基于萘酚吡喃的层层自组装薄膜和光响应胶囊的制备及其光致变色性能的研究
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摘要
萘酚吡喃类化合物作为一类重要的光致变色功能性材料，近年来引起了广泛的关注与研究。由于其具有较好的光响应性、易调节的消色速率和好的抗疲劳性等特殊的光学性质，所以在光敏性眼镜玻璃、光信息存储、光电开关和光制动器等商业应用领域有着很大的优势。
本文制备了含有萘酚吡喃的层层自组装薄膜，目的在于增强萘酚吡喃在潜在的应用方面的光致变色性能，并通过紫外-可见光谱(UV-Vis)、傅立叶红外光谱（FT-IR）、原子力显微镜（AFM）对其进行表征。此外，我们还利用萘酚吡喃的疏水性和光响应性制备了含有单分子萘酚吡喃的胶囊，通过紫外-可见光谱(UV-Vis)、透射电子显微镜(TEM)、荧光光谱、动态光散射（DLS）对其形貌和光响应行为进行研究。本论文的主要研究内容如下：
1.利用氢键层层自组装的方法，在含有萘酚吡喃-丙烯酸共聚物（PAA-NP）和含有聚(4-乙烯基吡啶)(P4VP)的有机溶液中交替沉积，制备了具有光致变色性质的聚合物多层膜。此多层膜的组装过程和形貌通过UV-Vis、FT-IR、AFM进行表征。结果表明该多层膜在每一次沉积过程中是以统一有序的方式增长的，表面是相对平滑的。对自组装薄膜中萘酚吡喃的光致变色性能进行研究，消色动力学结果证实：与之前的研究相比在自组装薄膜中的着色体部花青更加的稳定，表现出特别慢的消色速度（重要参数T1/2的消色时间在3层膜中增加到64min）。最后，着色-消色的可逆性测试(以最大吸收波长481nm处收集数据作图)显示在5个着色/消色的循环后，萘酚吡喃的着色程度有轻微的下降。
2.利用单分子的光致变色材料萘酚吡喃（NP）作为疏水性和光响应性组分，与聚乙二醇（PEG）通过“点击化学”方法合成了两亲性聚合物。这种两亲性聚合物在水溶液里能够自发的形成以NP为核，PEG为壳的光响应性胶囊，并且通过DLS和TEM进行确证。通过UV-Vis光谱测试可以确证萘酚吡喃的光致异构化行为能够快速可逆的调控胶囊的裂解和再生。在此基础上，将荧光染料尼罗红（NR）包裹在聚合物胶囊内部，通过紫外光刺激后其荧光光谱在60s内的变化可以表明：该聚合物胶囊可以作为纳米容器，通过紫外光刺激控制其对客体的封装，释放和再封装。此外，3次的循环测试确证了包裹-释放的可逆性能，结果显示了特别良好的耐疲劳性质。对聚合物胶囊快速高效的光控为其在生物领域的药物传输提供了潜在的可能。
3.我们设计合成了一种含有双磺酸基负离子的萘酚吡喃衍生物:DSNP。首先，DSNP可以用来制备层层自组装薄膜，通过将基片交替浸泡在含有阳离子的季氨化聚(4-乙烯基吡啶)（P4VPQ）和含有阴离子的DSNP的水溶液中。多层膜的组装过程通过UV-Vis进行表征，结果表明随着每一次沉积多层膜都是以统一有序的方式增长的。对自组装薄膜中萘酚吡喃的光致变色性能进行研究，消色动力学数据证实萘酚吡喃的消色速率呈现出的趋势如下：在溶液中的NP>在其他聚合物介质中的NP>以离子键形成的层层自组装薄膜中的NP>以氢键形成的层层自组装薄膜中的NP。其次，DSNP也可以作为光响应模块用来制备光响应性胶囊，通过与三乙胺溴化的聚乙二醇（PEG-NEt3）以离子键结合。胶囊的形貌通过TEM进行表征。通过UV-Vis光谱测试可以确证萘酚吡喃的光致变色行为能够快速可逆的调控胶囊的裂解和再组装。在此基础上，将荧光染料尼罗红（NR）包裹在在聚合物胶囊水溶液里，通过紫外光刺激后其荧光光谱的变化可以表明：该聚合物胶囊可以作为纳米容器，通过光刺激控制其对客体的封装，释放和再封装。此外，为了确证包裹-释放的可逆性能进行3次可逆循环测试，结果显示了特别良好的耐疲劳性质。
Naphthopyrans, which are an important class of photochromic dyes, attract muchattention and motivate interesting research in recent years. In addition, naphthopyranshave the advantages in commercial application in light-sensitive ophthalmic lenses,optical memories, optical and electrical switching and light-actuated nanovalves dueto their special optical properties, such as the fine control over fading kinetics andgood resistance to photochemical fatigue.
