(Supporting Information)
Pendant Structure Governed Anion Sensing Property for Sulfonamide-Functionalized
Poly(phenylacetylene)s Bearing Various -Amino Acids
Ryohei Kakuchi, Ryotaro Shimada, Yasuyuki Tago, Ryosuke Sakai, Toshifumi Satoh, and Toyoji
Kakuchi *
Division of Biotechnology and Macromolecular Chemistry, Graduate School of Engineering, Hokkaido
University, Sapporo 060-8628, Japan
1
Monomer synthesis.
1) The synthesis and polymerization of the N-(4-ethynylphenylcarbamoyl)-L-valine ethyl ester were
described below.
Synthesis of the N-(4-ethynylphenylcarbamoyl)-L-valine ethyl ester (PA-Val). To a solution of
the N-carbonyl-L-valine ethyl ester (3.09 g, 18.1 mmol) in CH2Cl2 (40 ml) was added 4-ethynylaniline
(2.95g, 25.2 mmol). After stirring at room temperature for overnight, the reaction mixture was washed
with HCl aq. The combined organic layer was dried with MgSO4, which gave the crude product. The
crude product was purified by column chromatography on silica gel with ethyl acetate/hexane (1/3, v/v)
to give PA-Val as a white crystal. Yield: 4.70 g (90.3 %). Mp 138 ºC. []D = +41.8º (c 1.0, CHCl3). 1HNMR (CDCl3)  0.94 (d, J = 6.8 Hz, (CH3)2CH-, 6H), 1.28 (t, J = 7.1 Hz, CH3CH2O-, 3H), 2.13-2.22
(m, -CH(CH3)2, 1H), 3.01 (s, CHCPh-, 1H), 4.13-4.28 (m, CH3CH2O-, 2H), 4.50 (dd, J1 = 4.9 Hz, J2 =
8.9 Hz, -CHC=O, 1H), 6.11 (d, J = 8.8 Hz, -CHNHC=O, 1H), 7.23 (d, J = 8.7 Hz, Ar, 2H), 7.34 (d, J =
8.7 Hz, Ar, 2H), 7.68 (s, -PhNHC=O, 1H). 13C-NMR (CDCl3)  14.3, 17.9, 19.2, 31.4, 58.0, 61.7, 76.4,
83.8, 116.2, 119.1, 133.1, 139.6, 155.3, 174.1. Anal. Calcd for C16H20N2O3 (288.34): C, 66.65; H, 6.99;
N, 9.72. Found: C, 66.53; H, 7.03; N, 9.71.
Polymerization of the N-(4-ethynylphenylcarbamoyl)-L-valine ethyl ester (PAU-Val).
The
polymerization of PA-Val was carried out in a dry flask under an argon atmosphere. In a argon
atmosphere, PA-Val (600 mg, 2.08 mmol) was weighed into a flask and dissolved in dry DMF (50.0
mL). To the solution was added a solution of Rh(nbd)BPh4 (23.2 mg, 41.6 μmol) in dry DMF (19.0 mL).
After stirring at room tempreture for 24 hours, triphenylphosphine (54.6 mg, 208 μmol) was added to
the reaction mixture. The solution was concentrated and then poured into a large amount of diethyl
ether. The precipitate was purified by reprecipitation using diethyl ether and then dried under reduced
pressure to give PPAU-Val as a yellow powder. Yield: 528 mg (87.2 %). Mn = 2.2  105, Mw/Mn = 1.8.
2
2) N-(4-Ethynylphenylsulfonyl)-L-amino acid ethyl esters were synthesized according to Scheme S-1.
The detailed experimental procedures are described below.
