Temperature and Carbon Assimilation Regulate the Chlorosome Biogenesis in Green Sulfur Bacteria

Green photosynthetic bacteria adjust the structure and functionality of the chlorosome—the light-absorbing antenna complex—in response to environmental stress factors. The chlorosome is a natural self-assembled aggregate of bacteriochlorophyll (BChl) molecules. In this study, we report the regulation of the biogenesis of the Chlorobaculum tepidum chlorosome by carbon assimilation in conjunction with temperature changes. Our studies indicate that the carbon source and thermal stress culture of C. tepidum grows slower and incorporates fewer BChl c in the chlorosome. Compared with the chlorosome from other cultural conditions we investigated, the chlorosome from the carbon source and thermal stress culture displays (a) smaller cross-sectional radius and overall size, (b) simplified BChl c homologs with smaller side chains, (c) blue-shifted $Q_y$ absorption maxima, and (d) a sigmoid-shaped circular dichroism spectra. Using a theoretical model, we analyze how the observed spectral modifications can be associated with structural changes of BChl aggregates inside the chlorosome. Our report suggests a mechanism of metabolic regulation for chlorosome biogenesis.Chemistry and Chemical Biolog

Arabinose substitution effect on xylan rigidity and self-aggregation

Substituted xylans play an important role in the structure and mechanics of the primary cell wall of plants. Arabinoxylans (AX) consist of a xylose backbone substituted with arabinose, while glucuronoarabinoxylans (GAX) also contain glucuronic acid substitutions and ferulic acid esters on some of the arabinoses. We provide a molecular-level description on the dependence of xylan conformational, selfaggregation properties and binding to cellulose on the degree of arabinose substitution. Molecular dynamics simulations reveal fully solubilized xylans with a low degree of arabinose substitution (lsAX) to be stiffer than their highly substituted (hsAX) counterparts. Small-angle neutron scattering experiments indicate that both wild-type hsAX and debranched lsAX form macromolecular networks that are penetrated by water. In those networks, lsAX are more folded and entangled than hsAX chains. Increased conformational entropy upon network formation for hsAX contributes to AX loss of solubility upon debranching. Furthermore, simulations show the intermolecular contacts to cellulose are not affected by arabinose substitution (within the margin of error). Ferulic acid is the GAX moiety found here to bind to cellulose most strongly, suggesting it may play an anchoring role to strengthen GAX-cellulose interactions. The above results suggest highly substituted GAX acts as a spacer, keeping cellulose microfibrils apart, whereas low substitution GAX is more localized in plant cell walls and promotes cellulose bundling

Modification of the nanostructure of lignocellulose cell walls via a non-enzymatic lignocellulose deconstruction system in brown rot wood-decay fungi

Abstract Wood decayed by brown rot fungi and wood treated with the chelator-mediated Fenton (CMF) reaction, either alone or together with a cellulose enzyme cocktail, was analyzed by small angle neutron scattering (SANS), sum frequency generation (SFG) spectroscopy, Fourier transform infrared (FTIR) analysis, X-ray diffraction (XRD), atomic force microscopy (AFM), and transmission electron microscopy (TEM). Results showed that the CMF mechanism mimicked brown rot fungal attack for both holocellulose and lignin components of the wood. Crystalline cellulose and lignin were both depolymerized by the CMF reaction. Porosity of the softwood cell wall did not increase during CMF treatment, enzymes secreted by the fungi did not penetrate the decayed wood. The enzymes in the cellulose cocktail also did not appear to alter the effects of the CMF-treated wood relative to enhancing cell wall deconstruction. This suggests a rethinking of current brown rot decay models and supports a model where monomeric sugars and oligosaccharides diffuse from the softwood cell walls during non-enzymatic action. In this regard, the CMF mechanism should not be thought of as a “pretreatment” used to permit enzymatic penetration into softwood cell walls, but instead it enhances polysaccharide components diffusing to fungal enzymes located in wood cell lumen environments during decay. SANS and other data are consistent with a model for repolymerization and aggregation of at least some portion of the lignin within the cell wall, and this is supported by AFM and TEM data. The data suggest that new approaches for conversion of wood substrates to platform chemicals in biorefineries could be achieved using the CMF mechanism with >75% solubilization of lignocellulose, but that a more selective suite of enzymes and other downstream treatments may be required to work when using CMF deconstruction technology. Strategies to enhance polysaccharide release from lignocellulose substrates for enhanced enzymatic action and fermentation of the released fraction would also aid in the efficient recovery of the more uniform modified lignin fraction that the CMF reaction generates to enhance biorefinery profitability

X-ray studies of mixed surfactants at the hexane-water interface and thin aqueous films.

