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Published on 30 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782628842-FP001
Molybdenum and Tungsten Enzymes

Spectroscopic and Theoretical Investigations
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5: Molybdenum and Tungsten Enzymes: Biochemistry
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Molybdenum and Tungsten

Enzymes
Spectroscopic and Theoretical Investigations
Edited by
Russ Hille
University of California, Riverside, CA, USA
Email: russ.hille@ucr.edu
Carola Schulzke
University of Greifswald, Germany
Email: carola.schulzke@uni-greifswald.de
and
Martin L. Kirk
University of New Mexico, Albuquerque, NM, USA
Email: mkirk@unm.edu
Published on 30 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782628842-FP001 View Online
RSC Metallobiology Series No. 7
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Preface
In the late 1950s and early 1960s, evidence was accumulating that molybde
num was not simply present in the enzyme xanthine oxidase from cow's milk
but that it was required for its activity and changed its oxidation state in the
course of the reaction with substrate. In a tour-de-force isotopic substitution
study reported in Nature in 1966, R.C. Bray and L.S. Meriwether demons
trated unequivocally that the EPR signals elicited by the enzyme upon treat
ment with xanthine arose from a molybdenum-containing active site. It is
a happy coincidence but altogether fitting that this volume marks the 50th
anniversary of this seminal work.
For many years, only five enzymes were recognized as possessing molyb
denum in their active sites: nitrogenase from bacteria such as Klebsiella
pneumoniae and Azotobacter vinelandii; xanthine oxidase from bovine milk
(and other vertebrate sources); aldehyde oxidase from vertebrate as well as
bacterial sources; the vertebrate sulfite oxidase; and the assimilatory nitrate
reductase from plants (and algae and fungi). That began to change in the
1980s with the demonstration by K. V. Rajagopalan that an organic cofac
tor accompanied the molybdenum in the active sites of these enzymes (with
the exception of nitrogenase), and with the contemporaneous discovery that
tungsten was also found in the active sites of enzymes in certain bacteria.
There are now several dozen molybdenum- and tungsten-containing
enzymes that have been crystallographically characterized, along with most
of the enzymes responsible for the biosynthesis of the organic cofactor vari
ously known as molybdopterin, tungstopterin and pyranopterin. The active
site metal centres of these enzymes have proven to be fascinating and chal
lenging targets for synthetic inorganic chemists, and both enzymes and
synthetic models have proven fertile ground for the application of a range
of physicochemical and spectroscopic methods probing their physical and
electronic structures as well as their intrinsic reactivity. At present, well

Molybdenum and Tungsten Enzymes: Spectroscopic and Theoretical Investigations
Edited by Russ Hille, Carola Schulzke, and Martin L. Kirk
Published by the Royal Society of Chemistry, www.rsc.org
v
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vi Preface
over 50 molybdenum- and tungsten-containing enzymes have been isolated
and characterized, and these have been found to catalyze a broad range of
oxidation-reduction reactions, and even reactions that (at least formally) do
not involve oxidation–reduction of substrate. These enzymes are found in
a wide range of metabolic pathways and play particularly prominent roles

in the global cycling of nitrogen, sulfur and carbon. Many have vital roles
in bacterial bioenergetics, catalyzing crucial energy-conserving reactions
under a variety of growth conditions. Indeed, they seem to have been among
the earliest enzyme systems to have arisen, as reflected in their near-universal
distribution in the biosphere. Finally, genomics analyses have led to the
identification of hundreds of genes encoding putative new proteins that are
likely to possess one or another metal. These systems represent an enormous
frontier of new enzymes that remains to be explored.
This title provides an up-to-date account of the state of our understanding
of molybdenum and tungsten enzymes and is divided into three volumes,
dealing with: (1) the enzymes themselves, along with pyranopterin cofac
tor biosynthesis and incorporation of the mature cofactor into apoprotein
(Molybdenum and Tungsten Enzymes: Biochemistry), (2) inorganic complexes
that model the structures and/or reactivity of the active sites of each major
group of molybdenum and tungsten enzymes (Molybdenum and Tungsten
Enzymes: Inorganic Chemistry) and (3) spectroscopic and related methods of
physical chemistry (including computational work) that have been applied
to both enzymes and model compounds (Molybdenum and Tungsten Enzymes:
Physical Methods). Each volume is introduced by an overview chapter written
by a leading expert in the field, followed by the individual chapters that detail
specific topics associated with each volume. The intent of these overview
chapters is to provide an overarching and unifying theme that places each of
the three major subject areas in proper context.
We are deeply indebted to each of the contributors for their efforts, which
lay out the current state of our understanding in each of the many subject
areas considered. The coverage of these volumes is inevitably incomplete
due to space constraints, however, and for this we apologize. However, the
topics that are covered are presented to the reader in considerable detail;
written in a style and spirit that will be fully accessible by current researchers
in the field as well as those who wish to learn more about these fascinating
metalloproteins. We sincerely hope that these volumes will underscore how
rapid the progress has been over the past decade or so, and also how rapidly
the field is expanding. The ultimate goal is to stimulate further research on
molybdenum and tungsten enzymes, and especially to encourage new inves
tigators to take up one or another aspect of these systems. It seems inevitable
that many exciting new discoveries lie in wait.
Russ Hille
Carola Schulzke
Martin L. Kirk
Dedication
It is all too fitting that these volumes dealing with the bioinorganic chemistry
of molybdenum and tungsten be dedicated to three outstanding chemists
whose contributions to the field over many years continues to inform, illumi-
nate and inspire: Richard H. Holm, C. David Garner and John H. Enemark.
Prof. Holm has over 500 research publications (cited over 35 000 times)
covering a wide range of nickel, iron and molybdenum chemistry (among
other transition metals). He is perhaps most widely recognized for studies,
beginning in the 1970s, that describe the synthesis and characterization
of iron-sulfur clusters. This work came to include modelling the M and P
clusters of nitrogenase, which perhaps provided the motivation to investi-
gate models of mononuclear molybdenum-containing enzymes. His molyb-
denum work achieved great success with the synthesis of MoO2 models for
enzymes of the sulfite oxidase, and later the DMSO reductase family, and the
characterization of their properties as oxygen atom transfer catalysts. A key
contribution was his use of bulky ligands to the metal that prevented µ-oxo

vii
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viii Dedication
dimerization, which had long stymied work in the field. He is Higgins Profes-
sor of Chemistry at Harvard University, a member of the National Academy
of Sciences and the recipient of many other awards.
Prof. Garner already had a strong track record in the synthesis of copper
and molybdenum complexes when, beginning in the late 1970s, he became

one of the first researchers to apply the then-new analytical method of X-ray
absorption spectroscopy not only to models of molybdenum enzymes but
also to the enzymes themselves. The discovery of thiolate-like sulfur, Mo=O
and Mo=S ligands to the metal in the active sites of enzymes such as sulfite
oxidase, xanthine oxidase and DMSO reductase was critical in establishing
the molybdenum coordination environment in these enzymes and greatly
focused efforts to synthesize accurate structural and functional mimics of
the enzymes. With over 300 publications (having over 8000 citations), he is
presently Professor Emeritus at the University of Nottingham and a Fellow of
the Royal Society. He is also past President of the Royal Society of Chemistry.
Prof. Enemark was already well recognized for his work on metal nitrosyls
and related systems when he began to exploit the tris-pyrazolylborate ligand
as a scaffold on which to construct and study MoO2 and MoO complexes.
This work led to the synthesis and characterization of the first model that
fully mimicked the catalytic cycle of oxotransferase enzymes such as sulfite
oxidase. Enemark also played an instrumental role in the work that led to
the first crystal structure of sulfite oxidase. Since that time, Enemark has
pioneered the application of pulsed EPR methods to molybdenum enzymes
and synthetic models of their active sites; work that has led to a deep under-
standing of not simply the physical but also the electronic structures of these
systems. With over 250 publications and 10 000 citations, he is Regents Pro-
fessor of Chemistry at the University of Arizona, a former Fulbright Scholar
and recipient of the Humboldt Research Prize, among other national and
international recognitions.
Contents
Chapter 1 Spectroscopic and Electronic Structure Studies

Probing Mechanism: Introduction and Overview 1
Martin L. Kirk
1.1 I ntroduction 1
1.2 Overview 2
1.2.1 Pyranopterin Molybdenum Enzymes 2
1.2.2 Nitrogenase 8
1.3 Summary 9
Acknowledgements 10
References 10
Chapter 2 Spectroscopic and Electronic Structure Studies of

Mo Model Compounds and Enzymes 13
Martin L. Kirk
2.1 I ntroduction and Scope 13

2.2 The Pyranopterin Dithiolene and the Molybdenum
Cofactor (Moco) 16
2.2.1 General Background 16
2.2.2 Model Studies Defining the Mo–Dithiolene
Interaction in Moco 17
2.2.3 Conformational Studies of the PDT 23
2.2.4 Spectroscopic Studies of the PDT 24
2.3 Sulfite Oxidase 26
2.3.1 Active Site Structure and General Reaction
Catalyzed 26
2.3.2 Select Spectroscopic Studies of Model Systems 28

ix
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x Contents
2.3.3 S pectroscopic Studies of SO and SO-Type
Enzymes 31
2.3.4 Active Site Electronic Structure
Contributions to Reactivity 33
2.4 Xanthine Oxidoreductase (XOR) 35

