Regiospecific Grafting of Chitosan Oligomers Brushes onto Silicon Wafers.

The functionalization of surfaces using chitosan oligomers is of great interest for a wide range of applications in biomaterial and biomedical fields, as chitosan oligomers can provide various functional properties including biocompatibility, wetting, adhesion, and antibacterial activity. In this study, an innovative process for the regiospecific chemical grafting of reducing-end-modified chitosan oligomers brushes onto silicon wafers is described. Chitosan oligomers (COS) with well-defined structural parameters (average DP ~19 and DA ~0%) and bearing a 2,5-anhydro-d-mannofuranose (amf) unit at the reducing end were obtained via nitrous acid depolymerization of chitosan. After a silanization step where silicon wafers were modified with aromatic amine derivatives, grafting conditions were studied to optimize the reductive amination between aldehydes of amf-terminated COS and aromatic amines of silicon wafers. Functionalized surfaces were fully characterized by AFM, ATR-FTIR, ellipsometry, contact angle measurement, and ToF-SIMS techniques. Smooth surfaces were obtained with a COS layer about 3 nm thick and contact angle values between 72° and 76°. Furthermore, it was shown that the addition of the reducing agent NaBH3CN could positively improve the COS grafting density and/or led to a better stability of the covalent grafting to hydrolysis. Finally, this study also showed that this grafting process is also efficient for chitosan oligomers of higher DA (i.e., ~21%).

Exploring the benefits of surface analysis techniques to develop double multilayer transfer printing of J-Aggregates cyanine dyes by integrating L-b-L and µCp processes.

Layer-by-layer self-assembly (L-b-L assembly) makes possible to obtain polyelectrolyte multilayers (PEMs) and one of the polyelectrolytes could be replaced by a dye molecule to obtain multilayers which may exhibit optical properties of great interest. On the other hand, µCp has become a routine technique for the preparation of micro- and nanostructured surfaces. In our development in progress of a surface engineering strategy to transfer J-Agg cyanine dyes onto surfaces by integrating L-b-L process and µCp, this contribution highlights how surface analysis imaging techniques can bring valuable information for the development of the process involving a double Multilayers Transfer Printing (MTP) with a Moiré effect. Key parameters sustaining image interpretation are difference in deposit thickness (optical microscopy, atomic force microscopy, scanning electron microscopy), in roughness (atomic force microscopy and scanning electron microscopy), in charge effect (scanning electron microscopy) and the chemical contrast between unprinted and printed areas (time-of-flight secondary ion mass spectrometry).

Cleaner degreasing of sheepskins by the Yarrowia lipolytica LIP2 lipase as a chemical-free alternative in the leather industry.

Conventional degreasing of skins and hides in the leather industry requires high amounts of organic solvents and detergents that cause environmental issues. In this study, the LIP2 lipase from the yeast Yarrowia lipolytica (YLLIP2) was shown to be effective in degreasing sheepskins, thus reducing the amount of harmful chemicals. Using 6 mg of lipase/kg of raw skin, successful degreasing was achieved in only 15 min at pH 8 and 30°C. ToF-SIMS mass spectra of chemically and enzymatically treated sheepskins are consistent with a selective elimination process for the enzymatic treatment. Comparative SEM microscopy, ATR-FTIR spectroscopy and physicochemical analyses showed better properties of the enzymatically treated leather than those of the chemical treatment. Effluent physicochemical parameters showed that the enzymatic treatment is a cleaner degreasing operation. Altogether, this work opens new horizons to use the YLLIP2 lipase as a more efficient alternative in the leather industry.

Hydrogen Production at a NiO Photocathode Based on a Ruthenium Dye-Cobalt Diimine Dioxime Catalyst Assembly: Insights from Advanced Spectroscopy and Post-operando Characterization.

