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1.
响应性表面微纳米图案可以通过外界刺激动态调控表面微纳米结构,从而实现对材料表面性能的动态调控。其中,利用材料表面不稳定性构筑褶皱是制备表面微纳米图案的通用方法,然而如何实现微纳米褶皱图案的动态调控仍然面临挑战。上海交通大学姜学松研究团队在刺激响应性高分子表面方面开展的研究工作取得了一系列阶段性成果。最近该团队提出了一种简单、普适的制备具有近红外光响应性的动态微纳米表面褶皱图案的策略,实现了对材料表面微纳米结构的多重刺激响应性调控,为构建智能材料表面开辟了新途径。  相似文献   

2.
本工作利用光响应温敏聚合物构筑了温控湿度响应褶皱图案,并探索其响应机制与应用.将1-乙烯基-3-蒽甲基氯化咪唑鎓(IMAN)、 N-异丙基丙烯酰胺(NIPAM)与聚乙二醇甲醚甲基丙烯酸酯(OEGMA)三元共聚物P(IMAN-co-NIPAM-co-OEGMA)作为表层,与聚二甲基硅氧烷(PDMS)基底形成双层褶皱体系.蒽基团的光二聚交联能够使体系区域选择性起皱,含NIPAM结构的聚合物链则赋予其温度控制的湿度响应性.在室温、加湿条件下,该褶皱图案消失,其响应机制是聚合物吸湿过程中的模量降低和应力松弛;而在较高温度下,褶皱图案无法由湿度擦除,这是由于顶层聚合物链疏水性增强所导致的.这种同时具有光敏性与温度控制的湿度响应性褶皱图案,在湿度传感、智能显示、智能窗户等领域具有潜在的应用前景.  相似文献   

3.
“黏附”是一种普遍存在的多尺度相互作用,其实质是界面处化学键、氢键或范德华力等的形成.近年来,在贻贝仿生的基础上将黏性因子邻苯二酚基团嵌入到动态硼酸酯聚合物中,成为了功能黏附性高分子的重要发展方向.本专论从分子黏附、微/纳表面黏附和宏观表面黏附3个尺度,介绍硼酸酯键管控邻苯二酚基团在高分子材料功能化方面的研究进展.分子黏附,主要讨论硼酸酯聚合物中邻苯二酚基团与分子或离子相互作用规律及其对材料形貌和刺激响应性能的调控;微/纳表面黏附,论述硼酸酯聚合物体系超分子驱动力和组装机制,介绍其在微/纳材料功能化改性方面的研究进展;宏观表面黏附,讨论硼酸酯键管控邻苯二酚基团与黏附性能调控的关联规律,介绍硼酸酯聚合物功能黏附材料在宏观组装、攀爬机器人领域的应用.最后,从新型硼酸酯聚合物设计、动态键精准管控和器件化应用的角度,对该领域未来前景和发展趋势做出了展望.  相似文献   

4.
崔聪聪  刘郭洁  高鹤  王敏  高峻 《高分子学报》2021,52(12):1568-1577
通过自由基共聚合的方法将光敏单体螺吡喃(SPMA)接枝在聚二甲基硅氧烷(PDMS)表面,制备了一种光响应可逆切换润湿性薄膜,并对其制备工艺进行了优化.该薄膜对环境光照敏感,在可见光条件下为无色透明状态,经365 nm紫外光激发15 s后,薄膜表面的SPMA响应光刺激后立即变为深紫色,并伴随着极性的变化,最终导致薄膜表现出润湿性转变.将薄膜重新放置在可见光或黑暗条件下时,其润湿性能又可逆恢复到初始状态.对薄膜进行润湿性能测试后发现,紫外光辐照前后的接触角差值最高可达38.5°.这一显著的可逆切换润湿性能赋予了该光响应薄膜在生物医用材料、细胞培养和无酶化脱附、智能窗涂层等领域的潜在应用价值.另外,经过多次紫外-可见光交替循环辐照之后该薄膜依然具有良好的光响应性及可逆润湿性能.  相似文献   

