1. Supplementary information
Figure S1 LC/MS/MS spectra of 1 and 2.
Figure S2 Apoptosis induction activity of 1 and 2.
Figure S3 Suppression of survivn and XIAP by 1 and 2.
Figure S4 Determination of the absolute configuration of amino acids in 1.

2. a b
Figure S1 LC/MS/MS spectra of 1 (a) and 2 (b).

3. Figure S2 Apoptosis induction activity of 1 and 2.
RAW264.7 cells were cultured with 1 or 2 in the presence of 0.2 M doxorubicin. After 24 h, caspase-3 activity of the whole cell lysate assessed by caspase-3 assay kit.

4. Survivin XIAP a-Tubulin
Compound 1
Compound 2
0.08
0.4 2 10
0.08
0.4 2 10 µM
Survivin
XIAP
a-Tubulin
Figure S3 Suppression of Survivn and XIAP by 1 and 2.

5. X: 1a 1b 1c AcPro-Iva-Iva-b-Ala-Gly-Aib-Aib-Iva-Aib-Aib-Aib-Pro-Iva-X
Partial hydrolysis {6 N HCl / formic acid (1:1) , 37 °C, 16 h }
Preparative HPLC (column: Shiseido CapcellPak C18 UG120 φ 20 × 250 mm, mobile phase A: 0.1% acetic acid, B: acetonitrile, gradient: 0 min 5% B, 30 min 5% B, 60 min 100% B, flow: 5 mL/min)
AcPro-Iva-Iva +
b-Ala-Gly-Aib-Aib-Iva-Aib-Aib +
Pro-Iva-X 1a 1b 1c
HPLC Rt: 52 min
ESI-MS (m/z): found, (M+H) +, calcd, (for C17H30N3O5)
MS/MS: 239.1, 140.1, 112.1
HPLC Rt: 47 min
ESI-MS (m/z): found, (M+H)+, calcd, , (for C26H48N7O8)
MS/MS: 483.3, 398.2, 299.2, 214.1, 129.1
HPLC Rt: min
ESI-MS (m/z): found, (M) +,
calcd, (C23H42N5O2),
MS/MS: 323.3, 125.1
Hydrolysis (6 N HCl, 110 °C, 24 h)
Advanced Marfey’s method
Hydrolysis (6 N HCl, 110 °C, 24 h)
Advanced Marfey’s method
Hydrolysis (6 N HCl, 110 °C, 24 h)
Advanced Marfey’s method
AcPro-Iva-Iva
b-Ala-Gly-Aib-Aib-Iva-Aib-Aib
Pro-Iva-X
(L)
(D)
(D)
(L)
(L)
(L)
Figure S4 Determination of the absolute configuration of amino acids in 1.