The photodimerization of a cinnamoyl moiety derivative in dilute solution based on the intramolecular chain interaction of gemini surfactant.
A Gemini surfactant, sodium N, N'-di(4-n-butyloxy cinnamoly)-L-cystine, containing a cinnamoyl moiety in the alkyl chains and disulfide bond in the spacer was designed and synthesized. The incorporation of a cinnamoyl moiety into the alkyl chains of Gemini surfactant makes it easy to probe the conformational information of the amphiphile molecule. The UV/vis absorption spectra and steady-state fluorescence were investigated at a concentration far below the critical micelle concentration (cmc). Both blue-shift of absorption and red-shift of fluorescence emission spectra indicate the existence of intramolecular interaction between the two alkyl chains in Gemini surfactant in the singly dispersed state. Results based on the breakdown of the disulfide bond by dithiotheritol (DTT) further confirmed the conclusion. Moreover, the characteristic of intramolecular chain interaction in Gemini surfactant improves the topochemical geometrical requirements of cinnamoyl moiety and increases the local concentration of reactant in dilute solution. Utilizing the incorporation of cinnamoyl moiety into the alkyl chains of Gemini surfactant, the cinnamoyl moiety upon irradiation undergoes dimerization in dilute aqueous solution with high yield of 78%.
Fan
Haiming
H
Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University, Beijing, P. R. China.
Zhu
Xiaoming
X
Gao
Lining
L
Li
Zichen
Z
Huang
Jianbin
J
D002627:Chemistry, Physical / Q000379:methods; D002934:Cinnamates / Q000737:chemistry / Q000494:pharmacology*; D003553:Cystine / Q000031:analogs & derivatives* / Q000737:chemistry* / Q000494:pharmacology; D019281:Dimerization; D004229:Dithiothreitol / Q000737:chemistry; D008027:Light; D008823:Micelles; D008956:Models, Chemical; D008968:Molecular Conformation; D019999:Pharmaceutical Solutions / Q000737:chemistry; D012996:Solutions; D013050:Spectrometry, Fluorescence / Q000379:methods; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D013501:Surface-Active Agents / Q000737:chemistry*; D013997:Time Factors
D002934:Cinnamates; D008823:Micelles; D019999:Pharmaceutical Solutions; D012996:Solutions; D013501:Surface-Active Agents; C531532:sodium N,N'-di(4-n-butyloxy cinnamoly)-L-cystine; D003553:Cystine; D004229:Dithiothreitol