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Photochromic Materials Preparation Properties and
Applications First Edition He Tian Digital Instant
Download
Author(s): He Tian, Junji Zhang
ISBN(s): 9783527683734, 3527683712
Edition: First Edition
File Details: PDF, 17.57 MB
Year: 2016
Language: english
Edited by
He Tian and Junji Zhang

Photochromic Materials
Edited by He Tian and Junji Zhang

Photochromic Materials

Preparation, Properties and Applications

Editors All books published by Wiley-VCH
are carefully produced. Nevertheless,
Dr. He Tian authors, editors, and publisher do not
East China University of Science warrant the information contained in
and Technology these books, including this book, to
Key Laboratory for Advanced Materials be free of errors. Readers are advised
200237 Shanghai to keep in mind that statements, data,
China illustrations, procedural details or other
items may inadvertently be inaccurate.
Dr. Junji Zhang
East China University of Science and Library of Congress Card No.: applied for
Technology
Key Laboratory for Advanced Materials British Library Cataloguing-in-Publication
200237 Shanghai Data
China A catalogue record for this book is
available from the British Library.
Cover
Imgram Publishing, UK Bibliographic information published by the
Deutsche Nationalbibliothek
The Deutsche Nationalbibliothek
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Printed on acid-free paper

 V

Contents

List of Contributors XI

1 Introduction: Organic Photochromic Molecules 1

Keitaro Nakatani, Jonathan Piard, Pei Yu, and Rémi Métivier
1.1 Photochromic Systems 1
1.1.1 General Introduction 1
1.1.2 Basic Principles 4
1.1.3 Photochromic Molecules: Some History 5
1.2 Organic Photochromic Molecules: Main Families 8
1.2.1 Proton Transfer 9
1.2.2 Trans–Cis Photoisomerization 12
1.2.3 Homolytic Cleavage 13
1.2.4 Cyclization Reaction 14
1.2.4.1 Spiropyrans, Spirooxazines, and Chromenes 14
1.2.4.2 Fulgides and Fulgimides 17
1.2.4.3 Diarylethenes 18
1.3 Molecular Design to Improve the Performance 20
1.3.1 Figures of Merit 20
1.3.2 Fatigue Resistance: Increasing the Number of Operating Cycles 21
1.3.3 Bistability: Avoiding Unwanted Thermal Back-Reaction in the
Dark 23
1.3.3.1 Influence of Ethenic Bridge on the Thermal Stability of the B
Form 24
1.3.3.2 Impact of the Heteroaryl Substituents on the Thermal Stability of the
B Form 24
1.3.4 Fast Photochromic Systems: Reverting Back Spontaneously to the
Colorless State in a Glance 25
1.3.5 Gaining Efficiency of the Photoreaction: the Example of
Diarylethenes 26
1.4 Conclusion 31
Irradiation at a Specific Wavelength: Isosbestic Point 32
VI Contents

Case A: When the Thermal Back-Reaction is Negligible Compared to

the Photochemical Reaction (Typically P-type) 33
Case B: When the Thermal Back-Reaction is More Efficient than the
Photochemical B → A Reaction (Typically T ype) 34
References 34

2 Photochromic Transitional Metal Complexes for

Photosensitization 47
Chi-Chiu Ko and Vivian Wing-Wah Yam
2.1 Introduction 47
2.2 Photosensitization of Stilbene- and Azo-Containing Ligands 48
2.3 Photosensitization of Spirooxazine-Containing Ligands 51
2.4 Photosensitization of Diarylethene-Containing Ligands 54
2.5 Photosensitization of Photochromic N∧ C-Chelate
Organoboranes 63
2.6 Conclusion 65
References 66

3 Multi-addressable Photochromic Materials 71

Shangjun Chen, Wenlong Li, and Weihong Zhu
3.1 Molecular Logic Gates 71
3.1.1 Two-Input Logic Gates 71
3.1.2 Combinatorial Logic Systems 74
3.1.2.1 Half-Adder and Half-Subtractor 74
3.1.2.2 Keypad Locks 77
3.1.2.3 Digital Encoder and Decoder 82
3.2 Data Storage and Molecular Memory 84
3.2.1 Fluorescence Spectroscopy 85
3.2.2 Infrared Spectroscopy 90
3.2.3 Optical Rotation 92
3.3 Gated Photochromores 95
3.3.1 Hydrogen Bonding 95
3.3.2 Coordination 98
3.3.3 Chemical Reaction 99
References 105

4 Photoswitchable Supramolecular Systems 109

Guanglei Lv, Liang Chen, Haichuang Lan, and Tao Yi
4.1 Introduction 109
4.2 Photoreversible Amphiphilic Systems 110
4.2.1 Photoreversible Diarylethene-Based Amphiphilic System 110
4.2.2 Photoreversible Azobenzene-Based Amphiphilic System 116
4.2.3 Photoreversible Spiropyran-Based Amphiphilic System 119
4.3 Photoswitchable Host–Guest Systems 122
4.3.1 Photocontrolled Supramolecular Self-Assembly 123
 Contents VII

4.3.2 Photocontrolled Capture and Release of Guest Molecules 128

4.3.3 Fluorescent Switching Promoted by Host–Guest Interaction 133
4.3.4 Photoswitchable Molecular Devices 137
4.4 Photochromic Metal Complexes and Sensors 141
4.4.1 Metal Complexes with Azobenzene Groups 141
4.4.2 Metal Complexes with Diarylethene Groups 144
4.4.3 Metal Complexes with Spirocyclic Groups 150
4.4.4 Metal Complexes with Rhodamine 152
4.5 Other Light-Modulated Supramolecular Interactions 153
4.6 Conclusions and Outlook 159
References 159

5 Light-Gated Chemical Reactions and Catalytic Processes 167

Robert Göstl, Antti Senf, and Stefan Hecht
5.1 Introduction 167
5.2 General Design Considerations 169
5.3 Photoswitchable Stoichiometric Processes 171
5.3.1 Starting Material Control 172
5.3.2 Product Control 175
5.3.3 Starting Material and Product Control 177
5.3.4 Template Control 178
5.4 Photoswitchable Catalytic Processes 182
5.4.1 Activity Control 182
5.4.2 Selectivity Control 185
5.5 Outlook 187
References 190

6 Surface and Interfacial Photoswitches 195

Junji Zhang and He Tian
6.1 Photochromic SAMs 196
6.1.1 Photochromic Electrode SAMs 196
6.1.2 Photoreversible Functional Surfaces 198
6.1.2.1 Photoswitchable Surface Wettability 198
6.1.2.2 Photocontrolled Capture-and-Release System 202
6.1.2.3 Smart Photochromic Surface Based on Supramolecular
Systems 203
6.1.2.4 Photochromic Surface for Molecular Data Processing 205
6.2 Photoregulated Nanoparticles 206
6.2.1 Photochromic Switches on Traditional Metal Nanoparticles 208
6.2.1.1 Photoswitching on the Metal Nanoparticles 208
6.2.1.2 Photoinduced Reversible Aggregation of Nanoparticles and Their
Versatile Applications 210
6.2.2 Photochromic Switches on Other Novel Functional
Nanoparticles 215
6.2.2.1 Photoswitchable Magnetic Nanoparticles 215
VIII Contents

6.2.2.2 Photomanipulated Quantum Dots 215

6.2.2.3 Photochromic with Upconversion Nanoparticles 218
6.2.3 Photocontrolled Mesoporous Silica Nanoparticles 220
6.2.3.1 Photo-nanovalves 220
6.2.3.2 Photo-nanoimpellers 223
6.2.3.3 NIR Light-Triggered MSN Drug Delivery and Therapeutic
Systems 224
6.3 Photocontrolled Surface Conductance 226
6.3.1 Photochromic Conductance Switching Based on SAMs 226
6.3.2 Photochromic Conductance on Single-Molecule Level 228
References 231

7 Hybrid Organic/Photochromic Approaches to Generate

Multifunctional Materials, Interfaces, and Devices 243
Emanuele Orgiu and Paolo Samorì
7.1 Introduction 243
7.1.1 Tuning the Charge Injection in Organic-Based Devices by Means of
Photochromic Molecules 245
7.2 Tuning the Polaronic Transport in Organic Semiconductors by
Means of Photochromic Molecules 251
7.2.1 Photochromic Molecules and Organic Semiconductors Incorporated
in Dyads, Multiads, and Polymers 251
7.2.2 The Multilayer Approach 254
7.2.3 The Blending Approach 255
7.3 Photoresponsive Dielectric Interfaces and Bulk 262
7.4 Conclusions and Future Outlooks 267
Acknowledgments 268
References 268

