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BIOPOLYMER MEMBRANES AND FILMS
 BIOPOLYMER
MEMBRANES
AND FILMS
Health, Food, Environment,
and Energy Applications

Edited by

PROF. MARIANA AGOSTINI DE MORAES

PROF. CLASSIUS FERREIRA DA SILVA
PROF. RODRIGO SILVEIRA VIEIRA
Elsevier
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 Dedication

To those who love us

To those who inspired us
To those who supported us
To those who always believed on us
 Contributors
Vera Alejandra Alvarez Composite Materials
Group (CoMP), Research Institute of Materials
Science and Technology (INTEMA), National
Scientific and Technical Research Council—
Argentina (CONICET)—National University
of Mar del Plata (UNMdP), Mar del Plata,
Argentina
Mariana Altenhofen da Silva Center of Agri-
cultural Sciences, Federal University of São
Carlos, Araras, São Paulo, Brazil
Ioannis Anastopoulos Department of Chemistry,
University of Cyprus, Nicosia, Cyprus
Rog
erio Aparecido Bataglioli School of Chemi-
cal Engineering, University of Campinas,
Campinas, SP, Brazil
Marisa Masumi Beppu School of Chemical
Engineering, University of Campinas, Campi-
nas, SP, Brazil
Andrea Cristiane Krause Bierhalz Department
of Engineering, Federal University of Santa
Catarina, Blumenau, Santa Catarina, Brazil
Fernanda Carla Bombaldi de Souza Department
of Materials Engineering and Bioprocess,
School of Chemical Engineering, University of
Campinas, Campinas, SP, Brazil
Renata Francielle Bombaldi de Souza Depart-
ment of Materials Engineering and Bioprocess,
School of Chemical Engineering, University of
Campinas, Campinas, SP, Brazil
Adrián Bonilla-Petriciolet Department of
Chemical Engineering, Aguascalientes Institute
of Technology, Aguascalientes, Mexico
Josiane Gonçalves Borges University of São
Paulo, Faculty of Animal Science and Food
Engineering (FZEA-USP), Pirassununga, São
Paulo, Brazil
xiii
Tito Roberto Sant’Anna Cadaval, Jr School of
Chemistry and Food, Federal University of
Rio Grande, FURG, Rio Grande, RS, Brazil
Bruna Gregatti de Carvalho School of Chemical
Engineering, University of Campinas, Campi-
nas, SP, Brazil
Rosemary Aparecida de Carvalho University of
São Paulo, Faculty of Animal Science and Food
Engineering (FZEA-USP), Pirassununga, São
Paulo, Brazil
Tecia Vieira Carvalho Nucleus of Studies and
Research of the Northeast, NEPEN, Fortaleza,
CE, Brazil
Pascale Chevallier Laboratory for Biomaterials
and Bioengineering, Department of Min-
Met-Materials Engineering, Laval University
and University Hospital Research Center,
Quebec City, QC, Canada
Viktor Oswaldo Cárdenas Concha Institute of
Environmental, Chemical and Pharmaceutical
Sciences, Federal University of São Paulo—
UNIFESP, Diadema, São Paulo, Brazil
Luana Roland Ferreira Contini Institute of En-
vironmental, Chemical and Pharmaceutical
Sciences, Federal University of São Paulo—
UNIFESP, Diadema, São Paulo, Brazil
Rodrigo Cu
e-Sampedro School of Engineering
and Sciences, Monterrey Institute of Technol-
ogy, Monterrey, Mexico
João Dias-Ferreira Department of Pharmaceutical
Technology, Faculty of Pharmacy, University of
Coimbra, Coimbra, Portugal
Guilherme Luiz Dotto Chemical Engineering
Department, Federal University of Santa
Maria–UFSM, Santa Maria, RS, Brazil
xiv Contributors
Meryem Sedef Erdal Department of Pharma-
ceutical Technology, Faculty of Pharmacy, Istan-
bul University, Istanbul, Turkey
Júlia Vaz Ernesto Department of Pharmaceuti-
cal Sciences, Institute of Environmental, Chem-
ical and Pharmaceutical Sciences, Federal
University of Sao Paulo, Diadema, Brazil
Ana R. Fernandes Department of Pharmaceutical
Technology, Faculty of Pharmacy, University of
Coimbra, Coimbra, Portugal
Emanuel M. Fernandes 3B’s Research Group,
I3Bs—Research Institute on Biomaterials, Biode-
gradables and Biomimetics, University of
Minho, Headquarters of the European Institute
of Excellence on Tissue Engineering and Regen-
erative Medicine, Guimarães; ICVS/3B’s—PT
Government Associate Laboratory, Braga/
Guimarães, Portugal
Eduardo de Paulo Ferreira Chemical Engineer-
ing Department—Campus Santa M^ onica, Fed-
eral University of Uberl^andia, Uberl^andia,
MG, Brazil
Classius Ferreira da Silva Institute of Environ-
mental, Chemical and Pharmaceutical Sciences,
Federal University of São Paulo—UNIFESP,
Diadema, São Paulo, Brazil
Ronaldo Ferreira do Nascimento Trace Analy-
sis Laboratory (LAT), Department of Analytical
and Physical Chemistry, Federal University of
Ceará—UFC, Fortaleza, CE, Brazil
Leonardo Fernandes Fraceto Environmental
Nanotechnology Lab, Science and Technology
Institute of Sorocaba (ICTS), São Paulo State
University (UNESP), Sorocaba, Brazil
Vitor Augusto dos Santos Garcia University of
São Paulo, Faculty of Animal Science and Food
Engineering (FZEA-USP), Pirassununga, São
Paulo, Brazil
Lucimara Gaziola de la Torre School of Chemi-
cal Engineering, University of Campinas, Cam-
pinas, SP, Brazil
Sandy Danielle Lucindo Gomes Adsorption
Separation Research Group, Department of
Chemical Engineering, Federal University of
Ceara, Fortaleza, CE, Brazil
Sevgi G€
ung€ or Department of Pharmaceutical
Technology, Faculty of Pharmacy, Istanbul
University, Istanbul, Turkey
Saartje Hernalsteens College of Chemistry,
Chemical Engineering and Material Science,
Soochow University, Suzhou, Jiangsu, China;
Department of Chemical Engineering, Institute
of Environmental, Chemical and Pharmaceuti-
cal Sciences, Federal University of São Paulo,
Diadema, SP, Brazil
Carmen Guadalupe Hernández-Valencia Bio-
technology Department, Laboratory of Bio-
polymers and Pilot Plant of Bioprocessing of
Agro-Industrial and Food By-Products, Auton-
omous Metropolitan University, Mexico City,
Mexico
Ahmad Hosseini-Bandegharaei Department of
Environmental Health Engineering, Sabzevar
University of Medical Sciences, Tehran, Iran
Mohd Ikmar Nizam Mohamad Isa Advanced
Nano Materials (ANoMa) Research Group, Ad-
vanced Materials Team, Ionic State Analysis
(ISA) Laboratory, Faculty of Science and
Marine Environment, Universiti Malaysia Te-
rengganu, Kuala Nerus, Terengganu; Frontier
Materials Research Group, Advanced Materials
Team, Ionic & Kinetic Materials Research
(IKMaR) Laboratory, Faculty of Science and
Technology, Universiti Sains Islam Malaysia,
Nilai, Negeri Sembilan, Malaysia
Emine Kahraman Department of Pharmaceuti-
cal Technology, Faculty of Pharmacy, Istanbul
University, Istanbul, Turkey
Theo Guenter Kieckbusch School of Chemical
Engineering, University of Campinas, Campi-
nas, São Paulo, Brazil
Henryk Koroniak Faculty of Chemistry, Adam
Mickiewicz University in Poznan, Poznan,
Poland
Ramón Dı́az de León Department of Polymeri-
zation Processes, Research Center of Applied
Chemistry, Saltillo, Mexico


