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Ionic liquid lignins are prepared from sodium lignosulfonate by a cation exchange reaction and display glass transition temperatures as low as −13 °C. Diethyleneglycol‐functionalized protic cations inhibit lignin aggregation to produce a free‐flowing “ionic liquid lignin”, despite it being a high‐molecular‐weight polyelectrolyte. Through this approach, the properties of both lignin and ionic liquids are combined to create a dispersant and binder for cellulose+gluten mixtures to produce small microphases. Biocomposite testing pieces are produced by hot‐pressing this mixture, yielding a material with fewer defects and improved toughness in comparison to other lignins. The use of unmodified lignosulfonate, acetylated lignosulfonate, or free ionic liquid for similar materials production yields poorer substances because of their inability to maximize interfacial contact and complexation with cellulose and proteins., Hot off the press: Lignosulfonate is functionalized to create an ionic liquid with a glass transition temperature (T g) of −13 °C. After mixing with cellulose+gluten and hot‐pressing, composite materials are produced and have fewer defects and improved toughness in comparison to other lignins.

Hydrogels constitute an important class of polymeric materials, mainly due to their promising applications in the biomedical field. Particularly, mechanical properties are a limiting factor for applications, and reinforcement and improved wear resistance are major directions in current research. In here, graphitic carbon nitride (g-CN)-based hydrogels are presented. The hydrogels are formed in a two-step procedure. In the first step, a prepolymer is synthesized that leads to a significantly improved g-CN dispersibility and stability of g-CN dispersions. Hence, the g-CN content in the final hydrogels can be increased to obtain tough hydrogels. More importantly, hydrogels from charged monomers can be formed as well, which leads to lubricant properties. As such, the investigated route opens up new opportunities to fabricate functional hydrogels with significant toughness, compressibility and lubricity.

Hydrogenation reactions in water at elevated temperatures are challenging for heterogeneous catalysts. Thus, we present a simple, cheap, scalable, and sustainable approach for synthesizing an efficient and stable Ni catalyst supported on highly porous nitrogen-doped carbon (NDC) in pellet form. The performance of this catalyst was evaluated in the aqueous-phase hydrogenation of lignocellulosic biomass-derived compounds, i.e., glucose (Glu), xylose (Xyl), and vanillin (V), using a continuous-flow system. The as-prepared 35 wt% Ni on NDC catalyst exhibited a high catalytic performance in all three aqueous-phase hydrogenation reactions, i.e., the conversion of Glu, Xyl, and V was 96.3 mol%, 85 mol%, and 100 mol% and the yield of sorbitol (Sor), xylitol (Xyt), and 2-methoxy-4-methylphenol (MMP) was 82 mol%, 62 mol%, and 100 mol%, respectively. This high activity was attributed to the high specific surface area of NDC and mainly to the heterojunction effects stabilizing and adjusting the homogenously and highly dispersed Ni nanoparticles (ANi = 20 m2 g−1) on the surface of NDC. Changing the electron density in the nickel nanoparticles allows the high performance of the catalyst for a long time on stream (40 h) with minimized Ni leaching and without the loss in catalytic performance.

Waste lignocellulosic biomass is sustainable and an alternative feedstock to fossil resources. Among the lignocellulosic derived compounds, 2,5-dimethylfuran (DMF) is a promising building block for chemicals, e.g., p-xylene, and a valuable biofuel. DMF can be obtained from 5-hydroxymethylfurfural (HMF) via catalytic deoxygenation using non-noble metals such as Ni in the presence of H2. Herein, we present the synthesis of DMF from HMF using 35 wt.% Ni on nitrogen-doped carbon pellets (35Ni/NDC) as a catalyst in a continuous flow system. The conversion of HMF to DMF was studied at different hydrogen pressures, reaction temperatures, and space times. At the best reaction conditions, i.e., 423 K, 8.0 MPa, and space time 6.4 kgNi h kgHMF&minus, 1, the 35Ni/NDC catalyst exhibited high catalytic activity with HMF conversion of 99 mol% and 80 mol% of DMF. These findings can potentially contribute to the transition toward the production of sustainable fine chemicals and liquid transportation fuels.

This study investigates the electronic configuration of titanium nitride-nickel (TiN-Ni) nanocomposites, in order to explain the high stability and activity of this hydrogenolysis catalyst. TiN-Ni is compared to a titanium oxide-nickel reference (TiO2-Ni). Strong metal support interactions are observed between the TiN and Ni. Scanning transmission electron microscopy (STEM) and energy-dispersive X-ray spectroscopy (EDS) illustrate that the Ni distributes more homogeneously on the nitride support. Computational comparison of TiN Ni and TiO2-Ni provides evidence of preferential Ni adsorption onto nitrogen sites of the nitride support. DFT calculations also predict a charge polarization between Ti and Ni atoms. X-ray photoelectron spectroscopy (XPS) corroborates computational analysis by revealing a suppression of surface nitride species upon deposition of Ni onto TiN. Shifts in Ti 2p and Ni 2p binding energy positions are also evident, which indicate an electronic perturbation between TiN and Ni. We conclude that the presence of nitrogen in the nitride support influences the electronic and structural properties of TiN-Ni and is partly responsible for the beneficial catalytic properties reported for this nanocomposite.

