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Published on 01 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782626954-FP001
Photochemistry
Volume 44
Published on 01 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782626954-FP001 View Online
View Online
A Specialist Periodical Report
Photochemistry
Volume 44
Editors
Angelo Albini, University of Pavia, Pavia, Italy
Elisa Fasani, University of Pavia, Pavia, Italy
Authors
Maria Abrahamsson, Chalmers University of Technology, Sweden
Massimo Baroncini, University of Bologna, Italy
Paula Caregnato, National University of La Plata, Argentina
Chuncheng Chen, Chinese Academy of Sciences, Beijing, China
Alberto Credi, University of Bologna, Italy
Marı́a Laura Dell’Arciprete, National University of La Plata, Argentina
Pooria Farahani, University of Sao Paulo, Brazil
T. A. Faunce, Australian National University, Australia
Antonio Francés-Monerris, University of Valencia, Spain
Ignacio Fdez. Galván, Uppsala University, Sweden
Mónica C. Gonzalez, National University of La Plata, Argentina
Hongwei Ji, Chinese Academy of Sciences, Beijing, China
M. Consuelo Jiménez, Polytechnic University of Valencia, Spain
Xianjun Lang, Chinese Academy of Sciences, Beijing, China
Cristian R. Lillo, National University of La Plata, Argentina
Roland Lindh, Uppsala University, Sweden
Ya-Jun Liu,,China
Wanhong Ma, Chinese Academy of Sciences, Beijing, China
Miguel A. Miranda, Polytechnic University of Valencia, Spain
Kazuhiko Mizuno, NAIST, Japan
Giulio Ragazzon, University of Bologna, Italy
Daniel Roca-Sanjuán, University of Valencia, Spain
Hernán B. Rodrı́guez, National University of La Plata, Argentina
Juan J. Romero, National University of La Plata, Argentina
Serena Silvi, University of Bologna, Italy
View Online
Takashi Tsuno, Nihon University, Japan

Margherita Venturi, University of Bologna and ISOF-CNR, Italy
Davide Vione, University of Torino, Italy
Jincai Zhao, Chinese Academy of Sciences, Beijing, China
ISBN: 978-1-78262-543-8
PDF eISBN: 978-1-78262-695-4
EPUB eISBN: 978-1-78262-750-0
ISSN: 0556-3860
DOI: 10.1039/9781782626954
A catalogue record for this book is available from the British Library
& The Royal Society of Chemistry 2017
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Apart from fair dealing for the purposes of research or private study for
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Preface
DOI: 10.1039/9781782626954-FP007
Volume 44 follows the pattern of previous issues from Volume 39 onwards,

which combines a review on the latest advancements in photochemistry
(every other year on a part of this discipline, in the present case, compu-
tational and organic) and highlights on some topics.
We thank the reviewers, who maintained once again the high level they
had established, as well as the contributors of highlights. It has been, as
usual, quite a tough job to complete all the contributions (almost) within
the planned deadlines. We must admit that, hard work as it may have
been, having the opportunity of reading and discussing such a large
wealth of photochemical research has been a really nice experience.
We thank the staff of Specialist Periodical Reports at the Royal Society
of Chemistry and our Colleagues of the Photochemical Group at the
University of Pavia, who made photochemistry such an entertaining
experience every day.
Angelo Albini and Elisa Fasani
Photochemistry, 2017, 44, vii–vii | vii

c The Royal Society of Chemistry 2017
CONTENTS
Cover
A quote (back cover) from a century
ago: ‘‘Aside from the previously
considered process Zm-Zn, let the

molecule in Zm state to also have
the capability of another
elementary ‘chemical’ process, e.g.
monomolecular dissociation [with a
larger rate] compared to the reaction
Zm-Zn. . . Under absorption of the
[effective frequency] radiation energy
the molecules will continually go from
state Zn to state Zm. Most, by far, will
suffer chemical dissociation [and]
per dissociating molecule, we will
practically find that the radiation energy
has been absorbed. . . The absorption
of light and the chemical process
appear as independent processes.’’
A. Einstein, Verh. Dtsch. Phys. Ges.,
1916, 18, 318–323.
Front cover image courtesy of
Sakkmesterke/Shutterstock.
Preface vii
Periodical Reports: Organic and Computational Aspects
Introduction and review of the year 2015 3

1 Introduction 3
2 Review of the year 2015 4
3 Highlights in volumes 37 to 44 13
References 14
Advances in computational photochemistry and chemiluminescence 16

of biological and nanotechnological molecules
Daniel Roca-Sanjuán, Antonio Francés-Monerris, Ignacio Fdez. Galván,
Pooria Farahani, Roland Lindh and Ya-Jun Liu
1 Introduction 16
Photochemistry, 2017, 44, ix–xiii | ix

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2 Development of methods and theory 17

3 Mechanisms of DNA/RNA damage and repair 28
4 Photo-induced mechanisms of relevance in biology and 37
technology
5 Chemiluminescence 44
6 Dark photochemistry 46
7 Bioluminescence 48
8 Summary 53
Acknowledgements 54
References 54
Alkenes, alkynes, dienes, polyenes 61

Takashi Tsuno
1 Introduction 61
2 Photochemistry of alkenes 61
3 Photochemistry of alkynes 109
4 Photochemistry of dienes and polyenes 110
5 Photochemistry of haloalkenes 113
6 Photooxygenation and photooxidation 114
7 Flow photochemistry 116
References 117
Photochemistry of aromatic compounds 132

Kazuhiko Mizuno
1 Introduction 132
2 Isomerization reactions 132
3 Addition and cycloaddition reactions 134
4 Substitution reactions 142
5 Intramolecular cyclization reactions 156
6 Rearrangements 166
7 Reduction and oxidation 168
References 181
Organic aspects. Oxygen-containing functions 188

M. Consuelo Jiménez and Miguel A. Miranda
1 Introduction 188
2 Norrish type I reactions 188
3 Hydrogen abstractions 190
4 Paternò–Büchi photocycloadditions 196
x | Photochemistry, 2017, 44, ix–xiii

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5 Photoreactions of multichromoporic systems: dicarbonyl 198

compounds, enones and quinones
6 Photoelimination 207
7 Photo-Fries and photo-Claisen rearrangements 209
8 Photocleavage of cyclic ethers 211
9 Photoremovable protecting groups 213
10 Miscellanea 218
References 218
Function containing a heteroatom different from oxygen 224

1 Nitrogen containing functions 224
2 Functions containing different heteroatoms 249
References 254
Highlights in Photochemistry
Global artificial photosynthesis: transition from 263

Corporatocene to Sustainocene
T. A. Faunce
1 Introduction 263
2 Governance challenges in artificial photosynthesis going 270
global
3 Ethical foundations of a global project on artificial 272
photosynthesis
4 Conclusion 280
Acknowledgements 281
References 281
Solar energy conversion using iron polypyridyl type 285

photosensitizers – a viable route for the future?
Maria Abrahamsson
1 Introduction 285
2 The dye sensitized solar cell 285
3 Photosensitizers for nanostructured wide band gap 287
semiconductor electrodes
4 Fe(II)-based photosensitizers for nanostructured TiO2 290
5 Other first row photosensitizers 293
6 Summary 294
References 294
Photochemistry, 2017, 44, ix–xiii | xi

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Azobenzene photoisomerization: an old reaction for activating 296

new molecular devices and materials
Massimo Baroncini, Giulio Ragazzon, Serena Silvi,
Margherita Venturi and Alberto Credi
1 Introduction 296
2 Basic properties of azobenzene 297
3 Threading and dethrading of a pseudorotaxane driven by 299

light
4 Reversible photoswitching of pseudorotaxane/rotaxane 300
character
5 Photoinduced relative unidirectional transit of a 304
macrocycle along an axle
6 An autonomous supramolecular pump powered 307
by light
7 Photoinduced memory effects in a molecular shuttle 311
8 Photoreactive porous molecular crystals based on rigid 315
azobenzene tetramers
9 Conclusion 319
References 321
Versatile silicon nanoparticles with potential uses as 324

photoluminiscent sensors and photosensitizers
Paula Caregnato, Marı́a Laura Dell’Arciprete, Mónica C. Gonzalez,
Cristian R. Lillo, Hernán B. Rodrı́guez and Juan J. Romero
1 Introduction 324
2 Silicon nanoparticles applications in photodynamic 328
therapy
3 SiCs as nano-photocatalysts 333
4 Synthesis of isolated silicon dots 335
5 Surface functionalization strategies 337
6 Conclusions 341
References 341
Photochemical reactions in sunlit surface waters: influence 348

of water parameters, and implications for the phototransformation
of xenobiotic compounds
Davide Vione
1 Introduction 348
2 Photochemical reactions in surface waters 350
3 Implications for xenobiotic phototransformation 354
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4 Possible impacts of long-term changes 358

5 Conclusions 359
References 360
Oxygen-atom transfer in titanium dioxide photoredox catalysis for 364

organic synthesis
Xianjun Lang, Chuncheng Chen, Wanhong Ma, Hongwei Ji and
Jincai Zhao
1 Introduction 364
2 O-atom transfer in aerobic oxidation of aliphatic 365
compounds in water by TiO2 photoredox catalysis
3 O-atom transfer in hydroxylation of aromatic compounds 368
by TiO2 photoredox catalysis
4 O-atom transfer in the selective reduction of organic 374
compounds by TiO2 photoredox catalysis
5 O-atom transfer in M/TiO2 photoredox catalysis 377
6 Concluding remarks 380
References 381
Photochemistry, 2017, 44, ix–xiii | xiii

