Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).

A multi-scale approach to shaping carbon nanotube structures for hollow microneedles

The concept of a carbon nanotube microneedle array is explored in this thesis from multiple perspectives including microneedle fabrication, physical aspects of transdermal delivery, and in vivo transdermal drug delivery experiments. Starting with standard techniques in carbon nanotube (CNT) fabrication, including catalyst patterning and chemical vapor deposition, vertically-aligned carbon nanotubes are utilized as a scaffold to define the shape of the hollow microneedle. Passive, scalable techniques based on capillary action and unique photolithographic methods are utilized to produce a CNT-polymer composite microneedle. Specific examples of CNT-polyimide and CNT-epoxy microneedles are investigated. Further analysis of the transport properties of polymer resins reveals general requirements for applying arbitrary polymers to the fabrication process.

The bottom-up fabrication approach embodied by vertically-aligned carbon nanotubes allows for more direct construction of complex high-aspect ratio features than standard top-down fabrication approaches, making microneedles an ideal application for CNTs. However, current vertically-aligned CNT fabrication techniques only allow for the production of extruded geometries with a constant cross-sectional area, such as cylinders. To rectify this limitation, isotropic oxygen etching is introduced as a novel fabrication technique to create true 3D CNT geometry. Oxygen etching is utilized to create a conical geometry from a cylindrical CNT structure as well as create complex shape transformations in other CNT geometries.

CNT-polymer composite microneedles are anchored onto a common polymer base less than 50 µm thick, which allows for the microneedles to be incorporated into multiple drug delivery platforms, including modified hypodermic syringes and silicone skin patches. Cylindrical microneedles are fabricated with 100 µm outer diameter and height of 200-250 µm with a central cavity, or lumen, diameter of 30 µm to facilitate liquid drug flow. In vitro delivery experiments in swine skin demonstrate the ability of the microneedles to successfully penetrate the skin and deliver aqueous solutions.

An in vivo study was performed to assess the ability of the CNT-polymer microneedles to deliver drugs transdermally. CNT-polymer microneedles are attached to a hand actuated silicone skin patch that holds a liquid reservoir of drugs. Fentanyl, a potent analgesic, was administered to New Zealand White Rabbits through 3 routes of delivery: topical patch, CNT-polymer microneedles, and subcutaneous hypodermic injection. Results demonstrate that the CNT-polymer microneedles have a similar onset of action as the topical patch. CNT-polymer microneedles were also vetted as a painless delivery approach compared to hypodermic injection. Comparative analysis with contemporary microneedle designs demonstrates that the delivery achieved through CNT-polymer microneedles is akin to current hollow microneedle architectures. The inherent advantage of applying a bottom-up fabrication approach alongside similar delivery performance to contemporary microneedle designs demonstrates that the CNT-polymer composite microneedle is a viable architecture in the emerging field of painless transdermal delivery.

Ionic Liquids and Cellulose: Dissolution, Chemical Modification and Preparation of New Cellulosic Materials

Due to its abundance and a wide range of beneficial physical and chemical properties, cellulose has become very popular in order to produce materials for various applications. This review summarizes the recent advances in the development of new cellulose materials and technologies using ionic liquids. Dissolution of cellulose in ionic liquids has been used to develop new processing technologies, cellulose functionalization methods and new cellulose materials including blends, composites, fibers and ion gels.

Temperature-and pH-Sensitive Nanohydrogels of Poly(N-Isopropylacrylamide) for Food Packaging Applications: Modelling the Swelling-Collapse Behaviour

Temperature-sensitive poly(N-isopropylacrylamide) (PNIPA) nanohydrogels were synthesized by nanoemulsion polymerization in water-in-oil systems. Several cross-linking degrees and the incorporation of acrylic acid as comonomer at different concentrations were tested to produce nanohydrogels with a wide range of properties. The physicochemical properties of PNIPA nanohydrogels, and their relationship with the swelling-collapse behaviour, were studied to evaluate the suitability of PNIPA nanoparticles as smart delivery systems (for active packaging). The swelling-collapse transition was analyzed by the change in the optical properties of PNIPA nanohydrogels using ultraviolet-visible spectroscopy. The thermodynamic parameters associated with the nanohydrogels collapse were calculated using a mathematical approach based on the van't Hoff analysis, assuming a two-state equilibrium (swollen to collapsed). A mathematical model is proposed to predict both the thermally induced collapse, and the collapse induced by the simultaneous action of two factors (temperature and pH, or temperature and organic solvent concentration). Finally, van't Hoff analysis was compared with differential scanning calorimetry. The results obtained allow us to solve the problem of determining the molecular weight of the structural repeating unit in cross-linked NIPA polymers, which, as we show, can be estimated from the ratio of the molar heat capacity (obtained from the van't Hoff analysis) to the specific heat capacity (obtained from calorimetric measurements).

Dehydration for a solid coordination network based on CuII-(py)2C(OH)2 trimers

Abstract de congreso: Póster presentado en 12th International Conference on Materials Chemistry (MC12), 20 - 23 July 2015, York, United Kingdom

Re-conceptualising value in the engineering design process: The value cycle map

Introducing a "Cheaper, Faster, Better" product in today's highly competitive market is a challenging target. Therefore, for organizations to improve their performance in this area, they need to adopt methods such as process modelling, risk mitigation and lean principles. Recently, several industries and researchers focused efforts on transferring the value orientation concept to other phases of the Product Life Cycle (PLC) such as Product Development (PD), after its evident success in manufacturing. In PD, value maximization, which is the main objective of lean theory, has been of particular interest as an improvement concept that can enhance process flow logistics and support decision-making. This paper presents an ongoing study of the current understanding of value thinking in PD (VPD) with a focus on value dimensions and implementation benefits. The purpose of this study is to consider the current state of knowledge regarding value thinking in PD, and to propose a definition of value and a framework for analyzing value delivery. The framework-named the Value Cycle Map (VCM)- intends to facilitate understanding of value and its delivery mechanism in the context of the PLC. We suggest the VCM could be used as a foundation for future research in value modelling and measurement in PD.