Catalyzed 35
2.4.3 Spectroscopic Studies of XOR 38
2.5 Carbon Monoxide Dehydrogenase 41
Catalyzed 41
2.5.2 EPR Spectroscopic Studies of a Key
Model System 42
2.5.3 Spectroscopic Studies of CODH 43
2.6 Dimethylsulfoxide (DMSO) Reductase 47
Catalyzed 47
2.6.3 Spectroscopic Studies of DMSOR 50
2.7 MOSC Family Enzymes 53
Catalyzed 53
2.7.2 Spectroscopic Studies of MOSC Proteins 55
2.8 Perspective 58
Acknowledgements 59
References 59
Chapter 3 Electron Paramagnetic Resonance Studies of

Molybdenum Enzymes 68
Stéphane Grimaldi, Frédéric Biaso, Bénédicte Burlat,
and Bruno Guigliarelli
3.1 I ntroduction 68
3.2 Principles of EPR Techniques and Application to
Mo/ W Enzymes 69
3.2.1 Basis of EPR Spectroscopy 69
3.2.2 EPR Properties of Mo and W Enzymes 72
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Contents xi
3.3 g -Tensor Analysis for Mo/W Enzymes 75
3.3.1 g-Tensor for a d1 Configuration 75
3.3.2 Magneto-Structural Correlations in the
Mo-Enzyme Family 76
3.3.3 g-Tensor Analysis of Mo-bisPGD Active Site:

Influence of the Protein Ligands 78
3.3.4 The g-Tensor of Mo(v)-monoPPT: The
Case Study of the Sulfite Oxidase Family 81
3.3.5 g-Tensor and Substrate Binding: The Xanthine
Oxidase Family 82
3.3.6 g-Tensor Calculation: Ab-initio and DFT
Methods 83
3.3.7 g-Tensor of W(v) Species in Tungsten
Enzymes 85
3.4 Detection and Analysis of Hyperfine Couplings to
Mo/W(v) Species 86
3.4.1 Hyperfine Coupling to the Metal Ion 86
3.4.2 Superhyperfine Couplings to the Mo(v)
Species in Xanthine Oxidase Enzyme Family 90
3.4.3 Superhyperfine Couplings to Mo(v) Species
Formed in Sulfite Oxidase Enzyme Family 96
3.4.4 Superhyperfine Couplings to the Mo(v)
Species in Mo/W-bisPGD Enzymes 104
3.5 Detection and Analysis of Spin–Spin Interactions
between the Mo Cofactor and other Metal Centres 108
3.6 Concluding Remarks 110
Acknowledgements 112
References 112
Chapter 4 X-Ray Absorption Spectroscopy of Molybdenum and

Tungsten Enzymes 121
Graham N. George

4.2 The Physical Basis of X-Ray Absorption
Spectroscopy 122
4.2.1 The EXAFS 125
4.2.2 The Fourier Transform 128
4.2.3 Determination of Structural Parameters
from the EXAFS 129
4.2.4 Confusion of EXAFS Backscatterers 134
4.2.5 EXAFS Cancellation 134
4.2.6 Multiple Scattering 134
4.2.7 The EXAFS Resolution and the
Debye–Waller Term 134
4.2.8 Number of Independent Variables 136
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xii Contents
4.3 E xperimental Aspects of XAS 137
4.3.1 Sample Preparation 140
4.3.2 Data Acquisition Strategies 142
4.3.3 Fluorescence Self-Absorption Effects 143
4.3.4 Combining XAS with Other

Methods – A Holistic Approach 144
4.4 The DMSO Reductase Family of Mo and W
Enzymes 145
4.4.1 DMSO Reductase 145
4.4.2 Arsenite Oxidase 149
4.4.3 The Archaeal Tungsten Enzymes 150
4.4.4 Other DMSO Reductase Family
Members 151
4.5 The Xanthine Oxidase Family of Mo Enzymes 152
4.5.1 Xanthine Oxidase 152
4.5.2 Carbon Monoxide Dehydrogenase 153
4.6 The Sulfite Oxidase Family of Mo Enzymes 154
4.7 Nitrogenase 158
4.8 Concluding Remarks 161
References 162
Chapter 5 Electrochemistry of Molybdenum and Tungsten

Enzymes 168
Palraj Kalimuthu and Paul V. Bernhardt

5.1.1 The Mo and W Enzyme Families 168
5.1.2 Enzyme Electrochemistry 169
5.2 Xanthine Oxidase Family 172
5.2.1 Xanthine Oxidoreductase 172
5.2.2 Aldehyde Oxidoreductase 180
5.3 Sulfite Oxidase Family 181
5.3.1 Sulfite Oxidoreductase 182
5.3.2 Eukaryotic Nitrate Reductase 192
5.4 DMSO Reductase Family 196
5.4.1 DMSO Reductase 197
5.4.2 DMS Dehydrogenase 203
5.4.3 Bacterial Nitrate Reductase 203
5.4.4 Arsenite Oxidase 208
5.4.5 Ethylbenzene Dehydrogenase 211
5.4.6 Formate Dehydrogenase 212
5.4.7 Glyceraldehyde 3-Phosphate
Oxidoreductase 214
5.5 Conclusions 214
Acknowledgement 215
References 215
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Contents xiii
Chapter 6 Nitrogen Fixation in Nitrogenase and Related
Small-Molecule Models: Results of DFT Calculations 223
Felix Tuczek

6.1.1 Structure and Function of Nitrogenase 224
6.1.2 Fe-Protein Cycle 224
6.1.3 Metal Clusters Within the MoFe-Protein 226
6.1.4 Thorneley–Lowe Cycle 227
6.1.5 Site-Directed Mutagenesis Experiments 227
6.1.6 Trapping and Spectroscopic Characterization
of Intermediates of N2 Reduction: Towards
an Experimentally Derived Mechanism of
Nitrogenase 228
6.2 DFT Treatments of N2 Reduction in Model
Systems 229
6.2.1 Schrock Cycle 231
6.2.2 Nishibayashi’s System 238
6.2.3 Chatt Cycle 239
6.2.4 Reduction and Protonation of N2 at Cubane
Clusters 241
6.2.5 Reduction and Protonation of N2 at Iron
Complexes 242
6.3 DFT Calculations on the FeMoco and its
Reactivity with N2 246
6.3.1 Noodleman and Coworkers 246
6.3.2 Nørskov and Coworkers 252
6.3.3 Blöchl, Kästner et al 256
6.3.4 Dance 259
6.3.5 Further Theoretical Studies 261
6.3.6 Mo(iii) Charge State of FeMoco 264
6.4 Summary and Conclusions 266
Acknowledgement 266
References 267
Chapter 7 Computational Studies of Molybdenum and Tungsten

Enzymes 275
Ulf Ryde, Geng Dong, Jilai Li, Milica Feldt, and
Ricardo A. Mata

7.2 Computational Methods to Study Metalloenzymes 279
7.2.1 QM Methods 280
7.2.2 Hybrid QM/QM Calculations 283
7.2.3 QM-Cluster Calculations 283
7.2.4 QM/MM Calculations 284
7.2.5 How to Model the MPT Ligand 287
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xiv Contents
7.3 DMSO Reductase 289
7.4 Sulfite Oxidase 298
7.5 Xanthine Oxidase 306
7.6 Comparison of the Three Families 311
7.7 Conclusions 314

References 316
Subject Index 322

Published on 30 September 2016 on http://pubs.rsc.org | doi:10.1039/9781782628842-00001
Chapter 1
Spectroscopic and Electronic

Structure Studies Probing
Mechanism: Introduction and
Overview
Martin L. Kirka
a
Department of Chemistry and Chemical Biology, The University of New
Mexico, MSC03 2060, 1 University of New Mexico, Albuquerque,
New Mexico 87131-0001, USA
*E-mail: mkirk@unm.edu
1.1 Introduction
The first Gordon Research Conference on “Molybdenum and Tungsten
Enzymes” was held July 4–9 1999 at Plymouth State College (now Plym-
outh State University) in New Hampshire and was chaired by Ed Stiefel
and Russ Hille. This meeting proved to be a transformative one for our
field in that it provided an intellectual forum for molecular biologists, syn-
thetic chemists, enzymologists, theorists, crystallographers and spectros-
copists to converge, discuss their latest results and develop long-standing
relationships that would foster new collaborations that have allowed us to
understand the structure and function of Mo- and W-containing enzymes
as well as the intricate details of their catalytic mechanisms of activity.