Published on 01 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782626954-00001
Computational Aspects
Periodical Reports: Organic and
Published on 01 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782626954-00001 View Online
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Introduction and review of the year 2015

Angelo Albini* and Elisa Fasani
DOI: 10.1039/9781782626954-00003
Some aspects of photochemistry and its applications on the basis of papers published in
2015 are discussed.
1 Introduction
As in previous years, the primary aim of this introduction is that of
maintaining a common background in photochemistry, while this
science finds always new applications. A potentially negative aspect is
that the truly chemical aspects sometimes are less apparent than physical
on one hand and biological aspects on the other one. This is clearly
shown by the events that have taken place during 2015, declared the
official UNESCO International Year of Light and Light-Based Technolo-
gies.1 More precisely, the year has been devoted to photonics, that is ‘‘the
science and technology of generating, controlling, and detecting
photons, which are particles of light’’. Attention of the general public is
called to the many applications of photonics that characterize ‘‘daily life
from smartphones to laptops to the Internet to medical instruments to
lighting technology’’. It is concluded that the 21st century will depend as
much on photonics as the 20th century depended on electronics. In fact,
photons travel at the rate of light and this is obviously advantageous to
transmit signals in a photonic rather than in an electronic circuit. Fur-
thermore, optical interconnections cross each other with no interference,
again making the introduction of photonic connections preferable to
wired connections, particularly in integrated circuits, where the space
available is limited.2 Certainly, photochemistry is close to photonics (see
further below), but the approach chosen in 2015 celebrations has been
almost exclusively based on the physical aspects (and indeed the events
have organized by the leading institutions of physical sciences), with little
attention to the chemical aspects.3 Thus, as it frequently occurs, physics
is in forefront, while chemistry seems at most to have an ancillary
function. On the other hand, Kemsley in C&ENews recalled4 the strict
relation between chemistry and light by quoting Neckers, who had
remarked two decades ago that ‘‘the history of chemistry itself winds
around photochemistry and spectroscopy, because it was at this interface
that the nature of the chemical bond was discovered’’.5 In a commentary,
Bach further remarked that photochemistry has now established itself
as a key discipline, first of all able to build in a predictable and controlled
way otherwise non accessible compounds, in particular those with
strained and complex structures.3 Furthermore, although at present the
low price of energy discourages efforts to minimize energy consumption,
Dept. Chemistry, University of Pavia, 27100 Pavia, Italy.

E-mail: angelo.albini@unipv.it
Photochemistry, 2017, 44, 1–15 | 3

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new photocatalytic systems activated by solar light are expected to be

increasingly developed and to be able to activate processes not involving
any external energy supply. Appropriate photocatalysts for stereoselective
reactions are likewise being developed.3
A lively portrait of the personal and scientific aspects of Michael
Kasha’s work,6 a scientific paper by him7 and a collection of 18 papers
dedicated to him8 have been published in Photochemistry and Photo-
biology. What makes molecules exhibit such an unusual behavior upon

the absorption of a photon? In some cases it would seem that a magician
is operating and keeps the cards behinds his back. However, the
rationalization of photochemistry has rapidly advanced and the appli-
cation of light-induced reactions has enormously expanded. A recently
published book highlights some aspects of the history of photochemistry
and attempts to connect them with the present and future role of this
science.9
A list of the highlights published in the last volumes is available at the
end of this chapter.
2 Review of the year 2015

As usual, what follows is simply a personal choice of papers, from a very
large number that would have been possible. Although, as indicated
above, the year of light has been dominated by physical aspects, it has
also stimulated the publication of collections of chemistry papers. An
excellent example is the special issue of Angewandte Chemie (instalment
39). This contains an essay on the unique position of light as the fastest
way to transport both information and energy through the space. The
possibility to convert solar light into electrical and chemical energy, and
hence into mechanical energy, artificial light and valuable chemicals is
illustrated by Balzani and coll.10 Furthermore, some reviews on highly
topic subjects are quoted below.
Graphene based photocatalysts have been shown to be highly useful
for solar fuel generation.11 Activation of molecular switches by visible
light allow a more extensive application of such components.12 Advanced
spectroscopic methods initially developed for photophysical targets, are
being increasingly used for photochemical reactions. Thus, coherent
multidimensional electronic spectroscopy has been employed for reac-
tions such as ring opening and ring closing, cis–trans isomerization,
coherent vibrational wave-packet motion, radical ion formation, and
population relaxation. In a recent report this approach has been used for
new applications, such as the spiropyran–merocianine isomerization.13
Precision surface functionalization in polymers is rapidly developing, as
demonstrated by a review by Delaittre et al.14 A number (35) of exciting
communications follows in the same instalment, ranging from solar cells
to hydrogen and oxygen evolution from water, molecular machines,
the varied uses of luminescence, photochemical gene delivery, synthesis
via photochemical reactions, the generation of reactive intermediates,
the use of luminescence for various analytic purposes. In every case, the
peculiarities of photochemistry are of great advantage.
4 | Photochemistry, 2017, 44, 1–15

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As for the relation between photonics and photochemistry, one may

name a recent study of a system where large-area single layer graphene is
integrated into a nanostructured silicon substrate. It has been shown that
the interaction of light with graphene and substrate photonic crystals can
be classified in distinct regimes, viz plasmonic, photonic and free-space,
depending on the relation of the photonic crystal lattice constant and
the relevant modal wavelengths. An appropriate choice increases the
absorption of graphene in the infrared, and improves the performance of

modulators, filters, sensors and photodetectors utilizing silicon photonic
platforms.15
A technical note of general interest has been published by Bolton,16
who, pursuing earlier work, has highlighted that measurements of
photochemical reactions should always been referred to the photons
absorbed, not to the energy absorbed.
Thus, when using a polychromatic source the measurement should be
referred to the photon fluence over the wavelength interval chosen
([Fp,o(l)], Einstein m2), not to fluence ([Fo(l)], J m2). This is not always
done, particularly when measuring the action spectrum of a substance.
Thus, the fluence measured by a radiometer must be corrected by taking
into account, besides geometric factors for imperfect collimation of the
ray, an average function weighted by the spectral emittance of the lamp
over the interval chosen. In this way, the quantum yield FB(l) is calcu-
lated from the (initial) reaction rate of compound B through expression
(1), where V is the volume, wB(l), the fraction of photon absorbed by B,
E0p(l) the incident photon irradiance hitting the centre of the exposed
vessel and the other factors take into account the geometry of the
experiment, including reflected light (eqn (1)).

d½B V
FB ðlÞ ¼ (1)
dt t ¼ 0 Ep0 ðlÞ AH ðPFÞ½RFðlÞwB ðlÞ
Bolton further recalls that the general expression for FB simplifies in

two limiting cases, on one hand almost complete and constant absorp-
tion [absorbance(l)E1] and thus apparent zero order, on the other one
low absorption [absorbance(l)o0.02] and thus apparent first order. In a
more general frame, one may remember that already Bodenstein in 1929
had remarked that such ‘‘order’’ had nothing to do with ‘‘what is known
as the velocity constant of a chemical dark reaction; it is indeed nothing
but the factor for calculating the energy absorbed in terms of the quantity of
matter reacting. It is thus of course independent of external circumstances,
such as temperature, addenda (if any), catalytic agents and aggregate state’’.
Properly speaking, there is therefore no order of photochemical reactions,
as indeed it has been clearly pointed out more than a century ago.17
The mechanism of photochemical reaction is intrinsically complex and
requires that all viable paths are explored. From the Franck Condon point
the molecule evolves according to the topography of the surface. The
excess energy available may be exchanged with the environment and any
cleavage or rearrangement may occur on the same PES (adiabatic path) or
after decay to another PES (nonadiabatic path) and then through direct

Fig. 1 Schematic of the potential energy profiles of the three states S0 (blue), S1 (red), and
T1 (green). Cross and cone marks represent the MESX points between the singlet and
triplet states and the MECI points between S0 and S1, respectively. This is an unofficial
adaptation of an article that appeared in an ACS publication.18 ACS has not endorsed the
content of this adaptation or the context of its use.
and concerted paths. Despite the difficulty of the topic, advancement in

theory continues at an impressive pace and, importantly, a synergy
between theory and experiment develops. An efficient computational
method, called the global reaction route mapping (GRRM) strategy, has
been developed. This allows a theoretical exploration of ground- and
excited-state PESs, their crossing seams (minimal energy conical inter-
sections, MECI), minimal energy seams of crossing (MESX) and the
location of transition states in an automatic manner, with no need of
choosing a best-guess structure that would exclude unexpected molecular
arangements. In the case of formaldehyde, cleavage to CO þ H2, radical
cleavage to HCO þ H and a path involving detachment of a hydrogen
atom that migrates towards the other one (‘‘roaming’’, HCO H) have
been characterized for singlet and triplet states (Fig. 1).18
Solvation has a key importance in determining the course of photo-
chemical reactions. In particular, this applies to the solvation of starting
excited states and of intermediates in charge transfer processes in polar
solvents, a phenomenon that is usually discussed by assuming that the
effect of the electrostatic fields of the solvent molecules on the internal
electronic dynamics of the solute are perturbative and that the solvent–
solute coupling is mainly an electrostatic interaction between the constant
permanent dipoles of the solute and the solvent molecules. This model
appears to be inaccurate for important classes of compounds, such as
transition metal complexes, where solvent molecules are not just spectators
of the electron density redistribution occurring, but significantly modulate
it. Thus, an appropriate description of the dynamical changes of excited
states during the solvent response demands an advanced computational
method able to treat the solute and (at least) the closest solvent molecules
and including the nonperturbative treatment of the interaction occurring.19