Si
I
I
NH2
Si
O
R
Pd(PPh3)2Cl2
PPh3 / CuI
O
O S O dry CH2Cl2 / dry NEt3 O S O
NH
Cl
dry DMF / dry NEt3
O
R
TBAF
O
R
O
THF / MeOH
O S O
NH
O
O S O
NH
O
R
O
R:
Me
Me
Me
PI-Ile
PSi-Ile
PAS-Ile
PI-Ala
PSi-Ala
PAS-Ala
PI-Val
PSi-Val
PAS-Val
PI-Phe
PSi-Phe
PAS-Phe
PI-Asp
PSi-Asp
PAS-Asp
PI-Glu
PSi-Glu
PAS-Glu
Me
Me
O
Et
O
O
Et
O
Scheme S-1
N-(4-Iodophenylsulfonyl)-L-alanine ethyl ester (PI-Ala). Method A: To a stirred mixture of the Lalanine ethyl ester (5.24 g, 44.7 mmol) and triethylamine (12.4 ml) in CH2Cl2 (120 ml) was slowly
added a solution of 4-iodobenzenesulfonyl chloride (14.9 g, 49.2 mmol) in CH2Cl2 (40 ml) under a N2
atmosphere, and reaction mixture was stirred for 1 h. After conversion of the starting material was
checked by 1H NMR, the solvent was removed under reduced pressure. The residue was dissolved in
dichloromethane, and the solution was washed with an HCl aqueous solution, NaHCO3 aqueous
solution, and water. The extracts were dried using anhydrous MgSO4, filtered, and evaporated. The
residue was purified by column chromatography on silica gel with ethyl acetate/hexane (1/2, v/v) to give
3
the N-(4-iodophenylsulfonyl)-L-alanine ethyl ester (PI-Ala) as a pale yellow solid. Yield: 13.3 g
(77.8 %). Mp 65 ºC. []D = +20.9º (c 1.0, CHCl3). 1H NMR (CDCl3); δ 1.15 (t, J = 7.1 Hz, -OCH2CH3,
3H), 1.40 (d, J = 7.1 Hz, CH3CHNHCOO-, 3H), 3.94-4.05 (m, CH3CHNHCOO-, -OCH2-, 3H), 5.38 (d,
J = 8.5 Hz, -NH-, 1H), 7.57 (d, J = 8.5 Hz, Ar, 2H), 7.86 (d, J = 8.5 Hz, Ar, 2H). 13C NMR (CDCl3); 
13.9, 19.8, 51.5, 61.9, 100.1, 128.6, 138.3, 139.6, 171.9. Anal. Calcd for C11H14O4NIS (383.20): C,
34.48; H, 3.68; N, 3.66; S, 8.37; I, 33.12. Found: C, 34.32; H, 3.58; N, 3.67; S, 8.45; I, 33.48.
N-[4-(Trimethylsilylethynyl)phenylsulfonyl]-L-alanine ethyl ester (PSi-Ala). Method B: To a
mixture of the N-(4-iodophenylsulfonyl)-L-alanine ethyl ester (12.8 g, 33.4 mmol), triphenylphosphine
(145 mg, 552 µmol), bis(triphenylphosphine)palladium (II) dichloride (186 mg, 265 µmol), and copper
(I) iodide (151 mg, 794 µmol) in degassed DMF/NEt3 (46 ml /135 ml) was added
(trimethylsilyl)acetylene (7.90 ml, 56.4 mmol) under a nitrogen atmosphere. After stirring at room
temperature overnight, the reaction mixture was evaporated under reduced pressure. The residue was
dissolved in dichloromethane, and the solution was washed with an HCl aqueous solution. The extracts
were dried using anhydrous MgSO4, filtered, and evaporated. The residue was purified by column
chromatography on
silica
gel
with
ethyl
acetate/hexane
(1/2,
v/v)
to
give
the N-[4-
(trimethylsilylethynyl)phenylsulfonyl]-L-alanine ethyl esters (PSi-Ala) as a pale yellow solid. Yield:
11.1 g (93.9 %). Mp 102 ºC. []D = +27.8º (c 1.0, CHCl3). 1H NMR (CDCl3);  0.25 (s, -Si(CH3)3, 9H),
1.16 (t, J = 7.3 Hz, -OCH2CH3, 3H), 1.38 (d, J = 6.7 Hz, CH3CHNHCOO-, 3H), 3.93-4.04 (m,
CH3CHNHCOO-, -OCH2-, 3H), 5.30 (d, J = 8.4 Hz, -NH-, 1H), 7.55 (d, J = 8.4 Hz, Ar, 2H), 7.77 (d, J
= 8.4 Hz, Ar, 2H).
13C
NMR (CDCl3);  0.2, 14.4, 20.4, 52.0, 62.4, 99.1, 103.5, 127.5, 128.4, 132.9,
139.7, 172.4. Anal. Calcd for C16H23O4NSSi (353.51): C, 54.36; H, 6.56; N, 3.96; S, 9.07. Found: C,
54.13; H, 6.33; N, 3.88; S, 8.98.
