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For the efficient degradation and bioconversion of cellulosic biomass, it is important to efficiently disrupt and convert crystalline regions of cellulose into easily hydrolyzable regions than to simply hydrolyze cellulose. Expansin-like proteins such as swollenins have disruptive functions on lignocellulose, including crystalline cellulose, via non-hydrolytic mechanisms. In this work, we produced the swollenin from Trichoderma asperellum in Escherichia coli. The recombinant protein was then refolded into the bioactive form with simultaneous purification via a novel cellulose-assisted process. We devised a novel, simple, and efficient method to quantitatively determine the non-hydrolytic disruptive activity of swollenin on crystalline cellulose. This method is based on the synergism of the swollenin and the endoglucanase FnCel5A from Fervidobacterium nodosum. The change from crystalline regions into easily hydrolyzable forms, due to non-hydrolytic disruption, might be slight and not easily be observed. However, disrupted regions of cellulose could be hydrolyzed by FnCel5A, and reducing sugars were formed by the synergism. The disruptive function of the swollenin was quantitatively characterized by measuring the release of reducing sugars. These methods and processes will be useful for further research on non-hydrolytic disruptive bioactivities and provide novel approaches for the efficient and economical bioconversion of cellulosic biomass.

Stable glasses are formed during physical vapor deposition (PVD), through the surface-mediated equilibration process. Understanding surface relaxation dynamics is important in understanding the details of this process. Direct measurements of the surface relaxation times in molecular glass systems are challenging. As such, surface diffusion measurements have been used in the past as a proxy for the surface relaxation process. In this study, we show that the absence of enhanced surface diffusion is not a reliable predictor of reduced ability to produce stable glasses. To demonstrate, we have prepared stable glasses (SGs) from two structurally similar organic molecules, 1,3-bis­(1-naphthyl)-5-(2-naphthyl)­benzene (TNB) and 9-(3,5-di­(naphthalen-1-yl)­phenyl)­anthracene (α,α-A), with similar density increase and improved kinetic stability as compared to their liquid-quenched (LQ) counterparts. The surface diffusion values of these glasses were measured both in the LQ and SG states below their glass transition temperatures (T gs) using gold nanorod probes. While TNB shows enhanced surface diffusion in both SG and LQ states, no significant surface T g diffusion is observed on the surface of α,α-A within our experimental time scales. However, isothermal dewetting experiments on ultrathin films of both molecules below Tg indicate the existence of enhanced dynamics in ultrathin films for both molecules, indirectly showing the existence of an enhanced mobile surface layer. Both films produce stable glasses, which is another indication for the existence of the mobile surface layer. Our results suggest that lateral surface diffusion may not be a good proxy for enhanced surface relaxation dynamics required to produce stable glasses, and thus, other types of measurements to directly probe the surface relaxation times may be necessary.