Vapor grown carbon nanofiber based cotton fabrics with negative thermoelectric power

Vapor grown carbon nanofiber (CNF) based ink dispersions were used to dip-coat woven cotton fabrics with different constructional parameters, and their thermoelectric (TE) properties studied at room temperature. Unlike the positive thermoelectric power (TEP) observed in TE textile fabrics produced with similar carbon-based nanostructures, the CNF-based cotton fabrics showed negative TEP, caused by the compensated semimetal character of the CNFs and the highly graphitic nature of their outer layers, which hinders the p-type doping with oxygen groups onto them. A dependence of the electrical conductivity (r) and TEP as a function of the woven cotton fabric was also observed. The cotton fabric with the largest linear density (tex) showed the best performance with negative TEP values around - 8 lV K-1 , a power factor of 1.65 9 10-3 lW m-1 K-2 , and a figure of merit of 1.14 9 10-6 . Moreover, the possibility of a slight e- charge transfer or n-doping from the cellulose onto the most external CNF graphitic shells was also analysed by computer modelling. This study presents n-type carbon-based TE textile fabrics produced easily and without any functionalization processes to prevent the inherent doping with oxygen, which causes the typical p-type character found in most carbon-based TE materialsFEDER funds through COMPETE and by national funds through FCT – Foundation for Science and Technology within the project POCI-01-0145- FEDER-007136. E. M. F. Vieira is grateful for financial support through FCT with CMEMS-UMinho Strategic Project UIDB/ 04436/202

The evolution of multiple active site configurations in a designed enzyme

Developments in computational chemistry, bioinformatics, and laboratory evolution have facilitated the de novo design and catalytic optimization of enzymes. Besides creating useful catalysts, the generation and iterative improvement of designed enzymes can provide valuable insight into the interplay between the many phenomena that have been suggested to contribute to catalysis. In this work, we follow changes in conformational sampling, electrostatic preorganization, and quantum tunneling along the evolutionary trajectory of a designed Kemp eliminase. We observe that in the Kemp Eliminase KE07, instability of the designed active site leads to the emergence of two additional active site configurations. Evolutionary conformational selection then gradually stabilizes the most efficient configuration, leading to an improved enzyme. This work exemplifies the link between conformational plasticity and evolvability and demonstrates that residues remote from the active sites of enzymes play crucial roles in controlling and shaping the active site for efficient catalysis