Preparation of pH-Sensitive Fluorescent Poly(acryl-2-aminoethy-lammonium hydrochloride) with Porphyrin or Fluorene by One-pot Method†

doi:10.7503/cjcu20130840

Abstract

Abstract:

Poly(N-tert-butoxycarbonyl-N'-acryloyl-1,2-diaminoethane)(PBAEN) with dithioester as end groups was prepared via reversible addition-fragmentation chain transfer polymerization(RAFT). The one-pot method, which the reduction of dithioester and Click reaction between thiol and epoxy group were conducted simultaneously, was used to prepared fluorescently label poly(N-acryloyl-1,2-diaminoethane hydrochloride)-porphyrin(PAEN-EPT) and poly(N-acryloyl-1,2-diaminoethane hydrochloride)-fluorene(PAEN-DEPF). The fluorescence intensity of PAEN-EPT and PAEN-DEPF in aqueous solution decreased dramatically as pH≥7 due to the polymer chain shrinking. The PAEN-EPT and PAEN-DEPF showed the pH-response. In addition, the quantum yield for PAEN-EPT aqueous solution could reach 0.096.

Key words: Water-soluble, Fluorescent polymer, Reversible addition-fragmentation chain transfer(RAFT) polymerization, Click reaction, One-pot method

CLC Number:

O631

TrendMD:

LIU Nan, WU Yonggang, BAI Libin, WANG Yuan, HUANG Haichao, ZHAO Hongchi, BA Xinwu. Preparation of pH-Sensitive Fluorescent Poly(acryl-2-aminoethy-lammonium hydrochloride) with Porphyrin or Fluorene by One-pot Method^†[J]. Chem. J. Chinese Universities, 2014, 35(5): 1111.

Figures/Tables 17

Fig.1 Reaction mechanism of preparing PAEN-EPT and PAEN-DEPF by one-pot method

Fig.2 FTIR spectra of PBAEN(a), PAEN-DEPF(b) and PAEN-EPT(c)

Fig.3 1H NMR spectra of PAEN-DEPF(A) and PAEN-EPT(B)

Fig.4 GPC traces of PBAEN(a) and PBAEN-EPT(b) at 30 ℃^ Flow rate: 1 mL/min.

Fig.5 GPC traces of PBAEN(a) and PBAEN-DEPF(b) at 30 ℃^ Flow rate: 1 mL/min.

Fig.6 UV-Vis spectra of PBAEN(a), PBAEN-EPT(b) and EPT(c) at 25 ℃^a. [PBAEN]=2.5×10-6 mol/L;b. [PBAEN-EPT]=2.5×10-6 mol/L;c. [EPT]=2.0×10-8 mol/L.

Fig.7 PL spectra of PBAEN(a), PBAEN-EPT(b) and EPT(c) at 25 ℃^a. [PBAEN]=2.5×10-6 mol/L, λex=288 nm;b. [EPT]=2.0×10-8 mol/L, λex=410 nm;c. [PBAEN-EPT]=2.5×10-6 mol/L, λex=410 nm.

Fig.8 UV-Vis spectra of PBAEN-EPT, PAEN-EPT and EPT at 25 ℃^a. [PAEN-EPT]=2.5×10-6 mol/L(aqueous solution);b. [EPT]=0(aqueous solution);c. [PBAEN-EPT]=2.5×10-6 mol/L(CH2Cl2 solution).

Fig.9 PL spectra of PBAEN-EPT, PAEN-EPT and EPT at 25 ℃(λex=410 nm)^a. [PAEN-EPT]=2.5×10-6 mol/L(aqueous solution); b. [EPT]=0(aqueous solution);c. [PBAEN-EPT]=2.5×10-6 mol/L(CH2Cl2 solution).

Fig.10 UV-Vis spectra of PBAEN, PBAEN-DEPF and DEPF at 25 ℃^a. [PBAEN]=7.5×10-6 mol/L; b. [PBAEN-DEPF]=7.5×10-6 mol/L; c. [DEPF]=2.0×10-8 mol/L.

Fig.11 PL spectra of PBAEN, PBAEN-DEPF and DEPF at 25 ℃^a. [PBAEN]=7.5×10-6 mol/L, λex=288 nm;b. [PBAEN-DEPF]=7.5×10-6 mol/L, λex=300 nm; c. [DEPF]=2.0×10-8 mol/L, λex=300 nm.

Fig.12 UV-Vis spectra of PBAEN-DEPF(a),PAEN-DEPF(b) and DEPF(c) at 25 ℃^a. [PBAEN-DEPF]=7.5×10-6 mol/L;b. [PAEN-DEPF]=7.5×10-6 mol/L(aqueous solution);c. [DEPF]=0(aqueous solution).

Fig.13 PL spectra of PBAEN-DEPF(a), PAEN-DEPF(b) and DEPF(c) at 25 ℃^a. [PBAEN-DEPF]=7.5×10-6 mol/L, λex=288 nm;b. [PAEN-DEPF]=7.5×10-6 mol/L(aqueous solution);c. [DEPF]=0(aqueous solution), λex=288 nm.

Fig.14 UV-Vis spectra of PAEN-EPT at different pH values at 25 ℃^ [PAEN-EPT]=2.5×10-6 mol/L.

Fig.15 PL spectra of PAEN-EPT at different pH values at 25 ℃^ [PAEN-EPT]=2.5×10-6 mol/L, λex=410 nm.

Fig.16 UV-Vis spectra of PAEN-DEPF at different pH values at 25 ℃^ [PAEN-DEPF]=7.5×10-6 mol/L.

Fig.17 PL spectra of PAEN-DEPF at different pH values at 25 ℃^[PAEN-DEPF]=7.5×10-6 mol/L, λex=300 nm.

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