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VOLUME FIFTY
ADVANCES IN
PHYSICAL ORGANIC
CHEMISTRY
ADVISORY BOARD
M. Abe Hiroshima University, Japan

J. Klinman University of California, Berkeley, USA
F. Nome Federal University of Santa Catarina, Brazil
S. Otto University of Groningen, The Netherlands
C. Perrin University of California, San Diego, USA
J. Richard University at Buffalo, State University of New York, USA
P. Scrimin University of Padova, Italy
C. Wentrup University of Queensland, Australia
VOLUME FIFTY
ADVANCES IN
PHYSICAL ORGANIC
CHEMISTRY
Edited by
IAN H. WILLIAMS
Department of Chemistry,
University of Bath,
Bath, United Kingdom
NICHOLAS H. WILLIAMS
Department of Chemistry,
University of Sheffield,
Sheffield, United Kingdom
Amsterdam • Boston • Heidelberg • London

New York • Oxford • Paris • San Diego
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CONTRIBUTORS
S. Caprasecca
University of Pisa, Pisa, Italy
S. Di Stefano
Sapienza Università di Roma, Roma, Italy
G. Ercolani
Università di Roma Tor Vergata, Roma, Italy
Marc M. Greenberg
Johns Hopkins University, Baltimore, MD, United States
C.A. Guido
C.A. Hunter
University of Cambridge, Cambridge, United Kingdom
B. Mennucci
P. Motloch
University of Cambridge, Cambridge, United Kingdom
vii j
PREFACE
The 50th volume of Advances in Physical Organic Chemistry exemplifies the

field by providing incisive analysis on fundamental principles, rigorous
analysis of important biological phenomena that can be understood in
quantitative molecular terms and describing the interplay of computational
and experimental understanding of the chemical environment.
Effective molarities, the subject of two of the most highly cited contri-
butions to this series (by Tony Kirby in Vol. 17 and Luigi Mandolini in
Vol. 22), is returned to in the context of equilibria and weak interactions
in two chapters in this volume. Stefano Di Stefano and Gianfranco Ercolani
describe the concept of equilibrium-effective molarity in rigorous detail to
create a precise method for analysing the balance between cyclization and
linear polymerization. The ideas expressed here allow a wide range of
complex systems, such as dynamic combinatorial chemistry and self-
assembly, to be explained quantitatively through a common thread of anal-
ysis. The contributions to cooperative binding are then dissected to highlight
the crucial role of chelation in quantifying multivalency and stability of
molecular assemblies. This clarity in exposing the fundamental principles
behind complicated behaviour is continued in the chapter by Petr Motloch
and Chris Hunter, where the experimental data for supramolecular complex
formation are described and collated to illustrate the enormous difference in
values that can be achieved in covalent or noncovalent systems.
The stability of nucleic acids is vital to the integrity of genetic informa-
tion, and oxidative damage through radical species is a major factor in
compromising this information. Marc Greenberg describes how independ-
ently generating and studying the reactive species believed to be involved in
damaging nucleic acids has both resolved mechanistic controversies and led
to the discovery of new reactive processes. In his comprehensive review, he
powerfully illustrates how this classical physical organic technique can be
used to illuminate the behaviour of complex biological systems.
Complex supramolecular systems may also be studied by modern com-
putational methods, which have become useful interpretative and predictive
tools. Benedetta Menucci, Stefano Caprasecca and Ciro Guido review envi-
ronmental effects on properties and processes involving molecular probes in
solution or in biomacromolecular systems. The capabilities of such techni-
ques are demonstrated with a particular focus on simulations of spectroscopic
properties, which allow for direct comparison between calculated and
ix j
x Preface
experimental data and which permit analysis of the relationship between the
nuclear and electronic structure of the probe and its interactions with the
environment.
As the current Editors of Advances in Physical Organic Chemistry, we are
pleased to note the milestone passed with publication of volume 50. We
acknowledge the contributions of previous Editors and of all past and
present authors, and we renew our commitment for this series to continue
to be the definitive resource for authoritative reviews of work in physical
organic chemistry.
NICHOLAS H. WILLIAMS
IAN H. WILLIAMS
CHAPTER ONE
Equilibrium Effective Molarity As

a Key Concept in Ring-Chain
Equilibria, Dynamic
Combinatorial Chemistry,
Cooperativity and Self-assembly
S. Di Stefano*, 1 and G. Ercolanix, 1
*Sapienza Universita di Roma, Roma, Italy
x
Universita di Roma Tor Vergata, Roma, Italy
1
Corresponding authors: E-mail: stefano.distefano@uniroma1.it; ercolani@uniroma2.it
Contents
1. Introduction 2
2. Effective Molarity 3
3. Equilibrium Macrocylizations 10
3.1 Ring-Chain Equilibria 10
3.2 RingeRing Equilibria 15
3.3 Self-Assembly Macrocyclizations 17
4. Dynamic Combinatorial Chemistry 22
4.1 One-Monomer Dynamic Libraries 25
4.1.1 Dynamic Libraries From Transesterification Reaction 25
4.1.2 Dynamic Libraries From Olefin Metathesis Reaction 27
4.1.3 Dynamic Libraries From Transacetalation (Formal Metathesis) Reaction 29
4.1.4 Dynamic Libraries From Imine Metathesis 31
4.1.5 Dynamic Libraries From Hydrogen Bonding Interactions (Supramolecular DLs) 34
4.2 Two-Monomer Dynamic Libraries 36
4.3 Templated Dynamic Libraries 39
5. Cooperativity and Self-Assembly 42
5.1 Statistical Factors and Microscopic Constants 43
5.1.1 The Symmetry Number Method 44
5.1.2 The Direct Counting Method 46
5.2 Allosteric Cooperativity 48
5.3 Chelate Effect and Chelate Cooperativity 51
5.4 Interannular Cooperativity 56
5.5 Stability of an Assembly 59
6. Conclusion 67
References 68
Advances in Physical Organic Chemistry, Volume 50

© 2016 Elsevier Ltd.
j
ISSN 0065-3160
http://dx.doi.org/10.1016/bs.apoc.2016.07.002 All rights reserved. 1
2 S. Di Stefano and G. Ercolani
Abstract
The growing interest towards cyclizations under thermodynamic control is witnessed
by the large number of papers dedicated to ring-chain equilibria, dynamic combinato-
rial chemistry, cooperativity and self-assembly. No doubt, in all these topics, cyclic or
polycyclic molecular entities play a dominant role. In this chapter, the concept of equi-
librium effective molarity (EM), which gives a quantification of the ease of formation of a
cyclic compound, is presented as a fil rouge that allows a quantitative analysis of the
phenomenology related to the title matters. Initially, the physicochemical bases on
which the concept of EM is founded are described together with connections to the
JacobsoneStockmayer theory on intramolecular reactions in linear systems. Distribu-
tions of the species in ring-chain and ringering systems in terms of the EM, and con-
ditions to obtain a selected macrocycle (self-assembly macrocyclization) are discussed.
The EM concept is further applied to dynamic combinatorial libraries based on a single
monomer, and two different monomers. The case of a templated dynamic library is also
considered. Finally, after a due discussion of the methods for the evaluation of statistical
factors, the phenomenon of cooperativity in binding processes is analysed by dissect-
ing it into three contributions, namely, allosteric, chelate and interannular cooperativity.
It is shown that the chelate effect, as measured by the EM, plays a key role for the quan-
tifications of the latter two contributions, which are crucial for the assessment of multi-
valency, and the stability of molecular assemblies.
1. INTRODUCTION
A cyclization or, more generally, the formation of any covalent or
noncovalent intramolecular bond always occurs in competition with the
corresponding intermolecular process. Thus, a measure of the propensity
for cyclization must take into account the relative driving force of the
two processes. This is customarily done by considering the ratio of the cor-
responding rate constants for kinetically controlled reactions (Fig. 1A and
Eq. [1]), or the ratio of the corresponding equilibrium constants for reactions
occurring under thermodynamic control (Fig. 1B and Eq. [2]):
kintra
EMk ¼ [1]
k
Kintra
EMe ¼ [2]
K
If the concentration is expressed in mol L1, the two ratios have units of
molarity and correspond to the definition of kinetic effective molarity (EMk)
and equilibrium effective molarity (EMe), respectively. The term effective
concentration, which is synonymous with effective molarity, is also in use,
Equilibrium Effective Molarity 3
Figure 1 (A) An irreversible intramolecular reaction with its intermolecular counterpart.

