• 2021

    26 April 2021, Chemistry—A European Journal
    Youzhen Zhuo, Xiuxiu Wang, Si Chen, Hang Chen, Jie Ouyang, Liulin Yang, Xinchang Wang,* Lei You,* Marcel Utz,* Zhongqun Tian, and Xiaoyu Cao*

    Quantitatively predicting the reactivity of dynamic covalent reaction is essential to understand and rationally design complex structures and reaction networks. Herein, the reactivity of aldehydes and amines in various rapid imine formation in aqueous solution by microfluidic NMR spectroscopy was quantified. Investigation of reaction kinetics allowed to quantify the forward rate constants k+ by an empirical equation, of which three independent parameters were introduced as reactivity parameters of aldehydes (SE, E) and amines (N). Furthermore, these reactivity parameters were successfully used to predict the unknown forward rate constants of imine formation. Finally, two competitive reaction networks were rationally designed based on the proposed reactivity parameters. Our work has demonstrated the capability of microfluidic NMR spectroscopy in quantifying the kinetics of label-free chemical reactions, especially rapid reactions that are complete in minutes.

    Gan-Yu Chen, Yi-Bin Sun, Pei-Chen Shi, Tao Liu, Zhi-Hao Li, Si-Heng Luo, Xin-Chang Wang, Xiao-Yu Cao, Bin Ren*, Guo-Kun Liu, Liu-Lin Yang* and Zhong-Qun Tian*

    Interfacial host–guest complexation offers a versatile way to functionalize nanomaterials. However, the complicated interfacial environment and trace amounts of components present at the interface make the study of interfacial complexation very difficult. Herein, taking the advantages of near-single-molecule level sensitivity and molecular fingerprint of surface-enhanced Raman spectroscopy (SERS), we reveal that a cooperative effect between cucurbit[7]uril (CB[7]) and methyl viologen (MV2+2I) in aggregating Au NPs originates from the cooperative adsorption of halide counter anions I, MV2+, and CB[7] on Au NPs surface. Moreover, similar SERS peak shifts in the control experiments using CB[n]s but with smaller cavity sizes suggested the occurrence of the same guest complexations among CB[5], CB[6], and CB[7] with MV2+. Hence, an unconventional exclusive complexation model is proposed between CB[7] and MV2+ on the surface of Au NPs, distinct from the well-known 1:1 inclusion complexation model in aqueous solutions. In summary, new insights into the fundamental understanding of host–guest interactions at nanostructured interfaces were obtained by SERS, which might be useful for applications related to host–guest chemistry in engineered nanomaterials.

    24 Feb 2021, CCS Chemistry
    Yibin Sun†, Hongxun Fang†, Xujing Lin, Xiuxiu Wang, Ganyu Chen, Xinchang Wang*, Zhongqun Tian, Liulin Yang*, Marcel Utz* & Xiaoyu Cao*

    It is challenging to investigate fast supramolecular processes due to the lack of appropriate characterization methods with high structural resolution. In this study, microfluidic nuclear magnetic resonance (μF-NMR) spectroscopy was employed to monitor the kinetics of threading and dethreading of a pseudo[6]rotaxane system. By employing high time resolution μF-NMR, 1H and two-dimensional (2D) rotating frame nuclear Overhauser effect spectroscopy (ROESY) NMR spectra were recorded at any time point within 1.5 s after the onset of the process. This technique enabled the successful identification of kinetic intermediates and rate-determining steps, usually impossible to determine by other spectroscopic techniques. Thus, our study demonstrates the capability of μF-NMR in investigating the mechanism of complex supramolecular systems.