Fig. 2 Nonadiabatic molecular dynamics of [Ru(bpy)3]21 in solution. Adapted with

permission from I. Tavernelli, Acc. Chem. Res., 2015, 48, 792. Copyright 2015 American
Chemical Society.
Theory is now able to offer an accurate characterization of the elec-

tronic structure of the ground and excited states and to describe the
molecular dynamics in its full unconstrained configuration space, and an
adequate representation of the interaction with the environment at
atomistic level (using either DFT or classical molecular mechanics). As an
example, the nonadiabatic molecular dynamics of [Ru(bpy)3]21 in solu-
tion has been explored, obtaining a series of ‘‘snapshots’’ that represent
the structure changes in the fs regime and predict possible trajectories.
The stabilization due to the action of all (3298) close-lying water mol-
ecules has been determined. The panels (Fig. 2) show the time series of
the relevant excited state energies corresponding to two representative
trajectories. Singlet excited states (seven in total) are represented by
dashed lines and triplet states (seven in total) by continuous thin lines.
The system hops from one to another PES (thick line); crossings between
singlet and triplet states and the largeness of spin orbit coupling (SOC,
white ¼ weak, gray ¼ medium and black ¼ large) are indicated.
Theory has been applied to rationalize (time-resolved) X-ray absorption
spectra, as well as to the interpretation of the ultrafast relaxation
dynamics of photoexcited dyes in solution and the design of specific laser
pulses (capable of inducing desired chemical reactions) using local
control theory.20
As is well known, the assumption that the nuclear and electronic wave
functions describing a molecular system can be determined independ-
ently (Born–Oppenheimer approximation) breaks down in many cases
due to the important contribution of nuclear–electronic (vibronic)
coupling. Spectroscopic experimental advances allows an unprecedented
time and spatial resolution. As an example, different variants of

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frequency-domain transient two-dimensional IR (T-2DIR) spectroscopy

have been used, based on a pulse sequence combining electronic and
vibrational excitations in the form of a UV-visible pump, a narrow band
(12 cm1) IR pump, and a broadband (400 cm1) IR probe. The appli-
cation of this approach to a donor–bridge–acceptor complex based on a
Pt(II) trans-acetylide design motif showed that the rate of electron transfer
is highly dependent on the amount of excess energy localized on the
bridge following electronic excitation. Indeed, it was possible to select-

ively perturb bridge-localized vibrational modes during charge separ-
ation, in such a way that the donor–acceptor charge separation path was
completely switched off, and all excess energy was redirected toward the
formation of a long-lived intraligand triplet state. A large change in the
photoproduct yield was observed only when the high-frequency bridging
CC stretching mode was operative, suggesting that it was possible to
perturb the electronic movement by stimulating a structural motion
along the reaction coordinate using IR light. Controlling the pathways
and efficiency of charge transfer certainly represents a breakthrough for
applications such as solar energy conversion and molecular electronics.21
A new approach for the manipulation of photochemical processes like
photoisomerization or photodissociation involves the use of short laser
pulses that are intense enough to reshape the potential energy surfaces.
Indeed, it has been demonstrated that chemical processes can be con-
trolled with strong laser fields, as are properties like the molecular
absorption spectrum, the state lifetimes, the quantum yields and the
velocity distributions in photodissociation processes.22
A way for characterizing non covalent interactions, such as hydrogen
bonding, is matrix spectroscopy. However, this approach find limitation,
e.g. because of a large concentration of 1 to 1 complexes that are other-
wise difficult to prepare (e.g. H2O O2), or the reaction with mobile
atoms occurring during annealing. The field has been reviewed and way
for characterizing unusual complexes have been suggested.23
Proton coupled electron transfer is an ubiquitous phenomenon in
chemistry and biology the underlying theory has been recently reviewed,
pointing out the limitations still present in the currently used methods.24
Supramolecular interactions in solution may guide the ensuing photo-
chemical reactions and the variety of possibilities that it offers continue to
be exploited. In a recent example, a cinnamoyl cation has been encapsu-
lated within a Ga4L612 (L ¼ diaminonaphthalenebiscatecholamide) tetra-
hedron. Under these conditions, the 2 þ 2 cycloaddition occurring in neat
solvent is no more observed, and rather a 1,3-shift occurs. This process
appears to involve electron transfer from the strongly donating ligand,
detachment and recombination of trimethylamine (Scheme 1).25
A linear polyethyleneimine, as the base, and a naphthol sulfonate,
which undergoes an enhancement of the acidity upon irradiation, have
been used as building blocks for a light-triggerable supramolecular
assembly (Scheme 2). A ionic bond between the sulfate anion and the
ammonium salt and a hydrogen bond between the phenol moiety and
the non protonated amine contribute to the formation of a complex
structure.26

Scheme 1
OH
H
N
n +
SO-3Na+
Scheme 2
The photochemistry in the troposphere continues to attract attention

because of the multitude of phenomena involved, such as inorganic
bulk photolysis and radical sources, transition metal ion (mainly iron)
complex photolysis, organic bulk photochemical reactions, interaction
between particles and interfaces, photoinduced transformation of
humic-like substances, photo-sensitized reactions in the bulk aqueous
phase.27,28
Further topics that have been comprehensively reviewed in the envir-
onmental field include the formation of urban particulate matter.29 The
atmospheric degradation of ozone depleting substances, their substitutes
and related compounds and the linkage between air quality and climate
change have been examined in detail.30,31
A rapidly growing topic has involved making synthetically significant
long known photochemical reactions. Thus, aliphatic amines are well
known electron transfer quenchers of excited states, innumerable times
used for kinetic studies.
However, in the last decades it has been demonstrated that photo-
sensitized oxidation (often by using visible light) and the ensuing
deprotonation can be developed into a valuable synthetic method for the
preparation of functionalized compound, including complex natural
products.32
The photochemistry of benzene and a number of its derivatives has
been discussed in terms of aromatic vs. antiaromatic character, con-
sidered as a sort of Dr Jekyll, Mr Hyde contrast. The reactions occurring
are viewed as arising from an attempt to alleviate the antiaromatic
character of the excited states.33 From the experimental point of view, a
matrix study in solid para-hydrogen has evidenced, besides the known

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H H
hν
h .. hν
h
+H +H
Scheme 3
*
S
S S
S
N N
N N
Ar N H H N Ar
Ar N H H N Ar
H H
O H H
O
OCH3
OCH3
*
*
S
S
N N S
S
Ar N HH N Ar N N
H H Ar N H H N Ar
O O
OCH3 H H
O
OCH3
OCH3
O
OCH3
Scheme 4
isomerization to benzvalene and Dewar benzene, hydrogen abstraction to

form a radical that further converts to hexatriene (Scheme 3).34
The 2 þ 2 photodimerization of cinnamates has been a major topic all
along the history of photochemistry. A recent study has evicenced that
carrying out the reaction in a flow system leads to a considerably larger
yield and further that using a phenylendiurea allows to obtain a mod-
erate diastereoselectivity (see the facial approach of the second molecule
of cinnamate in the scheme). Studies of this type should pave the way
for the next generation catalysts for highly diastereoselective and en-
antioselective intermolecular [2 þ 2] cycloadditions (Scheme 4).35
Biomolecule-compatible chemical bond-formation and bond-cleavage
reactions induced by visible light have been reviewed and include elec-
tron transfer involving oxidative as well as reductive quenching and
energy transfer promoted reactions.
The spatial and temporal resolution of light induced reactions com-
bined with the decreased damage with respect to UV irradiation makes
these reactions valuable for biomolecules labeling and manipulation.36
Solvent-less organic fluids have developed into a new class of func-
tional soft materials. Noteworthy, the key photochemical reactions of the
molecular systems, such as photoisomerization, energy/electron transfer,
photon upconversion and reversible dioxygen binding are conserved but,

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differently from solutions, they are not limited by solvent, solvent

polarity, the presence of oxygen etc., thus challenging the established and
accepted paradigms valid in solution and offering a ‘‘no worry’’ solution
for practical application.37
Photocontrollable capture and release of guest molecules from host
molecules, photoresponsive rotaxanes, catenanes, and pseudorotaxanes,
as well as photoresponsive supramolecular polymers and their assem-
blies and photoresponsive host–guest system on surfaces have been

reviewed.38
The biological activities in response to blue light involve three major
classes of flavin photosensors, viz. LOV (light-oxygen-voltage) domains,
BLUF (blue light sensor using FAD) proteins, and cryptochromes (CRYs).
Advances in the field have been reviewed and have identified the pho-
toexcitation of the flavin cofactor as the primary event that causes
changes in redox and protonation states and ultimately lead to protein
conformation remodel and molecular interactions.39
The photochemistry of transition metal complexes has been exploited
both for generating new complexes by ligand substitution (via LF states)
and to sensitize or catalyze chemical processes, e.g. by oxygen sensitiza-
tion (via MLCT states). As an example, a delicate tuning of the properties
has been achieved in Ru21 complexes by the appropriate modification of
the ligands.40
Photomedicinal applications are developing. An example is the use of
photosensitizing molecules for the inhibition of b-amiloid aggregation,
thus disclosing a way to rescue the post-synaptic toxicity of Alzheimer’s
disease in model systems.41
An informative approach in polymer photochemistry makes use of
polymers that have metal–metal bonds incorporated into their back-
bones. In this case, irradiation in the visible leads selectively to cleavage
of the metal–metal bond and then to degradation. The relatively simple
degradation paths contrasts with the complex phenomenon observed
with non metal containing polymers and allows a more detailed explor-
ation of the mechanism (e.g., by identifying two different environments
where radicals are formed causing a double degradation kinetics).42
The unique ability of spatial and temporal control photochemistry
offers makes contributions to medicinal chemistry more and more
important. New applications of photodynamic therapy based on oxidative
photocatalytic paths, promoted by titania nanoparticles, carbon nano-
materials (fullerenes, carbon nanotubes and graphene), liposomes and
polymeric nanoparticles.43 Among the most recently developed PDT
catalysts are metal complexes of the natural polyphenol curcumin.44 On
the other hand, the high rate of photochemical processes makes this
mode of reaction the preferred choice for understanding fast biological
processes, e.g. how do proteins work. A suitable method is time-
resolved X-ray solution scattering (TRXSS) that utilizes a pump-probe
scheme employing an optical pump pulse to initiate photoreactions of
proteins and an X-ray probe pulse to monitor ensuing structural changes.
Indeed, the technical advances in both ultrafast lasers and X-ray sources
make now possible to bring temporal resolution down to femtoseconds.

