Stable Cellulose Nanofibril Microcapsules from Pickering Emulsion Templates.

Electrostatic attractions are essential in any complex formation between the nanofibrils of the opposite charge for a specific application, such as microcapsule production. Here, we used cationized cellulose nanofibril (CCNF)-stabilized Pickering emulsions (PEs) as templates, and the electrostatic interactions were induced by adding oxidized cellulose nanofibrils (OCNFs) at the oil-water interface to form microcapsules (MCs). The oppositely charged cellulose nanofibrils enhanced the solidity of interfaces, allowing the encapsulation of Nile red (NR) in sunflower oil droplets. Microcapsules exhibited a low and controlled release of NR at room temperature. Furthermore, membrane emulsification was employed to scale up the preparation of microcapsules with sunflower oil (SFO) encapsulated by CCNF/OCNF complex networks.

Enzyme-Functionalized Cellulose Beads as a Promising Antimicrobial Material.

The extensive use of antibiotics over the last decades is responsible for the emergence of multidrug-resistant (MDR) microorganisms that are challenging health care systems worldwide. The use of alternative antimicrobial materials could mitigate the selection of new MDR strains by reducing antibiotic overuse. This paper describes the design of enzyme-based antimicrobial cellulose beads containing a covalently coupled glucose oxidase from Aspergillus niger (GOx) able to release antimicrobial concentrations of hydrogen peroxide (H2O2) (≈ 1.8 mM). The material preparation was optimized to obtain the best performance in terms of mechanical resistance, shelf life, and H2O2 production. As a proof of concept, agar inhibition halo assays (Kirby-Bauer test) against model pathogens were performed. The two most relevant factors affecting the bead functionalization process were the degree of oxidation and the pH used for the enzyme binding process. Slightly acidic conditions during the functionalization process (pH 6) showed the best results for the GOx/cellulose system. The functionalized beads inhibited the growth of all the microorganisms assayed, confirming the release of sufficient antimicrobial levels of H2O2. The maximum inhibition efficiency was exhibited toward Pseudomonas aeruginosa (P. aeruginosa) and Escherichia coli (E. coli), although significant inhibitory effects toward methicillin-resistant Staphylococcus aureus (MRSA) and S. aureus were also observed. These enzyme-functionalized cellulose beads represent an inexpensive, sustainable, and biocompatible antimicrobial material with potential use in many applications, including the manufacturing of biomedical products and additives for food preservation.

Multienzyme Cellulose Films as Sustainable and Self-Degradable Hydrogen Peroxide-Producing Material.

The use of hydrogen peroxide-releasing enzymes as a component to produce alternative and sustainable antimicrobial materials has aroused interest in the scientific community. However, the preparation of such materials requires an effective enzyme binding method that often involves the use of expensive and toxic chemicals. Here, we describe the development of an enzyme-based hydrogen peroxide-producing regenerated cellulose film (RCF) in which a cellobiohydrolase (TrCBHI) and a cellobiose dehydrogenase (MtCDHA) were efficiently adsorbed, 90.38 ± 2.2 and 82.40 ± 5.7%, respectively, without making use of cross-linkers. The enzyme adsorption kinetics and binding isotherm experiments showed high affinity of the proteins possessing cellulose-binding modules for RCF, suggesting that binding on regenerated cellulose via specific interactions can be an alternative method for enzyme immobilization. Resistance to compression and porosity at a micrometer scale were found to be tunable by changing cellulose concentration prior to film regeneration. The self-degradation process, triggered by stacking TrCBHI and MtCDHA (previously immobilized onto separate RCF), produced 0.15 nmol/min·cm2 of H2O2. Moreover, the production of H2O2 was sustained for at least 24 h reaching a concentration of ∼2 mM. The activity of MtCDHA immobilized on RCF was not affected by reuse for at least 3 days (1 cycle/day), suggesting that no significant enzyme leakage occurred in that timeframe. In the material herein designed, cellulose (regenerated from a 1-ethyl-3-methylimidazolium acetate/dimethyl sulfoxide (DMSO) solution) serves both as support and substrate for the immobilized enzymes. The sequential reaction led to the production of H2O2 at a micromolar-millimolar level revealing the potential use of the material as a self-degradable antimicrobial agent.

Kinetics of CO2 Hydrogenation to Hydrocarbons over Iron-Silica Catalysts.