5.
通过将具有光响应性的香豆素基团共价接枝到盘形多金属氧簇两侧,构筑了一类可光控聚合的杂化大阴离子簇单体.利用X-射线单晶衍射、核磁共振氢谱、红外光谱、元素分析和电喷雾质谱等手段对所获得的杂化物和组装体中的光照聚合过程进行了表征.通过离子替换,将抗衡离子由四丁基铵阳离子替换为具有更强自组装能力的双十八烷基二甲基铵阳离子.利用香豆素基团在不同紫外光照射条件下的光二聚反应,以及外围表面活性剂提供的疏水性,实现了超分子组装体中的聚合.通过研究亦发现,在光控二聚过程中,聚合物不仅展现新颖的自组装行为,而且表现出聚合诱导的荧光增强.  相似文献   

6.
通过Mannich反应在7-羟基-4-甲基香豆素的8-位上引入具有pH响应性能的4-甲基哌嗪的供电子哌嗪基团, 得到水溶性香豆素衍生物, 7-羟基-4-甲基-8-(4'-甲基哌嗪-1'-基)-亚甲基香豆素(HMPC), 利用哌嗪环上的叔胺给电子体系对酸碱的敏感特性调节HMPC的光二聚反应特征. 详细考察该香豆素衍生物在不同pH水溶液中的紫外光二聚性能, 紫外光谱分析显示, 通过调节HMPC水溶液的酸碱性可有效改变其紫外特征吸收; 在波长大于310 nm的紫外光照射下, 衍生物上的香豆素单元可进行光二聚, 并且紫外点光源光二聚反应实验表明, 其在中性水溶液中的反应速度最快, 其次为碱性条件中的反应, 最慢的则是酸性条件中的反应.  相似文献   

7.
陈帅  严淑珍  印杰  姜学松 《高分子学报》2021,52(10):1245-1261
微纳米图案赋予了材料表面独特的光学、电学、声学、力学以及生物学等特性,其中具有动态变化形貌的表面图案能够实现对材料表面性能原位实时调控,可用于构建智能表面.能够改变临时拓扑形貌并在外界刺激下恢复初始状态的一类动态表面材料称为图案记忆表面(pattern memory surface, PMS).PMS在浸润性调节、智能显示、电子器件和信息安全等多个领域具有重要的应用前景,涉及化学、物理、材料和生物多个学科交叉领域,是智能材料研究热点之一.然而,由于基底材料对高分子链在微观尺度上的运动具有束缚作用,如何构筑动态可调的拓扑形貌记忆表面一直是该领域面临的难题.基于此,本专论试图定义高分子材料图案记忆表面特征,并总结PMS有关研究的新进展.重点讨论基于褶皱图案构建PMS的优势,进而介绍了PMS作为智能材料在动态光栅、防伪、反射式显示、细胞培养等领域的应用,同时展望PMS的发展前景.  相似文献   

8.
范溦  李敏  洪春雁  潘才元 《化学学报》2015,73(4):330-336
设计并合成了含有香豆素基团的自引发单体, 与2-(2-甲氧基乙氧基)乙基甲基丙烯酸酯(MEO2MA)进行自缩合乙烯基共聚合后得到超支化聚合物H-PMEO2MA. 以其作为大分子引发剂, 进行二甲氨基乙基甲基丙烯酸酯(DMAEMA)的原子转移自由基聚合, 合成了具有温度响应性的超支化星形聚合物H-PMEO2MA-star-PDMAEMA. 将此超支化星形聚合物在水中自组装成胶束后, 利用支化点处香豆素基团的光二聚性能, 在λ=320 nm的紫外光照射下进行香豆素间的光交联反应, 形成核交联胶束. 此核交联胶束在254 nm紫外光照射下则会发生解交联反应. 采用尼罗红作为模型药物, 将其装载到超支化星形聚合物胶束中, 研究了不同条件下的药物释放行为.  相似文献   