1
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2 Chapter 1
These enzymes continue to be the subject of intense research efforts,
and this is a direct result of their unusual geometric and electronic struc-
tures, their key roles in the global C, N and S cycles, their pharmacologi-
cal importance, and their importance in human health. This volume will
detail how spectroscopy, structure, electrochemistry and theory have been

used to develop a comprehensive description of the active site electronic
structure contributions to reactivity in pyranopterin Mo enzymes and the
Mo-dependent nitrogenase. A particular emphasis is placed on how these
important studies have been used to reveal critical components of enzyme
mechanisms.
1.2 Overview
1.2.1 Pyranopterin Molybdenum Enzymes
With the sole exception of nitrogenase, the pyranopterin Mo (and W) enzymes
are the only metalloenzymes that utilize second-1,2 (and third-) row transition
metal ions to catalyze a myriad of redox transformations involving enzyme
substrates.3,4 The uniqueness of these enzymes is further underscored by the
fact that they possess the molybdenum cofactor (Moco, Figure 1.1),5,6 which
is comprised of a high-valent MoIV,V,VI (WIV,V,VI) ion coordinated by a unique
dithiolene ligand (the pyranopterin dithiolene). This dithiolene ligand is
connected to a pterin ring system by a pyran ring that may be in either a
closed (typical) or an open ring configuration. The pyranopterin dithiolene
(PDT) is a highly complex ligand (vide infra) that is unique to the mononu-
clear Mo (W) enzymes. The remarkable nature of this ligand is exemplified
by its potential for electronic flexibility, including changing its redox and/or
tautomeric state to exert additional control of the Mo redox potential.6 The
pyranopterin molybdenum enzymes have been historically divided into three
broad families: the sulfite oxidase (SO) family, the xanthine oxidase (XO) fam-
ily and the dimethylsulfoxide reductase (DMSOR) family of enzymes (Figure
1.2).5 This broad classification has been based on the coordination geometry
of their active sites, the nature of their respective protein folds and the type
and breadth of reactions that are catalyzed by the enzymes.
Figure 1.1
The molybdenum cofactor (Moco), comprised of a Mo ion bound to a
pyranopterin dithiolene (PDT) chelate. Note that the PDT shown here is
in the fully reduced “tetrahydro” oxidation state.5,6
View Online
Spectroscopic and Electronic Structure Studies Probing Mechanism 3

The vast majority of pyranopterin Mo (W) enzymes catalyze the formal trans-
fer of an oxygen atom between the substrate and the Mo ion. The generalized
oxygen atom transfer reactions possess the following stoichiometry:5,7–9
E-MoVI + R + H2O → E-MoIV + R–O + 2H+

Regarding substrate oxidations, reductive oxygen atom transfer is given

by the reverse of this reaction. In marked contrast to the oxotransferases,
substrate hydroxylations (formal insertion of an O atom into a substrate C–H
bond) follow the reaction stoichiometry given below:
E-MoVI + R–H + H2O → E-MoIV + R–OH + 2H+

Excellent reviews3,5,7–17 have highlighted recent advances in our under-
standing of these enzymes, in addition to reviews that have covered the
Mo-dependent nitrogenase,18–20 which will be introduced later in this chapter.
More specific reviews have focused on the sulfite oxidase,21,22 DMSO reduc-
tase23 and xanthine oxidase7,24 enzyme families, with additional reviews cov-
ering Moco biosynthesis,25–27 spectroscopic studies17,28 and computational
probes of the enzyme reaction coordinates.16,28
Although it has long been suggested that the PDT may play key roles in facil-
itating vectorial electron transfer, modulating enzyme reduction potentials
and providing an anchor for the Mo ion in the catalytic active site, there is still
much to be learned about this complex ligand. Some of the latest work on the
PDT has detailed a relationship between pyranopterin dithiolene geometric
structure and enzyme function.6 A bioinformatics study of 309 pyranopterins
from 109 separate enzyme structures showed that these enzymes possessed
Figure 1.2
Top: bond line drawings for the oxidized and reduced members of the
three canonical pyranopterin Mo enzyme families (SO, DMSOR and
XO). Bottom: active site coordination geometries for SO, DMSOR, and
XO as determined by X-ray crystallography.
View Online
4 Chapter 1
geometries that can be described by a well-defined distortion coordinate that
is related to the nature of PDT out-of-plane distortions that were revealed by
X-ray crystallography.6 This distortion coordinate was analyzed in the context of
DFT calculations that were performed on geometry-optimized PDT structures.
The results suggest that differences in the nature of the PDT out-of-plane dis-
tortions are related to PDTs that adopt different oxidation states. Specifically,
the analysis suggests that biological PDTs may not all exist in the fully reduced
“tetrahydro” oxidation state, as has been previously thought.5 These research-
ers hypothesized that the PDT may also be present in two electron oxidized
“dihydro” forms.6 Remarkably, the observed PDT distortions can be associated
with specific enzyme families. For example, the PDT distortions observed for
XO family enzymes are consistent with the PDT being in the fully reduced “tet-
rahydro” oxidation state, while SO family PDTs adopt “dihydro” structures.
Interestingly, DMSOR family enzymes, which contain two PDTs coordinated
to Mo, appear to possess one PDT that displays an SO type distortion and one
PDT possessing an XO type distortion. The results are of interest in that they
suggest a link between enzyme function and the oxidation state(s) of the PDT.6
In support of this idea, the first structurally characterized oxomolybdenum
complex to incorporate a pyranopterin dithiolene ligand was found to possess
the ligand in the “dihydro” oxidation state.29 A combination of X-ray crystal-
lography and 1H NMR spectroscopy was used to show that this complex pos-
sessed a complete pyranopterin dithiolene ligand, and that reversible pyran
ring opening and closing may represent a dynamic process in pyranopterin
molybdenum enzymes. Although these addressed apparent relationships
between PDT geometric structure, oxidation state and enzyme function, our
understanding of how PDT electronic structure contributes to enzyme catalysis
remains to be determined.
From a spectroscopic and electronic structure viewpoint, the pyranopterin
molybdenum (and tungsten) containing enzymes are unique among metal-
loenzymes. This primarily derives from the terminal Mo-oxo ligation cou-
pled with the high oxidation states accessible to the metal ion during the
course of catalysis. This results in a large splitting of the t2g orbital set with
the Mo(xy) redox active orbital being well separated energetically from the
Mo–Ooxo dπ* antibonding orbitals.30 Thus, the Mo(v) ion possesses an (xy)1
configuration with the redox orbital oriented perpendicular to a Mo–Ooxo
vector30 and the Mo(iv) ion possesses a low-spin (xy)2 configuration with a
diamagnetic ground state. Spectroscopic studies probing the Mo ion in pyra-
nopterin Mo enzymes have not been trivial. This results from the fact that
the majority of pyranopterin Mo enzymes possess strongly absorbing flavin,
iron–sulfur and/or heme chromophores5 that mask the electronic absorp-
tion spectra associated with the Mo active sites. Furthermore, this problem
is exacerbated by the fact that the only relevant paramagnetic state is the
Mo(v) oxidation state, which represents an obligatory catalytic intermedi-
ate in the electron transfer regeneration half-reaction that progresses via
sequential one-electron transfers that interconvert the diamagnetic Mo(iv)
and Mo(vi) oxidation states. Thus, in order to use high resolution paramag-
netic probes of pyranopterin Mo enzyme active site electronic structure, it is
View Online
Spectroscopic and Electronic Structure Studies Probing Mechanism 5

31
necessary to either trap reaction intermediates or study inhibited enzyme
forms.32,33 This critical issue cannot be overstated, as the general inability to
probe resting, fully oxidized or fully reduced enzyme forms using paramag-
netic spectroscopies has provided a significant challenge to understanding
crucial interrelationships between spectroscopic features of the active sites

