presents comprehensive and holistic consideration of these microbial bioplastics in the volumes.
    • Enables reader to learn about microbiological, enzymatic, genetic, synthetic biology, and metabolic aspects of PHA biosynthesis based on the latest scientific discoveries.
    • Discusses design and operate a PHA production plant.
    • Strong focus on post-synthetic modification, preparation of functional PHA and follow-up products, and PHA processing.
    • Covers all related engineering considerations

    Volume I

    Chapter 1: Monomer-Supplying Enzymes for Polyhydroxyalkanoate Biosynthesis

    1.1 Introduction

    1.2 PHA Biosynthesis Pathways and Related Enzymes

    1.3 Monomer-Supplying Enzymes

    1.4 Monomer-Supplying Pathways and Enzymes Involved

    1.5 Conclusions and Outlook


    Chapter 2: PHA Granule-Associated Proteins and their Diverse Functions

    2.1 Introduction

    2.2 Granule Assembly Models

    2.3 GAPs with Enzymatic Activity: PHA Synthases and Depolymerases

    2.4 Non-Enzymatic GAPs: Transcriptional Regulators and Phasins

    2.5 Functional Diversity of Phasins

    2.6 What Makes a Phasin a Phasin?

    2.7 Biotechnological Applications of GAPs

    2.8 Conclusions and Outlook


    Chapter 3: Genomics of PHA Synthesizing Bacteria

    3.1 Introduction

    3.2 Short-Chain-Length PHA (scl-PHA) Producing Bacteria

    3.3 Medium-Chain-Length PHA (mcl-PHA) Producing Bacteria

    3.4 Scl-co-mcl-Copolymer Producers

    3.5 Genomics of mcl-PHA Producing Bacteria

    3.6 The Genomics of mcl-PHA Metabolism

    3.7 Mcl-PHA Synthesis from Vegetable Oils and Fats

    3.8 Genome Analysis of Halomonas Species

    3.9 Genome Analysis of Paracoccus Species

    3.10 The PHA Production Machinery in Pseudomonas putida, Cupriavidus necator, Halomonas spp. and Paracoccus spp.

    3.11 Domain Organization and Structural Comparison of PhaC from Cupriavidus necator, Halomonas lutea and Paracoccus denitrificans


    Chapter 4: Molecular Basis of Medium-Chain Length-PHA Metabolism of Pseudomonas putida

    4.1 Pseudomonas putida, a Model Bacterium for the Production of Medium-Chain-Length PHA

    4.2 The PHA Cycle and its Key Proteins

    4.3 Metabolic Pathways Involved in mcl-PHA Production in P. putida

    4.4 PHA Metabolism Regulation

    4.5 Conclusions and Outlook


    Chapter 5: Production of Polyhydroxyalkanoates by Paraburkholderia and Burkholderia species: A Journey from the Genes through Metabolic Routes to their Biotechnological Applications

    5.1 Introduction

    5.2 PHA Synthases

    5.3 Genomic Analysis of pha Genes on Paraburkholderia and Burkholderia Species

    5.4 Metabolic Routes of PHA Synthesis

    5.5 PHA Production from Low-Cost Substrates

    5.6 Properties of PHA Synthesized by Paraburkholderia and Burkholderia Species

    5.7 Biomedical and Biotechnological Applications


    Chapter 6: Genetic Engineering as a Tool for Enhanced PHA Biosynthesis from Inexpensive Substrates

    6.1 Introduction

    6.2 Engineering Techniques Applied to Obtain Recombinant Strains for PHA Production

    6.3 The Use of Whey as Carbon Source

    6.4 The Use of Molasses as Carbon Source

    6.5 The Use of Lipids as Carbon Source

    6.6 The Use of Starchy Materials as Carbon Source

    6.7 The Use of Lignocellulosic Materials as Carbon Source

    6.8 Conclusions and Outlook


    Chapter 7: Biosynthesis and Sequence Control of scl-PHA and mcl-PHA

    7.1 Introduction

    7.2 The Key Factors of PHA Biosynthesis

    7.3 Sequence Control of scl-PHA and mcl-PHA



    Chapter 8: Inexpensive and Waste Raw Materials for PHA Production

      1. Introduction
      2. Oleaginous lipid-based feedstocks
      3. Mixed Organic Acid Feedstocks
      4. Mono- and Polysaccharide Feedstocks
      5. Carbon Dioxide as a Feedstock
      6. Other Carbon Feedstocks
      7. Conclusions and Outlook


