Silk Fibroin Micro-structures: From Design to Applications

丝素蛋白具有优异独特的力学性质，光学性质，生物相容性和可控的降解性。近年来，有着精细结构的丝素蛋白被证明在生物工程和医疗等方向上有许多潜在的应用价值。但在常见的微结构制备中，运用光刻构筑丝素蛋白图案的研究相对较少。另一方面，如何加入其他介观材料，调控丝素蛋白的组装，也一直是自组装领域的研究热点。 本硕士论文的主要贡献可以分为以下几个部分： 1、拓展了蚕丝素蛋白通过非共价建，在紫外光条件下引发自组装交联的微结构成型技术。利用光刻技术和光敏小分子在紫外光下释放质子的反应，引发蚕丝素蛋白水凝胶锁住水分的pH值降低，并在水溶液浸泡的条件下成胶，利用该技术，我们将蚕丝素蛋白的图案做到了10微米的尺度...Silk fibroin, as a general natural material, has great advantages based on its unique properties on mechanical strength, optical properties, biocompatibility and controllable degradation. Based on its great universality, high efficiency on constructing, low energy cost and environmental friendly, silk fibroin has intriguing lots of researchers digging on their structures and applications. With the...学位：工学硕士院系专业：材料学院_工程硕士(材料工程)学号：2072014115011

Preparation of Crack-free Inverse-opal Films by Template/Matrix Co-assembly

近年来,由于在光学、电学和生化等领域具有广泛的潜在应用,有序多孔反蛋白石结构薄膜的研究引起了人们的广泛关注.但是其在制备过程中常常会形成一些无法; 控制的缺陷,限制了这类材料的普及和实际应用.通过使用两种基质前驱体(正硅酸乙酯或丝素蛋白)与胶体小球混合共组装,探究了二元体系共组装法制备无裂痕; 反蛋白石结构薄膜的可行性.并用扫描电镜和可见光谱对薄膜结构进行了表征.结果表明,对于正硅酸乙酯体系,在不影响胶体小球有序排列的条件下,正硅酸乙酯; 在小球间的空隙中发生溶胶凝胶转变,与微球共同组装成有序致密的整体,去除微球模板后,可以得到大规模(>200; mum)无缺陷有序的反蛋白石结构薄膜.而对于大分子丝素蛋白体系,由于它和胶体小球有较强的相互作用力,会抑制胶体小球的有序组装,导致无法形成有序结; 构薄膜.对两种二元共组装体系进行了实验探索,实验结果不仅有助于人们了解共组装方式的适用范围,而且为设计和制备无缺陷反蛋白石薄膜提供了新的途径.Recently, there has been a significant interest in utilizing well-ordered, porous inverse-opal films for applications in optical, electronic and (bio) chemical fields. However, uncontrolled defects are always formed during their preparation process, which limit their practical applications. In this work, we examine the feasibility of using template/matrix co-assembly strategies to fabricate crack-free inverse opal thin films. Polystyrene spheres (PS) are chosen as a colloidal template, and two matrix precursors [tetraethoxysilane (TEOS) precursor and regenerated silk fibroin solution] are used for the current study. Our scanning electron microscope (SEM) and optical spectrum results show that, for the TEOS-based system, the resulting silica gel due to the sol-gel transition of TEOS can effectively fill the gap between particles, but cannot affect the self-assembly of PS colloidal particles. After selective removal of the PS template, centimeter-scale crack-free and well-ordered inverse opal films can be obtained. In addition, for a constant concentration of TEOS, the film thickness and order degree of structure can be simply tuned by adjusting the concentrations of colloidal spheres. In comparison with indirect approach through template self-assembly and liquid infiltration, such a co-assembly approach can effectively minimize the associated cracking and avoid the need for matrix infiltration into the preassembled colloidal spheres. On the other hand, macro-molecule silk fibroin has a relatively strong interaction with PS colloidal particles, which is demonstrated by SEM and confocal images. Due to their interaction, silk fibroin molecules are preferably adsorbed on the surface of PS spheres, which can restrain the self-assembly of colloidal particles. As a result, it cannot form well-ordered silk film based on such co-assembly strategy. That is to say, the co-assembly approach is not suitable for systems that matrices have strong interactions with templates. These findings pave the way to use the template/matrix co-assembly strategy for rationally designing and developing crack-free inverse opal films and to apply such well-ordered and porous materials in a variety of fields.National Natural Science Foundation of China [21401154, U1405226]; 111; Project [B16029]; Natural Science Foundation of Guangdong Province; [2014A030310005]; Fundamental Research Funds for the Central; Universities of China [20720170011