8 Photochromic Bulk Materials 281

Masakazu Morimoto, Seiya Kobatake, Masahiro Irie, Hari Krishna Bisoyi,
Quan Li, Sheng Wang, and He Tian
8.1 Photochromic Polymers 281
8.1.1 Glass Transition Temperature 281
8.1.2 Fluorescence 283
8.1.3 Conductivity 287
8.1.4 Living Radical Polymerization 288
8.1.5 Surface Relief Grating 290
8.1.6 Photomechanical Effect 290
8.2 Single-Crystalline Photoswitches 293
8.2.1 Crystalline-State Photochromic Materials 293
8.2.2 Photochromic Diarylethene Single Crystals 293
8.2.3 In situ X-ray Crystallographic Analysis of Photoisomerization
Reaction 295
8.2.4 Photoisomerization Quantum Yields 296
 Contents IX

8.2.5 Multicolor Photochromism of Multicomponent Crystals 297

8.2.6 Nanoperiodic Structures Fabricated by Photochromic
Reactions 299
8.2.7 Photoinduced Shape Changes and Mechanical Performance 301
8.3 Photochromic Liquid Crystals 305
8.3.1 Introduction 305
8.3.2 Spiropyran- and Spirooxazine-Based Photochromic Liquid
Crystals 309
8.3.3 Diarylethene-Based Photochromic Liquid Crystals 314
8.3.4 Azobenzene-Based Photochromic Liquid Crystals 320
8.3.5 Other Photochromic Liquid Crystals 327
8.3.6 Conclusions and Outlook 328
8.4 Photochromic Gels 329
8.4.1 Introduction 329
8.4.2 Azobenzene Gels 330
8.4.3 Spiropyran and Spirooxazine Gels 335
8.4.4 Diarylethenes Gels 337
8.4.5 Naphthopyran Gels 342
8.4.6 The Other Photochromic Gels 343
8.4.7 Conclusion 346
References 346

9 Photochromic Materials in Biochemistry 361

Danielle Wilson and Neil R. Branda
9.1 Introduction 361
9.2 Reversible Photochemical Switching of Biomaterial Function 362
9.3 General Design Strategies and Considerations 362
9.3.1 Photoswitchable Tethers 364
9.3.1.1 The Incorporation Method 364
9.3.1.2 Considerations 364
9.3.2 Photoswitchable Small Molecules 365
9.3.2.1 The Incorporation Method 365
9.3.2.2 Considerations 365
9.3.3 Chromophore Selection 367
9.4 Selected Examples 367
9.4.1 Photoswitchable Enzymes 367
9.4.1.1 Drug-Inspired Small Molecule Inhibitors 367
9.4.1.2 Phosphoribosyl Isomerase Inhibitor with Two Binding Units 370
9.4.1.3 Direct Modification of Enzymes with Photochromic Groups 372
9.4.2 Photoswitchable Peptides and Proteins 373
9.4.2.1 Peptide Cross-Linking 373
9.4.2.2 Cyclic Antimicrobial Peptide 375
9.4.2.3 Genetically Encoded Amino Acids 376
9.4.2.4 Control of Motor Protein Function Using Site-Selective
Mutation 377
X Contents

9.4.3 Photoswitchable Ion Channels and Receptors 379

9.4.3.1 Photocontrol of Channel Activation and Desensitization with a
Tethered Glutamate 380
9.4.3.2 Photocontrol of Insulin Release Using a Small Molecular
Sulfonylurea 380
9.4.3.3 Photocontrol of Receptors Using Red Light 381
9.4.4 Photoswitchable Nucleotides 382
9.4.4.1 Spiropyran-Modified Oligonucleotide Backbones 382
9.4.4.2 Controlling RNA Duplex Hybridization with Light 384
9.4.4.3 Diarylethene-Modified Oligonucleotides 385
9.5 Summary 386
References 386

10 Industrial Applications and Perspectives 393

Junji Zhang and He Tian
10.1 Industrialization and Commercialization of Organic Photochromic
Materials 393
10.1.1 Commercialized T-type Photochromic Materials 395
10.1.2 Commercialized P-Type Photochromic Materials 398
10.2 Perspectives for Organic Photochromic Materials 399
References 409

Index 417
 XI

List of Contributors

Hari Krishna Bisoyi Shangjun Chen

Kent State University Shanghai Normal University
Liquid Crystal Institute and Key Laboratory of Resource
Chemical Physics Chemistry of Ministry of
Interdisciplinary Program Education
Kent Shanghai Key Laboratory of Rare
OH 44242 Earth Functional Materials
USA Department of Chemistry
200234 Shanghai
Neil R. Branda China
Simon Fraser University
4D LABS, Department of Robert Göstl
Chemistry Humboldt-Universität zu Berlin
8888 University Drive Department of Chemistry
Burnaby Brook-Taylor-Str. 2
BC V5A 1S6 12489 Berlin
Canada Germany

Liang Chen Stefan Hecht

Fudan University Humboldt-Universität zu Berlin
Department of Chemistry and Department of Chemistry
Concerted Innovation Center of Brook-Taylor-Str. 2
Chemistry for Energy Materials 12489 Berlin
220 Handan Road Germany
200433 Shanghai
China
XII List of Contributors

Masahiro Irie Haichuang Lan

Rikkyo University Fudan University
Department of Chemistry and Department of Chemistry and
Research Center for Smart Concerted Innovation Center of
Molecules Chemistry for Energy Materials
3-34-1 Nishi-Ikebukuro 220 Handan Road
Toshima-ku 200433 Shanghai
171-8501 Tokyo China
Japan
Quan Li
Chi-Chiu Ko Kent State University
The University of Hong Kong Liquid Crystal Institute and
Institute of Molecular Functional Chemical Physics
Materials and Interdisciplinary Program
Department of Chemistry Kent
Pokfulam Road OH 44242
Chong Yuet Ming Chemistry USA
Building, 504
Hong Kong Wenlong Li
China East China University of Science
and Technology
and Shanghai Key Laboratory of
Functional Materials Chemistry
City University of Hong Kong Key Laboratory for Advanced
Department of Biology and Materials and Institute of Fine
Chemistry Chemicals
Tat Chee Avenu, Kowloon 200237 Shanghai
Hong Kong China
China
Guanglei Lv
Seiya Kobatake Fudan University
Osaka City University Department of Chemistry and
Department of Applied Concerted Innovation Center of
Chemistry Chemistry for Energy Materials
Graduate School of Engineering 220 Handan Road
Sugimoto 3-3-138 200433 Shanghai
Sumiyoshi-ku China
558-8585 Osaka
Japan Rémi Métivier
PPSM
ENS Cachan, CNRS
Université Paris-Saclay
61 avenue du Président Wilson
94235 Cachan
France
 List of Contributors XIII

Masakazu Morimoto Antti Senf

Rikkyo University Humboldt-Universität zu Berlin
Department of Chemistry and Department of Chemistry
Research Center for Smart Brook-Taylor-Str. 2
Molecules 12489 Berlin
3-34-1 Nishi-Ikebukuro Germany
Toshima-ku
171-8501 Tokyo He Tian
Japan East China University of Science
and Technology
Keitaro Nakatani Key Laboratory for Advanced
PPSM Materials and Institute of Fine
ENS Cachan CNRS Chemicals
Université Paris-Saclay No. 130 Meilong Road
61 avenue du Président Wilson Shanghai 200237
94235 Cachan China
France
Sheng Wang
Emanuele Orgiu Lingnan Normal University
ISIS and icFRC School of Chemistry and
Université de Strasbourg and Chemical Engineering
CNRS Zhanjiang 524048
Nanochemistry Laboratory China
8 allée Gaspard Monge
67000 Strasbourg Danielle Wilson
France Simon Fraser University
4D LABS, Department of
Jonathan Piard Chemistry
PPSM 8888 University Drive
ENS Cachan, CNRS Burnaby
Université Paris-Saclay BC V5A 1S6
61 avenue du Président Wilson Canada
94235 Cachan
France Vivian Wing-Wah Yam
University of Hong Kong
Paolo Samorí Institute of Molecular Functional
ISIS and icFRC Materials (Areas of Excellence
Université de Strasbourg and Scheme, University Grants
CNRS Committee) and Department of
Nanochemistry Laboratory Chemistry
8 allée Gaspard Monge Hong Kong
67000 Strasbourg China
France
XIV List of Contributors