    Chapter 9: Sustainable Production of Polyhydroxyalkanoates from Crude Glycerol

    9.1 Introduction – Polyhydroxyalkanoates (PHA)

    9.2 Crude Glycerol from Biodiesel Manufacture

    9.3 Metabolic Pathways of PHA Synthesis from Glycerol

    9.4 Production of PHA from Crude Glycerol

    9.5 Characterization of PHA Synthesized from Glycerol

    9.6 Metabolic Engineering for Glycerol-Based PHA Production

    9.7 Impact of Crude Glycerol on the Molecular Mass of PHA

    9.8 Conclusions and Outlook


    Chapter 10: Biosynthesis of Polyhydroxyalkanoates (PHA) from Vegetable Oils and its By-products by Wild-Type and Recombinant Microbes

    10.1 Introduction

    10.2 Biosynthesis of PHA from Plant Oils

    10.3 Challenges in Using Different Types of Microorganisms in Large Scale PHA Production

    10.4 Application of Waste Vegetable Oils and Non-Food Grade Plant Oils for Large Scale Production of PHA

    10.5 Conclusions and Outlook


    Chapter 11: Production and Modification of PHA Polymers Produced from Long-Chain Fatty Acid

    11.1 Introduction

    11.2 Strategies for Production of mcl-PHA

    11.3 Strategies for Maximum Volumetric Productivity

    11.4 Strategies for Improved Substrate Yields from MCFAs and LCFAs

    11.5 Extracellular Lipase for Triacylglyceride Consumption

    11.6 Biosynthesis and Monomer Composition

    11.7 Functional Modifications of mcl-PHA

    11.8 Cross-Linking

    11.9 Conclusions and Outlook


    Chapter 12: Converting Petrochemical Plastic to Biodegradable Plastic

    12.1 Introduction: The Plastic Waste Issue

    12.2 Strategies for Up-Cycling of Plastic Waste

    12.3 Enzymatic Degradation of Petrochemical Plastics

    12.4 Metabolism of Plastics’ Monomers and the Connection with PHA

    12.5 Conclusions and Outlook


    Chapter 13: Comparing Heterotrophic with Phototrophic PHA Production - Concurring or Complementing Strategies?

    13.1 Introduction – The Status Quo of PHB Production

    13.2 Heterotrophic PHA Production for Comparison

    13.3 PHB Synthesis in Cyanobacteria

    13.4 Light as Energy Source for Cyanobacteria

    13.5 CO2 as a Carbon Source for Cyanobacteria

    13.6 Nutrients for Cyanobacterial Growth

    13.7 Other Growth Conditions for Cyanobacteria

    13.8 Current Status of Phototrophic PHA Production

    13.9 Phototrophic Cultivation Systems

    13.10 Recombinant Cyanobacteria for PHA Production

    13.11 PHA Isolation from the Cells, Purification and Resulting Qualities

    13.12 Utilisation of Residual Cyanobacteria Biomass

    13.13 Comparing Heterotrophically with Phototrophically Produced PHB

    13.14 Conclusions and Outlook


    Chapter 14: Coupling Biogas (CH4) with PHA Biosynthesis

    14.1 Introduction

    14.2 Biogas Market

    14.3 Methanotrophs

    14.4 PHA Biosynthesis from Methane

    14.5 Genome Scale Metabolic Models as a Tool for Understanding the Metabolism of PHB in Methanotrophs

    14.6 Bioreactors for Biogas Bioconversion

    14.7 Techno-Economic Analysis of PHA Production from Biogas


    Chapter 15: Syngas as a Sustainable Carbon Source for PHA Production

    15.1 Introduction

    15.2 Syngas

    15.3 Production of Syngas from Organic Waste and Biomass

    15.4 Concept of Bacterial PHA Synthesis from Syngas

    15.5 Production of PHA by Acetogens Based on Syngas as Substrate

    15.6 PHA Production by Rhodospirillum rubrum Grown on Syngas

    15.7 Synthesis of PHA by Carboxydobacteria Grown on Syngas

    15.8 PHA Production by CO-Tolerant Hydrogen-Oxidizing Strains on Syngas

    15.9 Bioprocesses for PHA Production on Syngas

    15.10 Conclusions and Outlook


    Volume II

    Chapter 1: An Introduction to the Thermodynamics Calculation of PHA Production in Microbes