(B) A reversible intramolecular reaction with its intermolecular counterpart.
especially among polymer chemists. Kinetic effective molarity has played a

key role in physical organic chemistry for the understanding of proximity
effects, neighbouring group participation, intramolecular and supramolecu-
lar catalysis.1e6 Equilibrium effective molarity, although has a long history
that can be traced back to the seminal paper of Jacobson and Stockmayer
on ring-chain equilibria,7 only recently has found widespread usage. No
doubt, this has been due in large part to the development of supramolecular
chemistry, which is based on weak reversible interactions, such as hydrogen
bonding, metaleligand interactions, coulombic interactions and so on.
Accordingly, the focus of the present chapter is on equilibrium effective
molarity, starting from the basic theory and its role in ring-chain equilibria
up to the more recent applications in dynamic combinatorial chemistry,
cooperativity and self-assembly. For convenience, we henceforth drop the
subscript e in the symbol EM and just say effective molarity (EM) to
mean the equilibrium effective molarity.
2. EFFECTIVE MOLARITY
Consider the solution of a chain AeB where eA and eB are two
reactive end groups capable of reacting reversibly with each other so as to
form a new bond AB (Fig. 2).
If the reacting groups belong to the same chain, the reaction is intramo-
lecular and leads to the formation of a ring, whereas if the two groups belong
to different chains, the reaction is intermolecular and leads to the formation
of a dimeric chain. The probability that the reaction is intramolecular is
proportional to Kintra, whereas the probability that the reaction occurs
intermolecularly is proportional to K [AeB]. From these simple consider-
ations, two important conclusions can be drawn: an intramolecular process
is always favoured by an increasing dilution, and the EM represents the
limiting concentration of the chain AeB below which the intramolecular
process is more favoured than its intermolecular counterpart. Thus, for a
given concentration, the larger the EM the easier the cyclization.
Figure 2 Schematic representation of a chain molecule in solution illustrating the

competition between an intramolecular and an intermolecular process.
According to Eq. [2], the constant Kintra is the product of K, representing

the inherent chemical reactivity of end groups, and EM, representing a
connection factor that accounts for the fact that the two reactive groups
are connected to each other. Thus, the EM depends on the structure of
the chain connecting the two end groups, and is largely independent of
the nature of functional groups and solvent. This is generally true with
two caveats: (1) for short chains, where directional correlations between
end groups in the intramolecular process can be significant, a distinction
should be made between covalent and noncovalent bondeforming reac-
tions; (2) for very long chains, the effect of the excluded volume, causing
the ends of a polymer chain in solution to be on average further apart
than they would be in the ideal case, affects the EM in a way that is depen-
dent on the nature of the solvent. These two points are further discussed in
the following.
If Kintra and K are defined in terms of activities rather than concentra-
tions, the EM can be easily related to the corresponding enthalpic and
entropic components:3e6
0
DHintra
0 DH 0 DSintra DS 0
EM ¼ exp exp ¼ EMH EMS [3]
RT R
In most of the cases, the enthalpic contribution coincides with the strain
energy of the ring; thus for small and medium rings with significant strain
energies, EMH can be significantly lower than 1, whereas when a large
strainless ring is formed, EMH is equal to 1 and the EM coincides with the
entropic component. There are cases in which the chain undergoing ring
closure is more strained than the ring being formed,1 which translates into
EMH >> 1 because of strain relief, but these cases represent the exception
rather than the rule. It goes without saying that the enthalpic component
determines the dependence of the EM on temperature; the EM increases
on increasing temperature if the ring is strained whereas it is independent
of temperature for strainless rings. At present, the strain energy of a ring
can be easily evaluated by theoretical methods such as molecular mechanics
and quantum mechanical methods, whereas the evaluation of the entropic
contribution is more challenging.8 As a rule of thumb, an intramolecular re-
action has a large entropic advantage over the corresponding intermolecular
reaction, since the former is unimolecular whereas the latter is bimolecular.
This advantage is partially dissipated on increasing the number of rotatable
bonds in the linear precursor of the ring since torsional motion is more
restricted in a cyclic structure than in a linear chain. Page and Jencks faced
the question of the maximum entropic advantage for an intramolecular pro-
cess.9e13 They reasoned that when two molecules condense to form one,
three degrees of translational freedom and three degrees of overall rotational
freedom of the reactants are converted into six new degrees of vibrational
freedom of the adduct. Vibrations have a lower entropy content than
translations and rotations; the higher their frequency, the lower the entropy
content. Thus, an intermolecular reaction occurs with an entropy loss that
depends on the strength of the bond being formed. If the new bond is
covalent (tight) the frequencies of the new vibrations are high and the
entropy loss is large. In contrast if the new bond is noncovalent (loose)
the entropy loss is smaller. In the absence of solvent effects, the entropy
change for covalent bonds is about 150 J K1 mol1 at a standard state
of 1 mol L1, whereas in the case of weaker bonds such as hydrogen bonds,
it is about 40 J K1 mol1 at the same standard state. These changes do
not occur in intramolecular reactions and thus these entropic factors can
be translated into maximum EM values of 108 mol L1 and 102 mol L1
for intramolecular reactions involving the formation of tight and loose
bonds, respectively. There are other explanations to the high EM values
found in some intramolecular reactions, such as Koshland’s ‘orbital steer-
ing’,14 Flory’s ‘favourable directional correlation’,15 Menger’s ‘spatiotem-
poral hypothesis’16 and Bruice’s ‘near-attack conformers’,17 in which a
variable combination of entropic and enthalpic effects is invoked. Owing
to its relevance to enzyme catalysis, the question has been the object of
heated debates and is far from being settled, but the entropy theory of Page
and Jencks appears to be in substantial agreement with experimental data.
Indeed, as far as ‘covalent’ EMS values are concerned, Mandolini found
that the behaviour of short chains with up to seven single bonds is well
described by linear Eq. [4], where y is the number of skeleton single bonds
in the chain, and the entropy is given in J K1mol1 3,18:
DSintra
0
DS0 ¼ 126 16:7y [4]
The intercept of Eq. [4] refers to an intramolecular reaction taking place
with no conformational entropy loss, that is, DSintra
0 ¼ 0 when y ¼ 0. As a
result, the negative of the intercept corresponds to the loss of entropy
suffered by bimolecular reactions leading to covalent bonds, that is,
DS0 ¼ 126 J K1 mol1. This value translates to EMS ¼ exp(126/R) ¼
3.6 106 mol L1, that is not too far from the value of 108 mol L1
predicted by Page and Jencks. The slope of Eq. [4] implies a drop of
16.7 J K1 mol1 per added single bond, which indicates a nearly complete
freezing of the internal rotation of a CeC bond, which has been estimated as
contributing 19e20 J K1 mol1.19e21
As to noncovalent interactions, the picture is less clear. Based on a limited
number of experimental data regarding H-bonded supramolecular
complexes, Hunter and coworkers obtained a relationship for short chains
between the EM and the number of single bonds in the connecting chain22:
3
EMz10y 2 [5]
Since the noncovalent systems investigated were designed to be
strainless, the EM values obtained by Eq. [5] should be essentially dictated
by entropy. Eq. [5] gives a maximum value of EM ¼ 10 mol L1 for
y ¼ 1. Unfortunately, the value of EM for y ¼ 0 cannot be obtained by
extrapolation of Eq. [5] but, for a perfectly rigid system, it is reasonable to
expect a value consistent with the Page and Jencks upper limit of
102 mol L1. From Eq. [5] one can estimate an average entropy loss per
added single bond of about 3.8 J K1 mol1 in the range 1 y 7, much
lower than that obtained for covalent systems, and indicating that in
noncovalent systems internal rotations are far from being frozen. This loss
of entropy amounts to a free energy cost of 1.1 kJ mol1 at 25 C. The
fact that other studies have estimated that in supramolecular complexes
the cost of restricting torsional motion is in the range 0.5e5 kJ mol1 per
rotor casts doubts on the general applicability of Eq. [5].23e31 However,
from the available body of experimental data, two conclusions can be drawn:
(1) effective molarities for noncovalent processes are significantly lower than
those observed for covalent processes; (2) the decrease in EM due to the
introduction of conformational flexibility is generally lower than in covalent
systems, indicating that the losses in binding affinity caused by poor
preorganization of the ligands are limited. The group of Hunter carried
out extensive investigations aimed at clarifying the role of solvent and
intrinsic H-bond strength of the linkers on supramolecular effective molar-
ities.23e25,32e37 As expected, EM values are independent of solvent and
intrinsic H-bond strength, but depend on supramolecular architecture and
geometric complementarity. As to solvent effects, there are however, anom-
alies; for example, the phosphonate diesterephenol H-bond showed a
marked dependence of the EM on solvent which was related to the steric
bulk of this group.34e37
In contrast with short chains, the behaviour of long chains, say longer
than 25e30 skeletal bonds, is well established, both theoretically and exper-
imentally. The theory was set forward by Kuhn,38 and further refined by
Jacobson and Stockmayer (JS),7 and Flory and coworkers.15,39,40 In order
to illustrate the theory, which is commonly known as the JS cyclization the-
ory, it is useful to introduce, as JS did, the molar cyclization constant.7,15
This is the equilibrium constant for the reaction shown in Eq. [6], where
a linear oligomer Miþj, formed by i þ j monomer units, splits into a cyclic
oligomer Ci and a linear oligomer Mj. The molar cyclization constant turns
out to be identical to the effective molarity for a series of ring oligomers
(EMi). Indeed, it can be easily verified that the definition given in Eq. [2]
and Fig. 1B corresponds to the effective molarity of the cyclic monomer
EM1 (the value of j is irrelevant, provided that the reactivity of end groups
is independent of the length of the chain, as it is commonly agreed):
EMi
Miþj # Ci þ Mj [6]
The basic tenet of the theory is that the EM corresponds to the local
concentration of one chain end experienced by the other end of the
same chain. With reference to Fig. 2, the end group eA prefers to react
with the group eB of the same chain if the local eB concentration,
EM, is larger than its bulk concentration, [AeB]. This approximation holds
only if the chain is long and flexible enough that the end group eB is free
to assume any possible orientation with respect to the end group eA; in
Flory’s words, if the chain is long enough to suppress directional
correlations.15 Indeed for short chains this approximation fails as clearly

