)urqwlhuv 7klvmrxuqdolv wkh3duwqhu2ujdqlvdwlrqv · mmol) was then added with a syringe at once the...

1

Electronic Supplementary Material (ESI) for Materials Chemistry Frontiers.This journal is © the Partner Organisations 2018

Electronic supplementary information for the following manuscript:

Systematic Oligoaniline-based Derivatives: the ACQ-AIE Conversion with Tunable Insertion Effect and Quantitative Fluorescence "turn-on" Detection of BSA

Hao Lu, Kun Wang, Beibei Liu, Meng Wang, Mingming Huang, Yue Zhang, and Jiping Yang*

Key Laboratory of Aerospace Advanced Materials and Performance, Ministry of Education, School of Materials Science and Engineering, Beihang University, Beijing 100191, ChinaE-mail: [email protected]

Table of Contents

Chemicals and materials 2

Apparatus and analytical methods 2

Experimental procedures 3

Figures S1-S18 6

Table S1-S2 15

References 16

Electronic Supplementary Material (ESI) for Materials Chemistry Frontiers.This journal is © the Partner Organisations 2018

2

Chemicals and materials

Diphenylamine (A1, purity 98%), N,N’-diphenyl-1,4-phenylenediamine (A2, purity

98%), diphenylacetaldehyde (purity 95%), (±)-Camphor-10-sulfonic acid (purity 98%),

hydroquinone (purity 99%), 4-hydroxydiphenylamine (HDPA, purity 98%), sodium tert-

butoxide (purity 98%), 1,4-phenylenediamine (purity 98%), and tetrabutyl orthotitanate

(TBT) were purchased from TCI (Shanghai) development Co., Ltd. N-Pheny-1,4-

phenylenediamine (ADPA, purity 98%) was purchased from Alfa Aesar (China)

Chemical Co., Ltd. 4-Bromodiphenylamine (Br-A1, purity 99%) was purchased from

Adamas Reagent Shanghai Co., Ltd. Palladium(II) acetate (purity 99%), 2-(di-tert-

butylphosphino)biphenyl, bovine serum albumin (BSA, purity 99%), cholesterol (purity

99%), carbamide (purity 99%), L-arginine (purity 99%) and glucose (purity 99%) were

purchased from Innochem Chemical Reagent Beijing Co., Ltd. Phosphate buffer saline

powder (2L) and γ-globulin (purity 99%) were purchased from Beijing BioDee

Biotechnology Co., Ltd. 5Ǻ molecular sieves were purchased from Sinopharm Chemical

Reagent Beijing Co., Ltd, and activated for 4 h at 240 oC in a tube furnace prior to use.

Toluene and tetrahydrofuran (THF) were received from Beijing Chemical Works (Beijing,

China). Toluene was dried by calcium hydride over night, then refluxed and distilled for

use. All other raw materials were used without further purification.

Apparatus and analytical methods

Ultraviolet and visible (UV-vis) absorption spectra were recorded on a TU-1901 UV

spectrophotometer by using THF as the solvent. Proton nuclear magnetic resonance (1H-

NMR) spectra were measured on a Bruker AV 400M NMR spectrophotometer in

deuterated dimethyl sulfoxide, deuterated THF or deuterated chloroform using 0.05%

tetramethylsilane as an internal standard. Fourier transform infrared (FTIR) spectra were

obtained using a Nicolet iS50 FTIR spectrophotometer with KBr pellet technique at room

temperature. Single crystal X-ray structures were analyzed on a Rigaku CCD Saturn 724+

X-ray single crystal diffractometer using monochromatized Mo-Kα (λ=0.71073 Ǻ)

incident radiation. Mass spectra (MS) were carried out with an Autoflex III MALDI-TOF

3

mass spectrometer. Photoluminescence spectra (PL) were obtained using a F-5200

fluorescence spectrophotometer. All computational studies were performed using density

functional theory (DFT) method at a B3LYP/6-31G (d) level through Gaussian 09

package.[1]

Experimental procedures

Synthesis of B1-A1

A1 (0.642 g, 3.8 mmol), diphenyl acetaldehyde (0.745 g, 3.8 mmol), 5Ǻ molecular

sieves (1.011 g), toluene (8 ml) and THF (2 ml) were blended followed by mightily

stirring for 20 min. Then (±)-camphor-10-sulfonic acid (catalytic amount) was added and

the whole mixture refluxed at 70 oC for 8 h. Along with the system cooling to room

temperature, the resulting solution was filtered and the filtrate was evaporated under

reduced pressure. The crude product was dissolved in THF and recrystallized to afford

bright yellow powder (0.791 g, 57%).