and their corresponding geometric and electronic structures.
These caveats aside, paramagnetic spectroscopies, including EPR, ESEEM,
ENDOR, MCD and Mössbauer, have played critical roles in determining the
electronic structure of the Mo(v) state and have contributed to a greater
understanding of pyranopterin molybdenum enzyme reaction coordinates.
The first spectroscopic studies of pyranopterin Mo enzyme geometric and
electronic structure employed EPR spectroscopy. Notable among these are
the early work of Bray and coworkers, who used EPR to investigate rapidly
appearing Mo(v) EPR signals in reduced forms of XO.34 These early EPR
studies were often calibrated against data collected on small molecule mod-
els,35,36 as there were not yet any high-resolution protein crystal structures.
The xanthine oxidase very rapid species,37,38 which can be trapped under
turnover conditions with specific substrates,39 represents a clear example of
how multiple spectroscopic probes of an enzyme intermediate have played
a significant role in enhancing our understanding of the enzyme's mecha-
nism. The very rapid intermediate is a Mo(v)-product species that has been
extensively probed by a combination of EPR37–39 (Figure 1.3), ENDOR40 and
MCD31 spectroscopies. Collectively, these data have been used to show that
Figure 1.3
X-band EPR spectrum of the xanthine oxidase very rapid intermediate
generated with 2-hydroxy-6-methylpurine as reducing substrate. Data
were acquired at 150 K, 9.47 GHz and 10 mW microwave power. Note
the high value for g1, which has been used in conjunction with 33S
hyperfine analysis to indicate the presence of a highly covalent Mo=S
π bonding scheme in very rapid and, by inference, the oxidized Mo(vi)
form of the enzyme. Adapted with permission from ref. 31. Copyright
(1999) American Chemical Society.
View Online
6 Chapter 1
the very rapid intermediate (1) possesses an apical oxo and an equatorial
sulfido ligand that are oriented cis relative to one another,31 (2) possesses
a highly covalent Mo=S d–p π bonding interaction, (3) does not involve the
formation of an organometallic Mo–C bond in the catalytic cycle of the
enzyme40 and (4) possesses product bound to the Mo ion as the enolate tau-
tomer.40 The combination of computational, spectroscopic and reactivity
studies on xanthine oxidase very rapid has contributed greatly to our under-
standing of the reductive half-reaction in xanthine oxidase and related Mo
hydroxylase family enzymes.3 Of course, the xanthine oxidase very rapid
story is only one of many studies where paramagnetic spectroscopies have
proven to be crucial for developing a greater understanding of pyranopterin
molybdenum enzyme electronic structure contributions to reactivity.3,24
Diamagnetic probes of enzyme electronic structure have primarily involved
electronic absorption and resonance Raman spectroscopies. It is import-
ant to note that when spectroscopic studies on the enzymes can be directly
compared to analogous studies on small molecule analogs of their active
sites, tremendous insight into the relationships between electronic and geo-
metric structure contributions begins to emerge. This is due, in part, to the
fact that the small molecule analogs do not possess the competing chromo-
phores that are present in many of the enzymes, and they allow for specific
structural components found in the enzymes to be evaluated individually
(Figure 1.4). This has resulted in the detailed spectral probing of numer-
ous elegantly designed small molecules using electronic absorption spec-
troscopy, S K-edge XAS, resonance Raman and MCD spectroscopies.30,41–59
Spectroscopic studies on diamagnetic model compounds in the catalytically
relevant Mo(iv) and Mo(vi) oxidation states have also contributed greatly to
Figure 1.4
Specific structural components that are found in pyranopterin Mo
enzymes, which have also been incorporated into small-molecule
model systems for detailed spectroscopic studies.
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for approval and confirmation. And after they had prayed, they laid
their hands on them, in token of imparting to them the blessing and
the power of that divine influence which had inspired its previous
possessors to deeds so energetic and triumphant. The efficiency of
this prayer and benediction, in calling down divine grace on the
heads thus touched by the hands of the apostles, was afterwards
most remarkably demonstrated in the case of two of the seven, and
in the case of the first of them, almost immediately.
Greeks.――The original word here is not Ἑλληνες, (Hellenes,) but Ἑλληνιστοι,

(Hellenistoi,) which means not Grecians, but Grecizers; that is, those who imitated Grecian
language or customs.
Genuine Hebrews.――By these are meant those who used the Hebrew language still in
their synagogues, as the only sacred tongue, and looked with much scorn on the Hellenists,
that is, those foreign Jews, who, from birth or residence in other lands, had learned the
Greek as their sole language in common life, and were thus obliged to use the Greek
translation, in order to understand the scriptures. This matter will have a fuller discussion in
another place. Lightfoot has brought a most amazing quantity of learned and valuable
illustration of this difference, from Talmudic literature. (Horae Hebraica et Talmudicae in Acts
vi. 1.)
christ’s first martyr.
Stephen, after thus being set apart for the service of the church,
though faithfully discharging the peculiar duties to which he was
called, did not confine his labors to the mere administration of the
public charities. The word of God had now so spread, under the
ministry of the apostles, that the number of the disciples in
Jerusalem was greatly enlarged, and that not merely from the lower
and ignorant orders; but a great number of the priests, who, in their
daily service in the temple, had been frequently unintentional hearers
of the word preached in its courts, now professed themselves the
submissive friends of the new faith. This remarkable increase excited
public attention more and more, and required redoubled exertions to
meet the increasing call for instruction. Stephen, therefore,
immediately entered boldly and heartily on this good work; and,
inspired by a pure faith, and the confidence of help from above, he
wrought among the people such miracles as had hitherto followed
only the ministry of the apostles. The bold actions of this new
champion did not fail to excite the wrath of the enemies of the cause
of Christ; but as the late decision of the Sanhedrim had been against
any further immediate resort to violent measures, his opponents
confined themselves to the forms of verbal debate for a while. As
Stephen was one of those Jews who had adopted the Greek
language and habits, and probably directed his labors more
particularly to that class of persons, he soon became peculiarly
obnoxious to those Hellenist Jews who still held out against the new
doctrine. Of the numerous congregations of foreign Jews that filled
Jerusalem, five in particular are mentioned as distinguishing
themselves by this opposition,――that of the freed-men, or captive
Jews once slaves in Rome, and their descendants,――that of the
Cyrenians,――of the Alexandrians,――the Cilicians and the Asians.
Some of the more zealous in all these congregations came out to
meet Stephen in debate, with the polished points of Grecian logic
which their acquaintance with that language enabled them to use
against him. But not all the combined powers of sacred and profane
literature availed any thing against their learned and inspired
opponent. Prepared beforehand, thoroughly, in all sorts of wisdom,
and borne on resistlessly, moreover, by that divine influence whose
movements they could see but could not understand, he foiled them
completely at all their own weapons, and exposed them, in their low
bigotry and stupidity, baffled and silenced by his single voice. But
among all the refinements and elegances with which their classical
knowledge had made them acquainted, they had failed to learn that
noblest effort of the rhetorical art, which is to know how to bear a fair
defeat in open debate, gracefully. These low-minded, half-renegade
bigots, burning with brutal rage for this defeat, which their base
behavior made more disgraceful, determined to find a means of
punishing him, which no logic nor rhetoric could resist. They found
men base enough for their vile purposes, and instructed them to
testify that they had heard him speak blasphemous words against
Moses and against God. On the strength of this heinous charge, they
made out to rouse some of the people, as well as the elders and the
scribes, to a similar hostile feeling; and coming upon him with a
throng of these, they seized him and dragged him away to the
Sanhedrim, to undergo the form of a trial. They then brought forward
their perjured witnesses, who testified only in vague terms of abuse,
“This man ceases not to speak blasphemous words against this holy
place and the law. For we have heard him say that this Jesus, the
Nazarene, will destroy this place, and will do away with the customs
which Moses delivered to us.” This was, after all, a kind of
accusation which brought him more particularly under the invidious
notice of the Pharisees, whose leader had lately so decidedly
befriended the apostles; for that sect guarded with the most jealous
care all the minute details of their religion, and were ever ready to
punish, as a traitor to the national faith and honor, any one who
spoke slightingly, or even doubtingly, of the perpetuity of the law of
Moses, and its hallowed shrine. Perhaps there was no one of all the
sayings of Jesus himself, which had given deeper offense than his
remark about destroying the temple and re-building it in three days,
which his silly hearers took up seriously, and construed into a
serious, blasphemous insult of the chief glory of the Jewish name,
and bore it in mind so bitterly, as to throw it back on him, in his last
agonies on the cross. Such a saying, therefore, when laid to the
charge of Stephen, could not but rouse the worst feelings against
him, in the hearts of all his judges. But he, calm and undisturbed
amid the terrors of this trial, as he had been in the fury of the dispute,
bore such an aspect of composure, that all who sat in the council
were struck with his angelic look. The high priest, however, having
heard the accusation, solemnly called on the prisoner to say
“whether these things were so.” Stephen then, with a determination
to meet the charge by a complete exhibition of his views of the
character and objects of the Jewish faith, ran over the general
history of its rise and progress, and of the opinions which its
founders and upholders had expressed concerning the importance
and the perpetuity of those types and forms, and of the glorious
temple which was their chief seat, when compared with the
revelation to be expected through the prophet promised to them by
God and foretold by Moses. Warming as he went on, he quoted the
poetical words of Isaiah, on the dwelling-place of the Almighty, as not
being confined to the narrow bounds of the building which was to
them an object of such idolatrous reverence, as the sole place of
Jehovah’s abode, but as being high in the heavens, whence his
power and love spread their boundless grasp over sea and land, and
all nations that dwelt beneath his throne. As the words of the prophet
of the fire-touched lips rolled from the voice of Stephen, they kindled
his soul into an ecstacy of holy wrath; and in open scorn of their
mean cruelty, he broke away from the plan of his discourse, bursting
out into burning expressions of reproach and denunciation, which
carried their rage away beyond all bounds of reason. Conscious of
their physical power to avenge the insult, the mob instantly rose up,
and hurried him away from the court, without regard to the forms of
law; and taking him without the city, they stoned him to death, while
he invoked on them, not the wrath, but the mercy of their common
God. In such prayers, gloriously crowning such labors and
sufferings, he fell asleep, commending his spirit to the hands of that
Lord and Savior, whom it was his exalted honor to follow, first of all,
through the bitter agonies of a bloody death.
the persecution.
Among the nameless herd of Stephen’s murderers and disputants,