Tao Yi Weihong Zhu

Fudan University East China University of Science
Department of Chemistry and and Technology
Concerted Innovation Center of Shanghai Key Laboratory of
Chemistry for Energy Materials Functional Materials Chemistry
220 Handan Road Key Laboratory for Advanced
200433 Shanghai Materials and Institute of Fine
China Chemicals
200237 Shanghai
Pei Yu China
ICMMO
Université Paris-Sud, CNRS
Université Paris-Saclay
Bâtiment 420
91405 Orsay
France

Junji Zhang
East China University of Science
and Technology
Key Laboratory for Advanced
Materials and Institute of Fine
Chemicals
No. 130 Meilong Road
200237 Shanghai
China
 1

1
Introduction: Organic Photochromic Molecules
Keitaro Nakatani, Jonathan Piard, Pei Yu, and Rémi Métivier

1.1
Photochromic Systems

1.1.1
General Introduction

Nowadays, the word “photochromism” (or “photochromic”) has been entered

in several dictionaries [1]. It stems from the Greek words 𝛗𝛚𝜏ó𝛓 (photos) and
̃
𝛘𝛒𝛚𝛍𝛂 (chroma) meaning light and color, respectively. A simple definition of
photochromism is the property to undergo a light-induced reversible change of
color based on a chemical reaction [2].
Everyone, even without being familiar with this topic, can easily understand
that materials possessing such a feature can find useful applications. Generally,
using light as a stimulus is extremely attractive for at least two reasons: it can be
conveyed to long distances with the “speed of light”; and it is an unlimited energy
source although unevenly available in time and space. In addition, the notion of
reversible change can be easily connected to objects, useful in everyday life, such
as knobs, buttons, dials, handles, and levers, which are used to switch on and off
domestic appliance and other devices and machines. Photochromic substances
are widely present in glass lenses, initially clear, which turn dark under sunshine
[3] (Figure 1.1). They are also present in trendy cosmetics and clothes.
In addition to these objects that have been around for a long time, the digital age
has tremendously expanded the fields, where photochromic materials may play a
role. The broad and current interest is transmitting, gating, and storing digital
data [5]. CD and DVD are among the widely spread storage media, where light
writes (and erases) information and optical properties are used to read, just as in
photochromic systems. Due their reversible feature, photochromic species match
the requirement of the rewritable recording media (CD-RW, DVD-RW), where
memory bits have to commute between the two binary states (“0” and “1”) upon
request. In this domain, there is a race for high-capacity data storage media, where
information can be written and erased at high speed. As changes in photochromic

Photochromic Materials: Preparation, Properties and Applications, First Edition.

Edited by He Tian and Junji Zhang.
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2016 by Wiley-VCH Verlag GmbH & Co. KGaA.
 2 1 Introduction: Organic Photochromic Molecules

www.optiline.co.uk/index.php/information/common-knowledge/photochromic-sunglasses

www.firstvieweyecare.com/archives/ www.prweb.com/releases/2010/06/ 011101010.blogspot.fr/

1459 prweb4123744.htm

Figure 1.1 Photochromic lenses and clothes: contributions to comfort and to fashion [4].

systems occur in sub-nanosecond timescales, these are suitable for fast switch-
ing. Moreover, molecule is the elemental switching unit, comparable to a bit, and
occupies less than a cubic nanometer. This means that the memory density can
potentially reach a value of more than 1018 bit mm−3 . Proofs of concept of such
media are given in the literature (Figure 1.2a, b), where two-photon phenomena
are used to get a high resolution [6].
More recent contributions of photochromism can be found in the topic of fluo-
rescence microscopy imaging, which is spreading very fast in many scientific fields
of applications, such as biology, medicine, and materials science. Recent techno-
logical progresses have led to faster microscopes with better resolution, along with
the development of stable and bright fluorescent probes. However, the optical res-
olution of conventional microscopy instruments is restricted by the fundamental
diffraction limit, whereas the features to be probed are often smaller than 200 nm.
To break this severe constraint and limitation, “super-resolution techniques” (or
“sub-diffraction imaging methods”) were developed and have shown that reso-
lution beyond the diffraction limit was accessible by exploiting controlled opti-
cal deactivation processes of fluorescent probes. Among them, microscopy based
on photoswitchable fluorophores, such as photochromic fluorescent labels, has
been successfully implemented. Figure 1.3a–e shows an example of the compar-
ison between conventional wide-field microscopy and sub-diffractive imaging of
 1.1 Photochromic Systems 3

50 μm

50 μm
Laser Beam splitter 1st layer 4th layer 7th layer

Frequency
doubler
10th layer 13th layer 16th layer

Memory
medium 19th layer 23th layer 26th layer
(a) (b)

Figure 1.2 Rewritable optical memory medium based on photochromic compounds: (a)
general structure of the recording medium [6d] and (b) alphabet letters recorded on the dif-
ferent layers [6b].

(a) (b) (c) (d)

Fluorescence (norm.)

1.0
0.8
0.6
0.4
0.2
0.0
0 200 400 600 800 1000
(e) Line profile (nm)

Figure 1.3 Super-resolution image of HeLa fications of the highlighted area (c and d,
cells expressing keratin19 rsCherryRev1.4 scale bar = 500 nm). Line profiles (e) across
by wide-field conventional microscopy the region between the arrows marked in (c)
(a) and by RESOLFT microscopy (b) (scale (full line) and (d) (dashed line) [7].
bar = 5 μm) and the corresponding magni-

live HeLa cells expressing fluorescent photochromic proteins. No wonder pho-

tochromic compounds have entered the bio- and nano-worlds [8].
Light reflection or transmission change, used in the above-mentioned applica-
tion, is the representative property modified in the photochromic process. As for
color, in photochromic systems, traditionally, light is used as a trigger not only to
 4 1 Introduction: Organic Photochromic Molecules

UV

Vis

100 μm 100 μm
(a) (b)

Figure 1.4 (a) Concomitant color and solubility changes of a photochromic solution [13a]
and (b) color and shape changes of a photochromic crystal [14c].

induce the change but also to reveal the state of the system at a given moment.
Other properties related to light, such as refractive index [9], fluorescence [8c,
10], and even nonlinear optical properties [11], are employed to read out. Indeed,
concomitantly to the color, these properties are changed.
Photoswitching other physical or chemical characteristics, such as magnetic,
electrical, conductive, or redox properties, is also a matter of interest [12]. Fur-
thermore, one can take advantage of photochromism upon altering or taking the
control of features, such as phase, solubility, reactivity, stereochemistry, complex-
ation, or interaction between molecules or ions (Figure 1.4a) [13]. In materials,
photochromism can induce shape changes, and opens up a wide field of interest
in photo-induced mechanics (Figure 1.4) [14].

1.1.2
Basic Principles

In order to describe photochromism, the most common model introduced is a

simple two-way reaction between two molecular species A and B. Although it
may sometimes involve other species, the reaction is assumed to be unimolecular
(Figure 1.5a).
A and B are separated by a potential barrier (ΔE). If this barrier is low, B is
metastable and can revert back spontaneously to A. Previously described pho-
tochromic glass lenses operate according to this scheme. Such systems are called
T-type referring to the thermally induced reaction from B to A. On the contrary, a
high barrier features a bistable system. In this case, only photons are able to cause
the reaction, and such systems are called P-type. In other words, nothing changes
in the absence of light.
This last characteristic is important since it makes the difference between pho-
tochromic bistable systems and others, such as ferroelectric or (ferro)magnetic
systems. In the latter, shuttling between the two states of the bistable system does
not follow the same route, displaying the well-known hysteresis, when the polar-
ization or the magnetization is plotted versus the electric or the magnetic field.
In photochromic systems, no concept of hysteresis is involved in the rationale of
bistability.
 1.1 Photochromic Systems 5

A
εA

d B
cite
Ex te εB
s ta
hc/λA

sta nd

Absorption
ou
te
hc/λB
Energy

Gr
ΔE

B
A

Configuration coordinate λA λB Wavelength

(a) (b)

Figure 1.5 Photochromism: a two-way light-induced reaction between two molecules A and
B. (a) Potential energy diagram and (b) the related schematic absorption spectra.

