Impact of graphene oxide lateral dimensions on the properties of methacrylated gelatin nanocomposite hydrogels.

The size and shape of nanoparticles have a profound effect on the properties of nanocomposites. For instance, the lateral dimensions of graphene oxide (GO) platelets affect several properties, including their antibacterial and pharmacokinetic functions. However, the impact of lateral dimensions has been poorly studied in nanocomposites, and their effect on hydrogels is still unknown. The current study aims to determine the effect of GO lateral dimensions on the mechanical, rheological, thermal, and antibacterial properties of gelatin hydrogels. The hydrogels were fabricated via photopolymerization of methacrylated gelatin and GO derived from the oxidation of commercial graphene. The observations indicate that an increase in GO sheets improves the mechanical strength with an increase in compressive modulus and a low mechanical hysteresis (<10%). Furthermore, low mechanical energy is dissipated even after several deformation cycles. The nanocomposite hydrogels demonstrated bactericidal effects on two clinical strains with an extensively drug-resistant phenotype, primarily through contact. Additionally, an increment in lateral dimensions increased the bactericidal capacity of Gram-negative strains. Thus, the significant effect of the lateral dimensions of GO sheets on the properties of hydrogels is demonstrated.

Xanthurenic Acid in the Shell Purple Patterns of Crassostrea gigas: First Evidence of an Ommochrome Metabolite in a Mollusk Shell.

Ommochromes are one of the least studied groups of natural pigments, frequently confused with melanin and, so far, exclusively found in invertebrates such as cephalopods and butterflies. In this study focused on the purple color of the shells of a mollusk, Crassostrea gigas, the first evidence of a metabolite of ommochromes, xanthurenic acid (XA), was obtained by liquid chromatography combined with mass spectrometry (UPLC-MS). In addition to XA and various porphyrins previously identified, a second group of high molecular weight acid-soluble pigments (HMASP) has been identified with physicochemical and structural characteristics similar to those of ommochromes. In addition, fragmentation of HMASP by tandem mass spectrometry (MS/MS) has revealed a substructure common to XA and ommochromes of the ommatin type. Furthermore, the presence of melanins was excluded by the absence of characteristic by-products among the oxidation residues of HMASP. Altogether, these results show that the purple color of the shells of Crassostrea gigas is a complex association of porphyrins and ommochromes of potentially ommatin or ommin type.

Nanocellulose-derived carbon/g-C3N4 heterojunction with a hybrid electron transfer pathway for highly photocatalytic hydrogen peroxide production.

Using oxygen reduction for the photocatalytic production of hydrogen peroxide (H2O2) has been considered a green and sustainable route. In the present study, to achieve high efficiency, graphitic carbon nitride (g-C3N4) was obtained using thermal polymerization from a bi-component precursor and was then assembled with cellulose nanofibers. It was found that a small quantity of cellulose nanofibers that generates carbon fibers upon pyrolysis greatly improves the photocatalytic activity compared with that of g-C3N4 alone. The well-defined carbon/g-C3N4 heterojunction-type material exhibits as high as 1.10 mmol L-1h-1 of photo-production of H2O2 under visible light, which is 4.2 times higher than that yielded by pristine g-C3N4 from a single precursor. A comprehensive characterization of the photocatalyst enables us to delineate the effect of the carbon nanofiber with respect to porosity, electron-hole separation, band gap regulation, and especially the electron transfer pathway. Our results demonstrate that nanocellulose-derived carbon, when precisely assembled with other functional material such as a photocatalyst, is a promising promoter of their activity.

TinO2n-1 Suboxide Phases in TiO2/C Nanocomposites Engineered by Non-hydrolytic Sol-Gel with Enhanced Electrocatalytic Properties.

We report a non-hydrolytic sol-gel (NHSG) route to engineer original mesoporous TinO2n-1@TiO2/C nanocomposites. The synthetic approach is straightforward, solvent-free, additive-free, and meets the challenge of atom economy, as it merely involves TiCl4 and THF in stoichiometric amounts. We found that these nanocomposites present enhanced electrocatalytic properties towards the oxygen reduction reaction (ORR) in 0.1 M KOH. We believe that these preliminary results will open a window of opportunity for the design of metal suboxides/carbon nanocomposites through NHSG routes.

Glycerol-plasticized agarose separator suppressing dendritic growth in Li metal battery.

