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Synthesis, Properties, and Applications of Bio-Based Cyclic Aliphatic Polyesters

Cyclic polymers have long been reported in the literature, but their development has often been stunted by synthetic difficulties such as the presence of linear contaminants. Research into the synthesis of these polymers has made great progress in the past decade, and this review covers the synthesis, properties, and applications of cyclic polymers, with an emphasis on bio-based aliphatic polyeste

Self-assembly of ionic and non-ionic surfactants in type IV cerium nitrate and urea based deep eutectic solvent

Understanding and manipulating micelle morphology are key to exploiting surfactants in various applications. Recent studies have shown surfactant self-assembly in a variety of Deep Eutectic Solvents (DESs) where both the nature of surfactants and the interaction of the surfactant molecule with the solvent components influence the size, shape, and morphology of the micelles formed. So far, micelle

Rheological modification of partially oxidised cellulose nanofibril gels with inorganic clays

This study aimed to quantify the influence of clays and partially oxidised cellulose nanofibrils (OCNF) on gelation as well as characterise their physical and chemical interactions. Mixtures of Laponite and montmorillonite clays with OCNF form shear-thinning gels that are more viscous across the entire shear range than OCNF on its own. Viscosity and other rheological properties can be fine-tuned u

Salt-Responsive Pickering Emulsions Stabilized by Functionalized Cellulose Nanofibrils

Oil-in-water emulsions have been stabilized by functionalized cellulose nanofibrils bearing either a negative (oxidized cellulose nanofibrils, OCNF) or a positive (cationic cellulose nanofibrils, CCNF) surface charge. The size of the droplets was measured by laser diffraction, while the structure of the shell of the Pickering emulsion droplets was probed using small-angle neutron scattering (SANS)

Bottom-up cubosome synthesis without organic solvents

Hypothesis: Bottom-up synthesis of cubosomes is more energetically favourable than top-down approaches. However, bottom-up methods often rely on organic solvents such as ethanol as diluents, and lead to concurrent formation of liposomes. We propose using non-toxic diluents such as honey, glycerol and lactic acid for bottom-up cubosome synthesis. Experiments: Cubosomes were prepared using solutions

Non-volatile conductive gels made from deep eutectic solvents and oxidised cellulose nanofibrils

Ionogels offer huge potential for a number of applications including wearable electronics and soft sensors. However, their synthesis has been limited and often relies on non-renewable or non-biocompatible components. Here we present a novel two-component ionogel made using just deep eutectic solvents (DESs) and cellulose. DESs offer a non-volatile alternative to hydrogels with highly tuneable prop

Spin diffusion transfer difference (SDTD) NMR : An advanced method for the characterisation of water structuration within particle networks

Hypothesis: The classical STD NMR protocol to monitor solvent interactions in gels is strongly dependent on gelator and solvent concentrations and does not report on the degree of structuration of the solvent at the particle/solvent interface. We hypothesised that, for suspensions of large gelator particles, solvent structuration could be characterised by STD NMR when taking into account the parti

Structural evolution of iron forming iron oxide in a deep eutectic-solvothermal reaction

Deep eutectic solvents (DES) and their hydrated mixtures are used for solvothermal routes towards greener functional nanomaterials. Here we present the first static structural and in situ studies of the formation of iron oxide (hematite) nanoparticles in a DES of choline chloride : urea where xurea = 0.67 (aka. reline) as an exemplar solvothermal reaction, and observe the effects of water on the r

Microstructural, Thermal, Crystallization, and Water Absorption Properties of Films Prepared from Never-Dried and Freeze-Dried Cellulose Nanocrystals

In this paper, the microstructural, optical, thermal, crystallization, and water absorption properties of films prepared from never-dried (ND) and freeze-dried (FD) cellulose nanocrystals (CNCs) are reported. Morphology of the ND CNCs reveals a needle-like structure, while after freeze-drying, they show a flake-like morphology. Microstructural analysis of ND and FD CNCs are further studied via sma

