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EDITORS IN CHIEF

David L. Andrews is Professor of Chemical Physics at the University of East Anglia, located in the
cathedral city of Norwich in the United Kingdom. He heads a well-established research group
pursuing the development and applications of fundamental, photon-based theory for widely
ranging photonic and nanoscale processes, encompassing molecular chirality, multiphoton spec-
troscopy, nonlinear optics, quantum optics, energy transfer, optical nanomanipulation, inter-
molecular interactions, structured light and optical vortices. His current tally of research
publications approaches 400 papers, alongside twenty books: he is the author of a widely adopted
textbook on Lasers in Chemistry, edited volumes including Structured Light and its Applications,
another on the Angular Momentum of Light, and he is co-author of an Introduction to Photon
Science and Technology. The other main pillar of Andrews’s career is conference organisation; he
has instigated and championed numerous conferences, including the Nanophotonics conference at
Photonics Europe, which has now become the largest of its kind. He enjoys travel and is a widely
known speaker, who has given invited lectures in twenty different countries around the world.
Andrews is a Fellow of the Royal Society of Chemistry, the Institute of Physics, the Optical Society
of America, and SPIE – the international optics and photonics society.

Professor Rob Lipson received his Ph.D. in Physics in 1985 from the University of Toronto, and
did post-doctoral work in the Spectroscopy group at the National Research Council of Canada.
He was a faculty member in the Department of Chemistry at Western University from 1986
until 2010; serving as departmental Chair from 2000 to 2005, and Director of the Western
Institute for Nanomaterials Science from 2004-2009. He joined the University of Victoria as
Professor of Chemistry and Dean of Science in 2010, and was reappointed for a second term as
Dean in 2015. Externally, Dr. Lipson served as Senior Editor of the Canadian Journal of
Chemistry (2004-12). He was a former member and Chair of the NSERC Chemistry Grant
Selection Committee 026 (2004-06), and a member of the NSERC E. W. R. Steacie Fellowship
Committee (2008-10). He is currently in his second term as a member of the federal Tri-Council
Panel for the Responsible Conduct of Research. Dr. Lipson has published extensively in the
fields of laser spectroscopy, photonics materials and applications related to interference litho-
graphy, and analytical technique development for MALDI mass spectrometry. He is a Fellow of
the Chemical Institute of Canada.

Thomas Nann is an experienced teacher and researcher in the area of Nanoscience and tech-
nology. In 1997, he completed a PhD in Physical Chemistry (Electrochemistry) and started
working with nanomaterials shortly afterwards. He held teaching, research and leadership
positions at the Universities of Freiburg (Germany), East Anglia (UK), South Australia, and
Wellington (New Zealand). Thomas’s research focusses on the wet-chemical synthesis of various
nanomaterials and their application in the areas of energy and health. His electrochemical roots
and nanomaterials expertise come together in his research on photovoltaic and photocatalytic
systems, as well as different types of batteries. In the nanomedicine area, he is mainly interested
in using nanoparticles as contrast agents and markers. Thomas is passionate about teaching and
leading students and researchers to undertake excellent research with real-world impact.

vii
VOLUME EDITORS

Duncan H Gregory is the WestCHEM chair of Inorganic Materials, University of Glasgow having
previously been an EPSRC Advanced Fellow, Lecturer and Reader in Materials Chemistry at the
University of Nottingham. He is currently a Visiting Professor at Kyushu University and was Vice
President of the Royal Society of Chemistry (RSC) Materials Chemistry Division from 2009-
2014. He is the author of more than 150 papers, patents and book chapters and his research
interests focus on the synthesis and characterization of new solids including sustainable energy
materials (e.g. Li batteries, fuel storage, thermoelectrics), inorganic nanomaterials and the solid-
state chemistry of carbides, hydrides, nitrides and chalcogenides. His research also embraces the
sustainable production of materials including the microwave synthesis and processing of solids.
He won the inaugural RSC Sustainable Energy Award in 2009, is the founding Editor-in-Chief
of Inorganics and is an Associate Editor of Materials for Renewable and Sustainable Energy.

Professor Richard Tilley is the Director of Electron Microscope Unit and a Professor in
Chemistry at UNSW. His research is focused on the solution synthesis of nanoparticles and
quantum dots for applications ranging from catalysis to biomedical imaging. He graduated with
a Masters of Chemistry from Oxford University and did his PhD in the Department of
Chemistry, University of Cambridge. He was then a Postdoctoral Fellow for two years at the
Toshiba basic R&D Center, Japan followed by 10 years as an academic at Victoria University of
Wellington.

Renee Goreham completed a PhD in 2014 at the University of South Australia on the topic of
NanoBiotechnology. Since completion, she has held post-doctoral positions at Flinders Uni-
versity, University of South Australian, and Victoria University of Wellington. Recently, she was
accepted a permanent lecturing position at Victoria University of Wellington in physical
chemistry. Her research niche uses nanotechnology for biomedical applications. With two main
areas of interest; (1) using nanosized extracellular vesicles (EVs) for detection of disease or as
drug delivery agents and (2) metal nanoclusters stabilised by biomolecules (such as DNA and
protein).

Satoshi Kawata has been a Professor of Applied Physics at Osaka University since 1993 and a
Chief Scientist at RIKEN since 2001. He is now the Professor Emeritus of Osaka University and
the Honorary Scientist of RIKEN. He has developed a number of unconventional advanced
methods in optical microscopy, photolithography, and spectroscopy, including two-photon 3D
nano-fabrication based on polymerization, 3D optical data-storage with two-photon photo-
isomerization, tip-enhanced near-field Raman scattering microscopy, plasmonic 3D color
holography, and evanescent-field optical force. He is a Fellow of OSA, SPIE, IOP, and JSAP. He
served as the president of the Japan Society of Applied Physics and the Spectroscopic Society of
Japan and the Editor of Optics Communications. He has published B 500 research papers
(Web of Science), and authored and/or edited more than 30 books.

ix
x Volume Editors

David S. Bradshaw is an honorary research associate at the University of East Anglia in the UK. He
graduated twice from the same university, first receiving a Master’s degree in chemical physics
(which included a year at the University of Western Ontario, London, Canada) and then a PhD in
theoretical chemical physics. Overall, David has co-written over 80 research papers, all based on
molecular quantum electrodynamics. In addition, he has co-authored two books: one on optical
nanomanipulation and the other on nanophotonics. His long running research interests include
resonance energy transfer, optical binding and nonlinear optics. David is a Member of both the
Institute of Physics and the Royal Society of Chemistry.
LIST OF CONTRIBUTORS TO VOLUME 1

Sokhrab B. Aliev Mikkel F. Hansen

Bar Ilan University, Ramat Gan, Israel
Omar Azzaroni
INIFTA-CONICET, National University of La Plata,
La Plata, Argentina
Technical University of Denmark, Kongens Lyngby,
Denmark
Parisa Jafarzadeh
University of Waterloo, Waterloo, ON, Canada

Paul Bazylewski Tian Jiang

University of Western Ontario, London, ON, Canada
George Bepete
Durham University, Durham, United Kingdom
Poulami Chakraborty
S.N. Bose National Center for Basic Sciences,
Kolkata, India
National University of Defense Technology, Changsha,
China
Andrei N. Khlobystov
University of Nottingham, Nottingham, United Kingdom
Holger Kleinke
University of Waterloo, Waterloo, ON, Canada

Haitao Chen R. Krahne

National University of Defense Technology, Istituto Italiano di Tecnologia, Genoa, Italy
Changsha, China S. Kudera
Karl S. Coleman Max Planck Institute for Metals Research, Stuttgart,
Durham University, Durham, United Kingdom Germany
Geoffry Laufersky
Cintia B. Contreras
Victoria University of Wellington, Wellington, New
Instituto de Nanosistemas, National University of
Zealand; and The MacDiarmid Institute for Advanced
San Martin, San Martin, Argentina; and INIFTA-
Materials and Nanotechnology, Wellington, New Zealand
CONICET, National University of La Plata, La Plata,
Argentina Guixin Li
Southern University of Science and Technology,
Tilak Das
Shenzhen, China
University of Milan-Bicocca Studies, Milano, Italy
X. Liu
D. Dorfs National University of Singapore, Singapore
Istituto Italiano di Tecnologia, Genoa, Italy
L. Manna
A. Falqui Istituto Italiano di Tecnologia, Genoa, Italy
Istituto Italiano di Tecnologia, Genoa, Italy
N. Martin
Giovanni Fanchini Universidad Complutense de Madrid, Madrid, Spain
University of Western Ontario, London, ON,
Canada L. Maus
Max Planck Institute for Metals Research, Stuttgart,
Cathrine Frandsen Germany
Technical University of Denmark, Kongens Lyngby,
Denmark Steen Mørup
Technical University of Denmark, Kongens Lyngby,
C. Giannini Denmark
CNR-Istituto di Cristallografia (IC), Bari, Italy
Thomas Nann
D.M. Guldi University of Newcastle, Newcastle, Australia; and The
Friedrich-Alexander-Universität Erlangen–Nürnberg, MacDiarmid Institute for Advanced Materials and
Erlangen, Germany Nanotechnology, Wellington, New Zealand
Pham Nam Hai W.J. Parak
Tokyo Institute of Technology, Tokyo, Japan CIC Biomagune, San Sebastian, Spain

xi
xii List of Contributors to Volume 1

W.J. Parak Yutao Tang

Philipps Universitȧt Marburg, Marburg, Germany
B. Pelaz
Philipps Universitȧt Marburg, Marburg, Germany
P. del Pino
CIC Biomagune, San Sebastian, Spain
Guy Rahamim
Bar Ilan University, Ramat Gan, Israel
Graham A. Rance
University of Nottingham, Nottingham, United Kingdom
M. Remskar
Jozef Stefan Institute, Ljubljana, Slovenia
Southern University of Science and Technology,
Shenzhen, China
Nikita Toropov
ITMO University, St. Petersburg, Russia
Tigran Vartanyan
ITMO University, St. Petersburg, Russia
F. Wang
National University of Singapore, Singapore
Stephanie M. Willerth
University of Victoria, Victoria, BC, Canada; and
International Collaboration on Repair Discoveries,
Vancouver, BC, Canada

