“Greener” chemical modification of cellulose nanocrystals via oxa-Michael addition with N-Benzylmaleimide

Surface modification of cellulose nanocrystals (CNCs) was conducted by an oxa-Michael addition of primary hydroxyl groups on the CNC surface with N-Benzylmaleimide (BnM). Six principles of green chemistry were used to obtain the hydrophobized CNC. Two catalytic approaches were used, a self-catalyzed reaction where alkyl sulfuric acid on the surface of the CNC was the catalyst, and a base-catalyzed approach using triethylamine (TEA). DMSO was chosen as reaction solvent due to its low cost, low toxicity and ability to disperse native CNC compared to other polar diprotic solvents. NMR and FTIR studies confirmed the successful modification of CNCs in both reaction routes. The TEA-catalyzed reaction showed a higher BnM conversion at 70 ​°C after 72 ​h (46 ​± ​2%) compared to the self-catalyzed reaction at 100 ​°C (24 ​± ​2%). Since BnM was added at a two-fold excess compared to superficial primary –OH groups, these had estimated conversions of 92% and 48%, for the base catalyzed and acid catalyzed routes, respectively. Zeta potential measurements suggest, the sulfate groups were retained after the modification reaction. AFM demonstrated no change in particle morphology after modification. Modified CNCs degraded at a higher temperature (390 ​± ​8 ​°C) when the reaction was catalyzed by TEA compared to native CNCs and the self-catalyzed product (220 ​± ​10 ​°C). Contact angle measurements demonstrated the increased hydrophobicity of the modified nanoparticles. Visual inspection and UV–vis spectroscopy demonstrated the modified CNCs had an increased affinity towards organic solvents like acetone, acetonitrile and toluene

Facile fabrication and characterization of kraft lignin@Fe3O4 nanocomposites using pH driven precipitation: Effects on increasing lignin content

This work offers a facile fabrication method for lignin nanocomposites through the assembly of kraft lignin onto magnetic nanoparticles (Fe3O4) based on pH-driven precipitation, without needing organic solvents or lignin functionalization. Kraft lignin@Fe3O4 multicore nanocomposites fabrication proceeded using a simple, pH-driven precipitation technique. An alkaline solution for kraft lignin (pH 12) was rapidly injected into an aqueous-based Fe3O4 nanoparticle colloidal suspension (pH 7) under constant mixing conditions, allowing the fabrication of lignin magnetic nanocomposites. The effects of increasing lignin to initial Fe3O4 mass content (g/g), increasing in ratio from 1:1 to 20:1, are discussed with a complete chemical, structural, and morphological characterization. Results showed that nanocomposites fabricated above 5:1 lignin:Fe3O4 had the highest lignin coverage and content (\u3e20%), possessed superparamagnetic properties (Ms ≈ 45,000 A·m2/kg2); had a negative surface charge (−30 mV), and formed multicore nanostructures (DH ≈ 150 nm). The multicore lignin@Fe3O4 nanocomposites allowed rapid magnetically induced separations from suspension. After 5 min exposure to a rare-earth neodymium magnet (1.27 mm × 1.27 mm × 5.08 mm), lignin@Fe3O4 nanocomposites exhibited a maximum methylene blue removal efficiency of 74.1% ± 7.1%. These nanocomposites have potential in magnetically induced separations to remove organic dyes, heavy metals, or other lignin adsorbates

Adsorptive properties and on-demand magnetic response of lignin@Fe3O4 nanoparticles at castor oil–water interfaces

Lignin@Fe3O4 nanoparticles adsorb at oil–water interfaces, form Pickering emulsions, induce on-demand magnetic responses to break emulsions, and can sequester oil from water. Lignin@Fe3O4 nanoparticles were prepared using a pH-induced precipitation method and were fully characterized. These were used to prepare Pickering emulsions with castor oil/Sudan red G dye and water at various oil/water volume ratios and nanoparticle concentrations. The stability and demulsification of the emulsions under different magnetic fields generated with permanent magnets (0–540 mT) were investigated using microscopy images and by visual inspection over time. The results showed that the Pickering emulsions were more stable at the castor oil/water ratio of 50/50 and above. Increasing the concentration of lignin@Fe3O4 improved the emulsion stability and demulsification rates with 540 mT applied magnetic field strength. The adsorption of lignin@Fe3O4 nanoparticles at the oil/water interface using 1-pentanol evaporation through Marangoni effects was demonstrated, and magnetic manipulation of a lignin@Fe3O4 stabilized castor oil spill in water was shown. Nanoparticle concentration and applied magnetic field strengths were analyzed for the recovery of spilled oil from water; it was observed that increasing the magnetic strength increased oil spill motion for a lignin@Fe3O4 concentration of up to 0.8 mg mL−1 at 540 mT. Overall, this study demonstrates the potential of lignin-magnetite nanocomposites for rapid on-demand magnetic responses to externally induced stimuli

