Practical Guide to Antimicrobial Active Packaging Rafael Gavara Practical Guide to Antimicrobial Active Packaging Rafael Gavara, Gracia López-Carballo, Pilar Hernández-Muñoz, Ramón Catalá Virginia Muriel-Galet, Josep P. Cerisuelo and Irene Domínguez A Smithers Group Company Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.polymer-books.com First Published in 2015 by Smithers Pira Technology Ltd Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK ©Smithers Information Ltd., 2015 All rights reserved. Except as permitted under current legislation no part of this publication may be photocopied, reproduced or distributed in any form or by any means or stored in a database or retrieval system, without the prior permission from the copyright holder. A catalogue record for this book is available from the British Library. Every effort has been made to contact copyright holders of any material reproduced within the text and the authors and publishers apologise if any have been overlooked. ISBN: 978-1-91024-273-5 (hardback) 978-1-91024-209-4 (softback) 978-1-910-24210-0 (ebook) Typeset by Integra Software Services Pvt. Ltd. Printed and bound by Lightning Source Inc. P reface Active packaging technologies are being developed to control the various problems associated with food deterioration or spoilage, such as the control of oxygen, carbon dioxide, ethylene or humidity inside the packaging, addition of chemical preservatives, elimination of off-odours and undesirable substances, and the control of microbiological contamination. Among these technologies, antimicrobial active packaging systems, defined as those that beneficially interact with food or the surrounding environment to inhibit or reduce microbial growth, have undoubtedly become a fully accepted alternative to the direct addition of preservatives to foods and have excellent future prospects for improving the quality and extending the shelf life of industrially produced foods. Accordingly, active packaging has become one of the so-called emerging non-thermal food technologies, which are being implemented to provide the consumer with natural, fresh, quality food without compromising safety. The aim of this book is to develop a working knowledge and understanding of antimicrobial packaging. After a brief introduction on the antecedents and basics of active packaging, the various issues to be considered in order to manufacture successful, efficient active antimicrobial packaging are covered. In Chapters 1–5, the antimicrobial agents most commonly used and their mechanisms of action are described, the manufacturing methods available to manufacture the active system are detailed, the parameters that are critical to make an effective product are discussed and tools to optimise them are provided, in addition the various in vitro and in vivo methods for measuring the effectiveness of the antimicrobial system are described in detail. Chapter 6 provides a collection of references detailing the most interesting developments and commercially available antimicrobial packaging systems. Finally, Chapter 7 presents a case study, from conception to manufacture, validation and optimisation. This book also aims to develop an understanding of why a specific agent is selected for a particular food product, or why a specific polymeric material and manufacturing iii Practical Guide to Antimicrobial Active Packaging technology are chosen. The reader will become familiar with the different procedures for improving the activity of the developed packaging solution and ways of testing its efficacy. This will accelerate the formulation of the active packaging concept, reducing development time with respect to the trial-and-error processes common in many of the reports for which references are given. Finally, it will help to identify the best and most cost-effective solutions. iv A cknowledgements The authors acknowledge the financial support of the Spanish Ministry of Economy and Competitiveness for Project AGL2012-39920-C03-01. Irene Domínguez thanks the CSIC for the provision of a postdoctoral contract (JAE- DOC), which was cofunded by ESF. The authors are also grateful to Karel Clapshaw for language services. v C ontents Preface ..........................................................................................................iii Acknowledgements .........................................................................................v Contents .......................................................................................................vii About the Authors – Affiliation ....................................................................xi 1 Introduction to Active Packaging ..................................................................1 1.1 Packaging and Active Packaging ..........................................................1 1.2 Plastic Materials for Packaging ............................................................3 1.2.1 General Characteristics of Plastics ...........................................3 1.2.2 Important Properties of Plastics for Packaging ........................5 1.2.2.1 Mechanical Properties .............................................5 1.2.2.2 Optical Properties ...................................................5 1.2.2.3 Thermal Properties ..................................................5 1.2.2.4 Mass Transfer Properties .........................................6 1.2.3 Principal Plastics used for Packaging .......................................7 1.2.3.1 Polyolefins ...............................................................7 1.2.3.2 Polystyrenes ............................................................9 1.2.3.3 Vinyl Polymers ......................................................10 1.2.3.4 Polyesters ..............................................................11 1.2.3.5 Polyamides ...........................................................12 1.2.3.6 High-barrier Polymers ...........................................12 1.2.3.7 Bioplastics .............................................................13 1.2.4 Packaging Production Technologies ......................................13 1.2.4.1 Flexible Packaging .................................................13 1.2.4.2 Rigid Packaging ....................................................14 1.2.5 Food/Plastic Packaging/Environment Interactions .................15 1.2.5.1 Permeability ..........................................................16 1.2.5.2 Sorption ...............................................................17 1.2.5.3 Migration .............................................................17 vii Practical Guide to Antimicrobial Active Packaging 1.3 Active Packaging: Basic Characteristics .............................................18 1.3.1 Antimicrobial Active Packaging ............................................21 References ...................................................................................................22 2 Antimicrobial Agents ...................................................................................25 2.1 Minimum Inhibitory Concentration and Minimum Lethal Concentration .........................................................................25 2.2 Antimicrobial Agents used in Active Packaging .................................27 2.2.1 Enzymes ................................................................................28 2.2.1.1 Bacteriolytic Enzymes ............................................28 2.2.1.2 Antimicrobial Oxidoreductase Systems .................29 2.2.2 Bacteriocins ...........................................................................30 2.2.3 Bacteriophages ......................................................................33 2.2.4 Surfactants ............................................................................34 2.2.5 Plant Extracts ........................................................................36 2.2.6 Polysaccharides .....................................................................39 2.2.7 Organic Acids .......................................................................40 2.2.8 Metals ...................................................................................41 2.3 Factors which affect the Properties and Stability of Antimicrobial Agents during the Processing of Packaging Films ...............................43 References ...................................................................................................45 3 Active Packaging Systems ............................................................................53 3.1 Active Component Preparation ..........................................................53 3.1.1 Use of an Inorganic Substrate ................................................54 3.1.1.1 Clay Nanocomposites ...........................................56 3.1.1.2 Metal Nanoparticles ..............................................58 3.1.1.3 Mesoporous Silica .................................................60 3.1.2 Encapsulation in an Organic Substrate ..................................61 3.1.2.1 Criteria for Antimicrobial Agent Encapsulation .............................................62 3.1.2.2 Matrices for Encapsulation ...................................63 3.1.2.3 Encapsulation Methods .........................................65 3.2 Independent Devices ..........................................................................69 3.3 Incorporation into Packaging Structures ............................................72 3.3.1 Incorporation into Packaging Structures by Thermomechanical Methods .................................................72 viii Contents 3.3.1.1 Preparation of Active Materials by Compounding .......................................................74 3.3.1.2 Preparation of Active Materials by Extrusion ..............................................................75 3.3.1.3 Extrusion Coating .................................................77 3.3.2 Wet coating ...........................................................................78 3.3.2.1 Coating .................................................................79 3.3.2.2 Spraying ................................................................84 3.3.3 Surface Anchorage ................................................................85 3.3.3.1 Sample Preparation ...............................................86 3.3.3.2 Surface Modification .............................................87 3.3.3.3 Attachment of Biomolecules to the Surface ........................................................88 3.3.3.4 Surface Analysis and Determination of Film Activity .....................................................90 References ...................................................................................................90 4 Modelling and Optimisation of Active Packaging: Parameters Related to Antimicrobial Efficiency ...........................................97 4.1 Mass Transport..................................................................................98 4.2 Determination of Mass Transport Parameters ..................................105 4.3 Release Control ...............................................................................110 4.4 Modelling Release of the Agent .......................................................115 4.4.1 Modelling and Description using the Finite Difference Method ....................................................117 4.4.2 Modelling and Description using the Finite Element Method ........................................................120 References .................................................................................................122 5 Methods for the Analysis of Antimicrobial Packaging Efficiency ...............125 5.1 In Vitro Methods .............................................................................127 5.1.1 Disc Diffusion Method ........................................................128 5.1.2 Dilution Method .................................................................131 5.1.3 Japanese Industrial Standard Method .................................137 5.1.4 Surface Growth Method .....................................................139 5.1.5 Electron Microscopy ...........................................................140 5.1.6 Atomic Force Microscopy ...................................................142 5.1.7 Flow Cytometry ..................................................................144 ix
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