    1.1 Introduction

    1.2 Introduction to Thermodynamics and its Application to PHA Synthesis

    1.3 PHA Synthesis Under Aerobic Conditions

    1.4 PHA Synthesis under Anaerobic Conditions

    1.5 Conclusions and Outlook


    Chapter 2: Mathematical Modelling for Advanced PHA Biosynthesis

    2.1 Introduction

    2.2 Kinetics of PHA Biosynthesis

    2.3 Mathematical Modelling of PHA Biosynthesis

    2.4 Metabolic Pathway and Flux Analysis Methods in Modelling of PHA Biosynthesis

    2.5 Conclusions and Outlook


    Chapter 3: Interconnection between PHA and Stress Robustness of Bacteria

    3.1 Importance of Stress Robustness for Bacteria

    3.2 PHA and stress induced by high temperature

    3.3 Protective Functions of PHA Against Low Temperature and Freezing

    3.4 Osmoprotective Function of PHA Granules

    3.5 Protective Function of PHA Against Radiation

    3.6 Oxidative Stress and PHA

    3.7 Stress Induced by Heavy Metals and other Xenobiotics and PHA Metabolism

    3.8 Conclusions and Outlook


    Chapter 4: Linking Salinity to Microbial Biopolyesters Biosynthesis: Polyhydroxyalkanoate Production by Haloarchaea and Halophilic Eubacteria

    4.1 Introduction

    4.2 Halophilic microbes producing PHA

    4.3 PHA production by Halophilic Archaea ("Haloarchaea")

    4.4 Gram-Negative Halophilic Eubacteria as PHA Producers

    4.5 Gram-positive halophilic PHA producers

    4.6 Conclusions and Outlook


    Chapter 5: Role of Different Bioreactor Types and Feeding Regimes in Polyhydroxyalkanoates Production

    5.1 Introduction

    5.2 Process Optimization for PHA Production

    5.3 Reactor Operating Strategies for PHA Production

    5.4 Nutrient Feeding Regimes for PHA Production

    5.5 Conclusions and Outlook


    Chapter 6: Recovery of Polyhydroxyalkanoates from Microbial Biomass

    6.1 Introduction

    6.2 PHA Recovery Methods

    6.3 Mechanical Methods

    6.4 Biological Recovery Methods

    6.5 Physical Purification Methods

    6.6 Conclusions and Outlook


    Chapter 7: Polyhydroxyalkanoates by Mixed Microbial Cultures: The Journey so Far and Challenges Ahead

      1. The Journey so Far
      2. Definition of MMCs
      3. A Little Bit of History
      4. What Do We Know about PHA by MMCs?
      5. Presently Accepted Strategies

    7.6. Microorganisms and Metabolism

    7.7. Challenges Ahead

    7.8. Conclusions and Outlook


    Chapter 8: PHA Production by Microbial Mixed Cultures and Organic Waste of Urban Origin: Pilot Scale Evidences

    8.1. Introduction

    8.2. MMC-PHA Production in the Urban Biorefinery Model

    8.3. Pilot Scale Studies for Urban Waste Conversion into PHA

    8.4 Conclusions and Outlook


    Chapter 9: Production Quality Control of Mixed Culture Poly(3-Hydroxbutyrate-co-3-Hydroxyvalerate) Blends Using Full-Scale Municipal Activated Sludge and Non-Chlorinated Solvent Extraction