In this thesis, we fabricated the layer-by-layer assembled films containingnaphthopyrans, and aimed at enhancing the photochromic properties of naphthopyransfor potential applications. The properties of the films were well characterized by theUV-Vis, FT-IR, and AFM. In addition, the photochromic materials of single-moleculeNP were used as the hydrophobic and light-responsive group to fabricate micelles.The surface morphology and the light-responsive properties of micelles were wellcharacterized by UV-Vis, Transmission Electron Microscopy (TEM), Dynamic lightScattering (DLS) and Fluorescence Spectra. The main contents of this dissertation areas following:
1. A photochromic polymer film has been fabricated by the layer-by-layer (LBL)self-assembly through alternating the deposition of poly(acrylic acid) bearing anaphthopyran copolymer(PAA-NP) and poly(4-vinylpyridine)(P4VP) in an organicsolvent via H-bond. The multilayer assembly process and surface morphology weremonitored via UV-Vis, FT-IR, AFM. The results reveal that the multilayer films growin a uniform way in each deposition, and the surface was relatively smooth. Thephotochromic properties of the naphthopyran in the LBL films were investigated andthe kinetic results confirm that the colored merocyanine in the LBL films show asignificant slow fading speed (critical T1/2decoloration time increased to64min inthe3-bilayer film) and are more stable than those in previous reports. Finally, weconfirmed the reversibility of coloration and decoloration at481nm. After5cycles ofcoloration/decoloration, the coloration of naphthopyran was not complete, thereappeared to be minor degradation.
2. The photochromic materials of single-molecule naphthopyrans(NP) were usedas hydrophobic and light-responsive group to synthesize amphiphilic polymer withthe poly(ethylene glycol)(PEG) via Click-Chemistry. Such an amphiphilic polymer can self-assemble to light-responsive micelles with NP-core and PEG-shell in aqueoussolution, as were confirmed by DLS and TEM. The photoisomerization ofnaphthopyrans moieties can fast and reversibly tune the disassembly and re-assemblyof the micelle, as were confirmed by UV-Vis spectroscopy. The changes offluorescent spectra of nile red (NR) in water solution of polymeric micelle within60sdemonstrate that the polymeric micelle can be used as nanocarriers to encapsulate,release and re-encapsulate guest solutes on demand controlling of light irradiation.Moreover, we have tried three cycles to confirm the reversibility of encapsulation andrelease, the result shows a particularly good fatigue resistance. The fast and highlyefficient photo-control of polymeric micelles is a potential candidate in biomedicalarea for drug delivery.
3. We designed and synthesized a bifunctional naphthopyran derivative withnegative-charged di-sulfatoethoxy: DSNP. Firstly, DSNP can be used to prepare theLBL self-assembly films by dipping charged substrates alternately into aqueoussolutions of cationic quaternized poly(4-vinylpyridine)(P4VPQ) and anionic DSNP.The multilayer assembly process was monitored via UV-Vis, The results reveal thatthe multilayer films grow in a uniform way in each deposition. The photochromicproperties of the naphthopyran in the LBL films were investigated and the kineticresults confirm that the trend of fading speed is as following: NP in THF> NP inother polymeric matrix> NP in LBL self-assembly films via ionic-bond> NP in LBLself-assembly films via H-bond. Secondly, DSNP also can be used as thelight-responsive group to fabricate light-responsive micelles with polyethyleneglycol-triethylamine bromide (PEG-NEt3), as were confirmed by TEM. Thephotoisomerization of naphthopyrans moieties can fast and reversibly tune thedisassembly and re-assembly of the micelle, as were confirmed by UV-Visspectroscopy. The changes of fluorescent spectra of nile red (NR) in water solution ofpolymeric micelle demonstrate that the polymeric micelle can be used as nanocarriersto encapsulate, release and re-encapsulate guest solutes on demand controlling of lightirradiation. Moreover, we have tried three cycles to confirm the reversibility ofencapsulation and release, the result shows a particularly good fatigue resistance.