A high-throughput composite catalyst is prepared from porous carbon with an unconventional nanocube morphology decorated by nickel nanoparticles. Due to the advantageous properties of the designed carbon support, the composite combines a high surface area and a hierarchical pore structure with high functionality. Furthermore, the regularly shaped nanocubes allow for a good packing of a fixed-bed flow reactor, while the internal transport pores cannot be blocked and stay open for efficient column performance. The composite is employed as catalyst in the hydrogenation of 5 hydroxymethylfurfural (HMF) to 2,5-dimethylfuran showing good catalytic performance and overcoming the conventional problem of column blocking.

A non-ionic surfactant system is synthesized by standard grafting of poly(ethylene oxide) from renewable lignin fragments and used for the emulsion polymerization of styrene. The lignin precursors are formed by hydrogenolysis and utilized as initiator for the oxyanionic polymerization of ethylene oxide leading to amphiphilic polymers, very similar to standard nonionic surfactant synthesis. Subsequently, the formed amphiphilic polymers are employed as stabilizers in the heterophase polymerization of styrene with various initiators. Poly (styrene) latexes with solids contents of up to 21% depending on stabilizer concentration have been obtained. Stabilizer efficiencies and performances were nicely comparable with those of nonylphenol-based, non-ionic industrial performance surfactants.

Lignin is one of the most important candidates for the procurement of renewable aromatics. The development of successful strategies for the production of building blocks from lignin implies the design of effective depolymerization protocols. Here we propose a continuous flow approach for the hydrogenolysis of Kraft lignin utilizing a TiN-Ni heterogeneous catalyst. The refining of commercial Kraft lignin was evaluated, showing that the catalyst can facilitate the partial depolymerization of this sulfur-containing material under very mild conditions and with short residence times. The process restitutes lignin in the form of oligomers in combination with an array of valuable single-ring aromatic compounds.

Extremely compressible hydrogels are fabricated in one pot via sulfonic-acid-modified graphitic carbon nitride (g-CN-AHPA) as a visible light photoinitiator and reinforcer. The hydrogels show unusual compressibility upon applied stress up to 12 MPa, presenting temporary physical deformation, and remain undamaged after stress removal despite their high water content (90 wt%). Cyclic compressibility proves the fatigue resistance of the covalently and electrostatically reinforced system that possesses tissue adhesive properties, shock resistance, cut resistance, and little to no toxicity.

High concentration formulations of graphitic carbon nitride (g-CN) are utilized as photoinitiator and reinforcer for hydrogels. In order to integrate significant amounts of g-CN, ethylene glycol (EG) is employed as a co-solvent for the gel formation, which enables stable dispersion of up to 4 wt% g-CN. Afterwards, EG can be removed easily via solvent exchange to afford pure hydrogels. The diverse gels possess remarkably high storage moduli (up to 650 kPa for gels and 720 kPa for hydrogels) and compression moduli (up to 9.45 MPa for 4 wt% g-CN EG gel and 3.45 MPa for 4 wt% g-CN hydrogel). Full recovery without energy loss is observed for at least 20 cycles. Moreover, gel formation can be performed in a spatially controlled way utilizing photomasks with desired shapes. Therefore, the suggested method enables formation of hybrid gels by optical lithography with outstanding mechanical properties very similar to natural cartilage and tendon, and opens up opportunities for future applications in photocatalysis, additive manufacturing of biomedical implants and coating materials.

Molybdenum carbide and molybdenum nitride nanoparticles have been developed for catalyzing the hydrogen evolution reaction (HER). These nanocatalysts were synthesized by the ‘urea glass’ route. By simply changing the molar ratio of the urea/metal precursor, α-Mo2C and γ-Mo2N nanoparticles, both of which are crystalline, phase pure and monodisperse in size, were obtained. Hydrogen evolution was performed in both 1 M KOH and 0.5 M H2SO4 electrolytes, and characterized by linear sweep voltammetry and electrochemical impedance spectroscopy. The as-synthesized Mo2C showed excellent HER performance especially in KOH. At a catalyst loading of 102 μg cm−2, a low overpotential of 176 mV was needed to produce 10 mA cm−2 of H2. Its measured currents and turnover frequencies for hydrogen evolution at different overpotentials compare favorably against many other recently reported non-precious metal HER catalysts. Online gas chromatography demonstrated that the current efficiency for H2 production is ∼100%. Both Mo2C and Mo2N showed negligible overpotential losses after acceleration degradation tests in acid and alkali. This is noteworthy since very few catalysts are active in these two extreme pHs. An attractive aspect of the α-Mo2C and γ-Mo2N nanoparticles for electrochemical hydrogen evolution is that they are simple and well-characterized in chemical and physical composition. The excellent catalytic activity of the α-Mo2C catalysts can be attributed to their small particle size, which will facilitate a rapid electron transfer for the hydrogen evolution reaction. Our study has placed the as-synthesized α-Mo2C nanoparticles as highly promising alternatives to platinum in the alkaline water electrolyzer.