Tanusri Saha-Dasgupta D. Zanchet

S.N. Bose National Center for Basic Sciences, Kolkata, Laboratoŕ io Nacional de Luz Síncrotron, Campinas-SP,
India; and Indian Association for the Cultivation of Brazil
Science, Kolkata, India M. Zanella
Galo J.A.A. Soler-Illia Philipps Universitȧt Marburg, Marburg, Germany
Instituto de Nanosistemas, National University of Q. Zhang
San Martin, San Martin, Argentina Philipps Universitȧt Marburg, Marburg, Germany
Cheryl Sturm David Zitoun
University of Waterloo, Waterloo, ON, Canada Bar Ilan University, Ramat Gan, Israel
CONTENTS OF ALL VOLUMES

VOLUME 1

1.01 Physical Chemistry of Nanoparticle Syntheses

Geoffry Laufersky and Thomas Nann 1
1.02 Quantum Dots: Synthesis and Characterization
D Dorfs, R Krahne, A Falqui, L Manna, C Giannini, and D Zanchet 17
1.03 Noble Metal Nanoparticles: Synthesis and Optical Properties
Nikita Toropov and Tigran Vartanyan 61
1.04 Magnetic Nanoparticles
Steen Mørup, Mikkel F Hansen, and Cathrine Frandsen 89
1.05 III-V and Group-IV-Based Ferromagnetic Semiconductors for Spintronics
Pham Nam Hai 141
1.06 Inorganic Core–Shell Nanoparticles
S Kudera, L Maus, M Zanella, B Pelaz, Q Zhang, WJ Parak, P del Pino, and WJ Parak 171
1.07 Functionalized Fullerenes: Synthesis and Functions
DM Guldi and N Martin 187
1.08 Carbon Nanotubes: Electronic Structure and Spectroscopy
George Bepete and Karl S Coleman 205
1.09 Interactions Between Nanoparticles and Carbon Nanotubes: Directing the Self-Assembly of
One-Dimensional Superstructures
Graham A Rance and Andrei N Khlobystov 219
1.10 Inorganic Nanotubes beyond Cylindrical Matter
M Remskar 237
1.11 Inorganic Nanowires for Sensing Applications
Guy Rahamim, Sokhrab B Aliev, and David Zitoun 255
1.12 Electrospun Nanofibers for Diverse Applications
Stephanie M Willerth 275
1.13 Graphene: Properties and Applications
Paul Bazylewski and Giovanni Fanchini 287
1.14 Nonlinear Nanophotonics With 2D Transition Metal Dichalcogenides
Haitao Chen, Yutao Tang, Tian Jiang, and Guixin Li 305
1.15 MXene: A New Trend in 2D Materials Science
Poulami Chakraborty, Tilak Das, and Tanusri Saha-Dasgupta 319
1.16 Use of Confinement Effects in Mesoporous Materials to Build Tailored Nanoarchitectures
Cintia B Contreras, Omar Azzaroni, and Galo JAA Soler-Illia 331
1.17 Thermoelectric Nanomaterials
Cheryl Sturm, Parisa Jafarzadeh, and Holger Kleinke 349
1.18 Rare-Earth Doped Upconversion Nanophosphors
F Wang and X Liu 359

xiii
xiv Contents of all Volumes

VOLUME 2

2.01 Microemulsion Methods for Synthesis of Nanostructured Materials

Sonalika Vaidya and Ashok K Ganguli 1
2.02 Nucleic Acid Nanotechnology
Arun Richard Chandrasekaran 13
2.03 Metal-Organic Frameworks: New Functional Materials and Applications
Peiyu Cai, Wenmiao Chen, Gregory S Day, Hannah F Drake, Elizabeth A Joseph, Zachary T Perry,
Zhifeng Xiao, and Hong-Cai Zhou 35
2.04 Structure and Chemistry of 2D Materials
Min-Ho Kang, Donghoon Lee, Jongbaek Sung, Jihoon Kim, Byung Hyo Kim, and Jungwon Park 55
2.05 Catalysis by Supported Gold Nanoparticles
Josep Albero and Hermenegildo García 91
2.06 Functionalisation of Fullerenes for Biomedical Applications
Ilija Rasǒ vic ́ and Kyriakos Porfyrakis 109
2.07 Functionalization of Carbon Nanostructures
Paramita Karfa, Shrabani De, Kartick C Majhi, Rashmi Madhuri, and Prashant K Sharma 123
2.08 Thermoresponsive Core-Shell Nanoparticles and Their Potential Applications
Martina Schroffenegger and Erik Reimhult 145
2.09 Ligands for Nanoparticles
Z Hens, I Moreels, B Fritzinger, JC Martins, and RJ Groarke 171
2.10 Assembly of Nanoparticles
S Srivastava, NA Kotov, and RJ Groarke 201
2.11 Self-Assembly of Soft Nanoparticles
Tai-Lam Nghiem, Andrea Steinhaus, Ramzi Chakroun, Stefanie Tjaberings, Xiaolian Qiang, Chen Chen,
Alexander Tjaberings, Giada Quintieri, and André H Gröschel 217
2.12 Layer by Layer Assemble of Colloid Nanomaterial and Functional Multilayer Films for Energy
Storage and Conversion
Lei Zhou, Wellars Utetiwabo, Renjie Chen, and Wen Yang 255
2.13 ABC Toxins: Self-Assembling Nanomachines for the Targeted Cellular Delivery of Bioactive
Proteins
Irene R Chassagnon, Sarah J Piper, and Michael J Landsberg 279
2.14 Directed On-Surface Growth of Covalently-Bonded Molecular Nanostructures
Maryam Abyazisani, Vishakya Jayalatharachchi, and Jennifer MacLeod 299
2.15 Recent Development in Focused Ion Beam Nanofabrication
Charlie Kong, Soshan Cheong, and Richard D Tilley 327
2.16 Nanoimprint Lithography for Nanomanufacturing
Khairudin Mohamed 357
2.17 Optical Lithography
Patrick Naulleau 387

VOLUME 3

3.01 DNA Nanostructures

Ashley R Connolly, Nianjia Seow, Renzo A Fenati, and Amanda V Ellis 1
 Contents of all Volumes xv

3.02 Extracellular Vesicles: Nature's Own Nanoparticles

Renee V Goreham, Zeineb Ayed, Deanna Ayupova, and Garima Dobhal 27
3.03 Biomimetic Membranes
Jakob Andersson and Ingo Köper 49
3.04 Antibacterial Nanoparticles
Gemma C Cotton, Natalie R Lagesse, Liam S Parke, and Carla J Meledandri 65
3.05 Atomic Force Microscopy Applied to Biological Systems: Novel Applications and Advanced
Experimental Methods
Christopher T Gibson 83
3.06 Biosensing
Agnieszka A Zuber, Elizaveta Klantsataya, and Akash Bachhuka 105
3.07 Nanoparticles at Fluid Interfaces: From Surface Properties to Biomedical Applications
Catherine P Whitby 127
3.08 Photonic Nanoparticles for Cellular and Tissular Labeling
Alexander P Jankowski, Caroline Pao, and Gilbert C Walker 147
3.09 Graphene Quantum Dots: Syntheses, Properties, and Biological Applications
TA Tabish and S Zhang 171
3.10 Multifunctional Magnetic Nanoparticles: Design, Synthesis, and Biomedical Applications
Tristan D Clemons, Roland H Kerr, and Alexander Joos 193
3.11 Porous Silicon Nanoparticles for Applications in Nano-medicine
Morteza Hasanzadeh Kafshgari, Nicolas H Voelcker, and Frances J Harding 211
3.12 Cellular and Sub-Cellular Mechanics: Measurement of Material Properties
Ankita Gangotra and Geoff R Willmott 227

VOLUME 4

4.01 Super Resolution Fluorescence Microscopy

Alberto Diaspro, Paolo Bianchini, Francesca Cella Zanacchi, Luca Lanzano,̀ Giuseppe Vicidomini, and Colin
JR Sheppard 1
4.02 Tip Enhanced Raman Microscopy
Atsushi Taguchi, Jun Yu, and Kohta Saitoh 13
4.03 Atomic-Scale Elastic Property Probed by Atomic Force Microscopy
Yoshitaka Naitoh, Yan Jun Li, and Yasuhiro Sugawara 33
4.04 Nanoscale Magnetic Imaging
Yukio Hasegawa, Masahiro Haze, and Yasuo Yoshida 53
4.05 Optics of Metallic Nanostructures
GA Wurtz, RJ Pollard, W Dickson, and AV Zayats 67
4.06 Nanostructures and Surface-Enhanced Raman Spectroscopy
KM Kosuda, JM Bingham, KL Wustholz, RP Van Duyne, and RJ Groarke 117
4.07 The Use of Aluminum Nanostructures in Plasmon-Controlled Fluorescence Applications in the
Ultraviolet Toward the Label-Free Detection of Biomolecules
MH Chowdhury, K Ray, and JR Lakowicz 153
4.08 Optical Properties of Nanostructured Silicon
Yimin Chao 189
xvi Contents of all Volumes