there was one only whose name has been preserved from the
impenetrable oblivion which hides their infamy. And that name now is
brought to the mind of every Christian reader, without one emotion of
indignation or contempt, for its connection with this bloody murder.
That man is now known to hundreds of millions, and has been for
centuries known to millions of millions, as the bright leader of the
hosts of the ransomed, and the faithful martyr who sealed with his
blood the witness which this proto-martyr bore beneath the
messengers of death to which his voice had doomed him. In the
synagogue of the Cilicians, which was so active in the attack on
Stephen, was a young man, who was not behind the oldest and the
fiercest, in the steady, unrelenting hate which he bore to this
devouring heresy. He gave his voice amid the clamors of the mob, to
swell the cry for the death of the heretic; and when the stout
murderers hurled the deadly missiles on the martyr’s naked head, it
was he who took charge of the loose garments which they had
thrown off, that they might use their limbs with greater freedom.
Neither the sight of the saintly martyr, kneeling unresistingly to meet
his bloody death, nor the sound of his voice, rising in the broken
tones of the death-agony, in prayer for his murderers, could move
the deep hate of this young zealot, to the least relenting; but the
whole scene only led him to follow this example of merciless
persecution, which he here viewed with such deep delight. Abundant
opportunities for the exercise of this persecuting spirit soon occurred.
In connection with the charge against Stephen, which, however
unfounded, brought him to this illegal death, there was a general and
systematic disturbance raised by the same persons, against the
church in Jerusalem, more particularly directed, as it would seem,
against the Hellenist members, who were involved, by general
suspicion, in the same crime for which Stephen, their eminent
brother, had suffered. Saul now distinguished himself at once above
all others, by the active share which he took in this persecution.
Raging against the faithful companions of the martyred Stephen, he,
with the most inquisitorial zeal, sought them out, even in their own
quiet dwellings, and violating the sanctity of home, he dragged out
the inmates to prison, visiting even on helpless women the crime of
believing as their consciences prompted, and without regard to
delicacy or decency, shutting them up in the public dungeons. As
soon as the storm began to burst on the new converts, those who
were in any special danger of attack very properly sought safety in
flight from the city, in accordance with the wise and merciful
injunction laid upon the apostles by their Lord, when he first sent
them forth as sheep in the midst of wolves,――“When they
persecute you in one city, flee into another.” The consequences of
this dispersion, however, were such as to turn the foolish rage of the
persecutors to the solid advantage of the cause of Christ, and to
show in what a variety of ways God can cause the wrath of man to
praise him. For all those who were thus driven out of their peaceful
homes, became missionaries of the word of truth, among the people
of the various cities and countries through which they were
scattered. All those of whose wanderings we have any account,
seem to have journeyed northward and north-westward, probably all
of them foreign Jews, who naturally returned home when driven out
of Jerusalem. Some of these went, in this way, to the Phoenician
coast, to Antioch, and to Cyprus, all laboring to extend the
knowledge of that truth for which they were willing sufferers. But of
all those who went forth on this forced mission, none appear to have
been more successful than Philip, who stood next to the martyred
Stephen on the list of the seven Hellenist servants of the church, and
who appears to have been second not even to his great fellow-
servant in ability and energy. His home was in Caesarea, on the sea-
coast; but he had higher objects than merely to take refuge in his
own domestic circle; for instead of thus indulging his feelings of
natural affection, he also turned his course northward, and made his
first sojourn in the city of Samaria, where he immediately began to
preach Christ to them, as the common Messiah, so long desired by
Samaritans as well as Jews. Here, the people being ruled by no
tyrannical sectaries, like the Pharisees and Sadducees, and the
various orders of ecclesiastical power in Jerusalem, were left entirely
to follow the impulse of their better feelings towards the truth, without
the fear of any inquisition into their movements. Under these happy
circumstances of religious freedom, they all with one accord gave
heed to the preaching of Philip, hearing and seeing the wonderful
works of kindness which he did. For foul spirits, which, possessing
many sufferers, had long wasted their bodies and deranged their
minds, now at the word of this preacher of Christ, came out of many
of them, crying with a loud voice in attestation of the irresistible
power which had overcome them. Many also that were affected with
palsies and that were lame, were healed in the same miraculous
manner; so that, in consequence of this removal of so many bodily
and spiritual evils, there was great joy in the city, at the arrival of this
messenger of mercy. But before the coming of Philip, the people of
Samaria had been the subjects of arts of a somewhat different kind,
from a man who could claim for his works none of the holy character
of disinterested humanity, which belonged to those of the preacher of
Christ. This was one Simon, a man who, by the use of some magical
tricks, had so imposed upon the simple-minded citizens, that they
were profoundly impressed with the notion, which he was anxious to
make them believe, namely, that he was a great man. To him they
all, both young and old, paid the deepest reverence, in consequence
of the triumphant ability displayed by him in the arts of sorcery; and
so low were their notions of the nature of miraculous agency, that
they concluded that the tricks which he played were tokens of divine
interposition in his favor, and universally allowed that he was himself
a personification of the mighty power of God. But when Philip came
among them, and exhibited the genuine workings of the holy spirit of
God, they immediately saw how much they had been mistaken in
their previous estimate of its operations, and changed their degraded
notions, for a more just appreciation of its character. On hearing the
word of truth so fully revealed and supported, they believed in the
new view which he gave them of the kingdom of God on earth, and
in the name of Jesus Christ; and were baptized, both men and
women. Even Simon himself, overwhelmed with the evidences of a
higher power than any that he knew, confessed the fallacy of his own
tricks, and submissively owned the power of God as manifested in
the words and deeds of Philip, with whom he now remained, a
humble and wondering observer of the miracles and signs wrought
by him.
the visit to samaria.
In the mean time, the apostles had remained at Jerusalem,

apparently not directly affected by the persecution against Stephen
and his friends, or at least not disturbed by it so as to be prevented
from remaining at their original post, in the discharge of duty. For, a
true regard for the instructions long ago given them by their Master,
would have required them to leave Jerusalem, if the opposition to
their preaching became so settled and extensive as to prevent them
from advancing the cause of Christ there, more rapidly than they
might in other places. The spirit with which they had been taught to
meet tyrannical opposition, was not one of idle bravado or useless
pertinacity, but of deliberate and calculating steadiness in their plan,
which knew when to prudently give way, as well as when to boldly
withstand. It is therefore fair to conclude, that the persecution here
referred to, was so limited as not to be directed against the apostles
themselves, nor to hinder their useful labors. If any of them had been
imprisoned during this persecution, certainly the rest would have
been blamable for not escaping; but the fact that they remained
perfectly free, appears from their leaving the city without delay, on
the occasion which now required their presence and assistance
elsewhere. For as soon as they heard of the preaching of Philip at
Samaria, and of the willingness with which the Samaritans had
received and believed the first communications of the word, they
immediately sent to them Peter and John, who, as the chief teachers
of the doctrines of Christ, might give the new converts a fuller
preparation for their duties in their calling, than could be expected
from one so lately commissioned as the zealous preacher who had
first awakened them. These two great apostles, having come down
to Samaria, prayed for the believers there that they might receive the
Holy Spirit; for this heavenly gift had not yet been imparted to them;
the only sign of their acceptance into the new faith having been their
baptism by the hands of Philip, who does not seem to have been
empowered to indue others with the same divine spirit which he had
so abundantly received on himself. But the apostles laying their
hands on them, as they had before done with such powerful effect
on Stephen, Philip and their fellow-servants, now also inspired these
second fruits with the same divine energy, which was instantly made
manifest in them, by the usual signs. As soon as Simon saw the
display of the new powers, with which those were suddenly gifted
who had been made the subjects of this simple ceremony, he
immediately concluded that he had at last found out the means of
acquiring those miraculous powers at which he had been so deeply
amazed, and which he thought he could make vastly profitable to
himself in his business, as a very decided improvement upon his old
tricks. Thinking only of the motive which always moved his mind to
the bestowment of such favors, he immediately took out the money
he had gained by his impositions on the people, and offered the
apostles a handsome share of it, if they would simply give him the
valuable privilege of conferring this divine agency on all upon whom
he should lay his hands, in the same manner as they. But his
mercenary hopes were soon blasted by the indignant terms in which
Peter rejected his insulting proposal. “Thy money perish with thee,
because thou hast thought that the gift of God could be bought with
money. Thou hast neither part nor lot in this matter; for thy heart is
not right in the sight of God. Change thy mind, therefore, from this
wickedness of thine, and ask God, if indeed there is any possibility,
that the iniquity of thy heart may be forgiven thee; for I see that thou
art still full of the bitterness of thy former poisons, and bound fast in
the chains of thy old iniquities.” Simon, hushed and overawed in his
impertinent offers by this stern rebuke, sunk into a penitent tone
again, and begged of them that they would pray for him, that the
doom to perish with his money, as declared by Peter, might not fall
on him. Of the depth and sincerity of his penitence, no good
testimony is left us; but his submissive conduct, at best, seems to
have been rather the result of a personal awe of the apostles, as his
superiors in supernatural powers, than prompted by any true regard
for their pure faith, or any just appreciation of their character and
motives. The apostles, however, waited no longer to enlighten the
mind of one so dark in his views of the divine agency; but after they
had borne witness to the truth of Philip’s words and doctrines by their
own preaching, they returned to Jerusalem, proclaiming the gospel
in many villages of the Samaritans, on the way. Philip also, having
had his labors thus triumphantly crowned by the ministrations of the
apostles, left Samaria, and turned his course southwards, towards
Gaza, under the impulse and guidance of a divine spirit. On this
journey, occurred his most interesting adventure with the lord high
treasurer of the Ethiopian queen, after which Philip was found at
Ashdod, on the sea, from which place, journeying northwards again,
he went preaching through all the towns on the coast, till he arrived
at his home, at Caesarea.
JAFFA――JOPPA.
the beginning of peace.
Soon after the return of the apostles to Jerusalem, an event

