Synergy in a Solvent-Restrained Environment: Mechanochemical Control of Synthesis and Applications to Catalysis

在化学系化学合成计划的支持下，范德比尔特大学的蒂莫西·哈努萨教授将探索通过研磨或球磨发生的反应。化学反应通常在有毒和/或对环境不友好的溶剂中进行。因此，减少溶剂使用量可能是有利的，原因有很多。这个项目通过开发一种机械方法(机械化学)来解决这个问题，以便在很少或没有溶剂的情况下进行化学反应。机械力化学包括将固体反应物研磨在一起，使它们紧密接触，研磨过程提供启动和维持反应物之间反应所需的能量。机械力化学是一个相对不发达的领域，这项研究将努力寻找此类反应的最佳条件。目标产品包括生物可降解聚合物，这是一类具有广泛学术和工业兴趣的化合物。参与这个项目的学生将获得机械力化学方法论方面的洞察力和经验，这与大多数合成化学方法以溶剂为基础的方向有很大不同。此外，Hanusa教授还与Fisk-Vanderbilt硕士到博士过渡项目密切合作，该项目旨在通过Vanderbilt与历史上的黑人学院和大学之间的合作，扩大女性和代表不足的少数群体在科学领域的参与。这个项目将研究引入少量液体-太少而不能溶解试剂-如何影响机械力化学反应结果。这一“液体辅助研磨”(LAG)技术的改进将使用固体溶剂化试剂(“溶剂辅助研磨”，如使用固体吡啶加合物[Ni(Py)₄Cl₂]代替NiCl₂和液体吡啶)。主族和过渡金属配合物以及有机金属化合物都将被研究。这项研究还将考察固体试剂的晶格结构对机械力化学反应的影响。除了对学生进行培训外，该项目还将为妇女、弱势群体成员以及初中生提供教育和外展服务。一个例子是哈努萨教授在菲斯克-范德比尔特硕士到博士桥项目中的领导作用，该项目帮助硕士学生进入范德比尔特的博士项目并取得成功。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Synthesis Program of the Chemistry Division, Professor Timothy Hanusa of Vanderbilt University will explore reactions that occur through grinding or ball milling. Chemical reactions are often performed in solvents that are toxic and/or environmentally unfriendly. Thus, there are a number of reasons why reducing solvent use could be of advantage. This project addresses the problem by developing a mechanical approach (mechanochemistry) to run chemical reactions with little or no solvent. Mechanochemistry involves grinding solid reactants together so that they are in intimate contact and the milling process provides the energy required to initiate and maintain the reaction between reactants. Mechanochemistry is a relatively undeveloped area and this research will work to find optimal conditions for such reactions. Targeted products include biodegradable polymers, a class of compounds of broad academic and industrial interests. Students involved in this project will gain insight and experience in mechanochemical methodology, a significant departure from the solvent-based orientation of most synthetic chemistry approaches. In addition, Professor Hanusa works closely with the Fisk-Vanderbilt Masters-to-Ph.D. Bridge Program, which is designed to broaden the participation of women and underrepresented minorities in science through partnerships between Vanderbilt and Historically Black Colleges and Universities. This project will study how the introduction of small amounts of liquid—too little to dissolve the reagents—influences mechanochemical reaction outcomes. A modification of this “liquid-assisted grinding” (LAG) technique will employ solid solvated reagents (“solvate-assisted grinding”, such as using the solid pyridine adduct [Ni(py)₄Cl₂] instead of NiCl₂ and liquid pyridine). Both main-group and transition metal coordination complexes and organometallic compounds will be studied. The research will also examine the effect of the lattice structures of solid reagents on mechanochemical reactivity. In addition to training of students, the project will provide educational and outreach efforts for women, members of underserved groups, and middle and high school students. An example is Professor Hanusa’s leadership role in the Fisk-Vanderbilt Masters-to-Ph.D. Bridge Program, which facilitates the entry and success of Master’s degree students into the Ph.D. program at Vanderbilt.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.