Chen Yu, Mu Tiancheng
Department of Chemistry, Renmin University of China, Beijing 100872, China.
Appl Spectrosc. 2015 Jan;69(1):130-42. doi: 10.1366/14-07499. Epub 2014 Oct 1.
A rule to interpret perturbation-correlation moving-window two-dimensional correlation spectroscopy (PCMW2D) was developed. Compared with Morita's rule, this proposed rule retains the ability to obtain interval features (i.e., monotonicity, concavity, and convexity) and adds the function to quickly and accurately determine both tipping points (i.e., local extrema and inflection points). It could be described as follows: the local extrema and inflection point could be determined by the zero point with an opposite sign on its left and right side in ΠΦ (synchronous PCMW2D) and ΠΨ (asynchronous PCMW2D), respectively. Specifically, a negative left (right) side and a positive right (left) side of point indicates a local minimal (maximal) value. By using the rule to interpret ΠIR (PCMW2D infrared spectroscopy) of 1-ethyl-3-methyl-imidazolium acetate [EMIM][Ac]-atmospheric water (H2O) as a function of time, we found that the atmospheric water was absorbed only into the bulk of [EMIM][Ac] before 150 min by hydrogen-bonding interaction, only onto the surface of [EMIM][Ac] after 330 min by van der Waals force, and both to the bulk and surface of [EMIM][Ac] between 150 and 330 min by hydrogen-boding and van der Waals force simultaneously. The proportion of bulk water sorption and surface water sorption to [EMIM][Ac] was about 4 and 96%, respectively.
制定了一种解释扰动相关移动窗口二维相关光谱(PCMW2D)的规则。与森田规则相比,该规则保留了获取区间特征(即单调性、凹性和凸性)的能力,并增加了快速准确确定两个转折点(即局部极值和拐点)的功能。它可以描述如下:局部极值和拐点可以分别由ΠΦ(同步PCMW2D)和ΠΨ(异步PCMW2D)中左右两侧符号相反的零点确定。具体来说,点的左侧(右侧)为负且右侧(左侧)为正表示局部最小值(最大值)。通过使用该规则解释1-乙基-3-甲基咪唑鎓醋酸盐[EMIM][Ac]-大气水(H2O)随时间变化的ΠIR(PCMW2D红外光谱),我们发现,在150分钟之前,大气水仅通过氢键相互作用被吸收到[EMIM][Ac]的主体中;在330分钟之后,仅通过范德华力被吸附到[EMIM][Ac]的表面;在150至330分钟之间,通过氢键和范德华力同时被吸收到[EMIM][Ac]的主体和表面。被[EMIM][Ac]吸收的主体水和表面水的比例分别约为4%和96%。