1H-NMR (400 MHz, THF-d8), δ (ppm): 5.56-5.42 (m, 5H, Ar), 5.34 (t, 4H, J=8.0 Hz,

Ar), 5.27-5.16 (m, 9H, Ar), 5.11 (t, 2H, J=8.0 Hz, Ar), 4.99 (s, 1H,-N-CH=).

FTIR (KBr), cm-1: 3021 (C-H, Ar); 1583, 1586 (C=C); 1486, 1477 (C-C, Ar); 1342,

1315, 1251 (C-N); 754, 692 (C-H, Ar).

MALDI-TOF MS: m/z: calcd for C26H21N: 347.2; found: 347.2(M+H) +.

Synthesis of B1-A2, B2-A2

B1-A2 and B2-A2 were synthesized based on the previous literature with some

modifications. [2] A2 (0.880 g, 3.2 mmol), diphenyl acetaldehyde (1.393 g, 7.1 mmol) and

5Ǻ molecular sieves (1.023 g) were added into analytical THF (2 ml) and toluene (8 ml).

After stirring for 25 min, (±)-camphor-10-sulfonic acid (catalytic amount) was added.

Subsequently, the solution was step-heated to 70 oC and kept reaction for 48 h. After

cooling to environment temperature, filtered solvents were removed by reduced pressure

distillation and the mixture was separated by silica gel column chromatography using

petroleum ether/ethyl acetate (30:1 (v/v)) as the eluent. Ideal B1-A2 (Rf=0.43) and B2-A2

4

(Rf=0.61) were further purified by recrystallization in THF solvent. Yellow powder of

B2-A2 was acquired in a yield of 53% while B1-A2 with quantity of 27% exhibiting

bright yellow color was obtained.

B1-A2:1H-NMR (400 MHz, THF-d8), δ (ppm): 9.01 (s, 1H, NH), 5.44-4.79 (m, 25H, Ar and

-N-CH=).

FTIR (KBr), cm-1: 3047 (N-H); 3022 (C-H, Ar); 1595, 1569 (C=C); 1509, 1491 (C-C,

Ar); 1309, 1265 (C-N); 755, 693 (C-H, Ar).

MALDI-TOF MS: m/z: calcd for C32H26N2: 438.2; found: 438.3 (M+H) +.

B2-A2:1H-NMR (400 MHz, THF-d8), δ (ppm): 5.42-5.30 (m, 12H, Ar), 5.23 (t, 6H, J=2.0

Hz, Ar), 5.15-4.98 (m, 12H, Ar), 4.81 (s, 6H, Ar and -N-CH=).

FTIR (KBr), cm-1: 3022 (C-H, Ar); 1591, 1569 (C=C); 1502, 1490 (C-C, Ar); 1336,

1311, 1263 (C-N); 758, 696 (C-H, Ar).


Synthesis of aniline trimer (A3)

Aniline trimer was synthesized based on the previous literature with some

modifications. [3] ADPA (4.500 g, 24.0 mmol) was added to a 250 ml round-bottom flask

followed by dissolution with 75 ml dehydrated toluene. Afterwards, TBT (9.290 g, 80.0

mmol) was then added with a syringe all at once through the septum. The system was then

vacuumed and filled with argon gas atmosphere. Repeating this operation three times to

fully extirpate air, and then HDPA (4.501 g, 24.0 mmol) dissolved in 25 ml dehydrated

toluene was added to the reaction system with protection of an argon gas balloon. The

reaction system was step-heated to 100 oC to gain reflux condition and continued to stir

for 20 hours. After allowing cooling down to room temperature, the reaction solution was

filtered by sand core funnel and the resulting purple silver crystals were washed

repeatedly with 700 ml of toluene. Solid crude product was purified by recrystallization

5

using toluene/ethyl acetateas the solvent, followed by drying under reduced pressure to

obtain ideal A3 (6.307 g, 70%).