X-ray studies of mixed surfactants at the hexane-water interface and thin aqueous films

Nanostructural Changes Correlated to Decay Resistance of Chemically Modified Wood Fibers

Reactive chemical modifications have been shown to impart decay resistance to wood. These modifications change hydroxyl availability, water uptake, surface energy, and the nanostructure of wood. Because fungal action occurs on the micro and nano scale, further investigation into the nanostructure may lead to better strategies to prevent fungal decay. The aim of this article is to introduce our findings using small angle neutron scattering (SANS) to probe the effects of chemical modifications on the nanostructure of wood fibers. Southern pine wood fiber samples were chemically modified to various weight percentage gains (WPG) using propylene oxide (PO), butylene oxide (BO), or acetic anhydride (AA). After modification, the samples were water leached for two weeks to remove any unreacted reagents, homopolymers or by-products and then the equilibrium moisture content (EMC) was determined. Laboratory soil-block-decay evaluations against the brown rot fungus Gloeophyllum trabeum were performed to determine weight loss and decay resistance of the modifications. To assist in understanding the mechanism behind fungal decay resistance, SANS was used to study samples that were fully immersed in deuterium oxide (D2O). These measurements revealed that modifying the fibers led to differences in the swollen wood nanostructure compared to unmodified wood fibers. Moreover, the modifications led to differences in the nanoscale features observed in samples that were exposed to brown rot fungal attack compared to unmodified wood fibers and solid wood blocks modified with alkylene oxides

Nanostructural Changes Correlated to Decay Resistance of Chemically Modified Wood Fibers

Reactive chemical modifications have been shown to impart decay resistance to wood. These modifications change hydroxyl availability, water uptake, surface energy, and the nanostructure of wood. Because fungal action occurs on the micro and nano scale, further investigation into the nanostructure may lead to better strategies to prevent fungal decay. The aim of this article is to introduce our findings using small angle neutron scattering (SANS) to probe the effects of chemical modifications on the nanostructure of wood fibers. Southern pine wood fiber samples were chemically modified to various weight percentage gains (WPG) using propylene oxide (PO), butylene oxide (BO), or acetic anhydride (AA). After modification, the samples were water leached for two weeks to remove any unreacted reagents, homopolymers or by-products and then the equilibrium moisture content (EMC) was determined. Laboratory soil-block-decay evaluations against the brown rot fungus Gloeophyllum trabeum were performed to determine weight loss and decay resistance of the modifications. To assist in understanding the mechanism behind fungal decay resistance, SANS was used to study samples that were fully immersed in deuterium oxide (D2O). These measurements revealed that modifying the fibers led to differences in the swollen wood nanostructure compared to unmodified wood fibers. Moreover, the modifications led to differences in the nanoscale features observed in samples that were exposed to brown rot fungal attack compared to unmodified wood fibers and solid wood blocks modified with alkylene oxides

Designing Mixed Detergent Micelles for Uniform Neutron Contrast

Micelle-forming detergents provide an amphipathic environment that mimics lipid bilayers and are important tools used to solubilize and stabilize membrane proteins in solution for in vitro structural investigations. Small-angle neutron scattering (SANS) at the neutron contrast match point of detergent molecules allows observing the signal from membrane proteins unobstructed by contributions from the detergent. However, we show that even for a perfectly average-contrast matched detergent there arises significant core–shell scattering from the contrast difference between aliphatic detergent tails and hydrophilic head groups. This residual signal interferes with interpreting structural data of membrane proteins. This complication is often made worse by the presence of excess empty (protein-free) micelles. We present an approach for the rational design of mixed micelles containing a deuterated detergent analog, which eliminates neutron contrast between core and shell and allows the micelle scattering to be fully contrast-matched to unambiguously resolve membrane protein structure using solution SANS

Small Angle Neutron Scattering Shows Nanoscale PMMA Distribution in Transparent Wood Biocomposites

International audienceTransparent wood biocomposites based on PMMA combine high optical transmittance with excellent mechanical properties. One hypothesis is that despite poor miscibility the polymer is distributed at the nanoscale inside the cell wall. Smallangle neutron scattering (SANS) experiments are performed to test this hypothesis, using biocomposites based on deuterated PMMA and "contrast-matched" PMMA. The wood cell wall nanostructure soaked in heavy water is quantified in terms of the correlation distance d between the center of elementary cellulose fibrils. For wood/ deuterated PMMA, this distance d is very similar as for wood/ heavy water (correlation peaks at q ≈ 0.1 Å −1). The peak disappears when contrast-matched PMMA is used, indeed proving nanoscale polymer distribution in the cell wall. The specific processing method used for transparent wood explains the nanocomposite nature of the wood cell wall and can serve as a nanotechnology for cell wall impregnation of polymers in large wood biocomposite structures

Tension wood structure and morphology conducive for better enzymatic digestion

Abstract Background Tension wood is a type of reaction wood in response to bending or leaning stem as a corrective growth process. Tension wood is formed by both natural and man-made processes. Most attractively, tension wood contains higher glucan content and undergoes higher enzymatic conversion to fermentable sugars. Here, we have employed structural techniques, small-angle neutron scattering (SANS) and wide-angle X-ray diffraction (WAXD) to elucidate structural and morphological aspects of tension wood conducive to higher sugar yields. Results Small-angle neutron scattering data exhibited a tri-modal distribution of the fibril cross-sectional dimension. The smallest size, 22 Å observed in all samples concurred with the WAXD results of the control and opposite side samples. This smallest and the most abundant occurring size was interpreted as the cellulose elementary microfibril diameter. The intermediate size of 45 Å, which is most pronounced in the tension side sample and consistent with WAXD results for tension side sample, indicates association of neighboring elementary microfibrils to form larger crystallite bundles. The largest size 61 Å observed by SANS was however not observed by WAXD and therefore associated to mesopores. Conclusions Structure and morphology of tension wood is different from control wood. Cellulose crystallinity increases, lignin content is lower and the appearance of mesopores with 61 Å diameter is observed. Despite the presence of higher crystalline cellulose content in tension side, the lower lignin content and may be combined with the abundance of mesopores, substantially improves enzyme accessibility leading to higher yields in cellulose digestion