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Long‐range electron transfer (ET) in metalloenzymes is a general and fundamental process governing O2 activation and reduction. Lytic polysaccharide monooxygenases (LPMOs) are key enzymes for the oxidative cleavage of insoluble polysaccharides, but their reduction mechanism by cellobiose dehydrogenase (CDH), one of the most commonly used enzymatic electron donors, via long‐range ET is still an enigma. Using multiscale simulations, we reveal that interprotein ET between CDH and LPMO is mediated by the heme propionates of CDH and solvent waters. We also show that oxygen binding to the copper center of LPMO is coupled with the long‐range interprotein ET. This process, which is spin‐regulated and enhanced by the presence of O2, directly leads to LPMO−CuII−O2−, bypassing the formation of the generally assumed LPMO−CuI species. The uncovered ET mechanism rationalizes experimental observations and might have far‐reaching implications for LPMO catalysis as well as the O2‐ or CO‐binding‐enhanced long‐range ET processes in other metalloenzymes. [ABSTRACT FROM AUTHOR]

An integrated nanogold/expanded graphite based sensor was fabricated by a former electrochemical etching of the pencil lead electrode (PLE) and a later in-situ deposition of gold nanoparticles (AuNPs). The electrochemical pretreatment of PLE (EPLE) created a 3D graphene-like surface, enhanced the electrode surface area and facilitated the electron transfer ability within 5 min without any hazardous chemicals added. The obtained AuNPs/EPLE sensor had an excellent electrochemical response to glucose with a wide linear concentration range, from 0.05 to 38 mM and 38 to 60 mM, and a low detection limit of 5 μM (S/N = 3). Furthermore, the AuNPs/EPLE sensor was successfully employed to detect the glucose in human serum samples, and the results agreed well with those measured in hospital. Finally, the sensor exhibited efficient and reproducible surface-enhanced Raman scattering activities for the probe molecules. Unlabelled Image • A 3D graphene-like surface is rapidly created by expansion of pencil lead electrode (EPLE). • Density AuNPs are deposited on the resulting rougher surface. • The integrated AuNPs/EPLE sensor is suitable for glucose detection in human serum samples. • Trace SERS sensing is obtained with excellent stability and reproducibility. [ABSTRACT FROM AUTHOR]