In usual photochromic systems, A absorbs in the UV or near-UV, with a char-

acteristic absorption band at wavelength (𝜆A ). The absorption coefficient of A at
this wavelength is 𝜀A . When a photon at 𝜆A is absorbed, A is excited from the
ground to the excited state. The excited A yields B with a probability of 𝜙A→B (see
Appendix), known as the quantum yield. On the other hand, B reverts back to A,
with an analogous pattern, provided that the B is excited at 𝜆B , where it absorbs.
The spectral position of the absorption bands gives an indication of not only the
color of light needed to induce the reaction but also the color of the molecule
itself (Figure 1.5b). Further quantitative development of this scheme is given in
Appendix.

1.1.3
Photochromic Molecules: Some History

The historical reference of photochromism dates back to ancient times and the era
of the Alexander the Great (356–323 BC). As King of Macedonia, he got into a vast
world conquest. He conquered Asia Minor (now western Turkey) and extended
his kingdom to the northwest of India in the east and Egypt to the south. Strategy
and carefully coordinated attacks are essential conditions for victory. Thus, Mace-
donian head warriors were equipped with photochromic bracelets (the compound
remains unknown up to now) exhibiting a color change when exposed to sunlight.
Such color change was used by all warriors to indicate the right moment to begin
the fight [15].
Over 2000 years later in 1867, Fritzsche reported for the first time the follow-
ing peculiar behavior of tetracene solution: the initial orange color of the solution
fades when the sample is irradiated by sunlight but can be recovered as initially
when placed in a dark room (Figure 1.6) [16].
6 1 Introduction: Organic Photochromic Molecules

O
Sunlight, O2 O

Figure 1.6 Photochromic reaction of tetracene.

O
Cl
HN Cl
H N Cl
N N N
Cl
N

CHO

hν hν
hν

.
O
N Cl
H N .
HN N N Cl + Cl
N Cl

CHO
1-Benzylidene-2-phenylhydrazine Mesoaldehyde 1-allyl-1-phenyl-2- Tetrachloro-1,2-ketonaphthalenone
phenylosazone

Figure 1.7 Examples of photochromic compounds deriving from phenylhydrazine, pheny-

losazone, and naphthalenone.

.
O O
Cl Cl .
hν
+ Cl
Cl Cl
Cl Cl Cl

Figure 1.8 Solid-state photochromic reaction of 2,3,4,4-tetrachloronaphthalen-1-(4H)-one.

This first observation was followed by some studies [17] on solutions and
materials with a similar behavior. Wislicenus noticed the color change of
benzalphenylhydrazines (Figure 1.7) [17d]. Later, Biltz confirmed these obser-
vations and demonstrated the same behavior for some osazones (Figure 1.7)
[18]. Finally, in 1899 Markwald, apart from his work on 1-benzylidene-2-
phenylhydrazine (Figure 1.7) and tetrachloro-1,2-ketonaphthalenone (Figure 1.7),
discovered the first solid-state photochromic organic compound [19]: the 2,3,4,4-
tetrachloronaphthalen-1-(4H)-one (Figure 1.8). By that time, he was the first
person to recognize this phenomenon as a new reversible photoreaction and gave
the name (in German) of “Phototropie.”
Other main families of photochromic molecules dating back to this period
are fulgides [20], salicylideneanilines (also called anils) [21], stilbenes [22], and
nitrobenzylpyridines [23].
Other documents randomly have
different content
and secondly, in long standing cases, the large size of the uterine
cavity and the smoothness of the surface of the atrophied mucous
membrane, render the lodgment of the ovum in the uterus very
unlikely. A further powerful obstacle to impregnation in cases of
endometritis is offered by the profuse muco-purulent secretion which
usually, though not invariably, accompanies that disease. This
secretion, in some cases flowing freely over the surface of the
membrane, but in others adhering to it with tenacity, whitish-yellow
in colour, rendered cloudy by admixture of pus, or tinted red by
admixture of blood, sometimes of a gelatinous consistency with a
strongly alkaline reaction, contains globules of mucus, ciliated and
cylindrical epithelial cells, pus corpuscles, bacteria and cocci,—and, if
the endometritis is of gonorrhoeal origin, the gonococcus of Neisser.
This secretion, when profuse and thinly fluid, pours out through the
os, and sweeps away the semen; when tenacious and gelatinous, it
fills up the dilated cervical canal above the constricted os uteri
externum, and constitutes a powerful barrier to the upward passage
of the spermatozoa; when purulent, it is destructive to the vital
activity of the spermatozoa. The changes in the mucous membrane
in cases of long standing endometritis whereby the uterus is
rendered unfit for the implantation and incubation of the ovum, are
the following. The epithelial cells, as usual in cases of continued
catarrh, change in form, the ciliated cells disappear, and are
replaced, first by cylindrical cells, later by polymorphic cells,
approaching in type those of pavement epithelium. The mucous
membrane is swelled, the vessels are dilated, there is hyperplasia of
the glands, with a moderate amount of small-celled infiltration of the
interglandular tissue (Fig. 83). Ultimately the mucous membrane
undergoes atrophy, its glands disappear, it comes to resemble a thin
stratum of connective tissue.
 Fig. 83.—Uterine
Mucous Membrane in
Endometritis. (After A.
Martin.)