4.09 Colloidal and Self-Assembled Quantum Dots for Optical Gain

P Kambhampati, Z Mi, and RR Cooney 215
4.10 Structured Organic Non-Linear Optics
S-H Jang and AK-Y Jen 261
4.11 Laser Action in p-Conjugated Polymers
ZV Vardeny and RC Polson 297
4.12 Nanoscale Optical Response
Hajime Ishihara 323
4.13 Optical Nanomanipulation and Structured-Beam Optical Traps
Vincent R Daria and Woei M Lee 347

VOLUME 5

5.01 Organic Electronic Devices With Water-Dispersible Conducting Polymers

Jacob D Tarver, Melda Sezen-Edmonds, Joung Eun Yoo, and Yueh-Lin Loo 1
5.02 Quantum Dot Light Emitting Diodes
Ruidong Zhu, Hao Chen, Shin-Tson Wu, and Yajie Dong 35
5.03 Optical Biomimetics
Andrew R Parker 57
5.04 Spin-Based Data Storage
O Ozatay, T Hauet, PM Braganca, L Wan, P Mather, ML Schneider, and J-U Thiele 67
5.05 Random Nanosized Metal Grains and Interface-Trap Fluctuations in Emerging CMOS
Technologies
Yiming Li 123
5.06 Photo-Functional Applications of Semiconductor Nanomaterials
Yoshio Nosaka and Atsuko Y Nosaka 135
5.07 Nanomaterials for Electrical Energy Storage
Andrey B Yaroslavtsev, Irina A Stenina, Tatyana L Kulova, Alexander M Skundin, and Andrey V Desyatov 165
5.08 Nanofluidics
H Daiguji 207
5.09 Picoliter Printing
T Singh, E Gili, M Caironi, and H Sirringhaus 229
5.10 Advances in Nanotechnology Based Functional, Smart and Intelligent Textiles: A Review
Mangala Joshi and Bapan Adak 253
5.11 The Effect of Roughness Geometry on Superhydrophobicity and Related Phenomena
Neil Shirtcliffe, Philipp Comanns, Christopher Hamlett, Paul Roach, and Shaun Atherton 291
5.12 Tribology of Nanostructured Surfaces
Yuan-Zhong Hu and Tian-Bao Ma 309
5.13 Towards Nano-Risk Assessment With High Throughput Screening and High Content Analysis:
An Intelligent Testing Strategy
Deepti Mittal and Gautam Kaul 343
Subject Index 361
PREFACE

Volume 1: Nanomaterials

This volume considers the huge scope that now exists for inorganic, organic and hybrid nanomaterials. Since the publication
of the previous edition of Comprehensive Nanoscience and Nanotechnology, the breadth of known nanomaterials has expanded –
most notably perhaps in the burgeoning scientific field of two-dimensional materials – and our understanding of the growth,
structure, functionality and performance of nanomaterials has flourished with it. In nanomaterials science, the underpinning
chemistry and physics of materials at the nanoscale combines with growth and deposition towards the unique approaches to
device fabrication that characterise engineering in the nanometer regime. The applications of nanomaterials, both potential
and realised, have also proliferated as our grasp of new properties and phenomena improves. The importance of dimen-
sionality in structure and properties has helped redefine the limits of nanomaterials performance. The topics in this volume
are interwoven with this theme of dimensionality and illustrate the ranges of materials behaviour and phenomena that
depend upon this fundamental variable.
A consideration of nanomaterials of the lowest dimensionality - zero-dimensional nanoparticles - begins this volume in
Chapter 1.01. The chapter adopts a chemistry-oriented viewpoint to describe the parameters and mechanisms behind nanoparticle
formation and growth processes. The chapter emphasises how a physical understanding of the thermodynamics and kinetics of the
nucleation and growth phenomena are vital in the subsequent, more practical choices of synthesis technique and conditions.
Building on the underlying principles discussed above, the following chapter (Chapter 1.02) discusses wet-chemical synthesis and
characterization of 0D nanoparticles, with a strong emphasis on IIB/VI semiconductors. Manna et al. survey all the relevant
synthesis methods, including potentially scalable approaches such as continuous flow synthesis or thermospray methods. This
chapter is concluded with a comprehensive discussion on the most important characterisation methods.
In extending the discussion of nanoparticles to the noble metals, Toropov and Vartanyan present a comprehensive discourse on
the optical properties that distinguish these metal species (Chapter 1.03). Both top-down and bottom-up approaches are relevant
to the synthesis of noble metal nanoparticles and issues of purification, monodispersity and the stability of optical spectra are
central in the most appropriate choice of synthetic route and conditions. Such requirements are significant in the context of many
unique applications including sensors, surface-enhanced Raman scattering and transparent conductive electrodes. Magnetic
nanoparticles also have great potential for both new and commercially-important applications. Their proliferation as contrast
agents for magnetic resonance imaging illustrates the impact that such materials are already having in modern society. Mørup et al.
(Chapter 1.04) describe the properties of these materials in detail, highlighting underpinning phenomena such as super-
paramagnetism, magnetic fluctuations and magnetic anisotropy. This chapter concludes with a discussion of some of the key
applications of magnetic nanocrystals from data storage to medical uses and considers also their occurrences in nature. Arguably
the next level of complexity is then to combine and link the magnetic properties of metallic nanoparticles with semi-conductivity
to produce nanoparticles of ferromagnetic semiconductors that could typically be deposited as a thin film. This is the topic covered
in Chapter 1.05, where Hai introduces the concept of spintronics and the roles of nanostructured doped III-V and Group VI
semiconductors towards achieving this goal. The chapter discusses the practicalities of fabrication while also considering phe-
nomena such as the tunnelling magnetoresistance effect (TME) and how it might be controlled. A variety of III-V and Gp VI
materials are considered in more detail and it is demonstrated how the choice of dopant (for example Fe vs Mn) can have a
profound influence on properties and performance.
Building on the fundamentals and examples introduced in the previous chapters, Parak et al. (Chapter 1.06) describe the
increasingly influential area of core-shell nanoparticles and introduce the methods for the - often epitaxial - growth of
inorganic shells onto nanocrystals. The primary focus is on nanomaterials with semiconductor cores and how both chemical
and physical properties of this core can be modified by the presence (and activity) of the shell. Such a construction can lead to
so-called quantum dot-quantum well (QDQW) regimes in which the 0D behaviour of the core is complemented by the 1D
behaviour of the shell. The chapter concludes by considering lattice mismatch of core and shell and how shape control can be
exerted.
The emphasis changes gradually from 0D to 1D nano-objects in the immediately following chapters and there is perhaps
no better system in which to observe this evolution than carbon. Chapters 1.07, 1.08 and 1.09 consider Fullerenes,
nanotubes and nanotube superstructures respectively and it is possible to follow how these structures and superstructures
are derived from C 60 and closely-related building blocks. Chapter 1.07 establishes the basics of fullerenes before presenting
detailed information on the processes involved in their chemical functionalisation, expounding on the synthetic organic
chemistry that permits increasingly complex molecular entities to be constructed and leading to the concept of molecular
wires. The natural dimensional progression from Fullerenes is to carbon nanotubes and Chapter 1.08 explains how the
unique molecular crystal structure of single walled carbon nanotubes (SWCNTs) accounts for their electronic structure.
Moreover, Bepete and Coleman demonstrate how the intrinsic electronic and vibrational properties are manifested in the
spectra of nanotubes. Spectroscopy, combined with electron microscopy, provides a powerful means to verify the purity
and functionalisation of SWCNTs as well as providing information on defects, size and chirality. Controlling the