N-(4-Ethynylphenylsulfonyl)-L-alanine ethyl ester (PAS-Ala). Method C: To a solution of the N[4-(trimethylsilylethynyl)phenylsulfonyl]-L-alanine diethyl ester (10.3 g, 29.1 mmol) in MeOH (10 ml)
and THF (300 ml) was added a 1M TBAF THF solution (10 ml, 10.0 mmol). After stirring at room
temperature for 1 h, the reaction was quenched by a saturated NH4Cl aqueous solution. The complete
4
conversion of the starting material was monitored by TLC measurement. The solvent was removed
under vacuum. The residue was treated with water and extracted with dichloromethane, and the extracts
were dried over anhydrous MgSO4. After the solvent was removed under reduced pressure, the residue
was purified by column chromatography on silica gel with ethyl acetate/hexane (1/3, v/v) to give PASAla as a pale yellow liquid. Yield: 7.31 g (89.3 %). []D = +27.7º (c 1.0, CHCl3). 1H NMR (CDCl3); 
1.15 (t, J = 7.1 Hz, -OCH2CH3, 3H), 1.40 (d, J = 7.0 Hz, CH3CHNHCOO-, 3H), 3.26 (s, CH≡CPh-, 1H)
3.95-4.04 (m, CH3CHNHCOO-, -OCH2-, 3H), 5.35 (d, J = 8.5 Hz, -NH-, 1H), 7.60 (d, J = 8.5 Hz, Ar,
2H), 7.81 (d, J = 8.5 Hz, Ar, 2H). 13C NMR (CDCl3);  13.8, 19.6, 51.5, 61.7, 80.7, 81.8, 126.7, 127.0,
132.5, 139.9, 172.9. Anal. Calcd for C13H15O4NS (281.33): C, 55.50; H, 5.37; N, 4.98; S, 11.40. Found:
C, 55.55; H, 5.35; N, 4.97; S, 11.12.
N-(4-Iodophenylsulfonyl)-L-isoleucine ethyl ester (PI-Ile). Method A was applied for L-isoleucine
ethyl ester (8.5 g, 53.3 mmol), triethylamine (13.7 ml), and 4-iodobenzenesulfonyl chloride (16.4 g, 54.2
mmol). The purification was carried out using column chromatography on silica gel with ethyl
acetate/hexane (1/9 (v/v) → 1/0 (v/v)) to yield PI-Ile as a white crystal. Yield: 19.7 g (86.8 %). Mp 99
ºC. []D = +63.3º (c 1.0, CHCl3). 1H NMR (CDCl3);  0.85-0.93 (m, CH3CH2CH(CH3)-, 6H), 1.08-1.45
(m, -CH2CH(CH3)-, -OCH2CH3, 5H), 1.76-1.80 (m, -CH(CH3)-, 1H), 3.75 (dd, J1 = 10.0 Hz, J2 = 5.4
Hz, -NHCH-, 1H), 3.87-3.95 (m, -OCH2-, 2H), 5.19 (d, J = 10.0 Hz, -NH-, 1H), 7.54 (d, J = 8.4 Hz, Ar,
2H), 7.85 (d, J = 8.8 Hz, Ar, 2H)
13C
NMR (CDCl3);  11.1, 13.9, 15.2, 24.5, 38.3, 60.2, 61.4, 99.9,
128.6, 138.1, 139.4, 171.0. Anal. Calcd for C14H20O4NIS (425.28): C, 39.54; H, 4.74; N, 3.29; S, 7.54; I,
29.84. Found: C, 39.49; H, 4.67; N, 3.24; S, 7.72; I, 30.47.
N-[4-(Trimethylsilylethynyl)phenylsulfonyl]-L-isoleucine ethyl ester (PSi-Ile). Method B was
applied
for
PI-Ile
(17.0
g,
40.0
mmol),
triphenylphosphine
(177
mg,
674
µmol),
bis(triphenylphosphine)palladium (II) dichloride (227 mg, 323 µmol), copper (I) iodide (183 mg, 960
µmol), and (trimethylsilyl)acetylene (9.7 ml, 69 mmol). The purification of the obtained compound was
carried out using column chromatography on silica gel with ethyl acetate/hexane (1/4, v/v) to yield PSi5
Ile as a white crystal. Yield: 15.4 g (97.3 %) Mp 97 ºC. []D = +56.7º (c 1.0, CHCl3). 1H NMR (CDCl3);
 0.26 (s, -Si(CH3)3, 9H), 0.85-0.90 (m, CH3CH2CH(CH3)-, 6H), 1.07-1.43 (m, -CH2CH(CH3)-, OCH2CH3, 5H), 1.75-1.78 (m, -CH(CH3)-, 1H), 3.74 (dd, J1 = 10.0 Hz, J2 = 5.4 Hz, -NHCH-, 1H), 3.843.93 (m, -OCH2-, 2H), 5.32 (d, J = 10.0 Hz, -NH-, 1H), 7.52 (d, J = 8.5 Hz, Ar, 2H), 7.75 (d, J = 8.5 Hz,
Ar, 2H)
13C
NMR (CDCl3);  - 0.3, 11.2, 13.9, 15.3, 24.6, 38.4, 60.2, 61.4, 98.4, 103.0, 127.1, 127.8,
132.2, 139.1, 171.0. Anal. Calcd for C19H29O4NSSi (395.59): C, 57.69; H, 7.39; N, 3.54; S, 8.11.
Found: C, 57.52; H, 7.39; N, 3.47; S, 8.19.