The conversion of CO2 to hydrocarbons is increasingly seen as a potential alternative source of fuel and chemicals, while at the same time contributing to addressing global warming effects. An understanding of kinetics and mass transfer limitations is vital to both optimise catalyst performance and to scale up the whole process. In this work we report on a systematic investigation of the influence of the different process parameters, including pore size, catalyst support particle diameter, reaction temperature, pressure and reactant flow rate on conversion and selectivity of iron nanoparticle -silica catalysts. The results provided on activation energy and mass transfer limitations represent the basis to fully design a reactor system for the effective catalytic conversion of CO2 to hydrocarbons.

Electro-osmotic flow enhancement in carbon nanotube membranes.

In this work, experimental evidence of the presence of electro-osmotic flow (EOF) in carbon nanotube membranes with diameters close to or in the region of electrical double layer overlap is presented for two different electrolytes for the first time. No EOF in this region should be present according to the simplified theoretical framework commonly used for EOF in micrometre-sized channels. The simplifying assumptions concern primarily the electrolyte charge density structure, based on the Poisson-Boltzmann (P-B) equation. Here, a numerical analysis of the solutions for the simplified case and for the nonlinear and the linearized P-B equations is compared with experimental data. Results show that the simplified solution produces a significant deviation from experimental data, whereas the linearized solution of the P-B equation can be adopted with little error compared with the full P-B case. This work opens the way to using electro-osmotic pumping in a wide range of applications, from membrane-based ultrafiltration and nanofiltration (as a more efficient alternative to mechanical pumping at the nanoscale) to further miniaturization of lab-on-a-chip devices at the nanoscale for in vivo implantation.

Effect of nanostructured ceria as support for the iron catalysed hydrogenation of CO2 into hydrocarbons.

This paper demonstrates the key role of the property-structure relationship of the support on iron/ceria catalysts on the hydrocarbon selectivity and olefin-to-paraffin ratio for the direct hydrogenation of carbon dioxide into hydrocarbons. The effect is directly related to the reducibility of the different nanostructured ceria supports and their interaction with the iron particles. Herein, we demonstrate that the iron-based catalysts can be modified not only by the addition of promoters, commonly reported in the literature, but also by careful control of the morphology of the ceria support.

Flow enhancement in nanotubes of different materials and lengths.

The high water flow rates observed in carbon nanotubes (CNTs) have previously been attributed to the unfavorable energetic interaction between the liquid and the graphitic walls of the CNTs. This paper reports molecular dynamics simulations of water flow in carbon, boron nitride, and silicon carbide nanotubes that show the effect of the solid-liquid interactions on the fluid flow. Alongside an analytical model, these results show that the flow enhancement depends on the tube's geometric characteristics and the solid-liquid interactions.

Diaminated Cellulose Beads as a Sustainable Support for Industrially Relevant Lipases.

Environmentally persistent polystyrene or polyacrylic beads are used as supports in enzyme large-scale bioprocesses, including conversion glucose isomerization for high-fructose corn syrup production, hydrolysis of lactose, and synthesis of active pharmaceutical ingredients. In this paper, we report the development of a novel sustainable and scalable method to produce diaminated cellulose beads (DAB) as highly efficient alternative supports for industrially relevant lipases. Regenerated cellulose beads were grafted with diaminated aliphatic hydrocarbons via periodate oxidation and reductive amination. The oxidation step indicated that aldehyde content can be easily tuned through the reaction time and concentration of reactants. Reductive amination of dialdehyde cellulose was more efficient as the length of the diaminated hydrocarbon compound increased. Morphological analysis of DAB showed that cellulose chemical grafting enabled the preservation of the bead shape and internal structure upon freeze-drying. Enzymatic degradability studies demonstrated that chemical functionalization did not undermine enzyme cellulose hydrolysis. The addition of aminated moieties on cellulose dramatically increased absorption efficiency for all industrially relevant lipases used, reaching 100% for Thermomyces lanuginosus lipase (TLL). Storage and recyclability experiments demonstrated that enzymes were retained and recyclable for at least nine cycles, although the activity gradually declined after each cycle. Medium chain triacylglycerol hydrolysis in a SpinChem reactor using TLL immobilized on 1,6 DAB exhibited higher activity compared to acrylic beads (588 vs 459 U/g) suggesting that biodegradable cellulose-based materials could be a valid and attractive alternative to plastics carriers.

Study of fluid and transport properties of porous anodic aluminum membranes by dynamic atomic force microscopy.