Thus, in severe and long-continued endometritis, the changes that

occur in the uterine mucous membrane render the implantation of
the ovum and the formation of normal decidua impossible; even if
conception does occur, the fertilized ovum is speedily discharged.
Frequently, in cases of endometritis, there is consecutive
displacement of the uterus which acts as a contributory cause of
sterility. When endometritis lasts a long time, proliferation of
connective tissue in the uterine parenchyma also occurs, leading
often to hypertrophy of the cervix, and to stenosis of the cervical
canal. Since in so many different ways endometritis may give rise to
sterility, the importance that must be attached to this condition is
evident.
The great significance of gonorrhoeal infection in relation to
sterility in women depends, not only on the changes this disease
causes in the Fallopian tubes, leading to interference with the
necessary contact of ovum and spermatozoon, but further, upon the
occurrence of gonorrhoeal cervical and corporal endometritis, of
perimetritis, and secondary parenchymatous metritis. Still, under
appropriate treatment, the inflammatory changes consequent on
gonorrhoeal infection are in many cases curable, and, after
absorption of the exudations and restoration of the normal nutritive
conditions of the tissues, conception may take place. Fritsch, who
points out that in the woman infected with gonorrhoea, sterility
ensues in a manner analogous to that in which it occurs in the male
(for in the latter it is not the primary urethritis, the disease of the
passage, but the secondary inflammation of the testicle that leads to
sterility), states that he has observed cases in which beyond
question conception has occurred, notwithstanding the existence of
gonorrhoeal endometritis.
In my own experience, whilst gonorrhoeal endometritis is, among
inflammations of the endometrium, the most frequent cause of
sterility, the place of next importance in this connexion is occupied
by exfoliative endometritis, or membranous dysmenorrhœa. This
name is given to a pathological condition in which from time to time,
usually during menstruation, fragments of membrane, or even an
entire sac-like cast of the uterine cavity, are expelled from the
uterus; since this condition is apt to hinder the incubation of the
ovum, it is commonly associated with sterility—a fact mentioned
already by Denman in 1790, and since then confirmed by numerous
observers. I have had under observation several cases of
dysmenorrhœa membranacea; in two cases it existed from the time
of marriage—in one case 14 years, in the other 8 years—and in both
sterility was absolute. In the latter of the two cases, vigorous
treatment was undertaken, even curettage of the uterus, but quite
without avail. In other cases, the sterility was acquired, the
membranous dysmenorrhœa having begun after the woman had
already had one or more children; but as I have never seen a case in
which a woman became pregnant after the development of this
affection, I am compelled to regard it as one of the most severe
hindrances to conception.
As a general rule, exfoliative endometritis terminates only with the
onset of the climacteric age; in very exceptional cases, however, a
cure may take place earlier. In cases in which this premature
termination has been observed, pregnancy has been known to
ensue, cases of this nature having been observed by Solowieff,
Fordyce Barker, and Thomas. And recently, cases have been
reported, in which the disease has returned after such a pregnancy.
Fritsch, indeed, is of opinion that exfoliative endometritis does not
cause sterility, and that in this disease abortion is no commoner than
in other diseases of the uterus. Charpignon, Hennig, and Bordier
have also observed conception occur in the course of this disease. In
42 cases of membranous dysmenorrhœa collected by Kleinwächter,
pregnancy occurred in four during the existence of the disease.
Löhlein also reports that, among 27 patients affected with
membranous dysmenorrhœa, six became pregnant, after the
symptoms had been clear and unmistakable for a shorter or longer
period. Two of these patients had been already pregnant before the
first appearance of the exfoliative endometritis; subsequently they
became pregnant and were delivered at full term. The other four
had suffered for varying periods and with varying severity from the
affection, before they first became pregnant. In three of these cases
curettage of the uterus was performed; but in one only, in which
pregnancy ensued very speedily on the operation, could a causal
connexion be inferred. In two of the cases the mothers of the
patient had also suffered from the affection.
It has been asserted by B. Schultze and others that curettage of
the uterus renders it difficult or impossible for pregnancy
subsequently to occur. There is, however, no evidence to justify such
an opinion.
Especial attention should be given to inflammatory processes in
the perimetrium and the parametrium as diseases giving rise to
sterility in women. They are extremely common, and at times are so
insidious, running their course without giving rise either to pain or to
fever, that even when very extensive, and even when they have led
to the formation of secondary tumour-growths, they may yet be
overlooked. Hence their pathological significance in the causation of
sterility in women is still underestimated. Chronic pelvic peritonitis
and parametritis may lead to the onset of sterility in various ways:
changes may occur in the cervix, this organ becoming indurated,
fixed, and retroposed, and painful when the uterus is moved;
inflammatory changes may affect the body of the uterus, the
ligaments of the ovary, and various portions of the pelvic
peritoneum; displacement of the uterus may occur; one or both
ovaries or tubes may be dislocated and fixed, either to the side of
the uterus, or behind it, in the pouch of Douglas; all kinds of
adhesions or inflammatory nodules may result from these processes.
Further, in the scarred, contracted, sclerosed parametric tissue, the
blood and lymphatic vessels of the parametrium are compressed,
and in part obliterated, and the intimate connexion between the
pelvic cellular tissue and the uterus readily leads to the onset of
endometritis, whereby the implantation of the ovum is interfered
with. The occurrence of sterility in cases of pelvic peritonitis and
parametritis, depends in part on the indirect effects of the
inflammatory exudations, and in part on the direct result of the
extension of the inflammation to other regions. The perimetritis,
parametritis, and pelvic peritonitis that result from gonorrhoeal
infection have thus an especially disastrous influence, for the reason
that in these cases cervical metritis and endometritis with
blenorrhoea are commonly superadded. This is the principal cause of
the almost invariable sterility of prostitutes, in whom, however, we
must also take into consideration the influence of the absence of
voluptuous sensation in an act which to them has become a mere
matter of business. The investigations of Bandl in the post mortem
room show that residues of perimetritic and parametritic
inflammation are to be found in the bodies of 58.4% of parous
women, and 33.3% of the bodies of women (married or unmarried)
who have had experience of sexual intercourse but have never had a
child. This, he thinks, is the explanation of the great frequency of
childless marriages and of relative sterility in women. In the
nulliparae mentioned above, Bandl commonly found an indurated,
functionless, in places cicatrized, narrowed cervix, paraoophoritic
and perisalpingitic residues, and morbid changes in the tubes and
the ovaries. In some cases also the husbands of such sterile women
were found to be affected with azoospermia. The connexion
between azoospermia in men and the discovery of inflammatory
residues in their childless wives, is a very intimate one. The husband
at the time of marriage was suffering from an imperfectly cured
gonorrhoea, and infected his wife. In the other class of cases, in
which the women had had children, and subsequently become
sterile, the limitation of fertility depended chiefly upon inflammatory
residues in and around the ovaries and the tubes. In the majority of
such cases, pregnancy is not rendered impossible, but merely
difficult, for, notwithstanding the presence of very extensive
inflammatory residues, the tubes are often pervious, and the ovaries
fully or partially functional. Therefore, even in cases in which
intrapelvic inflammation has been very severe, we must be cautious
in giving a prognosis that pregnancy has been rendered impossible,
for the cases in which both ovaries are imbedded completely in
pseudo-membranes, or in which both tubes have been rendered
impervious, are unquestionably rare.
Carcinoma of the uterus rarely causes sterility. In its initial stages,
in which there is merely papillary proliferation of the portio vaginalis,
or carcinomatous infiltration of the deeper layers of the mucous
membrane, no hindrance is offered to conception; but even in the
later stages of the disease, when ulceration has occurred, and when
there is extensive necrosis of the cancerous masses, there is not
necessarily any absolute impossibility of the occurrence of
conception, so long as cohabitation remains possible, and no
insuperable hindrance has risen to the contact of ovum and
spermatozoon. The cases are numerous in which pregnancy has
been observed, notwithstanding extensive carcinomatous disease of
the cervix, with necrosis of the tumour tissue; and Cohnstein even
asserts, though in this he goes too far, that cancer of the cervix
actually favours impregnation. Among 127 cases of this kind, there
were 21 in which the disease had existed for a year or more before
the occurrence of conception.
Winckel summarizes in the three following propositions his
experience regarding the relation between uterine carcinoma and
sterility: 1. Married women form the very large majority of those
affected with carcinoma of the uterus; 2. The marriage of such
women has very rarely proved sterile; 3. On the contrary, the
women affected with this disease have generally been exceptionally
fertile.
Other tumours of the uterus cause sterility, not merely by giving
rise to mechanical interference with the necessary contact of ovum
and spermatozoon, but also by leading to catarrhal states and
hyperplasia of the mucous membrane, which interfere with the
implantation of the ovum, even when fertilization has been effected.
Uterine polypi give rise to mechanical obstruction of the os uteri
externum or of the cervical canal; but they predispose to sterility in
an additional way, inasmuch as in a woman affected with such a new
growth any vigorous bodily movement is apt to cause profuse
uterine haemorrhage.
In cases of myoma of the uterus, apart from the mechanical
hindrances to conception imposed by these tumours, there is also
interference with the implantation of the ovum. When numerous
myomata have formed in the uterine wall, the mucous membrane is
usually smooth and atrophied, and discharges a watery secretion,
and for these reasons the imbedding of the ovum in the uterine
cavity is rendered extremely difficult. But that there is often an
additional cause of sterility in cases of myomata uteri, has been
shown by the researches of Schorler, who examined 822 patients
affected with fibromyoma of the uterus. He found that in most of
those in whom sterility was observed, the tumours were not
submucous but subserous, and that the sterility was to be explained
in these cases by the frequent occurrence of partial peritonitis, with
its evil results to the uterine annexa.
Schorler appends the following table:
 Sterile. Percentage.
Of 85 women with interstitial myoma 21 24.7
Of 92 women with subserous myoma 44 47.8
Of 18 women with submucous myoma 7 38.8
Of 44 women with polypous myoma 4 9.0
Of 14 women with cervical myoma 3 18.7

