Structural changes in microcrystalline cellulose in subcritical water treatment.

Subcritical water is a high potential green chemical for the hydrolysis of cellulose. In this study microcrystalline cellulose was treated in subcritical water to study structural changes of the cellulose residues. The alterations in particle size and appearance were studied by scanning electron microscopy (SEM) and those in the degree of polymerization (DP) and molar mass distributions by gel permeation chromatography (GPC). Further, changes in crystallinity and crystallite dimensions were quantified by wide-angle X-ray scattering and (13)C solid-state NMR. The results showed that the crystallinity remained practically unchanged throughout the treatment, whereas the size of the remaining cellulose crystallites increased. Microcrystalline cellulose underwent significant depolymerization in subcritical water. However, depolymerization leveled off at a relatively high degree of polymerization. The molar mass distributions of the residues showed a bimodal form. We infer that cellulose gets dissolved in subcritical water only after extensive depolymerization.

Single-nanobelt electronic nose: engineering and tests of the simplest analytical element.

Electronic instruments mimicking the mammalian olfactory system are often referred to as "electronic noses" (E-noses). Thanks to recent nanotechnology breakthroughs the fabrication of mesoscopic and even nanoscopic E-noses is now feasible in the size domain where miniaturization of the microanalytical systems encounters principal limitations. Here we describe probably the simplest and yet fully functioning E-nose made of an individual single-crystal metal oxide quasi-1D nanobelt. The nanobelt was indexed with a number of electrodes in a way that each segment of the nanobelt between two electrodes defines an individual sensing elemental "receptor" of the array. The required diversity of the sensing elements is "encoded" in the nanobelt morphology via longitudinal width variations of the nanobelt realized during its growth and via functionalization of some of the segments with Pd catalyst. The proposed approach represents the combined bottom-up/top-down technologically viable route to develop robust and sensitive analytical systems scalable down to submicrometer dimensions.

Deposition of palladium nanoparticles on self-assembled, zinc-induced tubulin macrotubes and sheets.

Co-factors control the GTP-induced assembly of tubulin protein into a variety of superstructures with defined geometry at the nanometre scale: microtubules, macrotubes, sheets, or spirals/rings. We report the Zn2+ ion-induced assembly of tubulin protein into sheet-like or tubular structures. Free functional groups of amino acids on the surface of the protein biopolymer provide nucleation sites for further deposition of small metal nanoparticles. This study describes the synthesis of metal particle--protein hybrids by a two-step chemical process that directs metal nanoparticle nucleation at specific surface sites by applying these tubulin assemblies as biotemplates. The hybrids are characterized by transmission electron microscopy (TEM) and scanning force microscopy (SFM). The present study demonstrates the potential and general applicability of tubulin assemblies as tools for the nanofabrication of nanoparticle arrays exhibiting various geometries.

Exploring hydrothermally grown potassium titanate fibers by STEM-in-SEM/EDX and XRD.

During lab-scale experiments on the reforming of methanol by means of water at supercritical conditions (T > 374 degrees C, p > 22.1 MPa), a tubular reactor with a titanium liner was exposed to an aqueous solvent containing methanol (5 wt%) and KHCO3 (0.3 wt%). At the end of the run, a fibrous precipitate was found at two positions in the reactor. The material was studied in a field emission scanning electron microscope equipped with an energy dispersive X-ray analysis unit (FESEM/EDX). A thin-film support technique using carbon-filmed TEM grids was applied to perform scanning transmission-type imaging (STEM-in-SEM operation) and transmission current measurements. The analysis of the hydrothermally grown fibers resulted in a potassium titanate species composed of approximately K2TiO3, which has been confirmed by X-ray diffraction (XRD).

Synthesis of heterometallic bismuth/molydenum alkoxides and their behavior on silica surfaces.

The reaction of [(C(3)H(5))Mo(CO)(2)(CH(3)CN)(2)Cl], 2, with [Bi(OCH(2)CH(2)OCH(3))(3)](2) on a large scale leads to the novel molybdenum/bismuth alkoxide [(C(3)H(5))Mo(CO)(2)(mu-kappa O,2 kappa O'-OCH(2)CH(2)OCH(3))(2)(mu-kappa O-OCH(2)CH(2)OCH(3))BiCl], 6, as the main product as well as to [(C(3)H(5))Mo(CO)(2)(mu-kappa O,2 kappa O'-OCH(2)CH(2)OCH(3))(2)(mu-Cl)BiCl], 4, as a byproduct. Both compounds were characterized by elemental analysis, IR, and NMR spectroscopy as well as by X-ray diffraction. If 6 is brought into contact with a large excess of silica gel, aggregation and condensation reactions are initiated, which led to clusters of ca. 200 nm size spread over the silica surface. When the resulting material is calcinated at 350 degrees C in the presence of O(2), all organic ligands are eliminated and the metal oxo units rearrange: SEM/EDX measurements showed afterward Mo-free bismuth oxo clusters with sizes between 30 and 1000 nm, which are distributed together with molybdenum oxo particles of lower nuclearity over the silica surface. If such a material is employed as a potential catalyst for the propene oxidation under technical conditions, no activity is observed. If, however, the process is performed under very low pressures, a conversion of 5% is found. This result is discussed in the context of the mechanism proposed for the technical oxidation of propene to acrolein on bismuthmolybdate catalysts.