CAREER: Model Systems for Flavoenzyme Activity. Recognition and Catalysis within Sol-Gel Matrices

罗特罗教授的研究集中于三个目标：(1)将黄素衍生物引入透明的硅基溶胶-凝胶基质中；(2)利用黄素的电子光谱来探测溶胶-凝胶微环境；(3)探索结合黄素的热氧化还原和光催化化学。结合的黄素的光谱特性与凝胶的粘弹性测量相关联，以确定在凝胶和干燥过程中黄素微环境的变化。比较了黄素与液体溶液中黄素的电化学和光谱电化学行为，以确定基质引起的氧化还原电位的变化，同时通过典型硫醇和其他生物重要官能团的化学计量氧化来探索介质对氧化还原活性的影响。教育活动包括为大型有机化学课程开发分子建模部分，继续开展一项旨在提高高中生攻读物理学本科学位兴趣的外展计划，以及指导物理专业本科生参加旨在维持和促进他们对物理科学的兴趣的综合计划。通过这一职业奖项，有机动力学项目支持马萨诸塞大学化学系文森特·罗特洛教授的研究和教育活动。罗特洛教授探索了将活性分子结合到类似玻璃的环境中，基本上形成了人造酶，其中基质扮演着通常由天然酶的氨基酸骨架承担的角色，而活性分子充当酶的活性部位。这些人工酶系统提供了探索由天然酶影响的过程的各种特征的机会，并可能导致发现不同于酶的独特的反应化学。罗特洛教授的教育活动包括开发和整合计算机辅助分子结构研究的本科有机化学课程。通过外展计划，罗特洛教授鼓励高中生主修物理科学，一旦他们进入大学，他就通过教师研讨会、实地考察和互动实验室体验的综合计划来提高和维持本科生对物理专业的兴趣。

Professor Rotello's research focuses on three objectives: (1) incorporating flavin derivatives into transparent, silica-based, sol-gel matrices; (2) exploiting the electronic spectroscopy of flavins to probe sol-gel microenvironments; and (3) exploring the thermal redox and photocatalytic chemistry of bound flavins. Spectral properties of the incorporated flavins are correlated with viscoelastic measurements of the gel to identify changes in the flavin microenvironment during gelation and drying. The electrochemical and spectroelectrochemical behavior of the flavin incorporated in the matrix is compared with that in fluid solution to ascertain matrix induced changes in redox potential, while medium effects on redox activity are explored through stoichiometric oxidations of representative thiols and other biologically important functional groups. Educational activities include developing a molecular modeling component for large organic chemistry courses, continuing an outreach program designed to enhance high school students' interest in pursuing undergraduate degrees in the physical sciences, and mentoring undergraduate physical science majors in an integrated program designed to sustain and promote their interest in the physical sciences. With this CAREER award, the Organic Dynamics Program supports the research and educational activities of Professor Vincent Rotello of the Chemistry Department at the University of Massachusetts. Professor Rotello explores the incorporation of reactive molecules into glass-like environments, essentially forming artificial enzymes wherein the matrix plays the role ordinarily taken on by the amino acid backbone of a natural enzyme and the reactive molecule serves as the active site of the enzyme. These artificial enzyme systems offer the opportunity to probe various features of the processes effected by the natural enzymes and may also lead to the discovery of unique reaction chemistry distinct from that of the enzymes. Professor Rotello's educational activities include the development and integration into undergraduate organic chemistry courses of computer-assisted investigations of molecular structure. Through outreach programs, Professor Rotello encourages high school students to major in the physical sciences, and, once they are in college, he enhances and sustains the interest of undergraduate physical science majors through an integrated program of faculty seminars, field trips and interactive laboratory experiences.