253 79 31.2

When there are polypous new formations in the uterine cavity,

even if conception occurs, abortion follows, for the reason that the
rupture of the hypertrophied capillaries in the growths themselves
and in the neighbouring tissues, prevents the normal development of
the embryo. Horwitz has, however, described a case in which
pregnancy went on to full term, notwithstanding the existence of
growths of this nature.
Owing to the frequency with which chronic metritis and
endometritis ensue upon parturition, it can readily be understood
that delivery itself is often the primary cause of subsequent sterility.
A temporary sterility often follows the first delivery. It is well known
that the birth of boys is in general more difficult than the birth of
girls; Pfannkuch collecting information regarding the first and second
deliveries of 300 married women, ascertained that after 166 of the
first deliveries, in which boys were born, the average lapse of time
to the second delivery was 30.2 months, whereas after 134 of the
first deliveries in which girls were born, the average lapse of time to
the second delivery was only 27.4 months.
The importance of previous delivery in leading to sterility, in
consequence of mesometritis and diffuse connective tissue
hyperplasia of the uterus, is shown by von Grünewaldt, who
published the following figures as a result of his investigations. Of 56
women affected with chronic metritis, 46.4% were sterile; in 19.2%
of these the sterility was congenital, in 80.7% it was acquired. Of
134 women suffering from myometritis and its consequences, 71.6%
were sterile; in 17.7 of these the sterility was congenital, and in
82.2% it was acquired. On the other hand, of 321 women suffering
from endometritis, 29.5% were sterile; in 28.4% of these the
sterility was congenital, and in 71.5% it was acquired.
Lier and Ascher also insist upon the importance of puerperal
diseases in the causation of acquired sterility, basing their opinion
upon Prochownick’s clinical material. They draw, however, the
following distinction. If the puerperal infection takes place by way of
the external organs of reproduction, through the vagina to the cervix
and thence to the connective tissue of the pelvis—the most common
form, that which occurs soonest after delivery, and the most severe
in its course—the women thus affected are likely soon to become
pregnant again; if, on the other hand, the disease is pelvic
peritonitis, the exciting cause of the inflammation proceeding from
the interior of the uterus through the Fallopian tubes to reach the
peritoneum, in the majority of cases the women thus affected will
prove sterile for a long time or in perpetuity. In almost all the cases
in which sterility resulted, the pelvic peritoneum had been severely
affected by the puerperal inflammation. Regarding sterility in
women, the two following general propositions are laid down by Lier
and Ascher: 1. Hardly any single cause of sterility in women is so
severe as to be competent by itself to render sterility inevitable
throughout the period of sexual maturity, with the exception of
defects of development and premature cessation of sexual activity.
2. Most of the hindrances to conception in women depend upon
affections of the internal superficies of the reproductive organs, from
the vulval mucous membrane upwards to the pelvic peritoneum; of
these, the most important are affections of the endometrium.
On the other hand, it must not be forgotten, that the general
tendency of a previous delivery is to increase the capacity for
impregnation. Olshausen especially insists upon the well-known
gynecological fact, that as a result of the first delivery, there occurs
an enlargement of the os uteri, which facilitates conception
throughout the remainder of the period of sexual maturity. This is
well shown by the not infrequent cases in which sterility persists for
several years after marriage, and then, with or without artificial aid,
the first pregnancy occurs; thereafter one child after another
appears in rapid succession.
Spiegelberg has pointed out that cervical lacerations may give rise
to sterility by interference with the incubation of the ovum.
Olshausen maintains that this affection is liable to cause abortion,
for the reason that by the gaping of the cervical canal the inferior
pole of the ovum is from time to time exposed, and this gives rise to
reflex contractions of the uterus.
Von Grünewaldt publishes figures in support of his opinion that
disturbances of the integrity of the uterus, whereby the implantation
and further development of the ovum are interfered with, play on a
whole a greater part in the causation of sterility than the various
conditions previously described which interfere with contact of ovum
and spermatozoon. But in this, we think, he goes too far.
Finally, in this connexion, must be mentioned among the
hindrances to fertilization, sexual excesses, such as are so common
during the first weeks of married life. Too frequent coitus gives rise
to enduring congestion of the uterus, and hence to an irritable state
of the uterine mucous membrane, whereby the implantation of the
ovum is rendered difficult. In prostitutes chronic metritis, due to the
excessive frequency of intercourse, may be a contributory cause of
the sterility which is almost invariable in these women; doubtless,
however, the principal cause of their sterility is gonorrhoeal
perimetritis.
As a variety of the third kind of sterility, sterility due to incapacity
for implantation or further development of the ovum, must be
classed the cases in which, though conception and implantation of
the ovum are known to occur, and the first stages of development of
the embryo certainly take place, the woman proves incapable of
giving birth to a viable infant. Some of these cases depend upon
abnormal modes of development, myxoma of the chorion and the
like. In rare cases, women abort every month, discharging every
four weeks a fully developed decidua vera, in which sometimes no
trace of ovum can be detected. But this monthly abortion ceases as
soon as marital relations are interrupted.
It would be passing beyond the scope of this work to discuss the
pathological processes which lead to premature interruption of the
pregnancy, after conception, implantation of the ovum, and the first
stages of development, have occurred in a normal manner; to
discuss, in short, the causes of abortion. Moreover, these
pathological processes are outside the concept of sterility. It is
sufficient here to enumerate the principal conditions in which
abortion occurs. They are: various tissue disorders of the uterus,
chronic hyperaemia of the mucosa, displacement of the uterus with
fixation, parametric and perimetric exudations, laceration of the
cervix with ectropium; further, various constitutional disorders, such
as the specific fevers, acute infective processes, chronic circulatory
disturbances consequent upon cardiac, pulmonary, renal and hepatic
disease, syphilis, anæmia, chlorosis, diabetes, etc.

Only-Child-Sterility.

Until recently, only-child-sterility had received attention in England

only, for the reason that it is comparatively common in that country;
but this form of relative sterility is by no means rare with us (in
Germany and Austria) also. I had a collection made in Austria of the
number of children resulting from 2000 fruitful unions, and found
that among these there were 105 marriages in which one child only
had been born; thus the ratio of these marriages to those which
proved fully fruitful was about 1 : 19. But the figures are
untrustworthy, since abortions and deaths in infancy were not taken
into account. Ansell found that in England, among 1767 fruitful
marriages in which the mean age of the wives at marriage had been
25, there were 131 cases of only-child-sterility, giving a ratio of the
latter to the fully fruitful unions of 1 : 13.
This form of relative sterility, in which the wife gives birth to one
child, and thereafter remains barren, was referred by Matthews
Duncan, either to a premature exhaustion of the reproductive
capacity, the general bodily powers remaining unaffected, or else to
a simultaneous weakening of the sexual powers and of the
constitutional force in general. This explanation is a very inadequate
one. The significant fact upon which an understanding of the nature
of only-child-sterility must be based, is that the first delivery is the
one which entails the greatest dangers to the mother, and that the
subsequent sterility is attributable to the difficult delivery, and to the
illnesses that follow in its train. In fact, only-child-sterility is observed
chiefly after difficult deliveries, followed by long enduring
inflammatory processes of the uterus and the uterine annexa, which
seriously affect the woman’s reproductive capacity. It occurs
especially in delicately organized, anæmic, scrofulous women, whose
powers of resistance have been undermined by a single pregnancy
and parturition. Finally, it is met with in women suffering from
myoma uteri, a form of tumour which beyond others renders the
recurrence of pregnancy difficult and unlikely. This form of sterility
has been seen also in cases in which comparatively soon after the
birth of her first child, the mother has suffered from typhoid,
scarlatina, or some other severe infective fever, which appears in
some way to interfere for the future with the development of normal
ova. We must also take into consideration the fact that at the time of
the wife’s first confinement, when the love which brought about the
union has often already begun to diminish in intensity, the husband,
finding too irksome the continence enforced upon him by his wife’s
condition, is not unlikely to go elsewhere for temporary sexual
gratification, and to acquire a venereal disease, which he
subsequently transmits to his wife, and which is responsible for the
latter’s future sterility. And we must not forget to take into account
the adoption of means for the prevention of pregnancy after the first
child has been born. Again, I saw three cases of only-child-sterility in
which the husbands were respectively 24, 26, and 29 years older
than their wives, and in these instances no profound search was
needful for the discovery of the cause of the wife’s unfruitfulness; it
was obvious that in each case the elderly husband’s reproductive
powers had sufficed for the procreation of a single child, but had
then been completely exhausted. My experience in the mysteries of
sterility in women has informed me of yet another cause of only-
child-sterility, met with in cases in which the only child was born
after several years of unsuccessful marital intercourse. In most of
these cases, the wife has finally been impelled to seek a substitute
for her husband, whose reproductive powers have proved
insufficient; having succeeded in obtaining the child she desires, the
wife does not again wander in strange pastures, and consequently
remains sterile.
According to Kleinwächter—who gives a somewhat wider
significance to the term “only-child-sterility,” including as he does
cases of premature interruption of the first and only pregnancy,
since these even more frequently entail permanent sterilization—
only-child-sterility is by no means rare. Among 1081 gynecological
cases, he observed it in 90, that is, in 8.32% of the cases. In these
90 cases, there were 69 instances in which the sterility ensued upon
full term delivery, and 21 instances in which it followed abortion or
premature delivery. Kleinwächter, moreover, on the basis of his
personal experience, supports my view of the importance of the
sterilizing influence of the first delivery; but he has been unable to
determine whether early marriage has any influence in the
production of only-child-sterility.
Lier and Ascher also class as instances of only-child-sterility those
cases in which a woman has had a single miscarriage, and
subsequently remained sterile, since by this miscarriage the capacity
of the woman for impregnation has been proved, and the question
of capacity for full-term delivery has nothing to do with that of
capacity for conception. As causes of this form of sterility, they lay
especial stress upon puerperal infection, gonorrhoeal infection,
perimetritis, tubo-ovarian tumours, etc.