1H-NMR (400 MHz, DMSO-d6), δ (ppm): 7.78 (s, 2H, NH), 7.67 (s, 1H, NH), 7.15 (t,

4H, J=8.0 Hz, Ar), 7.04-6.84 (m, 12H, Ar), 6.69 (t, 2H, J=8.0 Hz, Ar).

FTIR (KBr), cm-1: 3388 (N-H); 3044, 3020 (C-H, Ar); 1529, 1494 (C-C, Ar); 1304,

1225 (C-N); 822,746, 694 (C-H, Ar).


Synthesis of B3-A3

Following the similar procedure as that of compound B2-A2, just replacing A2 by

A3, B3-A3 was successfully obtained. Yields of yellow B3-A3 was 17%.

B3-A3:1H-NMR (400 MHz, THF-d8), δ (ppm): 5.44-4.99 (m, 40H, Ar), 4.91-4.80 (m, 7H,

Ar and -N-CH=), 4.71 (t, 4H, J=8.0 Hz, Ar).

FTIR (KBr), cm-1: 3023, 2923 (C-H, Ar); 1590, 1569 (C=C); 1503 (C-C, Ar); 1312,

1260 (C-N); 752, 696 (C-H, Ar).


Synthesis of B2-A4Firstly, the enamine derivative (Br-B1-A1) was gained by the mixure of Br-A1

(1.736 g, 7.0 mmol) and diphenyl acetaldehyde (1.393 g, 7.1 mmol) follwing the

procedure of B1-A1. The product was light gray with a yeild of 79%. Next, Br-B1-A1

(2.125 g, 5.0 mmol) was added to a 50 ml round-bottom flask followed by dissolution

with 15 ml dehydrated toluene. Afterwards, the mixture solution of 1,4-phenylenediamine

(0.272 g, 2.5 mmol), sodium tert-butoxide (0.865 g, 9 mmol) and 2-(di-tert-

butylphosphino)biphenyl (0.700 g, 1.1 mmol ) in 15 ml dehydrated toluene was then

added with a syringe all at once through the septum. The system was then vacuumed and

filled with argon gas atmosphere. The reaction system was step-heated to 100 oC to gain

reflux condition and continued to stir for 16 hours. After allowing cooling down to room

temperature, the reaction solution was filtered by sand core funnel and the resulting

6

yellowish-green powder was washed repeatedly with 500 ml of toluene. Solid crude

product was purified by recrystallization using toluene/ethyl acetate as the solvent,

followed by drying under reduced pressure to obtain ideal B2-A4 (1.017 g, 42%).

1H NMR (400 MHz, DMSO-d6), δ (ppm): 7.26-6.90 (m, 34H, Ar and –NH-), 6.82 (t,

6H, J=8.0 Hz, Ar), 6.74 (t, 6H, J=8.0 Hz, Ar and -N-CH=).

FTIR (KBr), cm-1: 3419 (N-H); 3027 (C-H, Ar); 1590, 1568 (C=C); 1513, 1496 (C-C,

Ar); 1309, 1265 (C-N); 755, 695 (C-H, Ar).


Synthesis of B4-A4Following the similar procedure as that of compound A3, using new reaction

ingredients as 1,4-phenylenediamine and hydroquinone, the aniline tetramer (A4) was

successfully obtained. Then, as the same as the synthesis of B1-A1~B3-A3, just replacing

A3 by A4, B4-A4 was successfully obtained. Yield of yellow B4-A4 was 46%.

