gelation induced reversible syneresis via structural evolution · supplementary material (esi) for...

Supplementary Material (ESI) for Journal of Materials Chemistry This journal is (c) The Royal Society of Chemistry 2009

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Supplementary Information

Gelation Induced Reversible Syneresis via Structural Evolution

Junchen Wu,a Tao Yi,*a Ying Zou,a Tianmin Shu,a Qian Xia,a Feng Liu,a Yuhong

Yang,b Fuyou Li,a Zhigang Chen,a Zhiguo Zhou,a Chunhui Huang*a aDepartment of Chemistry & Laboratory of Advanced Materials, and bThe center of

analysis and measurement, Fudan University, 220 Handan Road, Shanghai 200433,

China

*Corresponding authors. E-mail: [email protected], [email protected]

Movie (Widows Media Player)

“In situ watching (video) on the dynamic change of the gel 1b by CLSM images after

the formation of the gel for 20 min”


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1000 1020 1040 1060 1080 1100

0.002

0.004

0.006

0.008

0.010

0.012

0.014

0.016

0.018

Abs

orba

nce

Wavelength / nm

0.0047 (χTAA) 0.0094 0.0140 0.0186 0.023 0.028 0.032

a

1020 1030 1040 1050 1060 1070 10800.003

0.004

0.005

0.006

0.007

0.008

Abs

orba

nce

Wavelength / nm

10 min 30 min 60 min 120 min

b

Fig. S1 (a) Near infrared absorption spectra of standard samples with different concentration

of TAA in toluene. The linear relationship of the TAA concentration (χTAA) vs integral area of

the absorbance is shown in the inset. (b) NIR spectra of the release solvent with deposition

time.

a b caa bb cc

Fig. S2 Pictures of gel formation on fixed mole fraction of n-butyl-amine (a), ethane-1,

2-diamine (b) and tri(2-aminoethyl)amine (c) in toluene (χmol/mol = 0.0019, 25 mg/mL)

0.00 0.01 0.02 0.030.00

0.02

0.04

0.06

0.08

Abso

rban

ce

χTAA

R = 0.9974Slope = 2.4666


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300 400 500 600 7000.0

0.2

0.4

0.6

0.8

1.0A

bsor

banc

e

Wavelength (nm)

a

385 nm

618 nm

500 600 700

0.0

0.2

0.4

0.6

0.8

1.0

Inte

nsity

Wavelength (nm)

b 655 nm

494 nm

400 500 600 7000.0

0.1

0.2

0.3

Abs

orpt

ion

Wavelength (nm)

c

388 nm

587 nm

656 nm

300 400 500 600 700

0.0

0.5

1.0

1.5

2.0

2.5

3.0

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

Abs

orpt

ion

Wavelength (nm)

Inte

nsity

d

399 nm

518 nm

Fig. S3 (a) The absorption and (b) emission spectra of 1 in CHCl3 (1.0×10-4 mol/L, 25 °C). (c) The absorption spectrum of 1/n-butylamine gel film in toluene (25 mg/mL). (d) The absorption and emission spectra (λex = 390 nm) of 1/TAA in the gel film (25 mg/mL) with the fixed mole fraction of TAA in toluene (χTAA = 0.019±0.001) at room temperature. From the absorption spectrum of 1/n-butylamine gel, one can clearly see two absorption bands centered at 586 and 657 nm, corresponding to the aggregated and isolated square acid, respectively. However, those absorption bands in 1/TAA gel are completely disappeared, indicating the strong interaction between TAA and 1, which also conformed by 1H NMR and Maldi-Tof mass spectra. TLC indicated the complete finish of the reaction after a heat-cool process for gel 1/TAA. Therefore, the solvent release process is mainly controlled by non-covalent interaction in the process of the aggregation rather than a reaction process. It seems that the reaction can be reversed in a certain case. For example, we observed the recovery of the color and the absorption when organic acid such as trifluoroacetic acid was added to the system (Fig. S4).


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300 400 500 600 7000.0

0.2

0.4

0.6

0.8

Abso

rptio

n

Wavelength (nm)

1 in CHCl3 1+TAA 1+TAA+TFA

1 1+TAA 1+TAA+H+

Fig. S4 The absorption spectra of 1, 1+TAA (10 eq) and 1+TAA (10 eq)+TFA (30 eq) (CF3COOH) in CHCl3 solution (1×10-5 M of 1, 25 ºC, 1 mm cell). The inset shows the color of the samples. (λex = 380 nm).

0.008 0.012 0.016 0.020 0.0240

10

20

30

40

50

262830323436384042444648

V%

χTAA

T g

(o C)

Fig. S5 TAA molar fraction variation of Tgel (a fresh gel) and the volume ratio of expelled solvent over a period of 1 h at 15 °C (χTAA= 0.007, 0.009, 0.012, 0.014, 0.016, 0.019, 0.021, 0.023).

10 100

0

20

40

60

She

ar v

isco

sity

(Pa.

S)

Shear Rate (1/S)

24 h 2 h 0 h

Fig. S6 Shear viscosity as a function of shear rate for the gel 1b as-prepared fresh gel, and aging for 2 hours and 24 hours (χTAA = 0.019±0.001, 25 mg/mL) .


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N

NH2

H2N

NH2

hydrophobic hydrophilic

N

NH2

H2NNH2

Release

Fig. S7 (a) The intermolecular hydrogen bonding between 1 and TAA before and after release. (b) The schematic presentation of the release mechanism. The arrows show direction of the process.

a

b


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2000 2010 2020 2030 2040 2050 2060

0102030405060708090

100

% In

tens

ity

Mass(m/z)

943.4

2027.552028.56

2037.51

2038.52

2039.51

2040.51

Voyager Spec#1=>BC=>NF0.7[BP = 983.4, 15469]b)

Fig. S8 a) 1H NMR spectra of 1 in CDCl3; b) MALDI-TOF spectra of 1.

gelation induced reversible syneresis via structural evolution · supplementary material (esi) for...

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