A low-cost laser-based printing setup is presented, which allows for the spot-wise patterning of surfaces with defined polymer nanolayers. These nanolayer spots serve as a “solid solvent,” embedding different chemicals, chemical building blocks, materials, or precursors and can be stacked on top of each other. By melting the spot pattern, the polymer-embedded molecules are released for chemical reaction. This enables researchers to quickly pattern a surface with different molecules and materials, mixing them directly on the surface for high-throughput chemical synthesis to generate and screen diverse microarray libraries. In contrast to expensive ink-jet or contact printing, this approach does not require premixing of inks, which enables in situ combinatorial mixing. Easy access and versatility of this patterning approach are shown by generating microarrays of various biomolecules, such as glycans for the first time, to screen interactions of antibodies and lectins. In addition, a layer-by-layer solid-phase synthesis of peptides directly on the microarray is presented. Amino acid–containing nanolayers are repeatedly laser-transferred and reacted with the functionalized acceptor surface in defined patterns. This simple system enables a reproducible array production, down to spot-to-spot distances of 100 μm, and offers a flexible and cheap alternative to expensive spotting robot technology.

A safe and simple method to fabricate air-stable nickel nitride and nickel embedded in carbon and nitrogen matrix, with high surface area for catalytic applications, is presented. The new synthesis employs molten inorganic salts as the reaction media. The use of salt melt opens new possibilities for safe, simple, and cheap synthesis of metal nitrides and metals for energy-related applications.

Aim: Targeted biocompatible nanoplatforms presenting multiple therapeutic functions have great potential for the treatment of cancer. Materials & methods: Multifunctional nanocomposites formed by polymeric nanoparticles (PNPs) containing two cytotoxic agents – the drug alisertib and silver nanoparticles – were synthesized. These PNPs have been conjugated with a chlorotoxin, an active targeting 36-amino acid-long peptide that specifically binds to MMP‑2, a receptor overexpressed by brain cancer cells. Results: The individual and synergistic activity of these two cytotoxic agents against glioblastoma multiforme was tested both in vitro and in vivo. The induced cytotoxicity in a human glioblastoma–astrocytoma epithelial‑like cell line (U87MG) was studied in vitro through a trypan blue exclusion test after 48 and 72 h of exposure. Subsequently, the PNPs’ biodistribution in healthy animals and their effect on tumor reduction in tumor‑bearing mice were studied using PNPs radiolabeled with 99mTc. Conclusion: Tumor reduction was achieved in vivo when using silver/alisertib@PNPs–chlorotoxin., JRC.I.4-Nanobiosciences

In the quest for biocompatible nanocarriers for biomedical applications, a great deal of effort is put on engineering the nanocomposites surface in order to render them specific to the particular purpose. We developed biocompatible PLGA-b-PEG-based nanoparticles carrying a double functionality (i.e., carboxylic and acetylenic) able to serve as flexible highly selective grafting centers for cancer diagnosis and treatment. As a proof of concept, the nanocarrier was successfully functionalized with a tailored fluorescent molecule by means of click chemistry and with a targeting agent specific for glioblastoma multiforme via amidic bond formation.

In the search for alternative materials to current expensive catalysts, Ni has been addressed as one of the most promising and, on this trail, its corresponding nitride. However, nickel nitride is a thermally unstable compound, and therefore not easy to prepare especially as nanoparticles. In the present work, a sol-gel-based process (the urea glass route) is applied to prepare well-defined and homogeneous Ni3N and Ni nanoparticles. In both cases, the prepared crystalline nanoparticles (∼25 nm) are dispersed in a carbon matrix forming interesting Ni3N- and Ni-based composites. These nanocomposites were characterised by means of several techniques, such as XRD, HR-TEM, EELS, and the reaction mechanism was investigated by TGA and IR and herein discussed. The catalytic activity of Ni3N is investigated for the first time, to the best of our knowledge, for hydrogenation reactions involving H2, and here compared to the one of Ni. Both materials show good catalytic activities but, interestingly, give a different selectivity between different functional groups (namely, nitro, alkene and nitrile groups).

Lignin from biomass can become a sustainable source of aromatic compounds. Its depolymerization can be accomplished through hydrogenolysis, although the development of catalysts based on cheap and abundant metals is lacking. Herein, a sustainable composite based on titanium nitride and nickel is synthesized and employed as catalyst for the hydrogenolysis of aryl ethers as models for lignin. The catalytic activity of the new material during hydrogenation reactions is proven to be superior to that of either component alone. In particular, different aryl ethers could be efficiently converted under relatively mild conditions into aromatic compounds and cycloalkanes within minutes.

A novel highly biocompatible nanosystem containing Mg nanoparticles is reported, characterized and tested as a suitable and non-toxic tool for photothermal therapy. This journal is © the Partner Organisations 2014.

An integrated method for the production of γ-valerolactone from cellulosic biomass is presented here. A combination of acidic water hydrolysis of the biomass followed by extraction with methyltetrahydrofuran is used to generate a levulinic acid feed, which is further hydrogenated into the platform chemical γ-valerolactone using RANEY® nickel as a catalyst.