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Graphical Abstract Angew. Chem. Int. Ed. 432004

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Contents
The following Communications are available online (in Wiley InterScience). You can find them, as
well as forthcoming Reviews, Highlights, and Essays, at www.angewandte.org, under Early View.
T. J. Lowery, S. M. Rubin, E. J. Ruiz, A. Pines, D. E. Wemmer*:
Design of a Conformation-Sensitive Xenon-Binding Cavity in the
Ribose-Binding Protein
DOI: 10.1002/anie.200460629
Published online: October 11, 2004
A. Tsuda,* E. Hirahara, Y.-S. Kim, H. Tanaka, T. Kawai,* T. Aida*:
A Molybdenum Crown Cluster Forms Discrete Inorganic–Organic Nanocomposites with Metalloporphyrins
DOI: 10.1002/anie.200460990
Published online: September 23, 2004
Articles judged by the referees or the editor as being either very important or very urgent are immediately edited, proof-read, and electronically
published once the manuscript has arrived in the editorial office in its final form. As long as there is no page number available these articles should
be cited in the following manner:
Author(s), Angew. Chem. Int. Ed., online publication date, DOI.
News
Nobel Prizes 2004: Protein degradation, Olfactory system, Strong interaction
5722
Books
The Chemistry of Nanomaterials
C. N. R. Rao, Achim M"ller, Anthony K.
Cheetham
reviewed by U. Simon
5723
Nanotechnology
Michael K$hler, Wolfgang Fritzsche
reviewed by M. R. Bockstaller
5723
Life, Death, and Nitric Oxide
Anthony Butler, Rosslyn Nicholson
reviewed by B. Mayer
5724
Highlights
Immobilized Catalysts
L.-X. Dai*
5726 – 5729
Chiral Metal–Organic Assemblies—A
New Approach to Immobilizing Homogeneous Asymmetric Catalysts
5712
Beyond classical immobilized catalysts,
metal–ligand polymers self-assembled
through coordination are easily prepared,
have a robust chiral structure, and display
a high density of catalytically active units.
These heterogeneous catalysts give excellent results for enantioselective reactions
and can be recovered and recycled without
significant loss of selectivity.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5712 – 5721
Angewandte
Chemie
Protein Analysis
S. Brakmann*
5730 – 5734
DNA-Based Barcodes, Nanoparticles, and
Nanostructures for the Ultrasensitive
Detection and Quantification of Proteins
Beyond the shadow of a doubt: Detecting
antigens, antibodies, pathogens, tumor
markers, and potential therapeutics on
the femto- to attomolar concentration
level is still challenging. Nanostructured
materials and the innovative combination
of immunoassays with (real-time) PCR
and magnetic separation techniques hold
promise for the field of ultrasensitive
protein analytics.
Reviews
Enzyme Chemistry
S. R. Hanson, M. D. Best,
C.-H. Wong*
Through the cleavage of sulfate esters
sulfatases modulate the activity of a broad
range of small molecules and proteoglycans (see picture). These enzymes play
critical roles in a number of biological
events, including lysosomal degradation,
hormone regulation, and signaling processes. The structures of sulfatases, their
mechanisms of action, their potential as
targets for small-molecule intervention,
and applications in synthesis are discussed.
5736 – 5763
Sulfatases: Structure, Mechanism,
Biological Activity, Inhibition, and
Synthetic Utility
Communications
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Angew. Chem. Int. Ed. 2004, 43, 5712 – 5721
A comparison of previously proposed
models of the C C bond-forming step of
the title reaction with density functional
methods indicate that the most favored
one involves an enamine intermediate
undergoing a concerted aldol cyclization
with proton transfer from the proline
carboxylic acid group (see structure). This
step is equal in energy to the intramolecular deprotonation leading to the enamine, and both are partially rate-determining steps.
Density Functional Calculations
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F. R. Clemente,
K. N. Houk*
5766 – 5768
Computational Evidence for the Enamine
Mechanism of Intramolecular Aldol
Reactions Catalyzed by Proline
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5713
Angewandte
Chemie
A stream of water molecules, held together by hydrogen bonding, forms a lefthanded helix within the helical channels of
a left-handed staircaselike metal coordination polymer. The result is a novel helixin-a-helix structure. The water-filled channel can be seen on viewing the coordination polymer along the b axis (see picture;
C gray, N blue, Ni green, O red).