xvii
xviii Preface

interactions of nanotubes with other nanoparticular species is key in extending structure and functionality beyond the
tubes themselves, opening further applications in microelectronics, sensing, catalysis and energy storage and conversion.
Rance and Khlobystov articulate the incredible extent of interactions available in assembling nanoparticle-carbon nano-
tube (NP-CNT) superstructures (Chapter 1.09). The potential of such a choice of strength and directionality of interaction
is undeniable but the authors are very clear about the challenges that remain in terms of superstructure control. They also
rightly highlight the health (cytotoxicity) issues that must be considered as such materials are developed further.
One dimensional (1D) inorganic nanostructures are introduced in Chapter 1.10 with examples of inorganic nanotubes.
Remskar first underscores the parallels with carbon nanotubes before going on to emphasise that despite some structural simi-
larities, the growth mechanisms of inorganic nanotubes are profoundly different from those of CNTs. Further, the extent of
compositional diversity afforded by drawing on elements from across the periodic table, gives rise to a wide range of contrasting
properties with possible applications as lubricants, inert reaction vessels or drug delivery systems. The theme of anisotropic 1D
inorganic nanomaterials is developed further in Chapter 1.11, where Zitoun et al. discuss how sensors can be fabricated from
either metallic or semiconducting nanowires. Vapour-liquid-solid (VLS) and solution-liquid-solid (SLS) phase synthesis
approaches are pivotal in the preparation of inorganic nanowires for devices where sensing can originate from a host of different
chemical and physical functionalities from thermal conductivity through optical properties to electrochemical activity to name
only three. Response time, extreme sensitivity and manufacturability can be issues that will need to be addressed as materials and
devices become more sophisticated. Electrospinning is one technique that might enable a progression from lab- to plant-scale
nanomaterial production. In Chapter 1.12, Willerth elaborates on this increasingly popular technique in which an electrical field is
applied to a polymer solution as it is discharged from a nozzle. The ensuing stream of charged liquid divides as it is repelled by the
applied voltage yielding polymeric fibres. Such fibres can be fashioned into three-dimensional scaffolds, for example, with
applications in filtration, regenerative medicine and energy storage. There is also the prospect of manufacturing increasingly
advanced functional and “smart” textiles.
As one moves from 1D to 2D materials, inevitably one is confronted with one of the major scientific breakthroughs of the
last several decades. Bazylewski and Fanchini provide a comprehensive overview of the graphene phenomenon in
Chapter 1.13. The authors describe the origin and fundamentals of its existence prior to presenting the essential aspects of its
isolation and fabrication. The unique electronic structure, vibrational structure and transport properties that have made
graphene the exciting discovery that it is are explained in detail before a selection of the most important applications are
appraised. The authors highlight how the many theoretical predictions of the properties and applications of the archetypal 2D
nanomaterial are one-by-one beginning to be realised. In the wake of the discovery of graphene, the emergence of inorganic
2D materials has by no means been unnoticed. In Chapter 1.14 the accent is on perhaps the largest family of 2D inorganics,
the transition metal dichalcogenides (TMDs). The electronic properties of TMDs can vary with composition and crystal
structure, but many are semiconducting with similar carrier mobilities to silicon. The particular subject of this chapter is the
exotic optical properties of 2D TMDs and especially the capacity for nonlinear photonics. Ultimately, the prospects for
development of concepts such as quantum photonics and the combination of TMDs with metasurfaces are assessed. Another
rapidly emerging family of 2D inorganic nanomaterials are the MXenes which are vying with TMDs as the most flexible in
terms of composition and multifunctionality. Chakraborty, Das and Saha-Dasgupta collate the various compositional and
structural groupings of MXenes in Chapter 1.15 and offer a full account of their electronic, magnetic and mechanical
properties. They also evaluate the prospects for MXene heterostructures (with graphene or TMDs), which to date are largely
the topic only of theoretical studies. Superconductivity and energy storage are just two interesting possibilities in terms of
properties and applications for further exploration.
Chapter 1.16 amalgamates concepts of 3D and 0D nanomaterials in its discussion of nanoconfinement of essentially isolated
species within three dimensional mesoporous frameworks. Soler-Illia et al. first introduce mesoporous materials and continue by
summarising the means by which they can be synthesised and their internal structures modified. The processes of nanocon-
finement and nanocomposite formation are illustrated with several examples relating especially to catalysis and adsorbing,
stabilising, releasing and delivering drugs. The chapter emphasises that nanoconfined systems can be regarded as much more than
simply high surface area solids and adsorbed species. Chapter 1.17 considers a completely different set of applications, showing
how the properties of thermoelectric materials can be enhanced hugely by processes of nanostructuring. Nanoscale thermoelectrics
can benefit from the full range of dimensional variation from nanoparticles, through nanowires to superlattices. As Kleinke et al.
convey in the chapter, most tellingly, all the best-performing, most efficient thermoelectric materials (with figures of merit, ZT 4 2) are
nanomaterials. Four prototypical thermoelectric systems are presented to elucidate how chemical and physical methods of size
reduction and control can impact electronic and thermal transport. Finally, Up-converting nanomaterials have a huge potential for
applications in both the physical and life sciences (for example. bioimaging, cancer therapy and electro-optics). Dominated by 0D
nanoparticles, but also embracing 1D and core-shell approaches, the preparation of luminescent up-converting nanomaterials is not
straightforward. Wang and Liu (Chapter 1.18) give a comprehensive overview of synthesis methods and applications of f-block
element doped nanophosphors. Surface modification and functionalisation is crucial in the continued development of new
upconversion nanomaterials.
This volume contains a wealth of exciting examples that reflect the dynamism associated with current nanomaterials research.
As one probes deeper into concepts of structure and properties at the nanoscale, more and more field-defining revelations continue
to materialise. Coupled with the implementation of progressively more imaginative and ingenious synthesis techniques, the
 Preface xix

chances of discovering new nanomaterials and with them, new phenomena, increases. I am very grateful to the all the expert
authors who have contributed to this volume and succeeded in communicating the vitality of this fast-moving area.

Duncan H. Gregory
University of Glasgow, Glasgow, United Kingdom
FOREWORD

Eight years have elapsed since the publication of the first edition of this Comprehensive, a forerunner to the present set of volumes.
It is interesting to observe how, over this period, the whole field of nanoscience and its associated technologies have undergone
both a remarkable and substantial growth and consolidation. The early days are now but a distant memory when the very term
‘nanoscience’ was viewed more as a buzzword than a reality, and gendered some degree of scepticism – perhaps even derision in
some quarters. As nanoscience has developed and grown, its increasing maturity has enabled a range of new technologies to reach
the marketplace, while at the research level newer topics continue to emerge, as well as a deeper understanding of the fundamental
underpinnings of the field.
It is therefore with great enthusiasm that we accepted the invitation to work with Elsevier to capture afresh the new state of the
art. In each volume, the majority of the content is entirely new, or it has been substantially updated, and we have ourselves learned
a great deal of new science in the course of soliciting contributions and putting the content together. In this endeavour we have
also been joined by an eminent team of Volume Editors whose tireless work has, more than anything, ensured the integrity and
success of this project. We gladly acknowledge our debt to them.
As with the first edition, each chapter aims to provide an amenable point of entry for scientists, engineers and specialist
technologists, covering key developments in a scholarly, readable, and critical discourse. Once again it has been a delight to find,
among the continually escalating numbers in nanoscience and nanotechnology, so many highly esteemed authors willing to
contribute suitably broad and incisive material. Full credit goes to these individuals. We also record our sincere thanks and
appreciation for the skills and professionalism of numerous Elsevier staff - especially Ruth Ireland and Claire Byrne, who have
been involved in this project with us since its inception.

David L. Andrews
Norwich, United Kingdom

Robert H. Lipson
Victoria, Canada

Thomas Nann
Newcastle, Australia

xxi
 1.01 Physical Chemistry of Nanoparticle Syntheses☆
Geoffry Laufersky, Victoria University of Wellington, Wellington, New Zealand and The MacDiarmid Institute for Advanced Materials
and Nanotechnology, Wellington, New Zealand
Thomas Nann, University of Newcastle, Newcastle, Australia and The MacDiarmid Institute for Advanced Materials and
Nanotechnology, Wellington, New Zealand
r 2019 Elsevier B.V. All rights reserved.

1.01.1 Physical Chemistry of Nanoparticle Synthesis 1

1.01.1.1 Thermodynamics of Nanoparticle Nucleation 1
1.01.1.2 Kinetics of Nanoparticle Nucleation 3
1.01.1.3 Kinetics of Nanoparticle Growth 4
1.01.1.3.1 Ostwald ripening 4
1.01.1.3.2 Thermally activated nanoparticle growth 5
1.01.1.4 Synthetic Adaptations 8
1.01.1.4.1 Hot-injection syntheses 10
1.01.1.4.2 Heat-up syntheses 10
1.01.1.4.3 Large particle syntheses 12
1.01.2 Conclusions 15
References 15

1.01.1 Physical Chemistry of Nanoparticle Synthesis

The synthesis of nanoparticles differs significantly from typical wet-chemical synthesis methods. In many chemical reactions, the
reagents are mixed or dissolved in a solvent and then reacted until equilibrium is reached. As a result, the product is usually the
thermodynamically most stable one. Nanoparticles are small objects with large surface to volume ratios. The free energy
(or Gibbs energy) of a surface is simply the product of its surface area s and its surface tension g:

GS ¼ sg ð1Þ

Since both s and g are positive values, the change in free energy when creating a surface is positive too. This means that creating
a large surface – what we do when we synthesize nanoparticles – is thermodynamically unfavorable. For example, a simple
reaction system that leads to a crystalline solid would try to minimize its free energy by reducing the surface contribution of the
resulting products, which would inevitably lead to large crystals.
There are two basic principles that can be used when synthesizing nanoparticles: strictly kinetically driven reactions and
syntheses that use thermodynamically stable templates. The former are primarily used for the preparation of inorganic nano-
particles, while the latter see use in the formation of both organic and inorganic nanoparticles. In the following sections, we will
investigate the physical chemistry of nanoparticle nucleation and growth, which are fundamental to kinetically driven reaction
schemes. While templated growth processes are extremely useful given their high degrees of reproducibility, the reaction mechanics
are vastly varied and different from the ones presented here. As such, the interested reader is directed toward several excellent
reviews for discussions of those methods [1–3].

1.01.1.1 Thermodynamics of Nanoparticle Nucleation

Two main reactions occur in a typical nanoparticle synthesis: the formation of new particle nuclei (seeds) and the growth of these
nuclei to larger (nano) particles. If both processes happen simultaneously, the method leads to a large range of nanoparticle sizes
(polydisperse distribution). If nucleation and growth reactions are well separated, the resulting nanoparticles are uniform in size
(monodisperse distribution). The easiest way to understand the factors that influence nucleation and growth reactions is to look at
the nuclei formation from a thermodynamic perspective.
Theories of nanoparticle nucleation and growth frequently use the concept of monomers to help describe the various processes
that can occur. Typically, a monomer is defined as the smallest subunit of the material. This is not to be confused with the unit cell,
as the unit cell itself is usually composed of multiple monomers. As an example, Fig. 1 depicts how a crystal of a binary compound

☆
Change History: All previous sections, figures, and equations have been removed. New sections outlining the theory and experimental evidence for nano-
particle nucleation and growth mechanism have been added. These sections are supported by 41 new equations and 18 new images.
This is an update of N. Vukmirović, L.-W. Wang, 1.07 - Quantum Dots: Theory, Editor(s): David L. Andrews, Gregory D. Scholes, Gary P. Wiederrecht,
Comprehensive Nanoscience and Technology, Academic Press, 2011, Volume 1, Pages 189-217.

