Table Of ContentNanotechnology Research Methods for Foods
and Bioproducts
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Nanotechnology Research Methods
for Foods and Bioproducts
Edited by
Graciela W. Padua
Department of Food Science and Human Nutrition
University of Illinois
Urbana, Illinois
USA
Qin Wang
Department of Nutrition & Food Science
University of Maryland
College Park, Maryland
USA
A John Wiley & Sons, Ltd., Publication
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Library of Congress Cataloging-in-Publication Data
Nanotechnology research methods for foods and bioproducts / edited by Graciela W. Padua, Qin Wang.
p. cm.
Includes bibliographical references and index.
ISBN 978-0-8138-1731-6 (hardcover : alk. paper)
1. Food–Biotechnology. 2. Nanotechnology. I. Padua, Graciela W. II. Wang, Qin, 1973-
TP248.65.F66N36 2012
664–dc23
2011039277
A catalogue record for this book is available from the British Library.
Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may
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1 2012
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Contents
Foreword xi
Contributors xiii
1 Introduction 1
Graciela W. Padua
References 3
2 Material components for nanostructures 5
Graciela W. Padua and Panadda Nonthanum
2.1 Introduction 5
2.2 Self-assembly 6
2.3 Proteins and peptides 8
2.3.1 Amyloidogenic proteins 8
2.3.2 Collagen 9
2.3.3 Gelatin 9
2.3.4 Caseins 10
2.3.5 Wheat gluten 10
2.3.6 Zein 10
2.3.7 Eggshell membranes 10
2.3.8 Bovine serum albumin 11
2.3.9 Enzymes 11
2.4 Carbohydrates 11
2.4.1 Cyclodextrins 11
2.4.2 Cellulose whiskers 12
2.5 Protein–polysaccharides 13
2.6 Liquid crystals 14
2.7 Inorganic materials 14
References 15
3 Self-assembled nanostructures 19
Qin Wang and Boce Zhang
3.1 Introduction 19
3.2 Self-assembly 20
3.2.1 Introduction 20
3.2.2 Micelles 20
3.2.3 Fibers 21
3.2.4 Tubes 23
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vi Contents
3.3 Layer-by-layer assembly 24
3.3.1 Introduction 24
3.3.2 Nanofilms on planar surfaces from LbL 25
3.3.3 Nanocoatings from LbL 27
3.3.4 Hollow nanocapsules from LbL 28
3.4 Nanoemulsions 29
3.4.1 Introduction 29
3.4.2 High-energy nanoemulsification methods 30
3.4.3 Low-energy nanoemulsification methods 31
3.4.4 Nanoparticles generated from different nanoemulsions
and their applications 33
References 34
4 Nanocomposites 41
Graciela W. Padua, Panadda Nonthanum and Amit Arora
4.1 Introduction 41
4.2 Polymer nanocomposites 42
4.3 Nanocomposite formation 43
4.4 Structure characterization 44
4.5 Biobased nanocomposites 45
4.5.1 Starch nanocomposites 46
4.5.2 Pectin nanocomposites 46
4.5.3 Cellulose nanocomposites 47
4.5.4 Polylactic acid nanocomposites 47
4.5.5 Protein nanocomposites 48
4.6 Conclusion 50
References 50
5 Nanotechnology-enabled delivery systems for
food functionalization and fortification 55
Rashmi Tiwari and Paul Takhistov
5.1 Introduction: functional foods 55
5.2 Food matrix and food micro-structure 56
5.3 Target compounds: nutraceuticals 58
5.3.1 Solubility and bioavailability of nutraceuticals 60
5.3.2 Interaction of nutraceuticals with food matrix 61
5.4 Delivery systems 64
5.4.1 Overcoming biological barriers 64
5.4.2 Nano-scale delivery systems 65
5.4.3 Types/design principles 67
5.4.4 Modes of action 69
5.5 Examples of nanoscale delivery systems for
food functionalization 72
5.5.1 Liposomes 72
5.5.2 Nano-cochleates 74
5.5.3 Hydrogels-based nanoparticles 75
5.5.4 Micellar systems 75
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Contents vii
5.5.5 Dendrimers 77
5.5.6 Polymeric nanoparticles 78
5.5.7 Nanoemulsions 80
5.5.8 Lipid nanoparticles 81
5.5.9 Nanocrystalline particles 83
5.6 Conclusions 85
References 85
6 Scanning electron microscopy 103
Yi Wang and Vania Petrova
6.1 Background 103
6.1.1 Introduction to the scanning
electron microscope 103
6.1.2 Why electrons? 104
6.1.3 Electron–target interaction 104
6.1.4 Secondary electrons (SEs) 105
6.1.5 Backscattered electrons (BSEs) 106
6.1.6 Characteristic X-rays 107
6.1.7 Overview of the SEM 107
6.1.8 Electron sources 108
6.1.9 Lenses and apertures 109
6.1.10 Electron beam scanning 109
6.1.11 Lens aberrations 110
6.1.12 Vacuum 111