Recent work on carbon nanotubes (CNT) has focused on their potential application in water treatment as a result of their predicted and observed enhanced flow rates. Recent work on the lesser-known porous anodic alumina membranes (PAAMs) has also shown flow enhancement, albeit at only a fraction of what has been observed in CNTs. Despite their potential applications, little research has been conducted on PAAMs' hydrodynamic properties, and in this Article we present experimental results and theoretical models that explore the fluid flow behavior around and through these membranes. The experiments were conducted using an atomic force microscope (AFM) that pushed a solid silica particle against PAAMs that were characterized with different pore diameters. Furthermore, the PAAMs were classified as either closed or open, with the latter allowing fluid to pass through. The theoretical model developed to describe the experimental data incorporates Derjaguin-Landau-Verwey-Overbeek (DLVO) effects, cantilever drag, and hydrodynamic forces. By using the slip boundary condition for the hydrodynamic forces, we were able to fit the model to experimental findings and also demonstrate that the difference between closed and open PAAMs was negligible. The slip lengths did not correspond to any physical feature of the PAAMs, but our model does provide a simple yet effective means of describing the hydrodynamics for not only PAAMs but for membranes in general.

Increased photocorrosion resistance of ZnO foams via transition metal doping.

ZnO is a widely studied photocatalyst, but practical use is hindered by its low resistance to photocorrosion in water, which leads to metal leaching and loss of performance over time. In this work, highly porous and mechanically stable ZnO foams, called MolFoams, were doped by adding 1% or 2% Co, Ni or Cu salts to the starting Zn salt, followed by air insufflation during a sol-gel rection and sintering. The resulting doped foams showed a major increase in stability, with a 60-85% reduction in Zn2+ leaching after irradiation, albeit with a reduction in photocatalytic activity. A systematic analysis using XRD, Raman, XPS and XANES allowed for the identification of dopant species in the foams revealing the presence of Co3O4, NiO and Cu2O within the ZnO lattice with doping leading to a reduced band gap and significant increases in the resistance to photocorrosion of ZnO while identifying the cause of the reduction in photocatalytic activity to be shifting of the band edge positions. These results provide a pathway to significantly reduce the photocorrosion of ZnO in water, with further work required to maintain the photocatalytic activity of undoped ZnO.

Correction: Increased photocorrosion resistance of ZnO foams via transition metal doping.

[This corrects the article DOI: 10.1039/D2RA06730G.].

Cellulose Acetate Microbeads for Controlled Delivery of Essential Micronutrients.

The controlled delivery of micronutrients to soil and plants is essential to increase agricultural yields. However, this is today achieved using fossil fuel-derived plastic carriers, posing environmental risks and contributing to global carbon emissions. In this work, a novel and efficient way to prepare biodegradable zinc-impregnated cellulose acetate beads for use as controlled release fertilizers is presented. Cellulose acetate solutions in DMSO were dropped into aqueous antisolvent solutions of different zinc salts. The droplets underwent phase inversion, forming solid cellulose acetate beads containing zinc, as a function of zinc salt type and concentration. Even higher values of zinc uptake (up to 15.5%) were obtained when zinc acetate was added to the cellulose acetate-DMSO solution, prior to dropping in aqueous zinc salt antisolvent solutions. The release profile in water of the beads prepared using the different solvents was linked to the properties of the counter-ions via the Hofmeister series. Studies in soil showed the potential for longer release times, up to 130 days for zinc sulfate beads. These results, together with the efficient bead production method, demonstrate the potential of zinc-impregnated cellulose acetate beads to replace the plastic-based controlled delivery products used today, contributing to the reduction of carbon emissions and potential environmental impacts due to the uptake of plastic in plants and animals.

Continuous production of cellulose microbeads by rotary jet atomization.

The replacement of plastic microbeads with biodegradable alternatives is essential due to the environmental persistence of plastics and their accumulation within the human food chain. HYPOTHESIS: Cellulose microbeads could be such alternative, but their production is hindered by the high viscosity of cellulose solutions. It is expected that this viscosity can be harnessed to induce filament thinning of jets of cellulose solutions to create droplets with diameters within the micrometre range, which can then be converted to solid cellulose microbeads via phase inversion. EXPERIMENTS: A 3D printed rotating multi-nozzle system was used to generate jets of cellulose dissolved in solutions of [EMIm][OAc] and DMSO. The jets were subject to Rayleigh breakup to generate droplets which were captured in an ethanol anti-solvent bath, initiating phase-inversion, and resulting in regeneration of the cellulose into beads. FINDINGS: Control of both process (e.g. nozzle dimensions) and operational (e.g. rotational speed and pressure) parameters has allowed suppression of both satellite droplets generation and secondary droplet break-up, and tuning of the filament thinning process. This resulted in the continuous fabrication of cellulose microbeads in the size range 40-500 µm with narrow size distributions. This method can produce beads in size ranges not attainable by existing technologies.