本文制备了含有萘酚吡喃的层层自组装薄膜，目的在于增强萘酚吡喃在潜在的应用方面的光致变色性能，并通过紫外-可见光谱(UV-Vis)、傅立叶红外光谱（FT-IR）、原子力显微镜（AFM）对其进行表征。此外，我们还利用萘酚吡喃的疏水性和光响应性制备了含有单分子萘酚吡喃的胶囊，通过紫外-可见光谱(UV-Vis)、透射电子显微镜(TEM)、荧光光谱、动态光散射（DLS）对其形貌和光响应行为进行研究。本论文的主要研究内容如下：
1.利用氢键层层自组装的方法，在含有萘酚吡喃-丙烯酸共聚物（PAA-NP）和含有聚(4-乙烯基吡啶)(P4VP)的有机溶液中交替沉积，制备了具有光致变色性质的聚合物多层膜。此多层膜的组装过程和形貌通过UV-Vis、FT-IR、AFM进行表征。结果表明该多层膜在每一次沉积过程中是以统一有序的方式增长的，表面是相对平滑的。对自组装薄膜中萘酚吡喃的光致变色性能进行研究，消色动力学结果证实：与之前的研究相比在自组装薄膜中的着色体部花青更加的稳定，表现出特别慢的消色速度（重要参数T1/2的消色时间在3层膜中增加到64min）。最后，着色-消色的可逆性测试(以最大吸收波长481nm处收集数据作图)显示在5个着色/消色的循环后，萘酚吡喃的着色程度有轻微的下降。
2.利用单分子的光致变色材料萘酚吡喃（NP）作为疏水性和光响应性组分，与聚乙二醇（PEG）通过“点击化学”方法合成了两亲性聚合物。这种两亲性聚合物在水溶液里能够自发的形成以NP为核，PEG为壳的光响应性胶囊，并且通过DLS和TEM进行确证。通过UV-Vis光谱测试可以确证萘酚吡喃的光致异构化行为能够快速可逆的调控胶囊的裂解和再生。在此基础上，将荧光染料尼罗红（NR）包裹在聚合物胶囊内部，通过紫外光刺激后其荧光光谱在60s内的变化可以表明：该聚合物胶囊可以作为纳米容器，通过紫外光刺激控制其对客体的封装，释放和再封装。此外，3次的循环测试确证了包裹-释放的可逆性能，结果显示了特别良好的耐疲劳性质。对聚合物胶囊快速高效的光控为其在生物领域的药物传输提供了潜在的可能。
3.我们设计合成了一种含有双磺酸基负离子的萘酚吡喃衍生物:DSNP。首先，DSNP可以用来制备层层自组装薄膜，通过将基片交替浸泡在含有阳离子的季氨化聚(4-乙烯基吡啶)（P4VPQ）和含有阴离子的DSNP的水溶液中。多层膜的组装过程通过UV-Vis进行表征，结果表明随着每一次沉积多层膜都是以统一有序的方式增长的。对自组装薄膜中萘酚吡喃的光致变色性能进行研究，消色动力学数据证实萘酚吡喃的消色速率呈现出的趋势如下：在溶液中的NP>在其他聚合物介质中的NP>以离子键形成的层层自组装薄膜中的NP>以氢键形成的层层自组装薄膜中的NP。其次，DSNP也可以作为光响应模块用来制备光响应性胶囊，通过与三乙胺溴化的聚乙二醇（PEG-NEt3）以离子键结合。胶囊的形貌通过TEM进行表征。通过UV-Vis光谱测试可以确证萘酚吡喃的光致变色行为能够快速可逆的调控胶囊的裂解和再组装。在此基础上，将荧光染料尼罗红（NR）包裹在在聚合物胶囊水溶液里，通过紫外光刺激后其荧光光谱的变化可以表明：该聚合物胶囊可以作为纳米容器，通过光刺激控制其对客体的封装，释放和再封装。此外，为了确证包裹-释放的可逆性能进行3次可逆循环测试，结果显示了特别良好的耐疲劳性质。
Naphthopyrans, which are an important class of photochromic dyes, attract muchattention and motivate interesting research in recent years. In addition, naphthopyranshave the advantages in commercial application in light-sensitive ophthalmic lenses,optical memories, optical and electrical switching and light-actuated nanovalves dueto their special optical properties, such as the fine control over fading kinetics andgood resistance to photochemical fatigue.