1H-NMR (400 MHz, CDCl3), δ (ppm): 7.41-7.32 (m, 8H, Ar), 7.30-7.16 (m, 28H,

Ar), 7.07 (d, 8H, J=4.0 Hz, Ar), 6.95 (t, 8H, J=8.0 Hz, Ar), 6.82 (d, 6H, J=8.0 Hz, Ar),

6.63 (d, 8H, Ar and -N-CH=).

FTIR (KBr), cm-1: 3026, 2917 (C-H, Ar); 1592, 1570 (C=C); 1500 (C-C, Ar); 1301,

1258 (C-N); 755, 696 (C-H, Ar).


B1-A1

348.

10

B1-A2

439.

30

438.

28

347.

09

B2-A2

617.

21

616.

21

799.

17

798.

17

B2-A4

B3-A3

886.

22885.

21

B4-A4

1155

.32

1154

.32

115611

5511

54886

885

79979

861

761

643

943

8348

347

Fig. S1 MALDI-TOF mass spectra of the synthesized oligoaniline derivatives.

7

5.6 5.4 5.2 5.0

Chemical shift (ppm)

(a)

4000 3000 2000 1000

50

100

692

754

1486,1477

15651583,

Wave number (cm-1)

Tran

smitt

ance

(%)

1342，1315，

1251

(b)

28462919，3021，

Fig. S2 1H-NMR (a) and FTIR (b) spectra of B1-A1.

10 9 8 7 6 5 4

5.4 5.2 5.0 4.8


(a)

4000 3000 2000 10000

50

100

28502917，

1595，12651309，1337，

755693

14911509，

1569

3407

Tran

smitt

ance

(%)

Wave number(cm-1)

3022，

(b)


5.4 5.2 5.0 4.8


(a)

4000 3000 2000 10000

50

100

28472919,

12631311，

Wave number (cm-1)

Tran

smitt

ance

(%)

3022,

1591,1502,15691490

1336，

758696

(b)


8

8.0 7.6 7.2 6.8 6.4 6.0Chemical shift (ppm)

(a)

200 400 6000

1000

2000

Inte

ns.[a

.u]

m/z

351.1

C24H21N3

351.17

(b)

4000 3000 2000 10000

50

100

694

746

1225

14941529，

3020

Wave number (cm-1)

Tran

smitt

ance

(%)

3388

3044，

1304

822

(c)

Fig. S5 1H-NMR (a), MS (b) and FTIR (c) spectra of aniline trimer A3.

5.4 5.2 5.0 4.8 4.6Chemical shift (ppm)

(a)

4000 3000 2000 10000

50

100

696

752

12601312，

1503

15691590，

2923

Wave number (cm-1)

Tran

smitt

ance

(%)

3023

(b)


9

7.3 7.2 7.1 7.0 6.9 6.8 6.7


(a)

4000 3000 2000 1000

0

50

100

695

755

3419

Tran

smitt

ance

(%)

Wave number(cm-1)

28562926，3027，

1590，1568

14961513，

12651309，1337，

(b)


7.6 7.4 7.2 7.0 6.8 6.6 6.4Chemical shift (ppm)

(a) Solvent peak

4000 3000 2000 1000

50

100

696

755

Wave number(cm-1)

Tran

smitt

ance

(%)

28502917，3026，

1592，1570

1500

12581301，1335，

(b)


10

400 450 500 550 600 6500.0

0.4

0.8

1.2 B4-A4 B2-A4 B3-A3 B2-A2 B1-A2 B1-A1

Wavelength (nm)

Nor

mal

ized

PL

Fig. S9 Normalized emission spectra of B1-A1, B1-A2, B2-A2, B3-A3, B2-A4 and B4-A4 in solid powder states (excitation wavelengths: 344 nm for B1-A1, 329 nm for B1-A2, 335 nm for B2-A2, 338 nm for B2-A4, 340 nm for B3-A3 and 353 nm for B4-A4; EX slit: 2.5 nm; EM slit: 2.5 nm).

300 400 500 600

0.0

0.2

0.4

0.6

0.8

1.0

content of water 90% 70% 60% 50% 40%

Abs

Wavelength (nm)

(b)

Fig. S10 Tyndall test (a) and UV absorption curves (b) of B2-A2 at various proportions of THF and water (concentrations: 10 μM).