Comprehensive Nanoscience and Nanotechnology, 2nd edition, Volume 1 doi:10.1016/B978-0-12-803581-8.11342-6 1

2 Physical Chemistry of Nanoparticle Syntheses

Fig. 1 Diagram of the formation of monomers of a binary compound AB from precursor sources and their assembly into a particle.

AB is formed from the assembly of subunits of AB. In order to keep things simple, we assume that we synthesize spherical
nanoparticles (this assumption is not far-fetched, because a sphere is the geometrical shape with the minimum surface to volume
ratio, which is, as established above, thermodynamically favorable). A sphere with the radius r has a surface area of s ¼ 4pr2. Thus,
when we form a spherical nucleus from molecular or ionic reagents, we will change the surface free energy DGS by
DGS ¼ 4pr 2 g ð2Þ
which is a positive value.
Then, the free energy for a bulk solid is comprised of the product of the volume of the object, v, and its lattice energy (in case of
a crystal). Comparing this to the free energy of an equimolar solution of fully dissolved crystal monomers, Gsol, will give us the
change in free energy imparted by crystal formation. However, this view is too simplistic, because lattice energies are usually
measured and calculated per mol (as opposed to per volume) and do not include non-crystalline solids. A general formula for the
volume free energy then includes an element that represents the free energy of formation of a “unit” volume element dGV*:
GV ¼ v dGV  ð3Þ

DGV ¼ Gsol  v dGV  ð4Þ

As inorganic monomer units are largely insoluble in solutions, Gsol is generally treated as a negligible constant, which implies
the change of volume free energy is usually a negative value. If we apply Eq. (4) to the formation of a spherical particle with the
volume v ¼ 4/3pr3, we obtain for the change of volume free energy DGV:
4 3
DGV ¼ pr DGV  ð5Þ
3
The total change in free energy, DGt, when forming a spherical nucleus from molecular or ionic precursors is then the sum of
change in free energy of the surface (2) and free energy of the volume (5):
4
DGt ¼ 4pr 2 g þ pr 3 DGV  ð6Þ
3
Fig. 2 shows a diagram where all three changes of free energy are plotted against the radius of an emerging nanoparticle. The surface
term scales with r2 while the volume term scales with r3. As a consequence, the overall change of free energy versus the particle radius
goes through a maximum and then becomes increasingly negative. The maximum of the total free energy of formation of a nanoparticle
nucleus is called the critical point. Associated with this is a critical radius, rc, and a critical free energy, DGc.
If we interpret Fig. 2 from a purely phenomenological point of view, we can state that nuclei smaller than the critical radius will
not be formed spontaneously. Sizes between rc and the radius associated with the root of DGt are still not likely to occur
spontaneously, however, larger radii are thermodynamically stable. The critical radius rc of a nanoparticle system can be simply
calculated by differentiating Eq. (6) with respect to r and setting the derivative to zero:
dðDGt Þ
¼ 8prg þ 4pr 2 DGV  ð7Þ
dr
8prc g þ 4prc2 DGV ¼ 0 ð8Þ
Rearrangement of (8) results in
2g
rc ¼  ð9Þ
DGV 
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circulation feeble, the respiration shallow and occasionally
interrupted by long-drawn sighs, the pupils are as a rule contracted,
constipation is present, often alternating with diarrhœa. When to
these conditions, for which no cause can be found upon careful
examination, there are added marked change in disposition, periods
of unaccountable dulness and apathy alternating with unusual
vivacity and brightness, especially when insomnia alternates with
periods of prolonged and heavy sleep, the abuse of morphia may be
suspected. If the hypodermic syringe be used the wounds made by
the needle confirm the diagnosis. These punctures are usually found
in groups upon the thighs, legs, arms, and abdomen. Close inquiry
into the habits of the patient, who either goes himself or sends at
short intervals for unusual quantities of opium or morphia to some
neighboring apothecary, is sometimes necessary to confirm the
diagnosis. Finally, the presence of morphine in the urine10 renders
the diagnosis positive, notwithstanding the most vehement
assertions of the patient as regards his innocence of the habit and
the extreme cunning with which it is concealed.
10 “According to Bouchardat, morphine, when taken in the free state or under the form
of opium, speedily appears in the urine, and may be detected by the liquid yielding a
reddish-brown precipitate with a solution of iodine in iodide of potassium. Since,
however, as we have already seen, this reagent also produces similar precipitates
with most of the other alkalies and with certain other organic substances, this reaction
in itself could by no means be regarded as direct proof of the presence of the alkaloid.
Moreover, we find that the reagent not unfrequently throws down a precipitate from
what may be regarded as normal urine, while, on the other hand, it sometimes fails to
produce a precipitate even when comparatively large quantities of the alkaloid have
been purposely added to the liquid” (Wormley, Micro-chemistry of Poisons).

The presence of meconic acid or morphine in the urine can only be positively
determined by elaborate chemical analysis. In cases of doubt the urine should be
submitted to a competent analyst. To make sure that opium or its derivatives are not
being taken, the feces must also be examined.

PROGNOSIS.—The prognosis is favorable as regards the

discontinuance of the habit for a time, doubtful as regards a
permanent cure. Relapses are apt to occur. They are more common
in men than in women, in the aged than in middle life, and in persons
of feeble physical and mental organization than in those who are
possessed of bodily and mental vigor. Relapses also occur more
frequently in those individuals addicted to alcohol, and in those who
are habitually subjected to temptation by reason of their avocation,
such as doctors, nurses, and apothecaries, than in others. The
danger of relapse is greater where the habit has been formed in
consequence of chronic painful affections than where it has been
rapidly developed in the course of acute illnesses. Of 82 men treated
by Levinstein, relapses occurred in 61; of 28 women, in 10; of 38
physicians, in 26. The danger of relapse diminishes with the lapse of
time; nevertheless, a single dose of morphine or a hypodermic
injection may, after an abstinence of months, precipitate a relapse.
Indeed, the return of the habit is in the majority of instances caused
by the thoughtlessness of medical men in prescribing in these cases
opiates for maladies which are often in themselves insignificant.

Chloral Hydrate.

The prediction made by B. W. Richardson, within two years of

Liebreich's announcement of the medicinal properties of chloral, that
its abuse would become widespread, has been abundantly fulfilled.
The consumption of this substance as a narcotic has reached an
extent in certain classes of society which raises it, after alcohol and
opium, to the third place among such agents.

SYNONYMS.—The Chloral habit, Chloralism.

ETIOLOGY.—A. Predisposing Influences.—Age exerts but little

predisposing influence. Cases occur almost exclusively in adults,
and the greater proportion of these are in middle life. The abuse of
chloral is relatively somewhat more common among males than
among females. Individuals addicted to this habit usually belong to
the refined and educated classes of society; the fascinations of
chloral remain thus far unknown to the great mass of the people.
Professional men and those engaged in literary work form a very
considerable proportion of the cases. Chloral is occasionally used by
hospital nurses, and very frequently by prostitutes. Chronic
alcoholism is an important predisposing element in the formation of
the chloral habit; in fact, morbid conditions attended by insomnia
from whatever cause tend to the formation of this habit.

B. The Exciting Cause.—Chloral is a powerful hypnotic, usually

without unpleasant after-effects. In full doses it is a depressant to the
nerve-centres at the base of the brain and to the spinal cord. It
enfeebles the action of the heart, depresses respiration, and lessens
reflex activity. It has no action on the secretions except that of the
kidneys, which it frequently augments.

The habit has in some few instances been developed in

consequence of the indulgence in a morbid desire to experience the
effects of the drug. In a majority of instances it is due to the
continuance of the medicine indefinitely after the sickness in which it
was originally prescribed has ceased. I have known apothecaries to
renew prescriptions of chloral often enough to supply a daily dose of
from forty to sixty grains for years—in one instance for more than
four years.

The dose taken by victims of the chloral habit varies greatly. Thirty or
forty grains daily is a moderate amount. Not rarely this quantity is
repeated twice or oftener within the space of twenty-four hours. The
tolerance after a time exhibited by the organism for enormous doses
of alcohol and opium is not established, as a rule, in regard to
chloral. The victim of the latter after a little time discovers the
average dose required to produce narcotic effects, and, while he
may vary it within limits, he is liable to acute toxic effects if it be
greatly exceeded. Death from such excesses is not uncommon.

SYMPTOMATOLOGY.—I. Symptoms Due to Habitual Excesses.—The

habitual use of chloral, notwithstanding its ruinous consequences in
a certain proportion of the cases, is less dangerous than that of
opium or morphine. Many individuals take chloral in considerable
doses for years without obvious ill effect. The craving for it is much
less intense than that for opium or morphine, and is readily satisfied
by other drugs. In point of fact, persons addicted to chloral very
frequently exchange it for other narcotics. For these reasons the
chloral habit is more easily cured.

Derangements of the digestive system are common, but by no

means constant. They are (1) primary, and due to the direct irritant
action of the drug upon the mucous tissues of the month and
stomach; and (2) secondary, due to its effects upon the nervous
system and the circulation. Irritation of the mucous membranes is
very common. This not rarely amounts to gastro-duodenal catarrh
with its characteristic symptoms. Jaundice is common, sometimes
intense. A sense of fulness with pain and tenderness in the hepatic
region is frequent. Constipation, with clay-colored stools, is the rule.
It occasionally alternates with diarrhœa. The tongue is often coated
and the breath foul. On the other hand, in a fair proportion of the
cases the digestive organs are not affected. Chloral has been said to
occasionally exert even a favorable influence upon appetite and
digestion when taken before meals. The recent observations of
Fiumi and Favrat11 in a man suffering from a gastric fistula and
insomnia have shown that chloral hydrate in twenty- or forty-grain
doses, administered before or at the beginning of a meal, retarded
digestion by increasing the secretion of mucus in the stomach. The
acidity of the gastric juice is diminished temporarily. The secretion of
pepsin is not changed. Taken two hours after meals, doses not
exceeding forty grains caused no derangement of gastric digestion.
11 Archives Ital. de Bioloqie, vol. vi. No. 3.