illustrated by EM values that exceed any realistic physical concentration.
It is interesting to note that the EM, as local concentration, is independent
of the covalent or noncovalent nature of the reaction. This fact together
with experimental evidences suggest that favourable directional correla-
tions in short chains are more important for covalent interactions than non-
covalent ones, in line with the notion that supramolecular systems are more
loosely linked.
If we let the end eA of the chain be the origin of a coordinate system,
the concentration of the end eB at the point (x,y,z) is given by the
probability density of the end-to-end vector r, W(r), expressed in
molecules per dm3. The local concentration of eB experienced by eA
corresponds to the density of the end-to-end vector when the two chain
ends are coincident, that is, W(0). Accordingly, the EM of an i-meric
ring is given by Eq. [7], where NA is the Avogadro constant and sCi is
the symmetry number of the i-meric ring that is expressed by the product
s$i, s being either 1 in the case of rings of the type c-(AeB)i, or 2 in the
case of rings of the type c-(AeA)i (for a discussion of symmetry numbers
and statistical factors, see Section 5.1). The factor i corresponds to the
number of skeletal bonds that can be opened in the cyclic Ci in the reverse
reaction of Eq. [6]:
Wi ð0Þ
EMi ¼ [7]
NA sCi
Long, flexible chains adopt random coil conformations in solution and in
the melt, and thus the density distribution function W(r) is Gaussian. As a
result, Wi (0) is given by Eq. [8], where <r2> is the mean-square end-to-
end distance of the i-meric chain:
3=2
3
Wi ð0Þ ¼ [8]
2phr 2 i
For long, flexible chains, the mean-square end-to-end distance unper-
turbed by excluded volume effects can be calculated by Eq. [9] where y is
the number of skeletal bond of length l per repeating unit, and CN is the
characteristic ratio in the limit of high chain length which measures the stiff-
ness of a chain15,39,40:
2
r ¼ CN yl 2 i [9]
Substituting Eq. [9] into Eq. [8], and Eq. [8] into Eq. [7], Eq. [10] is
obtained, where the factor B, equal to the effective molarity of the mono-
mer, is given by Eq. [11]:
EMi ¼ Bi5=2 [10]

3=2
1 3
B¼ [11]
NA s 2pCN yl 2
Eq. [10] points out that for a series of i-meric rings, the equilibrium
effective molarity varies inversely with the 5/2 power of the oligomerization
degree. The factor i5/2 may be regarded as the product of i3/2 and i1.
The former relates to the probability that a Gaussian chain of i repeating
units has its ends coincident and the latter to the number of equivalent bonds
available for the ring-opening of a cyclic i-mer. The factor B, equal to EM1,
in contrast, only depends on the Gaussian behaviour of the chain and varies
inversely with the 3/2 power of the number of its skeletal bonds, as stated by
Eq. [11].
It is useful to remark on the approximations underlying the JS theory: (1)
the thermodynamic reactivity of end groups is independent of the length of
the chain; (2) all of the i-meric rings are strainless and thus EMi values are
purely entropic; (3) angle correlations are neglected leading to Eq. [7]; (4)
the probability density of the end-to-end vector, W(r), is Gaussian, which
leads to Eq. [8]; (5) the mean square end-to-end distance is linear in the
number of skeletal bonds as stated by Eq. [9]. All of these approximations
must fail for insufficiently long chains.15 The last approximation also fails
when the effect of the excluded volume is important. This effect causing
chain expansion is expected to be maximal for very long chains at high
dilutions in good solvents.40 Although the deviation from Eq. [10] due to
excluded volume effects can be eliminated by the judicious selection of
solvent and temperature (the so-called theta conditions),40 the effect of a
good solvent in fact is merely to make the exponent appearing in Eq. [10]
slightly less than 5/2 for the higher members of the series. As a result,
for very long chain the assumption that the EM is independent of the nature
of solvent no longer holds.
Mandolini obtained a spectacular panoramic view of the entropic effec-
tive molarity by displaying in a semi-logarithmic plot the EM from Eq. [4] in
the range 0 y 7, the EM from Eq. [11] with CN ¼ 8,
l ¼ 1.54 109 dm, and s ¼ 1, in the range 12 y 100, and filling the
short gap in the range 7 y 12 with an arc of circle tangent to the two
curves.3,18 The obtained data, shown in Fig. 3 and Table 1, fit a large
body of experimental data regarding polymethylenic and polyoxaethylenic
chains in common organic solvents. They have been used both to predict
with good accuracy a large number of EM values related to the formation
of strainless rings4 and to evaluate the catalytic efficiency of supramolecular
catalysts.5,6 The dashed curve in Fig. 3, which is the continuation of the JS
plot, is in good agreement with the equation proposed by Hunter for non-
covalent interactions (Eq. [5]) suggesting that directional correlations for
short chains are less relevant in supramolecular complexes.
3. EQUILIBRIUM MACROCYLIZATIONS
3.1 Ring-Chain Equilibria
JS presented a general theory of ring-chain equilibria as early as 1950.7
Their theory has been extensively used by polymer chemists to describe the
cyclic populations of linear polymeric equilibrates in concentrated solutions
and in the melt,40e42 but for many years the theory has been largely ignored
Figure 3 Semi-logarithmic plot of entropic effective molarity, EMS, versus number of

rotatable bonds, y, in the unsymmetrical bifunctional chain undergoing cyclization.
Solid and dashed lines describe covalent and noncovalent interactions, respectively
(see text for details).
Table 1 Entropic effective molarities and entropy changes in the

cyclization of unsymmetrical bifunctional chains as a function of
the number of skeletal single bonds (y)
DS0intra DS0
1
y EMS (mol L ) (J K1 mol1)
0 3.6 106 126

1 4.8 105 109
2 6.4 104 92.0
3 8.6 103 75.3
4 1.1 103 58.6
5 1.5 102 41.8
6 2.0 101 25.1
7 2.7 8.4
8 8.0 101 1.9
9 4.0 101 7.6
10 2.6 101 11.2
11 1.9 101 13.8
12 1.6 101 15.3
14 1.3 101 17.2
16 1.0 101 18.9
20 7.4 102 21.6
25 5.3 102 24.4
30 4.0 102 26.7
40 2.6 102 30.3
50 1.9 102 33.1
75 1.0 102 38.1
100 6.6 103 41.7
outside the field of polymer chemistry. With the development of macrocy-

clic chemistry, there has been an increasing interest in the behaviour of mix-
tures of oligomeric macrocycles under thermodynamic control, and the JS
theory was restated to make it more easily understandable and popular,43
to the point that it can now be considered one of the prominent theories
in supramolecular chemistry.44
To illustrate the theory, let us consider a chain with two functional
groups eA and eB capable of reacting with each other in a reversible addi-
tion reaction. Let us assume, as usual, that the intermolecular equilibrium
constant for the addition reaction of end groups eA and eB, K, is indepen-
dent of the length of the chain to which they are attached. Initially we
consider only the process of linear polymerization. As a result, if [M1]0 is
the initial concentration of monomer, when the equilibrium is reached,
Scheme 1 Chainechain equilibria for an isodesmic polymerization.
the system is constituted of a mixture of all the possible i-meric chains Mi

with i ranging from 1 to N (Scheme 1).
Accordingly, the mass balance is given by Eq. [12].
X
N
½M1 0 ¼ i½Mi [12]
i¼1
The overall equilibrium between end groups eA and eB is illustrated in

Scheme 2 where x is the extent of reaction measured by the fraction of
reacted end groups.
From Scheme 2 and Eq. [12], Eq. [13] is easily obtained:
X
N
x
i½Mi ¼ [13]
i¼1 Kð1 xÞ2
The extent of reaction, x, and its complement, (1 e x), represent the
probability that an end group is either reacted or unreacted, respectively.
An i-meric chain, Mi, is constituted by (i 1) reacted groups, and two
unreacted chain ends; thus the concentration of Mi at equilibrium is given
by the product xi1(1 e x)2$[M1]0. Taking into account the expression
for [M1]0 given by Eqs [12] and [13], Eq. [14] is obtained:
xi
½Mi ¼ [14]
K
Now if we allow each chain to undergo a reversible ring closure, the final
mixture will consist of a virtually infinite number of oligomeric rings, Ci,
and chains, Mi, in equilibrium with each other (Scheme 3).
The mass balance is now given by Eq. [15], showing that the initial
monomer is partitioned among rings and chains:
X
N X
N
½M1 0 ¼ i½Ci þ i½Mi [15]
i¼1 i¼1
Scheme 2 Equilibrium between end groups eA and eB in the process of isodesmic

polymerization.
Scheme 3 Ring-chain equilibria in a macrocyclization under thermodynamic control.
Eqs [13] and [14] are still valid with the caveat that x now represents the
extent of reaction in the chain fraction only. Considering the definition of
EMi given in Eq. [6] and taking into account Eq. [14], Eq. [16] is easily
obtained:
½Ci ¼ EMi xi [16]
Now, by assuming that the smallest cyclic i-mers, say from i ¼ 1 to n, are
strained, whereas the larger ones follow the JS theory Eq. [10], Eq. [15] is
transformed into:
X
n X
N
1 x
½M1 0 ¼ iEMi xi þ B i3=2 xi þ [17]
i¼1 i¼nþ1
K ð1 xÞ2
In the presence of strained rings, B represents the EM of the hypothetical