The growth of dendrite is the major limitation to the development of the Li-metal battery. To solve it, we disclose the preparation and performances of separator (MAGly) with a complete "green" formulation using biosourced and sustainable compounds: agarose as biopolymer along with glycerol as plasticizing agent. The natural biopolymer films are non-porous in nature and possess high elasticity with high stiffness along a wide temperature range (-35 to 180 °C), able to prevent the perpendicular dendritic Li growth. Moreover, they provide high Li+ ionic conductivity, which was evident from electrochemical symmetrical battery tests resulted in efficient plating/stripping of Li metal, without dendrite formation. Preliminary tests in Li battery, with LiFePO4 as positive electrode show very satisfying performance regarding the same test with the commercial Celgard® separator. Furthermore, the application of this new sustainable separator can be extended to post Li-metal system as demonstrated by the electrochemical tests realized with K+/K.

Chemical evidence of rare porphyrins in purple shells of Crassostrea gigas oyster.

The colour of oyster shells is a very diverse characteristic morphotype, forming intriguing vivid patterns both on the inside and outside of the shell. In the present study, we have identified for the first time, the presence of several porphyrins as constituents of the shell pigmentation of the Crassostrea gigas oyster consumed worldwide. The precise molecular structures of halochromic, fluorescent and acid-soluble porphyrins, such as uroporphyrin and turacin, are unambiguously determined by reverse phase liquid chromatography combined with high resolution mass spectrometry. Their presence account for the purple colouration of shells but also for the dark colouration of adductor muscle scars. We have also defined the endogenous origin of these porphyrins, specifically secreted or accumulated by the shell forming tissue. These findings are pioneering analytical proofs of the existence of the haem pathway in the edible oyster Crassostrea gigas, evidenced by the chemical identification of haem side-products and supported by the recent publication of the corresponding oyster genome.

C-nanocoated ZnO by TEMPO-oxidized cellulose templating for improved photocatalytic performance.

Ultrafine C-doped ZnO/carbon nanocomposites with different photocatalytic activities have been prepared using TEMPO-oxidized cellulose as a template but also as the source of carbon. The result is an enhancement of the photocatalytic activity ascribed to different phenomena: a high mesoporosity beneficial to mass transport, a thin carbon layer onto ZnO increasing the charge transfer and hydrophobicity of ZnO, a narrowing of ZnO band gap and an increase of the zinc (VZn) and oxygen (Vo) vacancies effectively suppressing of the charge recombination. These are evidenced by photocatalytic test of photodegradation of methyl orange (MO) achieved to assess and compared the different photocatalysts. The highest rate constant value of photodegradation of MO is 0.0254 min-1, three times higher than that of ZnO prepared without templates (0.0087 min-1). The present results introduce a new vision of the use of template with multiple roles in the preparation of inorganic materials and specially photocatalysts.

Key Insights, Tools, and Future Prospects on Oyster Shell End-of-Life: A Critical Analysis of Sustainable Solutions.

Oyster farming represents one of the most developed aquaculture activities, producing delicacies unfortunately related to a direct accumulation of waste shells. Facing what is becoming an environmental issue, chemists are currently developing solutions to add value to this wild source of raw material in line with the principles of sustainable chemistry. An argumentative overview of this question is proposed here with a focus on recent data. Starting with a presentation of the environmental impact of oyster farming, existing and promising applications are then classified according to the type of raw materials derived from the oyster shell, namely the natural oyster shell (NOS), the calcined natural oyster shell (CNOS), and biomolecules of the organic matrix extracted from the oyster shell. Their relevance is discussed in regard to their scalability, originality, and sustainability. This review constitutes the first critical compilation on oyster shell applications, with the aim to provide essential elements to better comprehend the recycling of waste oyster shells.

Dehydration of Alginic Acid Cryogel by TiCl4 vapor: Direct Access to Mesoporous TiO2 @C Nanocomposites and Their Performance in Lithium-Ion Batteries.

A new strategy for the synthesis of mesoporous TiO2 @C nanocomposites through the direct mineralization of seaweed-derived alginic acid cryogel by TiCl4 through a solid/vapor reaction pathway is presented. In this synthesis, alginic acid cryogel can have multiple roles; i) mesoporous template, ii) carbon source, and iii) oxygen source for the TiO2 precursor, TiCl4 . The resulting TiO2 @alginic acid composite was transformed either into pure mesoporous TiO2 by calcination or into mesoporous TiO2 @C nanocomposites by pyrolysis. By comparing with a nonporous TiO2 @C composite, the importance of the mesopores on the performance of electrodes for lithium-ion batteries based on mesoporous TiO2 @C composite was clearly evidenced. In addition, the carbon matrix in the mesoporous TiO2 @C nanocomposite also showed electrochemical activity versus lithium ions, providing twice the capacity of pure mesoporous TiO2 or alginic acid-derived mesoporous carbon (A600). Given the simplicity and environmental friendliness of the process, the mesoporous TiO2 @C nanocomposite could satisfy the main prerequisites of green and sustainable chemistry while showing improved electrochemical performance as a negative electrode for lithium-ion batteries.

