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通过实施一个简单的有机系统来阐明机械化学复杂性方面的进展。

Advances in elucidating mechanochemical complexities via implementation of a simple organic system.

作者信息

Michalchuk Adam A L, Tumanov Ivan A, Drebushchak Valeri A, Boldyreva Elena V

机构信息

School of Chemistry, The University of Edinburgh, Edinburgh, UK.

出版信息

Faraday Discuss. 2014;170:311-35. doi: 10.1039/c3fd00150d.

Abstract

Mechanochemistry is becoming increasingly popular amongst both the academic and industrial communities as an alternative method for inducing physical and chemical reactions. Despite its rapidly expanding application, little is understood of its mechanisms, greatly limiting its capacity. In the present work the application of specialty devices allowed submission of the simple organic system, α-glycine + β-malonic acid, to isolated shearing and impact treatment. In doing so, unique products were observed to result from each of these major mechanical actions; shear inducing formation of the known salt, glycinium semi-malonate (GSM), and impact yielding formation of a novel phase. Correlation of these isolated treatments with a more common ball mill indicated two unique regions within the milling jar, each characterised by varying ratios of shear and impact, leading to different products being observed. It is widely accepted that, particularly when considering organic systems, mechanical treatment often acts by inducing increases in local temperature, leading to volatilisation or melting. A combination of DSC and TGA were used to investigate the role of temperature on the system in question. Invariably, heating induced formation of GSM, with evidence supporting a eutectic melt, rather than a gas-phase reaction. Shear heating alone is unable to describe formation of the novel phase obtained through impact treatment. By considering the formation and character of mechanically produced tablets, a model is described that may account for formation of this novel phase. This system and methodology for mechanochemical study offers intriguing opportunities for continued study of this widely used and exciting field.

摘要

机械化学作为一种引发物理和化学反应的替代方法,在学术界和工业界正变得越来越受欢迎。尽管其应用迅速扩展,但其作用机制却鲜为人知,这极大地限制了其应用能力。在本研究中,使用特殊装置对简单有机体系α-甘氨酸+β-丙二酸进行了单独的剪切和冲击处理。结果发现,这些主要机械作用分别产生了独特的产物;剪切作用诱导形成了已知的盐——甘氨酸半丙二酸酯(GSM),而冲击作用则产生了一种新相。将这些单独处理与更常见的球磨机处理进行关联,结果表明在研磨罐内存在两个独特区域,每个区域的剪切和冲击比例不同,从而导致观察到不同的产物。人们普遍认为,特别是在考虑有机体系时,机械处理通常是通过诱导局部温度升高来起作用,从而导致挥发或熔化。采用差示扫描量热法(DSC)和热重分析法(TGA)相结合的方法来研究温度对该体系的作用。加热总是会诱导形成GSM,有证据支持这是一种共晶熔体,而不是气相反应。仅靠剪切加热无法解释通过冲击处理获得的新相的形成。通过考虑机械压制片剂的形成和特性,描述了一个可能解释这种新相形成的模型。这种机械化学研究体系和方法为继续研究这个广泛应用且令人兴奋的领域提供了有趣的机会。

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