Persons not habituated to chloral usually experience a sense of

constriction upon swallowing it, and a disagreeable after-taste.

The circulation is much affected. Chloral weakens, and finally

paralyzes, the vaso-motor centre, and thus dilates the vessels; it at
the same time weakens the action of the heart. Its habitual use is
attended by flushing of the face, congestion of the eyes, and fulness
of the head. The heart's action is weak, intermittent, irregular;
palpitation occurs; the pulse is full and compressible or small and
weak. It is usually slow.

The blood undergoes changes corresponding to the general

disturbances of nutrition. What the special changes in its
composition may be is not known. Many of the cases, even after the
prolonged use of the drug in considerable doses, show few
evidences of malnutrition or of anæmia. In the greater number,
however, wasting is marked, and the physical signs and rational
symptoms of profound anæmia are present. Deterioration in the
composition of the blood is further indicated by petechiæ,
hemorrhage from mucous surfaces, sponginess of the gums, and
serous effusions.

The respiration is not permanently affected, save in grave cases. It is

then slow, irregular, and shallow. Dyspnœa is common and easily
provoked. It is usually accompanied by cough and abundant frothy
expectoration. These symptoms vanish upon the discontinuance of
the drug. In a fatal case of chloral-poisoning seen by the writer, in
which the daily use of the narcotic in non-poisonous amounts had
been for a long time varied at intervals of five or six weeks by doses
sufficient to induce prolonged coma, death was preceded by
Cheyne-Stokes respiration. This patient was a retired dentist, and
kept the solution of chloral in a large unlabelled bottle. The actual
doses taken were not ascertained.

The muscular system shares in the general malnutrition. The

muscles become flabby and wasted. Persons addicted to chloral are
very frequently of nervous organization and sedentary habits, and
hence of poor muscular development prior to the use of the drug.

The kidneys show no constant derangement. In a certain proportion

of the cases chloral acts as a diuretic, largely increasing the urinary
excretion. Albumen is present in a certain proportion of the graver
cases, when it is apt to be associated with anæmia, serous
effusions, and a tendency to hemorrhages from mucous tracts. The
occurrence of casts and the persistence of albuminuria after the
discontinuance of chloral suggest an antecedent or coincidently
developed nephritis. The reducing substance present in the urine
after small doses of chloral is uro-chloralic acid (Mering and
Musulus). It gives the reaction of sugar with the copper and bismuth
tests, but is levogyrate. Glycosuria is occasionally encountered.

Vesical and urethral irritation occurs in a small proportion of the

cases. When these symptoms vanish upon the discontinuance of the
drug and recur upon its resumption, it may be fairly assumed that
they are due to its action. A great number of morbid phenomena
relating to the genito-urinary tract and to the urine, that have been
ascribed to the action of chloral in those addicted to its use, are due
to associated conditions rather than to the drug itself.

It has been claimed upon evidence that does not appear to the writer
adequate that chloral sometimes acts upon the sexual system as an
aphrodisiac, sometimes as the reverse. More or less complete
impairment of sexual power and appetite is the rule in individuals
addicted to great excesses in narcotics of all kinds. Menstruation is
not arrested by chloral as by morphine, nor does it necessarily cause
sterility in the female.

The skin undergoes nutritive disturbances of a marked kind. As a

result of individual peculiarity, single doses or medicinal doses
continued for brief periods of time have occasionally caused
erythematous, urticarious, papular, vesicular, and pustular eruptions.
Of these, the first named is of most frequent occurrence. The
habitual abuse of chloral causes in many individuals chronic
congestion of the face, neck, and ears. This redness is often very
striking. It is increased by the use of alcohol. Erythematous patches
upon the chest, in the neighborhood of the larger articulations, and
upon the backs of the hands and feet, also occasionally occur. They
are often associated with urticaria. General eruptions resembling
measles, scarlatina, and even mild variola, are said to have been
observed after large doses of chloral. Purpura is by no means rare in
old cases, and falling of the hair and atrophy and loss of the nails
occur.
The nervous system bears the blunt of the disturbance, and the
more significant symptoms relate directly to it.

The hypnotic effect is usually preserved. Hence the chloral habitué is

dull, apathetic, somnolent, disposed to neglect his ordinary duties
and affairs. He passes much of his time in a state of dreamy lethargy
or in deep and prolonged sleep, from which he awakes unrefreshed
and in pain. In one of my cases, however, even larger doses than
usual at length failed to induce more than fitful slumber, and the
insomnia which led to the formation of the habit finally reasserted
itself, reinforced by the unutterable miseries of chloralism.

Headache is a frequent symptom. It is usually general, sometimes

frontal, often referred to the top of the head. It is commonly severe,
not rarely agonizing, and is described as a pressure, weight, or a
constricting band. It is associated with injection of the eyes, flushing
of the face, confusion of thought, inability to converse intelligently or
to articulate distinctly, and other evidences of cerebral congestion.
Vertigo is common.

Sensory disturbances are frequently present. They consist in local

areas of hyperæsthesia, more frequently of anæsthesia, numbness
of the hands and fingers or of the feet, formication of the surface of
the body and limbs, and burning or neuralgic pains in the face, chest,
and extremities. The pains in the limbs are almost characteristic.
They are acute and persistent, neuralgic in character, but not
localized to particular nerve-tracts. They are more common in the
legs than in the arms, and occupy by preference the calves of the
legs and the flexor muscles between the elbows and the wrists. They
do not implicate the joints, are not aggravated to any grave extent by
movement, and are often temporarily relieved by gentle frictions. The
pains of chloralism have been described as like encircling bands
above the wrists and ankles.

Sensations of chilliness alternating with flashes of heat are

experienced. The temperature is, in the absence of complications,
normal. Excessive doses are followed by a reduction of one or more
degrees Fahrenheit, lasting several hours.
Among the motor disturbances are the following:

Tremor.—This symptom is not common. It is neither so pronounced

nor so distinctly rhythmical as that of alcoholism or the opium habit. It
is increased upon voluntary effort. It affects chiefly the hands and
arms and the tongue.

Palsy.—Loss of power in the lower extremities has been observed in

a number of instances. It varies in degree from paresis to complete
paraplegia. Its occurrence may be gradual or sudden. It passes
away upon the discontinuance of the habit. In many respects this
condition resembles alcoholic paraplegia.

Impairment of Co-ordinating Power.—Ataxic phenomena are

sometimes present. The patient has difficulty in walking in the dark,
cannot stand with his eyes closed, has trouble in buttoning his
clothes, and the like.

Impairment or Abolition of the Knee-jerk.—In a man aged fifty, who

had taken thirty to sixty grains of chloral hydrate at night for eighteen
months, the writer observed complete loss of the knee-jerk, which,
however, reappeared in the course of a few weeks after the
discontinuance of the drug.

In rare cases epileptiform seizures have occurred.

Chloral produces in certain individuals, even as the result of a single

dose, congestion and irritation of the conjunctiva. Apart from this
idiosyncrasy, its habitual use not infrequently causes conjunctivitis.
This affection is occasionally of a severe grade and accompanied by
œdema of the eyelids and great photophobia. Retinal congestion
has been noted by several observers. Amblyopia, disappearing upon
the cessation of the habit, has also been observed.

Psychical Derangements.—The mental and moral perversion caused

by immoderate chloral-taking shows itself rapidly. The transient
stimulating effects of the dose of opium or morphine in those
accustomed to these drugs are seen not at all or to a very slight
extent in chloralism. Hence the mental state is characterized by
dulness, apathy, confusion, and uncertainty. These conditions
alternate with periods of irritability and peevishness. The physical
sufferings of the chloral-taker in the daily intervals of abstinence are
greater than those of the morphine-taker; his mental depression less.
The one is tormented by the agony of pain, the other by the anguish
of craving. To the former repetition of the dose brings stupor and
sleep, to the latter exhilaration and activity. In certain respects,
however, the effects of these drugs upon the mind are similar. They
alike produce intellectual enfeeblement, inability to concentrate the
mind, habitual timidity, and impairment of memory. In the worse
cases of chloralism hallucinations, delusions, and delirium occur.
Acute mania may occur, and dementia constitutes a terminal state.

II. Symptoms Due to Abstinence from Chloral.—The symptoms

occasioned by the abrupt discontinuance of even large habitual
doses of chloral are not, as a rule, severe. In this respect the
difference between this drug and opium and its derivatives is very
marked. The chloral-taker not infrequently substitutes some other
narcotic, as alcohol or opium, for his usual doses without discomfort,
and in many instances voluntarily abstains from the drug, without
replacing it by others for periods of weeks or months.

The more important of the symptoms induced by sudden

discontinuance relate to the nervous system. Insomnia is usual. It is
not always readily controlled, and constitutes one of the principal
difficulties in the management of these cases. Headache is rarely
absent; it is in many cases accompanied by vertigo. Occipital
neuralgia frequently occurs, and is often severe. Neuralgias of the
fifth pair also occur. Darting pains in the limbs are usual, and the
fixed aching pains already described as peculiar to habitual chloral
excess are present, and often persist for a long time after the
withdrawal of the drug.