软光刻法制备具有表面微结构的角蛋白膜

近年来,使用微纳米制造工艺将蛋白质或多肽进行高精度空间图案化,推动了细胞生物学、组织工程学、药物科学等领域的发展.同时,羊毛角蛋白作为一种储量大的天然生物蛋白质,具有优异的水溶性、良好的生物相容性和可控的降解性,但羊毛角蛋白通常不能自组装形成凝胶网络或其他不溶形式,因此,使用羊毛角蛋白制备如纤维、薄膜、凝胶等的成型结构存在很大困难.本工作通过使用化学修饰的方法,在角蛋白上接枝功能基团,使角蛋白获得光敏感性,探究了共价交联法制备具有表面微结构角蛋白膜的可行性.并用3D激光扫描显微镜、紫外可见近红外光谱仪和傅里叶变换显微红外光谱仪对薄膜结构进行了表征.结果表明,使用软光刻法可以得到表面微结构完整度很高的角蛋白膜.本工作对羊毛角蛋白共价交联法进行了实验探索,实验结果不仅为人们提供了一种软光刻技术制备具有表面微结构的角蛋白膜的方法,而且为羊毛角蛋白制备成型结构提供了新的途径.国家自然科学基金(Nos.21771150,21401154,U1405226)111计划(No.B16029)广东省自然科学基金(No.2014A030310005)中央高校基本业务费(No.20720170011)资助~

In Situ Electrohydrodynamic Jet Printing-Based Fabrication of Tunable Microlens Arrays

Tunable microlens arrays (MLAs) with controllable focal lengths have been extensively used in optical sensors, biochips, and electronic devices. The commonly used method is electrowetting on dielectric (EWOD) that controls the contact angle of the microlens to adjust the focal length. However, the fabrication of tunable MLAs at the microscale remains a challenge because the size of MLAs is limited by the external electrodes of EWOD. In this study, a highly integrated planar annular microelectrode array was proposed to achieve an electrowetting tunable MLA. The planar microelectrode was fabricated by electrohydrodynamic jet (E-jet) printing and the liquid microlens was then deposited in situ on the microelectrode. This method could realize 36 tunable liquid microlenses with an average diameter of 24 &mu;m in a 320 &times; 320 &mu;m2 plane. The fabricated tunable MLAs with higher integration levels and smaller sizes can be beneficial for cell imaging, optofluidic systems, and microfluidic chips.</p

Direct Writing of Silicon Oxide Nanopatterns Using Photonic Nanojets

The ability to create controllable patterns of micro- and nanostructures on the surface of bulk silicon has widespread application potential. In particular, the direct writing of silicon oxide patterns on silicon via femtosecond laser-induced silicon amorphization has attracted considerable attention owing to its simplicity and high efficiency. However, the direct writing of nanoscale resolution is challenging due to the optical diffraction effect. In this study, we propose a highly efficient, one-step method for preparing silicon oxide nanopatterns on silicon. The proposed method combines femtosecond laser-induced silicon amorphization with a subwavelength-scale beam waist of photonic nanojets. We demonstrate the direct writing of arbitrary nanopatterns via contactless scanning, achieving patterns with a minimum feature size of 310 nm and a height of 120 nm. The proposed method shows potential for the fabrication of multifunctional surfaces, silicon-based chips, and silicon photonics.</p

JUNO Sensitivity on Proton Decay p→νˉK+p\to \bar\nu K^+ Searches

The Jiangmen Underground Neutrino Observatory (JUNO) is a large liquid scintillator detector designed to explore many topics in fundamental physics. In this paper, the potential on searching for proton decay in $p\to \bar\nu K^+$ mode with JUNO is investigated.The kaon and its decay particles feature a clear three-fold coincidence signature that results in a high efficiency for identification. Moreover, the excellent energy resolution of JUNO permits to suppress the sizable background caused by other delayed signals. Based on these advantages, the detection efficiency for the proton decay via $p\to \bar\nu K^+$ is 36.9% with a background level of 0.2 events after 10 years of data taking. The estimated sensitivity based on 200 kton-years exposure is $9.6 \times 10^{33}$ years, competitive with the current best limits on the proton lifetime in this channel

JUNO sensitivity on proton decay p → ν K + searches*

The Jiangmen Underground Neutrino Observatory (JUNO) is a large liquid scintillator detector designed to explore many topics in fundamental physics. In this study, the potential of searching for proton decay in the $p\to \bar{\nu} K^+$ mode with JUNO is investigated. The kaon and its decay particles feature a clear three-fold coincidence signature that results in a high efficiency for identification. Moreover, the excellent energy resolution of JUNO permits suppression of the sizable background caused by other delayed signals. Based on these advantages, the detection efficiency for the proton decay via $p\to \bar{\nu} K^+$ is 36.9% ± 4.9% with a background level of $0.2\pm 0.05({\rm syst})\pm$$0.2({\rm stat})$ events after 10 years of data collection. The estimated sensitivity based on 200 kton-years of exposure is $9.6 \times 10^{33}$ years, which is competitive with the current best limits on the proton lifetime in this channel and complements the use of different detection technologies