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Biofuels and Biorefineries 9

Zhen Fang
Richard L. Smith, Jr.
Xiao-Fei Tian Editors

Production of
Materials from
Sustainable
Biomass
Resources
Biofuels and Biorefineries

Volume 9

Editors-in-Chief:
Professor Zhen Fang, Nanjing Agricultural University, Nanjing, China

Editorial Board Members:

Professor Jamal Chaouki, Polytechnique Montréal, Canada
Professor Liang-shih Fan, Ohio State University, USA
Professor John R. Grace, University of British Columbia, Canada
Professor Vijaya Raghavan, McGill University, Canada
Professor Yonghao Ni, University of New Brunswick, Canada
Professor Norman R. Scott, Cornell University, USA
Professor Richard L. Smith, Jr., Tohoku University, Japan
Professor Ying Zheng, University of Edinburgh, UK
Aims and Scope of the Series
The Biofuels and Biorefineries Series aims at being a comprehensive and integrated
reference for biomass, bioenergy, biofuels, and bioproducts. The Series provides
leading global research advances and critical evaluations of methods for converting
biomass to biofuels and chemicals. Scientific and engineering challenges in biomass
production and conversion are covered that show technological advances and
approaches for creating new bio-economies in a format that is suitable for both
industrialists and environmental policy decision makers.
The Biofuels and Biorefineries Series provides readers with clear and concisely
written chapters that are peer reviewed on significant topics in biomass production,
biofuels, bioproducts, chemicals, catalysts, energy policy, economics, and
processing technologies. The text covers major fields of plant science, green
chemistry, economics and economy, biotechnology, microbiology, chemical
engineering, mechanical engineering, and energy.

Series Description
Annual global biomass production is about 220 billion dry tons or 4,500 EJ,
equivalent to 8.3 times the world’s energy consumption in 2014 (543 EJ). On the
other hand, world-proven oil reserves at the end of 2011 reached 1652.6 billion
barrels, which can only meet just over 50 years of global production. Therefore,
alternative resources are needed to both supplement and replace fossil oils as the
raw material for transportation fuels, chemicals, and materials in petroleum-based
industries. Renewable biomass is a likely candidate because it is prevalent over the
Earth and is readily converted to other products. Compared with coal, some of the
advantages of biomass are (i) its carbon-neutral and sustainable nature when
properly managed, (ii) its reactivity in biological conversion processes, (iii) its
potential to produce bio-oil (ca. yields of 75%) by fast pyrolysis because of its high
oxygen content, (iv) its low sulfur and lack of undesirable contaminants (e.g.,
metals, nitrogen content), (v) its wide geographical distribution, and (vi) its potential
for creating jobs and industries in energy crop productions and conversion plants.
Many researchers, governments, research institutions, and industries are developing
projects for converting biomass, including forest woody and herbaceous biomass,
into chemicals, biofuels, and materials, and the race is on for creating new
“biorefinery” processes needed for future economies. The development of
biorefineries will create remarkable opportunities for the forestry sector,
biotechnology, materials, and the chemical processing industry and stimulate
advances in agriculture. It will help to create a sustainable society and industries
that use renewable and carbon-neutral resources.

More information about this series at http://www.springer.com/series/11687

Zhen Fang • Richard L. Smith, Jr.
Xiao-Fei Tian
Editors

Production of Materials
from Sustainable Biomass
Resources
Editors
Zhen Fang Richard L. Smith, Jr.
College of Engineering Graduate School of Environmental Studies,
Nanjing Agricultural University Department of Chemical Engineering,
Nanjing, China Research Center of Supercritical Fluid
Technology
Xiao-Fei Tian Tohoku University
School of Biology and Biological Sendai, Japan
Engineering
South China University of Technology
Guangzhou, China

ISSN 2214-1537     ISSN 2214-1545 (electronic)

Biofuels and Biorefineries
ISBN 978-981-13-3767-3    ISBN 978-981-13-3768-0 (eBook)
https://doi.org/10.1007/978-981-13-3768-0

Library of Congress Control Number: 2019931852

© Springer Nature Singapore Pte Ltd. 2019

This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of
the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation,
broadcasting, reproduction on microfilms or in any other physical way, and transmission or information
storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology
now known or hereafter developed.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication
does not imply, even in the absence of a specific statement, that such names are exempt from the relevant
protective laws and regulations and therefore free for general use.
The publisher, the authors, and the editors are safe to assume that the advice and information in this book
are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the
editors give a warranty, express or implied, with respect to the material contained herein or for any errors
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in published maps and institutional affiliations.

This Springer imprint is published by the registered company Springer Nature Singapore Pte Ltd.
The registered company address is: 152 Beach Road, #21-01/04 Gateway East, Singapore 189721,
Singapore
Preface

Lignocellulosic biomass consists of the biopolymers (cellulose, hemicellulose, and

lignin) that form a natural structural matrix with structural similarities but unique-
ness among its many forms. As one of the most abundant renewable resources, lig-
nocellulosic biomass can be transformed into materials, chemicals, and energy with
sustainable chemistry and engineering. The substitution of traditional fossil
resources by the three major biopolymers as sustainable feedstocks has been exten-
sively investigated for the manufacture of high value-added products, including bio-
fuels, commodity chemicals, bio-based functional materials, and heterogeneous
catalysts that could be directly applied for promoting the manufacturing processes.
Aimed at developing innovative materials and fuels for practical application, this
book was conceived for the collection of studies on state-of-the-art techniques
developed specifically for lignocellulose component derivation and producing func-
tional materials, composite polymers, carbonaceous biocatalysts, and pellets from
lignocellulosic biomass with emphasis on sustainable chemistry and engineering.
Technological strategies in terms of physical processing or biological conversion of
biomass for material production are also included. Each individual chapter was con-
tributed by experts or professionals in the field and globally selected to provide a
broad perspective of applications on the frontier.
This book is the ninth book of the series entitled “Biofuels and Biorefineries,”
and it contains 12 chapters contributed by leading experts in the field. The text is
arranged into five key areas:
Part I: Isolation and Purification of Lignocellulose Components (Chap. 1)
Part II: Composite Polymers Derived from Lignin and Cellulose (Chaps. 2 and 3)
Part III: Functional Materials Derived from Cellulose and Lignocelluloses
(Chaps. 4, 5, 6, 7, and 8)
Part IV: Biomass Pellets as Fuels (Chaps. 9, 10, and 11)
Part V: Biosynthesis of Polymers from Renewable Biomass (Chap. 12)

v
vi Preface

Chapter 1 summarizes current reports on extraction, purification, chemical com-

ponents, structural features, and functional properties of xylan. The preparation of
xylan derivatives and xylan-based materials, as well as their potential applications,
is discussed. Chemical modifications applied to functionalize xylan, especially to
modify its thermo-plasticity, hydrophobicity, conductivity, and stimuli responsive-
ness, are highlighted. Chapter 2 introduces a detailed literature review on how lignin
fits into the growing market for antioxidants, especially as replacements for poly-
olefins, and discusses hydrolytic depolymerization processes showing how depoly-
merization can improve the antioxidant activity of commercial lignin and how the
mechanical properties are affected after incorporating lignin into polymer matrixes.
Chapter 3 focuses on the properties and use of nanocellulose to achieve favorable
strength and barrier properties, as well as in coating and paper sheet forming.
Chapter 4 describes cellulose derivatization approaches and advanced material
designs that have been realized and materials that have potential application in bio-
medical areas. Chapter 5 gives a state-of-the-art overview of biochar production,
characterization, and applications in nontraditional areas. Potential use of biochar
for environmental remediation and for water desalination is demonstrated, as well
as sustainable energy applications related to supercapacitors and electrochemical
sensors. Chapter 6 covers progress on fabrication of biomass-derived nanostruc-
tured carbon materials for use as carbon electrodes. Correlations between carbon
structures and electrochemical properties are summarized along with performance
aspects. Chapter 7 summarizes the characteristics and properties of biomass-derived
catalysts and metal-free functionalized carbocatalysts and shows comparisons to
catalysts from other carbon sources and materials. The biomass-derived carbona-
ceous catalysts used in biodiesel production, gasification, and electro-Fenton oxida-
tion reaction are reviewed. Chapter 8 introduces designs, structural features, and
chemical and physical activation of engineered biocarbon-based materials with a
focus on the application and performance differences of novel engineered biochars
in lithium-ion batteries. Chapter 9 provides a state-of-the-art review of biomass pel-
letization on the laboratory, pilot, and industrial scales with particular emphasis on
its implementation in power generation. The chapter is rich with examples on the
status of large-scale biomass pellets firing and cofiring of worldwide operations.
Chapter 10 presents an overview of property differences among biocarbons pro-
duced from different thermal processes, including pyrolysis, gasification, and
hydrothermal treatment. Of particular importance is the use of biocarbon in the steel
industry to reduce carbon dioxide emissions. Techno-economic and environmental
aspects of biocarbon pellet combustion are analyzed. Chapter 11 highlights the
effects of the raw materials, binders, pretreatment, and process parameters on pellet
design and the pelletization process and includes practical models for development.
Mechanical aspects of charcoal and wood pelletization are covered with actual
examples that have resulted in commercial materials. Chapter 12 provides opportu-
nities and challenges regarding the production of lactic-acid-based polymers and
related oligomer precursors using genetically modified organisms and engineered
enzymes. Future developments show the advantages of using biological techniques
to replace fossil fuel feedstocks.
Preface vii

The text should be of interest to professionals in academia and industry who are
working in the fields of natural renewable materials, biorefinery of lignocellulose,
biofuels, and environmental engineering. It can also be used as comprehensive ref-
erences for university students with background in chemical engineering, material
science, and environmental engineering.