Helical Water Chain
Mimicking magnetic minerals: Controlled
hydrolysis of iron(iii) salts leads to allferric molecular fragments with the iron
and oxygen topology of magnetite and
large spin ground states (see structure;
yellow Fe, red O, blue N, gray C).
Magnetic Properties
B. Sreenivasulu, J. J. Vittal*
5769 – 5772
Helix inside a Helix: Encapsulation of
Hydrogen-Bonded Water Molecules in a
Staircase Coordination Polymer
G. W. Powell, H. N. Lancashire,
E. K. Brechin,* D. Collison,* S. L. Heath,*
T. Mallah, W. Wernsdorfer
5772 – 5775
Building Molecular Minerals: All Ferric
Pieces of Molecular Magnetite
Tetrathiometalates [WS4]2 are the nodal
building blocks in a new kind of heterometallic interpenetrating three-dimensional cluster coordination polymer (see
picture) that has interesting nonlinear
optical properties. The polymer exhibits
optical self-focusing behavior and reverse
saturable absorption effects.
Coordination Polymers
K. Liang, H. Zheng,* Y. Song,
M. F. Lappert, Y. Li, X. Xin, Z. Huang,
J. Chen, S. Lu
5776 – 5779
Self-Assembly of Interpenetrating
Coordination Nets Formed from
Interpenetrating Cationic and Anionic
Three-Dimensional Diamondoid Cluster
Coordination Polymers
Protein Interactions
The non-native states of the model protein
hen lysozyme (native state shown in
picture) were investigated by using sitedirected mutagenesis in combination with
high-resolution NMR spectroscopy. The
disruptions of the interactions between
hydrophobic clusters by single point
mutations dramatically alter the overall
compactness of the unfolded state: single
point mutations can turn a compact
unfolded state into an extended state.
Angew. Chem. Int. Ed. 2004, 43, 5712 – 5721
J. Wirmer, C. Schl$rb,
J. Klein-Seetharaman, R. Hirano, T. Ueda,
T. Imoto, H. Schwalbe*
5780 – 5785
Modulation of Compactness and LongRange Interactions of Unfolded Lysozyme
by Single Point Mutations
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5715
Contents
Nanoporous Films
C. Liang, K. Hong, G. A. Guiochon,
J. W. Mays, S. Dai*
5785 – 5789
Synthesis of a Large-Scale Highly Ordered
Porous Carbon Film by Self-Assembly of
Block Copolymers
Peptidomimetics
P. Tremmel, A. Geyer*
5789 – 5791
Coupled Hydrogen-Bonding Networks in
Polyhydroxylated Peptides
Made to order: The synthesis of welldefined porous carbon films involves four
steps: 1) monomer–block copolymer film
casting, 2) structure refining through solvent annealing, 3) polymerization of the
carbon precursor, and 4) carbonization.
The resulting films, such as that depicted,
have potential as separation membranes,
chemical sensors, and catalysts.
Information transfer: Crystal structures of
bicyclic dipeptide analogues within oligopeptides are described for the first time.
The bicyclic dipeptides occupy the i to
i + 1 positions of either bI or bII turns. The
rigidified dipeptides form hydrogenbonding networks which transfer structural information along chains of ambident proton donors and acceptors over
several O (see structures; arrows: hydrogen bonds, red O, blue N, yellow S).
Proton Transfer
O.-H. Kwon, Y.-S. Lee, H. J. Park, Y. Kim,
D.-J. Jang*
5792 – 5796
Asymmetric Double Proton Transfer of
Excited 1:1 7-Azaindole/Alcohol
Complexes with Anomalously Large and
Temperature-Independent Kinetic
Isotope Effects
Bridging alcohols, tunneling protons: The
intrinsic proton-transfer dynamics of
cyclic H-bonded 1:1 7-azaindole/alcohol
complexes in n-alkanes has been investigated at the lowest-lying excited singlet
state with variation of alcohol, solvent,
Making a good impression: Photocurable,
liquid perfluoropolyethers (PFPEs) are
ideal materials for high-resolution
(< 100 nm) pattern transfer and imprint
lithographic processes (see pictures).
