马来酰肼多形态的太赫兹光谱研究  

Terahertz Spectroscopic Investigation of Maleic Hydrazide Polymorphs

作　　者：郑转平 李爱东 董军 职言 巩稼民 ZHENG Zhuan-ping;LI Ai-dong;DONG Jun;ZHI Yan;GONG Jia-min(School of Electronic Engineering,Xi’an University of Posts and Telecommunications,Xi’an 710121,China)

机构地区：[1]西安邮电大学电子工程学院,陕西西安710121

出　　处：《光谱学与光谱分析》2022年第4期1104-1108,共5页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(11604263);陕西省教育厅资助项目(16JK1698)资助。

摘　　要：分子的多形态(多晶型)是指化学组成相同但存在不止一种晶体形式的物质。这些多形态广泛存在于自然界中,其中药物的多形态尤其普遍。这些药物多形态虽然具有相同的化学分子组成,但其理化性质却存在差异,最终会导致药物作用功能的不同。近年来,随着太赫兹(THz)辐射源的产生方式成为一种常规技术后,太赫兹时域光谱技术(THz-TDS)的应用领域逐渐被拓宽。因为THz波不仅与分子内作用模式有关,更与氢键和范德华力等弱相互作用模式密切相关;THz辐射可以诱发低频键振动、晶体声子振动、氢键拉伸和扭转振动,许多有机分子的集体振动模式处于该波段,尤其是药物分子。基于此,采用THz-TDS技术,研究了马来酰肼药物分子两种多形态(MH2和MH3)在0.25~2.25 THz波段的THz吸收谱。通过实验测试,发现MH2和MH3的THz特征吸收峰完全不同,MH2获取到了三个特征吸收峰,分别位于0.34,1.41和1.76 THz;MH3晶型获取两个特征吸收峰,分别位于0.75和1.86 THz处;此结果表明马来酰肼多形态可以通过其THz特征吸收峰进行辨别表征。接着,为了对THz实验吸收峰进行解析,采用固态密度泛函理论(DFT)模拟了马来酰肼的红外吸收模式;在实验和理论频谱数据匹配的情况下,分析讨论了特征吸收峰的来源,发现MH2和MH3的THz吸收峰对其三维空间结构非常敏感,吸收峰均来源于分子间相互作用力。最后,为使药物研究能够与实际应用结合,对马来酰肼的商用药品青鲜素进行了THz光谱测试,通过其与马来酰肼多形态的THz吸收峰比较,发现人们日常使用的青鲜素是MH3晶型。此研究结果表明,THz-TDS技术是一种很有潜力的药物多形态检测工具,此研究有望解决马来酰肼多形态在工业生产及临床应用上检测难的问题。Polymorphs refer to substances with the same chemical composition but in more than one crystal form.These polymorphs exist widely in nature,especially in pharmaceuticals.These polymorphs have the same chemical molecular composition,but their physical and chemical properties are different,ultimately affecting the effect of pharmaceuticals.In recent years,with the generation of terahertz(THz) wave becoming a conventional technology,the application fields of terahertz time-domain spectroscopy(THz-TDS) has been gradually broadened.THz wave is related to intramolecular interaction mode and closely related to weak interaction modes such as hydrogen bond and van der Waals force.THz radiation can induce low-frequency bond vibration,crystal phonon vibration,hydrogen bond stretching and torsional vibration,and the collective vibration modes of many organic molecules are located in this region,especially pharmaceutical molecules.Thus in this paper,THz-TDS was used to study the THz absorption spectra of maleic hydrazide polymorphs(MH2 and MH3) in the range of 0.25~2.25 THz.The experimental results show that the THz absorption peaks of MH2 and MH3 are completely different.Specifically,MH2 has three characteristic absorption peaks,which are located at 0.34,1.41 and 1.76 THz.MH3 has two characteristic absorption peaks at 0.75 and 1.86 THz.These results show that the polymorphs of maleic hydrazide can be distinguished and characterized by their THz absorption peaks.Then,to analyze the THz experimental peaks,solid-state density functional theory(DFT) is used to simulate.In matching experimental and theoretical spectral data,the origins of the THz absorption peaks are analyzed and discussed.The results suggest that the THz absorption peaks of MH2 and MH3 are very sensitive to their three-dimensional structures,and the absorption peaks all originate from intermolecular interactions Finally,the THz spectra of the commercial tablets of maleic hydrazide were tested.By comparing the THz absorption peaks between MH2(MH3) and Qingxiansu,

关 键 词：太赫兹时域光谱 密度泛函 马来酰肼 药物分子多形态 

分 类 号：O433.5[机械工程—光学工程]