occurred, which had a more mighty influence on the progress of the
Christian religion than any other that had occurred since the
ascension of Jesus. The members of the church who still withstood
the storm of persecution in the city, were struck with no small
amazement by the sudden appearance, before them, of Saul of
Tarsus, the most bloody persecutor of their Hellenist brethren, who,
having exhausted the opportunities for the gratification of his spite
against them in Jerusalem, had gone to Damascus, to seize such as
there supposed themselves safe in following the new faith. This man,
yet stained, as it were, with the blood of Stephen, now presented
himself to them as a convert to the gospel, prepared to join them as
a brother. The whole affair seemed to bear so decidedly the aspect
of a palpable imposition, that they altogether refused to have any
thing to do with him, and suspected the whole to be a deep-laid
snare, on the part of this bloody foe of the gospel, who now
appeared to be seeking, by false professions, to get into their
confidence, that he might have the means of betraying them to utter
ruin. But Barnabas, who was better acquainted with Saul, detailed to
the church all the wonderful circumstances so fully, that they no
longer hesitated to receive him as a brother and fellow-laborer. This
remarkable conversion was of vast benefit to the cause of the
gospel, not only by bringing to its aid the services of a laborer so
competent, but also by removing from among its adversaries one
who had been a leader and a contriver of every plot of mischief. As
soon as he left the ranks of the foe, the vindictive persecution, which
had raged ever since the death of Stephen, ceased, as though it had
lost its great author and main support, by the defection of Saul of
Tarsus. Indeed, the last act of this persecution, which is recorded,
was directed against this very man, who had once been a leader in
it, and drove him out of the city which had been the scene of his
cruelties. Therefore, the churches had rest throughout all Judea, and
Galilee, and Samaria, strengthening and advancing in piety, and
filled with the impulses of the Holy Spirit. This opportunity of quiet
seemed peculiarly favorable for a minute survey of the condition of
these scattered churches, most of which had grown up without any
direct agency of the apostles, and therefore needed their attention at
this critical period.
the survey of the churches.
The most proper person for this responsible charge, was the great
leader of the apostolic band; and Peter, therefore, taking the task
readily upon himself, went through all the churches, to give them the
advantages of the minute personal ministry of a chief apostle, who
might organize them, and instruct the disciples in their peculiar
duties as members of a new religious community. On this tour of
duty, passing down from the interior towards the sea-coast, he came
to Lydda, about forty or fifty miles from Jerusalem, and about twelve
from the sea. Here there was a company of the faithful, whom he
visited, to instruct them anew, and to enlarge their numbers, by his
preaching and miracles. A particular case is recorded as having
occurred here, which displayed both the compassion of Peter and
his divine power to heal and strengthen. Among the friends of Christ
whom he visited here, was an invalid, whose name, Aeneas, shows
him to have been a Hellenist. This man had for the long period of
eight years been deprived of the use of his limbs, by a palsy, which,
during that tedious interval, confined him to his bed. Peter, on seeing
him, said, “Aeneas, Jesus Christ heals thee. Arise, and make thy
bed for thyself.” The command to spread and smooth the couch,
which he now quitted in health, was given, that he might show and
feel, at once, how fully strength was restored to his hands as well as
his feet. This miracle soon became known, not only to the citizens of
Lydda, but also to the people inhabiting the extensive and fertile
plain of Sharon, which stretched to the northward of Lydda, along the
coast, from Joppa to Caesarea, bounded on the west by the
highlands of Samaria. The effect of this display of power and
benevolence, was such, on their minds, that, without exception, they
professed their faith in Christ.
Lydda.――This was a place of far more importance and fame, than would be supposed
from the brief mention of its name in the apostolic narrative. It is often mentioned in the
writings of the Rabbins, under the name of ‫( לוד‬Ludh,) its original Hebrew name, and was
long the seat of a great college of Jewish law and theology, which at this very period of
Peter’s visit was in its most flourishing state. This appears from the fact that Rabbi Akiba,
who raised the school to its greatest eminence, was contemporary with the great Rabban
Gamaliel, who bears an important part in the events of the apostolic history. (The data of
this chronological inference I find in Lightfoot.) It is easy to see, then, why so important a
seat of Jewish theology should have been thought deserving of the particular notice and
protracted stay of Peter, who labored with remarkable earnestness and effect here, inspired
by the consciousness of the lasting and extensive good, that would result from an
impression made on this fountain of religious knowledge. The members of the college,
however, did not all, probably, profess themselves followers of Christ.
It is also described as possessing some importance in addition to its literary privileges.

Josephus (Antiquities XX. vi. 3.) mentions “Lydda” as “a village not inferior to a city in
greatness.” Its importance was, no doubt, in a great measure derived from the remarkably
rich agricultural district which surrounded it. This was the plain of Sharon, so celebrated in
the Hebrew scriptures for its fruitful fields and rich pastures,――its roses and its flocks.
(Solomon’s Song ii. 1: Isaiah xxxiii. 9: xxxv. 2: lxv. 10: 1 Chronicles xxvii. 29.) “All this
country is described by Pococke as very rich soil, throwing up a great quantity of herbage;
among which he specifies chardons, rue, fennel, and the striped thistle, ‘probably on this
account called the holy thistle.’ A great variety of anemonies, he was told, grow in the
neighborhood. ‘I saw likewise,’ he adds, ‘many tulips growing wild in the fields (in March;)
and any one who considers how beautiful those flowers are to the eye, would be apt to
conjecture that these are the lilies to which Solomon, in all his glory, was not to be
compared.’”――[Modern Traveler, p. 57.] Its distance from Jerusalem is ascertained, by
Lightfoot, to be one day’s journey, as it is stated with some circumlocution in the Mishna. It
was destroyed, as Josephus relates, by Cestius Gallus, the Roman general, who marched
his army through that region, in the beginning of the war, which ended in the destruction of
Jerusalem. Under the peaceful times of the later Roman sway in Palestine, it was rebuilt,
and called Diospolis. But like many other such instances, it has lost its temporary heathen
name, and is now called by its old scripture appellation, Ludd. Travelers describe it as now
a poor village, though the stones to be seen in the modern buildings show that it has been a
place of great consequence.
The New Testament name Lydda, (Λυδδα,) by which Josephus also mentions it, is only
so much changed from the Hebrew Ludh, as was necessary to accommodate it to the
regular forms and inflexions of the Greek language. Lightfoot well refutes the blunder of
many modern geographers who make the two names refer to different places. This learned
author is remarkably full in the description of this place, and is very rich in references to the
numerous allusions which are made to it in the Talmudic writings. See his Centuria
Chorographica, (Chapter 16,) prefixed to Horae Hebraica et Talmudicae in Matthew.
Aeneas.――This name is unquestionably Greek, which seems to show the man to have
been a Hellenist; and that he was already a believer in Christ, would appear from the fact of
Peter’s finding him among the brethren there.
the visit to joppa.
Hardly had this instance of divine favor occurred in Lydda, when a

