物理化学学报

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自交联共轭亚油酸囊泡基荧光纳米点的构筑及其荧光特性

樊晔, 曹崇梅, 方云, 夏咏梅   

  1. 江南大学化学与材料工程学院, 合成与生物胶体教育部重点实验室, 江苏 无锡 214122
  • 收稿日期:2020-02-24 修回日期:2020-04-07 录用日期:2020-04-09 发布日期:2020-04-20
  • 通讯作者: 方云 E-mail:yunfang@126.com
  • 基金资助:
    国家重点研发计划项目(2017YFB0308705)资助

Fabrication of Fluorescent Nanodots by Self-Crosslinking Ufasomes of Conjugated Linoleic Acid and Their Unique Fluorescence Properties

Ye Fan, Chongmei Cao, Yun Fang, Yongmei Xia   

  1. The Key Laboratory of Synthetic and Biological Colloids (Ministry of Education), School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, Jiangsu Province, P. R. China
  • Received:2020-02-24 Revised:2020-04-07 Accepted:2020-04-09 Published:2020-04-20
  • Supported by:
    The project was supported by the National Key Research and Development Program of China (2017YFB0308705).

摘要: 提出了一种生物质碳源借助自组装和自交联手段“构筑”碳基荧光纳米点(FNDs)的新策略,不同于经历裂解、脱水、缩聚和碳化等复杂且不可控反应的“合成”途径。本文以共轭亚油酸(CLA)为碳源,利用其表面活性和聚合活性制得呈蓝绿光发射的自交联共轭亚油酸囊泡基荧光纳米点(SCU-FNDs),粒径易控(平均粒径为17 nm)且具有良好水分散性,FNDs产率高达73.9%。该法简便温和、绿色经济、有利于大规模制备。荧光实验结果显示SCU-FNDs的荧光强度随囊泡表面羧酸基团减少而减弱,随自交联度增大而增大;同时其荧光强度具有良好的温度线性响应性,升/降温过程均符合I/I0 = ?0.00977T + 1.229 (T = 25–85 ℃, R2 = 0.99)。这些荧光特性皆可以用SCU-FNDs的自组装和自交联结构特性予以解释。

关键词: 不饱和脂肪酸囊泡, 荧光纳米点, 共轭亚油酸, 荧光性质, 自组装, 自交联

Abstract: Carbon dots (CDs), as a kind of carbon-based fluorescent nanodots (FNDs), not only retain the advantageous characteristics of carbon-based materials (e.g., low toxicity and biocompatibility) but also exhibit tunable fluorescence emission, low photobleaching, and undergo facile surface functionalization. Therefore, the prospect of applying these materials for analysis and detection, cell imaging, drug delivery, light-emitting devices, photocatalysis, biosensing, and cancer treatment is promising. Although the synthesis of carbon dots from green and renewable feedstocks as biomass carbon sources is possible, the controllability of the involved chemical reactions is poor, resulting in poor atom economy, low quantum yields, and, especially, extremely low yields of carbon dots. In addition, these disadvantages could lead to an increase in equipment requirements and could pose a safety risk because of the need for hydrothermal and solvothermal synthesis. Certain methods even require large amounts of acid/alkali, strong oxidants, or organic solvents, thereby complicating the post-processing process and generating waste and emissions. This research aimed to implement a new idea, namely to “fabricate” rather than “synthesize” carbon-based FNDs from a certain kind of natural and small unsaturated molecule with surface activity relying on a self-assembling and self-crosslinking strategy in lieu of traditional approaches that involve uncontrollable reactions with unknown mechanisms including pyrolysis, dehydrolysis, polyconcensation, and carbonization. In this context, conjugated linoleic acid (CLA) has been studied extensively in our laboratory, and was found to have the self-assembly and self-crosslink characteristics required by the above innovative strategy. This motivated us to adopt CLA as a new carbon source in this study. First, CLA self-assembles into unsaturated fatty acid liposomes (ufasomes) in an aqueous solution of pH 8.6 at ambient temperature (15–25 ℃), and then, the initiator Ammonium persulfate is added to induce self-crosslinking of the ufasomes at 80 ℃ to obtain firm and uniform nanoparticles. On this basis, the possibility of using them as FNDs is investigated. Consequently, FNDs based on self-crosslinked ufasomes (SCU-FNDs) are prepared in high FND yield of 73.9% after dialysis, with a consistent particle size (17 nm), a degree of self-crosslink (DSC) of 75%, and emission of bluish green fluorescence excited at 320 nm. Furthermore the “fabrication” route provided a clear solution of FNDs that could be applied directly without separation and purification and with no wasteful emissions, which is therefore beneficial for large-scale preparation. The experimental results showed that the fluorescence intensities of the SCU-FNDs are positively correlated with both the surface carboxyl groups and DSC results. A reasonable explanation for the former relationship is the effect of the restricted geometry of the ufasomes on the accumulation of oxygen atoms at the surface of FNDs, whereas the latter could be explained by the confinement effect of the covalent crosslink on the motion of the hydrocarbon chain of the CLA molecules. The experimental results also showed that the SCU-FNDs have temperature-sensitive fluorescence properties, which is attributed to the motion of the residual hydrocarbon chain inside the SCU-FNDs even though they have been locally polymerized. The change in the fluorescence intensity of the FNDs as a function of the temperature was good in accordance with the linear relationship I/I>0 = ?0.00922T + 1.229 (R2 = 0.99) in the range of 25–85 ℃, which demonstrates the potential for preparing green and safe undoped FNDs for use as biocompatible and temperature-sensitive fluorescent probes.

Key words: Ufasomes, Fluorescent nanodots, Conjugated linoleic acid, Fluorescence property, Self-assembly, Self-crosslink

MSC2000: 

  • O644