Microbial Biomanufacturing Using Chemically Synthesized Non-Natural Sugars as the Substrate.

The bioproduction of valuable materials using biomass sugars is attracting attention as an environmentally friendly technology. However, its ability to fulfil the enormous demand to produce fuels and chemical products is limited. With a view towards the future development of a novel bioproduction process that addresses these concerns, this study investigated the feasibility of bioproduction of valuable substances using Corynebacterium glutamicum (C. glutamicum) with a chemically synthesized non-natural sugar solution. Cells were grown using the synthesized sugar solution as the sole carbon source and they produced lactate under oxygen-limited conditions. It was also found that some of the sugars produced by the series of chemical reactions inhibited cell growth since prior removal of these sugars increased the cell growth rate. The results obtained in this study indicate that chemically synthesized sugars have the potential to resolve the concerns regarding future biomass sugar supply in microbial biomanufacturing.

Construction of an autocatalytic reaction cycle in neutral medium for synthesis of life-sustaining sugars.

Autocatalytic mechanisms in carbon metabolism, such as the Calvin cycle, are responsible for the biological assimilation of CO2 to form organic compounds with complex structures, including sugars. Compounds that form C-C bonds with CO2 are regenerated in these autocatalytic reaction cycles, and the products are concurrently released. The formose reaction in basic aqueous solution has attracted attention as a nonbiological reaction involving an autocatalytic reaction cycle that non-enzymatically synthesizes sugars from the C1 compound formaldehyde. However, formaldehyde and sugars, which are the substrate and products of the formose reaction, respectively, are consumed in Cannizzaro reactions, particularly under basic aqueous conditions, which makes the formose reaction a fragile sugar-production system. Here, we constructed an autocatalytic reaction cycle for sugar synthesis under neutral conditions. We focused on the weak Brønsted basicity of oxometalate anions such as tungstates and molybdates as catalysts, thereby enabling the aldol reaction, retro-aldol reaction, and aldose-ketose transformation, which collectively constitute the autocatalytic reaction cycle. These bases acted on sugar molecules of substrates together with sodium ions of a Lewis acid to promote deprotonation under neutral conditions, which is the initiation step of the reactions forming an autocatalytic cycle, whereas the Cannizzaro reaction was inhibited. The autocatalytic reaction cycle established using this abiotic approach is a robust sugar production system. Furthermore, we found that the synthesized sugars work as energy storage substances that sustain microbial growth despite their absence in nature.

Structural Polymorphism of Resorcinarene Assemblies.

In 1997, a study based on X-ray crystallography revealed that resorcinarenes adopt a hexameric capsule-like structure. The function of resorcinarenes has been discussed on the basis of this structure; however, our recent study showed that the hexamer may be only one of resorcinarenes' polymorphic members. Here, we present the solvent dependence of the aggregation number of C-undecylresorcinarene in water-saturated toluene and chloroform using small-angle neutron and X-ray scattering and analytical ultracentrifugation measurements. We found that a new octamer was formed in toluene where the eight resorcinarene units were placed at the vertices of a regular cube; this contrasts to the previous structure in chloroform, namely, a hexamer with the six resorcinarenes located at the vertices of a regular octahedron that has a cavity inside where chloroform molecules are pooled.

Paramagnetic One-Dimensional Chain Complex Consisting of Three Kinds of Metallic Species Showing Magnetic Interaction through Metal-Metal Bonds.

A heterometallic and paramagnetic one-dimensional (1-D) chain (3) aligned as -Rh(+2)-Rh(+2)-Pt(+2)-Co(+2)-Pt(+2)- with direct metal-metal bonds was obtained by HOMO-LUMO interactions at the σ* (dz2) orbital between two kinds of complexes. The 1-D chains in 3 have relatively straight backbones because the raw material complexes, [Rh2(O2CCH3)4] and [Pt2Co(piam)4(NH3)4], are connected and stacked in a face-to-face fashion, where Co---Co are separated by about 13.3 Å with four different metals. Physical measurements revealed that 3 has a band gap between the σ-type conduction and valence bands, where d-orbitals of the Co ion with three unpaired electrons are laid among them. The magnetic behavior of 3 was investigated and found to be consistent with a complex interaction involving both zero-field splitting and Pauli paramagnetism attributed to band formation superimposed on relatively strong exchange coupling (zJ = -22.2 cm-1) between two high-spin Co(+2) ions separated by the diamagnetic Pt-Rh-Rh-Pt.

Dual and multiple stimuli-responsive platonic micelles bearing disaccharides.

We recently identified completely monodisperse micelles whose aggregation number (Nagg) coincides with the vertex number of regular polyhedra, named Platonic micelles. The combination of both the micellar properties and controlling their structures by external stimuli could be promising for producing precisely controlled self-assembled structures. From this perspective, we newly synthesized a calix[4]arene-based amphiphile bearing disaccharides, cellobioses. The crowded and bulky structure in the hydrophilic group could provide a novel stimuli-responsiveness of disaccharides in amphiphiles. The aggregation behavior such as the morphologies and the aggregation number of the calix[4]arene-based micelle was characterized using small angle scattering techniques and analytical ultracentrifugation measurements. Owing to hydrogen bonding among the disaccharide, the head volume became smaller than expected, resulting in the formation of cylindrical ones. However, cleaving the hydrogen bond by controlling temperature or pH induced morphological transition of the micellar structure from cylindrical to spherical. The dual-stimuli (temperature and pH) generated smaller micelles with Nagg of 12. Interestingly, when the amphiphile formed spherical micelles at various conditions, the Nagg matched the Platonic number, and the change of Nagg in response to the external stimuli was non-continuous, which is consistent with the concept of Platonic micelles.

Platonic Micelles: Monodisperse Micelles with Discrete Aggregation Numbers Corresponding to Regular Polyhedra.

The concept of micelles was first proposed in 1913 by McBain and has rationalized numerous experimental results of the self-aggregation of surfactants. It is generally agreed that the aggregation number (Nagg) for spherical micelles has no exact value and a certain distribution. However, our studies of calix[4]arene surfactants showed that they were monodisperse with a defined Nagg whose values are chosen from 6, 8, 12, 20, and 32. Interestingly, some of these numbers coincide with the face numbers of Platonic solids, thus we named them "Platonic micelles". The preferred Nagg values were explained in relation to the mathematical Tammes problem: how to obtain the best coverage of a sphere surface with multiple identical circles. The coverage ratio D(N) can be calculated and produces maxima at N = 6, 12, 20, and 32, coinciding with the observed Nagg values. We presume that this "Platonic nature" may hold for any spherical micelles when Nagg is sufficiently small.