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Supplementary Material Sarcoma-Targeting Peptide-Decorated Polypeptide Nanogel Intracellularly Delivers Shikonin for Upregulated Osteosarcoma Necroptosis and Diminished Pulmonary Metastasis Suoyuan Li 1,4,# , Tao Zhang 1,# , Weiguo Xu 2,# , Jianxun Ding 2, , Jing Xu 3 , Wei Sun 1 , Hongsheng Wang 3 , Mengxiong Sun 1 , Zhengdong Cai 1,3, , Yingqi Hua 1,3, 1. Department of Orthopedics, Shanghai General Hospital, Shanghai Jiao Tong University School of Medicine, Shanghai 200080, P. R. China 2. Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, P. R. China 3. Shanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, Suzhou Municipal Hospital, Nanjing Medical University, Suzhou 215000, P. R. China # These authors contributed equally to this work. Corresponding authors: Yingqi Hua, E-mail: [email protected]; Jianxun Ding, E-mail: [email protected]; Zhengdong Cai, E-mail: [email protected].

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Page 1: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

Supplementary Material

Sarcoma-Targeting Peptide-Decorated Polypeptide Nanogel Intracellularly Delivers

Shikonin for Upregulated Osteosarcoma Necroptosis and Diminished Pulmonary

Metastasis

Suoyuan Li1,4,#, Tao Zhang1,#, Weiguo Xu2,#, Jianxun Ding2,, Jing Xu3, Wei Sun1, Hongsheng

Wang3, Mengxiong Sun1, Zhengdong Cai1,3,, Yingqi Hua1,3,

1. Department of Orthopedics, Shanghai General Hospital, Shanghai Jiao Tong University School

of Medicine, Shanghai 200080, P. R. China

2. Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese

Academy of Sciences, Changchun 130022, P. R. China

3. Shanghai Bone Tumor Institution, Shanghai 201620, P. R. China

4. Department of Orthopedics, Suzhou Municipal Hospital, Nanjing Medical University, Suzhou

215000, P. R. China

#These authors contributed equally to this work.

Corresponding authors: Yingqi Hua, E-mail: [email protected]; Jianxun Ding, E-mail:

[email protected]; Zhengdong Cai, E-mail: [email protected].

Page 2: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

Figure Legends

Scheme S1. Synthesis of mPEG−P(LP-co-LC).

Scheme S2. Synthesis pathway for NH2-PEG−P(LP-co-LC).

Scheme S3. Synthesis process of STP-PEG−P(LP-co-LC).

Figure S1. 1H NMR spectra of t-Boc-NH-PEG113−P(LP12-co-LC4), NH2-PEG113−P(LP12-co-LC4),

MI-PEG113−P(LP12-co-LC4), STP, and STP-PEG113−P(LP12-co-LC4).

Figure S2. FT-IR spectra of t-Boc-NH-PEG113−P(LP12-co-LC4), NH2-PEG113−P(LP12-co-LC4),

MI-PEG113−P(LP12-co-LC4), STP, and STP-PEG113−P(LP12-co-LC4).

Figure S3. Binding of STP-FITC and vimentin antibody with peripheral white blood cells

(WBCs). Human WBCs were incubated with STP-FITC, anti-VIM 488, and Isotype IgG 488, and

analyzed by flow cytometry.

Figure S4. Cytotoxicity of STP-NG/SHK in vitro. Necroptosis in four groups in osteosarcoma

143B cells. Each set of data was represented as mean ± SEM (n = 3; &P < 0.001).

Figure S5. Effect of STP-NG/SHK on the cell cycle in vitro. Human osteosarcoma 143B cells

in subG1, G0–G1, S, and G2–M states of the cell cycle were measured with propidium iodide (PI).

SHK, NG/SHK or STP-NG/SHK treatment for 24 h did not change cell cycle status. Each set of

data was represented as mean ± SEM (n = 3).

Figure S6. Pulmonary metastasis accounted for the proportion of total lung area. The

proportion of area of pulmonary metastasis to the area of whole lung section was measured by

Image-Pro Plus 6.0 software and calculated. Each set of data was represented as mean ± SEM (n

= 3; &P< 0.001).

Figure S7. Toxicity of empty nanoparticle. (A) Cytotoxicity of empty nanoparticle toward 143B

and hFOB1.19 cells. (B) The AST and ALT level of mice after treated with empty nanoparticle (i.e.,

STP-NG). (C) Tumor volume and mice weight after treatment with empty nanoparticle. (D) Tumor

weight, lung weight, and lung metastases counting were calculated.

Page 3: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

Scheme S1. Synthesis of mPEG−P(LP-co-LC).