6.1.13 Conductive coatings 111
6.1.14 Environmental SEMs (ESEMs) 111
6.2 Applications 111
6.2.1 Zein microstructures 112
6.2.2 Controlled magnifications 115
6.2.3 Nanoparticles 117
6.3 Limitations 119
6.3.1 Radiation damage 120
6.3.2 Contamination 122
6.3.3 Charging 124
References 126
7 Transmission electron microscopy 127
Changhui Lei
7.1 Background 127
7.2 Instrumentations and applications 128
7.2.1 Interactions between incident beam and specimen 129
7.2.2 Conventional TEM 130
7.2.3 Scanning TEM 136
7.2.4 Analytical electron microscopy 139
7.3 Sample preparations 142
7.4 Limitations 143
References 143
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viii Contents
8 Dynamic light scattering 145
Leilei Yin
8.1 The principle of dynamic light scattering 145
8.2 Photon correlation spectroscopy 151
8.3 DLS apparatus 152
8.4 DLS data analysis 156
8.4.1 Multiple-decay methods 158
8.4.2 Regularization methods 158
8.4.3 Maximum-entropy method 159
8.4.4 Cumulant method 159
References 160
9 X-ray diffraction 163
Yi Wang and Phillip H. Geil
9.1 Background 163
9.1.1 Introduction 163
9.1.2 Classical X-ray setup 165
9.1.3 X-ray sources 165
9.1.4 X-ray detectors 168
9.1.5 Wide-angle X-ray scattering and small-angle X-ray
scattering 169
9.2 Applications 169
9.2.1 Example: X-ray characterization of zein–fatty acid films 170
9.2.2 Temperature-controlled WAXS 176
References 179
10 Quartz crystal microbalance with dissipation 181
Boce Zhang and Qin Wang
10.1 Background and principles 181
10.2 Instrumentation and data analysis 183
10.2.1 Sensors 183
10.2.2 Data analysis 184
10.3 Applications 185
10.4 Advantages 190
References 192
11 Focused ion beams 195
Yi Wang
11.1 Background 195
11.1.1 Introduction to the focused ion beam system 195
11.1.2 Overview of the FIB 196
11.1.3 Ion beam production 196
11.1.4 Ion–target interaction 198
11.1.5 Basic functions of the FIB system 199
11.1.6 SEM and SIM 200
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Contents ix
11.1.7 SEM and FIB combined system 201
11.1.8 3D nanotomography with application of real-time
imaging during FIB milling 201
11.1.9 3D nanostructure fabrication by FIB 202
11.2 Applications 202
11.2.1 Polymers 202
11.2.2 Biological products 203
11.2.3 Example: self-assembled protein structures 203
11.3 Limitations 207
References 214
12 X-ray computerized microtomography 215
Leilei Yin
12.1 Introduction 215
12.2 X-ray generation 215
12.3 X-ray images 217
12.4 X-ray micro-CT systems 220
12.5 Data reconstructions 226
12.6 Artifacts in micro-CT images 228
12.6.1 Ring artifacts 229
12.6.2 Center errors 230
12.6.3 Beam-hardening artifacts 230
12.6.4 Phase-contrast artifacts 231
12.7 A couple of issues in X-ray micro-CT practice 232
12.7.1 The spatial resolution, and associated issues of
contrast and field of view 232
12.7.2 Localized imaging and sample-size reduction 232
References 233
Index 235
A color plate section falls between pages 194 and 195
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Foreword
Ample Opportunities for Nanotechnology
in Foods and Bio-based Products to Benefit Society
Food, like clean water and fresh air, is essentially important to human living. However,
the current global agricultural production and food security are facing serious long-
term sustainability challenges, exacerbated by population growth and climate changes.
It has been estimated by authority that more than 1 billion people experienced food
insecurity in 2011 – a daunting image of one out of every seven people suffering hunger
and malnutrition. Yet the world population is expected to increase from 7 billion today
to more than 9 billion by 2050. The Food and Agriculture Organization (FAO) of the
United Nations predicts that food production will need to increase by 70% over the
next four decades to meet the anticipated demand. Given the fact that new land
resources for cultivation are extremely limited, the majority of the production increase
will have to come from technological innovations and new approaches. Nanotechnology
has been actively pursued for about 10 years to enhance our capabilities to address the
grand challenges facing agriculture and food systems, and its momentum is continuing.