strain-free monomeric ring. Eqs [14], [16] and [17] are the fundamental
equations to describe a system that can simultaneously polymerize and
cyclize under thermodynamic control. The fraction of reacted end groups
in the linear fraction, x, is obtained by solving Eq. [17] numerically.43
Knowing x, the concentration of each linear and cyclic oligomer can be
calculated by Eqs [14] and [16], respectively. It is interesting to note that
on increasing the initial monomer concentration, x tends to 1. Under this
condition, the cyclic fraction, represented by the sum of the two series on
the right-hand side of Eq. [17], is convergent.7,43,45 In the absence of
strained rings (n ¼ 0), the cyclic fraction converges to 2.612 B mol L1.45
This result translates into the physical fact that only a finite number of
monomer units can be hosted in the cyclic fraction. In contrast, under the
same conditions the chain fraction, represented by the third term in Eq.
[17], is divergent, meaning that it can host, in principle, an infinite number
of monomer units. Furthermore, if K in Eq. [17] is large enough, say larger
than 105 mol1 L,43 there will be a well-defined critical concentration (CC)
of monomer, below which only rings will be present at equilibrium and
above which the excess monomer is converted into chains only. The limit
value of the CC is calculated by Eq. [17], by taking x w 1 and neglecting the

third term in its right-hand side (the chain fraction). The phenomenon of
the CC is illustrated in Fig. 4 together with the distribution of the first
five i-meric rings for a typical ring-chain equilibration. The curves were
calculated by assuming K ¼ 106 mol1 L, EM1 ¼ 0.010 mol L1,
EM2 ¼ 0.015 mol L1, whereas from C3 onwards the EM values were
calculated according to JS theory, that is, by Eq. [10] with
B ¼ 0.20 mol L1. These values are typical for the cyclization of a bifunc-
tional chain leading to strained 10-membered C1 and 20-membered C2
rings, respectively.43 As evidenced by Eq. [16] and Fig. 4, for x tending to
1 the ring concentrations tend to a limit value, equal to their corresponding
EM, thus allowing their easy experimental determination.
Well-studied examples of covalent ring-chain equilibria include
macrocyclic dimethylsiloxanes,39,46 formals,47,48 amides,49 esters,43,50e54 ole-
55e57
fins, and even purely inorganic systems, such as liquid sulphur.58 In actual
years, there has been an increasing interest in supramolecular polymerizations
which very often give rise to ring-chain equilibria.44,59 For these systems the
presence and magnitude of the critical concentration is often investigated by
viscosimetry. Indeed, at low concentrations, low-viscosity cyclic species are
Figure 4 Equilibrium concentrations of C1eC5 rings and chain fraction showing the
phenomenon of critical concentration. Curves were calculated for K ¼ 106 mol1 L,
EM1 ¼ 0.010 mol L1, EM2 ¼ 0.015 mol L1 and B ¼ 0.20 mol L1 (see text for details).
formed, whereas at high concentrations, chain extension leads to high

viscosity values. As a result, a sharp increase of viscosity is indicative of the
CC. Hydrogen bonding has been a major theme for ring-chain equilibrium
studies because of its fixed stoichiometry, directionality and simplicity.60e70
Other noncovalent bonds that have been investigated in supramolecular
ring-chain equilibria are hosteguest interactions,71e76 metaleligand interac-
tions77e84 and even proteineprotein interactions.85e87
3.2 RingeRing Equilibria

It is possible to envisage a process of ring-expanding polymerization by
reversible ring fusion without the intermediacy of linear chains (Scheme 4).
A system obeying such an equilibration scheme has been proposed by
Grubbs and coworkers.88e91 It is the ring-expansion metathesis polymeriza-
tion of cyclic olefins catalysed by a cyclic ruthenium complex. The synthesis
of cyclic polyoctenamers using cis-cyclooctene as the monomer is illustrated
in Scheme 5.
The cyclic ruthenium complex 1 catalyses the polymerization of cis-
cyclooctene through the formation of a transient macrocyclic complex 2
Scheme 4 Ringering equilibria in a macrocyclization under thermodynamic control.
Scheme 5 Mechanism for the ring-expansion metathesis polymerization of cis-

cyclooctene catalysed by the cyclic ruthenium complex 1.
in which both ends of the growing polymer chain remain attached to the
Ru centre. Subsequent intramolecular chain transfer later releases cyclic
polymer 3 from the intermediate complex. The reaction has practical
importance since by this method, Grubbs obtained pure cyclic polyocte-
namers with a number average degree of polymerization of the order of
104.88 To appreciate this figure, one must consider that in ring-chain com-
petitions the final concentrations of large cyclic i-mers decrease as i5/2,
implying that the number average degree of polymerization of the cyclic
fraction is c. 2.92
The features of a system governed by ringering equilibria have been dis-
cussed by Ercolani and Di Stefano.92 For such a system the mass balance is
given by Eq. [18] which can be obtained from Eq. [17] by dropping the
term corresponding to the chain fraction:
X
n X
N
½M1 0 ¼ iEMi x þ B
i
i3=2 xi [18]
i¼1 i¼nþ1
Now [M1]0 corresponds to the initial cyclic monomer concentration and

x can be regarded as an empirical extent of reaction obtainable by solving
Eq. [18] numerically. Eq. [16] continues to hold for all of the rings, whereas
Eq. [10] holds for the large ring oligomers following the JS theory (i > n). As
has been pointed out earlier, the sum of the two series on the right-hand side
of Eq. [18] is convergent for x values in the range [0,1]. The limit to which
the right-hand side of Eq. [18] converges for x ¼ 1 is the critical concentra-
tion (CC). Thus in the range 0 x 1, the distribution of cyclic oligomers
is exactly the same as that which would be obtained in a reversible ring-
chain competition in the limit of an infinite value for the equilibrium
constant of linear propagation. The puzzling question is: what happens
when the initial monomer concentration is larger than the CC in a ring-
expanding polymerization where the formation of linear polymer is not
allowed? Indeed, the equilibrium condition expressed by Eq. [18] is not
compatible with an initial monomer concentration larger than the CC. It
was argued that any real mixture of cyclic oligomers cannot be in a state
of thermodynamic equilibrium above the CC.92 The logical consequence
of this statement is that the series of consecutive equilibria of ring fusion
shown in Scheme 4 must be completely shifted to the right, that is, towards
the formation of a single giant ring molecule. To support this view, it was
demonstrated that the Gibbs energy of the ring distribution at the CC is
equal to the Gibbs energy of a single ring incorporating all the monomer
units.92 Thus, at the CC, the collapse of the system into a single giant ring
molecule is consistent with the continuity of the Gibbs energy function.
Although above the CC, a single infinite ring constitutes the thermodynam-
ically stable state, its actual formation is not warranted. Indeed its formation
would require an ideal system, completely free of linear contaminants, and
an infinite time of reaction. In fact, the expected behaviour of the system
above the CC would be analogous to that of an irreversible step-growth
linear polymerization whose hypothetical outcome, given an infinite
amount of time, is the formation of a single chain molecule incorporating
all of the available monomeric units.
3.3 Self-Assembly Macrocyclizations