Eder Cláudio Lima Institute of Chemistry,
Federal University of Rio Grande do Sul,
UFRGS, Porto Alegre, RS, Brazil
 Contributors
Patricia Santos Lopes Department of Pharma-
ceutical Sciences, Institute of Environmental,
Chemical and Pharmaceutical Sciences, Federal
University of Sao Paulo, Diadema, Brazil
Vinı́cius Borges Vieira Maciel Department of
Food Engineering, Faculty of Animal Science
and Food Engineering, University of São Paulo,
Pirassununga, São Paulo, Brazil
Diego Mantovani Laboratory for Biomaterials
and Bioengineering, Department of Min-
Met-Materials Engineering, Laval University
and University Hospital Research Center, Que-
bec City, QC, Canada
Gustavo Martı́nez-Castellanos Biochemical En-
gineering Department, Misantla Institute of
Technology, Veracruz, Mexico
Agnes Batista Meireles Biomaterials Evalua-
tion and Development Center (BIOMAT)—
Campus I, Federal University of Jequitinhonha
and Mucuri Valleys, Diamantina, MG, Brazil
Enayde de Almeida Melo Department of Con-
sumer Science, Federal Rural University of
Pernambuco, Recife, Brazil
Ângela Maria Moraes Department of Materials
Engineering and Bioprocess, School of Chemi-
cal Engineering, University of Campinas, Cam-
pinas, SP, Brazil
Mariana Agostini de Moraes Institute of Envi-
ronmental, Chemical and Pharmaceutical
Sciences, Federal University of São Paulo—
UNIFESP, Diadema, São Paulo, Brazil
Anaftália Felismino Morais Adsorption Sepa-
ration Research Group, Department of Chemi-
cal Engineering, Federal University of Ceara,
Fortaleza, CE, Brazil
Nur Hafiza Mr Muhamaruesa Advanced Nano
Materials (ANoMa) Research Group, Advanced
Materials Team, Ionic State Analysis (ISA) Labo-
ratory, Faculty of Science and Marine Environ-
ment, Universiti Malaysia Terengganu, Kuala
Nerus, Terengganu, Malaysia
Roberto Nasser, Jr Department of Chemical En-
gineering, Institute of Environmental, Chemical
and Pharmaceutical Sciences, Federal University
of São Paulo, Diadema, SP, Brazil
xv
Beatriz C. Naveros Department of Pharmacy
and Pharmaceutical Technology, Faculty of
Pharmacy, University of Granada, Granada;
Nanoscience and Nanotechnology Institute
(IN2UB), University of Barcelona, Barcelona,
Spain
Deise Ochi Institute of Environmental, Chemical
and Pharmaceutical Sciences, Federal University
of São Paulo—UNIFESP, Diadema, São Paulo,
Brazil
Romina Paola Ollier Composite Materials
Group (CoMP), Research Institute of Materials
Science and Technology (INTEMA), National
Scientific and Technical Research Council—
Argentina (CONICET)—National University
of Mar del Plata (UNMdP), Mar del Plata,
Argentina
€
Yıldız Ozsoy Department of Pharmaceutical
Technology, Faculty of Pharmacy, Istanbul
University, Istanbul, Turkey
Neith Pacheco Center for Research and Assis-
tance in Technology and Design of the State
of Jalisco, AC, CIATEJ, Southeast Unit, Merida,
Mexico
Anderson Espirito Santo Pereira Environmental
Nanotechnology Lab, Science and Technology
Institute of Sorocaba (ICTS), São Paulo State
University (UNESP), Sorocaba, Brazil
Laura Oliveira P
eres Department of Chemistry,
Institute of Environmental, Chemical and Phar-
maceutical Sciences, Federal University of Sao
Paulo, Diadema, Brazil
Ana Luiza Resende Pires Postgraduate Pro-
gram in Biotechnology, Federal University of
Espı́rito Santo, Vitória, ES, Brazil
Rui L. Reis 3B’s Research Group, I3Bs—
Research Institute on Biomaterials, Biodegrad-
ables and Biomimetics, University of Minho,
Headquarters of the European Institute of
Excellence on Tissue Engineering and Regener-
ative Medicine; The Discoveries Centre for
Regenerative and Precision Medicine, Head-
quarters at University of Minho, Guimarães;
ICVS/3B’s—PT Government Associate Labora-
tory, Braga/Guimarães, Portugal
xvi Contributors
Ansorena Marı́a Roberta Chemical Engineering
Department, Food Engineering Group, Engi-
neering Faculty, National University of Mar
del Plata, Buenos Aires, Argentina; National
Research Council (CONICET), Buenos Aires,
Argentina
João Batista Maia Rocha Neto School of Chem-
ical Engineering, University of Campinas,
Campinas, SP, Brazil
Luı́sa C. Rodrigues 3B’s Research Group,
I3Bs—Research Institute on Biomaterials,
Biodegradables and Biomimetics, University
of Minho, Headquarters of the European Insti-
tute of Excellence on Tissue Engineering and
Regenerative Medicine, Guimarães; ICVS/
3B’s—PT Government Associate Laboratory,
Braga/Guimarães, Portugal
Laura Mabel Sanchez Composite Materials
Group (CoMP), Research Institute of Materials
Science and Technology (INTEMA), National
Scientific and Technical Research Council—
Argentina (CONICET)—National University
of Mar del Plata (UNMdP), Mar del Plata,
Argentina
J.A. Sánchez-Fernández Department of Poly-
merization Processes, Research Center of
Applied Chemistry, Saltillo, Mexico
Andrelina Maria Pinheiro Santos Department
of Chemical Engineering, Federal University
of Pernambuco, Recife, Brazil
Gilberto Dantas Saraiva Laboratory of Synthesis
and Characterization of Materials—LASCAM,
Department of Physics, State University of
Ceará (UECE-FECLESC), Quixadá, CE, Brazil
Patricia Severino Laboratory of Nanotechnology
and Nanomedicine (LNMED), Institute of Tech-
nology and Research (ITP), University of
Tiradentes, Industrial Biotechnology Program,
Aracaju, Brazil
Keiko Shirai Biotechnology Department, Labo-
ratory of Biopolymers and Pilot Plant of
Bioprocessing of Agro-Industrial and Food
By-Products, Autonomous Metropolitan Uni-
versity, Mexico City, Mexico
Simone S. Silva 3B’s Research Group, I3Bs—
Research Institute on Biomaterials, Biodegrad-
ables and Biomimetics, University of Minho,
Headquarters of the European Institute of
Excellence on Tissue Engineering and Regener-
ative Medicine, Guimarães; ICVS/3B’s—PT
Government Associate Laboratory, Braga/
Guimarães, Portugal
Mariangela de Fátima Silva Federal Institute of
Education, Science and Technology of Mato
Grosso do Sul (IFMS), Coxim, Mato Grosso
do Sul, Brazil
Jackson Wesley Silva dos Santos Institute of
Environmental, Chemical and Pharmaceutical
Sciences, Federal University of São Paulo—
UNIFESP, Diadema, São Paulo, Brazil
Vicente de Oliveira Sousa Neto Laboratory of
Study and Research in Pollutants Removal by
Adsorption, LERPAD, Department of Chemis-
try, State University of Ceará (UECE-
FECLESC), Quixadá, CE, Brazil
João Vinı́cios Wirbitzki da Silveira Institute of
Science and Technology—Campus JK, Federal
University of Jequitinhonha and Mucuri Val-
leys, Diamantina, MG, Brazil
e L. Soriano Department of Pharmacy and
Jos

