Adobe Bricks of the Champagne Region (France): Characterization of a Chalky Raw Earth Construction Material.

Raw earth bricks made from the soil of the Chalky Champagne region (France) have been used for at least two millennia in construction, a promising heritage in the context of reducing the carbon emissions of buildings. The present experimental study aims to measure the physical, mechanical, thermal, and hydric properties of adobes collected from a local village barn. The results show a high chalk content, estimated at 71%, and a clay content, acting as a binder, of 14%. Despite limited load-bearing capacity, these lightweight adobes are suitable for current single-story constructions, while their hydrothermal properties classify them as excellent moisture regulators for occupants. In association with other bio-sourced materials such as starch-beet pulp bricks, Chalky Champagne adobes yield promising insulating properties, and meet the criteria defined by current energy standards.

Spent Coffee Grounds as Building Material for Non-Load-Bearing Structures.

The gradual development of government policies for ecological transition in the modern construction sector leads researchers to explore new alternative and low environmental impact materials with a particular focus on bio-sourced materials. In this perspective, the mechanical, thermal insulation, and the sound absorption performances of a spent coffee grounds/potato starch bio-based composite were analyzed for potential application in buildings. Based on thermal conductivity and diffusivity tests, the coffee grounds waste biocomposite was characterized as an insulating material comparable with conventional thermal insulation materials of plant origin. Acoustical tests revealed absorption coefficients in the same range as other conventional materials used in building acoustical comfort. This bio-sourced material presented a sufficient compressive mechanical behavior for non-load-bearing structures and a sufficient mechanical capacity to be shaped into building bricks. Mechanical, thermal, and acoustic performances depend on the moisture environment. The groundwork was laid for an initial reflection on how this composite would behave in two opposite climates: the continental climate of Reims in France and the tropical climate of Belém in Brazil.

Hygric Behavior of Viticulture By-Product Composites for Building Insulation.

One possible approach to reducing the environmental impacts associated with the building sector is the development and use of bio-based building materials. The objective of this study is to determine the water properties of bio-based insulation materials, derived from winegrowing co-products, which promote energy efficiency. The water performance of these new bio-based materials is based on the measurement of the moisture buffer value, the sorption isotherm, and the water vapor permeability. Four by-products are analyzed: stalks, grape pomace, crushed stalks, and skins; they are combined with a potato starch binder. The performance of these composites is compared to two other bio-based composites (hemp/starch and beet pulp/starch). The stalk/starch composite can be classified as a hygroscopic and breathable material with excellent moisture retention capacity.

Novel Extruded Starch-Beet Pulp Composites for Packaging Foams.

This article concerns the elaboration and the characterization of a novel biobased potato starch-beet pulp composite for packaging applications as cushion foams. A twin-screw extruder was used to elaborate composite foams. SEM observations of these materials were conducted, and thermomechanical properties were studied in terms of thermal transitions (TGA, DSC) and viscoelastic properties (DMA). The effect of relative humidity content on viscoelastic properties was analyzed as a function of frequency. The different test results show that the composite structures are homogeneously mixed. The sponge-like structure of the beet-pulp disappears indicating a good compatibility between the two mixed constituents. The DSC curve of starch-beet pulp foam shows a single thermal transition at 153.6 °C, indicating the thermal homogeneity of the obtained composite material. The density value of starch-beet pulp foam is higher than conventional foams, but this can be optimized by adjusting the technological parameters of the extruder. The viscoelastic properties of the developed materials depend on the relative humidity.

Chemical Modification of Plasticized Lignins Using Reactive Extrusion.

The reaction of esterification of plasticized Kraft lignin (KL) with succinic and maleic anhydrides using reactive extrusion (REX) was studied in detail. DMSO, glycol and glycerol were found to be efficient plasticizers for lignin. The chemical structure of these new lignin esters was determined using Solid-state 13C CP-MAS NMR and FT-IR analysis. 31P NMR analysis of phosphitylated lignins showed that the aliphatic OH groups of lignin had superior reactivity under the reactive extrusion reaction conditions. The formation of monoesters was confirmed by HSQC NMR spectroscopy. Molecular weight changes after extrusion process were studied using GPC/SEC chromatography. Thermal properties of these polymers were assessed by TGA analysis. The results were compared to lignin esters modified in classical batch conditions. These results show that REX can be used as a new fast, solvent free, and continuous process for lignin valorization.

