• 2021

    25 November 2021, Chem

    Huihui Hu, Jieyu Zhu, Lingyun Cao, Zhiye Wang, Yuan Gao, Liulin Yang, Wenbin Lin, Cheng Wang*

    Photo-generation of a proton gradient over a lipid bilayer is of interest due to its essential role in photosynthetic bacteria. Membrane asymmetry is key to the proton gradient generation via directional proton transport. Here, we report a light-driven proton pump based on two-dimensional, porphyrin-based Janus metal-organic layers (Janus-MOLs). The Janus-MOL, functionalized with carboxyquinone on one side and Acitretin on the other via a microemulsion-based method, was attached to liposome surface. Upon photoexcitation, the porphyrins initiate electron and hole transfers to carboxyquinone and Acitretin, respectively, which undergo redox reactions with freely diffusing quinone (Q)/hydrosemiquinone (HQ·) in the lipid bilayer to produce a concentration gradient of quinone-based species. Owing to different pKa values of HQ+ and HQ·, these redox reactions trigger proton transport across the membrane to create a pH gradient, which drives ATP production by CFoF1-ATP synthase in a similar fashion as photosynthetic bacteria.

    12 June 2021, Advanced Materials

    Longzhu Liu, Shiyan Chen, Yangyang Qu, Xiang Gao, Liang Han, Zhiwei Lin, Liulin Yang, Wei Wang, Nan Zheng, Yongye Liang, Yuanzhi Tan,* Haiping Xia,* and Feng He*

    Interface engineering is a critical method by which to efficiently enhance the photovoltaic performance of nonfullerene solar cells (NFSC). Herein, a series of metal–nanographene-containing large transition metal involving dπ–pπ conjugated systems by way of the addition reactions of osmapentalynes and p-diethynyl-hexabenzocoronenes is reported. Conjugated extensions are engineered to optimize the π-conjugation of these metal–nanographene molecules, which serve as alcohol-soluble cathode interlayer (CIL) materials. Upon extension of the π-conjugation, the power conversion efficiency (PCE) of PM6:BTP-eC9-based NFSCs increases from 16% to over 18%, giving the highest recorded PCE. It is deduced by X-ray crystallographic analysis, interfacial contact methods, morphology characterization, and carrier dynamics that modification of hexabenzocoronenes-styryl can effectively improve the short-circuit current density (Jsc) and fill factor of organic solar cells (OSCs), mainly due to the strong and ordered charge transfer, more matching energy level alignments, better interfacial contacts between the active layer and the electrodes, and regulated morphology. Consequently, the carrier transport is largely facilitated, and the carrier recombination is simultaneously impeded. These new CIL materials are broadly able to enhance the photovoltaic properties of OSCs in other systems, which provides a promising potential to serve as CILs for higher-quality OSCs.

    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.