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2D IR indexing maps hIAPP helix-to-sheet kinetics

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Paired 13C18O labels report dihedral angles: monomeric hIAPP is partly helical at L12A13, then oligomers lose helix and fibers form β-sheets.

Source

Site-specific detection of protein secondary structure using 2D IR dihedral indexing: a proposed assembly mechanism of oligomeric hIAPP

Maj M, Lomont JP, Rich KL, et al. · Chemical science · 2018

doi.org/10.1039/c7sc03789aRead the full paper ↗41 citationscc by

Study at a glance

Design
Other — 13C18O isotope-edited 2D IR of hIAPP secondary structure during aggregation
N
Biophysical spectroscopy of peptide aggregation — no cohort N
Population
Human islet amyloid polypeptide (hIAPP) monomers/oligomers
Outcome
Site-specific helix vs sheet coupling and aggregation kinetics

Structured fields used in claim comparison tables when every cited study has a complete layer.

What they did

Authors 13C18O double-labelled neighbouring residues, calibrated couplings in SDS micelles, and recorded time-resolved 2D IR during aggregation versus singly labelled controls.

What they found

Helix coupling is +8.3 cm–1 vs +2.5 cm–1 in a β-sheet. Monomers are ~20–38% helical at L12A13; oligomers lack detectable helix; L12A13 shows three-state kinetics unlike two-state A13.

The limits

What it doesn't show

The leucine-rich-repeat oligomer model is postulated, not a high-resolution oligomer structure; only two labelled sites were tracked.

Key terms

2D IR spectroscopy
Ultrafast infrared method that reports vibrational couplings as cross-peaks and frequency shifts.
Dihedral indexing
Using two neighbouring isotope labels so coupling signs/magnitudes report helix vs sheet dihedrals.
hIAPP
Human islet amyloid polypeptide (amylin) that aggregates in type 2 diabetes.
Three-state kinetics
Monomer → oligomer intermediate → fiber, resolved here at L12A13.
13C18O label
Isotope pair that downshifts an amide I mode by ~65 cm–1.

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Dihedral indexing uses:

Common questions

How do helix and sheet couplings differ?

Helix ~+8.3 cm–1; nearest-neighbour β-sheet ~+2.5 cm–1 with opposite intensity pattern.

How helical is the monomer at L12A13?

About 20–38% (intensity ratios 27–38%).

Is the oligomer helical there?

No helix detected at L12A13 or L16V17 in the oligomer.

Why double labels?

Only pairs report dihedral coupling; single labels track fiber β-sheets.

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