Hygrothermal and Acoustical Performance of Starch-Beet Pulp Composites for Building Thermal Insulation.

This article deals with the elaboration and the characterization of an innovative 100% plant-based green composite made solely of beet pulp (BP) and potato starch (S). Using this type of material in insulation applications seems a good solution to reduce the CO2 gas emissions in building. The influence of the starch amount on composite characteristics was studied. Four mixtures were considered with different S/BP mass ratios (0.1, 0.2, 0.3 and 0.4). The physical properties of these materials were studied in terms of porosity, apparent and absolute densities, thermal conductivity, and hygric properties. The influence of humidity content on acoustical properties was studied as a function of frequency. Test results show a real impact of both starch and humidity contents on the hygrothermal and acoustical properties of the studied material due to the porosity. The composite with the lowest amount of starch (S/BP = 0.1) seems to be the optimal composition in terms of the hygrothermal and acoustical behaviors.

Starch carboxymethylation by reactive extrusion: Reaction kinetics and structure analysis.

An efficient reaction of carboxymethylation using reactive extrusion (REX) on plasticized starch was studied. The reaction products were characterized by Nuclear Magnetic Resonance (NMR) spectroscopy and high-performance liquid chromatography (HPLC). Several parameters affecting the reaction were investigated including the amount of plasticizer, reagent stoichiometry and reaction time. Reaction efficiency (RE) up to 65% was achieved in one step after 5 min of reaction, showing that the reaction kinetics is hundred times faster than the same reaction described in solution. The degree of substitution (DS) of 2.1 was obtained in 3 steps. The regioselectivity of the reaction on the anhydroglucose monomers units (AGU) was respectively C-2 > C-6 > C-3. A significant deviation from the Spurlin statistical model was observed. Multisubstituted AGU were analyzed by chromatography. Different multi-substitution patterns were obtained by using different starch sources. Tetra-carboxymethyl glucose corresponding to the complete modification of the terminal non-reducing glucoses from branched amylopectin chains was analysed.

Influence of chemically modified alginate esters on the preparation of microparticles by transacylation with protein in W/O emulsions.

Microencapsulation using the transacylation reaction in a W/O emulsion is based on the creation of amide bonds between the protein's amine functions and the ester groups of a polysaccharide in the aqueous phase after alkalization. Commercial propylene glycol alginate (PGA) has been the only modified polysaccharide involved in the process up to now. In the present work, we describe the effect of substituting the commercial PGA by other chemically modified alginates in the formation of microparticles. Alkyl and hydroxyalkyl alginate esters, were synthesized and tested in the encapsulation process with human serum albumin (HSA). It was found that the hydroxyalkyl alginates were suitable polysaccharide substitutes for PGA in the transacylation reaction, whereas the alkyl alginates did not lead to microparticle formation in the same process. Hydroxyalkyl alginates with high esterification degree (DE) (>50) led to microparticles when involved in the preparation procedure. However with lower DE (<30), no microparticles could be obtained from 2% ester solution concentrations. This difference in reactivity was explained by the formation of hydrophobic microdomains with the alkyl esters that hindered the transacylation reaction, as opposed to hydroxyalkyl esters that bore hydrophilic ester groups.

Selective ketopentose analysis in concentrate carbohydrate syrups by HPLC.

A new high performance liquid chromatographic (HPLC) method is described for the selective determination of small quantities of ketoses obtained by the action of immobilized isomerases on wheat bran hydrolysates, in the concentrated syrups of the corresponding glucose, arabinose, and xylose. This method uses MilliQ water instead of dilute sulfuric acid as a mobile phase on an Aminex HPX-87H column. Excellent discrimination between xylulose and ribulose was achieved. Selective detection of ketoses was made possible by the much higher UV absorbance at 210 nm. The sensitivity limit is 0.5 g/L for D-xylulose and L-ribulose. The response is linear up to a 20 g/L ketose concentration regardless of the presence of less than 50 g/L of D-xylose or L-arabinose.

Synthesis of pentose-containing disaccharides using a thermostable alpha-L-arabinofuranosidase.

