Ammonium
sulfate accelerated site-specific modification of antibody.
(a) Scheme for the site-specific biotin/drug conjugation to π-clamp
trastuzumab 5. Val-Cit-PABC is the valine-citrulline p-aminobenzyl carbamate linker. (b) The deconvoluted mass
spectra for antibody before conjugation (left), after conjugation
in the presence of ammonium sulfate (middle), and after conjugation
without ammonium sulfate (right). Reaction conditions: 40 μM
π-clamp trastuzumab 5, 500 μM probe 6, 100 mM phosphate, 10 mM TCEP, ± 1.25 M (NH4)2SO4, 37 °C, 3 h. (c) Biotinylated trastuzumab
(5-biotin) binds to recombinant HER2 in Octet BioLayer
Interferometry assay (KD = 122 ±
1.5 pM). 5-biotin was immobilized on the streptavidin
biosensors and sampled with serially diluted concentrations of recombinant
HER2; see Figure S24 for fitting and data
analysis. (d) The deconvoluted mass spectra for 5-MMAF and 5-MMAE synthesis. Reaction conditions for 5-MMAF: 40 μM π-clamp trastuzumab 5, 500 μM probe 6B, 100 mM phosphate, 10 mM TCEP,
± 1.25 M (NH4)2SO4, 37 °C,
210 min. Reaction condition for 5-MMAE: 40 μM π-clamp
trastuzumab 5, 500 μM probe 6C, 100
mM phosphate, 10 mM TCEP, ± 1.25 M (NH4)2SO4, 37 °C, 16 h. (e) 5-MMAF and 5-MMAE prepared with ammonium sulfate were functional, selectively
killing HER2 positive BT474 cells, while they were significantly less
toxic for HER2 negative HEK 293T cells. Experiments were performed
in triplicate. Error bars indicate the standard deviation from the
average of three experiments.