Self-assembly consists of the spontaneous generation of a well-defined,
discrete supramolecular architecture from a given set of components under
thermodynamic equilibration.93 While the selective formation of a specific
linear oligomer in solution is not achievable,94 there are innumerable exam-
ples in the literature of the self-assembly of discrete oligomeric macrocycles
(two-dimensional assemblies).77,95e100 The physical basis of self-assembly
macrocyclization has been discussed by Ercolani as a specific case of the
more general problem of ring-chain equilibria.101 The process of self-
assembly of a specific cyclic n-mer occurs in competition with the formation
of other cyclic oligomers and with the process of linear polymerization. Self-
assembly takes place when the monomer has a structure preorganized or
predisposed in such a way that formation of all the cyclic oligomers except
the n-mer is prevented by strain or, in the case of high-order cyclic
oligomers, by unfavourable entropic effects. This is equivalent to saying
that the EM of a specific cyclic n-mer is much larger than that of the other
cyclic oligomers. This condition is the first condition to be met for selective
self-assembly, and when it holds, Scheme 3 reduces to Scheme 6.
As a result, taking into account Eqs [13] and [16], the mass balance is
given by Eq. [19] and the yield of the self-assembling macrocycle
(Cn% ¼ 100n[Cn]/[M1]0) by Eq. [20]:
" #
x
½M1 0 ¼ EMn nx þ n
[19]
KEMn ð1 xÞ2
" #1
1
Cn % ¼ 100 1 þ [20]
nKEMn ð1 xÞ2 xn1
Scheme 6 Equilibrium scheme for the self-assembly of a macrocyclic n-mer.
Eqs [19] and [20] can be used to build plots of Cn% versus [M1]0/EMn for
a given n that only depend on the product K$EMn. This is done by
compiling a list of x values in the range 0 x < 1 and then calculating,
for a given value of the product K$EMn, the couple of [M1]0/EMn and
Cn% values corresponding to each x, by Eqs [19] and [20], respectively.
Such plots are shown, by way of illustration, in Fig. 5 for the cases n ¼ 4
and K$EMn ¼ 10, 25, 100 and 1000, respectively. It is apparent from
Fig. 5 that the driving force for self-assembly is given by the product K$EMn;
a large value of K$EMn is beneficial not only to the yield of the self-
assembling macrocycle but also to the amplitude of the concentration range
over which self-assembly takes place.
Figure 5 Plots of the yield of a self-assembled cyclic tetramer versus [M1]0/EM4. The
four curves from the bottom up, refer to K$EM4 ¼ 10, 25, 100 and 1000, respectively.
Fig. 5 shows that the plots of the yield of the assembly go through a
maximum. The coordinates of the maximum are approximately given by:
1
n
ðCn %Þmax z100 1 þ 1:85 [21]
KEMn
n
½M1 0 EMn z10 [22]
max ðCn %Þmax
The plot of Eq. [21] is useful to evaluate the maximum yield of a cyclic
assembly obtainable with a given driving force (Fig. 6).
From Eq. [21], it is easy to show that self-assembly can be virtually com-
plete, that is, (Cn%)max > 99%, when the condition in Eq. [23] is satisfied:
KEMn 2 102 n [23]
Eq. [23] is the second condition for self-assembly, namely, the condition
of stability of the self-assembling macrocycle over the acyclic oligomers. This
is an important relation showing that the required driving force for self-
assembly directly depends on the number of monomer units constituting
the cyclic oligomer. The plot in Fig. 6 illustrates this point, as well as the
plots reported in Fig. 5 showing that only the plot relative to
Figure 6 Plot of the maximum yield of a cyclic n-meric assembly as a function of KEMn/n.
The regions in which self-assembly can be complete, partial and not realizable are
evidenced.
KEMn ¼ 1000 satisfies the condition in Eq. [23]. Fig. 5 also shows that the
value of the monomer concentration [M1]0 is crucial to determine the
stability of a cyclic assembly in solution. If the concentration is too low,
the assembly lacks the driving force to form and thus only low-order linear
oligomers will be present in solution; on the other hand, if the concentration
is too high, the cyclic assembly loses the competition with the linear poly-
mer. The optimal monomer concentration is obtained by Eq. [22]. It is
interesting to note that when the condition in Eq. [23] is satisfied,
(Cn%)max z 100% and the optimal monomer concentration reduces to
([M1]0)max z 0.1nEMn. From Eq. [21] and Fig. 6 it also appears that a cyclic
assembly does not form to any significant extent at any concentration, that is,
(Cn%)max < 1%, if the condition in Eq. [24] is satisfied:
KEMn 2 102 n [24]
In Fig. 6, three regions are evidenced: the region obeying Eq. [23] in
which self-assembly can be complete in a given range of reactant concentra-
tion, that obeying Eq. [24] in which self-assembly cannot occur at any
reactant concentration, and that in between the two above regions in which
self-assembly can be partial at best.
Provided that Eq. [23] holds, it can be useful to establish the initial
monomer concentration at which half of the monomer is assembled into
the cyclic n-mer. This concentration has been dubbed lsac (lower self-
assembly concentration) and is given by101:
2
lsac ¼ 1=ðn1Þ n=ðn1Þ
[25]
n1=ðn1Þ EMn K
The expression in Eq. [25] is due to a slight revision of a previous expres-
sion published by Hunter et al. as the csac (critical self-assembly concentra-
tion),102 and is based on the approximation that the chain fraction is
essentially constituted by the monomer only.
Although the earlier treatment for self-assembly refers to a monomer of
the type AeB, Eqs [19] and [25] also hold for the case AeA þ BeB
provided that the concentrations of the two monomers are exactly equal
and the total monomer concentration is taken as the sum of the initial
concentrations of the two monomers. It must be noted that in the case
AeA þ BeB, only assemblies in which n is an even number are allowed.
In conclusion, a large EMn value is fundamental for the selective forma-
tion of a cyclic architecture. It allows the assembly to win the competition
with both the other cyclic oligomers (first condition for self-assembly) and
the linear polymer (second condition for self-assembly, expressed by Eq.

[23]). In this respect, it must be noted that self-assembly of high-order cyclic
oligomers is hampered by inherent difficulties. Indeed, preorganization of
monomers to give selectively a specific cyclic oligomer is increasingly diffi-
cult, if not impossible, on increasing the order of the assembly. Moreover,
the condition in Eq. [23], to maintain its validity on increasing n, would
require that EMn increases at least proportionally to n. In fact, even for a
perfectly rigid assembly devoid of any strain, EMn would decrease propor-
tionally to 1/n because of the availability of n equivalent bonds for the
ring-opening reaction of the cyclic assembly. A large value of K can provide
part of the driving force, though it is of no help to satisfy the first condition
for self-assembly, that is, the condition of selectivity with respect to the other
cyclic oligomers.
For the sake of illustration, two examples of macrocycles whose self-
assembly process has been carefully studied will be considered. The first
case regards the aggregation of zinc-5-(4-pyridyl)-10,15,20-triphenylpor-
phyrin that was studied by UVeVis spectroscopy both in toluene and
CHCl3.103 Ercolani et al. compared the experimental results with
both the models of linear polymerization alone, and cyclotetramerization
in competition with linear polymerization. The fitting procedure
gave unrealistic parameters for the first model, ruling out the polymeriza-
tion hypothesis previously suggested by Fleischer and Shachter,104
whereas the self-assembly of the cyclic tetramer 4 (meso-phenyl
groups omitted for clarity) was confirmed with the following constants:
in toluene, K ¼ 4.1 103 mol1 L, and EM4 ¼ 20 mol L1; in CHCl3,
K ¼ 1.3 103 mol1 L, and EM4 ¼ 15 mol L1. It is worth noting
that, as expected, the EM values are practically unaffected by the nature
of the solvent. The stability of this and other porphyrin assemblies
has been discussed by Ercolani on the basis of the corresponding K
and EM values.77 The second example regards a cyclic tetramer, 5,
whose units are held together by triple hydrogen bonding.105
Gonzalez-Rodríguez et al. reported the following constants for its forma-
tion: in DMF, K ¼ 5.7 mol1 L, and EM4 z 3 102 mol L1; in THF,
K ¼ 1.5 103 mol1 L, and EM4 z 4 102 mol L1; in CHCl3,
K ¼ 2.8 104 mol1 L, and EM4 z 9 102 mol L1 The value of the
EM for the tetramer 5 is much higher than that expected for typical
hydrogen bonding, thus suggesting that a triple hydrogen bonding must
be considered as a tight bond (see Section 2). It is noteworthy that in
the three solvents, the EM has the same order of magnitude in spite of a
change of four orders of magnitude of the intermolecular constant. There

is, however an undeniable correlation between the EM and the binding
strength K, modulated by the solvent, that could be ascribed to an
increasing tightness of the triple hydrogen bonding on decreasing solvent
polarity. Notably, the data for the assembly of 4 and 5 both satisfy the con-
dition in Eq. [23].
4. DYNAMIC COMBINATORIAL CHEMISTRY

The number of irreversible reactions used in the formation of synthet-
ically useful covalent bonds largely outweighs that of reversible ones. Yet,
the last period has witnessed a renewal of interest in the use of reversible re-
actions for synthetic purpose, thanks to the birth of dynamic combinatorial
chemistry (DCC).106e110 In particular, DCC has the potential to be a
powerful tool for the synthesis of macrocyclic species under thermodynamic
control mainly because efficient cyclic receptors may be selected among a
family of interconverting linear and cyclic members of a dynamic library
(DL) upon the addition of a suitable template (T), via repeatedly occurring
bond dissociationerecombination processes (see Scheme 7). Preorganiza-
tion of the cyclic species (macrocycle effect)111,112 makes them potentially
more effective receptors than their linear counterparts. Another major moti-
vation for the intense work dedicated to this research field is the ability of
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UNITED STATES OF AMERICA:
A. D. 1896 (JUNE-NOVEMBER); and 1900 (MAY-NOVEMBER).
SI-NGAN-FU,
SINGAN FU, The Chinese Imperial Court at.

CHINA: A. D. 1900 (AUGUST-SEPTEMBER).
SIRDAR, Egyptian.

EGYPT: A. D. 1885-1896; and 1897-1898.
SLAVERY: A. D. 1885.
Emancipation in Cuba.

CUBA: A. D. 1868-1885.
New anti-slavery law in Egypt.

EGYPT: A. D. 1895.
Abolition in Madagascar.

MADAGASCAR: A. D. 1894-1896.
SLAVERY: SLAVERY: A. D. 1897.

Abolished in Zanzibar.
AFRICA: A. D. 1897 (ZANZIBAR).
Compulsory labor in Rhodesia.

SOUTH AFRICA (BRITISH SOUTH AFRICA COMPANY):
A. D. 1897 (JANUARY).
Subjugation of Fulah slave raiders in Nupé and Ilorin.

AFRICA: A. D. 1897 (NIGERIA).
Forced labor in Congo State.

CONGO FREE STATE: A. D. 1899.
SLESWICK:
Complaints of German treatment.

GERMANY: A. D. 1899.
SMOKELESS POWDERS, Invention of.

SCIENCE, RECENT: CHEMISTRY AND PHYSICS.
SOCIAL DEMOCRACY, Encyclical Letter of Pope Leo XIII. on.

PAPACY: A. D. 1901.
SOCIALIST PARTIES.

AUSTRIA-HUNGARY: A. D. 1897, and after;
BELGIUM: A. D. 1894-1895;
FRANCE: A. D. 1896 (APRIL-MAY), and 1900 (JANUARY);
GERMANY: A. D. 1894-1895, and 1897 (JULY);
ITALY: A. D. 1898 (APRIL-MAY);
SWITZERLAND: A. D. 1894-1898;
UNITED STATES OF AMERICA: A. D. 1896 (JUNE-NOVEMBER),

and 1900 (MAY-NOVEMBER).
SOKOTO.

NIGERIA: A. D. 1882-1899.
SOLOMON ISLANDS, The:

Definite division between Great Britain and Germany.

SAMOAN ISLANDS.
SOMALIS, Rising of, in Jubaland.

BRITISH EAST AFRICA PROTECTORATE: A. D. 1900.
SOUDAN.
SUDAN.
"SOUND MONEY" DEMOCRATS.