Irregular flushes of heat, nervousness, restlessness, inability to fix

the attention, formication, burning sensations in various regions of
the surface of the body, are unimportant but annoying symptoms.
In a considerable proportion of the cases delirium occurs. It is
commonly associated with tremor, great prostration, complete
insomnia, sweating, inability to take food, and vomiting, and
resembles in every particular the delirium tremens of alcoholic
subjects. In the absence of this condition gastric derangements are
not of a grave kind. The nausea, vomiting, epigastric pain, and
diarrhœa which are induced by the discontinuance of opium are
absent, or if present at all only to a slight degree. As a matter of fact,
the functions of the digestive system are in a very short time much
more perfectly performed than before. Hemorrhage from the
stomach, bowel, or urinary tract may also occur.

The conjunctivitis and cutaneous eruptions usually disappear with

promptness as soon as the influence of the habitual chloral excesses
passes away.

DIAGNOSIS.—The diagnosis of the chloral habit is attended with much

less difficulty than that of the morphine habit. In the first place, there
is general and often serious derangement of health without adequate
discoverable cause. The appetite is poor and capricious, the
digestion imperfect and slowly performed; jaundice of variable
intensity, often slight, sometimes severe, occurs in many cases; the
bowels are not, as a rule, constipated. Dyspnœa upon slight exertion
is, in the absence of pulmonary, cardiac, or renal cause, of
diagnostic importance. The circulation is, as a rule, feeble. Disorders
of the skin, persistent or easily provoked conjunctivitis, puffiness
about the eyelids, and a tendency to hemorrhage from mucous
surfaces also occur. When with these symptoms, irregularly grouped
as they are, we find a tendency to recurring attacks of cerebral
congestion, persistent or frequently recurring headaches, and the
characteristic pains in the legs, the abuse of chloral must be
suspected. This suspicion becomes the more probable if there be a
history of protracted painful illness or of prolonged insomnia in the
past. The adroitness of these patients in concealing their vice, and
the astonishing persistency with which they deny it, are remarkable.
In the absence of the characteristic association of pains,
conjunctivitis, and affections of the skin the diagnosis is attended
with considerable difficulty. It becomes probable from the association
of chronic ill-health, not otherwise explicable, with perversion of the
moral nature, enfeeblement of the will and of the intellectual forces. It
is rendered positive, notwithstanding the denials of the patient, by
the discovery of the drug or the prescription by means of which it is
procured.

PROGNOSIS.—If the confirmed chloral habitué be left to himself, the

prognosis, after excessive doses or the stage of periodical
debauches has been reached, is highly unfavorable. The condition of
mind and body alike is abject. There is danger of sudden death from
cerebral congestion or heart-failure—a mode of termination by no
means rare.

On the other hand, the prognosis under treatment may be said to be

favorable. The habit is much more readily broken up, and the danger
of relapse is far less, than in cases of confirmed opium or morphine
addiction. Nevertheless, the underlying vice of organization which
impels so many individuals to the abuse of narcotics precludes a
permanent cure in a certain proportion of the cases of chloralism.
Sooner or later relapse occurs—if not relapse to chloral, relapse to
opium, morphine, or alcohol, or into that wretched condition in which
any narcotic capable of producing excitement and stupor is taken in
excess as occasion permits.

Paraldehyde.

The use of this hypnotic is not unattended with danger. In a single

case afterward under the observation of the writer paraldehyde was
used in large and increasing doses for the sake of its narcotic
properties. The patient, a young married woman whose family
history was bad, her mother having died insane, contracted the
chloral habit after an acute illness. After some months a cure was
effected without great difficulty. She relapsed into chloralism after a
second sickness which was attended with distressing insomnia. The
habit was again broken up. In consequence of over-exertion in social
life during a winter of unusual gayety insomnia recurred. For the
relief of this condition paraldehyde was prescribed with success.
Notwithstanding its disagreeable and persistent ethereal odor, and
the precautions taken by the physician, this lady managed to secure
paraldehyde at first in small quantities, afterward in half-pound
bottles from a wholesale druggist, and took it in enormous amounts,
with the result of producing aggravated nervous and psychical
disturbances corresponding to those produced by chloral, but without
the disturbances of nutrition attendant upon the abuse of the latter
drug. The patient remained well nourished, retained her appetite and
digestion, and was free from disorders of the skin and the intense
neuralgia which had been present during both periods of chloral
abuse. She suffered, however, from a persistent binding headache,
disturbances of accommodation, phosphenes, and brow-pains.
Under the influence of moderate doses she was enabled to take part
in social life with some of her old interest and vivacity. The brief
intervals of abstinence which occasionally occurred were
characterized by distressing indifference to her friends and
surroundings and by apathy and depression. At frequently-recurring
intervals the indulgence in excessive doses, constituting actual
paraldehyde-debauches, was followed at first by maniacal
excitement of some hours' duration, later by profound comatose
sleep lasting from one to three days. Upon the complete withdrawal
of the drug this patient manifested the symptoms produced by
complete abstinence in the confirmed morphine habit—yawning,
anorexia, epigastric pains, vomiting, diarrhœa, absolute
sleeplessness, extending over several days, heart-failure, collapse,
colliquative sweating, and finally well-characterized delirium tremens.
At the end of a week, under the influence of repeated small doses of
codeine, sleep was secured, and within a month convalescence was
complete. This person now continues free from addiction to any
narcotic, in good health, and able to sleep fairly well, after the lapse
of several months since the complete discontinuance of
paraldehyde.
 Cannabis Indica, Ether, Chloroform, and Cocaine.

These drugs are habitually used as narcotic stimulants by a limited

number of individuals. Cannabis indica, or Indian hemp, the
hashhish of the Arabians, is said to be largely used in India and
Egypt. It is occasionally taken by medical students and other youths
of an experimental turn of mind, but no case of habitual hashhish
addiction has come under the observation of the writer.

The use of ether as a narcotic stimulant is occasionally observed

among druggists, nurses, and other hospital attendants, but does not
give rise to clinical phenomena sufficiently marked or distinctive to
demand extended consideration in this article. The same remark
may be made of chloroform, which is also used in the same way to a
considerable extent among women suffering from neuralgia and
other painful or distressing affections of the nervous system. The fact
that individuals are every now and then found dead in bed with an
empty chloroform-bottle by their side serves to indicate the extreme
danger attending the vicious use of this substance.

Cocaine, within the short time that has elapsed since its introduction
into therapeutics, has unquestionably been largely abused, both
within the ranks of the profession and among the people. Highly
sensational accounts of the disastrous effects resulting from its
habitual use in excessive doses have appeared in the newspapers
and in certain of the medical journals. No case of this kind has fallen
under the observation of the writer, and it would appear premature to
formulate definite conclusions concerning the effects of cocaine
upon the data thus far available.

Treatment.

The treatment of the opium habit and kindred affections is a subject

which derives its importance from the following facts: First, the
gravity of the disease, as regards the functions both of the body and
of the mind; second, the enormous suffering and misfortune, alike on
the part of the patient himself and on the part of those interested in
him, which these affections entail; third, the fact that they are not
self-limited, and therefore cannot be treated with indifference or upon
the expectant plan, but are, on the other hand, progressive and
gradually destructive of all that makes life worth living, and at last of
life itself; and finally, because they are capable at the hands of skilful
and experienced physicians of a cure which in a considerable
proportion of the cases may be made permanent.

The treatment of these affections naturally arranges itself under two

headings: (a) the prophylactic, (b) the curative treatment.

a. Prophylaxis.—It is impossible to overrate the importance of a true

conception of the duty of practitioners of medicine in regard to the
prophylaxis of the opium habit and associated affections. In
communities constituted as are those in which the physicians
practise into whose hands this volume is likely to fall, a large—I may
say an enormous—proportion of the cases of habitual vicious
narcotism is due to the amiable weakness or thoughtlessness of
medical men. A majority of the cases occur either in chronic painful
affections attended or not by insomnia, or as a result of acute illness
in which narcotics have been employed to relieve pain or induce
sleep. The chronic affections constitute two classes: First, those
manifestly incurable, as visceral and external cancer, certain cases
of advanced phthisis, confirmed saccharine diabetes, and tabes
dorsalis. In such cases the use of morphine in large and often-
repeated doses, although attended with evils and likely to shorten
life, amounts to a positive boon. It is neither practicable, nor would it
be desirable, to interfere with it. To this class may be added those
cases of grave valvular or degenerative disease of the heart where
the patient has become addicted to the habitual use of narcotics.
Here, notwithstanding the evils resulting from these habits, among
which the likelihood of shortening the period of life must
unquestionably be counted, the dangers of the withdrawal of the
drug are so great that it must be looked upon as neither desirable
nor feasible. Attention must, at this point, be called to the fact that
great caution is required in the management of pregnant women
addicted to narcotics. Incautious attempts to withdraw the habitual
drug are almost certain to be followed by speedy loss of the fœtus;
and it is to my mind questionable whether anything more than the
most guarded reduction of the daily dose should be attempted while
the pregnancy continues.