Nanoscale science, engineering, and technology, often simply referred to as nano-
technology, emerged around the year 2000 as a new distinctive frontier for scientific
research and development in broad fields including physics, chemistry, biology,
engineering, materials sciences, social sciences, and in almost all industry sectors from
semiconductors and electronics, energy, space, medicine and pharmaceutics, food and
nutrition, agriculture and forestry, to natural resources and the environment, and many
others. The recognition of novel properties of matter at the nanoscale and the newly
developed capabilities to precisely study and manipulate such properties was necessary,
but not sufficient, to champion for a national R&D initiative. Visionary scholars and
government leaders articulated a long-term vision for the transformative potential of
nanotechnology R&D to benefit society, and thus ignited the establishment of national
nanotechnology initiatives first in the USA, followed by major research powerhouse
countries, and now by most countries in the world. Substantial investments in
nanotechnology R&D by governments and the private sector have sustained steady
advancement of new solutions and products over the last decade. The US National
Nanotechnology Initiative (NNI) has contributed a cumulative $14 billion, including
about $1.8 billion in 2011, in nanotechnology R&D. Many nanotechnology breakthroughs
have begun to impact the marketplace. The current value of nanotechnology-enabled
products in the USA is estimated at about $91 billion. Current trends suggest the market
impact of nanotechnology-enabled products will achieve $3 trillion worldwide by 2020.
Nanotechnology has been touted to have the potential to revolutionize agriculture
and food in the 21st century. Numerous exploratory research projects and publica-
tions have clearly shown ample evidence of this in a broad range of critical challenges
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xii Foreword
and opportunities facing agriculture and food systems. Innovative ideas have emerged
to develop nanotechnology-enabled solutions for global food security through
improving productivity and quality, adaptation and mitigation of agricultural produc-
tion systems to climate changes, improving nutritional quality of foods, enhancing
food safety and biosecurity through better detection of pathogens and contaminants
as well as novel intervention technologies, and development of biobased products
and bioenergy alternatives. Some examples include novel uses and high value-added
products of nano-biomaterials of agricultural origins for food and non-food applica-
tions, nanoscale-based sensing mechanisms and devices for reliable early detection
of diseases and monitoring of physiological biomarkers for optimal agricultural pro-
duction, precision agriculture technologies including ones to efficiently manage
applications of agricultural chemicals and water resources, and water quality
improvements. Persistent investment and support will bring these pioneer work and
many other creative ideas to fruition in the near future.
Responsible development and deployment of nanotechnology is critically impor-
tant to nanotechnology R&D not only because it will impact the ultimate success in
propelling economic growth and job creation, but also the environment, human health
and consumer safety. The food science community has a long tradition of ensuring
food safety. Agriculture production and allied industries are fully aware of the impor-
tance of safety and the environmental implications of agricultural chemical applica-
tions. Investigations in risk assessment and characterization of nanosized materials
and their uses in agricultural production and foods have been, and will continue to be,
a high priority in nanotechnology R&D. Analytical instrumentation, test standards and
experimental protocols, both in vitro and in vivo, will be further developed and used.
This book is among the first covering the intersection of foods and nanotechnology.
It is unique in presenting two interrelated but also independent sections, namely
materials and analytical techniques, in one combined volume to give the reader a
convenient access of references. The material section deals with common food com-
ponents, nanostructure formation, processes and mechanisms, macromolecular and
supramolecular structures and functionality, food and nutrition applications, and
nanocomposites in food packaging. The analytical section details seven instrumentations
that are among the most important characterization tools in nanoscale science research
and technology development. The reader will find rich information detailed by experts
in the fields of food science and nanotechnology from some of the most prominent
research institutes in the USA. Researchers and students may be inspired and empowered
to eagerly engage in addressing the key challenges in securing the supply and availability
of food to all, improving human health and wellbeing through better foods, and
developing high value-added bioproducts of agricultural origin. The potential of
nanotechnology to significantly advance technical solutions for sustainability,
vulnerability and human health can be clearly envisioned. These chapters may crystallize
new visions and innovative approaches to advance food science and technology in the
future. The book editors, Drs Padua and Wang, being two active practitioners and front
runners in this field, have indeed made a valuable contribution to the professionals of
food and biomaterials nanotechnology, and broadly, to food and agricultural sciences.
Hongda Chen
USDA National Institute of Food and Agriculture
US National Nanotechnology Initiative
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