UNITED STATES OF AMERICA: A. D. 1896 (JUNE-NOVEMBER).
{456}
----------SOUTH AFRICA: Start--------
SOUTH AFRICA: Cape Colony: A. D. 1881-1888.

Organization of the "Afrikander Bund."
The "Afrikander Bund" or National Party was formed in Cape

Colony in 1881, but held its first Congress, or convention, in
1888, at which meeting the following platform, or formal
statement of objects, was adopted:
"1. The Afrikander National party acknowledge the guidance of

Providence in the affairs both of lands and peoples.
2. They include, under the guidance of Providence, the

formation of a pure nationality and the preparation of our
people for the establishment of a 'United South Africa.'
3. To this they consider belong:
(a) The establishment of a firm union between all the

different European nationalities in South Africa, and
(b) The promotion of South Africa's independence.
4. They consider that the union mentioned in Article 3 (a)

depends upon the clear and plain understanding of each other's
general interest in politics, agriculture, stock-breeding,
trade, and industry, and the acknowledgment of everyone's
special rights in the matter of religion, education, and
language; so that all national jealousy between the different
elements of the people may be removed, and room be made for an
unmistakable South African national sentiment.
5. To the advancement of the independence mentioned in

Article 3 (b) belong:
(a) That the sentiment of national self-respect and of

patriotism toward South Africa should above all be
developed and exhibited in schools, and in families, and in
the public press.
(b) That a system of voting should be applied which not

only acknowledges the right of numbers, but also that of
ownership and the development of intelligence, and that is
opposed, as far as possible, to bribery and compulsion at
the poll.
(c) That our agriculture, stock-breeding, commerce, and

industries should be supported in every lawful manner, such
as by a conclusive law as regards masters and servants, and
also by the appointment of a prudent and advantageous
system of Protection.
(d) That the South African Colonies and States, either each
for itself or in conjunction with one another, shall
regulate their own native affairs, employing thereto the
forces of the land by means of a satisfactory burgher law;
and
(e) That outside interference with the domestic concerns of

South Africa shall be opposed.
6. While they acknowledge the existing Governments holding

rule in South Africa, and intend faithfully to fulfil their
obligations in regard to the same, they consider that the duty
rests upon those Governments to advance the interests of South
Africa in the spirit of the foregoing articles; and whilst, on
the one side, they watch against any unnecessary or frivolous
interference with the domestic or other private matters of the
burgher, against any direct meddling with the spiritual
development of the nation, and against laws which might hinder
the free influence of the Gospel upon the national life, on
the other hand they should accomplish all the positive duties
of a good Government, among which must be reckoned:
(a) In all their actions to take account of the Christian

character of the people.
(b) The maintenance of freedom of religion for everyone, so

long as the public order and honor are not injured thereby.
(c) The acknowledgment and expression of religious, social,

and bodily needs of the people, in the observance of the
present weekly day of rest.
(d) The application of an equal and judicious system of

taxation.
(e) The bringing into practice of an impartial and, as far

as possible, economical administration of justice.
(f) The watching over the public honor, and against the
adulteration of the necessaries of life, and the defiling
of ground, water, or air, as well as against the spreading
of infectious diseases.
7. In order to secure the influence of these principles, they

stand forward as an independent party, and accept the
cooperation of other parties only if the same can be obtained
with the uninjured maintenance of these principles.
SOUTH AFRICA: The Transvaal: A. D. 1884-1894.
The restored independence of the Boers and their
dissatisfaction with its terms.
Frustration of their desire for extended territory.
The London Convention of 1884.
After the British-Boer War of 1880-81

(see, in volume 4, SOUTH AFRICA: A. D. 1806-1881),
which had been caused by an arbitrary annexation of the
Transvaal State to the dominions of the British crown, the
sense of justice in Mr. Gladstone led him to restore to the
Transvaal Boers (by the Convention or Treaty of Pretoria,
1881) their right of internal self-government, with a
reservation of "the suzerainty of Her Majesty," supposably
relative to nothing but foreign affairs. The Boers were not
satisfied with that concession, and began at once to strive
for the complete independence they had previously possessed,
under a Convention agreed upon and signed at Sand River, 1852,
which guaranteed (quoting its precise terms) "in the fullest
manner, on the part of the British Government, to the emigrant
farmers (boers) beyond the Vaal River, the right to manage
their own affairs and to govern themselves, without any
interference on the part of Her Majesty the Queen's
Government." To regain that status of complete independence
became the first object of the Boers. They went far towards
success in this endeavor, as early as 1884, when the British
Colonial Secretary, Lord Derby, was induced to agree to a new
Convention with the South African Republic (as it was then
styled) which superseded the Convention of 1881. The terms of
the later instrument are given below. The second aim of the
Boers appears to have been the widening of their territory, by
advances, in the first instance, southward into Zululand and
westward into Bechuanaland. In the former movement they had
success; in the latter they were thwarted. English
missionaries complained of their treatment of the natives, and
stirred up the British government to take the Bechuana tribes
under its protection. Their eastern frontier they succeeded,
after long controversies with Great Britain, in stretching
beyond Swaziland, but they were not allowed to push it to the
sea. Northward, they would provably have gone far, had it not
been for the appearance, at this time, of Mr. Cecil Rhodes,
who came upon the scene of South African politics with
imperial ambitions, with great energies and capabilities, with
few apparent hesitations, and with a vast fortune acquired in the
Kimberley diamond mines. He organized the British South Africa
Company, under a royal charter, got some settlers into the
country north of the Limpopo and set up a government there, in
1890, just in time, it appears, to forestall the Boers
See, in volume 4,
SOUTH AFRICA: A. D. 1885-1893.
{457}
Of the effect of the two conventions, of 1881 and 1884, on the

relations of the British government to the South African
Republic, the following is an English view, by a well-known
publicist: "In the Treaty of Pretoria, bearing date the 5th of
April, 1881, it is stated that Great Britain guarantees
'complete self-government, subject to the Suzerainty of Her
Majesty, to the inhabitants of the Transvaal.' … Article 15
declares that 'the Resident will report to the High
Commissioner, as representative of the Suzerain, as to the
working and observance of the provisions of this Convention.'
… On the 31st of March, 1881, Lord Kimberley, who was then
Secretary of State for the Colonies, used these words in the
House of Lords with reference to the terms of the Convention,
upon which the Treaty of Pretoria was afterwards based: 'I
believe the word Suzerainty expresses very correctly the
relation which we intend to exist between this country and the
Transvaal. Our intention is that the Transvaal shall have
independent power as regards its internal government; and we
shall only reserve certain powers to be exercised by the
Queen. … With respect to our control over the relations of the
Transvaal with foreign Powers, … it is quite clear there ought
to be, as regards foreign relations, only one Government in
South Africa; that there ought to be no communication with
foreign Powers upon any subject except through the
representatives of the Queen.'
"On the 25th of June, 1881, Mr. Gladstone, while defending in

the House of Commons an assertion he had made during the
Midlothian Campaign about the blood-guiltiness of the war with
the Transvaal, referred to our Suzerainty in the following
words; 'I apprehend that the term which has been adopted, the
Suzerainty of the Queen, is intended to signify that certain
portions of Sovereignty are reserved. … What are these
portions of Sovereignty? The portions of Sovereignty we desire
to reserve are, first, the relations between the Transvaal
community and foreign governments, the whole care of the
foreign relations of the Boers. The whole of these relations
will remain in the hands of the Queen.'
"From these quotations it is obvious that when we agreed to

restore the independence of the Transvaal, the British public
were led to believe, both by the then Premier and the then
Colonial Minister, that this restoration left the control of
all relations between the Transvaal and foreign Powers
absolutely and entirely in the hands of Her Majesty's
Government. … It is possible, or even probable, that at the
time the Treaty of Pretoria was concluded, Mr. Gladstone, or
at any rate several of his colleagues, imagined that our
Suzerainty would really be made effective. But, when once the
treaty had been signed and sealed, and the South African
Republic had been granted absolute internal independence, it
became evident that our Suzerainty could only be rendered
efficacious, as against the sullen resistance of the Boers, by
the exercise of force—that is, by the threat of war in the
event of Boer non-compliance with the demands of the Suzerain
Power. …
"For the first two years which succeeded our surrender the
Boers were too much occupied in the reorganisation of the
Republic to trouble themselves greatly about their relations
to the Suzerain Power. … Disputes were mainly connected with
the treatment of the native chiefs, residing either within, or
on the borders of, the territory of the Republic, who
asserted, with or without reason, that they were the objects
of Boer hostility on account of the support they had given to
the British authorities during the period of British rule.
"In May 1883 Mr. Gladstone stated in Parliament, in answer to

certain protests about the proceedings of the Boers, that the
British Government had decided to send a Commissioner to the
Transvaal to investigate the working of the Convention
concluded at Pretoria in 1881. This intention, however, was
not carried out owing to the opposition of the South African
Republic. In lieu of the despatch of a British Commissioner to
the Transvaal, it was suggested at Pretoria that a Boer
deputation should be sent to London. The suggestion, as usual,
was accepted; and thereupon the Africander Bond in the Cape
Colony forwarded a petition to the Queen, praying Her Majesty
to entertain favourably the proposals of the Boer delegates
for the modification of the Treaty of Pretoria. The
deputation, consisting of President Kruger and Messieurs Du
Toit and Smit, arrived in London in October, and submitted to
the late Lord Derby, who had succeeded Lord Kimberley as
Minister for the Colonies, a statement of the modifications
they were instructed to demand. The memorandum in question
distinctly declared that the alleged impracticability of the
Treaty of Pretoria related, amongst other matters, 'to the
extent of the Suzerain rights reserved to Her Majesty by
Articles 2 and 18 of the Treaty of Pretoria, and to the vague
and indefinite terms in which the powers reserved to Her
Majesty's Government by the Convention are indicated.'
"To this memorandum Lord Derby replied, on the 20th of