N-(4-Ethynylphenylsulfonyl)-L-isoleucine ethyl ester (PAS-Ile). Method C was applied for PSi-Ile
(14.0 g, 35.4 mmol) and 1M TBAF THF solution (12.0 ml, 12.0 mmol). The purification of the obtained
compound was carried out using column chromatography on silica gel with ethyl acetate/hexane (1/2,
v/v) to yield PAS-Ile as a pale yellow crystal. Yield: 10.2 g (88.8 %) Mp 128 ºC. []D = +62.5º (c 1.0,
CHCl3). 1H NMR (CDCl3);  0.86-0.93 m, CH3CH2CH(CH3)-, 6H), 1.08-1.45 (m, -CH2CH(CH3)-, OCH2CH3, 5H), 1.77-1.80 (m, -CH(CH3)-, 1H), 3.25 (s, CHCPh-, 1H), 3.77 (dd, J1 = 9.8 Hz, J2 = 5.4
Hz, -NHCH-, 1H), 3.86-3.95 (m, -OCH2-, 2H), 5.12 (d, J = 9.8 Hz, -NH-, 1H), 7.58 (d, J = 8.6 Hz, Ar,
2H), 7.84 (d, J = 8.5 Hz, Ar, 2H).
13C
NMR (CDCl3);  11.2, 13.9, 15.3, 24.6, 38.4, 60.3, 61.5, 80.7,
81.9, 126.8, 127.2, 132.5, 139.7, 171.0. Anal. Calcd for C16H21O4NS (323.41): C, 59.42; H, 6.54; N,
4.33; S, 9.91. Found: C, 59.22; H, 6.53; N, 4.22; S, 10.10.
N-(4-Iodophenylsulfonyl)-L-valine ethyl ester (PI-Val). Method A was applied for L-valine ethyl
ester (13.2 g, 91.1 mmol), triethylamine (27.1 ml), and 4-iodobenzenesulfonyl chloride (32.7 g, 108
mmol). The purification of the obtained compound was carried out using column chromatography on
silica gel with ethyl acetate/hexane (1/15 (v/v) → 1/0 (v/v)) to yield PI-Val as a white crystal. Yield:
32.8 g (87.7 %). Mp 111 ºC. []D = +48.7º (c 1.0, CHCl3). 1H NMR (CDCl3);  0.87 (d, J = 6.8 Hz,
(CH3)(CH3)CH-, 3H), 0.97 (d, J = 7.0 Hz, (CH3)(CH3)CH-, 3H), 1.10 (t, J = 7.1 Hz, -OCH2CH3, 3H),
1.99-2.11 (m, (CH3)2CH- 1H), 3.70 (dd, J1 = 4.8 Hz, J2 = 10.2 Hz, -NHCH-, 1H), 3.93 (m, -OCH2-, 2H),
5.13 (d, J = 10.2 Hz, -NH-, 1H), 7.54 (d, J = 8.5 Hz, Ar, 2H), 7.85 (d, J = 8.8 Hz, Ar, 2H). 13C NMR
6
(CDCl3);  13.9, 17.3, 18.9, 31.5, 61.1, 61.5, 100.0, 128.7, 138.1, 139.4, 171.0. Anal. Calcd for
C13H18O4NIS (411.26): C, 37.97; H, 4.41; N, 3.41; S, 7.80; I, 30.86. Found: C, 37.79; H, 4.31; N, 3.35;
S, 7.92; I, 31.71.
N-[4-(Trimethylsilylethynyl)phenylsulfonyl]-L-valine ethyl ester (PSi-Val). Method B was applied
for
PI-Val
(30.8
g,
75.0
mmol),
triphenylphosphine
(332
mg,
1.69
mmol),
bis(triphenylphosphine)palladium (II) dichloride (427 mg, 808 µmol), copper (I) iodide (343 mg, 1.74
mmol), and (trimethylsilyl)acetylene (18.3 ml, 129 mmol). The purification of the obtained compound
was carried out using column chromatography on silica gel with ethyl acetate/hexane (1/4, v/v) to yield
PSi-Val as a pale yellow crystal. Yield: 27.3 g (95.4 %) Mp 99 ºC. []D = +58.1º (c 1.0, CHCl3). 1H
NMR (CDCl3);  0.26 (s, -Si(CH3)3, 9H), 0.87 (d, J = 6.9 Hz, (CH3)(CH3)CH-, 3H), 0.96 (d, J = 6.8 Hz,
(CH3)(CH3)CH-, 3H), 1.11 (t, J = 6.9 Hz, -OCH2CH3, 3H), 2.01-2.07 (m, (CH3)2CH- 1H), 3.72 (dd, J1 =
10.1 Hz, J2 = 4.9 Hz, -NHCH-, 1H), 3.90-3.94 (m, -OCH2-, 2H), 5.14 (d, J = 10.0 Hz, -NH-, 1H), 7.54
(d, J = 8.5 Hz, Ar, 2H), 7.76 (d, J = 8.7 Hz, Ar, 2H). 13C NMR (CDCl3);  - 0.3, 13.9, 17.3, 18.9, 31.6,
61.1, 61.5, 98.5, 103.0, 127.1, 127.9, 132.2, 139.2, 171.1. Anal. Calcd for C18H27O4NSSi (381.56): C,
56.66; H, 7.13; N, 3.67; S, 8.40. Found: C, 56.47; H, 7.11; N, 3.56; S, 8.55.