Ethers as Oxygen Donor and Carbon Source in Non-hydrolytic Sol-Gel: One-Pot, Atom-Economic Synthesis of Mesoporous TiO2 -Carbon Nanocomposites.

Mesoporous TiO2 -carbon nanocomposites were synthesized using an original non-hydrolytic sol-gel (NHSG) route, based on the reaction of simple ethers (diisopropyl ether or tetrahydrofuran) with titanium tetrachloride. In this atom-economic, solvent-free process, the ether acts not only as an oxygen donor but also as the sole carbon source. Increasing the reaction temperature to 180 °C leads to the decomposition of the alkyl chloride by-product and to the formation of hydrocarbon polymers, which are converted to carbon by pyrolysis under argon. The carbon-TiO2 nanocomposites and their TiO2 counterparts (obtained by calcination) were characterized by nitrogen physisorption, XRD, solid state 13 C NMR and Raman spectroscopies, SEM, and TEM. The nanocomposites are mesoporous with surface areas of up to 75 m2 g-1 and pore sizes around 10 nm. They are composed of aggregated anatase nanocrystals coated by an amorphous carbon film. Playing on the nature of the ether and on the reaction temperature allows control over the carbon content in the nanocomposites. The nature of the ether also influences the size of the TiO2 crystallites and the morphology of the nanocomposite. To further characterize the carbon coating, the behavior of the carbon-TiO2 nanocomposites and bare TiO2 samples toward lithium insertion-deinsertion was investigated in half-cells. This simple NHSG approach should provide a general method for the synthesis of a wide range of carbon-metal oxide nanocomposites.

Alginic acid aquagel as a template and carbon source in the synthesis of Li4Ti5O12/C nanocomposites for application as anodes in Li-ion batteries.

We report here a simple process for the synthesis of Li4Ti5O12(LTO)/carbon nanocomposites by a one-pot method using an alginic acid aquagel as a template and carbon source, and lithium acetate and TiO2 nanoparticles as precursors to the LTO phase. The carbon content can be tuned by adjusting the relative amount of alginic acid. The obtained materials consist of nanosized primary particles of LTO (30 nm) forming micron-sized aggregates covered by well-dispersed carbon (from 3 to 19 wt%). The homogeneous dispersion of carbon over the particles improves the electrochemical performance of LTO electrodes such as rate capability (>95 mA h g-1 at 40C) and cycling performance (>98% of retention after 500 cycles at 5C), even with only 3% of carbon black additive in the electrode formulation. With a simple and easily up-scalable synthesis, the LTO/carbon nanocomposites of this study are promising candidates as anode materials for practical application in lithium-ion batteries.

Reductive mineralization of cellulose with vanadium, iron and tungsten chlorides and access to MxOy metal oxides and MxOy/C metal oxide/carbon composites.

MxOy and MxOy/C composites (M=V, Fe and W) were obtained by mineralization of cellulose with several metal chlorides. Cellulose was used both as a templating agent and as an oxygen and a carbon source. Soluble chloride molecules (VOCl3 and WCl6) and a poorly soluble ionic chloride compound (FeCl3) were chosen as metal oxide precursors. In a first time, primary metal oxide/cellulose composites were obtained via a thermal treatment by reacting urea impregnated filter paper with the corresponding metal chlorides in an autoclave at 150°C after 3days. After either pyrolysis or calcination steps of these intermediate materials, interesting metal oxides with various morphologies were obtained (V2O5, V2O3, Fe3O4, WO3, H0.23WO3), composites (V2O3/C) as well as carbides (hexagonal W2C and WC, Fe3C) This result highlight the reductive role that can play cellulose during the pyrolysis step that allows to tune the composition of MxOy/C composites. The materials were characterized by FTIR, Raman, TGA, XRD and SEM. This study highlights that cellulose can be used for a convenient preparation of a variety of highly demanded MxOy and MxOy/C composites with original shapes and morphologies.

The Reductive Dehydration of Cellulose by Solid/Gas Reaction with TiCl4 at Low Temperature: A Cheap, Simple, and Green Process for Preparing Anatase Nanoplates and TiO2 /C Composites.