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As an example, in the case of hemoglobin the dynamics of complex al-

losteric transitions among transient intermediates has been unraveled by
applying structural refinement analysis based on rigid-body modeling. It
has been found that the allosteric transition of hemoglobin accompanies
the rotation of quaternary structure and the contraction between two
heme domains. This kind of studies suggest that TRXSS can be used to
probe the structural dynamics of various proteins and clarifying the
working mechanisms of their physiological operation. When combined

with femtosecond X-ray pulses generated from X-ray free electron lasers,
TRXSS will allow to explore ultrafast protein dynamics on sub-picosecond
time scales.45
In the field of photoinduced damage to DNA (compare this year Nobel
Price), an investigation on thymidine dimers has shown that, although
unconstrained, these compounds isomerizes quantitatively to the cor-
responding Dewar benzene (Scheme 5).46
The work on the photochemical activation of proteins by inserting
tetrazine derivatives has been further expanded. Thus, the tetrazine ring
has been introduced between two SH groups in protein thioredoxin (i.e.,
the chain has been stapled) and then the starting material has been
regenerated (unstapling) (Scheme 6).47
Multidentate lipoic acid (LA)-modified ligands have been used for
transferring ZnS-overcoated quantum dots to the aqueous phase. The
photoactive moiety is the deformed dithiolane present in the skeleton
that originates a characteristic band in the UV as well as various reac-
tions. Irradiation of the ligand alone, whether by a UV lamp or by using
solar light prior to mixing with hydrophobic QDs is sufficient to promote
ligand exchange. Ligation onto the QDs selectively favors oligomers,
presumably due to their higher coordination onto the metal-rich QD
surfaces. The use of mixed ligands allowed the preparation of reactive
nanocrystals. These are useful for cellular staining after coupling to
proteins and peptides further for developing fluorescent platforms for
the application in imaging and sensor design.48
An updated review on the photochemical fate of pharmaceuticals,
including a discussion of the factors that affect the photolability of drugs,
the choice of formulation in order to improve photostability and the
guidelines of photostability tests has been published.49
Among applications, a review of gel nail technologies may be
mentioned.50
O O
OH OH
HN N O HN N O
N hν N
O N O N
O O
HO O HO O
O OH O OH
X O X O
Scheme 5

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CO2H
N
O R O
H2N H H H
S N N R
R N N
H H
O
cysteine HS n SH
O R O N N
H H Cl Cl
N N R
R N N N N
H H
O
S n S
N N O R O
H H
N2 N N R
R N N
H H
O
hν n
N N
S S
N N
Scheme 6
3 Highlights in volumes 37 to 44
Azobenzene photoisomerization, 2017, 44, 294–321.
Cultural heritage, and photochemistry, 2011, 39, 256–284.
Cyclodextrins, photoresponsive, 2016, 43, 226–269.
Exiton fission, 2016, 43, 270–285.
Flow photochemistry, 2016, 43, 173–190.
Fluorescence Imaging, nanoscale, 2011, 39, 191–210.
Global artificial photosynthesis, 2017, 44, 259–282.
Industrial applications, of photochemistry, 2010, 38, 344–368.
Interfacial electronic processes, on the surface of nanostructured semi-
conductors, 2009, 37, 362–392.
History of photochemistry, IAPS, 2013, 41, 269–278.
History of photochemistry, EPA, 40, 197–229.
History of photochemistry, APA, 2012, 40, 230–244.
Human skin, photoprotection of, 2012, 40, 245–273.
Nitric oxide photorelease, 2013, 41, 302–318.
Nucleic acids, caged, 2013, 41, 319–341.
Organic solid-state luminescence, 2016, 43, 191–225.
OLEDs, 2009, 37, 393–406.
Photochromic, nanoparticles, 2011, 39, 211–227.
Photocatalyis for depollution, 2017, 44, 346–361.
Photolithography materials, 2010, 38, 369–387.
Photon–molecule coupling fields, 2011, 39, 228–255.
Photo-induced water oxidation, 2012, 40, 274–294.
Photoluminescence sensors, 2017, 44, 322–345.
Photo-oxygenation, 2010, 38, 307–329.
Polymerization, 2015, 42, 215–232.
Prebiotic atmosphere, 2013, 41, 342–359.

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Prebiotic photochemistry, 2010, 38, 330–343.

