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Au-Ag nanoparticles (Au-Ag NPs) with a core-shell structure are prepared and used for ultrasensitive electrochemical impedance (EI) discrimination of the isomers of tryptophan (Trp). As revealed by circular dichroism, rotary polarization caused by the Au-Ag NPs is consistent with D-Trp but opposite to L-Trp, and thus, the Au-Ag NPs can selectively combine with D-Trp through preferential interactions. Compared with Au-Ag NPs, the composites of D-Trp and Au-Ag NPs (Au-Ag NPs/D-Trp) display significantly increased charge transfer resistance ( R ct ); differently, the R ct of Au-Ag NPs/L-Trp remains almost unchanged because the Au-Ag NPs exhibit poor affinity toward L-Trp. Therefore, ultrasensitive EI enantiodiscrimination of the isomers of Trp is realized even at an extremely low concentration of the Trp isomers (0.1 nM). In addition, it is successfully applied in the ultrasensitive determination of D-Trp at a low concentration level (0.1 nM∼10 μM).

π-Conjugated porphyrins have aroused particular attention for nanofabrication and biomimics; however, little attention has been paid to porphyrins-based chiral analysis owing to the achiral feature of porphyrins. Here, we demonstrated a chiral self-assembly of achiral porphyrin induced by l- and d-lysine (l- and d-Lys), and the resultant porphyrin self-assembly exhibited alterable morphologies depending on the inducer used (l- or d-Lys). The supramolecular chirality of the self-assembly was characterized by circular dichroism (CD) spectra, confirming successful transfer of molecular chirality from l- and d-Lys to the self-assembly. The enantioselective property of the chiral self-assembly was also investigated by using tryptophan (Trp) isomers as the model, and the results indicated that the developed chiral self-assembly showed significantly higher affinity toward l-Trp than d-Trp. Also in this work, the l-/d-Lys-induced chiral self-assembly of porphyrin and the supramolecular interaction between the self-assembly and l-/d-Trp were also studied by density functional theory (DFT).

Molecularly imprinted polymers (MIPs) provide versatile sensor platforms to recognize targets by shape complementarity. However, the rigid structure of the classic MIPs compromises the signal transduction with necessary polymer and target modifications. Herein, we tried to use a flexible DNA that has a perfectly structured folding as the soft molecularly imprinted polymer (SMIP) for a straightforward sensor. As a proof of concept, the guanosine SMIP recognition was achieved by removal of a guanosine from a G-quadruplex-forming sequence (G4). The G4 folding structure with such an apurinic site (AP site) provides a well-defined MIP binding accommodation for guanosine according to the shape complementarity. The guanosine binding at the AP site subsequently leads to a conformation change suitable for remote readout using a G4-specific fluorescent ligand. The G4 sequence and AP site position were optimized for this SMIP behavior. Due to the G4 compact structure and the remaining hydrogen bonding pattern, nucleosides other than guanosine and negatively charged nucleotides exhibit no binding with the AP site, suggesting a high selectivity in the SMIP recognition. The proposed rationale was then convinced by the alkaline phosphatase-catalyzed GMP hydrolysis. Our work will inspire more interest in exploring nucleic acids as the SMIP frameworks due to their variant conformations and well-established molecular engineering.

Besides the canonical Watson-Crick (WC) linked antiparallel-stranded duplex (aps-DNA), DNA is also able to form bioactive parallel-stranded duplex (ps-DNA) with the two involving strands adopting the equal 5'-3' polarity. Discriminating ps-DNA from aps-DNA with an ideal selectivity is more challenging because of their comparable duplex topologies. Herein, we designed a unique probe of HPIN to fluorescently recognize ps-DNA but to keep an almost nonfluorescent response in binding with aps-DNA. The success of the Hoogsteen hydrogen bonding pattern in lighting up the HPIN fluorescence over the reverse Watson-Crick (rWC) one suggests the critical role of HPIN in structurally adaptive recognition to the strand polarity-determined base-pairing peculiarity. The turn-on fluorescence should result from restriction of the HPIN cis/trans isomerization upon the adaptive Hoogsteen base pair binding. Such high performance in recognizing ps-DNA against aps-DNA demonstrates the promising applications of HPIN in developing unique DNA polarity-based sensors.