Edwards Myles Quinn, Holden Dylan T, Cooks R Graham
Department of Chemistry, Purdue University 560 Oval Drive West Lafayette 47907 USA
Chem Sci. 2025 Mar 18;16(16):7057-7065. doi: 10.1039/d4sc08402k. eCollection 2025 Apr 16.
Understanding the chemical reactions that led to the origin of life is a fundamental challenge of chemistry. The formose reaction, an abiotic pathway to monosaccharides, provides a mechanism of sugar formation from simple aldehydes and ketones. However, the reaction requires the addition of base, metal catalysts, and is prone to side reactions, leaving questions about how such processes could have occurred on a primitive Earth. The abiotic formation of more complex sugars, such as disaccharides also require catalysts, and remains underexplored compared to other classes of biomolecules. This study investigates the role of microdroplets in the formation of hexoses and their subsequent condensation reactions to produce disaccharides, without the need for catalysts. The microdroplet-mediated synthesis of fructose and sorbose from glyceraldehyde or dihydroxyacetone, as well as that of disaccharides from various pentoses or hexoses, was monitored mass spectrometery. Products were confirmed by high resolution mass spectrometry and tandem mass spectrometry. The product distribution of glucose disaccharides was determined by matching the relative intensities of product ions to a mixture of six disaccharide and showed a maximum yield of 9.4% or 1.7 µg min emitter. This study demonstrates the abiotic formation of monosaccharides and disaccharides, such as xylobiose and maltose, providing a possible link between prebiotic sugar synthesis and extant carbohydrate biochemistry. Hexose formation and disaccharide synthesis are driven by the unique air water interface of microdroplets, where partial solvation, pH extremes, and fast mass transfer kinetics enable abiotic transformations.
理解导致生命起源的化学反应是化学领域的一项基本挑战。福尔摩斯反应是一种生成单糖的非生物途径，它提供了一种由简单醛类和酮类形成糖类的机制。然而，该反应需要添加碱、金属催化剂，并且容易发生副反应，这使得人们对这类过程在原始地球上如何发生存在疑问。更复杂糖类（如二糖）的非生物形成也需要催化剂，并且与其他类别的生物分子相比，这方面的研究仍未充分探索。本研究调查了微滴在己糖形成及其随后缩合反应生成二糖过程中的作用，而无需催化剂。通过质谱监测了由甘油醛或二羟基丙酮微滴介导合成果糖和山梨糖，以及由各种戊糖或己糖合成二糖的过程。产物通过高分辨率质谱和串联质谱得到确认。通过将产物离子的相对强度与六种二糖的混合物进行匹配，确定了葡萄糖二糖的产物分布，其最大产率为9.4%或1.7μg min发射器。这项研究证明了单糖和二糖（如木二糖和麦芽糖）的非生物形成，为益生元糖合成与现存碳水化合物生物化学之间提供了可能的联系。己糖形成和二糖合成是由微滴独特的气 - 水界面驱动的，在该界面处，部分溶剂化、极端pH值和快速的传质动力学使得非生物转化成为可能。