Proton transfer, in flavonols, 2012, 40, 295–322.
Reactive oxygen species, 2013, 41, 279–301.
Solar energy conversion, 2017, 44, 283–293.
Singlet oxygen, in biological media, 2015, 42, 233–278.
Solid-state, photoreactions, 2016, 43, 286–320 and 2016, 43, 321–329.
TiO2 photoredox catalysis, 2017, 44, 362–381.
UV spectra, calculated, 2015, 42, 197–214.
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Another random document with
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with Squire Thorneycroft’s pheasant-coops was too much for
hereditary proclivities. He stole eggs, sold them, was detected,
prosecuted, sentenced to a short term of imprisonment, and
disappeared. Miss Belmont herself met him on his discharge from
the jail gates, but he was not to be induced to return. The wild man
was in his brain, and off he had gone, with Parthian shots of
affection, in quest of fun. And for two years she had not seen him
again until to-night, when his scratch of red hair and beard—which
always looked as if he had just pulled his head out of a quickset—
suddenly blew into flame before her. And then there followed a shock
of distress.
“Jim! Why, what’s happened? What’s the matter with you?”
There was no need to specify. The man was obviously going off
his tramp—nearing the turn of the dark road. He was ghastly, and
constantly gave little spasmodic wrenching coughs during the minute
he stood beside her.
“Well,” he gasped, “I dunno. The rot has got into my stummick. I
be all touchwood inside like an old ellum.”
“Will you come and see me?”
“ ’Es. By’m-by.”
“Why not now? Where are you going to sleep?”
He grinned, and coughed, half suffocated, as he backed.
“I’ve got my plans, Missis. You—leave me alone.”
It did not sound gracious. One would not have guessed by it his
design, which was nothing less than a jolly throw against the devil in
the teeth of death. Miss Belmont, a little hurt, but more sad, got into
her fly and was driven home. Arrived there, she sat up an hour
contemplative. She was just preparing to go to bed in the grey dawn,
when she heard the garden-gate click and footsteps rapidly traverse
the path to the front door. Her heart seemed to stop. She stole
trembling into the hall. “Who’s there?” she demanded in a quavering
voice. The answer came, with a clearness which made her start,
through the letter-box.
“Me, Missis—Jim Hurley.”
Amazed, and a little embarrassed, she opened. The man burst,
almost fell in, and, staggering, recovered himself.
“ ’Ere!” he said, with eager manipulation trying to force something
upon her. “I’ve done ’er! I’ve got it for yer! Take it—make ’aste—
they’re arter me. It’s yourn as by rights, and she’s got to crow on the
wrong side of ’er woundy little mouth.”
But Miss Belmont, with instinctive repulsion, had put her hands
behind her back and retreated before him.
“Jim!” she said sickly. “What have you got? What do you mean? I’ll
take nothing from you.”
“O, go along!” he insisted. His cough was gone. He seemed
animated with a new masterfulness. “Ain’t I in the know? It’s yourn,
anyhow, and”—his eye closed in an ineffable rapture—“I done the
devil out of his own when I heard I be booked to go to him. He’ll pay
me, I reckon; but I don’t care. You take it. It’s your dooty as a good
woman.”
“No, no,” cried Miss Belmont, beating him away with her hands.
“Don’t let me even see it to know. How could you suppose such a
thing? Take it back while you’ve time.”
B’s 33 and 90 wore their list-footed boots; but Jim’s ear was a
practised one. Swiftly summoned, they had raced on his tracks from
the Assembly Rooms. He had known it, and had laboured merely to
keep his start of them by three minutes—two—one. Now, while their
sole was yet on the threshold, he darted into the dining-room and
was under the table at a dive. They had him out and handcuffed, of
course, in a jiffy; and then they stood to explain and expostulate.
“Well, you ain’t a cheeked one neither, Hurley! To run up here of all
places for cover! Don’t you mind him, Miss.” (She stood pale and
shivering. “The shock!” she had murmured confusedly.) “Why,” said
33, “the man was heard by plenty proposing of hisself to visit you;
and looked to your hold kindness to him to take and shelter, is
supposed.”
She found voice to ask: “What’s he done?”
“Done!” said 33. “Why, bless you, Miss! Treating of you as if you
was in collusion, ain’t I?” (She shivered.) “Why, he grabbed a jewel—
a gold button, as I understand—out o’ the buzzim o’ your own late
brother’s good lady as she was a-stepping into her broom, and
bolted with it. It’ll be on ’im now if we’re lucky.”
“You ain’t then, old cock,” said Jim, with a little hoarse laugh and
choke.
“Chuck it!” said 90, a saturnine man.
“That’s what I done, Kroojer,” said Jim. “You go and ’unt in the
bloomin’ ’edges if you don’t believe me.”
“It’s my duty to tell you,” said 33, “that whatever you says will be
took down in evidence agen you.”
“Not by you,” said Jim. “Why, you can’t spell.”
They carried him off dispassionately, with some rough, kindly
apologies to Miss Belmont for the trouble to which they had put her.
She locked and bolted the door when they were gone; mechanically
saw to the lamps, and went upstairs to bed in a sort of stunned
dream. So she committed herself to the sheets, and so, in a sort of
waking delirium, passed the remaining hours of slumber. She felt as
if the even tenor of her way, her stream of placid days, had been
suddenly dammed by a dead body, the self-destroyed corpse of her
own character. Sometimes she would start from a suffering negation
to feel B 90’s hand upon her shoulder. “What have I done—O! what
have I done?” she would moan in anguish; and B 90 would glower
from under his helmet like a passionless Rhadamanthus—
“What have you done? What but, like our second Henry, meanly,
by inference and innuendo, imposed upon your wretched tool the
responsibility for a deed which you dared not seek to compass by
the open processes of the law. Did you dispute the right ownership of
the button? Then why choose for your confidant an ex-thief and
poacher? No use to say you designed no harm. By the flower be
known the seed. Come along o’ me!”
She rose late, ate no breakfast, and sat awaiting, pinched and
grey, the inevitable ordeal. It opened, early enough, with the advent
of Mrs. John. The little widow came sailing in, with a face of floured
steel. When she saw, the edge of her tongue seemed to whet itself
on her lips. Miss Emma broke out at once in an unendurable cry—
“Inez! You can’t think I was a party to this!”
“Who said so, dear? Though the man was a protégé of yours, and
was known to have remained where he encountered me by your
instructions.”
“It is not true.”
“Isn’t it? Well, at least, the plan miscarried. Now, give me the
button, and I promise, to the best of my power, to hush the matter
up.”
“I haven’t got it, indeed; O, you must believe me! He told the
policeman himself that he had thrown it away while escaping.”
“Yes, yes. I give him credit for his loyalty to you. But, Emma—you
know I never put much faith in your sanctimoniousness. Don’t be a
fool, and drive me to extremities.”
“You can’t mean it. I blame my covetous heart. I envied you—I
admit it—this dear fetish of our family. But to think me capable of
such a wickedness! O, Inez!”
Then Mrs. John Belmont exploded. I muffle the report. It left Miss
Belmont flaccid and invertebrate, weakly sobbing that she would see
Hurley; would try to get him to identify the exact spot where he had
parted with the bauble; would move heaven and earth to make her
guiltless restitution. Yet all the time, remembering the scene of last
night, she must have known her promise vain. Jim had sought to
thrust no shadow of a fact upon her. He had not thrown the button
away. He alone knew where it now was; but would he so far play into
the hands of her enemy as to tell? She felt faint in the horror of this
doubt; and Mrs. John perceived the horror.
As for her, she was utterly hateful and incredulous. She had
friends, she screamed—one in particular—who would act, and
unmercifully, to see her righted. She hardly refrained from striking
her sister-in-law, as she rushed out in a storm of hysterics.
And at this point I was called in—by Miss Belmont, that is to say.
I found her utterly prostrated—within step of the brink of the final
collapse.
I coaxed her back, foot by foot; won the whole truth from her;
laughed her terrors to scorn, and staked her my professional credit
to have the matter put right, or on the way to right, by our next
meeting.
And I meant it, and was confident. For that very day—though of
this she did not know—I had officially ordered Jim Hurley’s removal
from the cell in which he had been lodged to the County Hospital.
The man was dying, that was the fact; and a fact which he had
known perfectly when he staked at one throw for an easy bed for
himself, and a repayment of his debt to his old benefactress.
He was ensconced in a little ward by himself, when I visited him
and sat down to my task. He cocked an eye at me from a red tangle,
and grinned.
“Now, Hurley,” I said, “I come straight from Miss Emma, by her
authority, to acquaint you with the results of your deed.”
“O!” he answered. “Hev the peelers been a-dirtyin’ of their pore
knees lookin’ for it in the ’edgerows? I ’opes as they found it.”
“You know they couldn’t. You’ve got it yourself.”
“S’elp me, I haven’t!”
Then I informed him, carefully and in detail, of the awful
miscarriage of his intentions. He was patently dumbfounded.
“Well, I’m blowed!” he whispered, quite amazed. “Well, I am
blowed!”
“You must undo this,” I said. “There’s only one way. Where is the
button?”
He gauged me profoundly a moment.
“On a ledge under the table,” he said. Then he thrust out a claw.
“Don’t you go lettin’ ’er ’ave it back,” he said, “or I’ll ’aunt you!”
I considered.
“You must undo what you’ve done,” I repeated. “Don’t you see?
Unless you can prove that it’s been in your possession all the time,
and is now, her character’s gone for ever. Mrs. John will see to that.”
He did not, professionally, lack wits. He understood perfectly.
“You’re ’er friend?” he asked.
I nodded.
“All right,” he said, “you get ’old of it private, and smuggle of it ’ere,
and I’ll manage the rest.”
“But, my good fellow! You’ve been overhauled, I suppose, and
pretty thoroughly. How can you convince—convince, you understand
—that you’ve kept the thing snug through it all?”
“You go and smuggle of it ’ere,” he repeated doggedly.
It needed only a very little manœuvring. I hurried back to Miss
Belmont’s, heard the lady was still confined to her room, forbade the
servant to report me, and claimed the privacy of the dining-room for
the purpose of writing a prescription. The moment I was alone, I
made an excited and perfectly undignified plunge under the table,
found the ledge (the thing, in auctioneer’s parlance, was a “capital
set,” in four leaves), and the button, which in a feverish ecstasy I
pocketed. Then, very well satisfied, I hurried back to Mr. Hurley.
I found him, even in that short interval, changed for the worse; so
much changed, that, in face of his condition, a certain sense of novel
vigour, an overweening confidence in my own importance which had
grown up, and lusty, in me during my return journey, seemed nothing
less than an indecency. However, curiously enough, this mood
began to ebb and sober from the very moment of my handing over
the pièce de conviction to its purloiner. He “palmed” it professionally,
cleared his throat, and took instant command of the occasion. “Now,”
he said, “tell ’em I’ve confessed to you, and let ’em all come.”
His confidence mastered the depression which had overtaken me.
I returned, with fair assurance, to Miss Belmont, who received my
news with a perfect rapture of relief. What she had suffered, poor
good woman, none but herself might know.
“Did he own to you where he had hidden it?” she asked. And
“Yes,” I could answer, perfectly truthfully.
By my advice, she prepared at once to go and fetch her sister-in-
law to the hospital—with a friend, if she desired it—that all might
witness to the details of the restitution.
In the meanwhile I myself paid a visit to the police station, and
thence returned to my post to await the arrival of my company.
It came in about an hour: Miss Belmont, tearfully expectant; Mrs.
John Belmont, shrill and incredulous; an immaculate tall gentleman,
Captain Naylor by name, whose chin was propped on a very high
collar, that he might perpetually sniff the incense of his own
superiority; and, lastly, and officially to the occasion, B 90.
I lost no time in conducting them to the bedside of the patient. He
had rallied wonderfully since our last encounter. He was sitting up
against his pillow, his red hair fluffed out like the aureole of a
dissipated angel, an expression on his face of a quite sanctimonious
relish. I fancy he even winked at me.
“Now, Hurley,” I said gravely, “as one on the threshold of the
grave” (which, nevertheless, I had my doubts about), “speak out and
tell the truth.”
He cleared his throat, and started at once in a loud voice, as if
repeating a lesson he had set himself—
“ ’Earing as ’ow my rash hact ’ave brought suspicion on a innercent
lady, I ’ereby makes affirmation of the fac’s. I stole the button, and ’id
it in my boot, where it is now.”
“No, it ain’t,” said B 90 suddenly. “Stow that.”
Mr. Hurley smiled pityingly.
“O, ain’t it, sir?” he said. “ ’Ow do you know?”
“Because I searched you myself,” said B 90 shortly.
“The patient, infinitely tolerant, waved his hand.
“ ’E searched me, ladies and gentlemen! Ho, lor! Look at ’im; I only
arsks that—look at ’im! Why, he doesn’t even know as there’s a smut
on his nose at this moment.” (B 90 hastily rubbed that organ, and
remembering himself, lapsed into stolidity once more.) Mr. Hurley
addressed him with exaggerated politeness—“Would you be so
good, sir, as to go and fetch my boots?”
B 90 thought profoundly, and officially, a minute; wheeled
suddenly, withdrew, and returned shortly with the articles, very
massive and muddy, which he laid on the counterpane before the
prisoner. The latter, cherishing the ineffable dénouement,
deliberately took and examined the left one, paused a moment,
smilingly canvassing his company, and then quickly, with an almost
imperceptible wrench and twirl, had unscrewed the heel bodily from
its place and held it out.
“ ’Ere!” he said; and, with his arm extended, sank back in an
invertebrate ecstasy upon his pillow.
The heel was pierced with a tiny compartment on its inner side,
and within the aperture lay the button.
They all saw it, but not as I, who, standing as I did at the bed-
head, and being something of an amateur conjurer myself, was
conscious in a flash of the rascal “passing” the trinket into its
receptacle even as he exposed it.
There followed an exclamation or two, and silence. Then Captain
Naylor said “Haw!” and Miss Belmont, with a gasp, turned a mild
reproachful gaze upon her sister-in-law. But Mrs. John had not the
grace to accept it. She gave a little vexed, covetous laugh, and
stepped forward. “Well,” she said to Miss Emma, “you must go
without it still, dear, it seems.” Then, coldly, to Hurley: “Give it me,
please.”
Now, so far so good; and, though I was enraged with, I could not
combat the decision. But truly I was not prepared for the upshot.
Jim, at Mrs. John’s first movement, had recovered possession of
the button.
“No, you don’t!” he said quite savagely. “I know all about it, and
’tain’t yourn by rights.”
“Jim, Jim,” cried Miss Belmont in great agitation; “it is hers, indeed;
please give it up. You don’t think what you make me suffer!”
But the man was black with a lowering determination.
“ ’Tain’t,” he said. “Keep off, you! I’ve not thrown agen the devil for
nothing. It’s goin’ to be Miss Emma’s or nobody’s.”
“Not mine,” cried the poor lady again. “I don’t want it. Not for
worlds. I wouldn’t take it now!”
And then Mrs. John Belmont, in one discordant explosion of fury,
gave away her case for ever.
“Insolent! Beyond endurance!” she shrieked, and whirled, with a
flaming face, upon her cavalier.
“Archibald! why do you stand grinning there? Why don’t you take it
from him?”
Thus prompted, Archibald, in great confusion, uttered an
inarticulate “Haw!” explained himself in a second and clearer one,
and strode threateningly towards the bed. Watching, with glittering
eyes, the advance, Jim, at the last moment, whipped the button into
his mouth and swallowed it!
*****
The case, as a pathological no less than as a criminological
curiosity, was unique. I will state a few particulars. The button lodged
in the pancreas, in which it was presently detected, comfortably
ensconced, by means of the Röntgen rays. And it is a fact that, from
the moment it settled there—never apparently (I use the emphasis
with a full sense of my responsibility) to be evicted—Mr. Hurley
began to recover, and from recovering to thrive—on anything.
Croton-oil—I give only one instance—was a very cream of
nourishment to him. Galvanic batteries but shook him into the
laughter which makes fat, but without stirring the button. It was
ridiculous to suggest an operation, though the point was long
considered. But in the meanwhile the button had continued piling up
over itself such impenetrable defences of adipose tissue that its very
locality had become conjectural. The question was dropped, only to
give rise to another. How could one any longer detain this luxuriant
man in hospital as an invalid? He was removed, therefore, beaming,
to the police court; received, for some inexplicable reason, a nominal
sentence, dating from the time of his arrest (everything, in fact, was
henceforward to prosper with him), and trundled himself out into the
world, where he disappeared. I have seen him occasionally since at
years-long intervals. He grows ever more sleek and portly, till the
shadows of the three dead Belmonts together would not suffice to
make him a pair of breeches. He has a colossal fortune; he is
respectable, and, of course, respected—a genial monster of
benevolence; and he never fails to remind me, when we meet, of the
time when I could pronounce his life not worth a button.
I have, can only have, one theory. The button, after many cross
adventures, “got home” at last—fatally for Mrs. John Belmont, who
fell into a vicious decline upon its loss, and, tenderly nursed by her
sister-in-law, departed this sphere in an uncertain year of her life.
And, unless the button itself comes to dissolve, Jim, I fear, is
immortal.
DOG TRUST
There was no reason why Richard Le Shore should not have made
a straightforward appeal for the hand of Miss Molly Tregarthen to her
papa. His credentials—of fortune, condition, and character—were
unexceptionable; the girl’s kind inclinations were confessed; the
father himself was an unexacting, indulgent, and ease-loving
Democritus. It was but a question of those two and of Mr. Dicky, their
favoured, their intimately favoured, guest.
There was no reason, and for the reason that the spirit of
Romance abhors reason; and that was why, without any reason,
Richard persuaded Mollinda to a clandestine engagement, to stolen
interviews, to a belief that love franked by authority was only the
skim-milk of human kindness. At least he chose to persuade himself
that he persuaded her, at all times when he could coax a certain
bewildered honesty in her eyes from dumbly questioning the
necessity of such tactics. In reality he loved that look, as the
sweetest earnest of a sweet quality. It was not her he studied to
deceive, but himself. Incurably eligible, he could never taste but
through make-believe, like the “Marchioness,” the sweet stimulant of
paternal interdiction.
At the end of the season he accompanied father and child to
“Tregarthen.” Here, you may be sure, he had not been twenty-four
hours without making choice for his love’s rendezvous of a little
wood which, approached through a tangled shrubbery, covered the
slopes which ran up from the back of the house to the high beeches
above.
Now Dicky would himself have allowed that everything (desirable)
had shone upon his suit save moonlight. That only, of all poetic
glamours, was yet lacking. And so he prevailed with Molly
Tregarthen to consent to a postprandial trysting among the trees, on
the very evening subsequent to that of his arrival.
He had no difficulty in escaping from papa, the imperturbable
sybarite. Seated in an open window over against shrouded lawns,
and a moon which rose like a bubble in liquid darkness; dreaming
betwixt decanter and cigar-case, papa would not have had his
luminous coma disturbed for anything less than a serious fire. So
Dicky left him, and going up alone to the woods, leaned his back
against a tree and smoked placidly.
It was very quiet, and fragrant, and beautiful there; and presently
the young gentleman lost himself somewhat in reflections. The
moonlight, penetrating the leaves, made of the sward a ghostly Tom
Tiddler’s Ground, which was all mottled with disks of faint gold. What
a soft, fine shower to fall upon the head of his Danae, as she should
come stealing up the alleys of light! Stealing—stealing! There was a
little thrill of ecstasy in the word. How wide her eyes would be, and
how would her bosom rise and fall in the breathlessness of some
phantom guilt!
Quite a nice little debauch of expectation, only—she did not come.
He waited on, desirous, impatient, hungry; and at last, it must be
said, cross. The touch of her hand, her lips, had never seemed so
indispensable to him; but he would not cheapen the virtues of his
own by carrying them back to market to a coquette. If she wanted
them, she knew where to find them. As for him, he was quite placid
and content; in proof of which he threw away his cigar-butt, and
began pacing with a noisy recklessness up and down.
That did not conjure her to him, but it seemed to evoke occasional
responsive rustlings, or the fancy of them, which would bring his
heart into his throat. They were only the stirring of woodland things, it
seemed. He got very angry, resentful, cruel in his thoughts. The
moon, the bubble of light, rose higher and higher—to the very
surface of night, where it floated a little, and then burst. At least, so it
seemed; for, all of a sudden, where it had been was a black cloud,
and drops began to patter on the leaves. Then Richard realized all in
a moment that his tryst had failed, that the moonlight was quenched,
and that it was beginning to rain. With a naughty word or two, he
braced up his loins, left the wood, and descended towards the
house.
As he went down, he heard the stable clock strike twelve. He
startled, and strode faster, faster, until he was fairly scuttling. It was
in vain. The Tregarthens were early people, and, even before he
reached the house, he knew that its every window was blind and
black. The whole family was abed, and he was shut out into the
night.
Twice, and vainly, he made the entire round of the building,
seeking for any loophole to enter by. The rain by then was pelting,
yet he did not dare raise a clatter on the front door, for fear he should
be pistolled from a window. The inmates knew nothing of his
absence, and the Squire held, for a Democritus, strong views on the
subject of undisturbed repose.
Coming to the porch again from his second circuit, and putting a
hand to rest upon one of its columns, he jumped, as if he had
touched a charged battery, to see a figure standing motionless in the
shadow.
“Hullo!” he gasped, in the sudden shock; then rallying, muttered
out in a fury at his own weakness, “Who the devil are you?”
Some faint gleam of moonshine, weltering through the flood,
enlightened him even as he spoke.
“Why, if it ain’t the butler!” he said.
It was the butler. The figure admitted it in a curt word. Le Shore
had already, on the occasions of his two dinners at “Tregarthen,”
noticed this man, and had taken a quite violent exception in his own
conscience to his manner and appearance. He thought he had never
known a leading trust bestowed upon one whose face so expressed
the very moral of acquisitiveness, whose conduct was marked by
such an uncouth inurbanity. Here, if there was any value in biology,
was Bill Sikes in broadcloth.
The tone of the fellow’s answer grated confoundedly on him—he
hardly knew why.
“Are you locked out, like me?” he said, putting violence on himself
to speak civilly.
“Yes, sir,” answered the man; “but for a better reason.”
“What do you mean by that?”
The creature was as thick-set as a bull. He could have broken this
elegant like a stick across his knee. He commanded the situation,
massive and impassive, from his own standpoint.
“Look’ee here, sir,” he said, speaking through a grip of little strong
teeth in a square jaw, “I’m going to tell you what I mean. I’m going to
make no bones about it. You meet Miss Molly fair and open, or you
don’t meet her at all. Do I know what I’m saying? Yes, I do know. She
didn’t come to you to-night—because why? Because I interdicted of
her. That’s it. She might have thought better—or worse—of it, bein’ a
woman, and soft; and that’s why I laid by, watchin’ that no harm
should come of it if she did. But she was wise, and didn’t. I seen you
all the time in the wood, and I tell you this. A word’s got to be
enough. You meet her by fair means, or not at all. Never mind the
Squire there. It’s me that says it. If she admires you, nine stun ten—
which there’s no accounting for tastes—I’m not the one to make
difficulties. But you go like a honest man and ask her straight of her
father. That’s the ticket, and don’t you make no error. Don’t you
flatter your fancy no more with randy-voos in the moonshine. Why, if
ever there’s a light calc’lated to lead a gentleman astray, it’s that. I
say it, and I know. You go to the girl’s father; and, after, we’ll see
what we’ll see.”
He cleared his throat with a quarrelling sound, and came out of the
shadow.
“Now,” said he, “here’s a house you’ve been locked out of, and
you want to get in without disturbin’ of the family—is that it? Very
well, sir; now we understand everything; and step this way, if you
please.”
Almost with the words, he had clawed himself up to a window-sill
of the ground-floor, and was very softly manipulating the sash. Mr. Le
Shore, voiceless, hardly gasping, stood, just conscious of himself, in
an absolute rigor of fury and astonishment. He was “stound,” as
Spenser would have put it. Presently he snapped his eyelids, and
woke aware that Mr. Hissey, standing on the grass, was loweringly
inviting him to enter by way of an opened window. With a shock, he
recovered his nerves of motion, and, stalking to the place, vaulted
stiffly to the sill, and sat thereon like a cavalryman.
“I’ve just a word or two for you, before I—I avail myself of this,” he
said. “You’ve been gadding, and got drunk, I suppose; and this is
your way of trying to make capital of a belated guest. Perhaps the
means you’ve adopted ’ll appear less excellent to you in the sober
morning. As to your method of entry, there’s nothing in it
incompatible with the character I’d already formed of you. But that,
and your quite outrageous insolence, will be made matters for your
master’s consideration to-morrow. I mention this in honour, before I
——” He waved his hand towards the room.
“I could twist your neck with two fingers, here and now,” said the
man.
“Exactly,” said Dicky. “And that’s why I decline to make use of this
window except on the plain understanding.”
The butler cleared his throat again, even with a strange note of
approval in the unseemly sound.
“Mayhap you’ll do,” he said. “Now go to bed, and don’t forgit your
prayers in your disappyntment.”
Mr. Le Shore hissed-in a breath, as though the rain had suddenly
become boiling spray, then tiptoed rigidly to his room.
The opening of the window, framed with creepers, whose shadows