Operative Sterility.
 Finally, in order to complete the etiologically classified series of
forms of sterility, we must allude to yet another variety of sterility
which is due to the surgical direction of modern gynecology, viz.,
operative sterility. However much we may prize the gains we owe to
modern operative gynecology, it cannot be denied that the new
developments have brought many evils in their train. Not the least of
these is operative sterility, due to operative procedures involving the
female reproductive organs, by which, whether intentionally or
unintentionally the reproductive capacity is destroyed. Doubtless, in
certain severe organic diseases of the female reproductive
apparatus, in which the use of the knife is indicated, the fact that by
operating we are sterilizing the patient cannot even be taken into
consideration; but many sins have been committed in this kind, and
with a ready hand, and, be it openly admitted, with an easy
conscience, many an eager operator has undertaken the destruction
of a woman’s potentialities for motherhood, without having given the
careful consideration that is demanded by the irreparable character
of his undertaking. Happily, however, the time has nearly passed
away, in which it could be said of many a gynecologist, that no
ovaries and no Fallopian tubes were safe from his operative zeal, and
from his desire to heap up a mountain of statistics.
Three operative measures very commonly undertaken at the
present day are responsible for the production of operative sterility:
ovariotomy, oophorectomy, and salpingotomy.
The removal of the ovaries, with the object of permitting to the
women concerned unbridled sexual indulgence without risk of
consequences, was performed, according to Strabo, by the ancient
Egyptians and Lydians. The same practice is described by modern
writers as occurring in Hindustan (Roberts), and in Australia
(Miklucho-Mackay).
With a curative aim, the removal of the ovaries was first
undertaken in the early years of the nineteenth century, although
the operation had already been discussed as a possibility by leading
physicians of the eighteenth century. The first ovariotomy for the
removal of an ovarian tumour was performed by MacDowell in the
year 1809. During the last three or four decades, the operation has
become an extremely common one, and is performed by the
surgeons of all nations. Removal of a single ovary, as long as the
other ovary is healthy, does not necessarily lead to any impairment
of fertility; but when both ovaries are removed, operative sterility is
the necessary result. In order to avoid this, Schröder has
recommended that a fragment, at least, of healthy ovarian tissue
should be left behind, in order to preserve the reproductive capacity.
In discussing the subject of impaired ovulation, we have already
mentioned cases in which pregnancy has occurred after bilateral
removal of the ovaries, a circumstance explicable only on one of two
assumptions, either that a fragment of ovarian tissue was left
behind, or else that a supernumerary ovary existed.
The extirpation of healthy ovaries, or at any rate, of ovaries which
are not notably enlarged, is known as oophorectomy (spaying,
Battey’s operation, in Germany, castration). It dates from the year
1869 (Koeberlé); but in the strictly modern sense the operation was
first performed by Hegar in the year 1872. [Lawson Tait removed
both ovaries for pain in October, 1871. Battey’s first operation of this
kind was successfully performed on August 17th, 1872; this was
three weeks subsequent to the first performance of the operation by
Hegar of Freiburg. But Hegar’s patient died from the operation, and
Hegar did not publish the case at the time—Transl.] The aim of
ovariotomy is to remove an ovarian cystoma; if the other, apparently
healthy, ovary is removed, it is with the object of removing an
ovarian tumour in the initial stage. Oophorectomy has an altogether
different purpose, namely, to relieve or cure pathological
manifestations in other organs which are believed to depend on the
periodical recurrence of ovulation, to cure them by instituting a
premature menopause. At one period, when overzealous operators
performed oophorectomy for the supposed relief of comparatively
unimportant nervous affections, and the statistics of the operation
began to assume gigantic proportions, operative sterility actually
came to play no inconspicuous part on the stage of sterility in
general. But a reaction inevitably followed; severe diseases were
alone considered as furnishing sufficient indications for the
operation; of late it has been performed chiefly in cases in which the
primary disorder has already rendered the occurrence of pregnancy
impossible, or at any rate very unlikely, or, finally, if probable, yet to
be avoided, on account of the dangers it would entail. In short, the
fertility of women is no longer seriously threatened by this operation.
Some years ago, I was consulted by a beautiful married woman,
26 years of age, of a blooming and healthy aspect. When a young
girl, she had suffered every month at the time of the menstrual flow
from violent vomiting, accompanied by various spasmodic troubles.
Just at this time, oophorectomy was the fashionable operation for
the relief of nervous troubles; this girl was subjected to the
operation, and the vomiting at the periods ceased, but the other
nervous symptoms persisted without alleviation—indeed were at
times worse than before. Since then, she had married a man
belonging to the upper circles of society; and now, after living for
four years in sterile wedlock, she came to me to ask my advice as to
whether anything could be done to enable her to have a child! Two
other cases have come within my own knowledge, in which women
whose ovaries had been removed on account of nervous troubles,
had subsequently married, and felt most unhappy owing to their
hopeless state of sterility.
It is impossible to make even an approximate estimate of the
number of women who in recent years have had their ovaries
removed during the period of sexual maturity, and who have thus
been made the subjects of operative sterility; nor is it possible to
ascertain in what proportion of cases the healthy ovaries, the normal
female reproductive glands, have been removed for the
problematical relief of nervous troubles or of uterine haemorrhage,
and in what proportion of cases there has existed a genuine
indication, owing to the presence of fibromyoma of the uterus, for
the induction of an artificial and premature menopause.
Unquestionably, the number of women thus operated on during the
menacme is by no means a small one. In a work by Hermes, “On the
Results of Oophorectomy in Cases of Myoma of the Uterus,” Archiv
für Gynecologie, 1894, we find that, among 55 women whose
ovaries were removed on account of myoma of the uterus, there
were 52 who were between the ages of 21 and 45, i. e., in the
period of sexual maturity. The assumption that all these patients
were already sterile before the operation, on account of a
degenerate condition of the uterine annexa, cannot be justified.
Keppler, indeed, puts forward a very remarkable defence of the
removal of the ovaries of women who are competent to become
mothers, asserting that such oophorectomy offers no obstacle to
marriage, and that many women who have been operated on in this
manner are extremely happy in conjugal life. Marriage with a wife
whose ovaries have been removed is the ideal Malthusian marriage,
the one way in which Malthusianism can be practised without
endangering the health and life-happiness of the participators!
Another danger soon appeared, one which threatened the fertility
of women to an even greater extent, in the form of operations on
the uterine annexa—the first salpingotomy was performed by Hegar
in 1877. As knowledge advanced of the various diseases of the
Fallopian tubes, salpingitis, hydrosalpinx, and pyosalpinx, whilst at
the same time the development of the antiseptic method rendered
operative gynecology continually bolder and bolder in its
undertakings, there was disclosed an extensive field for radical
measures in removal of the tubes, generally combined with removal
of the ovaries, since these latter organs commonly were found to
have suffered from association in the destructive inflammatory
process. The operation of salpingo-oophorectomy soon became a
very common one; and since patients with diseased tubes are for
the most part still comparatively young, in the period of sexual
maturity, there arose a new and frequent variety of operative
sterility, and one which the zeal of American gynecologists made
especially common on the other side of the Atlantic. An American
gynecologist, indeed, has sarcastically observed that “It is the dish-
full of excised tubes that shows the master gynecologist”; and
Landau has been impelled to lament that “salpingotomy has been
performed on a very large number of women who have complained
of nothing more serious than uterine haemorrhages, or of
insignificant pains, and even on some women who have come to the
gynecologist with no other complaint than that—they are sterile”!
Fritsch, also, writing of the too rapidly formed diagnosis “tumor of
the annexa,” and the consequent resort to operation, remarks: “I
know many a happy mother who at one time had worn every variety
of pessary, had been through every kind of ‘cure,’ and had visited
every accessible spa; until, at last, she came to consult me, with the
express wish to have her ovaries removed. Latterly, she had been
advised to this course by every physician she had consulted. I
agreed, in such cases, to perform the operation, with the stipulation
that first of all, for the space of an entire year, the patient should not
see a single doctor, should visit no spa, should take no medicine,
and, in short, should pay no attention whatever to her health. The
success of this course of ‘treatment’ was often extraordinary. As
soon as the reproductive organs were left in peace, recovery
ensued.” The conservative tendencies of the surgery of the last
decade, have manifested themselves also in the department of
gynecology, for the happy protection of woman and her reproductive
capacity. Operative measures are now commonly restricted to the
relief of certain severe forms of disease of the uterine annexa; in
cases of chronic inflammation of the annexa, the surgeon often
contents himself with dividing or breaking down the adhesions, and
leaves the organs in situ; even in cases of bilateral disease, one tube
only may be removed; whilst in the most recent method of all, after
opening the abdomen, and separating the pelvic organs from their
adhesions, an aperture is made in the closed tube, and this artificial
ostium is brought into apposition with the ovary by the insertion of
sutures. In a word, surgeons have come to realize that they have in
the past been too ready to sterilize their patients by the performance
of double salpingo-oophorectomy, and are much more reluctant than
formerly to sacrifice the ovaries and the Fallopian tubes.
Porro’s operation is another cause of operative sterility, excision of
the ovaries being combined with the partial excision of the uterus,
whereas sterility was seldom the consequence of the older method
of Caesarian section. Indeed, Porro’s operation has been extolled
precisely on this account, that, indicated as it is for the relief of
extremely difficult labour, it renders it impossible for the same
difficulty and danger ever to recur.
The classical operation of Caesarian section, if the patient makes a
favourable recovery, does not involve sterility, unless in very
exceptional cases (as in one described by Lecluyse, in which, after
the Caesarian section, a communication persisted between the
uterine cavity and the cavity of the abdomen, through which the
semen passed during coitus). Occasionally, also, in performing the
older operation, the operator has thought it right to prevent the
future recurrence of pregnancy by adding an oophorectomy to the
primary operation.
Pregnancy and parturition are still possible after the healing of
spontaneous or traumatic ruptures of the uterus; but it must be
remembered that after such serious injuries, as after extensive
operative procedures on the pelvic organs, widespread peritoneal
inflammation is apt to occur, with perimetritic and parametritic
exudations, leading commonly to sterility.
Amputation of the vaginal portion of the cervix, an operation
sometimes undertaken for the relief of sterility in cases of
hypertrophy of the cervix, may on the other hand lead to sterility in
cases in which a cicatricial stenosis of the cervical canal results from
the operation.
By the too frequent application of caustics to the cervical canal, or
by the employment of these agents in too powerful a form, occlusion
of the os externum may be caused, or even adhesion of the
opposing walls of the vagina just below the cervix, thus giving rise to
sterility. Rough use, also, of the uterine sound, and maladroit and
violent gynecological massage, have often enough been responsible
for the occurrence of sterility, by giving rise to perimetritic
inflammation. Landau enumerates among the causes of intrapelvic
abscesses, “whereby the specific functions of womanhood are
nullified in consequence of degeneration of the tubes or the ovaries,”
“certain therapeutic procedures,” and more especially, intra-uterine
therapy, (the use of the sound, curettage, injections, cauterization),
and operations on the cervix or the vagina, on which intrapelvic
inflammation and even suppuration has ensued. How easily pelvic
peritonitis and its consequences lead to sterility in women, has been
shown many times in the course of our exposition of this subject.
Finally, we must class with operative sterility the result of surgical
procedure undertaken by gynecologists to save women, whose lives
have already been seriously threatened by pregnancy or parturition,
from a repetition of this experience. In such cases, Blundell
recommends division of the Fallopian tubes, having found from
experiments upon rabbits that this is a safe and certain means for
the prevention of conception. Frorieps and Kocks have both
frequently brought about an artificial sterility in women by closure of
the tubes, the first-named by cauterization with nitrate of silver—the
caustic being attached to the end of a piece of whalebone and
introduced through a canula into the uterine orifice of the Fallopian
tube—whilst Kocks has constructed for the same purpose a galvano-
caustic uterine sound, which is only rendered red-hot by passage of
the current after it has been introduced into the uterine ostium of
the tube. Both these methods are in the first place too uncertain to
be relied upon for the attainment of the desired end, and in the
second place their employment appears to be neither easy, nor free
from danger.
As the importance of conservative methods of procedure becomes
once more fully recognized in modern gynecology, cases of operative
sterility will become ever more and more rare.
TABLE SHOWING THE CAUSES OF STERILITY
IN WOMEN.