Interactions of water and amphiphiles with deep eutectic solvent nanostructures

Deep eutectic solvents (DES) are extensively hydrogen-bonded eutectic mixtures with low melting points. The presence of H-bonding makes them highly susceptible to interactions with water and also allows them to support amphiphile self-assembly, both for surfactants and biological lipids. Water disrupts the DES nework through intermolecular H-bonding, leading to changes in physicochemical propertie

Composite Hydrogel Spheroids Based on Cellulose Nanofibrils and Nanofibrous Chiral Coordination Polymer by Green Synthesis

Cellulose-based hydrogels are promising sustainable materials for a variety of applications, including tissue engineering, water treatment, and drug delivery. However, the tailoring of diverse properties by efficient green chemistry methods is an ongoing challenge. Here, composite hydrogels of consistent spheroidal structure, incorporating TEMPO-oxidized cellulose nanofibrils and nanofibrous chira

Core-Shell Spheroidal Hydrogels Produced via Charge-Driven Interfacial Complexation

Through charge-driven interfacial complexation, we produced millimeter-sized spheroidal hydrogels (SH) with a core-shell structure allowing long-term stability in aqueous media. The SH were fabricated by extruding, dropwise, a cationic cellulose nanofibril (CCNF) dispersion into an oppositely charged poly(acrylic acid) (PAA) bath. The SH have a solid-like CCNF-PAA shell, acting as a semipermeable

Small angle X-ray scattering from MCM-41 and its synthesis gels : optimisation of the synthesis parameters

We have found optimised conditions for alkaline synthesis of the large pore molecular sieve, MCM-41, by determining small angle X-ray scattering and adsorption isotherms from materials at various stages of the preparation. The presence of highly curved surfaces, sealed structures, and quasicrystalline hexagonal products coexisting with true MCM-41 are all detected by transmission electron microsco

Methane dynamics in the 36 Å mesopores of MCM-41 studied by neutron scattering

The capillary melting of methane adsorbed into the uniform parallel mesopores of the new silicate MCM-41 has been studied by neutron inelastic scattering and neutron quasielastic scattering at an energy resolution of about 80 microelectron volts. Differences from bulk methane in both the rotational melting and the solid to liquid transition have been identified. Rotational melting occurs at about

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-pr

Self-assembly of amphiphilic polyoxometalates for the preparation of mesoporous polyoxometalate-titania catalysts

Amphiphilic polyoxometalate (POM) surfactants were prepared by covalently grafting double hydrophobic tails with chain lengths C12H25, C14H29, C16H33 or C18H37 onto the lacunary Wells-Dawson {P2W17O61} headgroup. The critical micelle concentrations (CMCs) of these novel surfactants in aqueous solutions were determined by conductivity, and micelle formation was studied by small angle neutron scatte

Deep eutectic solvent in water Pickering emulsions stabilised by cellulose nanofibrils

Deep eutectic solvent (menthol : dodecanoic acid) in water (30 : 70) emulsions stabilised with partially oxidised cellulose nanoparticles remained stable for 200 days at room temperature. Deep eutectic-based emulsions offer potential for non-aqueous reaction systems, chemical extraction, and controlled release. Pickering emulsions using polysaccharides are less toxic and more stable than surfactan

Thermal resilience of ensilicated lysozyme via calorimetric and in vivo analysis

Ensilication is a novel method of protein thermal stabilisation using silica. It uses a modified sol-gel process which tailor fits a protective silica shell around the solvent accessible protein surface. This, electrostatically attached, shell has been found to protect the protein against thermal influences and retains its native structure and function after release. Here, we report the calorimetr

Structural and chemical heterogeneity in ancient glass probed using gas overcondensation, X-ray tomography, and solid-state NMR

Rare ancient glasses have complex, multi-scale structures requiring more sophisticated and non-destructive pore characterisation techniques than usual. Homotattic patch models for nitrogen adsorption gave better fits to the isotherm data, more accurate void space descriptors, and also greater understanding of the underlying physical factors affecting adsorption, than standard BET. These homotattic