The second class of chronic cases includes individuals suffering

from diseases which are remediable or capable of decided or
prolonged amelioration. Among these affections are painful diseases
curable by surgical procedures, such as certain obstinate and
intractable localized neuralgias, painful neuromas, irritable cicatrices,
pelvic and abdominal tumors, and surgical affections of the joints
and extremities. Here, either before or after radical surgical
treatment, an effort to relieve the patient from the bondage of
habitual narcotism should be made. For reasons that are obvious,
measures having this end in view should be instituted by preference
subsequently to surgical treatment. To this class also belong certain
painful affections occupying the border-region between surgery and
medicine. These are floating kidney, renal and hepatic abscess,
calculous pyelitis, cystitis, impacted gall-stones, and thoracic and
abdominal aneurism. In these cases the possibility of a cure renders
it in the highest degree desirable that the opium habit should be
stopped. Whether this attempt should be made while the patient is
under treatment for the original affection, or deferred until relief has
been obtained, is a question to be decided by the circumstances of
the particular case under consideration. Finally, we encounter a large
group of chronic painful affections coming properly under the care of
the physician in which the opium habit is frequently developed. This
group includes curable neuralgias of superficial nerves, as the
trigeminal, occipital, brachial, intercostal, crural, and sciatic, and
visceral neuralgias, as the pain of angina, gastralgia, enteralgia, and
the pelvic and reflex neuralgias of women. Here also are to be
mentioned the pains of neurasthenia, hypochondriasis, and hysteria.
In this group of affections the original disease constitutes no obstacle
to the attempt to break up the habit to which it has given rise.
The practice of using narcotics, especially the preparations of opium,
in large and increasing doses for the relief of frequently-recurring
pains, especially in neurotic individuals, is a dangerous one. When
necessary at all, the use of these drugs should be guarded with
every possible precaution. In the first place, in so far as is
practicable, the patient should be kept in ignorance of the character
of the anodyne used and of the dose. In the second place, the
physician should personally supervise and control, in so far as is
possible, the use of such drugs and the frequency of their
administration, taking care that the minimum amount capable of
producing the desired effect is employed. In the third place, the
occasional alternation of anodyne medicaments is desirable.
Fourthly, an effort—which, unfortunately, is too often likely to be
unsuccessful—should be made to prevent repeated renewals of the
prescription without the direct sanction, or indeed without the written
order, of the physician himself. Finally, the danger of yielding to the
temptation to allow a merely palliative treatment to assume too great
importance in the management of painful affections must be
sedulously shunned. Too often these precautions are neglected, and
the patient, betrayed by a dangerous knowledge of the drug and the
dose by which he may relieve not only physical pain, but also mental
depression, and tempted by the facility with which the coveted
narcotic may be obtained, falls an easy victim to habitual excesses.
The lowered moral tone of convalescence from severe illness and of
habitual invalidism increases these dangers. Yet more reprehensible
than the neglect of many physicians in these matters is the folly of
the few who do not hesitate to fully inform the patient in regard to the
medicines given to relieve pain or induce sleep, and to place in his
hands designedly the means of procuring them without restriction for
an indefinite period of time. Almost criminal is the course of those
who entrust to the patient himself or to those in attendance upon him
the hypodermic syringe. No trouble or inconvenience on the part of
the physician, no reasonable expense in procuring continuous
medical attendance on the part of the patient for the sake of relief
from pain, can ever offset, save in cases of the final stages of
hopelessly incurable painful affections, the dangers which attend
self-administered hypodermic injections.
The uniform and efficient regulation of the sale of narcotic drugs by
law would constitute an important prophylaxis against habitual
narcotism. Unfortunately, the existing laws relating to this subject are
a dead letter. They are neither adequate to control the evil nor is
their enforcement practicable. Nostrums containing narcotics, and
particularly opium and morphine, in proportions that occasionally
produce fatal results are freely dispensed at the shops to all comers.
Prescriptions calling for large amounts of opium, morphine, codeia,
chloral, cannabis indica, etc. are dispensed to the same individuals
at short intervals over the counters of apothecaries for months or
years after the illness in which they were originally prescribed is
over. Yet more, occasional cases come to light which serve to
indicate the appalling frequency with which opium, its tincture,
morphine, and solutions of chloral are directly sold to unauthorized
individuals. If the evil thus accomplished were better understood, the
paltry profit realized from such nefarious trading would rarely tempt
men to the commission of the crime which these practices constitute.

Finally, the dissemination of a wholesome knowledge of the methods

by which the opium habit and kindred affections are induced, of the
serious character of these affections, and of the dangers attendant
upon an ignorant and careless employment of narcotics, would
constitute an important measure of prophylaxis. I am fully aware of
the evils resulting from the publication of sensational writings relating
to this subject. Notwithstanding these dangers, I am convinced that a
reasonable and temperate presentation of the facts in the popular
works upon hygiene used in schools and in the family would exercise
a wholesome influence in restraining or curing the tendency to the
practice of these vices.

Where these habits have resulted in consequence of the medicinal

abuse of narcotics in acute cases from which the patient has long
recovered, a determined effort to break them up should at once be
instituted.

b. The Curative Treatment.—The responsibility assumed by the

physician in attempting to cure patients suffering from the confirmed
abuse of narcotics is often a serious one. Much judgment must be
exercised in the selection of cases. The responsibility of the
physician, beginning as it does with the judicious selection of the
cases, does not cease with the active management of the patient
until the habit has been completely broken up, but involves for a
considerable period of time such continued personal influence and
supervision as is needed to avert relapse. It is needless to say that
such supervision and influence must, after a more or less extended
period, in nearly every case come to an end, but the important fact is
to be borne in mind that the danger of relapse becomes less and
less with the progress of time; therefore, the more extended the
period during which the personal control of the physician may act as
a safeguard to his patient the better.

The question as to whether the cure should be attempted in the

patient's own home or away from it does not appear to the writer to
admit of discussion. Some trustworthy observers12 have reported
successful cases not only of the home-treatment of opium-addiction,
but even under circumstances in which the patients have been
permitted to go at large. Many physicians do not hesitate to
undertake the treatment with certain precautions at the home of the
patient. On the other hand, those whose experience in the
management of these cases is most extended look upon attempts of
this kind as likely to be unsuccessful in the great majority of the
cases of the opium or morphine habit. In cases of chloralism and the
abuse of less formidable narcotics, as cannabis indica, paraldehyde,
etc., the home-treatment, if judiciously carried out, usually succeeds,
but the cases in which the home-treatment proves successful in
curing the confirmed addiction to opium or morphine must be looked
upon as exceptional. The reasons for this are obvious. They relate to
a variety of circumstances which tend to weaken the mutual relations
of control and dependence between the physician and his patient.
The doubts, criticisms, remonstrances, even the active interference,
of the patient's friends tend to weaken the authority of the physician
and to hamper him in the management of the case; the discipline of
the sick-room is maintained with greater difficulty; the absolute
seclusion of the attendant with his patient is a practical impossibility.
Affectionate but foolish friends come with sympathy at once
disturbing and dangerous. Some devoted and trusty servant
cunningly conveys from time to time new supplies of the coveted
drug, or, if these accidents be averted, the very consciousness of the
separation which amounts to a few feet of hall-way only is in itself a
source of distress to the patient and his friends alike. Furthermore,
the period of convalescence following the treatment is attended with
the greatest danger of relapse—a danger which is much increased
by the facility of procuring narcotics enjoyed by the patient in his own
home as contrasted with the difficulties attending it away from home
under the care of a watchful attendant. The desirability of
undertaking the treatment away from the patient's home can
therefore scarcely be questioned. That this plan is more expensive,
and that it involves a radical derangement of the ordinary relations of
the patient's life, are apparent rather than real objections to it. The
very expense of the cure within the limits of the patient's ability to
pay, and the mortification and annoyance of temporary absence from
usual occupations and seclusion from friends, are in themselves
hardships that enhance the value of the cure when achieved, and
constitute, to a certain extent, safeguards against relapse. Whether
the treatment can be more advantageously carried out in a private
asylum designed for the reception of several such cases, or in a
private boarding-house, or at the home of the physician himself, is a
question to be determined by circumstances. The writer is of the
opinion that with well-trained and experienced attendants, well-
lighted, airy rooms in the upper part of a private house are to be
preferred on account of the seclusion thus secured.
12 See, for example, Waugh, “A Confirmed Case of Opium-addiction treated
Successfully at the Patient's Home, with Remarks upon the Treatment, etc.,”
Philadelphia Medical Times, vol. xvi., March 20, 1886.

In general, two methods are recognized: (a) that of the abrupt

suppression of the drug, and (b) that of the gradual diminution of the
dose. Both of these methods demand the isolation of the patient, and
to some extent at least the substitution of other narcotics. The
isolation of the patient under the care of skilled and experienced
attendants may be secured in a suitable private boarding-house, in
the home of a physician, or in a private room of a well-appointed
general or special hospital. Favorable opportunities are also afforded
in private institutions devoted to this purpose. The apartment
occupied by the patient should be so arranged as to guard against
attempts at suicide, and the furniture should be of the simplest
character. The heating and lighting arrangements must be such as to
render any accidental injury to the patient during paroxysms of
sudden maniacal excitement quite impossible. From the beginning of
the treatment the patient must under no circumstances be left alone.
Two attendants are required, one for the day and one for the night.
They should be not only skilful and experienced, but also patient and
firm; and, as a considerable proportion of the patients are persons of
education and refinement, intelligence and good manners are
desirable on the part of those who must be for a length of time not
only the nurses, but also the companions, of the sufferer. It is
desirable that the separation of the patient from his family and
friends should be made as complete as possible. During the
continuance of the active treatment no one should be admitted to the
patient except his physician and regular attendants. Communication
with his friends by letter should be interdicted. The enforcement of
this rule must be insisted upon. So soon as the acute symptoms
caused by the withdrawal of the drug subside and convalescence is
fairly established, brief visits from judicious members of the family in
the presence of the nurse may be permitted. At the earliest possible
moment open-air exercise by walking or driving must be insisted
upon, and change of scene, such as may be secured by short
journeys or by visits to the seashore, is useful. These outings require
the constant presence of a conscientious attendant.

The Treatment of the Opium and Morphine Habit.—a. The Abrupt

Discontinuance of the Drug: the Method of Levinstein.—This method
is thus described by the observer whose name it bears: Directly
upon admission the patient is given a warm bath, during which time
careful examination of his effects is made by a responsible person
for the purpose of securing the morphine which the patients,
notwithstanding their assertions to the contrary, frequently bring with