Amontonian frictional behaviour of nanostructured surfaces.

With nanotextured surfaces and interfaces increasingly being encountered in technological and biomedical applications, there is a need for a better understanding of frictional properties involving such surfaces. Here we report friction measurements of several nanostructured surfaces using an Atomic Force Microscope (AFM). These nanostructured surfaces provide well defined model systems on which we have tested the applicability of Amontons' laws of friction. Our results show that Amontonian behaviour is observed with each of the surfaces studied. However, no correlation has been found between measured friction and various surface roughness parameters such as average surface roughness (R(a)) and root mean squared (rms) roughness. Instead, we propose that the friction coefficient may be decomposed into two contributions, i.e., µ = µ(0) + µ(g), with the intrinsic friction coefficient µ(0) accounting for the chemical nature of the surfaces and the geometric friction coefficient µ(g) for the presence of nanotextures. We have found a possible correlation between µ(g) and the average local slope of the surface nanotextures.

Keratin-Chitosan Microcapsules via Membrane Emulsification and Interfacial Complexation.

The continuous fabrication via membrane emulsification of stable microcapsules using renewable, biodegradable biopolymer wall materials keratin and chitosan is reported here for the first time. Microcapsule formation was based on opposite charge interactions between keratin and chitosan, which formed polyelectrolyte complexes when solutions were mixed at pH 5.5. Interfacial complexation was induced by transfer of keratin-stabilized primary emulsion droplets to chitosan solution, where the deposition of chitosan around droplets formed a core-shell structure. Capsule formation was demonstrated both in batch and continuous systems, with the latter showing a productivity up to 4.5 million capsules per minute. Keratin-chitosan microcapsules (in the 30-120 µm range) released less encapsulated nile red than the keratin-only emulsion, whereas microcapsules cross-linked with glutaraldehyde were stable for at least 6 months, and a greater amount of cross-linker was associated with enhanced dye release under the application of force due to increased shell brittleness. In light of recent bans involving microplastics in cosmetics, applications may be found in skin-pH formulas for the protection of oils or oil-soluble compounds, with a possible mechanical rupture release mechanism (e.g., rubbing on skin).

Enhanced nanoparticle rejection in aligned boron nitride nanotube membranes.

The rejection of particles with different charges and sizes, ranging from a few Ångstroms to tens of nanometers, is key to a wide range of industrial applications, from wastewater treatment to product purification in biotech processes. Carbon nanotubes (CNTs) have long held the promise to revolutionize filtration, with orders of magnitude higher fluxes compared to commercial membranes. CNTs, however, can only reject particles and ions wider than their internal diameter. In this work, the fabrication of aligned boron nitride nanotube (BNNT) membranes capable of rejecting nanoparticles smaller than their internal diameter is reported for the first time. This is due to a mechanism of charge-based rejection in addition to the size-based one, enabled by the BNNTs surface structure and chemistry and elucidated here using high fidelity molecular dynamics and Brownian dynamics simulations. This results in ∼40% higher rejection of the same particles by BNNT membranes than CNT ones with comparable nanotube diameter. Furthermore, since permeance is proportional to the square of the nanotubes' diameter, using BNNT membranes with ∼30% larger nanotube diameter than a CNT membrane with comparable rejection would result in up to 70% higher permeance. These results open the way to the design of more effective nanotube membranes, capable of high particle rejection and, at the same time, high water permeance.

Shedding Light Onto the Nature of Iron Decorated Graphene and Graphite Oxide Nanohybrids for CO2 Conversion at Atmospheric Pressure.