9.
邹鸿雁  郭青娟  黄承志 《分析化学》2021,49(7):1228-1236
通过合理的设计制备多功能纳米复合材料是当前实现多模式联合肿瘤治疗领域中的研究热点。本研究合成了在近红外区有局域表面等离子吸收(LSPR)的非计量铜硫属纳米颗粒(Cu2-xSySe1-yNPs),利用聚多巴胺对其进行表面修饰(Cu2-xSySe1-y@pDA),进一步通过共价结合,负载叶酸(FA)和抗癌药物硼替佐米(Bortezomib,BTZ),制备了FA-Cu2-xSySe1-y@pDA-BTZ复合纳米材料。研究表明,此复合纳米材料在生物应用最佳的近红外二区窗口呈现有效吸收,光热转化效率可达30.8%。复合材料可通过表面的叶酸靶向过度表达叶酸受体的癌细胞。此外,聚多巴胺的邻苯二酚基团与BTZ通过动态硼酸酯键交联,利用硼酸酯键的pH响应性质,在肿瘤微酸性环境下, BTZ被可控的释放。将上述FA-Cu2-xSySe1-y@pDA...  相似文献   

10.
以聚苯乙烯(PS)纳米球为核,利用紫外光引发聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)接枝到PS纳米球上,得到对CO_2有刺激响应的聚甲基丙烯酸N,N-二甲基氨基乙酯刷(PS-PDMAEMA)。动态光散射(DLS)、电导率结果表明PS-PDMAMEA具有CO_2刺激响应性。该微粒可以作为Pickering乳液的乳化剂,通过导入CO_2或N_2作为开关,进而破坏或稳定Pickering乳液。用数码照片、偏光显微镜等方法表征了乳液的稳定情况。结果表明:PS-PDMAEMA具有很好的CO_2刺激响应性,利用PS-PDMAEMA作为乳化剂稳定Pickering乳液,仅仅依靠气体开关(CO_2或N_2)就可改变乳液的稳定性。  相似文献   

11.
We apply thermal wrinkling, which is a surface instability that occurs during thermal annealing of polymer films geometrically confined by a rigid substrate and a flexible superstrate, to study the elasticity and viscosity of chemically crosslinked polymer systems. Specifically, we study the thermal wrinkling of aluminum‐capped polyhydroxystyrene films with different extent of chemical crosslinking and find that that the rate of change of the wrinkling wavelength with annealing time and temperature has unique relationships with the elasticity and viscosity of the polymer network. With the aid of analytical expressions that relate the time‐ and temperature‐dependent evolution of the wrinkle wavelength to the elasticity and viscosity, we are able to quantify the elastic modulus and shear viscosity of geometrically confined polymer thin films as a function of the degree of crosslinking. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012  相似文献   

12.
Anisotropic wrinkling which utilizes the anisotropic nature of liquid crystalline polymer (LCP) is demonstrated as a means of physical self-assembly to produce periodic microstructures. Through the plasma treatment on the molecularly aligned LCP film surface, one-dimensionally ordered wrinkle pattern was spontaneously formed on glass substrates without employing external thin-film deposition or prestrain control of the system. Experimental results indicate that the directionality of the wrinkle pattern can be tailored by the structural ordering of LCP molecules in the bilayer system of a hard skin layer on a soft substrate. Studies on process variables, such as the plasma treatment time and the film thickness, were conducted to figure out the effect on the wrinkling morphology. Due to its spatial periodicity over a large area and undemanding requirement of the process, this approach can be a candidate for the microfabrication in various applications.  相似文献   