The production of hydrogen by efficient, low-cost, and integrated photoelectrochemical water splitting processes represents an important target for the ecological transition. This challenge can be addressed thanks to bioinspired chemistry and artificial photosynthesis approaches by designing dye-sensitized photocathodes for hydrogen production, incorporating bioinspired first-row transition metal-based catalysts. The present work describes the preparation and photoelectrochemical characterization of a NiO photocathode sensitized with a phosphonate-derivatized ruthenium tris-diimine photosensitizer covalently linked to a cobalt diimine dioxime hydrogen-evolving catalyst. Under simulated AM 1.5G irradiation, hydrogen is produced with photocurrent densities reaching 84 ± 7 µA·cm-2, which is among the highest values reported so far for dye-sensitized photocathodes with surface-immobilized catalysts. Thanks to the unique combination of advanced spectroscopy and surface characterization techniques, the fast desorption of the dyad from the NiO electrode and the low yield of electron transfer to the catalyst, resulting in the Co demetallation from the diimine dioxime framework, were identified as the main barriers limiting the performances and the stability of the system. This work therefore paves the way for a more rational design of molecular photocathodes for solar fuel production and represents a further step toward the development of sustainable processes for the production of hydrogen from sunlight and water.

Cellulose phosphorylation comparison and analysis of phosphorate position on cellulose fibers.

Chemical modifications of cellulose fibers as pretreatment for cellulose nanofibrils (CNF) production have been investigated to improve the production process and the quality of obtained cellulosic nanomaterial. In this study, phosphorylation of cellulose fibers was done in anticipation of a future nanofibrillation. Different phosphate salts, namely NH4H2PO4, (NH4)2HPO4, Na2HPO4, NaH2PO4 and LiH2PO4 with different constants of solubility (Ks) were used to increase the efficiency of the modification. Phosphorylated cellulose pulps were analyzed using elemental analysis, solid-state 13C and 31P NMR, or conductimetric titration method. No effect of Ks was observed whereas a counterion effect was pointed out. The study also reported the effect of pH, cellulose consistency, temperature and urea content in phosphorylation efficiency. Finally, chemical functionalization and penetration of phosphorylation reagents in the cellulose fibers were evaluated using XPS, SEM-EDX, ToF-SIMS and solid-state NMR.

Insights into the mechanism and aging of a noble-metal free H2-evolving dye-sensitized photocathode.

Dye-sensitized photo-electrochemical cells (DS-PECs) form an emerging technology for the large-scale storage of solar energy in the form of (solar) fuels because of the low cost and ease of processing of their constitutive photoelectrode materials. Preparing such molecular photocathodes requires a well-controlled co-immobilization of molecular dyes and catalysts onto transparent semiconducting materials. Here we used a series of surface analysis techniques to describe the molecular assembly of a push-pull organic dye and a cobalt diimine-dioxime catalyst co-grafted on a p-type NiO electrode substrate. (Photo)electrochemical measurements allowed characterization of electron transfer processes within such an assembly and to demonstrate for the first time that a CoI species is formed as the entry into the light-driven H2 evolution mechanism of a dye-sensitized photocathode. This co-grafted noble-metal free H2-evolving photocathode architecture displays similar performances to its covalent dye-catalyst counterpart based on the same catalytic moiety. Post-operando time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis of these photoelectrodes after extensive photoelectrochemical operation suggested decomposition pathways of the dye and triazole linkage used to graft the catalyst onto NiO, providing grounds for the design of optimized molecular DS-PEC components with increased robustness upon turnover.

Aqueous Photocurrent Measurements Correlated to Ultrafast Electron Transfer Dynamics at Ruthenium Tris Diimine-Sensitized NiO Photocathodes.

Understanding the structural and electronic factors governing the efficiency of dye-sensitized NiO photocathodes is essential to optimize solar fuel production in photoelectrochemical cells (PECs). For these purpose, three different ruthenium dyes, bearing either two or four methylphosphonate anchoring groups and either a bipyridine or a dipyridophenazine ancillary ligand, were synthesized and grafted onto NiO films. These photoelectrodes were fully characterized by XPS, ToF-SIMS, UV-vis absorption, time-resolved emission and femtosecond transient absorption spectroscopies. Increasing the number of anchoring groups from two to four proved beneficial for the grafting efficiency. No significant modification of the electronic properties compared to the parent photosensitizer was observed, in accordance with the non-conjugated nature of the grafted linker. The photoelectrochemical activity of the dye-sensitized NiO electrodes was assessed in fully aqueous medium in the presence of an irreversible electron acceptor and photocurrents reaching 190 µA.cm-2 were recorded. The transient absorption study revealed the presence of two charge recombination pathways for each of the sensitizers and evidenced a stabilized charge separated state in the dppz derivative, supporting its superior photoelectrochemical activity.