Nanjing, China Zhen Fang

Sendai, Japan Richard L. Smith, Jr.
Guangzhou, China Xiao-Fei Tian
Acknowledgments

First and foremost, we would like to cordially thank all the contributing authors for
their great efforts in writing and revising the chapters and insuring the reliability of
information given in their chapters. Their contributions have really made this proj-
ect realizable.
Apart from the efforts of the authors, we would also like to acknowledge the
individuals listed below for carefully reading the book chapters and giving many
constructive comments that significantly improved the quality of the chapters:
Prof. E.J. “Ben” Anthony, Cranfield University, UK
Dr. Ing. Marco Barbanera, Università degli Studi di Perugia, Italy
Dr. Marc Borrega, VTT Technical Research Centre of Finland Ltd, Finland
Dr. Pedro Castaño, University of the Basque Country (UPV/EHU), Spain
Dr. Greta Faccio, Empa Swiss Federal Laboratories for Materials Science &
Technology, Switzerland
Prof. Dr. Anton Friedl, Technische Universität Wien (TU Wien), Austria
Mr. Stefan Frodeson, Karlstad University, Sweden
Prof. Thomas Heinze, Friedrich-Schiller-University Jena, Germany
Prof. Fang Huang, Fujian Agriculture and Forestry University, China
Mr. Fohr Jarno, Lappeenranta University of Technology, Finland
Prof. Charles Q. Jia, University of Toronto, Canada
Dr. Junhua Jiang, Idaho National Laboratory, USA
Dr. Andreas Koschella, Universität Jena, Germany
Dr. Konstantina Kourmentza, University of Reading, UK
Prof. Richard A Larson, University of Illinois at Urbana-Champaign, USA
Dr. Seung Woo Lee, Georgia Institute of Technology, USA
Dr. James McGregor, The University of Sheffield, UK
Prof. Emilia Morallon, Universidad de Alicante, Spain
Dr. Oleksandr Nechyporchuk, Swerea IVF; Chalmers University of Technology,
Sweden
Dr. Ioanna G. Ntaikou, Foundation for Research and Technology, Hellas (FORTH/
ICE-HT), Greece

ix
x Acknowledgments

Dr. Tobias Placke, University of Münster, Germany

Dr. Hema Ramsurn, University of Tulsa, USA
Prof. Dr. Junli Ren, South China University of Technology, China
Dr. MA Sanchez-Monedero, CEBAS-CSIC, Campus Universitario de Espinardo,
Spain
Dr. Takafumi Sato, Utsunomiya University, Japan
Dr. Olena Sevastyanova, Fibre and Polymer Technology/Wood Chemistry and Pulp
Technology, Sweden
Dr. Arjan Smit, Energy research Centre of the Netherlands (ECN), the Netherlands
Dr. Juan José Villaverde, INIA - National Institute for Agricultural and Food
Research and Technology, Spain
Prof. Shubin Wu, South China University of Technology, China
Dr. Seunghyun Yoo, North Carolina State University, USA
We are also grateful to Ms. Becky Zhao (senior editor) and Ms. Abbey Huang
(editorial assistant) for their encouragement, assistance, and guidance during the
preparation of the book.
Finally, we would like to express our deepest gratitude toward our families for
their love, understanding, and encouragement, which help us in the completion of
this project.

Zhen Fang, October 18, 2018 in Nanjing (Zhen Fang)

Richard L. Smith, Jr., October 18, 2018 in Sendai (Richard L. Smith, Jr.)

Xiao-Fei Tian, October 18, 2018 in Guangzhou (Xiao-Fei Tian)

Contents

Part I Isolation and Purification of Lignocellulose Components

1 Isolation, Purification, and Potential Applications of Xylan����������������    3
Gen-Que Fu, Ya-Jie Hu, Jing Bian, Ming-Fei Li,
Feng Peng, and Run-Cang Sun

Part II Composite Polymers Derived from Lignin and Cellulose

2 Development of Lignin-Based Antioxidants for Polymers ������������������   39
Afsana S. Kabir, Zhong-Shun Yuan, Takashi Kuboki,
and Chunbao (Charles) Xu
3 Nanocellulose Applications in Papermaking ����������������������������������������   61
Carlos Salas, Martin Hubbe, and Orlando J. Rojas

Part III Functional Materials Derived from Cellulose

and Lignocelluloses
4 Recent Advances in Cellulose Chemistry
and Potential Applications����������������������������������������������������������������������   99
Poonam Trivedi and Pedro Fardim
5 Production, Characterization and Alternative
Applications of Biochar �������������������������������������������������������������������������� 117
Aldrich Ngan, Charles Q. Jia, and Shi-Tang Tong
6 Carbons from Biomass for Electrochemical Capacitors���������������������� 153
Lu Wei, Wen Zhao, and Gleb Yushin
7 Carbonaceous Catalysts from Biomass�������������������������������������������������� 185
Melanie J. Hazlett, Ross A. Arnold, Vicente Montes,
Ye Xiao, and Josephine M. Hill

xi
xii Contents

8 Synthesis and Design of Engineered Biochars

as Electrode Materials in Energy Storage Systems������������������������������ 233
Omid Norouzi, Pejman Salimi, Francesco Di Maria,
S. E. M. Pourhosseini, and Farid Safari

Part IV Biomass Pellets as Fuels

9 Biomass Pelletization: Contribution to Renewable
Power Generation Scenarios ������������������������������������������������������������������ 269
Roberto García, María V. Gil, María P. González-Vázquez,
Fernando Rubiera, and Covadonga Pevida
10 Biocarbon Production and Use as a Fuel���������������������������������������������� 295
Pietro Bartocci, Liang Wang, Øyvind Skreiberg, Federica Liberti,
Gianni Bidini, and Francesco Fantozzi
11 Mechanical Aspects and Applications of Pellets Prepared
from Biomass Resources�������������������������������������������������������������������������� 325
Pietro Bartocci, Øyvind Skreiberg, Liang Wang, Hu Song,
Hai-Ping Yang, Mauro Zampilli, Gianni Bidini,
and Francesco Fantozzi

Part V Biosynthesis of Polymers from Renewable Biomass

12 Microbial Production and Properties of LA-based Polymers
and Oligomers from Renewable Feedstock ������������������������������������������ 361
John Masani Nduko and Seiichi Taguchi

Index������������������������������������������������������������������������������������������������������������������ 391
Contributors

Ross A. Arnold Department of Chemical and Petroleum Engineering, University

of Calgary, Calgary, AB, Canada
Pietro Bartocci Department of Engineering, University of Perugia, Perugia, Italy
Jing Bian Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry
University, Beijing, China
Gianni Bidini Department of Engineering, University of Perugia, Perugia, Italy
Francesco Di Maria Department of Engineering, University of Perugia, Perugia,
Italy
LAR5 Laboratory, Dipertimento di Ingegneria, University of Perugia, Perugia, Italy
Francesco Fantozzi Department of Engineering, University of Perugia, Perugia,
Italy
Pedro Fardim Laboratory of Fibre and Cellulose Technology, Åbo Akademi
University, Turku, Finland
Department of Chemical Engineering, KU Leuven, Leuven, Belgium
Gen-Que Fu Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing
Forestry University, Beijing, China
Roberto García Instituto Nacional del Carbón, INCAR-CSIC, Oviedo, Spain
María V. Gil Instituto Nacional del Carbón, INCAR-CSIC, Oviedo, Spain
María P. González-Vázquez Instituto Nacional del Carbón, INCAR-CSIC,
Oviedo, Spain
Melanie J. Hazlett Department of Chemical and Petroleum Engineering,
University of Calgary, Calgary, AB, Canada
Josephine M. Hill Department of Chemical and Petroleum Engineering, University
of Calgary, Calgary, AB, Canada

xiii
xiv Contributors

Martin Hubbe Department of Forest Biomaterials, North Carolina State

University, Raleigh, NC, USA
Ya-Jie Hu Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry
University, Beijing, China
Charles Q. Jia Department of Chemical Engineering and Applied Chemistry,
University of Toronto, Toronto, ON, Canada
Afsana S. Kabir Institute for Chemicals and Fuels from Alternative Resources,
Western University, London, ON, Canada
Takashi Kuboki Department of Mechanical and Materials Engineering, Western
University, London, ON, Canada
Federica Liberti CRB (Biomass Research Centre), University of Perugia, Perugia,
Italy
Ming-Fei Li Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing
Forestry University, Beijing, China
Vicente Montes Department of Organic Chemistry, University of Cordoba,
Cordoba, Andalucia, Spain
John Masani Nduko Department of Dairy and Food Science and Technology,
Faculty of Agriculture, Egerton University, Egerton, Kenya
Aldrich Ngan Department of Chemical Engineering and Applied Chemistry,
University of Toronto, Toronto, ON, Canada
Feng Peng Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry
University, Beijing, China
Covadonga Pevida Instituto Nacional del Carbón, INCAR-CSIC, Oviedo, Spain
S. E. M. Pourhosseini School of Chemistry, College of Science, University of
Tehran, Tehran, Iran
Orlando J. Rojas Department of Bioproducts and Biosystems, School of Chemical
Engineering, Aalto University, Espoo, Finland
Fernando Rubiera Instituto Nacional del Carbón, INCAR-CSIC, Oviedo, Spain
Farid Safari Faculty of Engineering and Applied Science, University of Ontario
Institute of Technology, Oshawa, ON, Canada
Omid Norouzi Department of Engineering, University of Perugia, Perugia, Italy
LAR5 Laboratory, Dipertimento di Ingegneria, University of Perugia, Perugia, Italy
Carlos Salas Department of Forest Biomaterials, North Carolina State University,
Raleigh, NC, USA
Contributors xv