Metal oxides and metal oxide/carbon composites are entering the development of new technologies and should therefore to be prepared by sustainable chemistry processes. Therefore, a new aspect of the reactivity of cellulose is presented through its solid/gas reaction with vapour of titanium(IV) chloride in anhydrous conditions at low temperature (80 °C). This reaction leads to two transformations both for cellulose and titanium(IV) chloride. A reductive dehydration of cellulose is seen at the lowest temperature ever reported and results in the formation of a carbonaceous fibrous solid as the only carbon-containing product. Simultaneously, the in situ generation of water leads to the formation of titanium dioxide with an unexpected nanoplate morphology (ca. 50 nm thickness) and a high photocatalytic activity. We present the evidence showing the evolution of the cellulose and the TiO2 nanostructure formation, along with its photocatalytic activity. This low-temperature process avoids any other reagents and is among the greenest processes for the preparation of anatase and also for TiO2 /carbon composites. The anisotropic morphology of TiO2 questions the role of the cellulose on the growing process of these nanoparticles.

Synthesis of Titania@Carbon Nanocomposite from Urea-Impregnated Cellulose for Efficient Lithium and Sodium Batteries.

Nanostructured TiO2 and TiO2@C nanocomposites were prepared directly from urea-impregnated cellulose by a simple reaction/diffusion process and evaluated as negative electrode materials for Li and Na batteries. By direct treatment with TiCl4 under anhydrous conditions, the urea impregnation of cellulose impacts both the TiO2 morphology and the carbon left by cellulose after pyrolysis. Hierarchical TiO2 structures with a flower-like morphology grown from-and-at the surface of the cellulose fibers are obtained without any directing agent. The resulting TiO2/cellulose composite is then transformed either into pure TiO2 flowers by calcination in air at 600 °C, or into TiO2@C nanocomposites by pyrolysis under Ar at 600 °C. Electrochemical studies demonstrate that both samples can (de)insert lithium and sodium ions and are promising electrode materials.

Conversion of Nanocellulose Aerogel into TiO2 and TiO2@C Nano-thorns by Direct Anhydrous Mineralization with TiCl4. Evaluation of Electrochemical Properties in Li Batteries.

Nanostructured TiO2 and TiO2@C nanocomposites were prepared by an original process combining biotemplating and mineralization of aerogels of nanofibrillated cellulose (NFC). A direct one step treatment of NFC with TiCl4 in strictly anhydrous conditions allows TiO2 formation at the outermost part of the nanofibrils while preserving their shape and size. Such TiO2@cellulose composites can be transformed into TiO2 nanotubes (TiO2-NT) by calcination in air at 600 and 900 °C, or into TiO2@C nanocomposites by pyrolysis in argon at 600 and 900 °C. Detailed characterization of these materials is reported here, along with an assessment of their performance as negative electrode materials for Li-ion batteries.

The layered double hydroxide route to Bi-Zn co-doped TiO2 with high photocatalytic activity under visible light.

In this work, a co-doped Bi-Zn-TiO2 photocatalist is synthesized by an original synthesis route of layered double hydroxide followed by heat treatment at 670 °C. After characterization the photocatalyst efficiency is estimated by the photo-discoloration of an anionic dye (indigo carmine) under visible light and compare to TiO2-P25 as reference material. In this new photocatalyst, anatase and ZnO wurtzite are the only identified crystalline phase, rutile and Bi2O3 being undetected. Moreover, the binding energy of Bi determined (XPS analysis) is different from the one of Bi in Bi2O3. Compared to TiO2-P25, the absorption is red shifted (UV-vis DRS) and the Bi-Zn-TiO2 photocatalyst showed sorption capacity toward indigo carmine higher than that TiO2-P25. The kinetics of the photo-discoloration is faster with Bi-Zn-TiO2 than with TiO2-P25. Indeed, a complete discoloration is obtained after 70 min and 120 min in the presence of Bi-Zn-TiO2 and TiO2-P25 respectively. The identification of the responsible species on photo-discoloration was carried out in the presence of different scavengers. The study showed that the first responsible is h(+) specie with a moderate contribution of superoxide anion radical and a minor contribution of the hydroxyl radical. The material showed high stability after five uses with the same rate of photo-discoloration.

Ordered hybrids from template-free organosilane self-assembly.