13.
The irradiation (λ > 400 nm) in air of a copolymer of phenyl vinyl ketone with 4-vinylbenzil (VBZ) containing 1.5 wt % VBZ structural units in film, followed by the thermal decomposition of the resulting pendant benzoyl peroxide groups, leads to crosslinking. The subsequent irradiation of the crosslinked polymer at 366 nm results in the cleavage of the poly(phenyl vinyl ketone) chain between the junction points of the polymer network through a Norrish type II reaction. Therefore, poly(phenyl vinyl ketone-co-4-vinylbenzil) represents a novel type of photoresist based on polymer network decrosslinking. The process involves three steps: photogeneration of peroxide, crosslinking by its thermal decomposition, and subsequent photodecrosslinking of the polymer network. This material provides positive-tone images after UV exposure (λ > 330 nm) and development in an organic medium such as isopropyl methyl ketone. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 765–771, 2004  相似文献   

14.
We present immunoassay-based desorption electrospray ionization mass spectrometry imaging (immuno-DESI-MSI) to visualize functional macromolecules such as drug targets and cascade signaling factors. A set of boronic acid mass tags (BMTs) were synthesized to label antibodies as MSI probes. The boronic ester bond is employed to cross-link the BMT with the galactosamine-modified antibody. The BMT can be released from its tethered antibody by ultrafast cleavage of the boronic ester bond caused by the acidic condition of sprayed DESI microdroplets containing water. The fluorescent moiety enables the BMT to work in both optical and MS imaging modes. The positively charged quaternary ammonium group enhances the ionization efficiency. The introduction of the boron element also makes mass tags readily identified because of its unique isotope pattern. Immuno-DESI-MSI provides an appealing strategy to spatially map macromolecules beyond what can be observed by conventional DESI-MSI, provided antibodies are available to the targeted molecules of interest.  相似文献   

15.
The authors report the formation of highly oriented wrinkling on the surface of the bilayer [polystyrene (PS)/poly(vinyl pyrrolidone) (PVP)] confined by a polydimethylsiloxane (PDMS) mold in a water vapor environment. When PVP is subjected to water vapor, the polymer loses its mechanical rigidity and changes to a viscous state, which leads to a dramatic change in Young's modulus. This change generates the amount of strain in the bilayer to induce the wrinkling. With a shape-controlled mold, they can get the ordered wrinkles perfectly perpendicular or leaned 45 degrees to the channel orientation of the mold because the orientation of the resultant force changes with the process of water diffusion which drives the surface to form the wrinkling. Additionally, they can get much smaller wrinkles than the stripe spacing of PDMS mold about one order. The wrinkle period changes with the power index of about 0.5 for various values of the multiplication product of the film thicknesses of the two layers, namely, lambda approximately (h(PS)h(PVP))(1/2).  相似文献   

16.
Topological patterns on polymer surfaces can significantly alter and control adhesion. In this study, the effect of surface wrinkles on a spherical surface on adhesion has been studied. Surface wrinkling induced by swelling of a crosslinked polydimethylsiloxane elastomer constrained by a stiff, thin surface layer (silicate) is used to produce topographic features of various length scales over a large curved area. By controlling the properties of the stiff layer and the applied strain conditions, surface wrinkles of varying amplitude and wavelength are obtained. The effect of wrinkle morphology on adhesion is quantified, and the results display a transition from enhancement of adhesion to decrease depending upon wrinkle dimensions. A simple phenomenological model is proposed that describes the change of adhesion behavior as a function of wrinkle morphology. Our results provide a critical understanding toward tuning the adhesion behavior of nonplanar surfaces consisting of periodic topographic structures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011  相似文献   