Pejman Salimi Department of Physical Chemistry, Faculty of Science, Tarbiat

Modares University, Tehran, Iran
Øyvind Skreiberg SINTEF Energy Research, Trondheim, Norway
Hu Song China-EU Institute for Clean and Renewable Energy, Huazhong
University of Science and Technology, Wuhan, China
State Key Laboratory of Coal Combustion, School of Energy and Power Engineering,
Huazhong University of Science and Technology, Wuhan, China
Run-Cang Sun Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing
Forestry University, Beijing, China
Seiichi Taguchi Department of Chemistry for Life Sciences and Agriculture,
Faculty of Life Sciences, Tokyo University of Agriculture, Tokyo, Japan
CREST, JST, Tokyo, Japan
Shi-Tang Tong Department of Chemical Engineering, Wuhan University of
Science and Technology, Wuhan, China
Poonam Trivedi Laboratory of Fibre and Cellulose Technology, Åbo Akademi
University, Turku, Finland
Liang Wang SINTEF Energy Research, Trondheim, Norway
Lu Wei School of Materials Science and Engineering, Huazhong University of
Science and Technology, Wuhan, China
Ye Xiao Department of Chemical and Petroleum Engineering, University of
Calgary, Calgary, AB, Canada
Chunbao (Charles) Xu Institute for Chemicals and Fuels from Alternative
Resources, Western University, London, ON, Canada
Hai-Ping Yang State Key Laboratory of Coal Combustion, School of Energy and
Power Engineering, Huazhong University of Science and Technology, Wuhan,
China
Zhong-Shun Yuan Institute for Chemicals and Fuels from Alternative Resources,
Western University, London, ON, Canada
Gleb Yushin School of Materials Science and Engineering, Georgia Institute of
Technology, Atlanta, GA, USA
Mauro Zampilli Department of Engineering, University of Perugia, Perugia, Italy
Wen Zhao School of Materials Science and Engineering, Huazhong University of
Science and Technology, Wuhan, China
About the Editors

Zhen Fang is professor and leader of biomass group,

Nanjing Agricultural University. He is the inventor of
the “fast hydrolysis” process. He is listed in the “Most
Cited Chinese Researchers” in energy for 2014–2017
(Elsevier-Scopus). Professor Fang specializes in ther-
mal/biochemical conversion of biomass, nanocatalysts
synthesis and their applications, pretreatment of bio-
mass for biorefineries, and supercritical fluid processes.
He obtained his PhDs from China Agricultural
University and McGill University. Professor Fang is
associate editor of Biotechnology for Biofuels and the
Journal of Supercritical Fluids. He has more than
20-year international research experiences at top uni-
versities and institutes around the world, including 1
year in Spain (University of Zaragoza), 3 years in Japan
(Biomass Technology Research Center, AIST; Tohoku
University), and more than 8 years in Canada (McGill)
in renewable energy and green technologies. He has
worked for 7 years as engineer in energy, bioresource
utilization, and engine design in industry before mov-
ing to academia.

xvii
xviii About the Editors

Richard L. Smith, Jr. is professor of Chemical

Engineering, Graduate School of Environmental
Studies, Research Center of Supercritical Fluid
Technology, Tohoku University, Japan. Professor Smith
has a strong background in physical properties and sep-
arations and obtained his PhD in chemical engineering
from the Georgia Institute of Technology (USA). His
research focuses on developing green chemical pro-
cesses especially those that use water and carbon diox-
ide as the solvents in their supercritical state. He has
expertise in physical property measurements and in
separation techniques with ionic liquids and has pub-
lished more than 200 scientific papers, patents, and
reports in the field of chemical engineering. Professor
Smith is the Asia regional editor for the Journal of
Supercritical Fluids and has served on editorial boards
of major international journals associated with proper-
ties and energy.

Xiao-Fei Tian is associate professor of School of

Biology and Biological Engineering, South China
University of Technology. Dr. Tian obtained his PhD
from the University of Chinese Academy of Sciences.
His research focuses on solvent deconstruction and
enzymatic saccharification of lignocelluloses for
renewable cellulosic materials and biofuels. He also
has experience in the development of fermentation
techniques for functional fungal pigments. Dr. Tian has
coauthored more than 30 research papers, reviews, and
patents in his research specialty and has served as peer
reviewer for major scientific journals.
 Part I
Isolation and Purification
of Lignocellulose Components
Chapter 1
Isolation, Purification, and Potential
Applications of Xylan

Gen-Que Fu, Ya-Jie Hu, Jing Bian, Ming-Fei Li, Feng Peng,
and Run-Cang Sun

Abstract There is great interest in replacing fossil fuel resources with renewable
raw materials. Widely distributed lignocellulosic biomass is viewed as a potential
candidate to address energy and environmental demands. In this chapter, the use of
the hemicellulose component of lignocellulosic biomass, xylan, is considered. Due
to the presence of ester and ether lignin-carbohydrate linkages, extraction of xylan
is generally restricted to cell wall matrices of wood and lignified grass. Many extrac-
tion methods of xylan have been proposed, however, the subsequent purification
and analyses are needed on its fine structure. An effective way to modify xylan with
advanced properties is through etherification. This chapter points out new function-
alities, for example, thermoplasticity, hydrophobicity, conductivity, and stimuli-­
responsiveness of xylan by chemical modification and it summarize recent reports
on xylan, including extraction, purification, chemical components, structural fea-
tures, and functional properties. Xylan derivatives, xylan-based materials, and their
potential applications are discussed and future research areas are highlighted.

1.1 Introduction

Demand for energy is high worldwide and with the instability of oil resources and
concerns about global climate change, initiatives have been issued for alternative
energy development that can replace fossil fuels. Consequently, much interest exists
in developing alternative fuels and sources of chemicals. For creation of a sustain-
able society, renewable feed stocks must be used in the production of life necessi-
ties. Presently, lignocellulosic biomass provides numerous industrial and non-food
consumer products for society, including materials, chemicals, and fuels. However,
every year, there are many biomass residues produced in agriculture that are treated

G.-Q. Fu · Y.-J. Hu · J. Bian · M.-F. Li · F. Peng (*) · R.-C. Sun

Beijing Key Laboratory of Lignocellulosic Chemistry, Beijing Forestry University,
Beijing, China
e-mail: fengpeng@bjfu.edu.cn

© Springer Nature Singapore Pte Ltd. 2019 3

Z. Fang et al. (eds.), Production of Materials from Sustainable Biomass
Resources, Biofuels and Biorefineries 9,
https://doi.org/10.1007/978-981-13-3768-0_1
4 G.-Q. Fu et al.

OH
OH OH
4 6 OH
5 O 4 5 O 4 6
5 O
HO 1 1 HO
HO OH 1 OH
2 2 HO
3 OH 3 OH 2
3

¦Â-xylose mannose galactose

HO OH
O
2 3 6
4 1 O
OH OH 1 4 5
HO
5 OH
4 6 HO
5 O O HO OH
HO 3 2
HO 1 OH
2 OH
3 OH

glucose arabinose glucuronic acid

Fig. 1.1 Main sugar units of hemicelluloses

as wastes and used inefficiently. Wastes cause many problems related to space,
release of greenhouse gases such as methane and contamination with chemicals
such as dioxins [1]. Renewable and abundant lignocellulosic biomass is regarded as
a sustainable resource and since it is widely distributed in nature, it can be used to
produce fuels and necessary chemicals [2]. Cellulose, lignin, and hemicelluloses are
well known as the major constituents of lignocellulosic biomass [3]. Up to now,
cellulose and lignin are being used for commercial applications, while the hemicel-
lulose constituent of biomass has practically no commercial application. As an
enormous biopolymer resource, hemicelluloses have a wide variety of structural
types and consist of main sugar units including xylose, mannose, D-glucose, galac-
tose, arabinose, and glucuronic acid as shown in Fig. 1.1. The β-(1→4)-D-­
xylopyranose is the basic structure unit of xylan, and the 2- or 3- position is randomly
substituted with side groups. Gradually, researchers have focused more on xylan to
make progress on its application to the food and non-food fields. Xylan has been
studied in many fields and some of its promising properties are documented in
reviews [4–10].

1.2 Structure of Xylan

The structure diversity of xylan affects its functionality [11]. Generally, xylan can
be divided into several parts according to its primary structure in plant tissues:
homoxylans and glucuronoxylan (GX), arabinoglucuronoxylan (AGX), glucurono-
arabinoxylan (GAX), arabinoxylan (AX) and heteroxylan [12].
1 Isolation, Purification, and Potential Applications of Xylan 5

OH 3 OH OH
2
O O 1 O O
HO HO HO
O 5 O O
4
(a)

HO HO
1 3
2 O
O O OH OH
OH O O
O O 5 4
HO
(b)

Fig. 1.2 Structural conformations of homoxylan, (a) β-(1→3)-D-xylan; (b) β-(1→3 and
1→4)-D-xylan

1.2.1 Homoxylan

Xylan polysaccharides can be found in the oldest plant species botanically.

Homoxylan is the form of xylan that consists of xylose residues only. It has been
reported that homoxylan with β-(1→3) glycosidic linkages (Fig. 1.2a) is from green
algae (Caulerpa sp.) and homoxylan, which has a structure of β-(1→3 and 1→4)
(Fig. 1.2b), can be found in Palmariales and Nemaliales [11, 13]. Analyses indicate
1, 3-linkages are regularly distributed in the form of pentamers in the cell wall [14].