Pharmaceutical Technology, Faculty of Phar-
macy, University of Granada, Granada, Spain
Eliana B. Souto Department of Pharmaceutical
Technology, Faculty of Pharmacy, University
of Coimbra, Coimbra; CEB—Centre of Biologi-
cal Engineering, University of Minho, Braga,
Portugal
Clayton Campelo de Souza Laboratory for Bio-
materials and Bioengineering, Department of
Min-Met-Materials Engineering, Laval Univer-
sity and University Hospital Research Center,
Quebec City, QC, Canada
Thiago Bezerra Taketa School of Chemical En-
gineering, University of Campinas, Campinas,
SP, Brazil
Bruno Thorihara Tomoda Institute of Environ-
mental, Chemical and Pharmaceutical Sciences,
Federal University of São Paulo—UNIFESP,
Diadema, São Paulo, Brazil
 Contributors
Fernanda Maria Vanin University of São Paulo,
Faculty of Animal Science and Food Engineer-
ing (FZEA-USP), Pirassununga, São Paulo,
Brazil
Anna Cecilia Venturini Institute of Environ-
mental, Chemical and Pharmaceutical Sciences,
Federal University of São Paulo—UNIFESP,
Diadema, São Paulo, Brazil
Rodrigo Silveira Vieira Adsorption Separation
Research Group, Department of Chemical
Engineering, Federal University of Ceara,
Fortaleza, CE, Brazil
xvii
Justyna Walkowiak-Kulikowska Faculty of
Chemistry, Adam Mickiewicz University in
Poznan, Poznan, Poland
Joanna Wolska Faculty of Chemistry, Adam
Mickiewicz University in Poznan, Poznan,
Poland
Patrı́cia Hissae Yassue-Cordeiro Federal Uni-
versity of Technology—Paraná, Londrina,
Paraná, Brazil
Cristiana Maria Pedroso Yoshida Institute of
Environmental, Chemical and Pharmaceutical
Sciences, Federal University of São Paulo—
UNIFESP, Diadema, São Paulo, Brazil
 Preface and acknowledgment
Biopolymers can be processed in several
forms, such as micro/nanoparticles, films/
membranes, gels, and sponges. The book fo-
cuses on the use of membranes or films, for
example, two-dimensional systems, cover-
ing a wide range of types of natural polymers
and applications. The book is divided into
chapters written by experts in the field of
membrane applications in health, environ-
ment, energy, and food. This book can be
used as a valuable reference for biopolymer
scientists and researchers looking for cut-
ting-edge applications of natural polymers.
First of all, the topics presented in this
book are avant-garde themes. One of the
challenges of those working with two-di-
mensional polymer devices (membranes,
films, and coatings) is to get out of the com-
fort zone and to know a little more about the
applications that are not part of their exper-
tise. Therefore, a broader view of the applica-
tion horizon of these devices is still lacking.
This book presents three parts with very dif-
ferent applications (Health, Environment
and Energy, and Food); these applications
were not chosen randomly; we intend to
show the public that specific methods of
preparation and characterizations of a given
application can be perfectly adapted to an-
other use. The researchers often find difficul-
ties in the development of two-dimensional
materials (membranes, films, and coatings);
however, they do not realize that many pub-
lications focusing on other applications pre-
sent similar problems that have already
been solved. Even disastrous results in one
application may represent a good result in
xix
another field. As an example, researchers
spend a lot of time developing a membrane
for application as a wound dressing for
burns treatment; however, sometimes they
find that the material has inappropriate
properties for dressings, but that presents ex-
cellent properties for packaging (they usu-
ally do not know that such developed
material could be used for packaging!
Wow! It does not work as a dressing but
would be an excellent packaging!). In this
sense, this book is intended to show a broad
range of two-dimensional biopolymer appli-
cations, proving that good results in one ap-
plication can guide good results in other uses
as well. And why not say bad outcomes for
one application can drive good results in
other applications? The three key features
and contents refer precisely to the fact that
the proposed book focus on biopolymers,
techniques for preparing membranes, and
characterizing them. These contents are often
convergent in different applications and may
suggest new possibilities for novel applica-
tions and materials development.
We are deeply grateful to all chapter au-
thors for agreeing to be a part of this project.
Authors used their experience from
researching and teaching students to give
chapters the relevance and appropriate con-
tent. We worked closely with them, propos-
ing revisions to enhance harmony between
the chapters; even with their full schedules,
fortunately, the authors were very cordial
and patient with us. We wish to thank the au-
thors of books and articles, as well as the
publishers for their permission to reproduce
xx Preface and acknowledgment
materials used here. We are also grateful to
all those colleagues that even not being chap-
ter authors devoted their precious time to
help us to review the chapters. Thanks are
also expressed to Elsevier Inc., especially
Mr. Edward Payne, Mrs. Mariana K€ uhl
Leme, and Mr. Vijayaraj Purushothaman
for their support during this project. Finally,
we have appreciated continued support and
encouragement from our families, to whom
we can never thank enough!
Mariana Agostini de Moraes,
Classius Ferreira da Silva
Institute of Environmental,
Chemical and Pharmaceutical Science,
Federal University of São Paulo—UNIFESP,
Diadema, SP, Brazil
Rodrigo Silveira Vieira
Department of Chemical Engineering,
Federal University of Ceará—UFC,
Fortaleza, CE, Brazil
 Acknowledgment to the chapters’
reviewers

Prof. André Bezerra dos Santos
Department of Hydraulic and
Environmental Engineering
Federal University of Ceará
Fortaleza, CE, Brazil
Prof. Judith Pessoa de Andrade Feitosa
Department of Organic and Inorganic
Chemistry
Federal University of Ceará
Fortaleza, CE, Brazil