In this thesis, we fabricated the layer-by-layer assembled films containingnaphthopyrans, and aimed at enhancing the photochromic properties of naphthopyransfor potential applications. The properties of the films were well characterized by theUV-Vis, FT-IR, and AFM. In addition, the photochromic materials of single-moleculeNP were used as the hydrophobic and light-responsive group to fabricate micelles.The surface morphology and the light-responsive properties of micelles were wellcharacterized by UV-Vis, Transmission Electron Microscopy (TEM), Dynamic lightScattering (DLS) and Fluorescence Spectra. The main contents of this dissertation areas following:
1. A photochromic polymer film has been fabricated by the layer-by-layer (LBL)self-assembly through alternating the deposition of poly(acrylic acid) bearing anaphthopyran copolymer(PAA-NP) and poly(4-vinylpyridine)(P4VP) in an organicsolvent via H-bond. The multilayer assembly process and surface morphology weremonitored via UV-Vis, FT-IR, AFM. The results reveal that the multilayer films growin a uniform way in each deposition, and the surface was relatively smooth. Thephotochromic properties of the naphthopyran in the LBL films were investigated andthe kinetic results confirm that the colored merocyanine in the LBL films show asignificant slow fading speed (critical T1/2decoloration time increased to64min inthe3-bilayer film) and are more stable than those in previous reports. Finally, weconfirmed the reversibility of coloration and decoloration at481nm. After5cycles ofcoloration/decoloration, the coloration of naphthopyran was not complete, thereappeared to be minor degradation.
2. The photochromic materials of single-molecule naphthopyrans(NP) were usedas hydrophobic and light-responsive group to synthesize amphiphilic polymer withthe poly(ethylene glycol)(PEG) via Click-Chemistry. Such an amphiphilic polymer can self-assemble to light-responsive micelles with NP-core and PEG-shell in aqueoussolution, as were confirmed by DLS and TEM. The photoisomerization ofnaphthopyrans moieties can fast and reversibly tune the disassembly and re-assemblyof the micelle, as were confirmed by UV-Vis spectroscopy. The changes offluorescent spectra of nile red (NR) in water solution of polymeric micelle within60sdemonstrate that the polymeric micelle can be used as nanocarriers to encapsulate,release and re-encapsulate guest solutes on demand controlling of light irradiation.Moreover, we have tried three cycles to confirm the reversibility of encapsulation andrelease, the result shows a particularly good fatigue resistance. The fast and highlyefficient photo-control of polymeric micelles is a potential candidate in biomedicalarea for drug delivery.
3. We designed and synthesized a bifunctional naphthopyran derivative withnegative-charged di-sulfatoethoxy: DSNP. Firstly, DSNP can be used to prepare theLBL self-assembly films by dipping charged substrates alternately into aqueoussolutions of cationic quaternized poly(4-vinylpyridine)(P4VPQ) and anionic DSNP.The multilayer assembly process was monitored via UV-Vis, The results reveal thatthe multilayer films grow in a uniform way in each deposition. The photochromicproperties of the naphthopyran in the LBL films were investigated and the kineticresults confirm that the trend of fading speed is as following: NP in THF> NP inother polymeric matrix> NP in LBL self-assembly films via ionic-bond> NP in LBLself-assembly films via H-bond. Secondly, DSNP also can be used as thelight-responsive group to fabricate light-responsive micelles with polyethyleneglycol-triethylamine bromide (PEG-NEt3), as were confirmed by TEM. Thephotoisomerization of naphthopyrans moieties can fast and reversibly tune thedisassembly and re-assembly of the micelle, as were confirmed by UV-Visspectroscopy. The changes of fluorescent spectra of nile red (NR) in water solution ofpolymeric micelle demonstrate that the polymeric micelle can be used as nanocarriersto encapsulate, release and re-encapsulate guest solutes on demand controlling of lightirradiation. Moreover, we have tried three cycles to confirm the reversibility ofencapsulation and release, the result shows a particularly good fatigue resistance.
引文
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