N-(4-Ethynylphenylsulfonyl)-L-valine ethyl ester (PAS-Val). Method C was applied for PSi-Val
(25.9 g, 67.9 mmol) and 1M TBAF THF solution (23.0 ml, 23.0 mmol). The purification of the obtained
compound was carried out using column chromatography on silica gel with ethyl acetate/hexane (1/4,
v/v) to yield PAS-Val as a pale yellow crystal. Yield: 16.2 g (77.2 %) Mp 133 ºC. []D = +58.9º (c 1.0,
CHCl3). 1H NMR (CDCl3);  0.87 (d, J = 6.8 Hz, (CH3)(CH3)CH-, 3H), 0.97 (d, J = 6.8 Hz,
(CH3)(CH3)CH-, 3H), 1.10 (t, J = 7.0 Hz, -OCH2CH3, 3H), 2.03-2.07 (m, (CH3)2CH- 1H), 3.25 (s,
CHCPh-, 1H), 3.72 (dd, J1 = 4.9 Hz, J2 = 10.1 Hz, -NHCH-, 1H), 3.91 (q, J = 7.0 Hz, -OCH2-, 2H),
5.15 (d, J = 10.1 Hz, -NH-, 1H), 7.58 (d, J = 8.6 Hz, Ar, 2H), 7.76 (d, J = 8.7 Hz, Ar, 2H). 13C NMR
(CDCl3);  13.9, 17.3, 18.9, 31.6, 61.1, 61.5, 80.7, 81.9, 126.8, 127.2, 132.5, 139.7, 171.0. Anal. Calcd
7
for C15H19O4NS (309.38): C, 58.23; H, 6.19; N, 4.53; S, 10.36. Found: C, 58.01; H, 6.19; N, 4.45; S,
10.59.
N-(4-Iodophenylsulfonyl)-L-phenylalanine ethyl ester (PI-Phe). Method A was applied for Lphenyl alanine ethyl ester (7.89 g, 40.8 mmol), triethylamine (12.4 ml), and 4-iodobenzenesulfonyl
chloride (14.6 g, 48.3 mmol). The purification of the obtained compound was carried out using column
chromatography on silica gel with ethyl acetate/hexane (1/10 (v/v) → 1/0 (v/v)) to yield PI-Phe as a
white crystal. Yield: 16.7 g (89.3 %). Mp 103 ºC. []D = +9.5º (c 1.0, CHCl3). 1H NMR (CDCl3);  1.13
(t, J = 7.1 Hz, -OCH2CH3, 3H), 2.96-3.10 (m, PhCH2-, 2H), 3.97 (q, J = 7.1 Hz, -OCH2-, 2H), 4.15-4.20
(m, -NHCH-, 1H), 5.09 (d, J = 8.5 Hz, -NH-, 1H), 7.05-7.26 (m, Ar, 5H), 7.43 (d, J = 8.8 Hz, Ar, 2H),
7.77 (d, J = 8.8 Hz, Ar, 2H). 13C NMR (CDCl3);  13.9, 39.3, 56.8, 61.8, 100.0, 127.2, 128.46, 128.55,
129.4, 134.9, 138.1, 139.4, 170.7. Anal. Calcd for C17H18O4NIS (459.30): C, 44.46; H, 3.95; N, 3.05; S,
6.98; I, 27.63. Found: C, 44.39; H, 3.94; N, 2.99; S, 7.14; I, 28.80.