Prof. Andrea Cristiane Krause Prof. Julio Cesar Serafim Casini

Bierhalz Department of Control and Automation
Department of Engineering Engineering
Federal University of Santa Catarina— Federal Institute of São Paulo
Campus Blumenau São José dos Campos, SP, Brazil
Blumenau, SC, Brazil
Prof. Melissa Gurgel Adeodato Vieira
Dra. Daniele Farias Department of Chemical Processes
Toulouse White Biotechnology (UMS School of Chemical Engineering—
INRA/INSA/CNRS) UNICAMP
NAPA Center Bat B Campinas, SP, Brazil
Ramonville-Saint-Agne, France
Prof. Odair P. Ferreira
Prof. Elizama Aguiar de Oliveira Laboratory of Advanced Functional
Department of Exact Science and Materials
Technology Department of Physics
State University of Santa Cruz Federal University of Ceará
Ilhéus, BA, Brazil Fortaleza, CE, Brazil

Prof. Gilcenara de Oliveira Prof. Rinaldo Araujo

Núcleo de Pesquisa em Biologia Department of Chemistry and
Experimental Environmental
Universidade de Fortaleza Federal Institute of Ceará
Fortaleza, CE, Brazil Fortaleza, CE, Brazil

Prof. João Vinı́cios Wirbitzki da Silveira Prof. Roque Machado de Senna

Institute of Science and Technology Institute of Environmental, Chemical and
Federal University of Jequitinhonha and Pharmaceutical Sciences
Mucuri Valleys—Campus JK Federal University of São Paulo
Diamantina, MG, Brazil Diadema, SP, Brazil

xxi
 C H A P T E R

1
Fundamentals on biopolymers and
global demand
Simone S. Silvaa,b, Luı́sa C. Rodriguesa,b,
Emanuel M. Fernandesa,b, Rui L. Reisa,b,c
a
3B’s Research Group, I3Bs—Research Institute on Biomaterials, Biodegradables and
Biomimetics, University of Minho, Headquarters of the European Institute of Excellence on Tissue
Engineering and Regenerative Medicine, Guimarães, Portugal bICVS/3B’s—PT Government
Associate Laboratory, Braga/Guimarães, Portugal cThe Discoveries Centre for Regenerative and
Precision Medicine, Headquarters at University of Minho, Guimarães, Portugal

Nomenclature
AV Aloe vera
BC bacterial cellulose
CAGR compound annual growth rate
CNCs cellulose nanocrystals
2D two-dimensional
3D three-dimensional
EC ethylene carbonate
ECM extracellular matrix
HA hyaluronic acid
IL ionic liquid
MB methylene blue
TA ambiental temperature
Tg glass transition temperature
SPEs dry solid polymer electrolytes
SF silk fibroin
SPI soy protein isolate

Biopolymer Membranes and Films 3 # 2020 Elsevier Inc. All rights reserved.
https://doi.org/10.1016/B978-0-12-818134-8.00001-8
4 1. Fundamentals on biopolymers and global demand

1 Introduction

The growing concerns for a sustainable environment and enhancement of the quality of
people’s lives have been the starting points to evaluate the potential of natural polymers from
renewable resources to create greener ways to address the problems of shortage of fossil fuel,
health hazards, environmental issues, and solid waste management. Biopolymers can be clas-
sified as polysaccharides (e.g., chitin/chitosan, alginate, agarose, cellulose-based polymers,
starch, and carrageenan) or proteins (e.g., soy protein, fibroin, sericin, gelatin, and collagen)
and have been used alone or combined to produce membranes for multiple applications.
However, large-scale commercialization biopolymer membranes are still a challenge. There-
fore many processing techniques are available to produce membranes, and the choice of the
appropriate one will depend not only on the features of the material itself but also on each
particular application. Although the feasibility of the use of biopolymer membranes in differ-
ent fields such as biomedical, food, energy, and the environment has been described in sev-
eral studies, its use sometimes implies its modification and/or blending with other polymers
(either natural or synthetic) to achieve adequate features for its application.
This chapter addresses fundamental features in terms of intrinsic characteristics, main
properties, and applications of biopolymers as membranes. Moreover, a look at the market
trend is also discussed.

2 Polysaccharides and proteins: General characteristics

2.1 Polysaccharides
Ranging from linear to highly branched structures, polysaccharides are, from a general
point of view, polymeric carbohydrates composed of long monosaccharide units bounded
by glycosidic linkages. As a consequence of their structure, they may assume different prop-
erties from their monosaccharide building blocks. Generally, polysaccharides from natural
origins are simple carbohydrates with a unique monosaccharide repeat unit, which may
be obtained or synthesized from a plethora of renewable resources. Natural polysaccharides
are nontoxic and biodegradable, which increases their potential application. The most used
biopolysaccharides summarized in Table 1 are obtained or synthesized from algae origin
(e.g., alginate, agarose, carrageenan, fucoidan, and ulvan), plant origin (e.g., acemannan, cel-
lulose, and starch), microbial origin (bacterial cellulose [BC], dextran, and gellan gum), and
animal origin (e.g., chitin/chitosan, chondroitin sulfate, glycosaminoglycans, heparin, and
hyaluronan).
Moreover, these natural derivatives present a considerable number of reactive functional
groups (e.g., hydroxyl, carboxyl, and amino groups), which significantly increase their appli-
cability through chemical modification or physical blend.
In the following sections a detailed description of selected polysaccharides’ physicochem-
ical and biological properties is presented.

2.1.1 Alginate
Alginic acid, also called alginate, is an anionic polysaccharide that is present in nature,
mostly as one of the constituents of brown algae (Phaeophyceae) [88]. It is a linear unbranched

I. Fundamentals on biopolymers membranes and films

 2 Polysaccharides and proteins: General characteristics 5
TABLE 1 General characteristics of the natural biomacromolecules.
Polymer Source Characteristic features References
Agarose Derived from agar and found in red • Composed of repeating units of [1,2]
seaweeds (1 ! 3)-β-D-galactopyranose-(1 ! 4)-
3,6-anhydro-β-L-galactopyranose
• Water-soluble and neutral
polysaccharide
• Low gelling temperature (32°C)

Alginate Brown algae (Phaeophyceae) • Gel formation in the presence of [3–9]

divalent cations (e.g., Ca2+, Mg2+)
• Composed of β(1 ! 4)-linked
D-mannuronic acid and α(1 ! 4)-
linked L-guluronic acid
• Processed as hydrogels, membranes,
capsules, fibers, or scaffolds

Bacterial Gluconacetobacter xylinus or Acetobacter • Glucan chains bound together by [10–16]

cellulose xylinum hydrogen bonds
• Crystalline nanofibrillar structure
• Conjugated with chitosan, alginate,
gelatin, hyaluronic acid, and
xyloglucan to improve performance

Carrageenan Red algae • Made up of repeating galactose units [17–19]

and 3,6-anhydrogalactose, both
sulfated and nonsulfated
• Three main types of carrageenan can
be obtained: kappa (κ), iota (ι), and
lambda (λ)

