The tunneling mode of scanning electrochemical microscopy (SECM) was developed recently and applied to studies of charge-transfer reactions at single metal nanoparticles (NPs). When an SECM tip is brought within the tunneling distance from a conductive NP, the particle begins to act as a part of the nanoelectrode. Herein, we demonstrate the possibility of using carbon nanoelectrodes with a very thin insulating sheath for electrochemical tunneling experiments at flat samples. In this way, electrocatalytic activity, conductivity, and charging properties of and faradaic processes in layered nanomaterials can be characterized by single-nanoflake voltammetry without making direct ohmic contact with them. A broad applicability of tunneling SECM experiments is demonstrated by probing nanomaterials with different size, geometry, and electrocatalytic properties, including metallic/pseudo-metallic (1T/1T′) and semiconducting (2H) MoS 2 nanoflakes, N-doped porous carbon catalyst, and MXene nanosheets. The Tafel plots for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at individual nanoflakes are compared to analogous measurements for an ensemble of flakes attached to the surface of a macroscopic electrode. Moreover, we observed variations in catalytic activities of individual MXene flakes toward HER and OER caused by non-uniform doping.
The regioselective synthesis of multiple disulfide bonds
in peptides
has been a significant challenge in synthetic peptide chemistry. In
this work, two disulfide bonds in peptides were regioselectively synthesized
via an approach of MetSeO oxidation and deprotection reaction (SeODR),
in which the first disulfide bond was constructed through oxidation
of dithiol by MetSeO in a neutral buffer, and the second disulfide
bond was then directly constructed through the deprotection of two
Acm groups or one Acm group and one Thz group by MetSeO in acidic
media. Synthesis of two disulfide bonds by the SeODR approach was
achieved through a one-pot manner. Moreover, the SeODR approach is
compatible with the synthesis of peptides containing methionine residues.
Both H+ and Br– drastically promoted
the reaction rate of SeODR. The mechanistic picture for the SeODR
approach was delineated, in which the formation of a stable Se–X–S
bridge as the transition state plays a critical role. The SeODR approach
was also utilized to construct the three disulfide bonds in linaclotide,
conferring a reasonable yield.
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