MUST: MicroflUidics for Structure-reactivity relationships aided by Thermodynamics & kinetics

必须：热力学辅助的结构-反应性关系的微流体

• 批准号: 446436621
• 负责人: Privatdozent Dr.-Ing. Christoph Held
• 金额: --
• 依托单位: Institut National des Sciences Appliquées (INSA) Rouen
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/446436621?language=en
• 关键词: MUST; MicroflUidics; Structure; reactivity; relationships

The relationships between the structure of chemicals (reactants or products) and their reactivity (kinetics and thermodynamics) is a research area that crosslinks thermodynamics, kinetics, organic chemistry and chemical engineering. This project will investigate this research area by German and French specialists. The concept of Linear Free Energy Relationships (LFER), including Taft equation, is a powerful structure-reactivity tool that accounts for steric, polar and resonance effects on a series of chemical reactions. Taft equation shows that there is a relationship between the structure of reactants (i.e., the substituent near to the reaction center) and their reactivities within a reaction series. It is state-of-the art to apply this to chemical reactions (e.g. esterification), and it is claimed that the developed parameters are valid independent of the reaction conditions. However, mainly esterification and hydrolysis reactions were used in one kind of solvent, which in principle limits the general validity of the relationships. Thus, generalizing LFER concepts to vast number of solvents or solvent mixtures and even to multiphase reaction systems requires intrinsic kinetic profiles in the absence of concentration and temperature gradients, expressed in terms of thermodynamic activities. This will be developed in this project.The redeveloped Taft-based method will be mainly applied to three chemical reaction systems that involve lignocellulosic-derived platform molecules: 1) glucose solvolysis to levulinate ester using different alcohol solvents, 2) esterification-hydrolysis of levulinic acid-levulinate ester and 3) hydrogenation of levulinic acid or levulinate ester to gamma-valerolactone by H2 and solid catalyst. For these systems, we will vary the reactants, i.e., different alcohols for 1) and 2), and different levulinate esters for 3). System 2) will prove the validity of the LFER concept to enzyme catalysis. The goal is to use the redeveloped method to study and predict the -R substituent effect in the reactant and the solvent effect on kinetic profiles.Reaching the goal requires different research expertise. The use of microfluidic technologies will allow performing kinetic experiments avoiding transport limitations. Activities of the reactants and products will be predicted based on the experimental kinetic profiles and the equation of state ‘ePC-SAFT’. This will ultimately allow predicting reaction properties (standard enthalpies, standard Gibbs energies) as well as intrinsic activity-based reaction kinetic constants. Furthermore, ePC SAFT will be used to predict the required phase behavior of the reaction systems (e.g. H2 solubility in reaction medium); all predictions (phase behavior and reaction characteristics) will be validated by experiments.The association of both methods –LFER & ePC-SAFT– will mean a significant new understanding and a new dimension in designing chemical syntheses.

化学品（反应物或产物）的结构及其反应性（动力学和热力学）之间的关系是一个交叉热力学、动力学、有机化学和化学工程的研究领域，该项目将由德国和法国专家研究这一研究领域。线性自由能关系 (LFER)，包括塔夫脱方程，是一种强大的结构反应工具，可解释一系列化学反应的空间效应、极性效应和共振效应。塔夫脱方程表明，空间、极性和共振效应之间存在关系。反应物的结构（即靠近反应中心的取代基）及其在反应系列中的反应性将其应用于化学反应（例如酯化）是最先进的，并且据称开发的参数是然而，主要在一种溶剂中使用酯化和水解反应，这原则上限制了关系的一般有效性，因此，将 LFER 概念推广到大量溶剂或溶剂混合物。甚至多相反应系统也需要在没有浓度和温度梯度的情况下以热力学活动表示的内在动力学曲线。重新开发的基于塔夫脱的方法将主要应用于三个化学反应系统：涉及木质纤维素衍生的平台分子：1）使用不同的醇溶剂将葡萄糖溶剂解成乙酰丙酸酯，2）乙酰丙酸-乙酰丙酸酯的酯化-水解以及3）氢化对于这些系统，我们将改变反应物，即 1) 和 2) 的不同醇，以及 3) 的不同乙酰丙酸酯。 LFER概念对酶催化的有效性目标是使用重新开发的方法来研究和预测反应物中的-R取代基效应以及溶剂对酶催化的影响。实现这一目标需要不同的研究专业知识，使用微流体技术将可以根据实验动力学曲线和状态方程“ePC-SAFT”来预测反应物和产物的传输限制。这最终将允许预测反应特性（标准焓、标准吉布斯能量）以及基于本征活性的反应动力学常数，此外，ePC SAFT 将用于预测反应系统所需的相行为。 （例如反应介质中的 H2 溶解度）；所有预测（相行为和反应特征）都将通过实验进行验证。LFER 和 ePC-SAFT 两种方法的结合将意味着化学合成设计中的重大新理解和新维度。