Cellulose Woods • High degree of crystallinity and rigid [20–25]

intra/intermolecular hydrogen
bonds
• Constituted by β-1,4-
glycosidic-linked D-glucose units
• Insoluble in water and most organic
solvents
• Solubility and processability
achieved by using ionic liquids
• Undergoes chemical modification
through esterification, graft
copolymerization, or selective
oxidation

Collagen Cornea, blood vessels, skin, cartilage,
bone, tendon, ligament, marine sponges,
and fish skin
• Main component of the extracellular [26–29]
matrix and the most abundant
protein present in mammalian tissues
• Provides mechanical strength to
tissues and stimulates cell adhesion
and proliferation

Continued

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6 1. Fundamentals on biopolymers and global demand

TABLE 1 General characteristics of the natural biomacromolecules—cont’d

Polymer Source Characteristic features References
• Can be chemically modified or
combined with polysaccharides and/
or bioactive molecules to improve
their physicochemical properties and
biological performance

Chitin Cell walls of fungi, exoskeletons of • Strong intermolecular bonding [9,30–48]

arthropods such as crustaceans and
insects, radulas of mollusks, and beaks
of cephalopods
• Insoluble in common solvents
• Solubilization using ionic liquids
• Molded into different forms (e.g.,
gels, beads, membranes, sponges,
tubes, and fibers)

Chitosan N-Deacetylated derivative of chitin • Solubilization in aqueous acidic [31,37,39,41,

solutions 49–68]
• Designed as 2D- and 3D-based
architectures such as fibers, particles,
membranes, and composites at
micro/nanolevel

Dextran Produced by several microorganisms • Composed of (1 ! 6)-linked α-D- [27,46,69]

glucopyranosyl units
• Soluble in water and organic solvents
• Biocompatible and biodegradable

Gellan gum Bacterium Sphingomonas elodea • Anionic exopolysaccharide [15,70–75]

• Consists of a repeating unit of a
tetrasaccharide: 1,3-linked-D-glucose,
1,4-linked-D-glucuronic acid, 1,4-
linked-D-glucose, and 1,4-linked-L-
rhamnose
• Thermally reversible gel with
excellent stability and high gel
strength
• Forms gels in the presence of metal
cations

Hyaluronic Rooster combs or aqueous humors of • Composed of D-glucuronic acid and [18,19,49,
acid cow’s eyes N-acetyl-D-glucosamine 76–84]
• Water-soluble polysaccharide
• Low shape stability and poor
mechanical properties

Pectin Structural material of all land-based • Composed of poly-D-galacturonic [27,47,85]

plants acid molecules
• Water-soluble biopolymer
• Ability to form gels

Sericin Waste during silk processing • Soluble protein [86]

I. Fundamentals on biopolymers membranes and films

 2 Polysaccharides and proteins: General characteristics 7
TABLE 1 General characteristics of the natural biomacromolecules—cont’d
Polymer Source Characteristic features References
• Antioxidant, moisturizing ability, pH
responsiveness, and mitogenic effect
on mammalian cells

Silk fibroin Nonmulberry and mulberry silkworm • Beta sheet formation after metanol/ [1,2]
Bombyx mori, insects, and spiders water solution treatment

Soy protein Soy beans • Low price, nonanimal origin, [87]

relatively long storage time, and
stability

Starch Corn, wheat, potato, and rice starch • Composed of amylose and [80–83]
amylopectin
• Starch can be transformed into
thermoplastic materials or blended
with synthetic polymers

polysaccharide composed of different amounts of β(1 ! 4)-linked D-mannuronic acid and

α(1 ! 4)-linked L-guluronic acid [89]. One of the most relevant features of alginate is its ability
to form gels in the presence of various divalent cations, e.g., Ca2+, Mg2+, due to the carboxylate
groups of the guluronate cross-linking on the polymer backbone. Alginate is a biocompatible
and antimicrobial polymer with immunogenicity, low toxicity, and stability in physiological
conditions [3,4,90–92]. This polysaccharide may be processed in different forms as hydrogels,
membranes, capsules, fibers, or scaffolds [5,6,93–96], which significantly enlarge the scope of
application [6,7,76,77,91,93,94,97–100].
Furthermore, to optimize the physical properties of hydrogels, alginate has been cova-
lently cross-linked and oxidized [8,101]; however, an associated drawback is the limited deg-
radation of the covalently cross-linked alginate gels, since cells do not secrete the necessary
enzymes for polymer cleavage. Nevertheless, alginate properties can be tailored or enhanced
using other strategies based on conventional chemical modification such as graft polymeri-
zation, sulfation, or esterification [20,102,103].

2.1.2 Cellulose
Cellulose is the most abundant polysaccharide from natural origin in the world, and is
mostly produced by plants. It is a polydisperse linear polysaccharide constituted by β-1,4-
glycosidic linked D-glucose units (so-called anhydroglucose units) [21] giving origin to a rigid
straight chain due to the many inter- and intramolecular hydrogen bonds established among
the many hydroxyl groups to form what is known as a cellulose microfibril, or simply fibril.
This close packaging of the cellulose chains leads to areas of high crystallinity within the
polymer and to high stability structures, which as a consequence promote considerable
strength, remarkable inertness, and insolubility in water and common organic solvents.
Significant efforts have been made to overcome these drawbacks, such as the chemical

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8 1. Fundamentals on biopolymers and global demand

modification of cellulose through esterification, graft copolymerization, or selective oxidation

[104–107] to improve resistance to heat or abrasion [108–110], mechanical strength [111,112],
water or oil repellency [113–115], or antibacterial activity [116]. Moreover, most of the chem-
ical functionalization procedures are based on hydroxyl groups. To date, several studies have
reported different designs, fabrications, and processing of cellulose. Grafted cellulose copol-
ymers present a well-defined architecture, which promotes potential applicability in broader
fields. Moreover, when stimuli-responsive side polymer chains were grafted into the poly-
meric chain [10,22,49,117], it gave foundation to cellulose-based smart materials [11,105].
A more recent approach allows a homogeneous modification and functionalization of cellu-
lose through the use of ionic liquids (ILs), which may represent a green approach to cellulose
processing, enlarging its range of applicability [12,118].

2.1.3 Bacterial cellulose

BC, similarly to plant-derived cellulose, is a natural polymer composed of microfibrils
containing glucan chains bound together by hydrogen bonds. BC is produced extracellularly
by Gram-negative bacterial cultures, most efficiently secreted from Gluconacetobacter xylinus
(Acetobacter xylinum). It is a highly pure, biocompatible, and versatile material that can be uti-
lized in several applications. Biosynthesized as a pellicle comprised of a random microfibril-
lar network of cellulose chains aligned in parallel, BC presents a large surface area capable of
retaining a large amount of liquid [23].
However, like plant-derived cellulose, BC is quite inert, and its interaction (e.g., entrap-
ment or grafting) with several bioactive compounds significant in tissue regeneration, such
as drugs, polyelectrolytes, or proteins, is difficult. To overcome BC inertness, several
functionalization techniques were performed as well as several conjugations with chitosan
[13,119], alginate [14], gelatin [120], hyaluronic acid (HA) [15], and xyloglucan [78].