17.
利用后重氮偶合反应,将4-(三氟甲基)苯胺的重氮盐与两种具有高苯胺残基密度的环氧树脂类前体聚合物在极性有机溶剂中反应,制备了两种具有高生色团密度的环氧树脂类偶氮聚合物PEP-AZ-CF3和PEP-35AZ-CF3.利用1H-NMR、FTIR、UV-Vis和DSC等分析方法对2种偶氮聚合物结构、热性能及吸收光谱性能进行了分析及表征.研究了在不同波长的激光(488、532及589 nm)照射下,2种偶氮聚合物薄膜光致表面自结构的形成.研究结果表明,入射激光的波长对偶氮聚合物表面自结构现象的形成有明显影响.仅在波长488 nm的偏振激光(线偏振光或圆偏振光)照射下,2种偶氮聚合物薄膜表面能观察到自结构现象.圆偏光比线偏光更有利于诱导表面起伏结构的形成,但形成的表面结构不具备长程取向有序性.聚合物生色团中偶氮键邻位的取代甲基对表面自结构的形成起到阻碍作用.  相似文献   

18.
We reported a facile and bio-inspired strategy for obtaining antireflective(AR) coating through polymerization-induced self-wrinkling. Upon irradiation of light, the complex wrinkle micro-patterns with different morphologies were generated spontaneously on the surface of coating during photo-crosslinking, which enables the photo-curing coating can decrease reflection. The resulting photo-curing coating exhibits a high transmittance over 90% and low reflection below 5%~8%, with an efficiency antireflection of 4%~7% compared to the flat blank coating. The successful application of these AR coatings with wrinkles pattern to encapsulate the thin film solar cells results in appreciable photovoltaic performance improvement of more than 4%~8%, which benefits from the decrease of the light reflection and increase of optical paths in the photoactive layer by the introduction of wrinkling pattern.Furthermore, the efficiency improvements of the solar cells are more obvious, with a remarkable increase of 8.5%, at oblique light incident angle than that with vertical light incident angle  相似文献   

19.
Wrinkles and photo-oxidation reactions are widely found in soft materials, which are intimately associated with the failure of materials and structures. It is expected that the photo-oxidation process could also have a positive effect on the material and its surface. Here, we report the photo-oxidation of 2-(4-dietheylaminophenyl)-4,5-bis(4-methoxyphenyl) imidazole (DEA-TAI) into a wrinkled bilayer system to control surface wrinkle and fluorescent patterns, in which a supramolecular polymer network composed of carboxylic acid-containing copolymer (PS-BA-AA; PS=poly(styrene), BA=butyl acrylate; AA=acrylic acid) and DEA-TAI were used as the skin layer. Ultraviolet (UV) irradiation can induce photo-oxidation of the imidazole ring of DEA-TAI to weaken the intermolecular hydrogen bonding between PS-BA-AA and DEA-TAI, resulting in the release of stress in the bilayer system. The wrinkled morphology and fluorescence of the surface can be simultaneously regulated by photo-oxidation of DEA-TAI under UV light, and the resulting wrinkles are extremely sensitive to the pH value, which can be quickly and reversibly erased by NH3 gas. Smart surfaces with specific hierarchical wrinkles and fluorescence can be achieved by selective irradiation with photomasks, which may find potential applications in smart displays and multi-code information storage.  相似文献   

20.
Here, a simple combined strategy of surface wrinkling with visible light irradiation to fabricate well tunable hierarchical surface patterns on azo‐containing multilayer films is reported. The key to tailor surface patterns is to introduce a photosensitive poly(disperse orange 3) intermediate layer into the film/substrate wrinkling system, in which the modulus decrease is induced by the reversible photoisomerization. The existence of a photoinert top layer prevents the photoisomerization‐induced stress release in the intermediate layer to some extent. Consequently, the as‐formed wrinkling patterns can be modulated over a large area by light irradiation. Interestingly, in the case of selective exposure, the wrinkle wavelength in the exposed region decreases, while the wrinkles in the unexposed region are evolved into highly oriented wrinkles with the orientation perpendicular to the exposed/unexposed boundary. Compared with traditional single layer‐based film/substrate systems, the multilayer system consisting of the photosensitive intermediate layer offers unprecedented advantages in the patterning controllability/universality. As demonstrated here, this simple and versatile strategy can be conveniently extended to functional multilayer systems for the creation of prescribed hierarchical surface patterns with optically tailored microstructures.

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