shrank or dilated softly in the muslin curtains, gave on to a soothful
picture of lawn and herbaceous border which, withdrawing to cool
caverns of leafiness under a remote cedar tree, seemed to gather
themselves to a head of prettiest expression in the person of little
Miss Mollinda swinging there in a hammock. Within, at the luncheon-
table, Tregarthen poured himself out a glass of Madeira with a hand
so limp and white in appearance that one would have thought it
incapable of the task of poising the heavy decanter. Here was
delicate seeming only, however. The perpetual sybarite reads an
incorruptible constitution. The white hand held the bottle horizontal,
as steady as a rock, during the minute the indolent, good-humoured
eyes of its owner were directed to those of his visitor.
“My dear good Richard, the man is a burglar.”
He laughed at the other’s expression, filled his glass, sipped at it,
and, hooking his thumbs in his arm-holes, lolled back in his chair.
“I am not justified in the confidence, perhaps. I don’t know.
Anyhow, it is the short way out of a fatiguing explanation. The man is
a burglar—not figuratively, but actually, by breeding, education,
profession—appelez-le comme vous voudrez. He has the stamp of it
so distinctly on him that one need not ask him to produce his
skeleton key.”
“Then I have nothing more to say.”
“Ah! the devil take the honest thief! Your obvious grievance forces
me to the explanation, after all. My dear boy, I imply nothing, argue
from no premises but such as a long experience of this capital,
troublesome fellow suggest to me. Speaking from these (I may be
wrong), I should conclude that he is somehow in process of
safeguarding, as he thinks, the interests of my girl, to whom he is
quite romantically attached. Honestly, I don’t know to whom I would
rather commit them. Poor motherless child!”
He had, it seemed, no thought of himself as pledged to the task.
‘Himself’ should be a fair one-man’s burden.
“He is very right to be attached to Miss Tregarthen,” muttered Le
Shore dryly, and a little sullenly.
“He is very right indeed,” answered his host; “righter (pardon the
solecism) than you might think. In this excellent rogue is provided
such an illustration of the ‘harmony not understood’ of discords, as
circumstance has ever given to an ennuyé world. The dear creature
has decided to stultify his every instinct for a sentiment. It is the most
interesting psychological phenomenon you can imagine. He has
conceded nothing of his nature but the means to its practical
achievement. Conceive a wolf of his own determination forgoing
blood. Such is this dear, admirable brute. Perfossor parietum
nascitur. He cannot change his spots. To this day, I think, he will
always of choice enter by a window rather than a door; to this day he
regards plate with a most melting look. But for all that, I think I may
swear that at the present moment the tally of my spoons is to an
ounce what it was when he took service with me eighteen years
ago.”
“Your servant for eighteen years!”
“My servant—titularly: in reality, my mentor, my vizier. Dog Trust is
a rather sweetly demoralizing acquisition. He takes the burden of
conscience from one—steals it, in this case, I may say. But then,
after all, he may use his vicegerency to ends so far beyond the moral
grasp of the master he represents, as more than to vindicate that
master in his withdrawal from the vexatious problems of duty.
Through sheer force of affection this admirable George has
mastered himself, and bettered his master in the parental ethics.”
“Indeed, sir?” (Mr. Dicky spoke very dryly.) “And how does Miss
Tregarthen approve the viziership?”
“As she loves and respects the vizier, Richard. I do not think she
would willingly run counter to his dictates, which, by the way, he
never imposes in a manner to alarm one’s pride. Ah! did you catch
that whiff of scabious? There is a bush of it under the window there.
It always seems to me to embody in itself the whole warmth and
fragrance of summer. My dear fellow, your eyes are relentless
inquisitors. No more wine? Well, I suppose I shall have to tell you
how it came about.”
He sighed, drained his glass, laughed slightly, and smoothed a
stray wisp of hair from his forehead.
“Once,” he said—“it was particularly disagreeable to a person of
my temperament—I was called upon by Fate to suffer the ugly and
sordid experience of a conflagration in my house. You, who are also
a little inclined, I believe, to create for yourself an atmosphere of
romance, to regard the great world only as a quarry, from which to
gather materials most exquisite and most apt to the enrichment of
the hermitage, which it is your design and your delight to build apart
for your soul, will appreciate what were my feelings upon seeing my
fairy fabric doomed to destruction, to positive annihilation, by the
flames. I have never spoken to you of the disaster before. You will
know that I do so now under the mere stress of fitness, as a means
to your proper understanding of George Hissey’s conduct. The
recollection is painful and horrible to a degree.
“The alarm, the escape, the catastrophe were all accomplished in
the dark hours of a winter’s morning. My dear wife (she sleeps,
awaiting my coming, in Elysium) followed me down the stairs and out
of the house at a short interval. She found me devoted to a frantic
endeavour to secure from destruction such of my poor treasures as
were accessible—few enough, alas! though the tears I shed should
have quenched the hate of a Hecla. What had I done with her child?
she cried to me—with our sweet Molly, our little three-year-old babe?
Richard, I felt as stunned as if she, the pretty, gentle mother, had
struck me across the mouth. I could only stare and gasp. She uttered
a heart-shaking scream, and turned to where the servants stood
huddled together in the garden. They were all there, and the two
nurses were crying and moaning and accusing one another. My God!
mad with terror, they had deserted their charge to perish by itself in
the burning house!”
He paused. “Don’t go on, sir, if it distresses you,” said Le Shore
quietly.
“No,” answered Tregarthen. “Like the Ancient Mariner, I must be
quit of it now I have begun. But I will have a glass of wine.”
He poured himself out one, daintily as to the drop on the decanter
lip.
“There followed a fearful scene,” he said. “It was all I could do to
prevent my angel from precipitating herself through the blazing
doorway. The whole building seemed by now a furnace—no
possibility of further salvage from those priceless accumulations—
not, of course, that at such a pass it was to be thought of. I mingled
my tears with my wife’s. I offered half my fortune to any one of the
crowd who would save, and a large reward to any one who would
venture to save, our darling. But it was in vain; and in my heart I
knew it.
“Now, in this extremity of despair, a sudden roar went up from a
hundred throats, and passed on the instant. Richard, a man,
shedding flakes of fire as Venus cast her birth-slough of spray, had
emerged overhead from the sea of flame, and in his arms was our
child. Who was he? Whence did he come? No one knew. Our house
was isolated. The engine from the neighbouring town had not
arrived. He was not a friend, nor a neighbour, nor an employé. It was
only evident that innocence had somehow evolved its champion.
“We watched, stricken, as castaways watch the glimmer of a
remote sail. The figure had broken its way through the skylight in the
roof, only, it might be, to symbolize in the burden it bore the leaping
of a little flame heavenward. The situation was the very sublimity of
tragedy. Beneath those two the roof, sown with a very garden of fire,
dropped at a sickening angle.
“Suddenly, shutting, as it seemed, upon his charge, the man rolled
himself up like a hedgehog, and came bowling down the slope. It
was a terrible and gasping moment. His body, as it whirled, reeled
out a hiss of sparks. The next instant it had bounded over the edge,
and plunged among the smoking bushes beneath.
“They broke his fall; but it was the verandah awning which in the
first instance saved his life—his, and our dear devoted cherub’s. But
he had never once, through all the stunning vertigo of his descent,
failed to shield the little body which his own enwrapped.
“Now, my dear Richard, comes the strange part. When I was
sufficiently recovered to seek our preserver, I found him sitting
handcuffed, in charge of the local policeman. He was very white,
with two or three ribs broken; but he took it all unconcerned, as being
in the day’s, or the night’s, business. Who was he? Well, here is the
explanation. He was a renowned cracksman, as I think they call it,
who had been operating in the neighbourhood for some weeks past
—the hero of many a shuddering midnight adventure. Without doubt
he had taken his toll of my ‘crib,’ had not circumstance dropped him
ripe into the gaping mouth of the law. He had entered, and was
actually at work, when fire cut the ground, as it were, from under his
feet. Almost before, intensely occupied, he realized his position,
escape by the lower rooms was debarred him. Was ever situation so
dramatic? It was to be compared only with that of a huntsman who,
entering some cave to steal bear cubs, turns to find the dam blocking
his outlet. Still, Mr. Hissey might have escaped, and without
detection, by dropping to the lawn from a back window, had his
burglarious ears not pricked suddenly to the wailing of a child.
“My dear fellow, need I explain further? The child he risked his
own life to rescue was our—I may almost say, at this day, was his
Molly. It was the strangest thing. I did not, as a consequence, quite
see my way to holding him altogether absolved; but my dear,
emotional partner was of a different opinion. We had quite a little
scene about it. In the end she prevailed—with the whole boiling of
the law, too; and the man was sentenced to come up for judgment if
called upon. Then straightway, and by his own desire, she took the
disinfected burglar into her service. It was one of those daring
psychologic essays which may once and again be carried to a
successful issue through the white-hot faith of the experimenter; but
which must not be given authority as a precedent. My wife fairly
redeemed this burglar, by committing, without hesitation, to his loyal
trust the little waif of fire whose destinies he had earned the right to a
voice in. From that day to this, I will say, he has never abused the
faith we reposed in him. On her deathbed, my dear girl (pardon me a
moment, Le Shore), my dear wife most solemnly recommitted her
child to his care. I did not complain, I do not complain now. I, who
make no pretence of competence in the paternal rôle, thank the gods
only for my vizier, who is quite willing to accord me the ritual of
authority, while taking its practical business on his own shoulders.
With a man of my temperament it works; and I am satisfied, if Molly
gives me her respect, that she should give Hissey her duty.”
He ceased, with a little smiling sigh, and lifted a cigarette from a
silver case which lay on the table. Le Shore regarded him steadily.
“Mr. Tregarthen,” said he, “Molly and I are engaged. I should have
told you before.”
The older man did not pause in the act of lighting his cigarette; but
enjoyed an inhalation of smoke before he answered—
“I plead guilty to a suspicion, Richard. I am confident our vizier has
been safeguarding the proprieties. You remember what I said to you
in his excuse just now?”
“I have your sanction, sir?”
“Certainly, as a form. But I am afraid, from the practical side, you
will have to satisfy that same inquisitor.”
“Mr. George Hissey,” said Dicky, “I have papa’s authority to marry

