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.

Sublimation of Drugs from the Site of Application of Topical Products.

The objective of the project was to investigate the plausibility of active pharmaceutical ingredients (APIs) to undergo sublimation from topical application following evaporation of solvent. Topical formulations with different APIs were subjected to a sublimation screening test. The APIs in the selected topical products were found to undergo sublimation to a different extent. The salicylic acid topical product was found to undergo a significant loss due to sublimation. The extent of sublimation of salicylic acid was significantly greater at skin temperature compared to room temperature. When the APIs were subjected to the sublimation screening test in their neat form at 32 ± 1 °C, the natural log of the rate of sublimation decreased linearly with the standard enthalpy of sublimation of compound (R2 = 0.89). The formulation composition was found to have a significant impact on the extent of sublimation of the representative API, salicylic acid. The sublimation of APIs from the topical product was found to affect the mass balance studies in the case of the salicylic acid ointment. Furthermore, the results of the human studies agreed with the in vitro experimental results demonstrating the plausibility of loss of API due to sublimation from the site of application.

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.

Fundamental aspects of nanocellulose stabilized Pickering emulsions and foams.

Nanocelluloses in recent years have garnered a lot of attention for their use as stabilizers of liquid-liquid and gas-liquid interfaces. Both cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs) have been used extensively in multiple studies to prepare emulsions and foams. However, there is limited literature available that systematically discusses the mechanisms that affect the ability of nanocelluloses (modified and unmodified) to stabilize different types of interfaces. This review briefly discusses key factors that affect the stability of Pickering emulsions and foams and provides a detailed and systematic analysis of the current state knowledge on factors affecting the stabilization of liquid-liquid and gas-liquid interfaces by nanocelluloses. The review also discusses the effect of nanocellulose surface modifications on mechanisms driving the Pickering stabilization of these interfaces.

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 (>20%), 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.

Surface and Interfacial Interactions in Dodecane/Brine Pickering Emulsions Stabilized by the Combination of Cellulose Nanocrystals and Emulsifiers.

Interfacial properties of cellulose nanocrystals (CNC) and surfactants were studied in high ionic strength (I) brines and correlated to the stability of dodecane/brine Pickering emulsions. Bis-(2-hydroxyethyl) cocoalkylamine (CAA), dodecyltrimethylammonium bromide (DTAB), and octyl-ß-d-glucopyranoside (OGP) were adsorbed onto CNC in American Petroleum Institute (API) brine (I = 1.9 M) and synthetic seawater (SSW), with I = 0.65 M. Raman spectroscopy indicated that hydroxyl groups on the CNC surface interact with all three surfactants in high ionic strength media. Ionic interactions still play a role at the very large ionic strengths studied herein. Despite all surfactants adsorbing onto CNC, only the surface tension of CAA solutions in both brines was increased by the addition of 0.5 wt % CNC. The effect was much more prominent in API than in SSW. Contact angle measurements indicated that CAA increased the wettability of CNC by both brines in dodecane; DTAB, on the other hand, decreased wettability. Emulsion stability studies revealed that ionic strength, wettability, adsorption energy, and oil content strongly affect emulsion stability, more so than surfactant adsorption. In API, CNC aggregates alone stabilized the emulsions better compared to samples with additional emulsifiers; the same was true in SSW for oil contents below 50% v/v. For oil contents above 50% v/v in SSW, CAA was either detrimental or failed to improve emulsion stability. On the other hand, DTAB increased the stability of dodecane in SSW emulsions. Emulsions stable for over 21 months were prepared with oil contents of 75% v/v. The adsorption of CAA onto CNC limits the migration of both CNC and CAA to the dodecane/brine interface, while DTAB adsorption has the opposite effect.

Quantitative detection of single walled carbon nanotube in water using DNA and magnetic fluorescent spheres.

Carbon nanotubes (CNTs) possess unique properties that have led to an increase in their research and usage for a wide variety of fields. This growing demand of CNTs poses a major public health risk given its unregulated release into the environment. Unfortunately there is a significant information gap on the actual quantity of CNTs in the environment due to limitation of existing detection methods. This is mainly owing to the ubiquitous carbon chemistry of CNT. In response we developed a method (CNT-capture method) that is able to structurally differentiate CNT from other interference carbon materials in an aqueous medium. The affinity between single walled nanotubes (SWNTs) and specific single stranded DNA (ssDNA) was employed to capture SWNTs in water. SWNT-specific separation was obtained via magnetic separation. Dual fluorescent labels attached to sandwich ssDNA probes were used for quantification. The specific affinity between DNA and SWNTs was verified and no significant side-interactions were observed. With optimized incubation duration (30 min) and buffer composition (10(-7) % sodium dodecyl sulfate and pH 7.9), a calibration curve of quantification (R(2) = 0.90) was obtained with a range of SWNT concentration (0.05-10 µg/mL) against graphene as a planar analog. Comparison to other spectroscopy based methods was carried out to highlight the specificity and sensitivity of the presented method for CNT detection in aquatic sample.

Effect of jet stretch and particle load on cellulose nanocrystal-alginate nanocomposite fibers.

Alginate fibers have found many applications such as the preparation of dressings to treat exuding wounds, drug delivery, enzyme immobilization, etc.; however, their use is limited due to poor mechanical properties. Cellulose nanocrystals (CNCs) were isolated from cotton and introduced into calcium alginate fibers with the goal of improving their strength and modulus. The isolated CNCs are elongated nanoparticles of crystalline cellulose with an average length of 130 nm with a standard deviation (s) of 63 nm, an average width of 20.4 nm (s = 7.8 nm), and an average height of 6.8 nm (s = 3.3 nm). The CNCs were mixed with an aqueous sodium alginate dope solution and wet spun into a CaCl(2) bath to form fibers. It was found that if the apparent jet stretch (ratio of the fiber draw velocity to extrusion velocity) is kept constant, addition of the nanocrystals reduces the tensile strength and modulus of the material; however, a small concentration of CNCs in the dope solution increases the tensile energy to break and enables an increase in the fiber spinning apparent jet stretch ratio by nearly 2-fold at up to 25% CNCs load; the maximum ratio of 4.6 is observed at 25 wt % CNC loading as compared to a maximum of 2.4 for the native alginate. Mechanical testing showed a 38% increase in tenacity and a 123% increase in tensile modulus with 10 wt % CNCs loading and an apparent jet stretch of 4.2. The data suggest that alignment of the nanocrystals in the composites is a key factor influencing the mechanical properties. CNCs have potential to become a biocompatible, renewable, and cost-effective solution to reinforce alginate fibers.