Effect of Air Velocity and Initial Conditioning on the Moisture Buffer Value of Four Different Building Materials.

Porous materials are able to exchange moisture with the surrounding air. The more hygroscopic they are, the more they contribute to regulate ambient humidity. This ability is characterized by the moisture buffer value (MBV) which is measured under dynamic solicitations according to different protocols. The NORDTEST protocol is the most commonly-used. It gives recommendations regarding the air velocity and the ambient conditions for initial stabilization. The purpose of this article is to measure the MBV according to the NORDTEST protocol and to study the effect of air velocity and of initial conditioning on the MBV results for different materials. Two mineral and two bio-based materials are considered: gypsum (GY), cellular concrete (CC), thermo-hemp (TH) and fine-hemp (FH). Following the NORDTEST classification, GY is a moderate hygric regulator, CC is good, TH and FH are excellent. When the air velocity ranges from 0.1 to 2.6 m/s, the MBV of GY and CC materials remains constant, but the MBV of TH and FH materials is highly affected. The initial conditioning has no effect on the MBV, but has an effect on the water content of the material, whatever the material.

Hygrothermal Behavior of a Washing Fines-Hemp Wall under French and Tunisian Summer Climates: Experimental and Numerical Approach.

This study experimentally and numerically investigates the hygrothermal behavior of a wall made of washing fines hemp composite under typical French and Tunisian summer climates. Actually, insulating bio-based building materials are designed in order to reduce energy and non-renewable resources consumptions. Once their multiphysical properties are characterized at material scale, it is necessary to investigate their behavior at wall scale. Washing fines hemp composite shows low thermal conductivity and high moisture buffer ability. The test wall is implemented as separating wall of a bi-climatic device, which allows simulating indoor and outdoor climates. The numerical simulations are performed with WUFI Pro 6.5 Software. The results are analyzed from the temperature, relative humidity and vapor pressure kinetics and profiles and from heat and moisture transfer and storage. The thermal conductive resistance calculated at the end of the stabilization phase is consistent with the theoretical one. The hygric resistance is consistent for simulation up to steady state. The dynamic phase under daily cyclic variation shows that for such cycles two thirds of the thickness of the wall on the exterior side are active. It also highlights sorption-desorption phenomena in the wall.

Hemp-Straw Composites: Gluing Study and Multi-Physical Characterizations.

In order to meet the requirement of sustainable development, building materials are increasingly environmentally friendly. They can be partially or fully bio-based or recycled. This paper looks at the development of fully bio-based composites where agro-resources are valued as bio-based aggregates (hemp) and as binding materials (wheat). In a previous work, a feasibility study simultaneously investigated the processing and ratio of wheat straw required to ensure a gluing effect. In this paper, three kinds of hemp-straw composites are selected and compared with a hemp-polysaccharides composite. The gluing effect is analyzed chemically and via SEM. The developed composites were characterized multi-physically. They showed sufficiently high mechanical properties to be used as insulating materials. Furthermore, they showed good thermal performances with a low thermal conductivity (67.9-69.0 mW/(m · K) at 23 ° C, dry).

Intermolecular C-H amination of complex molecules: insights into the factors governing the selectivity.

Transition-metal-catalyzed C-H amination via nitrene insertion allows the direct transformation of a C-H into a C-N bond. Given the ubiquity of C-H bonds in organic compounds, such a process raises the problem of regio- and chemoselectivity, a challenging goal even more difficult to tackle as the complexity of the substrate increases. Whereas excellent regiocontrol can be achieved by the use of an appropriate tether securing intramolecular addition of the nitrene, the intermolecular C-H amination remains much less predictable. This study aims at addressing this issue by capitalizing on an efficient stereoselective nitrene transfer involving the combination of a chiral aminating agent 1 with a chiral rhodium catalyst 2. Allylic C-H amination of terpenes and enol ethers occurs with excellent yields as well as with high regio-, chemo-, and diastereoselectivity as a result of the combination of steric and electronic factors. Conjugation of allylic C-H bonds with the π-bond would explain the chemoselectivity observed for cyclic substrates. Alkanes used in stoichiometric amounts are also efficiently functionalized with a net preference for tertiary equatorial C-H bonds. The selectivity, in this case, can be rationalized by steric and hyperconjugative effects. This study, therefore, provides useful information to better predict the site of C-H amination of complex molecules.

Catalytic C-H amination: the stereoselectivity issue.

Catalytic C-H amination has recently emerged as a unique tool for the synthesis of amines. This tutorial review highlights the existing protocols catalyzed by metal complexes (rhodium, copper, ruthenium, manganese and palladium) allowing diastereo- and enantioselective C-H amination. Substrate-, catalyst- and reagent-controlled methodologies are detailed. They involve either catalytic nitrene C-H insertion or C-H activation.

Studies in catalytic C-H amination involving nitrene C-H insertion.

Stereoselective catalytic intermolecular C-H amination of complex molecules is reported. Site-selective functionalizations occur with very good yields up to 91% and excellent d.e.s up to 99%. However, the precise nature of the nitrene C-H insertion remains a matter of debate despite several physical organic experiments.

Catalytic C-H amination: recent progress and future directions.

Recent developments in catalytic C-H amination are discussed in this feature article. The careful design of reagents and catalysts now provides efficient conditions for exquisitely selective intramolecular as well as intermolecular nitrene C-H insertion. The parallel emergence of C-H activation/amination reactions opens new opportunities complementary to those offered by nitrenes.

Stereoselective rhodium-catalyzed imination of sulfides.

The preparation of optically active sulfilimines via the catalytic diastereoselective imination of sulfides using a chiral nitrene is described. Excellent yields up to 97% and good diastereoselectivities up to 96% have been obtained. Oxidation of the sulfilimines then stereospecifically affords the corresponding sulfoximines with very good yields in the 88-96% range.

Toward a synthetically useful stereoselective C-H amination of hydrocarbons.

Reaction between a sulfur(VI) compound and an iodine(III) oxidant in the presence of a catalytic quantity (<=3 mol %) of a rhodium(II) catalyst leads to the formation of a chiral metallanitrene of unprecedented reactivity. The latter allows intermolecular C-H amination to proceed in very high yields up to 92% and excellent diastereoselectivities up to 99% with C-H bond containing starting materials as the limiting component. The scope of this C-H functionalization includes benzylic and allylic substrates as well as alkanes. Secondary positions react preferentially, but insertion into activated primary C-H bonds or sterically accessible tertiary sites is also possible. Cooperative effects between the nitrene precursor and the chiral catalyst at the origin of these good results have also been applied to kinetic resolution of racemic sulfonimidamide. This methodology paves the way to the use of Csp3-H bonds as synthetic precursors for the introduction of a nitrogen functionality into selected positions.