11

400 500 600

0

100

200

300

400

500B1-A1

Lum

ines

cenc

e in

tens

itycontent of water 90% 80% 70% 60% 50% 40% 30% 20% 10% 0%

Wavelength(nm)

(a)

400 500 6000

20

40

60

80

100B1-A2

Lum

ines

cenc

e in

tens

ity

content of water 90% 80% 70% 60% 50% 40% 30% 20% 10% 0%

Wavelength(nm)

(b)

400 500 6000

50

100

150content of water 90% 80% 70% 60% 50% 40% 30% 20% 10% 0

B2-A4

Lum

ines

cenc

e in

tens

ity

Wavelength(nm)

(c)

400 500 6000

300

600

900

1200 content of water: 90% 80% 70% 60% 50% 40% 30% 20% 10% 0%

Lum

ines

cenc

e in

tens

ity

Wavelength(nm)

(d) B3-A3

0 90%

400 500 6000

200

400

600

800

Lum

ines

cenc

e in

tens

ity

content of water: 90% 80% 70% 60% 50% 40% 30% 20% 10% 0%

0

Wavelength(nm)

0 90%

B4-A4(e)

Fig. S11 PL spectra of B1-A1 (a), B1-A2 (b), B2-A4 (c), B3-A3 (d) and B4-A4 (e) in THF-water mixtures (concentrations: 10 μM; excitation wavelengths: 344 nm for B1-A1, 329 nm for B1-A2, 338 nm for B2-A4, 340 nm for B3-A3 and 353 nm for B4-A4; EX slit: 5 nm; EM slit: 10 nm).

12

0 2 4 6 80

2000

4000

6000

8000

10000 B1-A2-L B1-A2-S

Cou

nts

Time/ns

(b)

0 2 4 6 80

2000

4000

6000

8000

10000 B1-A1-L B1-A1-S

Cou

nts

Time/ns

(a)

Fig. S12 Fluorescence-decay profiles for B1-A1, B1-A2, B2-A2, B2-A4, B3-A3 and B4-A4 (L: solution state; S: solid powder state).

0 2 4 6 80

2000

4000

6000

8000

10000 B2-A2-L B2-A2-S

Coun

ts

Time/ns

(c)

0 2 4 6 80

2000

4000

6000

8000

10000 B2-A4-L B2-A4-S

Cou

nts

Time/ns

(d)

0 2 4 6 80

2000

4000

6000

8000

10000 B3-A3-L B3-A3-S

Cou

nts

Time/ns

(e)

0 2 4 6 80

2000

4000

6000

8000

10000 B4-A4-L B4-A4-S

Cou

nts

Time/ns

(f)

13

3.68eV

-0.89eV

-4.57eV

3.52eV

-0.93eV

-4.45eV

3.53eV

-0.94eV

-4.47eV

4.02eV

-0.81eV

-4.83eV

3.78eV

-0.78eV

-4.56eV

3.62eV

-0.77eV

-4.39eV

LUMO

HOMO

LUMO

HOMO

B2-A2 B3-A3 B4-A4

B1-A1 B1-A2 B2-A4

Fig. S13 Molecular orbital and energy levels of all aniline derivatives.

B1-A2

a1

a2

a1=68.0°a2=44.2°a1=70.5°

a2=67.2°

B1-A1 B1-A2

B1-A1

a1=55.0°a2=52.1°

B2-A2

B2-A2

a1=67.3°a2=67.3°

a1a2

a1=75.1°a2=45.1°

a1a2

a1=65.6°a2=52.2°

(a)

(b)

Fig. S14 Geometrical structures of B1-A1, B1-A2 and B2-A2 (a: ground states; b: excited states)

14

0 5 10 15 20 25

0

4

8

12

16

Concentration of BSA (mg/ml)

(b)

R2=0.962

I/I0-

1

400 500 6000

40

80

120

160

200VBAS (uL) 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0

Wavelength (nm)

Lum

ines

cenc

e in

tens

ity

(a)B3-A3

0

25.1 mg/ml

Fig. S15 (a) Emission spectra of B3-A3 solution (10 μM; excitation wavelength: 340 nm; EX slit: 5 nm; EM slit: 10 nm) in various amount of BSA, (b) The fitted linear curve of luminescence intensity changes of B3-A3 solution in response to different amounts of BSA.

