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UNTERRICHT<br />
titania, where the PO(OH) 2 moiety is known to tightly bind to<br />
ZrO 2 surfaces. While in the bulk diacids, only hydrogen-bonded<br />
homodimers (head-to-head, tail-to-tail) are present, hydrogenbonding<br />
among carboxylic and phosphonic acid groups (headto-tail)<br />
is found in multilayers of the diacids on ZrO 2 nanopowder.<br />
Notably, the monolayers appeared less ordered compared<br />
to respective multilayers, possibly due to a superposition of<br />
intramonolayer and interparticle hydrogen-bonding. 80<br />
4. CONCLUSION<br />
Highly resolved solid-state MAS NMR spectra of supramolecular<br />
organic systems can nowadays be recorded on rather<br />
small amounts (10 - 15 mg) of as-synthesized compounds.<br />
The methodology, however, can be applied in general. For instance,<br />
double-quantum fi ltered heteronuclear correlation experiments<br />
have been used to selectively study interactions of<br />
water molecules and solid microcrystalline proteins, which play<br />
a major role in protein folding, structure, and function. Notably,<br />
the experimental data revealed no evidence for solid-like water<br />
molecules, thus indicating that residence times of solvent molecules<br />
in the proximity of the protein are shorter than required<br />
for DQ creation. 82 Similarly, heteronuclear dipolar couplings can<br />
be exploited for the structure determination of transmembrane<br />
proteins. 83 In the fi eld of metabonomics, proton double-quantum<br />
fi lter have been applied for the quantifi cation of highly relevant<br />
γ-aminobutyric acid (GABA) levels in the human brain. 84<br />
Furthermore, in earlier studies, high resolution DQ MAS NMR<br />
spectroscopy of isotopically labelled systems yielded torsional<br />
angles in peptides 85,86 and thus important information about<br />
the chain conformation. In addition, the secondary structure<br />
and topology of an entire seven-helix receptor protein in a native<br />
membrane environment could be determined via both<br />
homonuclear dipolar correlation and heteronuclear scalar correlation<br />
MAS NMR spectra. 87 High-resolution solid-state NMR<br />
also facilitated an assessment of structural features that defi<br />
ne interfaces among proline-rich motifs that are frequently<br />
involved in signaling events. 88 The sensitivity of 1 H chemical<br />
shifts to ring currents in aromatic systems has been exploited<br />
in determining the packing of porphyrines. 89 The full information<br />
about distances and the relative orientation of specifi c<br />
moieties is available from DQ-NMR spectroscopy on static<br />
samples of specifi cally labeled materials 90 and has provided<br />
important information about the chain conformation and the<br />
packing of synthetic macromolecules. 91<br />
The development of the technique is far from being complete. 55<br />
Major advances are expected in the years to come so that solid<br />
state NMR is envisaged to become a rather indispensable tool<br />
in macromolecular, supramolecular and biological science as<br />
is solution state NMR today.<br />
This work highly benefi ted from fi nancial support of the <strong>Deutsche</strong><br />
Forschungsgemeinschaft (DFG) (SFB 625).<br />
72<br />
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