1.2.2 Arabinoxylan (AX)

The primary structure of arabinoxylan is shown in Fig. 1.3. AX readily occurs in a

variety of tissues in many kinds of plants [15–18]. AX is primarily substituted by
arabinose at carbon position 2 or 3 (may be di-substituted or mono-substituted,
Fig. 1.3a, b) of the xylose units along the backbone of xylan [13, 19]. The degree of
substitution affects the solubility of AX in water or other solvents. Water-insoluble
AX is mono-substituted by α-L-arabinose at position 3 of the xylan backbone and
the ratio of arabinose to xylose is in the range of 0.3–1.2 [20].

1.2.3 Glucuronoxylan (GX)

In hardwood, glucuronoxylan is the largest hemicellulose constituent and it makes

up 15–30% proportion of the dry mass weight of hemicellulose [21, 22]. The back-
bone of GX is (1→4)-linked β-D-xylopyranosyl (β-D-Xylp), and it is always substi-
tuted by 4-O-methyl-α-D-glucopyranosyl uronic acid residues (4-O-MeGlcA) at
6 G.-Q. Fu et al.

O
OH
HOH2C
HO 5 OH O
O OH O 1 O OH
O O O
O 3 O
4 2
O O
O OH
OH
HOH2C
HOH2C OH
OH
(a)

HO HO
5 1
O OH O O OH
O OH O
O 3 O
4 2
O
O
OH
HOH2C
OH
(b)

Fig. 1.3 Primary structure of arabinoxylan (a) 2, 3-arabino-D-xylan; (b) 3-arabino-D-xylan

HO 1 HO
5
O OH O O OH
O OH O
O 3 O
4 2
O
HO
OH
MeO
O
COOH

Fig. 1.4 Structure of glucuronoxylan, 4-O-methyl-D-glucurono-D-xylan

position 2 (Fig. 1.4). The polysaccharide framework consists of around 200 β-D-­
Xylp residues. Some xylose units only carry a single and terminal side chain of
glucuronic acid residue at position 2 [23]. Teleman et al. [24] extracted hemicellu-
loses from birch and beech by dimethyl sulphoxide (DMSO). Through NMR analy-
sis, they found that the main constituent is O-acetyl-(4-O-methylglucurono)-xylan
containing one 4-O-MeGlcA substituent for approximately every 15 D-xylose resi-
dues. Mais et al. [25] found that the main hemicellulose in hardwood pulp is
4-O-methylglucurono-xylan with a 4-O-MeGlcA: Xyl ratio of 5:100 at maximum.
1 Isolation, Purification, and Potential Applications of Xylan 7

COOH
O
MeO
OH
HO
HO 1 O
5 3
2
O OH O O 1 OH
O O O
O 3 O 5
4O 2 4
O
O OH
OH
HOH2C
HOH2C OH
OH

Fig. 1.5 Structure of glucuroarabinoxylan (GAX), 2, 3-arabino-2-(4-O-methylglucurono

acid)-xylan

1.2.4 Arabinoglucuronoxylan (AGX)

and Glucuroarabinoxylan (GAX)

The predominant fraction of non-woody materials is GAX, which has a backbone

of β-(1→4)-D- Xylp substituted at C-2 or 3 with MeGlcA and α-L-arabinofuranosyl
(α-L-Araf) units (Fig. 1.5), and it might also be slightly acetylated [3]. GAX has an
AX backbone, and its uronic acid side chain is ten times less in number than α-L-­
Araf, and some Xylp residues are double in number of those sugars [14]. Different
extraction methods and sources finally lead to different degrees and substitution
pattern of GAX [26, 27]. Shi et al. [28] examined alkali-extracted dendrocalamus
hemicelluloses. Neutral sugar analysis suggested that the soluble hemicelluloses
were mainly GAX with structure of linear β-(1→4)-Xylp backbone substituted by
α-L-Araf and/or 4-O-MeGlcA units at position 2 or 3. Arabinoglucuronoxylans
were isolated from the holocellulose of sugi (Cryptomeria japonica) and Hinoki
(Chamaecyparis obtusa) by Yamasaki et al. [29]. The obtained AGX was mainly
contained one 4-O-MeGlcA per 6.2 D-Xylp and one 4-O-Me-D-GlcA residue per
3.8 D-Xylp. By means of size exclusion chromatography and electrospray-­ionization
mass spectroscopy, the presence of xylooligosaccharides was found and was deter-
mined to have a degree of polymerization of 2–8 in addition to D-Xyl, suggesting
that the AGXs from Sugi and Hinoki contained unsubstituted chains consisting of at
least eight D-Xyl residues.

1.3 Isolation of Xylan

In daily life, xylan is used in cosmetics and shaving creams, while it also found in
wood meal, forest chips, and plant crops. Xylan can be extracted directly from
plants or it can be obtained as a by-product in wood and agriculture processing.
Xylan occurs in sources of oligomers or mono sugars from degradation of
8 G.-Q. Fu et al.

hemicelluloses mixed in black liquor in conventional Kraft pulping industries. For

the case of Kraft pulping however, xylan is rarely recovered as the black liquor is
used to produce steam and electricity. For the case of bioethanol production, it is
necessary to remove hemicelluloses for high accessibility of cellulosic materials
and to improve the yields of ethanol. Much attention has been paid to the isolation
of xylan that has high purity and high yield. Typical fractionation methods of xylan
from biomass materials will be introduced in the next sections.

1.3.1 Alkali Isolation

Hemicelluloses are interconnected with other cell wall components via covalent
linkages and hydrogen bonds. Alkaline treatment is a commonly used method to
destroy the covalent link or H-bond between hemicelluloses and some other compo-
nents such as cellulose, lignin, and silica. On the other hand, cellulose swells with
alkali treatment and its crystallinity decreases [30]. Yields of hemicellulose are
influenced by the type of alkali used in the isolation process. NaOH and KOH are
both recommended because they are effective to obtain a high yields of xylan, and
NaOH is better than KOH for the same concentration, but KOH-extracted fractions
tend to have higher purity [31–34]. On the other hand, Ca(OH)2 can be used to
extract xylan, but the obtained xylan fraction has low solubility in water. It has been
reported that Ba(OH)2 is effective in the fractional extraction of AX from some
crops [18, 35–37]. Hutterer et al. [38] found that xylan is effectively fractionated by
alkaline treatment in the study of hardwood kraft pulps. In their work, uronic acid
was marked with fluorescencing compounds, and this indicated that a large amount
of uronic acid in the cellulosic fraction was separated as the alkalinity increased
during pulp treatment. In the work of Singh et al., an alkali extraction method with
two-stages was evaluated [39]. In the first stage, the xylan obtained was from canut
husk, which was treated with 10% NaOH for 8 h at 65 °C, and then with hydrother-
mal treatment for the second-step. About 40–52% of the available xylan was
obtained in the first step, and the overall xylan recovery was more than 90%.
Arumugam et al. [40] conducted one and two-step alkaline-extractions of peanut
shell. On the basis of characterization by NMR and MALDI ToF MS analysis, the
extracted hemicelluloses were mainly GX, which was similar to a hardwood GX,
with a high degree of substitution of the main chain with 4-O-methyl-D-
glucuronicxylan acid (Xyl: MeGlcA ratio ~6–7).

1.3.2 Organic Solvent Isolation

Organic solvent extraction of biomass preserve the structure of xylan, such as its
acetyl groups. Some organic solvents including alcohols or organic acids are con-
sidered to be neutral solvents for xylan due to the process of extracting xylan
1 Isolation, Purification, and Potential Applications of Xylan 9

without major alteration or degradation of its native structure [41, 42]. Researchers
found that the proportion of DMSO-extracted xylan husk of sorghum grain was
about 24% of the total lignocellulosic content, and the extracts were highly branched
AX, and had negative specific optical rotations [43]. DMSO/LiCl system has also
been used to extract xylan from vegetables or fruits, and relatively fine structures
were obtained [44]. Fu et al. [45] compared properties of DMSO and NaOH extract-
able hemicelluloses from Neosinocalamus affinis and found that ethanol precipita-
tion was effective after extraction with NaOH, but that ethanol precipitation could
not separate the fraction with different degrees of branching for DMSO-extracted
hemicellulose (main component, xylan). However, DMSO-extracted fractions had
fine structures of 4-O-methyl-glucuronoarabinoxylans with acetyl substitution at
C-2, C-3.

1.3.3 Steam Explosion

For lignocellulosic biomass, high-pressure steam treatment is popular due to its

high-efficiency [46, 47]. With high-pressure steam, raw materials are saturated and
the pressure is released abruptly so that the materials are rapidly degraded. Steam
explosion destroys the basic structure of plant materials and hydrolyzes the xylan
[48]. Steam explosion works well for a variety of biomass feedstock such as wood
and agricultural residues [49–53]. The production of xylooligosaccharides from
corncobs was studied by Teng et al. with a two-stage process involved steam explo-
sion pretreatment and alkali treatment [54] in which conditions for steam explosion
were 188 °C to 204 °C for 2.5–2.7 min; optimal conditions were determined to be
at 196 °C for 5 min with a yield of 22.8%. Although steam explosion is an
environmentally-­friendly method, problems still remain including degradation and
solubilization of xylan yielding oligomeric products [55–57].