PFPEs possess attributes of both elastomers and rigid materials, exhibit a
remarkably low surface energy, mold
extremely small features with high fidelity,
resist swelling by organic solvents, and
endure repetitive molding procedures.
Lithography
J. P. Rolland, E. C. Hagberg,
G. M. Denison, K. R. Carter,*
J. M. De Simone*
5796 – 5799
High-Resolution Soft Lithography:
Enabling Materials for
Nanotechnologies
5716
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
isotope, and temperature by using static
and time-resolved spectroscopy. The
proton transfer occurs asymmetrically,
and the rate is governed by tunneling
although it is assisted by heavy-atom
motions.
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5712 – 5721
Angewandte
Chemie
Expressed-protein ligation has been used
for the semisynthetic preparation of a
Smad2 protein with caged activating
phosphoserine residues. Biochemical and
cell biological experiments show that the
caged protein is activated upon irradiation
with UV light (see scheme). This sets the
stage for the detailed kinetic analysis of
Smad2 function in living cells.
Bioorganic Chemistry
M. E. Hahn, T. W. Muir*
Photocontrol of Smad2, a Multiphosphorylated Cell-Signaling Protein, through
Caging of Activating Phosphoserines
A discrete cyclic nanostructure was
obtained through the self-assembly of
oligonucleotide-branched metal complexes. The picture shows the metal–DNA
nanostructure, which contains two DNA
double-helical arms and two relatively
rigid redox- and photoactive [Ru(bpy)3]2+
vertices.
DNA Superstructures
The 3D starshaped Ru–bpy–DNA complex
pictured comprises a ruthenium(ii)
tris(bipyridyl) center with six DNA 20-mer
sequences tethered through linkers at its
4- and 4’-positions. The complexes 1 and 2
hybridize with six complementary 20-mer
strands to form duplex arms. Alternatively,
the complementary DNA strands in 1 and
2 hybridize with each other to form larger
nanoscale assemblies.
DNA Superstructures
D. Mitra, N. Di Cesare,
H. F. Sleiman*
5804 – 5808
Self-Assembly of Cyclic Metal–DNA
Nanostructures using Ruthenium Tris(bipyridine)-Branched Oligonucleotides
K. M. Stewart, J. Rojo,
L. W. McLaughlin*
5808 – 5811
Ru(ii) Tris(bipyridyl) Complexes with Six
Oligonucleotide Arms as Precursors for
the Generation of Supramolecular
Assemblies
Reducing size helps to oxidize: Unsupported gold particles behave as an efficient catalyst for the aerobic oxidation of
glucose, showing a similar activity to
enzymatic systems. The catalytic activity
is inversely proportional to the particle
diameter (d, see graph). With carbonsupported gold, no gold–support interaction is found; however, the use of a
support avoids particle aggregation thus
preserving the original activity for longer.
Angew. Chem. Int. Ed. 2004, 43, 5712 – 5721
5800 – 5803
www.angewandte.org
Heterogeneous Catalysis
M. Comotti, C. Della Pina, R. Matarrese,
M. Rossi*
5812 – 5815
The Catalytic Activity of “Naked” Gold
Particles
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5717
Contents
Host–Guest Systems
A particularly challenging task is the
design of anion receptors, because anions
are larger than cations and are pH- and
solvent-sensitive. The first host for anionic
guests is a dendritic octadentate N ligand,
which upon reaction with CuCl2, encapsulates chloride ions (Cl6, see picture) as
guests by means of anion–p interactions
in an electron-deficient cavity formed by
four pyridine rings.
P. de Hoog, P. Gamez,* I. Mutikainen,
U. Turpeinen, J. Reedijk*
5815 – 5817
An Aromatic Anion Receptor:
Anion–p Interactions do Exist
Stirring stuff: The morphological evolution of polyaniline from nanofibers to
agglomerates during its chemical polymerization shows that the key to producing pure nanofibers is to suppress secondary growth after formation of the
nanofibers. A simple and effective method
for the synthesis of nanofibers was thus
developed in which the polymerization is
carried out in a rapidly mixed single-phase
reaction (see scheme).