I. Sterility due to Incapacity for Ovulation.

ABSOLUTE AND IRREMEDIABLE.

Complete absence of the ovaries.

Congenital atrophy of both ovaries.
Premature atrophy of the ovaries, in consequence of infectious
disorders, constitutional diseases, and toxic influences.
New-growths of the ovaries, destroying all the follicles.
Senile changes in the ovaries.
Complete oophorectomy, or any equivalent form of operative
sterility.

RELATIVE AND TRANSIENT.

Incomplete development of the ovaries.

Imperfect formation of ova, owing to marriage when still too
young (amenorrhœa).
Ovarian tumours and oophorectomy, whereby, however, a remnant
of healthy ovarian tissue is spared.
Chronic oophoritis and perioophoritis; syphilitic disease of the
ovaries.
Excessive obesity, anæmia, chlorosis, scrofula, morphinism,
alcoholism, various conditions affecting unfavourably the
innervation or nutrition of the ovary; change of climate or mode
of life; emotional disturbance; inbreeding, hereditary
predisposition.

II. Sterility due to Interference with the Contact of Normal

Spermatozoon and Ovum.

A. On the Part of the Wife.

ABSOLUTE AND IRREMEDIABLE.

Congenital or acquired universal thickening of the tunica albuginea

of the ovaries, preventing the dehiscence of the follicles.
Absence of both tubes, developmental defects of these organs.
Absence or rudimentary condition of the uterus. Foetal uterus.
Congenital atresia of the uterus with arrest of development.
Complete absence of the vagina.
Extreme contraction of the pelvis, whereby the vagina is rendered
inaccessible.
Hermaphroditism.

RELATIVE AND TRANSIENT.

Remediable thickening of the tunica albuginea, inflammatory

remnants of perioophoritic processes, diseases of the cervical
glands, dislocations and adhesions of the tubes, narrowing or
 obliteration of the ostia, inflammation of the tubes, pyosalpinx,
obliteration of the lumen of the tube.
Retro-uterine haematocele.
New growths in the uterine cavity.
Infantile and pubescent uterus.
Primary atrophy of the uterus.
Puerperal atrophy of the uterus.
Displacements of the uterus—versions and flexions.
Hypertrophy or atrophy or changes in the shape of the cervix,
cervical stenosis.
Cervical catarrh, especially when gonorrhoeal.
Ectropium of the cervix.
Spasmodic dysmenorrhœa.
Atresia of the vagina, obliteration of the canal by scars or tumours.
Abnormal termination of the vagina—vesico-vaginal and recto-
vaginal fistula.
Absence of the external organs of generation and partial absence
of the vagina, without defect of the internal organs of
generation.
Abnormalities of the hymen.
Pathological states of the genital secretions.
Vaginismus.
Dyspareunia.
Perversion of the sexual impulse.

B. On the Part of the Husband.

 ABSOLUTE AND IRREMEDIABLE.

Diseases of the central nervous system, and certain constitutional

diseases.
Congenital or acquired absence of both testicles.
Atrophy of the testicles.
Complete azoospermia and aspermatism.
Senile impotence.

RELATIVE AND TRANSIENT.

Developmental defects of the penis, and acquired deformities of

that organ.
Stricture of the urethra.
Oligozoöspermia.
Nervous impotence.
Gonorrhoeal and syphilitic infection.
The employment of measures for the prevention of pregnancy
(facultative sterility).

III. Sterility due to Incapacity for the Implantation and further

Development of the Ovum.

ABSOLUTE AND IRREMEDIABLE.

Arrested development of the uterus.

Complete atrophy of the uterine mucous membrane.
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