1.3.4 Hydrothermal (Autohydrolysis)

The hydrothermal method or autohydrolysis method is highly consistent with the

concept of “biomass refining” and it is very successful for separating lignocellulosic
materials. The application of hydrothermal technology to biomass has application
for reactions and separations. At high temperatures and pressures, hydronium ions
from both water and in situ-generated compounds catalyze xylan depolymerization
[58]. Kim et al. [59] proposed a low acid hydrothermal fraction method. The yield
of xylose was up to 74.8% when the Miscanthus sacchariflorus were treated with
0.3 wt% of sulfuric acid for 10 min at 180 °C. In this condition, the decomposed
xylose was transformed into furfural, and the maximum concentration of furfural
was up to 1.87 g/L (the loss of xylan was 25.9%). Chen et al. [60] developed a flow-­
through hydrothermal system for increasing xylan recovery. It was found that the
10 G.-Q. Fu et al.

xylose recovery, lignin removal and total sugar yield were improved by this flow-­
through hydrothermal system when compared with the batch hydrothermal process.
The maximum sugar yield was 84% with the optimum conditions being 200 °C for
10 min at a flow rate of 160 mL/min.

1.3.5 Microwave Irradiation

Microwave-assisted extraction has been deemed as an alternative method to tradi-

tional extraction methods, because of its unique mechanism, low-cost, high extrac-
tion rates, and selective product isolation that proceeds, without changing the
molecular structure of the target compounds [61]. Panthapulakkal et al. [62] have
found that the result of microwave treatment is significantly better than the tradi-
tional methods, and that the recovery of xylan from birch wood is up to 60%, while
the xylan is degraded to some degree during microwave treatment. Panthapulakkal
et al. [63] hypothesized that the selective heating ability of microwaves leads to the
generation of hot spots through interaction with the alkali present in the fibers, and
the resulting “explosive effect” relaxes the stubborn fibrous structural network.
Under optimized extraction conditions of a 8 wt % NaOH solution with a 1:8 (g:mL)
solid-to-liquid ratio for 25 min, low power input microwave heating can be used to
extract about 75% of the xylan present in birch wood. However, obtaining good
yields without degradation of xylan and contamination is still an issue in microwave-­
assisted extractions.

1.3.6 Ultrasonic Treatment

Ultrasonic irradiation during the separation of plant material with a solvent can
significantly improve the extraction of polysaccharides, in particular, the extraction
of low molecular weight substances [64–66]. With ultrasonic treatment, the swell-
ing and hydration of cell walls in biomass promote diffusion and mass transfer
[67–69]. It has been shown that the ultrasonic treatment is applicable to xylan [70].
Under ultrasonic conditions, no substantial changes in the structural and molecular
properties of the corn cob and corn shell xylan are detected [71].

1.3.7 Subcritical or Supercritical Fluids

Researchers are using subcritical or supercritical fluids, with or without the use of
catalysts, to remove hemicellulose from biomass. Microwave hot water extraction
of arabinoxylans, galactomannans, arabinogalactans and mannans from hops grains
(BSG) and waste coffee grounds (SCG) has been proposed [72–74]. The results
1 Isolation, Purification, and Potential Applications of Xylan 11

confirm that hot water extraction is an effective technique for the quantitative recov-
ery of xylan from BSG and SCG. Subcritical CO2 is also popular for the pretreat-
ment for extraction of xylan. Researchers [75] studied CO2-assisted autohydrolysis
of wheat straw and found that the initial formation of carbonic acid resulted in high
dissolution of xylose and xylooligosaccharides. In addition, CO2-assisted autohy-
drolysis towards elevated xylooligosaccharides at elevated levels under very severe
conditions has been proposed.

1.3.8 Ionic Liquid Extraction

Ionic liquids (ILs) are non-volatile and green solvents that dissolve lignocellulosic
materials under mild conditions and they also have applications as pretreatment
solvents [12, 76, 77]. Due to the dual ionic and organic properties of ILs, the intrac-
tability of biomass is effectively reduced, so that they can be better processed in
other solvent systems [78, 79]. Imidazolium-based ILs such as 1-ethyl-3-­
methylimidazolium acetate [C2C1Im][OAc] is well known to be effective at reduc-
ing biomass recalcitrance by disrupting the lignin-carbohydrate complex and
increasing the accessibility of the cellulose to saccharification. New types of ILs,
bio-derived cholinium ILs, are regarded as promising solvents to improve the bio-
compatibility [80–83]. Wang et al. [84] compared imidazolium-based ILs with dif-
ferent anionic constituents ([HSO4]−, [Cl]−, [MeCO2]−) in pretreatment of hardwood.
The acidity of [HSO4]− caused extensive hydrolysis of xylan, which facilitated pre-
treatment of xylan-rich hardwood. Half or more of the xylan in materials can be
dissolved in [C4C1im][HSO4], but many of the products were recovered as xylose or
xylooligosaccharides. Payal et al. [85] studied the dissolving mechanism of xylan in
ILs with molecular simulation. They found that inter- and intramolecular hydrogen
bonding are important in the dissolution processes and that complexes of xylan with
the ions of the ionic liquid were stable with large negative binding energies ranging
between −21 and −55 kcal/mol−1. Fewer number of hydroxyl groups in xylan would
not affect the number of cations present in its first solvation shell while the number
of anions would be reduced.

1.3.9 Deep Eutectic Solvents Extraction

As a potential extraction method with ideal physical and chemical properties, deep
eutectic solvents (DESs) were introduced for fractionation of lignocellulosic frac-
tions [86]. DESs have attracted interest in dissolving polysaccharides such as cel-
lulose, xylose, arabinose, starch and chitin, and they are regarded as alternatives to
ILs [87]. In comparison with conventional solvents, DESs are easy to synthesize,
renewable in nature, cost-effective, biocompatible and biodegradable [88]. Usually,
there are two components in a DES solvent system: one component is a hydrogen
12 G.-Q. Fu et al.

Table 1.1 General formulas for classification of DESs

Type Components General formula Example
I Metal salt + organic salt Cat+ X− zMClx; M = Zn, Sn, Fe, Al, Ga, In ZnCl2+ ChCl
II Metal salt hydrate + Cat+ X− zMClx.yH2O; M = Cr, Co, Cu, Ni, CoCl2.6H2O +
organic salt Fe ChCl
III HBD + organic salt Cat+ X− zRZ; Z = CONH2, COOH, OH Urea + ChCl
IV Zinc/aluminium MClx + RZ = MClx-1+ RZ + MCl-x+1-;M =Al, ZnCl2 + urea
chloride + HBD Zn & Z = CONH2,OH
Reprinted with permission from Ref. [89]. Copyright © 2018, Elsevier

bond acceptor and the other component is a hydrogen bond donor. Table 1.1 shows
a classification of DESs [89]. Morais et al. [90] used DESs (choline chloride and
urea or acetic acid) as solvents to extract hardwood xylan. The yield of solubiliza-
tion of xylan was 328.23 g/L under conditions of using 66.7 wt% DES in water at
80 °C. They also found that 4-O-methyl groups were eliminated from the
4-O-methylglucuronic acids moieties and uronic acids (15%) were cleaved from the
xylan backbone during this process. In the works of Agrawal et al. [91], about 80%
hemicelluloses were hydrolyzed into monosaccharides including xylose, arabinose,
mannose, and galactose above 120 °C and acidic pH (~1.5 to 2) in less than 30 min.
A big disadvantage of DESs is the high viscosity, thus, further research needs to
focus in developing DESs with favorable transport properties so that applications on
an industrial scale can be realized [92].

1.3.10 Twin-Screw Extruder

Harper suggested starch conversion in twin-screw extruders for applications in the

agricultural industry [93]. The high shear forces generated by the twin-screws on
the material disrupt the cell structure and provide an easier way for the hemicellu-
lose to be removed with an extractant. In the screw extrusion process, xylan will not
degrade if a lower barrel temperature is used, but higher temperatures used in hydro-
thermal pretreatment causes structural changes [94]. Marechal et al. [95] developed
a method for directly atomizing extracts by using twin-screw extrusion and ultrafil-
tration. Twin-screw extrusion is effective in alkali impregnation of wheat bran,
although the shortcomings in this method should not be ignored, namely, that the
xylan extraction needs large liquid/solid ratios.

1.4 Purification of Xylan

Extracted xylan cannot be used directly because the product normally contains con-
taminants. Thus, fractions need further purification to meet the specifications
required for a chemical product. Some hemicelluloses combine with lignin through
1 Isolation, Purification, and Potential Applications of Xylan 13

covalent bonds and this kind of structure is called lignin-carbohydrate complexes,

which are obstacles to the total separation of the hemicelluloses from other compo-
nents in the plant cell wall. The next section provides some methods for improving
the purity of xylan.

1.4.1 Ethanol Precipitation

In continuous and exploratory experiments, it has been found that ethanol is a good
anti-solvent for some hemicelluloses, so that it can be applied to the separation and
purification of hemicellulose polysaccharides. Similarly, acetone, methanol, and
other organic solvents also have similar properties to ethanol for this purpose [96].
Graded ethanol precipitation has been successfully used as an evaluation tool for
xylan purification. It has been reported that, the less branched hemicelluloses with
large molecules can be precipitated by ethanol with low concentration, while with
an increase in ethanol concentration, more branched hemicelluloses with low
molecular weights are obtained [3, 97–101]. Compared with other purification
methods, fractionated ethanol precipitation has several advantages such as high effi-
ciency, low-cost, simple operation, and ethanol recovery.