O NH2

ONH

HNm

O HN

O

SS

NH

HN

j

ji

NHO

OHN

OO

SS

k x m

NH

O

HN

NH

O

O

x

y

m

m +HN

OO O

S SNH

OO

NH

O

O

O

O

+

0 oC, 72 h

DM

F

mPEG-NH2 LP NCA LC NCA

mPEG-P(LP-co-LC)

Page 4: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

O NH2

O NH

HNm

O HN

O

SS

NH

HN

j

ji

NHO

OHN

OO

SS

k x m

NH

O

HN

NH

O

O

x

y

m

mSN

HO

+HN

OO O

S SNH

OO

NH

O

O

O

O

+

0 oC, 72 h

DM

F

SNH

SHN O

O

O

O

HB r/ H

A c30 oC

, 1 h

O NH

HNm

O HN

O

SS

NH

HN

j

ji

NHO

OHN

OO

SS

k x m

NH

O

HN

NH

O

O

x

y

mSH2N

S NH2

S

SNH

NH2

O

t-Boc-NH-PEG-NH2 LP NCA LC

NCA

t-Boc-NH-PEG-P(LP-co-LC)

NH2-PEG-P(LP-co-LC)

O

Scheme S2. Synthesis pathway for NH2-PEG−P(LP-co-LC).

Page 5: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

O NH

HNm

O HN

O

SS

NH

HN

j

ji

NHO

OHN

OO

SS

k x m

NH

O

HN

NH

O

O

x

y

mSH2N

S NH2

SNH2

NH2-PEG-P(LP-co-LC)

EDC

HC

l , NH

S

N

HO

OO

O

O NH

HNm

O HN

O

SS

NH

HN

j

ji

NHO

OHN

OO

SS

k x m

NH

O

HN

NH

O

O

x

y

mSNH

SHN

SNH

MI-PEG-P(LP-co-LC)

NO

N

N

O

O

O

O

O

O

O

O

HS -C

VNTAN

S T

O NH

HNm

O HN

O

SS

NH

HN

j

ji

NHO

OHN

OO

SS

k x m

NH

O

HN

NH

O

O

x

y

mSNH

SHN

SNH

STP-PEG-P(LP-co-LC)

NO

N

N

O

O

O

O

O

O

O

O

S

S

S

CVNTANHST

CVN

TANH

STC

VNTAN

ST

Scheme S3. Synthesis process of STP-PEG−P(LP-co-LC).

Page 6: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

O NH

HNm

O HN

O

SS

NH

HN

j

ji

NHO

OHN

OO

SS

k x m

NH

O

HN

NH

O

O

x

y

mSNH

SHN

SNH

NO

N

N

O

O

O

O

O

O

O

O

S

S

S

CVNTANHST

CVN

TANH

STC

VNTAN

ST

d

c eba

Figure S1. 1H NMR spectra of t-Boc-NH-PEG113−P(LP12-co-LC4), NH2-PEG113−P(LP12-co-LC4),

MI-PEG113−P(LP12-co-LC4), STP, and STP-PEG113−P(LP12-co-LC4).

Page 7: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

Figure S2. FT-IR spectra of t-Boc-NH-PEG113−P(LP12-co-LC4), NH2-PEG113−P(LP12-co-LC4),

MI-PEG113−P(LP12-co-LC4), STP, and STP-PEG113−P(LP12-co-LC4).

Page 8: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

Figure S3. Binding of STP-FITC and vimentin antibody with peripheral white blood cells

(WBCs). Human WBCs were incubated with STP-FITC, anti-VIM 488, and Isotype IgG 488, and

analyzed by flow cytometry.

Page 9: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

Figure S4. Cytotoxicity of STP-NG/SHK in vitro. Necroptosis in four groups in osteosarcoma

143B cells. Each set of data was represented as mean ± SEM (n = 3; &P < 0.001).

Page 10: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

Figure S5. Effect of STP-NG/SHK on the cell cycle in vitro. Human osteosarcoma 143B cells

in subG1, G0–G1, S, and G2–M states of the cell cycle were measured with propidium iodide (PI).

SHK, NG/SHK or STP-NG/SHK treatment for 24 h did not change cell cycle status. Each set of

data was represented as mean ± SEM (n = 3).

Page 11: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

Figure S6. Pulmonary metastasis accounted for the proportion of total lung area. The

proportion of area of pulmonary metastasis to the area of whole lung section was measured by

Image-Pro Plus 6.0 software and calculated. Each set of data was represented as mean ± SEM (n

= 3; &P< 0.001).

Page 12: Supplementary Material - thno. · PDF fileShanghai Bone Tumor Institution, Shanghai 201620, P. R. China 4. Department of Orthopedics, ... Synthesis of mPEG−P(LP-co-LC). Scheme S2

Figure S7. Toxicity of empty nanoparticle. (A) Cytotoxicity of empty nanoparticle toward 143B

and hFOB1.19 cells. (B) The AST and ALT level of mice after treated with empty nanoparticle (i.e.,

STP-NG). (C) Tumor volume and mice weight after treatment with empty nanoparticle. (D) Tumor

weight, lung weight, and lung metastases counting were calculated.