new occasion for a similar effort presented itself, in the neighboring
seaport town of Joppa. A female disciple of the faith of Christ, in that
city, by name Tabitha, or in the Greek, Dorcas, (both names meaning
Gazelle,) had distinguished herself and honored her religious
profession, by the generous and charitable deeds which constantly
employed her hands. This lady, so respected by all, and so loved by
the poor, who gave witness to her goodness,――such an honor to
the religious community which she had joined,――seemed to have
so nobly done her part in life, that the order of Providence had
apparently called her to rest from these labors, in that sleep from
which no piety nor usefulness can save or recall their possessor.
After a few days of illness, she died, and was, after the usual funeral
ablutions, laid in an upper chamber, to await the burial. In the midst
of the universal grief for this sad loss, the members of the church at
Joppa, knowing that Peter was in Lydda, within a few hours’ journey,
sent two messengers to him, to beg his presence among them, as
some consolation in their distress. Peter, on hearing of this occasion
for his presence, with great readiness accompanied the messengers
back, and on arriving at Joppa, went straight to the house of
mourning. He was immediately led into the chamber, where he found
a most affecting testimony to the nature of the loss which the afflicted
community had suffered. Around the dead, stood the widows who, in
their friendlessness, had been relieved by the sympathy of Dorcas,
now pouring their tears and uttering their lamentations over her, and
showing that even the garments which they wore were the work of
her industrious hand,――that hand which, once so untiring in these
labors of love, was now cold and motionless in death. From that
resistless doom, what mortal voice could ever recall even one so
amiable and useful? But, while they were sorrowing thus, Peter
ordered them all to leave him alone with the dead; and when all
witnesses were removed, he kneeled and prayed. The words of that
prayer are not recorded; and it is only by its successful efficiency that
we know it to have been that fervent effectual prayer of a righteous
man, which availeth much. It was such a prayer as, of old, the son of
Shaphat offered over the dead child of the Shunamite, when alone
with him; and its effect was not less mighty. Rising at length, and
turning towards the body, he said “Tabitha, arise!” Awaking from the
unbreathing sleep of death, as from a light slumber of an hour, she
opened her eyes, and when she saw the majestic man of God alone,
and herself robed for the tomb, she sat up and gazed in amazement.
Peter, then, giving her his hand, lifted her from the funeral couch,
and calling in the brethren and the widows; he presented her to their
astonished eyes, alive. Their overwhelming joy and wonder, we are
left to imagine. The story, when made known through the city,
brought many to acknowledge the truth of that religion whose
minister could work such wonders; and many believed in Christ. The
field of labor which now opened to Peter in this place, seemed so
wide that he did not continue his journey any further at that time, but
took up his abode, for several days, in Joppa, lodging in the house of
Simon, a tanner, whose house stood by the sea, near the water.
Joppa, now called Jaffa.――This was from very early times a place of great importance,
from the circumstance of its being the nearest seaport to Jerusalem. It is mentioned in
reference to this particular of its situation, in 2 Chronicles ii. 17, where it is specified (in
Hebrew ‫ יפו‬Japho) as the port to which the cedar timber from Lebanon should be floated
down in rafts, to be conveyed to Jerusalem for building the temple. It stood within the
territories of the tribe of Dan, according to Joshua xix. 46, and lies about East-North-east
from Jerusalem. Strabo, (xvi.) in describing it, refers to it as the scene of the ancient
Grecian fable of Andromeda rescued from the sea-monster by Perseus. He describes its
site as “quite elevated,――so much so, indeed, that it was a common saying that Jerusalem
might be seen from the place; the inhabitants of which city use it as their seaport, in all their
maritime intercourse.” Josephus mentions that it was added to the dominions of Herod the
Great by Augustus. Its present appearance is thus described by travelers.
“It is situated in latitude 32 degrees 2 minutes North, and longitude 34 degrees 53

minutes East, and is forty miles West of Jerusalem. Its situation, as the nearest port to the
Holy City, has been the chief cause of its importance. As a station for vessels, according ♦to
Dr. Clarke, its harbor is one of the worst in the Mediterranean. Ships generally anchor about
a mile from the town, to avoid the shoals and rocks of the place. The badness of the harbor
is mentioned, indeed, by Josephus. (Josephus, Antiquities, book xv. chapter 9.) * * * The
road is protected by a castle built on a rock, and there are some storehouses and
magazines on the sea-side. The coast is low, but little elevated above the level of the sea;
but the town occupies an eminence, in the form of a sugar-loaf, with a citadel on the
summit. The bottom of the hill is surrounded with a wall twelve or fourteen feet high, and
two or three feet thick. * * * There are no antiquities in Jaffa: the place would seem to be too
old to have any――to have outlived all that once rendered it interesting. The inhabitants are
estimated at between four and five thousand souls, of whom the greater part are Turks and
Arabs; the Christians are stated to be about six hundred, consisting of Roman Catholics,
Greeks, Maronites, and Armenians.” [Modern Traveler, Palestine, pp. 41, 42.]
♦ “io” replaced with “to”
Dorcas.――This is the Greek translation of the old Hebrew ‫( צבי‬Tsebi,) in the Aramaic
dialect of that age, changed into ‫( תביתא‬Tabitha,) in English, “gazelle,” a beautiful animal of
the antelope kind, often mentioned in descriptions of the deserts of south-western Asia, in
which it roams; and not unfrequently the subject of poetical allusion. The species to which it
is commonly supposed to belong, is the Antilopa Dorcas of Prof. Pallas, who named it on
the supposition that it was identical with this animal, called by the Greeks, Δορκας, (Dorkas,)
from Δερκο, (Derko,) “to look,” from the peculiar brightness of “its soft black eye.”
the call to the heathen.
The apostles had now, with great zeal and efficiency, preached
the gospel of Jesus Christ to the worshipers of the true God,
beginning at Jerusalem, and spreading the triumphs of his name to
the bounds of the land of Israel. But in all their devotion to their
Master’s work, they had never had a thought of breaking over the
bounds of the faith of their fathers, or of making their doctrine
anything else than a mere completion or accompaniment to the law
of Moses; nor did they imagine that they were ever to extend the
blessings of the gospel to any who did not bow down to all the
tedious rituals of the ancient covenant. The true power of their Lord’s
parting command, “Go and teach all nations,” they had never felt;
and even now, their great chief supposed that the change of heart
and remission of sins, which he was commissioned to preach, were
for none but the devout adherents of the Jewish faith. A new and
signal call was needed, to bring the apostles to a full sense of their
enlarged duties; and it is among the highest honors vouchsafed to
Peter, that he was the person chosen to receive this new view of the
boundless field now opened for the battles and triumphs of the cross.
To him, as the head and representative of the whole band of the
apostles, was now spread out, in all its moral vastness and its
physical immensity, the coming dominion of that faith, whose little
seed he was now cherishing, with but a humble hope; but whose
stately trunk and giant branches were, from that small and low
beginning, to stretch, in a mighty growth, over lands, and worlds, to
him unknown. Thus far he had labored with a high and holy zeal, in a
cause whose vastness he had never appreciated,――every moment
building up, unwittingly, a name for himself, which should outlast all
the glories of the ancient covenant; and securing for his Master a
dominion which the religion of Moses could never have reached. He
had never had an idea, that he with his companions was founding
and spreading a new religion;――to purify the religion of the law and
the prophets, and to rescue it from the confusion and pollutions of
warring sectaries, was all that they had thought of; yet with this end
in view, they had been securing the attainment of one so far above
and beyond, that a full and sudden view of the consequences of their
humble deeds, would have appalled them. But though the mighty
plan had never been whispered nor dreamed of, on
earth,――though it was too immense for its simple agents to endure
its full revelation at once,――its certain accomplishment had been
ordained in heaven, and its endless details were to be fully learned
only in its triumphant progress through uncounted ages. But, limited
as was the view which the apostles then had of the high destiny of
the cause to which they had devoted themselves, it was yet greatly
extended from the low-born notions with which they had first followed
the steps of their Master. They now no longer entertained the vagary
of a worldly triumph and a worldly reward; they had left that on the
mount where their Lord parted from them, and they were now
prayerfully laboring for the establishment of a pure spiritual kingdom
in the hearts of the righteous. To give them a just idea of the exalted
freedom to which the gospel brought its sons, and to open their
hearts to a Christian fellowship, as wide as the whole human family,
God now gave the apostolic leader an unquestionable call to tell to
the world the glad tidings of salvation, for all men, through a new and
living way, by change of heart and remission of sins. The incidents
which led to this revelation are thus detailed.
The peace and good order of Palestine were now secured by

several legions, whose different divisions, larger or smaller according
to circumstances, were quartered in all the strong or important
places in the country, to repress disorders, and enforce the authority
of the civil power, when necessary. Besides this ordinary peace-
establishment of the province, there was a cohort which took its
name from the circumstance that it had been levied in Italy,――a
distinction, now so rare, in consequence of the introduction of foreign
mercenaries into the imperial hosts, as to become the occasion of an
honorable eminence, which was signified by the title here given,
showing that this division of the Roman armies was made up of the
sons of that soil which had so long sent forth the conquerors of the
world. Of all the variety of service required of the different
detachments of the army, in the province which it guarded, by far the
most honorable was that of being stationed next the person of the
governor of the province, to maintain the military dignity of his vice-
imperial court, and defend his representative majesty. Caesarea, on
the sea-shore, was now the seat of the Roman government of
Palestine; and here, in attendance on the person of the governor,
was this aforesaid Italian cohort, at the head of a company in which,
was a centurion named Cornelius. Though nothing is given
respecting his birth and family but this single name, a very slight
knowledge of Roman history and antiquities enables the historian to
decide, that he was descended from a noble race of patricians,
which had produced several of the most illustrious families of the
imperial city. Eminent by this high birth and military rank, he must
have been favored with an education worthy of his family and
station. It is therefore allowable to conclude, that he was an
intelligent and well-informed gentleman, whom years of foreign
service, in the armies of his country must have improved by the
combined advantages of a traveler and a disciplined warrior. Of his
moral and religious character such an account is given, as proves
that his principles, probably implanted in early life, had been of such
firmness as to withstand the numerous temptations of a soldier’s life,
and to secure him in a course of most uncommon rectitude in his
duties towards God and towards man. In the merciful exercise of his
power over the people whose safety and quiet he came to maintain,
and, moreover, in the generous use of his pecuniary advantages, he
passed his blameless life; and the high motive of this noble conduct,
is discovered in the steady, pure devotion, in which he employed
many hours of daily retirement, and in which he caused his whole
family publicly to join, on proper occasions. Thus is he briefly and
strongly characterized by the sacred historian: “devout, and fearing
God with all his house; giving much alms, and praying to God
always.”
Noble race of patricians.――The gens Cornelia, or “Cornelian race,” was unequaled in

