Understanding Mesoscale Structures of Nanocrystalline Domains in Silk using Sum Frequency Generation Vibrational Spectroscopy

在化学系（CHE）化学测量和成像（CMI）项目的支持下，以及材料研究部（DMR）生物材料项目（BMAT）的共同资助下，宾夕法尼亚州立大学的Seong Kim博士和他的团队正在开发强大的探针，研究生物体组装水溶性材料的方式，以产生不溶性半结晶聚合物，以服务于各种机械功能，如结构支撑和能量储存。他们的工作旨在推进目前对生物体如何利用结构秩序来定制晶体生物聚合物（如在丝绸纤维中发现的那些）的机械性能的理解。该方法将利用复杂的光谱工具定量探测天然丝内部的结构顺序和组装。来自代表性不足群体的学生，包括第一代大学生，将参与这些现代光谱研究，与金博士及其研究生密切合作。研究动机和方法将整合到研究生水平的材料表征课程中。与宾夕法尼亚州立大学弗罗斯特昆虫学博物馆相关的外展活动将帮助公众熟悉节肢动物产生的材料科学。这项工作的主要表征方法是振动和频率产生（SFG）光谱学-一种源于非中心对称的非线性光学过程。虽然SFG通常被认为是一种表面敏感的工具，但它也可以区分非中心对称排列的分子及其无序环境。虽然作为分散在无定形聚合物基体中的非中心对称晶体的纳米到中观尺度顺序的探针可能有用（例如，丝纤维中的β -片结构域），但在分析多尺度三维结构时遇到的挑战远远超出了二维表面的复杂性。为了解决这一障碍，Kim小组正在努力：(i)建立天然丝纤维中普遍存在的β -片段的SFG光谱解释；（ii）破译丝中晶体β片的中尺度三维顺序；（iii）在控制湿度条件下，对无应力状态和拉伸应变状态下的丝纤维进行operando SFG分析。从本研究中建立的operando SFG方法和知识可能适用于其他天然生物聚合物的研究，如几丁质、胶原蛋白和弹性蛋白以及仿生材料，突出了这项工作具有广泛科学影响的潜力。该奖项反映了美国国家科学基金会的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

With support from the Chemical Measurement and Imaging (CMI) program in the Division of Chemistry (CHE), and co-funding from the Biomaterials Program (BMAT) in the Division of Materials Research (DMR), Dr. Seong Kim and his team at Penn State University are developing powerful probes of the way living organisms assemble water-soluble materials to produce insoluble semi-crystalline polymers to serve various mechanical functions such as structural support and energy storage. Their work aims to advance current understanding of how structural order is exploited by living organisms to tailor mechanical properties of crystalline biopolymers like those found in silk fibers. The approach will utilize sophisticated spectroscopic tools to quantitatively probe structural order and assembly inside natural silk. Students from underrepresented groups, including first-generation college students, will be involved in these modern spectroscopic studies, working in close collaboration with Dr. Kim and his graduate students. The research motivations and methodologies will be integrated into a graduate-level materials characterization course. Outreach activities associated with the Frost Entomological Museum at Penn State will help familiarize the general public with the science of materials produced by arthropods The main characterization method of this work is vibrational sum-frequency-generation (SFG) spectroscopy - a nonlinear optical process originating from noncentrosymmetry. While SFG is typically considered to be a surface-sensitive tool, it can also distinguish noncentrosymmetric arrangements of molecules from their disordered surroundings. While potentially useful as a probe of nano- to meso-scale order of noncentrosymmetric crystals dispersed in an amorphous polymer matrix (e.g., beta-sheet domains in silk fibers), the challenges encountered in the analysis of multi-scale three-dimensional structures are far beyond the complexity of two-dimensional surfaces. To address this obstacle, the Kim group is working to: (i) establish the SFG spectral interpretation of beta-sheet moieties prevalent in natural silk fibers; (ii) decipher mesoscale three-dimensional order of crystalline beta-sheets in silk; and (iii) conduct operando SFG analysis of silk fibers under stress-free and tensile strain states in controlled humidity conditions. The operando SFG methodology and knowledge established from this study will likely be applicable to studies of other natural biopolymers such as chitin, collagen and elastin as well as biomimetic materials, highlighting the potential for broad scientific impact of this work.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.