N-[4-(Trimethylsilylethynyl)phenylsulfonyl]-L-phenylalanine ethyl ester (PSi-Phe). Method B
was applied for PI-Phe (15.7 g, 34.3 mmol), triphenylphosphine (151 mg, 575 µmol),
bis(triphenylphosphine)palladium (II) dichloride (194 mg, 276 µmol), copper (I) iodide (156 mg, 819
µmol), and (trimethylsilyl)acetylene (8.3 ml, 59 mmol). The purification of the obtained compound was
carried out using column chromatography on silica gel with ethyl acetate/hexane (1/3, v/v) to yield PSiPhe as a pale yellow crystal. Yield: 14.3 g (97.0 %) Mp 101 ºC. []D = +17.4º (c 1.0, CHCl3). 1H NMR
(CDCl3);  0.26 (s, -Si(CH3)3, 9H), 1.09 (t, J = 7.1 Hz, -OCH2CH3, 3H), 3.04 (d, J =6.0 Hz, PhCH2-,
2H), 3.94 (q, J = 7.1 Hz, -OCH2-, 2H), 4.14-4.22 (m, -NHCH-, 1H), 5.12 (d, J = 9.2 Hz, -NH-, 1H),
7.06-7.26 (m, Ar, 5H), 7.49 (d, J = 8.8 Hz, Ar, 2H), 7.67 (d, J = 8.8 Hz, Ar, 2H). 13C NMR (CDCl3);  0.2, 13.9, 39.4, 56.7, 61.8, 98.5, 103.0, 127.0, 127.3, 127.9, 128.6, 129.4, 132.3, 134.9, 139.1, 170.6.
Anal. Calcd for C22H27O4NSSi (429.60): C, 61.51; H, 6.33; N, 3.26; S, 7.46. Found: C, 61.26; H, 6.34;
N, 3.17; S, 7.63.
8
N-(4-Ethynylphenylsulfonyl)-L-phenylalanine ethyl ester (PAS-Phe). Method C was applied for
PSi-Phe (13.0 g, 30.3 mmol) and 1M TBAF THF solution (10.3 ml, 10.3 mmol). The purification of the
obtained compound was carried out using column chromatography on silica gel with ethyl
acetate/hexane (2/3, v/v) to yield PAS-Phe as a pale yellow crystal. Yield: 10.4 g (96.1 %) Mp 102 ºC.
[]D = +11.5º (c 1.0, CHCl3). 1H NMR (CDCl3);  1.09 (t, J = 7.0 Hz, -OCH2CH3, 3H), 3.04 (d, J = 5.9
Hz, PhCH2-, 2H), 3.24 (s, CHCPh-, 1H), 3.95 (q, J =7.0 Hz, -OCH2-, 2H), 4.14-4.22 (m, -NHCH-,
1H), 5.10 (d, J = 9.2 Hz, -NH-, 1H), 7.08-7.26 (m, Ar, 5H), 7.53 (d, J = 8.4 Hz, Ar, 2H), 7.69 (d, J = 8.4
Hz, Ar, 2H). 13C NMR (CDCl3);  13.8, 39.4, 56.8, 61.8, 80.6, 81.9, 126.8, 127.0, 127.3, 128.5, 129.4,
132.5, 134.9, 139.7, 170.7. Anal. Calcd for C19H19O4NS (357.42): C, 63.85; H, 5.36; N, 3.92; S, 8.97.
Found: C, 63.57; H, 5.37; N, 3.87; S, 8.91.
N-(4-Iodophenylsulfonyl)-L-gulutamic acid diethyl ester (PI-Glu). Method A was applied for Lgulutamic acid diethyl ester (10.0 g, 49.2 mmol), triethylamine (13.6 ml), and 4-iodobenzenesulfonyl
chloride (16.4 g, 54.1 mmol) to yield PI-Glu as a white crystal. The purification of the obtained
compound was carried out using column chromatography on silica gel with ethyl acetate/hexane (1/2,
v/v). Yield: 21.9 g (94.8 %) Mp 80 ºC. []D = +48.7º (c 1.0, CHCl3). 1H NMR (CDCl3);  1.13 (t, J =
7.0 Hz, -OCH2CH3, 3H), 1.27 (t, J = 7.3 Hz, -OCH2CH3, 3H), 1.83-2.17 (m, -CH2CH-, 2H), 2.41-2.51
(m, -CH2CH2CH-, 2H), 3.93-4.01 (m, -CHCOOCH2-, -COOCH2-, 3H), 4.15 (q, J = 7.3 Hz, CH2COOCH2-, 2H), 5.30 (d, J = 9.2 Hz, -NH-, 1H), 7.54 (d, J = 8.5 Hz, Ar, 2H), 7.85 (d, J = 8.7 Hz,
Ar, 2H) 13C NMR (CDCl3);  13.9, 14.2, 28.2, 29.6, 55.0, 60.8, 62.1, 100.3, 128.7, 138.3, 138.4, 171.1,
172.5. Anal. Calcd for C15H20O6NIS (469.29): C, 38.39; H, 4.30; N, 2.98; S, 6.83; I, 27.04. Found: C,
38.35; H, 4.20; N, 2.92; S, 6.73; I, 28.45.