Miss Molly. Now, with your permission, I will relieve you of your
trust.”
“Dicky!” cried the girl reproachfully; and she put her kind young
arms round the ex-burglar’s neck.
“Unless,” said Le Shore, “you care to transfer that to my ‘crib,’ Mr.
Hissey.”
The butler cleared his throat.
“Well, I do care, sir,” he said, hoarsely, nevertheless, “since you
seen fit to cut that moonshinin’ lay, And as to cribs——”
“Molly” said Richard, “there’s papa calling.”
A MARTYR TO CONSCIENCE
“I have nothing to do with your scruples,” said the magistrate; “the
law is the law, and I am here to administer it.”
Mr. Plumley licked his hand, and stolidly smoothing down his black
hair with it, answered, as if at a distance, being a well-fed, unctuous
man, “too full for sound and foam,” “I’m a conscientious objector.”
“Passive resister!” corrected a friend, a little eager man, among
the audience near him.
“Eh?” said Mr. Plumley immovably, and without a glance in the
direction of the voice, “I said passive resister, didn’t I?”
“Whether you said it or not,” answered the magistrate sharply, “you
look it. I make an order against you for the amount.”
“As man to man——” began Mr. Plumley.
“Not in the least,” said the magistrate; “as debtor to creditor. Stand
down.”
“I shan’t pay it,” said Mr. Plumley, preparing to obey.
“If you say another word, I’ll commit you for contempt,” said the
magistrate. “Stand down, sir!”
Mr. Plumley stood down, with an unspeakable expression—it
might have been of satisfaction—on his huge, stolid face. Arrived at
the floor, he beckoned his little friend to follow him, and heavily left
the court.
He steered—the other acting as his rudder, as it were, and
keeping his position behind—straight for his own domestic shrine,
hight Primrose Villa, semi-detached. It was a beautiful little home for
a widower unencumbered, calculated, like an india-rubber collar, to
afford the maximum of display at a minimum of cost in washing. The
doorsteps were laid with a flaming pattern in tiles; red-aspinalled
flower pots, embellished with little dull glazed shrubs, stood on the
lowest window-sill; the bell-knob was of handsome porcelain, painted
with the gaudiest flowers in miniature. Within, too, it was all furnished
on a like hard principle of lustre—red and yellow oilcloth in the hall,
with marbled paper to match; earthenware-panned mahogany hat-

