Molybdenum oxide with a varied valency ratio to enable selective d-galactose epimerization to d-talose†

IF 3.4 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Bhawana Devi, Senthil Murugan Arumugam, Ravi Kumar Kunchala, Paramdeep Kaur, Sangeeta Mahala and Sasikumar Elumalai
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Abstract

D-Talose, classified as a rare and expensive sugar molecule, is gaining attraction due to its antimicrobial and anti-inflammatory properties. Its production is widely investigated by adopting biological enzymes, which is costly. However, alternative chemical methodologies have reported its formation as a side product and in minor amounts. We report for the first time its significant synthesis using D-galactose (which comprises whey and hemicellulose) by employing a finely tuned molybdenum oxide (MoO3) solid acid catalyst. The nitric acid treatment of MoO3 modulated the valency ratio in Mo species (Mo5+/6+), resulting in an improved Lewis acidity with up to 199 μmol g−1 acidic sites and porosity of up to 48% relative to the pristine MoO3, attributed to the generated oxygen vacancies. Combined together these have assisted in an augmented D-talose synthesis with as high as 25% yield, 70% selectivity and 98% carbon balance in a water medium under modest reaction conditions (120 °C and 30 min). As proposed, Mo's interaction with D-galactose to form a Mo–sugar complex has influenced the C1–C2 carbon shift to yield D-talose. Furthermore, the typical isotopic labelling NMR characterization has confirmed the Bílik mechanism of C2-galactose epimerization. Overall, the heterogeneous catalytic setup represents a sustainable and feasible method for producing rare sugar for food additive and pharma applications.

Abstract Image

具有不同价比的氧化钼,可选择性地将 D-半乳糖表聚为 D-塔罗糖
D-Talose 是一种稀有而昂贵的糖分子,因其具有抗菌和消炎特性而备受青睐。迄今为止,人们广泛研究通过生物酶生产 D-塔罗糖,但这种方法成本高昂。然而,有报告称,替代化学方法只能生成少量的副产品。我们首次报道了使用精细调节的氧化钼(MoO3)固体酸催化剂,利用 D-半乳糖(由乳清和半纤维素组成)合成 D-半乳糖的重大进展。经过硝酸处理的 MoO3 调节了钼物种(Mo5+/6+)的价比,与原始 MoO3 相比,酸性位点的路易斯酸度提高到 199 µmol/g,孔隙率提高到 48%,这归功于产生的氧空位。这些因素结合在一起,有助于在适度的反应条件(120 °C、30 分钟)下,在水介质中提高 D-Talose 的合成率,其产率高达 25%,选择性高达 70%,碳平衡高达 98%。正如所提出的,钼与 D-半乳糖相互作用形成的钼-糖复合物影响了 C1-C2 碳转移,从而产生了 D-塔罗糖。此外,典型的同位素标记核磁共振表征也证实了 C2-半乳糖表聚的 Bílik 机制。总之,这种异相催化装置是生产稀有糖的一种可持续的可行方法,可用于食品添加剂和制药领域。
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来源期刊
Reaction Chemistry & Engineering
Reaction Chemistry & Engineering Chemistry-Chemistry (miscellaneous)
CiteScore
6.60
自引率
7.70%
发文量
227
期刊介绍: Reaction Chemistry & Engineering is a new journal reporting cutting edge research into all aspects of making molecules for the benefit of fundamental research, applied processes and wider society. From fundamental, molecular-level chemistry to large scale chemical production, Reaction Chemistry & Engineering brings together communities of chemists and chemical engineers working to ensure the crucial role of reaction chemistry in today’s world.
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