How elevated CO2 affects our nutrition in rice, and how we can deal with it.

Increased concentrations of atmospheric CO2 are predicted to reduce the content of essential elements such as protein, zinc, and iron in C3 grains and legumes, threatening the nutrition of billions of people in the next 50 years. However, this prediction has mostly been limited to grain crops, and moreover, we have little information about either the underlying mechanism or an effective intervention to mitigate these reductions. Here, we present a broader picture of the reductions in elemental content among crops grown under elevated CO2 concentration. By using a new approach, flow analysis of elements, we show that lower absorption and/or translocation to grains is a key factor underlying such elemental changes. On the basis of these findings, we propose two effective interventions-namely, growing C4 instead of C3 crops, and genetic improvements-to minimize the elemental changes in crops, and thereby avoid an impairment of human nutrition under conditions of elevated CO2.

The Christiansen effect of brightly colored colloidal dispersion with an amphiphilic polymer.

A novel coloration phenomenon in a colloidal dispersion with an amphiphilic polymer was found. The dispersion consists of tetrahydrofuran (THF), an aqueous solution of sodium thiosulfate (Na(2)S(2)O(3).5H(2)O), and hydroxypropylcellulose (HPC). The dispersion was emulsified by HPC as an amphiphilic polymer, so that the aqueous phase was confined in droplets in the THF matrix. It typically appeared bluish violet at room temperature and turned into blue with increasing temperature. In this system, the refractive indices of the inside and outside of the droplet coincided at a certain wavelength at which the light passes through without scattering, which is called the Christiansen effect. The color observed was successfully simulated by Mie's scattering theory in combination with the Christiansen effect.

Compression behavior of Langmuir-Blodgett monolayers of regioselectively substituted cellulose ethers with long alkyl side chains.

Regioselectively substituted alkylcellulose ethers having long alkyl side chains, 6-O- (6C18), 2,3-di-O- (23C18), and tri-O-octadecyl-cellulose (triC18) were successfully synthesized. The key step of these syntheses was removal of the residual alkylation reagent by an isothermal crystallization procedure to isolate and purify the compounds, since a physical entanglement between the long alkyl side chains in the cellulose derivatives and the reagent had caused difficulty in obtaining the purified derivatives. After the monolayers from these cellulose ethers were fabricated on a water surface, they were deposited on substrates by a vertical dipping method to be Langmuir-Blodgett (LB) monolayers. During the compression process of each monolayer, a surface pressure (pi)-area (A) isotherm behaved in a different way. Atomic force microscopy (AFM) was employed to interpret changes of the surface topography of the obtained LB monolayers depending on the surface pressure. The compressed 23C18 LB monolayer was observed to be more homogeneous than other samples. On the basis of the LB monolayer thickness estimated by AFM as well as X-ray reflection measurements, the 23C18 LB monolayer was assumed to possibly possess the vertical arrangement of an up-ordering of all the alkyl side chains on the individual glucose ring against the water surface. In other words, with increase in the surface pressure, the usual conformation of a 2(1) screw of cellulose backbone may be changed into an unusual conformation with a certain phi-psi dihedral angle resulting in 1-fold axis without a symmetry element. These results suggest that the formation of such compressed LB monolayers was strongly influenced by the hydrophobic interaction among the distribution of the long alkyl side chains in the anhydroglucose unit and further lack of inter- and/or intramolecular hydrogen bonds engaged in cellulose ethers, and as a result, those effects may even change the main chain conformation.

Novel tool for characterization of noncrystalline regions in cellulose: a FTIR deuteration monitoring and generalized two-dimensional correlation spectroscopy.

Our previous results indicated that noncrystalline regions in a regenerated cellulose film comprised at least three domains engaged in different manners of molecular assembly [Kondo et al. In Cellulose Derivatives; Heinze, T. J., Glasser, W. G., Eds.; ACS Symposium Series 688; American Chemical Society: Washington, DC, 1998; Chapter 12]. In this article, we attempt to characterize each of the three noncrystalline domains in the film. The method used was a FTIR monitoring of deuteration from hydroxyl (OH) groups to OD, leading to the two-dimensional (2D) correlation analysis. The time-scan spectra in the OH-OD exchanging reaction were transformed into two kinds of 2D correlation spectra, the synchronous and the asynchronous spectra. Of the two, some cross-peaks were found in the latter spectrum. This suggests that the asynchronous 2D correlation spectrum could differentiate the contribution of OH groups due to different frequencies of hydrogen bonds in each domain. Here we will show the validity of this 2D correlation method as a powerful tool to predict hydrogen-bonding networks of the noncrystalline domains in cellulose.