Despite considerable achievements over the last two decades, nonporous organic-inorganic hybrid materials are mostly amorphous, especially in the absence of solvothermal processes. The organosilane self-assembly approach is one of the few opportunities for creating a regular assembly of organic and inorganic moieties. Additionally, well-established organosilicon chemistry enables the introduction of numerous organic functionalities. The synthesis of periodically ordered hybrids relies on mono-, bis-, or multisilylated organosilane building blocks self-assembling into hybrid mesostructures or superstructures, subsequently cross-linked by siloxane Si-O-Si condensation. The general synthesis procedure is template-free and one-step. However, three concurrent processes underlie the generation of self-organized hybrid networks: thermodynamics of amphiphilic aggregation, dynamic self-assembly, and kinetically controlled sol-gel chemistry. Hence, the set of experimental conditions and the precursor structure are of paramount importance in achieving long-range order. Since the first developments in the mid-1990s, the subject has seen considerable progress leading to many innovative advanced nanomaterials providing promising applications in membranes, pollutant remediation, catalysis, conductive coatings, and optoelectronics. This work reviews, comprehensively, the primary evolution of this expanding field of research.

Surface modification of titania powder P25 with phosphate and phosphonic acids--effect on thermal stability and photocatalytic activity.

Phosphorus is frequently reported as a doping element for TiO(2) as photocatalyst; however, the previously reported methods used to prepare P-doped TiO(2) do not allow control over the location of the phosphorus either in the bulk or at the surface or both. In this study, we report on the surface modification of Evonik P25 with phosphonic (H(3)PO(3)) and octylphosphonic acid [C(8)H(17)-PO(OH)(2)], done to limit the introduction of phosphorus only to the photocatalyst surface. The effect of this element on the thermal behavior and photocatalytic properties is reported through characterization using elemental analyses, solid state (31)P NMR, X-ray powder diffraction, N(2) porosimetry, dilatometry, etc. Thus, the objective of the work reported here is to focus on the role(s) that phosphorus plays only at TiO(2) crystallite surfaces. For comparison, other samples were treated with phosphoric acid.

Polymorphs and colors of polydiacetylenes: a first principles study.

Polydiacetylenes (PDAs) are exceptional polymeric materials with pi-conjugated backbones. Several of them can undergo chromogenic transitions under a wide range of external stimuli. Herein we investigate the electronic structure and the resulting properties of model and experimental PDAs, by means of first principles condensed matter calculations. It is shown that torsional isomers with a twist of the lateral groups can be formed at small energetic costs. We also show the relationship that exists between these twists and the observed changes in the electronic and physical properties. In particular, the calculated changes in the absorption, Raman and NMR spectra agree with the color and property changes as observed experimentally. Therefore, these isomers are excellent models for the structures involved in the chromogenic transitions.

Molecular assemblies from imidazolyl-containing haloalkenes and haloalkynes: competition between halogen and hydrogen bonding.

The structural characterization of molecular assemblies constructed from imidazolyl-containing haloalkenes and haloalkynes is reported. 1-(3-Iodopropargyl)imidazole (2) and 1-(2,3,3-triiodoallyl)imidazole (5) were synthesized from 1-propargylimidazole (1). In the solid state, these wholly organic modules self-assemble through N...I halogen-bonding interactions, thus giving rise to polymeric chains. The N...I interaction observed in 2 (d(N...I)=2.717 A, angle-spherical C(sp)-I...N=175.8 degrees) is quite strong relative to previously reported data. The N...I interaction in 5 (d(N...I)=2.901 A, angle-spherical C(sp2)-I...N=173.6 degrees) is weaker, in accordance with the order C(sp)-X<--base>C(sp2)-X<--base. Compound 5 was found to give a 1:1 cocrystal 4 with morpholinium iodide (6). In the X-ray crystal studies of 4, N...I halogen-bonding interactions similar to those observed in 5 were shown not to be present, as the arrangement of the molecules is governed by two interwoven hydrogen-bonding networks. The first network involves N-H...O interactions between nearby morpholinium cations, and the second network is based on N-H...N hydrogen bonding between morpholinium cations and imidazolyl groups. Both hydrogen-bonding schemes are charge-assisted. Halogen bonding is not completely wiped out, however, as the triiodoalkene fragment forms a halogen bond with an iodide anion in its vicinity (d(I...I)=3.470 A, angle-spherical C(sp2)-I...I=170.7 degrees). X-ray crystal studies of 6 show a completely different arrangement from that observed in 4, namely, N-H...O interactions are not present. In crystalline 6, morpholinium cations are interconnected through C-H...O bridges (d(H...O)=2.521 and 2.676 A), and the NH2+ groups interact with nearby iodide anions (d(H...I)=2.633 and 2.698 A).