Overview of the instrumentation for the Dark Energy Spectroscopic Instrument

The Dark Energy Spectroscopic Instrument (DESI) embarked on an ambitious 5 yr survey in 2021 May to explore the nature of dark energy with spectroscopic measurements of 40 million galaxies and quasars. DESI will determine precise redshifts and employ the baryon acoustic oscillation method to measure distances from the nearby universe to beyond redshift z > 3.5, and employ redshift space distortions to measure the growth of structure and probe potential modifications to general relativity. We describe the significant instrumentation we developed to conduct the DESI survey. This includes: a wide-field, 3.°2 diameter prime-focus corrector; a focal plane system with 5020 fiber positioners on the 0.812 m diameter, aspheric focal surface; 10 continuous, high-efficiency fiber cable bundles that connect the focal plane to the spectrographs; and 10 identical spectrographs. Each spectrograph employs a pair of dichroics to split the light into three channels that together record the light from 360–980 nm with a spectral resolution that ranges from 2000–5000. We describe the science requirements, their connection to the technical requirements, the management of the project, and interfaces between subsystems. DESI was installed at the 4 m Mayall Telescope at Kitt Peak National Observatory and has achieved all of its performance goals. Some performance highlights include an rms positioner accuracy of better than 0.″1 and a median signal-to-noise ratio of 7 of the [O ii] doublet at 8 × 10−17 erg s−1 cm−2 in 1000 s for galaxies at z = 1.4–1.6. We conclude with additional highlights from the on-sky validation and commissioning, key successes, and lessons learned

Effect of the Interactions between Oppositely Charged Cellulose Nanocrystals (CNCs) and Chitin Nanocrystals (ChNCs) on the Enhanced Stability of Soybean Oil-in-Water Emulsions

Chitin nanocrystals (ChNCs) and cellulose nanocrystals (CNCs) have been recently used to stabilize emulsions; however, they generally require significant amounts of salt, limiting their applicability in food products. In this study, we developed nanoconjugates by mixing positively charged ChNCs and negatively charged CNCs at various ChNC:CNC mass ratios (2:1, 1:1, and 1:2), and utilized them in stabilizing soybean oil–water Pickering emulsions with minimal use of NaCl salt (20 mM) and nanoparticle (NP) concentrations below 1 wt%. The nanoconjugates stabilized the emulsions better than individual CNC or ChNC in terms of a reduced drop growth and less creaming. Oppositely charged CNC and ChNC neutralized each other when their mass ratio was 1:1, leading to significant flocculation in the absence of salt at pH 6. Raman spectroscopy provided evidence for electrostatic interactions between the ChNCs and CNCs, and generated maps suggesting an assembly of ChNC bundles of micron-scale lengths intercalated by similar-size areas predominantly composed of CNC. The previous measurements, in combination with contact angles on nanoparticle films, suggested that the conjugates preferentially exposed the hydrophobic crystalline planes of CNCs and ChNCs at a 1:1 mass ratio, which was also the best ratio at stabilizing soybean oil–water Pickering emulsions

Novel Castor Oil/Water/Ethanol Pickering Emulsions Stabilized by Magnetic Nanoparticles and Magnetically Controllable Demulsification

A novel castor oil/water/ethanol Pickering emulsion, stabilized by magnetic nanoparticles (NPs), was developed to allow on-demand demulsification by an external magnetic field for the extraction of ethanol from aqueous solution using the castor oil. The emulsion was stabilized by Fe3O4-coated cellulose nanocrystals (CNC@Fe3O4) and lignin-coated Fe3O4 NPs (lignin@Fe3O4). The stability of the emulsions was investigated at various castor oil to ethanol-water ratios (50/50 and 70/30), various NP concentrations, and ethanol concentrations in the aqueous phase. The magnetically controlled demulsification ability of the emulsions was investigated by using a permanent magnet. The results showed that the 70/30 emulsions were more stable than the 50/50 emulsions for all the ethanol concentrations. Moreover, increasing the NP concentration increased the emulsion stability and hence, 1 w/v% NPs concentration provided the more stable systems. However, all the emulsions were successfully broken by the permanent magnet. Yet, the presence of ethanol improves the ability of the external magnetic field to demulsify these dispersions. Furthermore, the used hybrid NPs were recovered and recycled for three cycles. The recycled NPs were characterized with X-ray diffraction (XRD) and vibrating sample magnetometry (VSM) indicating that they retained their saturation magnetization and crystalline structure, demonstrating their lack of degradation over multiple recycling cycles. This study facilitates the exploration of innovative two-phase Pickering emulsions comprising three distinct liquid components and their utilization in liquid-liquid extraction processes

Liquid-liquid equilibria of water + ethanol + castor oil and the effect of cellulose nanocrystal/Fe3O4 and lignin/Fe3O4 nanoparticles

Castor oil has been proposed as a renewable solvent for the liquid extraction of ethanol from water as an alternative to more traditional energy intensive distillation-based methods. The liquid–liquid equilibrium (LLE) of the ternary system water + ethanol + castor oil was determined at 295.15 K using high performance liquid chromatography (HPLC). Castor oil was herein treated as a pseudo-component with the molecular weight of the triglyceride of ricinoleic acid. The experimental data was fitted to the UNIQUAC and NRTL models to obtain parameters for castor oil, and binary interaction parameters for castor oil/ethanol and castor oil/water pairs. The separation factors and distribution coefficients of water and ethanol were calculated at ethanol concentrations ranging from 2.73 ± 0.35 to 55.8 ± 1.1 wt%, with a high separation factor of 12.7 ± 3.3, and a distribution coefficient of 0.352 ± 0.078, at the lowest ethanol concentration tested. Moreover, iron oxide-coated cellulose nanocrystals (CNC@Fe3O4) and Kraft lignin-coated iron oxide (lignin@Fe3O4) nanoparticles (NPs) were added to the castor oil + water + ethanol mixtures at 0.01 g/g mixture, to investigate the effect of the NPs in altering the LLE of the system. It was found that the NPs had a negligible (\u3c1%) effect on the thermodynamic equilibrium, which opens the possibility of using them in advanced applications such as the magnetically controlled demulsification of stable dispersions generated during liquid–liquid extraction process