"Nanocellulose" as a single nanofiber prepared from pellicle secreted by Gluconacetobacter xylinus using aqueous counter collision.

This study attempted to prepare a single cellulose nanofiber, "nanocellulose", dispersed in water from 3D networks of nanofibers in microbial cellulose pellicle using aqueous counter collision (ACC), which allows biobased materials to be down-sized into nano-objects only using water jets without chemical modification. The nanocellulose thus prepared exhibited unique morphological properties. In particular, the width of the nanocellulose, which could be controlled as desired on nanoscales, was smaller than that of just secreted cellulose nanofiber, resulting in larger specific surface areas. Moreover, ACC treatment transformed cellulose I(α) crystalline phase into cellulose I(ß) phase with the crystallinity kept >70%. In this way, ACC method depending on the treatment condition could provide the desired fiber width at the nanoscale and the different ratios of the two crystalline allomorphs between cellulose I(α) versus I(ß), which thus opens further pathways into versatile applications as biodegradable single nanofibers.

Fabrication of honeycomb-patterned cellulose films.

This paper reports for the first time on the fabrication of honeycomb-patterned cellulose films by casting water in oil emulsion of cellulose acetate onto a glass substrate and subsequent deacetylation treatment. The honeycomb pore size could be controlled from 1 to 100 microm under a saturated water vapor condition. Both cellulose and cellulose acetate films with honeycomb-pattern are expected to be a two-dimensional model of plant cell walls as well as of micro-wells for single cell cultivation. Surface topographic image of a honeycomb-patterned cellulose film (scalebar: 50 microm).

Autonomous bottom-up fabrication of three-dimensional nano/microcellulose honeycomb structures, directed by bacterial nanobuilder.

We investigated the autonomous bottom-up fabrication of three-dimensional honeycomb cellulose structures, using Gluconacetobacter xylinus as a bacterial nanoengine, on cellulose honeycomb templates prepared by casting water-in-oil emulsions on glass substrates (Kasai and Kondo, Macromol. Biosci., 4, 17-21, 2004). The template film had a unique molecular orientation state along the honeycomb frames, but was non-crystalline. When G. xylinus, used as a nanofiber-producing bacterium, was incubated on the honeycomb scaffold in a culture medium, it secreted cellulose nanofibers only on the upper surface of the honeycomb frame. The movement was regulated by a selective interaction between the synthesized nanofiber and the surface of the honeycomb frames of the template. The relationship between directed deposition of synthesized nanofibers and ordered fabrication from the nano- to the micro-scale could provide a novel bottom-up methodology, using bacteria, for the design of three-dimensional honeycomb structures as functional materials with nano/micro hierarchical structures, with low energy consumption.

Aqueous counter collision using paired water jets as a novel means of preparing bio-nanofibers.

This study involved a detailed investigation of a novel approach to reducing naturally occurring cellulose fibers into nanofibers solely by the use of aqueous counter collision (ACC) without any chemical modification. In this process, equivalent aqueous suspensions of cellulose are ejected from dual nozzles and collide at high speed and pressure. Even a few repetitions of the collision process are sufficient to produce nano-sized fibers dispersed in water. This work compared the ACC nano-pulverization of stable Iß-rich and meta-stable Iα-rich cellulose samples. The ACC method is applicable to various kinds of polymeric materials with hierarchical structures, either natural or synthetic, as a means of preparing aqueous dispersions of nano-sized structures.

Regioselective modification of a xyloglucan hemicellulose for high-performance biopolymer barrier films.

Biobased polymers such as starch and hemicelluloses from wood are of interest for packaging applications, but suffer from limitations in performance under moist conditions. Xyloglucan from industrial tamarind seed waste offers potential, but its Tg is too high for thermal processing applications. Regioselective modification is therefore performed using an approach involving periodate oxidation followed by reduction. The resulting polymer structures are characterized using MALDI-TOF-MS, size-exclusion chromatography, FTIR and carbohydrate analysis. Films are cast from water and characterized by thermogravimetry, dynamic mechanical thermal analysis, dynamic water vapor sorption, oxygen transmission and tensile tests. Property changes are interpreted from structural changes. These new polymers show much superior performance to current petroleum-based polymers in industrial use. Furthermore, this regioselective modification can be carefully controlled, and results in a new type of cellulose derivatives with preserved cellulose backbone without the need for harmful solvents.

Regulated patterns of bacterial movements based on their secreted cellulose nanofibers interacting interfacially with ordered chitin templates.

Gluconacetobacter xylinus, a gram-negative bacterium that synthesizes and extrudes a cellulose nanofiber in SH media moves in random manners, resulting in 3D-network structure of the secreted nanofibers termed a pellicle. In this study, the bacterial movement was successfully regulated to be in a waving manner when cultured on ordered templates made of chitin. Interestingly, by addition of more cellulose into the chitin ordered templates, the waving pattern was getting close to a linear or straight manner. Real time video analysis and other visualization techniques clarified that the regulation of the moving manners was due to the interfacial interaction between the secreted nanofibers and the template surfaces. Furthermore, the changing of the pattern due to the cellulose content in the ordered templates appeared to depend on the magnitude of the interaction between the template and nanofibers. This regulated autonomous deposition of the fibers will build patterned 3D-structure with unique properties on the surface of the templates, leading to a novel type of nanotechnology using biological systems with biomolecular nano-templates to design 3D-structures.