    9.1 Introduction

    9.2 Materials and methods

    9.3 Results and Discussion

    9.4 Conclusions and Outlook


    Chapter 10: Economics and Industrial Aspects of PHA Production

    10.1 Introduction

    10.2 A Brief History of PHA

    10.3 Physical Properties

    10.4 Cost and Economics


    Chapter 11: Next Generation Industrial Biotechnology (NGIB) for PHA Production

    11.1 Introduction

    11.2. Chassis for NGIB

    11.3. Production of PHA by Halophiles

    11.4. Genetic Tools for Halophile Engineering

    11.5. Engineering Halomonas spp. for PHA production

    11.6. Morphology Engineering for Easy Separation

    11.7. Conclusions and Outlook


    Chapter 12: PHA Biosynthesis Starting from Sucrose and Materials from Sugar Industry

    12.1. Introduction of Sucrose for PHA production

    12.2. Use of Molasses for PHA Production

    12.3. Bacterial strains for PHA production from sucrose

    12.4. Setting up a biorefinery to produce PHA in Brazil

    12.5. A new Biorefinery for PHA Production in Brazil

    12.6. Conclusions and Outlook


    Chapter 13: LCA, Sustainability and Techno-economic Studies for PHA Production

    13.1 Introduction

    13.2 Economic Analysis

    13.3 Sustainability of PHA Production

    13.4. Conclusions and Outlook


    Volume III

    Chapter 1: Recent Advances in Chemically Modifiable Polyhydroxyalkanoates

    1.1 Introduction

    1.2 Fluorination of the PHA α-Carbon; a Biosynthetic Approach

    1.3 Development of Azido-PHA

    1.4 Chemical Modifications of Unsaturated PHA

    1.5 Conclusions and Outlook


    Chapter 2: The Design of Functionalized PHA-Based Polymeric Materials by Chemical Modifications

    2.1 Introduction

    2.2 Chemical modifications in homogeneous conditions

    2.3 Synthesis of copolymers

    2.4 Networks based on PHA

    2.5 Modification of PHA Surface

    2.6 Conclusions and Outlook


    Chapter 3: Amphiphiles from Poly(3-hydroxyalkanoates)

    3.1 Poly(3-hydroxyalkanoates) (PHA)

    3.2 Amphiphilic Polymers, General Introduction

    3.3 Amphiphilic PHA via Chemical Modification Reactions

    3.4 Amphiphilic PHA

    3.5 Epoxidation

    3.6 The Polycationic PHA

    3.7 PHOU with Pendant PEG Units

    3.8 Click Reactions

    3.9 Saturated PHA with Hydrophilic Groups

    3.10 Polyesterification of PHB-Diol and PEG-Diacid

    3.11 Stimuli Responsive PHA Graft Copolymers

    3.12 Enhanced Hydrophilicity via Radical Formation onto Saturated PHA

    3.13 PEG Grafting onto Saturated mcl-PHA

    3.14 Ozonization of PHB and PHBV

    3.15 Chlorination of PHA

    3.16 PHB Graft Copolymers with Natural Hydrophilic Biopolymers

    3.17 Conclusions and Outlook


    Chapter 4: Bioactive and Functional Oligomers derived from Natural PHA and their Synthetic Analogues

    4.1 Introduction

    4.2 Oligomers Derived from Natural Storage

    4.3 Oligomers of Synthetic Analogues of Natural PHA

    4.4 Conclusions and Outlook


    Chapter 5: Processing and Thermomechanical Properties of PHA

    5.1 Introduction

    5.2 Polyhydroxyalkanoates: Physical Properties

    5.3 PHA Processing Methods

    5.4 PHA Rheology

    5.5 Additives for PHA Processing

    5.6. Conclusions and Outlook


    Chapter 6: Additive Manufacturing of PHA

    6.1 Introduction

    6.2 Processing Properties of PHA

    6.3 Additive Manufacturing (AM) of PHA

    6.4 Conclusions and Outlook


    Chapter 7: Mechanical and Permeation Properties of PHA-Based Blends and Composites

    7.1 Introduction

    7.2 Properties of PHA Films

    7.3 Additives

    7.4 Conclusions and Outlook


    Chapter 8: Competitive Advantage and Market Introduction of PHA Polymers and Potential Use of PHA Monomers