Nanostructures
J. Huang, R. B. Kaner*
5817 – 5821
Nanofiber Formation in the Chemical
Polymerization of Aniline: A Mechanistic
Study
Natural Products Synthesis
A. F. Petri, A. Bayer,
M. E. Maier*
5821 – 5823
Total Synthesis of Apicularen A through
Transannular Pyran Formation
A macrocyclization–transannulation
strategy is the crux of an efficient total
synthesis of the benzolactone enamide
apicularen A (see scheme; Bn = benzyl).
Key steps include a four-component coupling, a Stille cross-coupling to introduce
C N Activation
S. Caddick,* F. G. N. Cloke,*
P. B. Hitchcock,
A. K. de K. Lewis
5824 – 5827
Unusual Reactivity of a Nickel N-Heterocyclic Carbene Complex: tert-Butyl Group
Cleavage and Silicone Grease Activation
5718
the aromatic moiety, and the formation of
the enamide from a hemiaminal. The sizeselective macrolactonization of the
ethoxyvinyl ester shown was followed by
transannular etherification in excellent
yield.
Reaction lubrication? The reaction
between [Ni(1,5-cod)2] (cod = cyclooctadiene) and 1,3-bis-tert-butylimidazol-2-ylidene in the presence of silicone grease
affords the siloxane bridged dimer
[{Ni[C(NtBuCH)2][O(Me2SiOSiMe2)-mO]}2]. In a greaseless apparatus, the same
reaction yields the dimer 1 (see structure),
via two structurally characterized intermediates.
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
Angew. Chem. Int. Ed. 2004, 43, 5712 – 5721
Angewandte
Chemie
Multilayer Assemblies
H. Van Ryswyk,* E. E. Moore, N. S. Joshi,
R. J. Zeni, T. A. Eberspacher,
J. P. Collman*
5827 – 5830
The modular assembly of metalloporphyrin oligomers through the stepwise
addition of Ru–porphyrin units and a
bidentate linking ligand (L, see graphic)
onto a surface-confined isonicotinate
ligand is reported. Electrochemical measurements of the resulting oligomer show
that electrons are transported along the
length of its backbone.
Surface-Confined Metalloporphyrin
Oligomers
Metallocryptands
An As2L3 metallocryptand is the result of a
new predictive design strategy for forming
self-assembled supramolecular arsenic
complexes. The assembly is remarkably
stable to a variety of competing metal
ions, harsh acid, and excess ligand. X-ray
crystallographic studies and density functional calculations suggest that a strong
arsenic–p interaction adds stability to the
structure.
W. J. Vickaryous, R. Herges,
D. W. Johnson*
5831 – 5833
Arsenic–p Interactions Stabilize a
Self-Assembled As2L3 Supramolecular
Complex
Room for expansion: Insertion of a benzene ring into the natural adenine heterocycle to generate the analogue yA
results in the formation of base pairs that
are 2.4 O wider than natural ones (see
structure). Melting temperature and free
energy data show that yA·T and T·yA pairs
can self-assemble into cooperative helices
that are considerably more stable than
natural DNA. Thus, yDNA may be a
candidate for a new genetic system.
DNA Structures
H. Lu, K. He, E. T. Kool*
5834 – 5836
yDNA: A New Geometry for SizeExpanded Base Pairs
C S Bond Cleavage
M. Li, A. Ellern,
J. H. Espenson*
Rhenium reactions: A reaction under mild
conditions between oxo(dithiolato)rhenium(v) complex 1 and triphenylphosphine gives 2. In the reaction a ReO
bond is cleaved, P=O and ReS bonds are
Angew. Chem. Int. Ed. 2004, 43, 5712 – 5721
formed at the expense of a CH2S Re
bond, and a new Re C bond is formed
converting a six-membered chelate ring
into a five-membered one.