To date, the enzymatically-catalysed synthesis of pentose-containing compounds has been limited to the production of oligo-beta-(1-->3) and oligo-beta-(1-->4)-linked xylopyranosides. To our knowledge, no such syntheses have involved arabinofuranose or, indeed, any other sugars in the furanose configuration. In this report, we describe the use of a thermostable alpha-L-arabinofuranosidase for the synthesis of p-nitrophenyl alpha-L-arabinofuranosyl-(1-->2)-alpha-L-arabinofuranoside, p-nitrophenyl beta-D-xylopyranosyl-(1-->2)-beta-D-xylopyranoside, p-nitrophenyl beta-D-xylopyranosyl-(1-->3)-beta-D-xylopyranoside and benzyl alpha-D-xylopyranosyl-(1-->2)-alpha-L-arabinofuranoside. Importantly, this latter compound is synthesised in a highly regiospecific reaction, which leads to the production of a single disaccharide.

Enzymatic degradation of hydroxypropyltrimethylammonium wheat starches.

The enzymatic degradation of hydroxypropyltrimethylammonium modified starches synthesised by dry process was compared with that of hydroxypropyltrimethylammonium modified starches synthesised in glycerol-water plasticised molten medium. The enzymatic degradation rate of products from both origins decreased as the degree of substitution increased. However, two distinct enzymatic degradation profiles were obtained. Dry process products displayed a regular decrease pattern as DS increased. Molten medium synthesised cationic starches displayed a constant degradation level on a wide DS range with alpha,beta-amylase and amyloglucosidase, whereas isoamylase degradation rapidly reached its degradation limit at DSs 0.05. The various plasticising conditions used to synthesise cationic starch in molten medium show no influence on the enzymatic degradation. By measuring the affinity of alpha-amylase, beta-amylase and isoamylase for native, extruded non-modified and hydroxypropyltrimethylammonium-modified starches. It was evident that the enzymes' affinity for the substrate diminishes with increasing chemical modification, particularly in the case of alpha-amylase, suggesting that the location of cationic groups impairs the enzyme's recognition of the substrate. Structural elements of limit dextrins were analysed by (1)H NMR.

Probing the catalytically essential residues of the alpha-L-arabinofuranosidase from Thermobacillus xylanilyticus.

The alpha-L-arabinofuranosidase D3 from Thermobacillus xylanilyticus is an arabinoxylan-debranching enzyme which belongs to family 51 of the glycosyl hydrolase classification. Previous studies have indicated that members of this family are retaining enzymes and may form part of the 4/7 superfamily of glycosyl hydrolases. To investigate the active site of alpha-L-arabinofuranosidase D3, we have used sequence alignment, site-directed mutagenesis and kinetic analyses. Likewise, we have shown that Glu(28), Glu(176) and Glu(298) are important for catalytic activity. Kinetic data obtained for the mutant Glu(176)-->Gln, combined with the results of chemical rescue using the mutant Glu(176)-->Ala, have shown that Glu(176) is the acid-base residue. Moreover, NMR analysis of the arabinosyl-azide adduct, which was produced by chemical rescue of the mutant Glu(176)-->Ala, indicated that alpha-L-arabinofuranosidase D3 hydrolyses glycosidic bonds with retention of the anomeric configuration. The results of similar chemical rescue studies using other mutant enzymes suggest that Glu(298) might be the catalytic nucleophile and that Glu(28) is a third member of a catalytic triad which may be responsible for modulating the ionization state of the acid-base and implicated in substrate fixation. Overall, these findings support the hypothesis that alpha-L-arabinofuranosidase D3 belongs to the 4/7 superfamily and provide the first experimental evidence concerning the catalytic apparatus of a family 51 arabinofuranosidase.

The endopolysaccharide metabolism of the hyperthermophilic archeon Thermococcus hydrothermalis: polymer structure and biosynthesis.

The endopolysaccharide accumulated by Thermococcus hydrothermalis was extracted and purified from a 4 h culture. It presented an "amylopectin-like" structure with an average chain length of 14 and a ramification degree of 7.5%. The glucosyltransferase was isolated, partially purified and characterized. The molecular mass was 42 kDa by SDS PAGE and 85 +/- 5 kDa by gel filtration. This enzyme was able to use both Uridine-5'-DiPhosphoGlucose (UDPG) and Adenosine-5'-DiPhosphoGlucose (ADPG) as substrates. Optimal pH and temperature for the enzyme were 5.5 and 80 degrees C, respectively. In the presence of 3.2 mM ADPG, the half life of the protein was 6 min at 110 degrees C. The apparent Km value with the two substrates was 0.9 mM, but the Vmax was 9.7 fold higher for ADPG. A branching activity was also detected at high temperature, up to 80 degrees C by different methods: phosphorylase stimulation, iodine, and branching linkage assays.