    8.1 Introduction

    8.2 Polyhydroxyalkanoates and their Properties

    8.3 Certifications and Labelling of PHA

    8.4 Market Introduction and Applications of PHA

    8.5 PHA Monomers as Bulk Chemicals

    8.6 End-of-Life Options

    8.7 Conclusions and Outlook


    Chapter 9: Linking the Properties of Polyhydroxyalkanoates (PHA) to Current and Prospective Applications

    9.1 Introduction

    9.2 PHA Properties

    9.3 Current PHA Applications

    9.4 Prospective applications

    9.5 Conclusions and Outlook


    Chapter 10: Hydrogen-Oxydizing Producers of Polyhydroxyalkanoates: Synthesis, Properties, and Applications

    10.1 Introduction

    10.2 PHA Synthesis from Autotrophic and Heterotrophic Substrates

    10.3 Synthesis of PHA of Different Composition

    10.4 PHA Properties

    10.5 PHA Applications

    10.6 Conclusions and Outlook


    Chapter 11: Polyhydroxyalkanoates, their Processing and Biomedical Applications

    11.1 Introduction

    11.2 Processing of PHA for Medical Applications

    11.3 Applications of PHA in Nerve Tissue Engineering

    11.4 Bone Tissue Engineering

    11.5 Cartilage Tissue Engineering

    11.6 Drug Delivery Application

    11.7 Cardiac Tissue Engineering

    11.8 Conclusions and Outlook


    Chapter 12: Polyhydroxyalkanoates (PHA) Based Materials in Food Packaging Applications. State of the Art and Future Perspectives

    12.1 Brief Introduction on PHA´s Structural Features and Production

    12.2 Biodegradability of Polyhydroxyalkanoates

    12.3 Future Perspective of PHA in Food Packaging: Within the Circular Economy Expectations

    12.4 Conclusions and Outlook


    Chapter 13: Aerobic and Anaerobic Degradation Pathways of PHA

    13.1 Introduction

    13.2 Plastic Waste

    13.3 Bioplastics

    13.4 Biodegradation of PHA

    13.5 Biodegradation of PHA Under Aerobic and Anaerobic Conditions

    13.6 Conclusions and Outlook


    Chapter 14: Factors Controlling Lifetimes of Polyhydroxyalkanoates and their Composites in the Natural Environment

    14.1 Introduction

    14.2 Overview of Biopolymer Degradation

    14.3 Biologically Driven Biopolymer Degradation

    14.4 PHA biodegradation in natural environments

    14.5 Biodegradation of PHA-Based Blends

    14.6 Biodegradation of PHA-Based Composites

    14.7 UV Degradation

    14.9 Mechanical Degradation

    14.10 Strategies for Modification of Degradation Rate

    14.11 Accelerated Aging for Lifetime Estimation

    14.12 Conclusions and Outlook




    Martin Koller was awarded his PhD degree by Graz University of Technology, Austria, for his thesis on polyhydroxyalkanoate (PHA) production from dairy surplus streams which was enabled by the EU-project WHEYPOL (“Dairy industry waste as source for sustainable polymeric material production”), supervised by Gerhart Braunegg, one of the most eminent PHA pioneers. As senior researcher, he worked on bio-mediated PHA production, encompassing development of continuous and discontinuous fermentation processes, and novel downstream processing techniques for sustainable PHA recovery. His research focused on cost-efficient PHA production from surplus materials by bacteria and haloarchaea and, to a minor extent, to the development for PHA for biomedical use.
    He currently holds more than 70 Web-of-science listed articles in high ranked scientific journals (h-index 23), authored twelve chapters in scientific books, edited three scientific books and four journal special issues on PHA, gave plenty of invited and plenary lectures at scientific conferences, and supports the editorial teams of several distinguished journals.
    Moreover, Martin Koller coordinated the EU-FP7 project ANIMPOL (“Biotechnological conversion of carbon containing wastes for eco-efficient production of high added value products”), which, in close cooperation between academia and industry, investigated the conversion of animal processing industry´s waste streams towards structurally diversified PHA and follow-up products. In addition to PHA exploration, he was also active in microalgal research and in biotechnological production of various marketable compounds from renewables by yeasts, chlorophyte, bacteria, archaea, fungi or lactobacilli.
    At the moment, Martin Koller is active as research manager and external supervisor for PHA-related projects.