November, 1883, admitting that 'expediency of substituting a
new agreement for that of 1881 might be matter for discussion,
but asking for information, in what sense it is wished that in
such new agreement some connection with England should be
maintained, and, if it is the desire of the Transvaal people
that their State should hereafter stand in any special
relation to this country, what is the form of connection which
is proposed?' In reply to this request the Boer delegates
answered as follows in the somewhat evasive fashion: 'In the
new agreement any connection by which we are now bound to
England should not be broken; but that the relation of a
dependency "publici juris" in which our country now stands to
the British Crown be replaced by that of two contractive
Powers.'
"The above documents were submitted to the Governor of Cape

Colony, the then Sir Hercules Robinson. Characteristically
enough, Sir Hercules recommended the surrender of our
Suzerainty on the ground that 'The Transvaal burghers
obviously do not intend to observe any condition in it (the
Convention of 1881) distasteful to themselves, which Her
Majesty's Government are not prepared to insist on, if
necessary, by the employment of force. Her Majesty's
Government, I understand, do not feel justified in proceeding
to this extremity; and no provision, therefore, of the
Convention which is not agreeable to the Transvaal will be
carried out.'
{458}
"A few days later the delegates submitted a draft treaty, in

which the following clause stands first: 'It is agreed that
Her Britannic Majesty recognises and guarantees by this treaty
the full independence of the South African Republic, with the
right to manage its own affairs according to its own laws,
without any interference on the part of the British
Government; it being understood that this system of
non-interference is binding on both parties.' To the letter
enclosing this draft treaty Lord Derby replied that the
proposed treaty was 'neither in form nor in substance such as
Her Majesty's Government could adopt.' Meanwhile the
discussion between the British Government and the Boer
delegates seems to have turned mainly upon the extension of
the territories of the Transvaal and the relations between the
Republic and the native chiefs, subjects which had only an
indirect bearing on the question of Suzerainty. It was only on
the 25th of January, 1884, that the Colonial Office wrote to
the delegates stating that if a certain compromise with regard
to the frontier line were accepted, the British Government
would be prepared 'to proceed at once with the consideration
of the other proposals for the modification of the Treaty of
Pretoria.' The delegates replied on the next day virtually
accepting the proposed frontier compromise, and requested the
British Government to proceed at once with the substitution of
a new Convention. … The draft treaty was signed on the 27th of
February, 1884. …
"The Convention of London did not repeat the preamble of the

original Convention in which the words 'subject to the
Suzerainty of Her Majesty' are to be found. Nor is the word
Suzerainty mentioned in the Convention of 1884, which declares
that the articles contained therein, if endorsed by the
Volksraad, 'shall be substituted for those of the Convention
of 1881.' No formal withdrawal, however, of the Queen's
Suzerainty is to be found in the Convention of 1884. On the
contrary, it is distinctly affirmed in Article 4 of the
modified Convention that 'the South African Republic will
conclude no treaty or engagement with any State or nation,
other than the Orange Free State, until the same has been
approved by Her Majesty the Queen.'"
Edward Dicey,
British Suzerainty in the Transvaal
(Nineteenth Century, October, 1897).
In its preamble, the Convention of 1884 recites that—"Whereas
the Government of the Transvaal State, through its Delegates,
consisting of [Kruger, Du Toit and Smit], have represented
that the Convention signed at Pretoria on the 3rd day of
August, 1881, and ratified by the Volksraad of the said State
on the 25th of October, 1881, contains certain provisions
which are inconvenient, and imposes burdens and obligations
from which the said State is desirous to be relieved, and that
the south-western boundaries fixed by the said Convention
should be amended with a view to promote the peace and good
order of the said State, … now, therefore, Her Majesty has
been pleased to direct," &c.—substituting the articles of a
new Convention for those signed and ratified in 1881.
Article I. of the new Convention describes the lines of

boundary as amended. Article II. binds the two governments,
respectively, to guard said boundaries against all
trespassing. Article III. provides for the reception and
protection, at Pretoria, of a resident British officer, "to
discharge functions analogous to those of a consular officer."
Article IV. reads as follows: "The South African Republic will

conclude no Treaty or engagement with any State or nation
other than the Orange Free State, nor with any native tribe to
the eastward or westward of the Republic, until the same has been
approved by Her Majesty the Queen. Such approval shall be
considered to have been granted if Her Majesty's Government
shall not, within six months after receiving a copy of such
Treaty (which shall be delivered to them immediately upon its
completion), have notified that the conclusion of such Treaty
is in conflict with the interests of Great Britain, or of any
of Her Majesty's possessions in South Africa."
Articles V. and VI. relate to public debts. Article VII.

guarantees the non-molestation of persons in the South African
Republic who "remained loyal to Her Majesty during the late
hostilities." Article VIII. is a declaration against slavery
in the Republic. Article IX. is in language as follows: "There
will continue to be complete freedom of religion and
protection from molestation for all denominations, provided
the same be not inconsistent with morality and good order; and
no disability shall attach to any person in regard to rights
of property by reason of the religious opinions which he
holds." Article X. relates to graves of British soldiers; XI.
to former grants of land which the present arrangement of
boundary places outside of the Republic; XII. to the
independence of the Swazis; XIII. to non-discrimination in
import duties on both sides.
Articles XIV. and XV. read thus: Article XIV. "All persons,
other than natives, conforming themselves to the laws of the
South African Republic, (a) will have full liberty, with their
families, to enter, travel or reside in any part of the South
African Republic; (b) they will be entitled to hire or possess
houses, manufactories, warehouses, shops and premises; (c)
they may carry on their commerce either in person or by any
agents whom they may think fit to employ; (d) they will not be
subject, in respect of their persons or property, or in
respect of their commerce or industry, to any taxes, whether
general or local, other than those which are or may be imposed
upon citizens of the said Republic." Article XV. "All persons,
other than natives, who establish their domicile in the
Transvaal between the 12th day of April, 1877, and the 8th day
of August, 1881, and who within twelve months after such last
mentioned date have had their names registered by the British
resident, shall be exempt from all compulsory military service
whatever." Article XVI. provides for a future extradition
treaty; XVII. for the payment of debts in the same currency in
which they were contracted; XVIII. establishes the validity of
certain land grants; XIX. secures certain rights to the
natives; XX. nullifies the Convention if not ratified by the
Volksraad within six months from the date of its
signature—February 27, 1884.
{459}
With considerable reluctance, the Convention was ratified by

the Volksraad of the South African Republic in the following
terms: "The Volksraad having considered the new Convention
concluded between its deputation and the British Government at
London on 27th February 1884, as likewise the negotiations
between the contracting parties, which resulted in the said
Convention, approves of the standpoint taken by its deputation
that a settlement based upon the principle of the Sand River
Convention can alone fully satisfy the burghers of the
Republic. It also shares the objections set forth by the
deputation against the Convention of Pretoria, as likewise
their objections against the Convention of London on the
following points:
1st.
The settlement of the boundary, especially on the western
border of the Republic, in which the deputation eventually
acquiesced only under the express conditions with which the
Raad agree.
2nd.
The right of veto reserved to the British Crown upon treaties
to be concluded by the Republic with foreign powers; and
3rd.
The settlement of the debt.
Seeing, however, that in the said Convention of London

considerable advantages are secured to the Republic,
especially in the restoration of the country's independence,
Resolves, With acknowledgment of the generosity of Her
Britannic Majesty, to ratify, as it hereby does, the said
Convention of London."
Selected Official Documents of the South African
Republic and Great Britain
(Supplement to the Annals of the American Academy
of Political and Social Science, July, 1900).
Also in:
State Papers, British and Foreign, volume 75.
SOUTH AFRICA: The Transvaal: A. D. 1885-1890.