0 5 10 15

0.0

0.5

1.0

1.5

2.0


I/I0-

1

(a)

0 5 10 150

2

4

6

8


I/I0-

1

(b)

0 5 10 150

1

2

3

4


I/I0-

1

(c)

Fig. S16 Plot of (I/I0)-1 concerning B1-A1 (a), B1-A2 (b) and B2-A4 (c) in response to different amounts of BSA, where I0 is the luminescence intensity without the addition of BSA.

15

0 10 20 30 40 50

0

5

10

15

20

25

5.00mg/mL

3.75mg/mL

2.50mg/mL

1.25mg/mL

6.25mg/mL

(I-I

0)/I 0

Time (s)

(a)

0 10 20 30 40 50

0

5

10

15

20

25 18.75mg/mL

15.00mg/mL

11.25mg/mL

7.50mg/mL

3.75mg/mL

(I-I

0)/I 0

Time (s)

(b)

Fig. S17 (a) Fluorescence response of B2-A2 with different BSA concentrations (1.25-6.25 mg/ml) at the different time, (b) Fluorescence response of B3-A3 with different BSA concentrations (3.75-18.75 mg/ml) at the different time.

A B C D E F G H I J0.0

0.5

1.0

1.5

2.0

2.5

(I-

I 0)/I

0

(a)

A B C D E F G H I J0.00.51.01.52.02.53.03.5

(I-I 0

)/I0

(b)

Fig. S18 Dependence of the PL intensity of B2-A2 (a) ([B2-A2]=10 μM; [component] = 0.8mg/ml) and B3-A3 (b) ([B3-A3]=10 μM; [component] = 3 mg/ml) on different mixed components of blood serum in PBS buffer. (A) BSA; (B) γ-globulin; (C) cholesterol; (D) carbamide; (E) glucose; (F) L-arginine; (G), cholesterol, glucose, carbamide, L-arginine; (H) γ-globulin, cholesterol, glucose, carbamide, L-arginine; (I) BSA, cholesterol, glucose, carbamide, L-arginine; (J) BSA, γ-globulin, cholesterol, glucose, carbamide, L-arginine.

Table S1 Spectroscopic parameters of 6 aniline derivatives. (THF, 10μM)Compounds λmax abs/

nmλem/nm

Stokes shift/cm−1

B1-A1 312 408 7541B1-A2 330 467 8890B2-A2 332 451 7948B3-A3 342 464 7688B2-A4 339 488 9007B4-A4 353 479 7452

16

Table S2 Fluorescent lifetimes and quantum yields of 6 aniline derivatives in THF solutions and in solid powder states

Compounds State Fluorescent lifetime / ns Quantum yield / % B1-A1

In THF solution

2.51 0.01 B1-A2 1.41 0.02 B2-A4 1.14 0.05 B2-A2 0.07 0.07 B3-A3 0.05 0.09 B4-A4 0.19 0.22 B1-A1

In solid powder

1.41 0.02 B1-A2 0.25 0.05 B2-A4 0.83 0.14 B2-A2 0.32 0.55 B3-A3 0.51 0.63 B4-A4 0.39 1.56

Reference1 R. Misra, T. Jadhav, B. Dhokale and S. M. Mobin, Chemical Communications, 2014,

50, 9076.2 R. Paspirgelyte, J. V. Grazulevicius, S. Grigalevicius and V. Jankauskas, Designed

Monomers & Polymers, 2009, 12, 579.3 W. Wang and A. G. MacDiarmid, Synthetic Metals, 2002, 129, 199.

)urqwlhuv 7klvmrxuqdolv wkh3duwqhu2ujdqlvdwlrqv · mmol) was then added with a syringe at once the...

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