Electronic Supplementary Information for Polynorbornenes

Electronic Supplementary Information for

Switchable Two-Photon Imaging of RGD-Functionalized

Polynorbornenes with Enhanced Cellular Uptake in Living Cells

Nan Xie,a Ke Feng,*b Bin Chen,b Chen-Ho Tungb and Li-Zhu Wu*b

aBeijing Area Major Laboratory of Peptide and Small Molecular Drugs, Engineering Research

Center of Endogenous Prophylactic of Ministry of Education of China, Beijing Laboratory of

Biomedical Materials, School of Chemical Biology and Pharmaceutical Sciences, Capital Medical

University, Beijing 100069, P. R. China. bKey Laboratory of Photochemical Conversion and

Optoelectronic Materials, Technical Institute of Physics and Chemistry, The Chinese Academy of

Sciences, Beijing 100190, P. R. China.

Email: kefeng@mail.ipc.ac.cn; lzwu@mail.ipc.ac.cn.

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Electronic Supplementary Material (ESI) for New Journal of Chemistry.This journal is © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2016

Fig. S1 Plot of Mn vs the monomer-to-initiator ratios for the ROMP of NB-mPEG monomer.

Table S1 GPC data for NB-mPEG homopolymers.

Polymera [M]/[C] Mn /kDa Mw /kDa PDI

PNB-mPEG25 25 18.4 20.4 1.11

PNB-mPEG50 50 32.1 36.2 1.13

PNB-mPEG75 75 55.3 65.7 1.19

PNB-mPEG100 100 72.1 85.3 1.18aMeasured in THF at 298 K.

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Fig. S2 Carbene 1H NMR signals for Grubbs’ third-generation initiator (top), and during the

polymerizations of NB-mPEG monomer (bottom) in CDCl3.

Fig. S3 UV-Vis absorption spectra upon UV @ 365 nm irradiation and normalized fluorescence

spectra of nonfluorescent SP form (black) and fluorescent MC form (red) for PNB-RGDS10-co-

SP10-co-mPEG80 with the concentration of 0.082 mg·mL–1 in 10 mM PBS buffer.

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Fig. S4 1H NMR spectrum for N-(Acp-Arg(Pbf)-Gly-Asp(OtBu)-Ser(tBu))-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxamide in CDCl3.

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Fig. S5 13C NMR spectrum for N-(Acp-Arg(Pbf)-Gly-Asp(OtBu)-Ser(tBu))-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxamide in CDCl3.

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Fig. S6 MALDI-TOF MS spectrum for N-(Acp-Arg(Pbf)-Gly-Asp(OtBu)-Ser(tBu))-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxamide.

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Fig. S7 1H NMR spectrum for PNB-pRGDS polymer in DMSO-d6.

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Fig. S8 1H NMR spectrum for N-(Acp-Arg(Pbf)-Gly-Asp(OtBu)-Val)-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxamide in CDCl3.

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Fig. S9 13C NMR spectrum for N-(Acp-Arg(Pbf)-Gly-Asp(OtBu)-Val)-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxamide in CDCl3.

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Fig. S10 MALDI-TOF MS spectrum for N-(Acp-Arg(Pbf)-Gly-Asp(OtBu)-Val)-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxamide.

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Fig. S11 1H NMR spectrum for PNB-pRGDV polymer in DMSO-d6.S11

Fig. S12 1H NMR spectrum for N-(Acp-Arg(Pbf)-Gly-Asp(OtBu)-Phe)-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxamide in CDCl3.

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Fig. S13 13C NMR spectrum for N-(Acp-Arg(Pbf)-Gly-Asp(OtBu)-Phe)-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxamide in CDCl3.S13

Fig. S14 MALDI-TOF MS spectrum for N-(Acp-Arg(Pbf)-Gly-Asp(OtBu)-Phe)-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxamide.

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Fig. S15 1H NMR spectrum for PNB-pRGDF polymer in DMSO-d6.S15

Fig. S16 1H NMR spectrum for methoxypolyethylene-glycol-550-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxylate in CDCl3.S16

Fig. S17 MALDI-TOF MS spectrum for methoxypolyethylene-glycol-550-exo-bicyclo[2.2.1]-hept-5-ene-2-carboxylate.

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Fig. S18 1H NMR spectrum for PNB-mPEG550 in CDCl3.S18

Fig. S19 1H NMR spectrum for PNB-pRGDS10-co-SP10-co-mPEG80 in DMSO-d6.S19

Fig. S20 1H NMR spectrum for PNB-RGDS10-co-SP10-co-mPEG80 in DMSO-d6.S20

Fig. S21 1H NMR spectrum for PNB-pRGDV10-co-SP10-co-mPEG80 in DMSO-d6.S21

Fig. S22 1H NMR spectrum for PNB-RGDV10-co-SP10-co-mPEG80 in DMSO-d6.S22

Fig. S23 1H NMR spectrum for PNB-pRGDF10-co-SP10-co-mPEG80 in DMSO-d6.S23

Fig. S24 1H NMR spectrum for PNB-RGDF10-co-SP10-co-mPEG80 in DMSO-d6.S24

Fig. S25 1H NMR spectrum for PNB-NBoc10-co-SP10-co-mPEG80 in CDCl3.S25

Fig. S26 1H NMR spectrum for PNB-NH210-co-SP10-co-mPEG80 in CDCl3.S26