Nano-building block based-hybrid organic–inorganic copolymers with self-healing properties

New dynamic materials, that can repair themselves after strong damage, have been designed by hybridization of polymers with structurally well-defined nanobuilding units. The controlled design of cross-linked poly(n-butyl acrylate) (pBuA) has been performed by introducing a very low amount of a specific tin oxo-cluster. Sacrificial domains with non-covalent interactions (i.e. ionic bonds) developed at the hybrid interface play a double role. Such interactions are strong enough to cross-link the polymer, which consequently exhibits rubber-like elasticity behavior and labile enough to enable, after severe mechanical damage, dynamic bond recombination leading to an efficient healing process at room temperature. In agreement with the nature of the reversible links at the hybrid interface, the healing process can speed up considerably with temperature. 1H and 119Sn PFG NMR has been used to evidence the dynamic nature of these peculiar cross-linking nodes

“Chimie douce”: A land of opportunities for the designed construction of functional inorganic and hybrid organic-inorganic nanomaterials

Abstract“Chimie douce” based strategies allow, through the deep knowledge of materials chemistry and processing, the birth of the molecular engineering of nanomaterials. This feature article will highlight some of the main research accomplishments we have performed during the last years. We describe successively the design and properties of: sol–gel derived hybrids, Nano Building Blocks (NBBs) based hybrid materials, nanostructured porous materials proceeds as thin films and ultra-thin films, aerosol processed mesoporous powders and finally hierarchically structured materials. The importance of the control of the hybrid interfaces via the use of modern tools as DOSY NMR, SAXS, WAXS, Ellipsometry that are very useful to evaluate in situ the hybrid interfaces and the self-assembly processes is emphasized. Some examples of the optical, photocatalytic, electrochemical and mechanical properties of the resulting inorganic or hybrid nanomaterials are also presented

Transcriptional Analysis of Lactobacillus brevis to N-Butanol and Ferulic Acid Stress Responses

The presence of anti-microbial phenolic compounds, such as the model compound ferulic acid, in biomass hydrolysates pose significant challenges to the widespread use of biomass in conjunction with whole cell biocatalysis or fermentation. Currently, these inhibitory compounds must be removed through additional downstream processing or sufficiently diluted to create environments suitable for most industrially important microbial strains. Simultaneously, product toxicity must also be overcome to allow for efficient production of next generation biofuels such as n-butanol, isopropanol, and others from these low cost feedstocks.This study explores the high ferulic acid and n-butanol tolerance in Lactobacillus brevis, a lactic acid bacterium often found in fermentation processes, by global transcriptional response analysis. The transcriptional profile of L. brevis reveals that the presence of ferulic acid triggers the expression of currently uncharacterized membrane proteins, possibly in an effort to counteract ferulic acid induced changes in membrane fluidity and ion leakage. In contrast to the ferulic acid stress response, n-butanol challenges to growing cultures primarily induce genes within the fatty acid synthesis pathway and reduced the proportion of 19:1 cyclopropane fatty acid within the L. brevis membrane. Both inhibitors also triggered generalized stress responses. Separate attempts to alter flux through the Escherichia coli fatty acid synthesis by overexpressing acetyl-CoA carboxylase subunits and deleting cyclopropane fatty acid synthase (cfa) both failed to improve n-butanol tolerance in E. coli, indicating that additional components of the stress response are required to confer n-butanol resistance.Several promising routes for understanding both ferulic acid and n-butanol tolerance have been identified from L. brevis gene expression data. These insights may be used to guide further engineering of model industrial organisms to better tolerate both classes of inhibitors to enable facile production of biofuels from lignocellulosic biomass

Design of Hybrid Organic-Inorganic Nanocomposites Synthesized Via Sol-Gel Chemistry

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Luminescence properties of pHEMA-TiO2TiO_2 gels based hybrids materials

International audiencePhotoluminescence (PL) of photochromic pHEMA-TiO2 gels-based hybrids was studied by means of time- and energy-resolved spectroscopy at temperatures between 300 K and 10 K. The PL band at 485 nm is assigned to S0←T1 transition of methoxyphenol (organic molecule added to the commercial monomer hydroxyethyl methacrylate, HEMA and used as an inhibitor of spontaneous polymerisation) in the polymer environment, while the PL band at 600 nm is assigned to the self-trapped exciton onto octahedral TiO6 site of the inorganic component. The mechanisms of the excited states population are discussed. In particular it is shown that both singlet-triplet energy transfer in methoxyphenol and methoxyphenol–TiO2 charge transfer are strongly affected by the material composition and temperature. The hypothesis about the photoexcited holes annihilation with the trapped electrons is confirmed to be one of main mechanisms limiting the Ti3+ centres concentration