1.4.2 Ammonium Sulfate Precipitation

Selective precipitation by (NH4)2SO4 is generally used in the fractionation of pro-

teins, although this precipitation method has received little attention in the area of
fractionation of polysaccharides from aqueous solution [102]. Peng et al. [103]
reported that alkali-soluble bamboo (Sinocalamus affinis) xylans could be fraction-
ated by gradient ammonium sulphate precipitation. It was found that more linear
xylan was obtained at relatively low concentrations of saturated ammonium sulfate.
Using precipitation by stepwise addition of 50% and 80% saturated (NH4)2SO4
solutions, DMSO, Ba(OH)2, and NaOH-extracted Arundo donax hemicelluloses
could be fractionated into two products [97]. Sugar composition and NMR analysis
indicated that the highly acetylated and linear xylans were precipitated at the rela-
tively lower concentrations of 50% saturated (NH4)2SO4, however, the DMSO-­
extracted hemicelluloses obtained by saturated (NH4)2SO4 (80%) mainly consisted
of highly branched xylans and β-D-glucan. Therefore, this method can separate
acetyl and non-acetyl xylan. Peng et al. also found that stepwise precipitation with
(NH4)2SO4 was effective for separating β-glucans from arabinoxylan.
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 PLATE 99

No. 47 BEDFORD SQUARE.

PLATE 100

CEILING OVER STAIRCASE

CHIMNEYPIECE, FRONT ROOM,
FIRST FLOOR
No. 47, BEDFORD SQUARE

PLATE 101

No. 47, BEDFORD SQUARE, CEILING,

FRONT ROOM, FIRST FLOOR
 PLATE 102

No. 48, BEDFORD SQUARE, CHIMNEYPIECE, FRONT ROOM,

FIRST FLOOR

PLATE 103
No. 48, BEDFORD SQUARE, CEILING,
FRONT ROOM, FIRST FLOOR

PLATE 104
No. 50, BEDFORD SQUARE,
FANLIGHT IN ENTRANCE HALL

PLATE 105
No. 51, BEDFORD SQUARE, CEILING,
FRONT ROOM, FIRST FLOOR

PLATE 106
No. 68, GOWER STREET, DOORCASE

No. 84, GOWER STREET, DOORCASE

 PLATE 107

CHIMNEYPIECE, FRONT ROOM,

FIRST FLOOR HOUSE IN REAR OF No.
196, TOTTENHAM COURT ROAD
EXTERIOR
 [Click image for larger version.]