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Photochemistry Volume 44 1st Edition

Paradigms in Green Chemistry and Technology 1st Edition

Studies in Natural Products Chemistry Volume 44 1st

Halliday Resnick s Fundamentals of Physics 12e Volume 2

Inside Company Valuation 1st Edition Angelo Corelli

Trading Places Awesome Office Romance 1st Edition

Flight Mechanics Theory of Flight Paths 1st Edition

Rabaul 1943-44: Reducing Japan's Great Island Fortress

Management: A Practical Introduction 7th Edition Angelo

A Specialist Periodical Report

Takashi Tsuno, Nihon University, Japan

& The Royal Society of Chemistry 2017

All rights reserved

Published by The Royal Society of Chemistry,

Registered Charity Number 207890

For further information see our web site at www.rsc.org

Printed in the United Kingdom by CPI Group (UK) Ltd, Croydon,

Volume 44 follows the pattern of previous issues from Volume 39 onwards,

Angelo Albini and Elisa Fasani

Photochemistry, 2017, 44, vii–vii | vii

considered process Zm-Zn, let the

Periodical Reports: Organic and Computational Aspects

Introduction and review of the year 2015 3

Advances in computational photochemistry and chemiluminescence 16

Photochemistry, 2017, 44, ix–xiii | ix

2 Development of methods and theory 17

Alkenes, alkynes, dienes, polyenes 61

Photochemistry of aromatic compounds 132

Organic aspects. Oxygen-containing functions 188

x | Photochemistry, 2017, 44, ix–xiii

5 Photoreactions of multichromoporic systems: dicarbonyl 198

Function containing a heteroatom diﬀerent from oxygen 224

Global artificial photosynthesis: transition from 263

Solar energy conversion using iron polypyridyl type 285

Photochemistry, 2017, 44, ix–xiii | xi

Azobenzene photoisomerization: an old reaction for activating 296

3 Threading and dethrading of a pseudorotaxane driven by 299

Versatile silicon nanoparticles with potential uses as 324

Photochemical reactions in sunlit surface waters: influence 348

xii | Photochemistry, 2017, 44, ix–xiii

4 Possible impacts of long-term changes 358

Oxygen-atom transfer in titanium dioxide photoredox catalysis for 364

Photochemistry, 2017, 44, ix–xiii | xiii

Introduction and review of the year 2015

2015 are discussed.

Dept. Chemistry, University of Pavia, 27100 Pavia, Italy.

Photochemistry, 2017, 44, 1–15 | 3

new photocatalytic systems activated by solar light are expected to be

biology. What makes molecules exhibit such an unusual behavior upon

2 Review of the year 2015

4 | Photochemistry, 2017, 44, 1–15

As for the relation between photonics and photochemistry, one may

absorption of graphene in the infrared, and improves the performance of

Bolton further recalls that the general expression for FB simplifies in

Photochemistry, 2017, 44, 1–15 | 5

and concerted paths. Despite the diﬃculty of the topic, advancement in

6 | Photochemistry, 2017, 44, 1–15

Fig. 2 Nonadiabatic molecular dynamics of [Ru(bpy)3]21 in solution. Adapted with

Theory is now able to oﬀer an accurate characterization of the elec-

Photochemistry, 2017, 44, 1–15 | 7

frequency-domain transient two-dimensional IR (T-2DIR) spectroscopy

bridge following electronic excitation. Indeed, it was possible to select-

8 | Photochemistry, 2017, 44, 1–15