N-carboxy-L-aspartic anhydride benzyl ester.

The structure of the title compound, benzyl (1,2,3,4-tetrahydro-2,5-dioxo-1,3-oxazol-4-yl)acetate, C(12)H(11)NO(5), has been determined in an attempt to explain the polymerization observed in the solid state. The molecules are linked by intermolecular hydrogen bonds between the imino group of the five-membered ring and an adjacent carbonyl O atom, along the c axis. Intramolecular hydrogen bonds are also formed, between the imino group and the carbonyl O atom of the ester group. The five-membered rings are arranged in a layer, sandwiched by layers incorporating the benzyl groups. This structure is thought to be preferable for the polymerization of the compound in the solid state, because the five-membered rings can react with each other in the layer.

Rheology and dynamic light scattering of silk fibroin solution extracted from the middle division of Bombyx mori silkworm.

Dynamic light scattering (DLS) and rheological measurements were performed on aqueous silk fibroin solutions extracted from the middle division of Bombyx mori silkworm over a wide range of polymer concentration C from 0.08 to 27.5 wt %. DLS results obtained in the dilute region of C less than 1 wt % are consistent with a model that an elementary unit is a large protein complex consisting of silk fibroin and P25 with a 6:1 molar ratio. Rheological measurements in the dilute C region reveal that those units (or clusters) with the hydrodynamic radius of about 100 nm form a network extending over the whole sample volume with small pseudoplateau modulus mainly by ionic bonding between COO(-) ions of the fibroin molecules and divalent metallic ions such as Ca(2+) or Mg(2+) ions present in the sample and also that, after a yield stress is reached, steady plastic flow is induced with viscosity much lower than the zero-shear viscosity estimated from creep and creep recovery measurements by 4-6 orders of magnitude. Angular frequency omega dependencies of the storage and the loss shear moduli, G'(omega) and G' '(omega), measured in the linear viscoelastic region, indicate that all solutions possess the pseudoplateau modulus in the low omega region and samples become highly viscoleastic for C greater, similar 4.2 wt %. Above C = 11.2 wt % another plateau appears at the high omega end accompanied by a distinct maximum of G' ' in the intermediate omega region. The relaxation motion with tau = 0.5 s corresponding to the maximum of G' ' is one of characteristic properties of the fibroin solutions in the high C region. Thermorheological behaviors of the solution with C = 27.5 wt % show that the network structure formed in the MM part of the silk gland is susceptible to temperature and a more stable homogeneous network is realized by raising the temperature up to T = 65 degrees C.

Dynamic light scattering of native silk fibroin solution extracted from different parts of the middle division of the silk gland of the Bombyx mori silkworm.

Dynamic light scattering (DLS) measurements were performed on aqueous solutions of native silk fibroin extracted from three parts, the posterior (MP), the middle (MM), and the anterior parts (MA), of the middle division (M) of the silk gland of the Bombyx mori silkworm to study the dynamics and aggregation properties of silk fibroin. In the MP part, fibroin molecules are present as aggregates (or clusters) being composed of several large protein complexes or elementary unit (EU), which are further associated to make a large assembly connected via divalent metallic ions. In the MM part, such clusters of EU take more compact structure, and finally in the MA part, clusters disappear, but EUs are more or less aligned to keep the assembly, and the EU takes the conformation of wormlike cylinder capped with hemispheres at both ends. The overall conformational change in solution structure was interpreted as being due to the change in ionic environment in the solution. DLS study was also performed on regenerated silk fibroin solutions, which revealed that fibroin is present as a single molecule dominantly and their association behavior seems completely different from that of native samples and does not depend on types and concentration of added metallic ions.

Uptake of atmospheric carbon dioxide into silk fiber by silkworms.

The relation between the uptake of atmospheric CO(2) and insect's production of silk fiber has not yet been reported. Here, we provide the first quantitative demonstrations that four species of silkworms (Bombyx mori, Samia cynthia ricini, Antheraea pernyi, and Antheraea yamamai) and a silk-producing spider (Nephila clavata) incorporate atmospheric CO(2) into their silk fibers. The abundance of (13)C incorporated from the environment was determined by mass spectrometry and (13)C NMR measurements. Atmospheric CO(2) was incorporated into the silk fibers in the carbonyl groups of alanine, aspartic acid, serine, and glycine and the C(gamma) of aspartic acid. We show a simple model for the uptake of atmospheric CO(2) by silkworms. These results will demonstrate that silkworm has incorporated atmospheric CO(2) into silk fiber via the TCA cycle; however, the magnitude of uptake into the silk fibers is smaller than that consumed by the photosynthesis in trees and coral reefs.