2.1.4 Chitin and chitosan

Chitin is a biopolymer of N-acetylglucosamine with some glucosamine, which is the main
component of the cell walls of fungi, exoskeletons of arthropods such as crustaceans and
insects, radulas of mollusks, and beaks of cephalopods; it is considered the second most
abundant natural polymer after cellulose. Chemically, chitin is made of monomer units of
2-acetamido-2-deoxy-β-D-glucose connected through β(1 ! 4) linkages. Because of its highly
crystalline structure and strong inter- and intramolecular bonds between the polymer chains,
chitin is insoluble in common solvents. On its glucose ring, chitin has acetamido groups that
undergo incomplete hydrolysis into primary amine groups, N-deacetylation of chitin, which
leads to the formation of chitosan that can be easily dissolved in aqueous acidic solutions,
which makes it suitable for various applications. Moreover, chitin is also widely used for con-
trolled drug delivery systems, protein and enzyme carriers, and packaging material based on
its natural antimicrobial activity [121].
Chitin and its derivatives (e.g., chitosan) have many useful properties that make them suit-
able for a wide variety of applications. Chitin and chitosan can be molded into different forms
(e.g., gels, beads, membranes, sponges, tubes, and fibers). Also, their products are known to
be antibacterial, antifungal, antiviral, nontoxic, and nonallergic [16,30–32,122–124].
Chitin structure modification and combination with other polymers and bioactive mole-
cules are being studied to enhance its mechanical and chemical properties.

I. Fundamentals on biopolymers membranes and films

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Fig. 274. Coniopteris arguta. (Nat. size. From a specimen in the Sedgwick
Museum, Cambridge.)
 Fig. 275.
A. Coniopteris arguta. (Fertile pinnae; nat. size.)
B. C. hymenophylloides.
A, from the Inferior Oolite of Yorkshire (British Museum); B, from Jurassic
rocks in Turkestan.
Lower Cretaceous casts of tree-fern stems in the Prague Museum
have been described under the names Alsophilina and Oncopteris;
the figures of the latter (fig. 276) given by Feistmantel[918] and by
Velenovský[919] show the petiole-bases arranged in vertical rows and
characterised by leaf-traces consisting of two separate strands in the
form of two Vs lying on their sides.
Tree-fern stems described under various generic names are not
infrequently found in European Lower Cretaceous rocks: their
comparative abundance affords an example of striking changes in
geographical distribution since the latter part of the Mesozoic epoch.
The Cyatheaceae no longer exist in Europe and the arborescent
species of the genus have retreated to more southern regions.
 Fig. 276. Oncopteris Nettvalli. (After Velenovský; ¾ nat. size.)

Fig. 277. Protopteris punctata. (After Heer; very slightly reduced.)

Protopteris punctata (Sternb.). Fig. 277.

The earliest information in regard to the anatomy of this widely
spread Lower Cretaceous fern we owe to Corda, who showed that
the species agrees in essentials with existing tree-ferns. The English
example described by Carruthers[920] from Upper Greensand beds in
Dorsetshire (now in the British Museum) shows only the external
features. The sandstone cast (14 cm. in diameter), of which a portion
is seen in fig. 277, was described by Heer from Disco Island
(Greenland) as a Carboniferous species[921], but afterwards correctly
assigned to the Cenomanian series[922] This species is recorded also
from the Lower Cretaceous of Bohemia by Frič and Bayer[923] Among
examples of petrified stems exhibiting a general agreement with
Protopteris punctata are those described by Stenzel[924] from
Turonian rocks in Germany. In one of these, Rhizodendron
oppoliense Göpp., attention is drawn to branches given off from the
stem stele which have a solenostelic structure in contrast to the
dictyostele of the stem; also to the minute structure of the tracheae
which appear to have their ends perforated, a feature shown by
Gwynne-Vaughan[925] to be characteristic of the xylem elements of
many ferns.
 Fig. 278.
A. Laccopteris polypodioides, Brongn. [From a specimen (39275) in the
British Museum; slightly reduced.]
B. L. Muensteri.
C. Dicksonia (petiole stele).
D. Onychiopsis Mantelli (fertile segments).
E. Hausmannia Sewardi Richt.
F. H. Kohlmanni Bicht.
G, H. Protopteris Witteana, Schenk. (x, xylem; R, roots.)
(B, after Schenk; E, F, after Richter.)
 Protopteris Witteana Schenk[926] (fig. 278, G, H), a Wealden
species recorded from Germany and England, represents a closely
allied or possibly an identical type. The section of the stem (fig. H)
shows the narrow vascular bands, x, of a dictyostele similar to that of
recent Cyatheaceous tree-ferns and a form of meristele (fig. G, x)
resembling that of P. punctata. Adventitious roots are seen in section
at R (figs. G and H).

Polypodiaceae.
Sections of petrified sporangia from the English Coal-Measures
(Pteridotheca sp.) occasionally exhibit a striking resemblance to
those of recent Polypodiaceae[927], but in the absence of material in
which it is possible to recognise the true orientation of the sporangia,
the exact position of the annulus is almost impossible to determine.
We have as yet no satisfactory evidence of the existence of true
Polypodiaceae in the Palaeozoic era. It is noteworthy that apart from
the absence of ferns which can reasonably be included in this family,
the anatomical features of the Botryopterideae (Coenopterideae) and
of the Cycadofilices or Pteridosperms do not foreshadow those of
Polypodiaceous ferns. On the other hand, as we have already
noticed, anatomical characters of such families as the
Gleicheniaceae, Hymenophyllaceae, and Schizaeaceae are met with
in certain generalised Palaeozoic types. These facts are perhaps of
some importance as supplying collateral evidence in favour of the
relatively more recent origin of the dominant family of ferns in
modern floras.
 Fig. 279.
A. Adiantides antiques (Ett.). (½ nat. size.)
B. A. Lindsayoides (Sew.). (B′ nat. size.)
(A, after Kidston.)
The use of the generic name Adiantites for fern-like fronds of
Lower Carboniferous age characterised by cuneate pinnules like
those of species of Adiantum, suggests an affinity which is in all
probability non-existent. It has been pointed out that this generic
name was applied in the first instance to the leaves of the Jurassic
plant Ginkgo digitata[928] and should, therefore, be discarded.
Schimper[929] used the designation Adiantides, and
[930]
Ettingshausen , more rashly than wisely, preferred Adiantum. The
specimens described by Kidston[931] as Adiantides antiquus (Ett.) (fig.
279, A) from the Carboniferous limestone of Flintshire are portions of
tripinnate fronds bearing cuneate segments with numerous forked
veins radiating from the contracted base of the lamina. It is not
improbable, in view of Dr White’s[932] discovery of seeds on a very
similar plant from the Pottsville beds of North America, that this
characteristic Lower Carboniferous genus is a Pteridosperm.
From Jurassic rocks in various parts of the world numerous fossils
have been described under the generic names Aspidium, Asplenium,
Davallia, Polypodium, and Pteris. In the great majority of cases such
records leave much to be desired from the point of view of students
who appreciate the dangers of relying on external similarity between
vegetative organs, and on resemblances founded on obscure
impressions of sori. The generic term Woodwardites[933], which
suggests affinity with the recent genus Woodwardia, has been used
for Rhaetic plants belonging to the Dipteridinae.
A plant described as Adiantides Lindsayoides from Jurassic rocks
of Victoria[934], characterised by marginal sori which appear to be
protected by the folded-over edge of the leaflets, and by the
resemblance of the pinnules to those of recent species of Lindsaya,
may be a true Polypodiaceous fern; but in this case, as in many
similar instances, nothing is known of the structure of the sporangia.
Some sterile pinnae described by Yabe from Jurassic rocks of Korea
as Adiantites Sewardi[935] may perhaps be identical with the
Australian species.
In such a species as Polypodium oregonense Font., from Jurassic
rocks of Oregon, the generic name is chosen because the
“fructification seems near enough to that of Polypodium to justify the
placing of the plant in that genus[936].” But the fact that no sporangia
have been found is a fatal objection to this identification.

