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.

化学物质（反应物或产品）的结构及其反应性（动力学和热力学）之间的关系是一个研究领域，该研究领域可以交叉链接热力学，动力学，有机化学和化学工程。该项目将由德国和法国专家调查该研究领域。线性自由能力关系（包括TAFT方程）的概念是一种强大的结构反应性工具，可对一系列化学反应产生空间，极性和共振影响。 TAFT方程表明，反应物（即接近反应中心的亚物质）的结构与反应系列中的反应之间存在关系。将其应用于化学反应（例如酯化）是最先进的，据称所开发的参数与反应条件无关。然而，主要是一种溶剂中使用的酯化和水解反应，这原则上限制了关系的一般有效性。这样一来，将概念推广到大量的溶液或溶液混合物，甚至多相反应系统都需要在没有浓度和温度梯度的情况下，就热力学活性表达。这将在该项目中开发。基于重建的TAFT方法将主要应用于涉及木质纤维素衍生的平台分子的三种化学反应系统：1）使用不同酒精溶液的葡萄糖溶剂化对葡萄糖溶剂化，2）酯化酯化酯化酯化酯酸酯酸酯和液光的水解酯酸酯酸酯酸酯和液光的水解酸酯酸酯酸酯酸酯酸酯化的水素化酶酸酯化酶酸酸盐剂的水溶作剂H2和固体催化剂的γ-谷元。对于这些系统，我们将改变反应物，即1）和2）的不同醇和3）的脱肌酯。系统2）将证明FER概念对酶催化的有效性。目的是使用重建方法来研究和预测反应物中的-r亚tit效效应，以及对动力学概况的溶剂效应。实现目标需要不同的研究专家。微流体技术的使用将允许进行动力学实验，以避免运输限制。反应物和产品的活性将根据实验动力学曲线和状态“ EPC-SAFT”的方程进行预测。这最终将允许预测反应特性（标准焓，标准Gibbs能量）以及基于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（阶段行为和反应特征）将通过实验验证。两种方法（LFER＆EPC-SAFT）的关联将意味着在设计化学合成方面具有重大的新理解和新的维度。