N-[4-(Trimethylsilylethynyl)phenylsulfonyl]-L-gulutamic acid diethyl ester (PSi-Glu). Method B
was applied for PI-Glu (21.0 g, 44.7 mmol), triphenylphosphine (198 mg, 755 µmol),
bis(triphenylphosphine)palladium (II) dichloride (254 mg, 362 µmol), copper (I) iodide (205 mg, 1.08
mmol), and (trimethylsilyl)acetylene (10.9 ml, 77.1 mmol). The purification of the obtained compound
9
was carried out using column chromatography on silica gel with ethyl acetate/hexane (1/3, v/v) to yield
PSi-Glu as a pale yellow crystal. Yield: 18.6 g (94.8 %) Mp 131 ºC. []D = +58.2º (c 1.0, CHCl3). 1H
NMR (CDCl3);  0.25 (s, -Si(CH3)3, 9H), 1.13 (t, J = 7.0 Hz, -COOCH2CH3, 3H), 1.26 (t, J = 7.3 Hz, COOCH2CH3, 3H), 1.83-2.14 (m, -CH2CH-, 2H), 2.41-2.49 (m, -CH2CH2CH-, 2H), 3.92-3.99 (m, CHCOOCH2-, -CHCOOCH2-, 3H), 4.13 (q, J = 7.0 Hz, -CH2COOCH2-, 2H), 5.30 (d, J = 9.2 Hz, -NH-,
1H), 7.54 (d, J = 8.7 Hz, Ar, 2H), 7.75 (d, J = 8.6 Hz, Ar, 2H)
13C
NMR (CDCl3);  - 0.3, 13.9, 14.1,
28.2, 29.6, 55.0, 65.7, 62.0, 98.7, 103.0, 127.1, 128.0, 132.4, 138.8, 171.1, 172.5. Anal. Calcd for
C20H29O6NSSi (439.60): C, 54.64; H, 6.65; N, 3.19; S, 7.29. Found: C, 54.50; H, 6.61; N, 3.21; S, 7.13.
N-(4-Ethynylphenylsulfonyl)-L-gulutamic acid diethyl ester (PAS-Glu). Method C was applied for
PSi-Glu (18.1 g, 41.6 mmol) and 1M TBAF THF solution (14.0 ml, 14.0 mmol). The purification of the
obtained compound was carried out using column chromatography on silica gel with ethyl
acetate/hexane (1/2, v/v) to yield PAS-Glu as a pale yellow crystal. Yield: 14.5 g (95.0 %) Mp 73 ºC.
[]D = +55.6º (c 1.0, CHCl3). 1H NMR (CDCl3);  1.12 (t, J = 7.1 Hz, -COOCH2CH3, 3H), 1.27 (t, J =
7.3 Hz, -COOCH2CH3, 3H), 1.85-2.14 (m, -CH2CH-, 2H), 2.43-2.48 (m, -CH2CH2CH-, 2H), 3.26 (s,
CHCPh-, 1H), 3.94-4.00 (m, -CHCOOCH2-, -CHCOOCH2-, 3H), 4.14 (q, J = 7.3 Hz, -COOCH2CH3,
2H), 5.36 (d, J = 9.2 Hz, -NH-, 1H), 7.59 (d, J = 8.7 Hz, Ar, 2H), 7.79 (d, J = 8.7 Hz, Ar, 2H). 13C NMR
(CDCl3);  13.9, 14.1, 28.2, 29.6, 55.0, 60.7, 62.0, 80.8, 81.8, 127.0, 127.2, 132.6, 139.4, 171.1, 172.5.
Anal. Calcd for C17H21O6NS (367.42): C, 55.57; H, 5.76; N, 3.81; S, 8.73. Found: C, 55.48; H, 5.70; N,
3.82; S, 8.46.
10
1H
NMR spectra of the sulfonamide-functionalized poly(phenylacetylene)s.
All the 1H NMR
spectra of the polymers were recorded in DMSO-d6.
Figure S-1. 1H NMR spectrum of PPAS-Ala in DMSO-d6.
Figure S-2. 1H NMR spectrum of PPAS-Ile in DMSO-d6.
11
Figure S-3. 1H NMR spectrum of PPAS-Val in DMSO-d6.
Figure S-4. 1H NMR spectrum of PPAS-Phe in DMSO-d6.
12
Figure S-5. 1H NMR spectrum of PPAS-Glu in DMSO-d6.
13
CD titration experiments for the sulfonamide-functionalized poly(phenylacetylene)s. All the CD
spectra of the polymers were recorded in THF with various amount of guest anions.
1) CD titration experiments for PPAS-Ala
Figure S-6. CD (upper) and UV (lower) spectra of
Figure S-7. CD (upper) and UV (lower) spectra of
PPAS-Ala in the presence of TBAF in THF at 25C.
PPAS-Ala in the presence of TBAClO4 in THF at 25C.
The concentration of PPAS-Ala was 1 mg･mL-1.
The concentration of PPAS-Ala was 1 mg･mL-1.