Onychiopsis.
This generic name was instituted by Yokoyama[937] for a Japanese
Wealden species, previously described by Geyler[938] as Thyrsopteris
elongata, on the ground that, in addition to a similarity in habit of the
sterile fronds, the fertile pinnae present a close agreement to those
of the recent genus Onychium.

Onychiopsis Mantelli[939] (Brongn.). Figs. 278, D; 280, A and B.

 The Japanese species Onychiopsis elongata may perhaps be
identical with this common Wealden fern which, as Fontaine points
out, should be called O. psilotoides if the rule of priority is to be
observed irrespective of long usage.
Hymenopteris psilotoides, Stokes and Webb, Trans. Geol.
1824.
Soc. [ii.], Vol. i. p. 423, Pl. xlvi. fig. 7.
Sphenopteris Mantelli, Brongniart, Hist. vég. foss. p. 170, Pl.
1828.
xlv. figs. 3–7.
Onychiopsis Mantelli, Nathorst, Denksch. Wien Akad. Vol.
1890.
lvii. p. 5.
Onychiopsis Mantelli may be defined as follows:—
Frond bipinnate, ovate lanceolate, rachis winged; pinnae approximate, given
off at an acute angle; pinnules narrow, acuminate, with a single vein; the larger
segments serrate and gradually passing into pinnae with narrow ultimate
segments. Fertile segments sessile or shortly stalked, linear ovate, sometimes
terminating in a short awn-like prolongation.

The fertile segments (fig. 278, D) bear so close a resemblance to

those of species of Onychium that it would seem justifiable to regard
the plant as a member of the Polypodiaceae. This fern is one of the
most characteristic members of the Wealden floras; it occurs in
abundance in the English Wealden, in Portugal, Germany, Belgium,
Japan, Bohemia, South Africa, and elsewhere. A piece of rhizome
figured from the English Wealden[940] is very similar to the creeping
rhizomes of recent species of Polypodiaceae. The English Wealden
specimens shown in fig. 280, A and B, illustrate the difference in
form presented by leaves of this species; the smaller pinnae
reproduced in fig. A are more characteristic of the species than are
those of the slightly enlarged example represented in fig. 280, B.
 Fig. 280. Onychiopsis Mantelli. (From Wealden specimens in the British
Museum; No. 13495 and No. V. 2615. A, natural size; B, very
slightly enlarged.)
Among British Tertiary species referred to Polypodiaceae, it is
interesting to find what may well be an authentic record of a fern
closely allied to the recent tropical species Acrostichum
(Chrysodium) aureum. This Eocene species from Bournemouth is
described as Chrysodium lanzaeanum[941]. The frond is simply
pinnate and apparently coriaceous in texture, with lanceolate or
oblong lanceolate pinnules (fig. 261, A, A′, p. 350), differing from
those of Acrostichum aureum in being sessile. A prominent midrib
gives off numerous anastomosing veins. No fertile pinnules have
been found.
 Specimens described by Forbes from the Eocene beds of the
Island of Mull as Onoclea hebraidica[942] bear a strong likeness to the
North American and Japanese recent species Onoclea sensibilis.
Fertile specimens referred to the latter species are recorded by
Knowlton[943] from Tertiary beds of Montana.
A species described by Saporta[944] from the Eocene of Sézanne
as Adiantum apalophyllum is recorded by Gardner and
Ettingshausen from Bournemouth; an identification which is based
on somewhat meagre evidence.
The following remarks by Gardner and Ettingshausen are worthy
of repetition as calling attention to circumstances often overlooked in
analyses of fossil floras. They speak of ferns as relatively rare in
British Eocene rocks and add,—“the floras consist principally of
deciduous dicotyledonous leaves, which ... fell into the water and
were tranquilly silted over. Ferns, on the other hand, would require
some violence to remove them from the place of their growth, and
their preservation would consequently be exceptional, and they
would be mutilated and fragmentary. This may account for their
rarity. Few as the British ferns are in the number of species, they
nevertheless form the largest and most important series of Eocene
ferns, even of Tertiary ferns, yet described from one group of
beds[945].”

Dipteridinae.
Dictyophyllum.
This genus was founded by Lindley and Hutton for a pinnatifid leaf
from the Jurassic rocks of Yorkshire which they regarded as probably
dicotyledonous and named D. rugosum[946]. Several ferns of this
genus have since been found with well-preserved sori which
demonstrate a close similarity to the recent fern Dipteris.
Dictyophyllum may be defined as follows:—
Fronds large and palmate, characterised by the equal dichotomy
of the main rachis into two arms which curve outwards and then
bend inwards (fig. 281); from the surface of each arm are given off
numerous spreading pinnae with a lamina more or less deeply
dissected into lobes varying in breadth and in the form of the apex.
Each lobe has a median vein, from which branches are given off
approximately at right angles and then subdivide into a reticulum, in
the meshes of which the veinlets end blindly (fig. 282, A and E). Sori
composed of annulate sporangia are crowded on the lower surface
of the lamina. In habit and in sporangial characters the genus closely
resembles Dipteris, and in the branching of the frond suggests
comparison with Matonia. The rhizome (Rhizomopteris) is creeping
and dichotomously branched, bearing leaf-scars with a horse-shoe
form of vascular strand.
 Fig. 281. Dictyophyllum exile. (After Nathorst; much reduced.)
Dictyophyllum is represented by several types to which various
specific names have been assigned, the distinguishing features
being the form of the pinna lobes, the degree of concrescence
between the basal portions of the pinnae, and similar features which
in some cases can only be safely used as criteria when large
specimens are available for comparison.

Dictyophyllum exile (Brauns). Figs. 281, 282, D, E.