1. Survey of London, Vol. III., p. xviii.

2. “Exinde secundum quod via extra idem gardinum protenditur usque ad
metas dividentes Mersland et parochiam S. Ægidii.”
3. Survey of London, Vol. III. (St. Giles-in-the-Fields, Part I.), p. xvi.
4. Middlesex Feet of Fines, 37 Henry VIII., Mich.
5. British Museum Addl. MS., Charters, 15636.
6. Namely, reckoning west to east: (i.) Star; (ii.) unnamed house of John
Bishop; (iii.) Sun and Dolphin; (iv.) Gridiron (easternmost house in St. Giles); (v.)
Eagle and Child; (vi.) Cock and Coffin; (vii.) unnamed house in occupation of
Thos. Fisher. (Close Rolls, (a) 1652, Alexander Goddard, etc., and Philip Cotham;
(b) 1652, Alexander Goddard, etc., and Jonathan Read; (c) 13 Chas. II., Samuel
Bishopp and William Rymes).
7. Sale by Robert Harris to John Coke (Land Revenue Enrolments and
Grants, vol. 311, p. 204.)
8. Survey of London, Vol. III. (St. Giles-in-the-Fields, Part I.), p. 3.
9. British Museum MS. Claudius E VI, 218b–219.
 10. Grant to Thos. Ellys, 22 Henry VIII (Land Revenue Miscellaneous Books,
No. 62); grant to Thomas Bochier (Patent Roll, 36 Henry VIII. (745)).
11. Lease of 21st July, 8 Chas. I., by Henry Hurlestone to John Allen and
Thomas Clements (Chancery Proceedings, Bridges 5–105,—Suit of John King);
Close Roll, 6 Chas. I. (2853)—Indenture between Wm. Newton and Anthony Bailey
and John Johnson.
12. Survey of London, Vol. III. (St. Giles-in-the-Fields, Part I.), pp. 3–4.
13. Certain properties, some of which include houses, are mentioned as
extending from Holborn on the north to Fickett’s Field on the south, but some, at
least, of these may have been to the west of Little Turnstile. The records in
question, when dateable, may be referred to the time of Henry III. or Edward I.
14. Parliamentary Survey (Augmentation Office), No. 25.
15. It was afterwards occupied by Chamberlain’s Stable (Survey of Crown
Lands) and this formed the eastern boundary of a piece of ground, 21 feet in width
“abutting upon the footeway leading from Master Newman’s building [west
portion of north side of Lincoln’s Inn Fields] to the Little Turnstile on the west,”
purchased by John Weston [Whetstone] from Edmond Gregory in 1661, (Close
Roll, 13 Chas. II. (4087).)
16. Close Roll, 2 Elizabeth (566).
17. Inquisitiones Post Mortem, II. Series, Vol. 149 (74).
18. Close Roll, 18 Elizabeth (990).
19. Burrard Cranigh, M.D., by his will proved 21st November, 1578, left his
lands, etc., in Holborn to be sold to pay his debts and legacies (Somerset House
Wills, Langley, 41).
20. Patent Roll, 20th July, 18 Elizabeth (1144).
21. Close Roll, 18 Elizabeth (990).
22. Close Roll, 18 Elizabeth (994).
23. Close Roll, 31 Elizabeth (1318).
24. Close Roll, 21 Charles II. (4270).
25. Blott’s Blemundsbury, p. 201.
26. Close Roll, 33 Elizabeth (1375).
27. Daughter of Sir Nicolas Harvey, and widow of George Carew, dean of
Windsor, who died in June, 1583, and was buried in the church of St. Giles-in-the-
Fields (Dictionary of National Biography).
28. No doubt the same afterwards occupied by Sir William and Lady Segar,
and Lord Bothwell (see plan of 1658 in Black Books of Lincoln’s Inn, Vol, II.) The
easternmost portion of the northern boundary of Purse Field is described as “the
late garden wall of Sir William Seager, Knt.” in the grant of the field to Newton in
1638 (Patent Roll, 13 Charles I. (2775)), and as “the garden of Bothwell House” in
the sale of that part of the field in 1653 (Close Roll, 1653 (3715))—(Indenture
between Humfrey Newton and Arthur Newman).
29. It is no doubt this intermixture of gardens and houses that caused the
peculiar shape of Partridge Alley, seen on the map accompanying Strype’s edition
of Stow (Plate 5), and better still on Hollar’s Plan of 1658 (Plate 3).
30. It is strange, however, that her will (Somerset House Wills, Hayes, 61)
bequeathing her property to her son, Sir George Carew, only mentions “all such
leases as are in my possession, as inter alia Savoy, St. Giles.”
31. Close Roll, 16 Charles I. (3228).
32. Chancery Proceedings, Bridges XX, 45. Suit of Henry Harwell.
33. Chancery Decree Roll, 1922. Suit of William Duckett and Hugh Speaks
against Henry Harwell, George Smithson, Daniel Thelwall and William Byerly.
34. Privy Council Register, Vol. 47, p. 24.
35. Chancery Proceedings, Bridges, 447–82. Suit of Peter Broome and Thos.
Barker.
36. Close Roll, 28 Elizabeth (1263).
37. On 13th June, 1592, administration of probate was granted to John Buck’s
widow, Margaret Buck. He had, therefore, died quite a short time previously (Arch.
London Probate Acts, II., 88).
38. Close Roll, 25 Elizabeth (1155).
39. Close Roll, 10 Charles I. (3018).
40. Close Roll, 13 Charles II. (4086).
41. Middlesex Registry Memorials, 1716, III., 63.
42. Close Roll, 15 Charles II. (4143).
43. John Apsley sold the inn in 1639 to Daniel Thelwall, William Bierley and
Sir Chas. Dallison. See Close Roll, 22 Charles I. (3343)—Indenture between
Dallison, Thelwall, Bierley, and George Smithson and George Gentleman.
44. Close Roll, 5 James I. (1910). Indenture between Gregory Miller and Geo.
Flower.
45. Parton (Hospital and Parish of St. Giles-in-the-Fields, p. 354) records the
fact of the residence of Sir Anthony Ashley and Sir John Cowper (see above) in
Thornton’s Alley.
46. Middlesex Feet of Fines, 16 Elizabeth, Easter.
47. Close Roll, 2 Charles I. (2677). Indenture between Frederick Johnson and
Mary Worliche and Francis Cole.
 48. Close Roll, 5 Charles I. (2800). Indenture between Francis Cole and
Robert Offley.
49. See warrant given in Indenture of 9th April, 1630, between Wm. and Joan
Newton and Anthony Bailey and John Johnson. (Close Roll, 6 Charles I. (2853).
Newton, the designer of Lincoln’s Inn Fields, had married the daughter and heir of
Gregory Miller, son of John.)
50. Survey of London, Vol. III. (St. Giles-in-the-Fields, Part I.) pp. 5–6.
51. Close Roll, 15 Chas. I. (3193).
52. Close Rolls, 20th July, 1639, between William Newton and Lewis Richard
(15 Chas. I. (3191)); 15th March, 1638–9, between Wm. Newton and John Giffard
(15 Chas. I. (3188)); 1st October, 1657, between Humfrey Newton and Arthur
Newman (1657 (3945)).
53. The houses to the south of Fortescue’s premises seem to have been built
originally as three houses. The southern boundary of Fortescue’s houses is said to
be “a greate house lately built by the said William Newton.” This, according to the
Hearth Tax Rolls, was the Earl of Northampton’s mansion. Then came “a faire
messuage or howse of one Master Crewe,” and to the south of this, at the corner of
Great Queen Street, and having a width from north to south of 42 feet, was in 1648
a plot of ground on which “Henry Massingberd intends to erect a house.” (Close
Roll, 24 Chas. I. (3411.) Indenture between Humfrey Newton and Henry
Massingberd.) If, however, only one house was built on this plot, it was divided
quite early, as the premises already appear in two occupations in the Hearth Tax
Roll for 1666.
54. One of the two houses was in 1643 in the tenure of Sir John Thimbleby
(Close Roll, 18 Chas. I. (3295)—Indenture between John Fortescue and John
Pynchon and Wm. Barnard).
55. Moved to No. 1, Lincoln’s Fields, in 1743 (Survey of London, Vol. III., p.
24.)
56. British Museum Additional MS., 11,411, ff. 70 and 77.
57. Ibid., f. 17b.
58. Reproduced here.
59. See Land Revenue Enrolments, Book IV., No. 52, p. 120.
60. Patent Roll, 7 Jas. I. (1802) (Translated from the Latin).
61. Parliamentary Survey (Augmentation Office), No. 25. Middlesex—
tenements in St. Giles-in-the-Fields and High Holborn.
62. Close Roll, 7 Jas. I. (1971).
63. Close Roll, 8 Jas. I. (2032).
64. See p. 36.
 65. Close Roll, 9 Jas. I. (2083).
66. Middlesex Feet of Fines, 10 Jas. I., Easter.
67. Close Roll, 13 Chas. II. (4084). Indenture between Thos. Newton and Geo.
Goodman and Arthur Newman. William Lane, by his will dated 15th February,
1653–4, left nine messuages in Holborn to his grandson, who enjoyed two-thirds
leaving one-third to his grandmother Elinor. The premises were rebuilt about
1698–1701. (Chancery Proceedings, Bridges, 328–31. Suit of Roger Reading, 3rd
February, 1703–4.)
68. In 1618 William Taylor was reported to the Privy Council for building a
house “in Fawlcon yard in the upper end of Holborne where none was before.”
(Privy Council Register, No. 29, 493).
69. Survey of London, Vol. III. (St. Giles-in-the-Fields, Part I.), p. 7.
70. Privy Council Register, Vol. 47, p. 410.
71. Inquisitio Ad Quod Damnum—Brevia Regia, Petty Bag Office, No. 17.
72. Petition of the Lord Mayor, etc., dated 10th April, 1635. (Calendar of State
Papers, Domestic, 1635–6, p. 17).
73. Privy Council Register, Vol. 47, p. 370.
74. Close Roll, 16 Chas. I. (3232)—Indenture between Henry Darrell and Mary
Blague.
75. I.e., “very well with brick and covered with tyle.”
76. In the case of Shenton’s tenements, built probably at about the same time,
it is known that rebuilding was carried out before October, 1682. (Chancery
Proceedings, Bridges, 271–13. Suit of Elizabeth Stratton).
77. 3rd Report of H.M. Commissioners of Woods and Forests (1819), App. 2,
pp. 38–9.
78. Reproduced here.
79. Close Roll, 1650 (3510)—Indenture between William Short, Gregory Short
and William and Magdalen Curtis and Thomas and Elinor Vaughan.
80. Middlesex Feet of Fines, 1650, Easter.
81. Close Roll, 18 Chas. II. (4195).
82. Exchequer Pleas 582 (2)—Suit of William Bell (Easter term, 18 Chas. I.)
against Sir Samuel Somaster.
83. Blott’s suggestion (Blemundsbury, pp. 201–2) that the place referred to
was Little Turnstile, has nothing to recommend it.
84. Calendar State Papers, Domestic, 1629–31, p. 284.
85. Ibid., pp. 321–2.
 86. Exchequer Pleas 582 (2), cited above.
87. See p. 107.
88. Close Roll, 9 Eliz. (742)—Indenture, dated 1st February, 1566–7, between
Lord and Lady Mountjoy and Edward Kingston.
89. The southernmost of the three northerly houses mentioned above.
90. Close Roll, 24 Eliz. (1129)—Indenture, dated 30th July, 1582, between Jas.
Briscowe, etc., and Jas. Mascall.
91. See p. 27.
92. It will be remembered that the houses, including, and for a little distance
west of, No. 198, High Holborn (the Public Library), are on the site of Rose Field
(see p. 18).
93. Inquisitiones Post Mortem, Middx., Series II., vol. 208.
94. Together with a moiety of the three northernmost of the 8 houses and of
other property on the north side of High Holborn, acquired by Mascall of Edward
Kingston.
95. Close Roll, 11 Chas. I. (3057)—Indenture between Thos. Godman and Olive
his wife and Francis Gerard and Frances his wife.
96. Blott’s Blemundsbury, p. 381.
97. As showing the connection between the Gerard and Cole families attention
may be drawn to the fact that Philip Gerard, successor of Francis Gerard in Drury
Lane, and probably his son, was associated with Salomon Cole in a deed relating to
property at King’s Gate. (Close Roll, 1658—Indenture between Sir Thos. Fisher,
Gerard and Cole and John Plumer).
98. Close Roll, 1655 (3857)—Indenture between Chas. Lovell, etc., and Philip
Wetherell.
99. Middlesex Registry Memorials, 1756, II., 325–6—Indenture between John
Smart and John Higgs.
100. Middlesex Registry Memorials, 1717, II., 272.
101. Reproduced here.
102. Parton’s Hospital and Parish of St. Giles-in-the-Fields, p. 71.
103. From deeds quoted by Parton (Hospital and Parish of St. Giles) it is
evident that in the 13th century Drury Lane was known as “Aldewych” or “Via de
Aldewych.” The name “Drury Lane,” given later, was no doubt due to the existence
of Drury House near the Strand end of the road. How late “Via de Aldewych” was
used there is nothing to show. In certain deeds of the 17th century (e.g., Close Roll,
24 November, 8 Charles I.—Indenture between Francis, Lord Russell, and Earl of
Bedford and John, Earl of Bristol, etc.) the road is called “Drury Lane alias
Fortescue Lane.” It is just possible that the latter name is to be connected with Sir
John Fortescue, who held the Elm Field (i.e., the land between Castle Street and
Long Acre) in the reign of Henry VI. (Close Roll, 30 Henry VI. (302)—Grant by
John Crouton and Wm. Horn to John and Katherine Nayler); in fact there is
reason for thinking that the “viam regiam ducentem ... a villa Sci. Egidii versus
Bosomysynne modo Johis. Fortescue militis” mentioned in the same deed is
actually Drury Lane. The road seems also to have gone by the name of St. Giles’s
Lane in the early part of the 17th century. (See p. 35n.)
104. See p. 107.
105. They appear together as witnesses in many deeds. Two deeds bearing the
name of William Christmas as witness can be dated with certainty 1257–8 and
1276.