The gold discoveries on the Rand and the influx
of Uitlanders (Outlanders or Foreigners).
"It was not until 1884 that England heard of the presence of
gold in South Africa. A man named Fred Stuben, who had spent
several years in the country, spread such marvellous reports
of the underground wealth of the Transvaal that only a short
time elapsed before hundreds of prospectors and miners left
England for South Africa. When the first prospectors
discovered auriferous veins of wonderful quality on a farm
called Sterkfontein, the gold boom had its birth. It required
the lapse of only a short time for the news to reach Europe,
America, and Australia, and immediately thereafter that vast
and widely scattered army of men and women which constantly
awaits the announcement of new discoveries of gold was set in
motion toward the Randt [the Witwatersrand or
Whitewatersridge]. … In December, 1885, the first stamp mill
was erected for the purpose of crushing the gneiss rock in
which the gold lay hidden. This enterprise marks the real
beginning of the gold fields of the Randt, which now yield one
third of the world's total product of the precious metal. The
advent of thousands of foreigners was a boon to the Boers, who
owned the large farms on which the auriferous veins were
located. Options on farms that were of little value a short
time before were sold at incredible figures, and the prices
paid for small claims would have purchased farms of thousands
of acres two years before. In July, 1886, the Government
opened nine farms to the miners, and all have since become the
best properties on the Randt. … On the Randt the California
scenes of '49 were being re-enacted. Tents and houses of sheet
iron were erected with picturesque lack of beauty and
uniformity, and during the latter part of 1886 the community
had reached such proportions that the Government marked off a
township and called it Johannesburg. The Government, which
owned the greater part of the land, held three sales of
building lots, or 'stands,' as they are called in the
Transvaal, and realized more than $300,000 from the sales. …
Millions were secured in England and Europe for the
development of the mines, and the individual miner sold his
claims to companies with unlimited capital. The incredibly
large dividends that were realized by some of the investors
led to too heavy investments in the Stock Exchange in 1889,
and a panic resulted. Investors lost thousands of pounds, and
for several months the future of the gold fields appeared to
be most gloomy. The opening of the railway to Johannesburg and
the re-establishment of stock values caused a renewal of
confidence, and the growth and development of the Randt was
imbued with renewed vigour. Owing to the Boers' lack of
training and consequent inability to share in the development
of the gold fields, the new industry remained almost entirely
in the hands of the newcomers, the Uitlanders [so called in
the language of the Boers], and two totally different
communities were created in the republic. The Uitlanders, who,
in 1890, numbered about 100,000, lived almost exclusively in
Johannesburg and the suburbs along the Randt. The Boers,
having disposed of their farms and lands on the Randt, were
obliged to occupy the other parts of the republic, where they
could follow their pastoral and agricultural pursuits. The
natural contempt which the Englishmen, who composed the
majority of the Uitlander population, always have for persons
and races not their intellectual or social equals, soon
created a gulf between the Boers and the newcomers."
H. C. Hillegas,
Oom Paul's People,
chapter 3
(with permission of D. Appleton & Co., copyright, 1899).
As the influx of newcomers increased and advanced, "the Boers

realized that the world and civilisation were once more upon
them. In spite of all the opposition that patriarchal
prejudice could muster, railways usurped the place of the slow
moving ox-waggon, and in the heart of their solitude a city
had arisen; while to the north and to the east between them
and the sea were drawn the thin red lines of British boundary.
… A primitive pastoral people, they found themselves isolated,
surrounded—'shut in a kraal for ever,' as Kruger is reported
to have said,—while the stranger was growing in wealth and
numbers within their gates. Expansion of territory, once the
dream of the Transvaal Boers, as their incursions into
Bechuanaland, into Zululand, and the attempted trek into
Rhodesia, all testify, was becoming daily less practicable.
One thing remained,—to accept their isolation and strengthen
it. Wealth, population, a position among the new States of the
world had been brought to them, almost in spite of themselves,
by the newcomer, the stranger, the Uitlander. What was to be
the attitude towards him politically? Materially he had made
the State—he developed its resources, paid nine-tenths of its
revenue. Would he be a strength or a weakness as a citizen—as
a member of the body politic? Let us consider this new element
in a new State—how was it constituted, what were its component
parts? Was it the right material for a new State to
assimilate?
{460}
Cosmopolitan to a degree—recruited from all the corners of the
earth—there was in it a strong South African element,
consisting of young colonists from the Cape Colony and
Natal—members of families well known in South Africa—and many
of them old schoolfellows or in some other way known to each
other. Then the British contingent, self-reliant, full of
enterprise and energy—Americans, for the most part skilled
engineers, miners and mechanics—French, Germans, and
Hollanders. A band of emigrants, of adventurers, and
constituted, as I think all emigrants are, of two great
classes—the one who, lacking neither ability nor courage, are
filled with an ambition, characteristic particularly of the
British race, to raise their status in the world, who find the
conditions of their native environment too arduous, the
competition too keen, to offer them much prospect, and who
seek a new and more rapidly developing country elsewhere; and
another, a smaller class who sometimes through misfortune,
sometimes through their own fault, or perhaps through both,
have failed elsewhere.
"Adventurers all, one must admit; but it is the adventurers of

the world who have founded States and Kingdoms. Such a class
as this has been assimilated by the United States and absorbed
into their huge fabric, of which to-day they form a huge and
substantial portion. What should the Transvaal Boers have done
with this new element so full of enterprise and vigour? This
had been for the last ten years the great question for them to
solve. … Enfranchisement, participation in the political life
of the State by the Uitlander,—this means, they said, a
transference of all political power from our hands to those of
men whom we do not trust. 'I have taken a man into my coach,'
said President Kruger, 'and as a passenger he is welcome; but
now he says, Give me the reins; and that I cannot do, for I
know not where he will drive me.' To the Boer it is all or
nothing; he knows no mean, no compromise. Yet in that very
mean lies the vital spirit of republicanism. What is the
position of the Boers in the Cape Colony? Are they without
their share, their influence, their Africander bond in the
political affairs of the country? And so it is throughout the
world today,—in the United States, in England, in France, in
the British Colonies, wherever the individual thrives and the
State is prosperous—the compromise of divided political power
among all classes, all factions, is the great guarantee of
their well being. … That the enfranchisement of the Uitlander
would mean a complete transference of political power into his
hands involves two assumptions: the first is that the
Uitlanders would form a united body in politics; the second is
that their representatives would dominate the Volksraad. The
most superficial acquaintance with the action of the
inhabitants of the Witwatersrand district on any public matter
will serve to refute the first of these. … The second of these
assumptions—though it is continually put forward—almost
answers itself. The number of representatives from the
Uitlander districts under any scheme of redistribution of
seats which the Boer could reasonably be expected to make
would fall considerably short of those returned from the Boer
constituencies. Such was the attitude of the Boers on this
vital question which led to the Reform Movement of 1895; and I
have stated what I believe to be the injustice of it as
regards the Uitlanders and the unwisdom of it in the true
interests of the Boers."
A. P. Hillier,
Raid and Reform,
pages 24-29 (London: Macmillan & Co.).
SOUTH AFRICA:
Portuguese Possessions: A. D. 1891.
Delagoa Bay Railway question.

DELAGOA BAY ARBITRATION.
SOUTH AFRICA:
The Transvaal: A. D. 1894.
Estimated population.
In October, 1894, the British agent at Pretoria, J. A. de Wet,

estimated the population of the Transvaal (on the basis of a
census taken in 1890) as follows:
"Transvaalers and Orange Free Staters, 70,861:
British subjects, 62,509:

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Advances in Physical Organic

Chemistry 50 1st Edition Ian H. Williams

Advances in Physical Organic Chemistry 47 1st Edition

Advances in Physical Organic Chemistry Volume 48 First

Nutrition for Health, Fitness and Sport Melvin H.

Organic Chemistry 8th Edition William H. Brown

General Organic and Biological Chemistry 6th Edition H.

Introduction to Organic Chemistry 5th Edition William

Electron Flow in Organic Chemistry A Decision Based

Teaching English in East Asia A Teacher s Guide to

M. Abe Hiroshima University, Japan

Amsterdam • Boston • Heidelberg • London

First edition 2016

Copyright Ó 2016 Elsevier Ltd. All rights reserved.

For information on all Academic Press publications

Publisher: Zoe Kruze

Typeset by TNQ Books and Journals

The 50th volume of Advances in Physical Organic Chemistry exempliﬁes the

Equilibrium Effective Molarity As

Advances in Physical Organic Chemistry, Volume 50

Figure 1 (A) An irreversible intramolecular reaction with its intermolecular counterpart.

especially among polymer chemists. Kinetic effective molarity has played a

Figure 2 Schematic representation of a chain molecule in solution illustrating the

According to Eq. [2], the constant Kintra is the product of K, representing

correlations.15 Indeed for short chains this approximation fails as clearly

EMi ¼ Bi5=2 [10]

Figure 3 Semi-logarithmic plot of entropic effective molarity, EMS, versus number of

Table 1 Entropic effective molarities and entropy changes in the

0 3.6 106 126

outside the ﬁeld of polymer chemistry. With the development of macrocy-

Scheme 1 Chainechain equilibria for an isodesmic polymerization.

the system is constituted of a mixture of all the possible i-meric chains Mi

The overall equilibrium between end groups eA and eB is illustrated in

Scheme 2 Equilibrium between end groups eA and eB in the process of isodesmic

Scheme 3 Ring-chain equilibria in a macrocyclization under thermodynamic control.

In the presence of strained rings, B represents the EM of the hypothetical

value of the CC is calculated by Eq. [17], by taking x w 1 and neglecting the

formed, whereas at high concentrations, chain extension leads to high

3.2 RingeRing Equilibria

Scheme 4 Ringering equilibria in a macrocyclization under thermodynamic control.

Scheme 5 Mechanism for the ring-expansion metathesis polymerization of cis-

Now [M1]0 corresponds to the initial cyclic monomer concentration and

3.3 Self-Assembly Macrocyclizations

Scheme 6 Equilibrium scheme for the self-assembly of a macrocyclic n-mer.

the linear polymer (second condition for self-assembly, expressed by Eq.

change of four orders of magnitude of the intermolecular constant. There

4. DYNAMIC COMBINATORIAL CHEMISTRY

See (in this volume)

See (in this volume)

See (in this volume)

See (in this volume)

See (in this volume)

SLAVERY: SLAVERY: A. D. 1897.

See (in this volume)

See (in this volume)

See (in this volume)

See (in this volume)

SMOKELESS POWDERS, Invention of.

See (in this volume)

SOCIAL DEMOCRACY, Encyclical Letter of Pope Leo XIII. on.

See (in this volume)

See (in this volume)

FRANCE: A. D. 1896 (APRIL-MAY), and 1900 (JANUARY);