1862. Camptopteris exilis, Brauns, Palaeontograph. ix. p. 54.
Dictyophyllum acutilobum, Schenk, Foss. Flor. Grenz. p. 77,
1867.
Pls. xix. xx.
1878. D. exile, Nathorst, Flora vid Bjuf, i. p. 39, Pl. v. fig. 7.
— D. acutilobum, ibid. Pl. xi. fig. 1.
The restoration, after Nathorst[947], shown in fig. 281 illustrates the
habit of this striking fern, examples of which or of closely allied
species are recorded from Rhaetic rocks of Germany, Scania,
Persia, Bornholm, Tonkin, China, and elsewhere[948]. The petiole,
reaching a length of 60 cm., forks at the apex into two equal arms
leaving between them an oval space and occasionally crossing one
another. The axes of these branches are twisted so that the pinnae,
which may be as many as 24 on each arm, and arise from the inner
side, by torsion of the axes assume an external position. An
interesting analogy as regards the twisted rachis of Dictyophyllum
exile and Camptopteris is afforded by the leaves of the Cycads,
Macrozamia Fawcettiae and M. corallipes, which are also
characterised by the torsion of the rachis. The habit, justly compared
by Nathorst with that of Matonia pectinata, affords another illustration
of the common occurrence in older ferns of a dichotomous system of
branching. The pinnae, characterised by circinate vernation, reach a
length of 60 cm. and are divided into linear lobes inclined obliquely
or at right angles to the pinna axis. The whole of the under surface of
the lamina may be covered with sporangia, 4–7 sporangia in each
sorus; the annulus is incomplete and approximately vertical (fig. 282,
D). The rhizome is probably represented by the dichotomously
branched axis described by Nathorst from Scania as Rhizomopteris
major; the leaf-scars show a horse-shoe leaf-trace.
 Fig. 282.
A. Dictyophyllum Nilssoni.
B. Rhizomopteris Schenki.
C. Camptopteris spiralis.
D, E. Dictyophyllum exile.
(After Nathorst; A, B, C, E, ⅔ nat. size.)

Dictyophyllum Nathorsti Zeiller[949].

This type, represented by a splendid series of specimens from the
Rhaetic beds of Tonkin, agrees very closely with D. exile. It differs,
however, in the basal parts of the pinnae which are concrescent for a
length of 5 to 8 cm. instead of free as in D. exile; and, to a slight
degree, in the form of the ultimate segments. In habit and in soral
characters the two species are practically identical. Each sorus
contains 5 to 8 sporangia, which are rather larger than those of
Dipteris.
Dictyophyllum rugosum, Lind. and Hutt. Fig. 283.
1828. Phlebopteris Phillipsii, Brongniart, Hist. vég. foss. p. 377, Pl.
cxxxii. fig. 3; Pl. cxxxiii. fig. 1.
1829. Phyllites nervulosis, Phillips, Geol. Yorks. p. 148, Pl. viii. fig.
9.
1834. Dictyophyllum rugosum, Lindley and Hutton, Foss. Flor. ii. Pl.
civ.
1836. Polypodites heracleifolius, Goeppert, Foss. Farn. p. 344.
1849. Camptopteris Phillipsii, Brongniart, Tableau, p. 105.
1880. Clathropteris whitbyensis, Nathorst, Berättelse, p. 83.
This species, which is characteristic of Jurassic rocks, is less
completely known than the two types described above, but in the
form and venation of the pinnae there is little difference between the
Rhaetic and Jurassic plants. The leaves of the Jurassic species
appear to have been smaller and more like those of Dipteris
conjugata (fig. 231); there are no indications of the existence of the
two curved arms at the summit of the petiole which form so striking a
feature in D. exile and D. Nathorsti. No sporangia have been found
on English specimens, but it is safe to assume their agreement with
those of other species. A more complete list of records of D.
rugosum is given in the first volume of the British Museum Catalogue
of Jurassic plants[950].
 Fig. 283. Dictyophyllum rugosum (Lind. and Hutt.). (Brit. Mus. Nat. size.)
Nathorst[951] has recently drawn attention to certain differences
between Dictyophyllum and Dipteris. The pinnate division of the
pinnae is not represented in the fronds of the recent species, but this
method of lobing, which is a marked characteristic of Dictyophyllum,
is less prominent in Clathropteris; and in Camptopteris lunzensis
Stur[952], an Austrian Upper Triassic species, the pinnae are entire. In
Dictyophyllum the sori cover the whole lower surface of the leaf; in
Dipteris they are more widely separated and the sporangia have a
diameter of 0·02 mm., but in Dictyophyllum the diameter is 0·4–0·6
mm. Moreover in Dictyophyllum the sori contain 5 to 8 sporangia,
whereas in Dipteris they are much more numerous. Despite these
differences it is clear, as Nathorst says, that Dictyophyllum,
Clathropteris, and Camptopteris are existing types very closely allied
to Dipteris. It is a matter of secondary importance whether we
include all in the Dipteridinae or follow Nathorst’s suggestion and
refer the fossil genera to the separate family Camptopteridinae.

Thaumatopteris.
This genus, founded by Goeppert[953] for a Rhaetic plant from
Bayreuth, is by some authors[954] regarded as identical with
Dictyophyllum, but it has recently been resuscitated by Nathorst[955]
for specimens which he names T. Schenki, formerly included by
Schenk in his species T. Brauniana[956]. It bears a close
resemblance, in the long linear pinnules with an entire or crenulate
margin, to Dictyophyllum Fuchsi described by Zeiller[957] from Tonkin,
and it would seem hardly necessary to adopt a distinctive generic
designation. The sporangia have a vertical or slightly oblique
annulus and the rhizome is similar to that of Dictyophyllum exile. The
habit of the genus is shown in fig. 284, which represents one of the
German Rhaetic species.
 Fig. 284. Thaumatopteris Münsteri. (From a specimen in the
Bergakademie, Berlin; ⅓ nat. size.)

Clathropteris.

Clathropteris meniscoides, Brongn. Fig. 285.

Clathropteris, founded by Brongniart[958] for Rhaetic specimens
from Scania, agrees very closely with some species of
Dictyophyllum, but in view of the more rectangular form of the
venation-meshes it is convenient to retain both names. The type-
species was originally named Filicites meniscoides[959] and
afterwards transferred to Clathropteris. An examination of
Brongniart’s specimens has convinced Nathorst of the specific
identity of C. meniscoides and C. platyphylla. The Tonkin leaves
described by Zeiller[960] under the latter name should, therefore, be
included in C. meniscoides, which may be thus defined:
The petiolate frond is characterised by an equal dichotomy of the rachis, as
in Dictyophyllum; each branch bore 5–15 pinnae, disposed en éventail,
reaching a length of 20–30 cm. and fused basally as in D. Nathorsti Zeill.
Pinnae linear lanceolate, slightly contracted at the lower end and gradually
tapered distally. The lamina, 3–14 cm. broad, is characterised by obtusely
pointed marginal lobes. From the midrib of each pinna lateral veins are given
off at a wide angle, and adjacent veins are connected by a series of branches
which divide the lamina into a regular reticulum of rectangular and polygonal
meshes (fig. 285). The sori are abundant and contain 5–12 sporangia like those
of Dictyophyllum.