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Not all diazirine proteomics tags photoactivate alike

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Comparing fully functionalized diazirine tags shows dialkyl tags LD/BD photolyze at 365 nm in minutes, while a new tiny terminal tag needs 302 nm light and labels fewer peptides.

Source

Evaluation of fully-functionalized diazirine tags for chemical proteomic applications

Conway LP, Jadhav AM, Homan RA, et al. · Chemical science · 2021

doi.org/10.1039/d1sc01360bRead the full paper ↗62 citationscc by

What they did

Authors synthesised a 109 Da terminal diazirine, measured 365 vs 302 nm photolysis by LC-MS, then profiled tag-only, fragment, staurosporine and JQ1 probes in HEK293T/K562 proteomes including TMT and crosslink-site mapping.

What they found

LD–F and BD–F t½ = 5.4 and 2.6 min at 365 nm; aryl Ar–F has a 29 min slow phase; DF/Tm barely activate at 365 nm (λmax 300–310 nm) but photolyze at 302 nm (t½ 10 and 5.8 min). LD/BD mapped 11.6/11.3% of enriched proteins to modified peptides versus fewer for Tm.

The limits

What it doesn't show

The ‘best’ tag still depends on the recognition ligand; St-series probes were not cell-permeable, so live-cell ranking is incomplete.

Key terms

Fully functionalized (FF) tag
A compact photoreactive plus reporter (alkyne) cassette appended to a ligand.
Diazirine
Three-membered CN2 ring that yields a carbene (or diazo) upon UV.
LD / BD / Tm / Ar / DF
Linear dialkyl, branched dialkyl, terminal, aryl, and difluoromethylalkynyl tag chemotypes.
CuAAC reporter
Alkyne handle used to attach biotin/fluorophore after photocapture.
Minimalist tag
The 109 Da terminal diazirine built to shrink background interactions.

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At 365 nm, the fastest dialkyl tag half-life is about:

Common questions

Which tags photolyze well at 365 nm?

Dialkyl LD–F and BD–F (t½ 5.4 and 2.6 min).

What is the new tag’s mass and yield?

109 Da, 35% over three steps.

Do DF and Tm work at 365 nm?

Little photoactivation; they absorb near 300–310 nm.

Staurosporine probes live-cell permeable?

No—used in lysates.

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