Figure S-8. CD (upper) and UV (lower) spectra of
PPAS-Ala in the presence of TBANO3 in THF at 25C.
The concentration of PPAS-Ala was 1 mg･mL-1.
14
2) CD titration experiments for PPAS-Ile
Figure S-9. CD (upper) and UV (lower) spectra of
Figure S-10. CD (upper) and UV (lower) spectra of
PPAS-Ile in the presence of TBAF in THF at 25C. The
PPAS-Ile in the presence of TBAA in THF at 25C.
concentration of PPAS-Ile was 1 mg･mL-1.
The concentration of PPAS-Ile was 1 mg･mL-1.
Figure S-11. CD (upper) and UV (lower) spectra of
Figure S-12. CD (upper) and UV (lower) spectra of
PPAS-Ile in the presence of TBABr in THF at 25C.
PPAS-Ile in the presence of TBAClO4 in THF at 25C.
The concentration of PPAS-Ile was 1
mg･mL-1.
The concentration of PPAS-Ile was 1 mg･mL-1.
15
Figure S-13. CD (upper) and UV (lower) spectra of
Figure S-14. CD (upper) and UV (lower) spectra of
PPAS-Ile in the presence of TBAN3 in THF at 25C.
PPAS-Ile in the presence of TBANO3 in THF at 25C.
The concentration of PPAS-Ile was 1 mg･mL-1.
The concentration of PPAS-Ile was 1 mg･mL-1.
16
3) CD titration experiments for PPAS-Val
Figure S-15. CD (upper) and UV (lower) spectra of PPAS-Val in the presence of TBAF in THF at 25C. The
concentration of PPAS-Val was 1 mg･mL-1. ([TBAF]/[sulfonamide] = left) 0~2.0, right) 2.5~5.5)
Figure S-16. CD (upper) and UV (lower) spectra of
Figure S-17. CD (upper) and UV (lower) spectra of
PPAS-Val in the presence of TBAA in THF at 25C.
PPAS-Val in the presence of TBAClO4 in THF at 25C.
The concentration of PPAS-Val was 1 mg･mL-1.
The concentration of PPAS-Val was 1 mg･mL-1.
17
Figure S-18. CD (upper) and UV (lower) spectra of
PPAS-Val in the presence of TBANO3 in THF at 25C.
The concentration of PPAS-Val was 1 mg･mL-1.
18
4) CD titration experiments for PPAS-Phe
Figure S-19. CD (upper) and UV (lower) spectra of PPAS-Phe in the presence of TBAF in THF at 25C. The
concentration of PPAS-Phe was 1 mg･mL-1. ([TBAF]/[sulfonamide] = left) 0~1.0, right) 1.5~5.0)
Figure S-20. CD (upper) and UV (lower) spectra of
Figure S-21. CD (upper) and UV (lower) spectra of
PPAS-Phe in the presence of TBABr in THF at 25C.
PPAS-Phe in the presence of TBAClO4 in THF at
The concentration of PPAS-Phe was 1
mg･mL-1.
25C. The concentration of PPAS-Phe was 1 mg･mL-1.
19
Figure S-22. CD (upper) and UV (lower) spectra of
Figure S-23. CD (upper) and UV (lower) spectra of
PPAS-Phe in the presence of TBAN3 in THF at 25C.
PPAS-Phe in the presence of TBANO3 in THF at 25C.
The concentration of PPAS-Phe was 1
mg･mL-1.
The concentration of PPAS-Phe was 1 mg･mL-1.
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5) CD titration experiments for PPAS-Glu
Figure S-24. CD (upper) and UV (lower) spectra of
Figure S-25. CD (upper) and UV (lower) spectra of
PPAS-Glu in the presence of TBAF in THF at 25C.
PPAS-Glu in the presence of TBAA in THF at 25C.
The concentration of PPAS-Glu was 1 mg･mL-1.
The concentration of PPAS-Glu was 1 mg･mL-1.
Figure S-26. CD (upper) and UV (lower) spectra of
Figure S-27. CD (upper) and UV (lower) spectra of
PPAS-Glu in the presence of TBAClO4 in THF at
PPAS-Glu in the presence of TBAN3 in THF at 25C.
25C. The concentration of PPAS-Glu was 1
mg･mL-1.
The concentration of PPAS-Glu was 1 mg･mL-1.
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Figure S-28. CD (upper) and UV (lower) spectra of
PPAS-Glu in the presence of TBANO3 in THF at 25C.
The concentration of PPAS-Glu was 1 mg･mL-1.
Figure S-29. Visible color changes of the urea-functionalized polymers upon the addition of TBAA
(from left to right; PPAU-Asp, PPAU-Phe, PPAU-Glu, PPAU-Ile, and PPAU-Val).
22