www.angewandte.org
5837 – 5839
Phosphine-Promoted Conversion of
Oxo(dithiolato)rhenium(v) into
Thio(thiolatoalkyl)rhenium(v)
Compounds
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5719
Contents
Protein Synthesis
G. Kragol, M. Lumbierres, J. M. Palomo,
H. Waldmann*
5839 – 5842
Solid-Phase Synthesis of
Lipidated Peptides
Blockers, anchors, and reporters: A solidphase method for the synthesis of lipidated peptides (see scheme) relies on the
base-labile Fmoc group to block the Nterminus, an oxidation-labile hydrazide
Polymers
M. Ballauff,* L. Li, S. Rosenfeldt,
N. Dingenouts, J. Beck,*
P. Krieger-Beck
5843 – 5846
Analysis of Poly(carbon suboxide) by
Small-Angle X-ray Scattering
Band substances: The polymerization of
C3O2 (see picture left, at 10 8C) into a
red-brown, solid polymer (right) having
identical composition has been known for
almost 100 years. However, the constitution of the polymer remained unknown.
Small-angle X-ray scattering studies of the
dissolved polymer show that it forms a
stiff bandlike molecule with approximately
40 monomeric units, thus confirming the
predicted bandlike structure with condensed a-pyrone rings.
Cyclophanes
B. Hellbach, F. Rominger,
R. Gleiter*
linker for anchoring to the solid support,
and lipidated amino acid building blocks
incorporating labels or photoactivatable
groups.
Cobalt studs the beltenes shown (R = H,
CO2Me, SiMe3, 5 Me), which consist of
annelated, conjugated four- and eightmembered rings. These strained molecules were synthesized in a one-pot reaction by a template supported trimerization of 5,6,11,12-tetradehydrodibenzo[a,e]cyclooctene.
5846 – 5849
Synthesis of Beltenes by Reactions of
5,6,11,12-Tetradehydrodibenzo[a,e]cyclooctene with [CpCo(CO)2] Derivatives
Asymmetric Synthesis
T. Aechtner, M. Dressel,
T. Bach*
5849 – 5851
Hydrogen Bond Mediated Enantioselectivity of Radical Reactions
5720
The chiral complexing reagent 1 used in
the reductive cyclization of 3-(w-iodoalkylidene)piperidin-2-ones in the presence of Bu3SnH and with BEt3 as the
initiator (see scheme) leads to good
enantioselectivities thanks to its hydrogen
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
bond mediated association with the radical intermediate. As this example shows,
high stereoselectivities are possible for
radical reactions proceeding through
H-bonded intermediates.
Angew. Chem. Int. Ed. 2004, 43, 5712 – 5721
Angewandte
Chemie
Electron Transfer
Maintaining neutrality: A perchlorinated
triarylmethyl radical and a triarylamine
redox center were combined in the design
of a neutral organic mixed-valence compound (see picture). The neutral character
of this compound facilitated a detailed
study of its solvatochromic behavior and
the direct determination of the electronic
coupling and the dipole moments in the
ground and excited state by electroptical
absorption measurements.
A. Heckmann, C. Lambert,* M. Goebel,
R. Wortmann
5851 – 5856
Synthesis and Photophysics of a Neutral
Organic Mixed-Valence Compound
Communications labeled with this symbol have been judged by two referees as being “very important papers”.
Service
Keywords
5858
Authors
5859
Preview
5861
Apology
*
Nanofibers from Functionalized Dendritic
Molecules**
M. Ornatska, K. N. Bergman, B. Rybak,
S. Peleshanko, V. V. Tsukruk* 5246–5249
This Communication contains content that overlaps significantly with a Full Paper by
the same group “Assembling of Amphiphilic Highly Branched Molecules in Supramolecular Nanofibers” J. Am. Chem. Soc. 2004, 126, 9675–9684. Although submitted at
the same time the authors did not provide the Editors of Angewandte Chemie with a copy
of the Full Paper. This oversight resulted in the simultaneous appearance of the same
information in two publications. The authors apologize for this mistake.
Angew. Chem. Int. Ed. 2004, 43
DOI 10.1002/anie.200460315
Angew. Chem. Int. Ed. 2004, 43, 5712 – 5721
www.angewandte.org
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5721
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