106. Blott’s statement that here “stood the mansion house of the Christmasse
family, with its pasture land and orchard bordering the King’s Highway, Oldborne,
the domain reaching to Ficquet Fields,” goes beyond the evidence, and his
imaginative history, based on an identification of “John of Good Memory,” late
chaplain of St. Giles, mentioned in Henry II.’s Charter (not the original foundation
charter, as Blott says), with a John Christmas = John de Cruce the elder = John de
Fonte the elder (all equally hypothetical persons) is absolutely unjustifiable
(Blemundsbury, pp. 333–4).
107. Augmentation Office, Deeds of purchase and exchange, E. 19.
108. The premises, together with a cottage and Purse Field with the pightells,
were farmed to her on 6 June, 1524, by the Master of Burton Lazars, and it is
stated that she was then living there. (Patent Roll, 7 Elizabeth, pt. 3, Grant to Thos.
Jordayne.)
109. “Et de liijs iiijd de Willelmo Hosyer pro redditu cujusdam messuagii
vocati le White Harte in Hamelett Sci Egidii et xviij acr’ pasture ac unius parvi
clausi vocati Pale Close.” (Ministers’ Accounts, 2101, Henry VIII.)
110. Uncertainty on this point and on the date of the period of his tenancy
unfortunately stands in the way of accepting the following note as a contribution to
the history of The White Hart. “Will. Hosyer, of St. Giles-in-the-Fields, London—
Licence (he having had his house burnt down 9th Oct. last [1539] and lost all his
goods therein to the value of £200) to collect alms in England and Wales for his
relief.” (Patent Roll, 32 Henry VIII. pt. 4.)
111. Close Roll, 9 Eliz. (733)—Indenture between Lord Mountjoy and Geo.
Harrison; and Close Roll, 24 Eliz. (1129)—Indenture between Jas. Briscowe, etc.,
and Jas. Mascall. Cockshott was apparently there in 1579, for the piece of ground
or garden plot which 12 years before had been used as “a greate garden belonginge
to ... the White Harte,” (Close Roll, 9 Eliz. (742)—Indenture between Lord
Mountjoy and Edward Kyngston) was in that year described as “then or late in the
tenure of Richard Cockeshute.” (Close Roll, 21 Eliz. (1058)—Indenture between Ed.
Kyngston and James Mascall.)
 112. Parton, Hospital and Parish of St. Giles-in-the-Fields, pp. 131–2.
113. See Land Revenue Enrolments, Book IV., No. 52, p. 120.
114. Situated on the north side of High Holborn, just to the west of the present
junction with New Oxford Street.
115. It will be seen that the present Ye Olde White Hart, No. 191, Drury Lane,
is not on the site either of the old White Hart, or even of the land formerly
belonging to it.
116. Parton, Hospital and Parish of St. Giles, p. 238.
117. Reproduced here.
118. The course of this stream as shown in the map accompanying Volume III.
of the Survey of London requires a slight modification, as deeds, which have since
come to light, show that to the south of High Holborn it followed exactly the
winding red line indicating the course of the later sewer, and not the straight line
there suggested.
119. Close Roll, 1657 (3940).—Indenture between William Short and Edward
Tooke.
120. Thomas Burton’s land, which included the site of all the houses in Drury
Lane mentioned in the above deed, had a width along that street of 233 feet. These
houses reached as far south as the house belonging to Mr. Fotherley, on whose
garden St. Thomas’s Street was subsequently formed. (Parton, Hospital and Parish
of St. Giles-in-the-Fields, p. 275.) The distance between the boundary line and the
northern side of Shelton Street, the modern representative of St. Thomas’s Street,
is 243 feet, thus allowing a 10 feet extension of the garden northwards beyond the
street.
121. See p. 20.
122. The occupier of The Rose at this time was Richard Taylor. See Petition of
Geo. Sutton complaining of a confederacy between Taylor and “one Thomas
Barnett, brewer,” to whom Taylor had let the premises after Sutton had given him
lawful warning to avoid. (Augmentation Proceedings, 22–25.) The property is
described as “one tenement called The Roose, lieing and being within the said
parish of Saint Gyles in the feldes, with one barne and syxe acres of land, with
appurtenances to the same.”
123. Close Roll, 42 Elizabeth (1666).
124. Augmentation Office, Miscellaneous Books, 140, p. 56.
125. Hospital and Parish of St. Giles-in-the-Fields, p. 239.
126. Close Roll, 22 Chas. II. (4290).—Indenture between Sarah Hooper, etc.,
and Anthony Hannott.
127. Middlesex Registry Memorials, 1723, III., 289, 390.
 128. The entries in the ratebook, from the corner of Duke Street (now
represented by the first courtyard to the east of Grape Street) to the corner of Bow
Street, are as follows:—Jonathan Dodswell, 2 houses (£20); Samuel Chandler
(£20); Nathaniel Chandler (£25); John Lacost (£25); Mr. Anthony Elmes (£70);
Thomas Gwilliam (£20); Alexander Masters (£16); John Pettit (£10).
129. This rough identification is confirmed by the fact that The Rose can be
shown by comparison of particulars given in various deeds to have been the 8th
house westward from the Pale Pingle, the westernmost limit of which seems to
have been opposite the centre of the frontage of the White Hart property. (See
Plate 2).
130. Middlesex Feet of Fines, 16 Chas. I., Trin. Of course, in the absence of
more definite details, there is nothing to prove that this refers to The Rose.
131. Close Roll, 1650 (3542).—Indenture between William Short and Thos.
Walker, Peter Mills and Richd. Horseman.
132. See p. 31.
133. “July 8, 1640. Warrant to the Petty Constables of the parishes of St. Giles-
in-the-Fields and St. Clement’s Danes to give notice to the persons whose names
are underwritten to appear ... before Sir John Hippisley and Sir Henry Spiller to
show cause why they neglect and refuse to cleanse and repair their parts of a
common sewer near Lewknor’s lane, St. Giles-in-the-Fields, which has become a
public nuisance.” (Calendar of State Papers, Domestic, 1640, p. 459). This sewer,
which ran about 74 feet north of Lewknor’s lane (Parton’s Hospital and Parish of
St. Giles, p. 101), seems to have originally, as an open ditch, formed the boundary
between Rose Field and Bear Close.
134. Either this means that Short had purchased a portion of Bear Close, or,
more probably, it refers to that portion of Rose Field which bounded Bear Close on
the east. This had before 1650 been sold to Thomas Grover. (Close Roll, 1654
(3813).—Indenture between William Short and Wm. Atkinson.)
135. Close Roll, 1657 (3940)—Indenture between William Short and Edward
Tooke.
136. Privy Council Register, vol. 258, 46.
137. See letters from him addressed to (a) the Earl of Pembroke, 22nd
November, 1620; (b) Secretary Conway, 23rd November, 1623 (Calendar of State
Papers, Domestic, 1619–23, p. 194, and 1623–5, p. 117).
138. It need hardly be said that Blott’s (Blemundsbury, pp. 357–362)
identification of Lewknor’s house with “Cornwallis House, Drury Lane,” the
residence of Sir William Cornwallis, “adjoining the grounds of the White Hart
Inn ... at the Holborn end of Drury Lane” is a pure fiction. There is no evidence
that Sir William Cornwallis ever lived in Drury Lane. His statement that “it is a
long task to trace how the Christmasse estate passed into the Cornwallis family,
who appears to have been the immediate successors to the great inheritance in
Drury Lane,” is delightful, seeing that “the Christmasse estate” was situated at
White Hart corner, and the Cornwallis “inheritance,” which, by the way, was
acquired only in 1613, some years after Sir William Cornwallis’s death, consisted of
Purse Field, which nowhere reached within 500 feet of Drury Lane.
139. Coram Rege Roll, Easter term, 17 Chas. II., No. 469.
140. Close Roll, 1650 (3542).—Indenture between William Short and Thomas
Walker, Peter Mills and Richard Horseman.
141. This is stated in the deed (20 June, 1652) relating to the sale of the
property by George Evelyn (who had married Sir John Cotton’s widow) to John
Fotherley (Common Pleas, Recovery Roll, 1652, Trin., 278), and Cotton’s name is
given in respect of the house in the Subsidy Roll of 1646.
142. See, e.g.—Indenture between Henry Fotherley Whitfield and Joseph King
(Middlesex Registry Memorials, 1766, I., 379) concerning a parcel of ground in
“St. Thomas’s Street, now intended to be called King Street.”
143. Lease dated 23rd February, 1619–20, by Thomas Burton to Edmund
Edlyn, quoted in Blott’s Blemundsbury, pp. 358–9. It should be explained that
Walter Burton had sublet to Thomas Burton a portion of the ground leased to him
by William Short.
144. It should be noticed that the eastern portion of Parker Street (beyond the
alley lying to the east of the Kingsway Theatre) is on the site of Purse Field, not of
Rose Field.
145. Hospital and Parish of St. Giles, p. 358.
146. “Philip Parcar, for 5 houses built neare Drury Lane in Parcar’s Lane, to
the Star Chamber.” (Privy Council Register (1633–4), vol. 258, No. 46).
147. Philip Parker is seen in a different role in the following: “Recognisances ...
for the appearance of ... William Hartoppe ... to answer ... for refusinge to ayde
Phillip Parker to search for a seminary priest in the house of John Clarke, of St.
Gyles in the Feildes” (11th April, 1626) (Middlesex Sessions Rolls, III., p. 160).
148. Reproduced here.
149. A change of tenancy in 1775 is accompanied by an increase in the rateable
value from £8 to £18.
150. Reproduced here.
151. Close Roll, 9 Elizabeth (748)—Indenture, dated 20th January, 1566–7,
between Lord and Lady Mountjoy and Richard Holford.
152. From other documents it is quite obvious that this must be another name
for Purse Field, but the name has not been met with elsewhere.
153. The deeds show that all the western portion of Parker Street, both south
and north sides, was in Rose Field, and all the western part of Great Queen Street
was in Aldwych Close.
154. This was the line of the sewer, or open stream, which formed the western
boundary of Purse Field. In later deeds relating to the central portion of Aldwych
Close, the latter is described as extending to the common sewer on the east side
towards Lincoln’s Inn. (See e.g. Recovery Roll, 1633, 9 Chas. I., Easter (201).)
155. See p. 124.
156. Inquisitiones Post Mortem (Middlesex), 18 Eliz., vol. 174 (32).
157. I.e., according to a deed referred to in the inquisition on Henry Holford
(16th June, 1624) (Ibid., 22 Jas. I., vol. 428 (87)). There was also, however, or
there had been three years before, “a little howse, forge or shedd” on what was
afterwards the north-west corner of Great Queen Street (Close Roll, 40 Eliz. (1597)
—Demise by Henry Holford to Henry Foster, Margaret Foster and Henry Warner).
158. Recited in lease of 30th April, 1607, by Walter Burton to Thomas Burton,
in possession of the London County Council.
159. See p. 40.
160. See indentures between Richard Holford and Robert Stratton and
Edward Stratton respectively, dated 28th July, 1635, and 24th April, 1658. (Close
Rolls, 11 Chas. I. (3060) and 1658 (3984)).
161. This triangular piece, and the ground on which the houses on the south
side of Kemble Street are built, both originally being portions of Aldwych Close,
have recently been taken out of the Parish of St. Giles-in-the-Fields.
162. “The private way in Oldwitch Close for the King and Councell to passe
through leading from St. Giles his lane in the feildes east towardes Holborne.”
(Close Roll, 22 James I. (2601)—Indenture between Jane and Richard Holford and
Jeoffery Prescott.)
163. The two gates are referred to in the petition (ascribed to March, 1632), of
the Surveyor-General of His Majesty’s Ways, who complained that on the day
before the King and Queen went last to Theobalds, he warned Richard Powell, the
scavenger for High Holborn, to cleanse the passage between the two gates in
Holborn, where many loads of noisome soil lay stopping up the way; but Powell
neglected to do this, and at the time of the Royal passage a cart laden with soil
stood in the passage blocking the way. (Calendar of State Papers, Domestic, 1631–
3, p. 298.)
164. On 31st October, 1617, a warrant was issued to Thos. Norton, “Surveyor of
His Majesty’s Wayes and Passages,” calling attention to the fact that in spite of the
King’s commands, “sundry persons have gotten and used false keyes for opening
the lockes and gates of His Majesties private passages through the feildes neere the
Cittie of London, and that divers unruly coachmen, carters, and others, have and
doe use with great hammers and other like tools to breake open the said gates.”
(Privy Council Register, XXIX., 153.) This warrant seems almost too late to refer to