We report on the design and testing of new graphite and graphene oxide-based extended π-conjugated synthetic scaffolds for applications in sustainable chemistry transformations. Nanoparticle-functionalised carbonaceous catalysts for new Fischer Tropsch and Reverse GasWater Shift (RGWS) transformations were prepared: functional graphene oxides emerged from graphite powders via an adapted Hummer's method and subsequently impregnated with uniform-sized nanoparticles. Then the resulting nanomaterials were imaged by TEM, SEM, EDX, AFM and characterised by IR, XPS and Raman spectroscopies prior to incorporation of Pd(II) promoters and further microscopic and spectroscopic analysis. Newly synthesised 2D and 3D layered nanostructures incorporating carbon-supported iron oxide nanoparticulate pre-catalysts were tested, upon hydrogen reduction in situ, for the conversion of CO2 to CO as well as for the selective formation of CH4 and longer chain hydrocarbons. The reduction reaction was also carried out and the catalytic species isolated and fully characterised. The catalytic activity of a graphene oxide-supported iron oxide pre-catalyst converted CO2 into hydrocarbons at different temperatures (305, 335, 370 and 405 °C), and its activity compared well with that of the analogues supported on graphite oxide, the 3-dimensional material precursor to the graphene oxide. Investigation into the use of graphene oxide as a framework for catalysis showed that it has promising activity with respect to reverse gas water shift (RWGS) reaction of CO2 to CO, even at the low levels of catalyst used and under the rather mild conditions employed at atmospheric pressure. Whilst the γ-Fe2O3 decorated graphene oxide-based pre-catalyst displays fairly constant activity up to 405 °C, it was found by GC-MS analysis to be unstable with respect to decomposition at higher temperatures. The addition of palladium as a promoter increased the activity of the iron functionalised graphite oxide in the RWGS. The activity of graphene oxide supported catalysts was found to be enhanced with respect to that of iron-functionalised graphite oxide with, or without palladium as a promoter, and comparable to that of Fe@carbon nanotube-based systems tested under analogous conditions. These results display a significant step forward for the catalytic activity estimations for the iron functionalised and rapidly processable and scalable graphene oxide. The hereby investigated phenomena are of particular relevance for the understanding of the intimate surface morphologies and the potential role of non-covalent interactions in the iron oxide-graphene oxide networks, which could inform the design of nano-materials with performance in future sustainable catalysis applications.

Enhancing the photo-corrosion resistance of ZnO nanowire photocatalysts.

Zinc oxide (ZnO) displays superior properties as a photocatalyst, compared to the more widely used TiO2. However, widespread application of ZnO is hampered by its high photo-corrosion in aqueous environments under UV irradiation. A systematic investigation of the effect of (i) post-production annealing, (ii) dissolved oxygen levels during photocatalysis and (iii) reactor configuration on the stability and photocatalytic activity (PCA) of ZnO nanowires, grown on either flat or circular supports, was conducted. Results show, for the first time, that it is possible to significantly enhance the photo-corrosion resistance of ZnO in water under UV irradiation while also increasing PCA. Oxygen plasma post-annealing of ZnO nanowire films led to a 46% higher photocatalytic degradation of phenol compared to as-produced films. In oxygen-saturated solutions, both thermally and oxygen plasma annealed ZnO revealed similar photo-corrosion resistance. Switching from a batch to a flow-through reactor, tripled phenol photodegradation under the same irradiation conditions from 19 to 57% due to enhanced mass transfer, while significantly increasing the stability and re-usability of the ZnO, with 5 repeat uses over 3 days showing no decrease in PCA. These results pave the way to more widespread use of photo-corrosion resistant ZnO in the degradation of organic pollutants in water.

3D Printed Fouling-Resistant Composite Membranes.

Fouling remains a long-standing unsolved problem that hinders the widespread use of membrane applications in industry. This article reports the use of numerical simulations coupled with extensive material synthesis and characterization to fabricate fouling-resistant 3D printed composite membranes. The membranes consist of a thin polyethersulfone selective layer deposited onto a 3D printed flat and double sinusoidal (wavy) support. Fouling and cleaning of the composite membranes were tested by using bovine serum albumin solution in a cross-flow ultrafiltration setup. The transmembrane pressure was regulated at 1 bar and the cross-flow Reynolds number (Re) varied between 400 and 1000. In comparison to the flat membrane, the wavy membrane showed superior performance in terms of pure water permeance (PWP) (10% higher) and permeance recovery ratio (87% vs 53%) after the first filtration cycle at Re = 1000. Prolong testing showed that the wavy membrane could retain approximately 87% of its initial PWP after 10 complete filtration cycles. This impressive fouling-resistant behavior is attributed to the localized fluid turbulence induced by the 3D printed wavy structure. These results show that not only the lifetime of membrane operations could be favorably extended but also the operational costs and environmental damage of membrane-based processes could also be significantly reduced.