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. 2020 Jul 2;11(29):7722–7729. doi: 10.1039/d0sc02508a

Values for kDO, kHO, and pKas of the DKPs studied at 25 °C and I = 1.0 M (KCl).

k DO (M−1 s−1) k HO b (M−1 s−1) k rel c pKad
c(Gly–Gly) 6.33 × 10−2 3.17 × 10−2 12.2 20.9
c(l-Ala–l-Ala) 7.80 × 10−3 3.90 × 10−3 3.00 22.7
c(Gly–l-Pro) 1.87 × 10−1 9.35 × 10−2 144 18.8
c(H2-Glyl-Pro) 2.09 × 10−2 1.05 × 10−2 16.2 21.2
c(H3-Glyl-Pro) 6.59 × 10−2 3.30 × 10−2 50.8 19.9
c(d-Ala–l-Pro) 9.45 × 10−2 4.73 × 10−2 72.8 19.6
c(d-Alal-Pro) 5.51 × 10−3 2.76 × 10−3 4.25 22.6
c(d-Pro–l-Pro) 9.69 × 10−2 4.85 × 10−2 37.3 20.0
c(d-Pro–d-Pro) 8.62 × 10−3 4.31 × 10−3 3.30 22.6
c(l-Prol-Tyr) 1.19 × 10−1 5.95 × 10−2 91.5 19.3
c(l-Pro–l-Tyr) 2.09 × 10−3 1.05 × 10−3 1.60 23.7
graphic file with name d0sc02508a-u1.jpg 2.6 × 10−3 1.3 × 10−3 1.00 23.9
a

H/D-exchange kinetic data for N-acyl glycyl amide, a linear analogue of a DKP, is included for comparison.48

b

Calculated from experimental kDO values using a secondary solvent isotope effect kDO/kHO = 2.00 (see text).

c

k rel = relative rate constants for deprotonation compared to value for linear N-acyl glycyl amide as reference. The krel values have been statistically corrected for the number of exchangeable protons.

d

Interpolated values from a Brønsted analysis (see text).