Rome for the great number of noble families sprung from its stock. The Scipios, the Sullas,
the Dolabellas, the Cinnas, the Lentuli, the Cethegi, the Cossi, and many other illustrious
branches of this great race, are conspicuous in Roman history; and the Fasti Consulares,
record more than sixty of the Cornelian race, who had borne the consular dignity previous to
the apostolic era. This is always a family name, and Ainsworth very grossly errs in calling it
“the praenomen of several Romans.” Every Roman name of the middle and later ages of
the commonwealth, had at least three parts, which were the praenomen, marking the
individual,――the nomen marking the gens, (“race,” “stock,”) and the cognomen, marking
the family or division of that great stock. Thus in the name “Publius Cornelius Scipio,” the
last word shows that the person belonged to the Scipio family, which by the second word is
seen to be of the great Cornelian stock, while the first shows that this member of the family
was distinguished from his relations, by the name of Publius. (See Adams’s Roman
Antiquities, on Names.) Wherever this name, Cornelius, occurs, if the whole appellation of
the man is given, this comes in the middle, as the nomen, marking the race; as is the case
with every one of those quoted by Ainsworth, in his blundering account of the word. See
also Sallust, (The Catilinarian Conspiracy, 47, 55,) in defense of this peculiar limitation of
the word to the gens. Not a single instance can be brought of its application to any person
not of this noble patrician race, or of its use as a mere individual appellation. I am therefore
authorized in concluding that this Cornelius mentioned in the Acts was related to this line of
high nobility. It might, perhaps, be conjectured, that he had borrowed this name from that
noble race, from having once been in the service of some one of its families, as was
common in the case of freedmen, after they had received their liberty; but this supposition is
not allowable; for he is expressly particularized as belonging to an Italian division of the
army, which fact excludes the idea of that foreign origin which would belong to a slave. The
Jews having but one name for each man, seldom gave all of a Roman’s name, unless of a
very eminent man, as Pontius Pilate, Sergius Paulus, and other official characters; but
selecting any one of the three parts which might be most convenient, they made that the
sole appellative, whether praenomen, nomen, or cognomen. As in Luke ii. 2: Acts xxiii. 24:
xxv. 1: xxvii. 1: xxviii. 7, &c.
JERUSALEM,
from the Latin Convent.
Luke xxi. 24.
The Italian cohort.――The word Σπειρα (Speira) I translate “cohort,” rather than “legion,”
as the older commentators did. Jerome translates it “cohortem,” and he must have known
the exact technical force of the Greek word, and to what Latin military term it corresponded,
from his living in the time when these terms must have been in frequent use. Those who
prefer to translate it “legion,” are misled by the circumstance, that Tacitus and other writers
on Roman affairs, mention a legion which had the distinctive appellation of “the Italian
Legion;” while it has been supposed that these ancient authors make no mention of an
Italian cohort. But the deeply learned Wetstein, with his usual vast classical research, has
shown several such passages, in Arrian and others, in which mention is made of an Italian
cohort; and in Gruter’s inscriptions, quoted by Kuinoel, there is an account of “a volunteer
cohort of Italian soldiers in Syria;” and Palestine was at this time included with Syria, under
the presidency of Petronius. This inscription, too, justifies my remark as to the high
character of those who served in this corps. “Cohors militum Italicorum voluntaria” seems to
imply a body of soldiers of a higher character than the ordinary mercenary mass of the
army, being probably made up of volunteers from respectable families of Italy, who chose to
enlarge their knowledge of the world by foreign military service, in this very honorable
station of life-guard to the Roman governor, as Doddridge and others suppose this to have
been. (See Doddridge on this passage; also C. G. Schwartz in Wolff, Cur. Philology in loc.)
It is considered also as fairly proved that the “Italian legion” was not formed till a much later
period; so that it is rendered in the highest degree probable and unquestionable, that this
was a cohort, and, as Schwartz and Doddridge prove, not a mere ordinary cohort, making
the tenth part of a common legion of 4200, but a distinct and independent corps, attached to
no legion, and devoted to the exclusive honorable service above mentioned. (See
Bloomfield, Kuinoel, Rosenmueller, &c.)
Devout.――Some have tried hard to make out that Cornelius was what they call “a
proselyte of the gate;” that is, one who, though not circumcised, nor conforming to the
rituals generally, yet was an observer of the moral law. But Lardner very fully shows that
there were not two sorts of proselytes; all who bore that name fully conforming to the Jewish
rituals, but still called “strangers,” &c.; because, though admitted to all the religious
privileges of the covenant, they were excluded from the civil and political privileges of Jews,
and could not be freeholders. Cornelius must then have been a mere Gentile. (See Lardner
in his life of Peter; also Kuinoel and Bloomfield.)
Caesarea.――This is another of those cities enlarged or rebuilt by the princes of the

Herodian line, and honored with the names of the imperial family. This city stood on the sea-
shore, about 30 miles north of Joppa; and (Modern Traveler) 62 north-north-west from
Jerusalem. (600 stadia Josephus.) It has been idly conjectured by the Rabbinical writers,
that this was the same with Ekron, of the Old Testament, Zephaniah ii. 4; while the Arabic
version gives it as Hazor, Joshua xi. 1,――both with about equal probability. The earliest
name by which it can be certainly recognized, is Apollonia, which it bore when it passed
from the Syro-Grecians to the Maccabean princes. Its common name, in the time of Herod
the Great, was πυργος Στρατωνος, turris Stratonis, “Straton’s castle,” from the name of a
Greek pirate who had built a strong hold here. Herod the Great made it the most splendid
city in his dominions, and even in all the eastern part of the Roman empire; and in honor of
Augustus Caesar, called it Caesarea Augusta. It was sometimes called Caesarea
Palestinae, to distinguish it from Caesarea Philippi; for Palestine was then a name limited to
the southern part of the coast of the Holy Land, and was bounded on the north by
Phoenicia. This city was the capital of the whole Holy Land throughout the period of the
later Herodian and Roman sway.

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Molybdenum and Tungsten

Spectroscopic and Theoretical Investigations

RSC Metallobiology Series No. 7

Print ISBN: 978-1-78262-878-1

© The Royal Society of Chemistry 2017

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Published by The Royal Society of Chemistry,

Registered Charity Number 207890

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

RSC Metallobiology Series No. 7

a wide range of metabolic pathways and play particularly prominent roles

RSC Metallobiology Series No. 7

and molybdenum complexes when, beginning in the late 1970s, he became

Chapter 1 Spectroscopic and Electronic Structure Studies

Chapter 2 Spectroscopic and Electronic Structure Studies of

2.1 I ntroduction and Scope  13

RSC Metallobiology Series No. 7

2.4 Xanthine Oxidoreductase (XOR)  35

Chapter 3 Electron Paramagnetic Resonance Studies of

3.3.3 g-Tensor Analysis of Mo-bisPGD Active Site:

Chapter 4 X-Ray Absorption Spectroscopy of Molybdenum and

4.1 I ntroduction  121

4.3.4 Combining XAS with Other

Chapter 5 Electrochemistry of Molybdenum and Tungsten

5.1 I ntroduction  168

6.1 I ntroduction  223

Chapter 7 Computational Studies of Molybdenum and Tungsten

7.1 I ntroduction  275

7.7 Conclusions  314

Subject Index  322

Spectroscopic and Electronic

RSC Metallobiology Series No. 7

detail how spectroscopy, structure, electrochemistry and theory have been

Spectroscopic and Electronic Structure Studies Probing Mechanism 3

E-MoVI + R + H2O → E-MoIV + R–O + 2H+

Regarding substrate oxidations, reductive oxygen atom transfer is given

E-MoVI + R–H + H2O → E-MoIV + R–OH + 2H+

Spectroscopic and Electronic Structure Studies Probing Mechanism 5

crucial interrelationships between spectroscopic features of the active sites

Greeks.――The original word here is not Ἑλληνες, (Hellenes,) but Ἑλληνιστοι,

christ’s first martyr.

Among the nameless herd of Stephen’s murderers and disputants,

the visit to samaria.

In the mean time, the apostles had remained at Jerusalem,

Chapter 1 Spectroscopic and Electronic Structure Studies

Chapter 2 Spectroscopic and Electronic Structure Studies of

2.1 I ntroduction and Scope 13

2.4 Xanthine Oxidoreductase (XOR) 35

Chapter 3 Electron Paramagnetic Resonance Studies of

3.3.3 g-Tensor Analysis of Mo-bisPGD Active Site:

Chapter 4 X-Ray Absorption Spectroscopy of Molybdenum and

4.1 I ntroduction 121

4.3.4 Combining XAS with Other

Chapter 5 Electrochemistry of Molybdenum and Tungsten

5.1 I ntroduction 168

6.1 I ntroduction 223

Chapter 7 Computational Studies of Molybdenum and Tungsten

7.1 I ntroduction 275

7.7 Conclusions 314

Subject Index 322