Acoustic radiation force of a Bessel beam on a porous sphere.

The possibility of using acoustic Bessel beams to produce an axial pulling force on porous particles is examined in an exact manner. The mathematical model utilizes the appropriate partial-wave expansion method in spherical coordinates, while Biot's model is used to describe the wave motion within the poroelastic medium. Of particular interest here is to examine the feasibility of using Bessel beams for (a) acoustic manipulation of fine porous particles and (b) suppression of particle resonances. To verify the viability of the technique, the radiation force and scattering form-function are calculated for aluminum and silica foams at various porosities. Inspection of the results has shown that acoustic manipulation of low porosity (<0.3) spheres is similar to that of solid elastic spheres, but this behavior significantly changes at higher porosities. Results have also shown a strong correlation between the backscattered form-function and the regions of negative radiation force. It has also been observed that the high-order resonances of the particle can be effectively suppressed by choosing the beam conical angle such that the acoustic contribution from that particular mode vanishes. This investigation may be helpful in the development of acoustic tweezers for manipulation of micro-porous drug delivery carrier and contrast agents.

Separating poroviscoelastic deformation mechanisms in hydrogels

Hydrogels have applications in drug delivery, mechanical actuation, and regenerative medicine. When hydrogels are deformed, load-relaxation arising from fluid flow - poroelasticity - and from rearrangement of the polymer network - viscoelasticity - is observed. The physical mechanisms are different in that poroelastic relaxation varies with experimental length-scale while viscoelastic does not. Here, we show that poroviscoelastic load-relaxation is the product of the two individual responses. The difference in length-scale dependence of the two mechanisms can be exploited to uniquely determine poroviscoelastic properties from simultaneous analysis of multi-scale indentation experiments, providing insight into hydrogel physical behavior. © 2013 American Institute of Physics.

Numerical modelling of chirality-Induced bi-Directional swimming of artificial flagella

Biomimetic micro-swimmers can be used for various medical applications, such as targeted drug delivery and micro-object (e.g. biological cells) manipulation, in lab-on-a-chip devices. Bacteria swim using a bundle of flagella (flexible hair-like structures) that form a rotating cork-screw of chiral shape. To mimic bacterial swimming, we employ a computational approach to design a bacterial (chirality-induced) swimmer whose chiral shape and rotational velocity can be controlled by an external magnetic field. In our model, we numerically solve the coupled governing equations that describe the system dynamics (i.e. solid mechanics, fluid dynamics and magnetostatics). We explore the swimming response as a function of the characteristic dimensionless parameters and put special emphasis on controlling the swimming direction. Our results provide fundamental physical insight on the chirality-induced propulsion, and it provides guidelines for the design of magnetic bi-directional micro-swimmers. © 2013 The Author(s) Published by the Royal Society. All rights reserved.

Dry oxidation and vacuum annealing treatments for tuning the wetting properties of carbon nanotube arrays.

In this article, we describe a simple method to reversibly tune the wetting properties of vertically aligned carbon nanotube (CNT) arrays. Here, CNT arrays are defined as densely packed multi-walled carbon nanotubes oriented perpendicular to the growth substrate as a result of a growth process by the standard thermal chemical vapor deposition (CVD) technique.(1,2) These CNT arrays are then exposed to vacuum annealing treatment to make them more hydrophobic or to dry oxidation treatment to render them more hydrophilic. The hydrophobic CNT arrays can be turned hydrophilic by exposing them to dry oxidation treatment, while the hydrophilic CNT arrays can be turned hydrophobic by exposing them to vacuum annealing treatment. Using a combination of both treatments, CNT arrays can be repeatedly switched between hydrophilic and hydrophobic.(2) Therefore, such combination show a very high potential in many industrial and consumer applications, including drug delivery system and high power density supercapacitors.(3-5) The key to vary the wettability of CNT arrays is to control the surface concentration of oxygen adsorbates. Basically oxygen adsorbates can be introduced by exposing the CNT arrays to any oxidation treatment. Here we use dry oxidation treatments, such as oxygen plasma and UV/ozone, to functionalize the surface of CNT with oxygenated functional groups. These oxygenated functional groups allow hydrogen bond between the surface of CNT and water molecules to form, rendering the CNT hydrophilic. To turn them hydrophobic, adsorbed oxygen must be removed from the surface of CNT. Here we employ vacuum annealing treatment to induce oxygen desorption process. CNT arrays with extremely low surface concentration of oxygen adsorbates exhibit a superhydrophobic behavior.

Mechanical characterisation of hydrogel materials

Interest in hydrogel materials is growing rapidly, due to the potential for hydrogel use in tissue engineering and drug delivery applications, and as coatings on medical devices. However, a key limitation with the use of hydrogel materials in many applications is their relatively poor mechanical properties compared with those of (less biocompatible) solid polymers. In this review, basic chemistry, microstructure and processing routes for common natural and synthetic hydrogel materials are explored first. Underlying structure-properties relationships for hydrogels are considered. A series of mechanical testing modalities suitable for hydrogel characterisation are next considered, including emerging test modalities, such as nanoindentation and atomic force microscopy (AFM) indentation. As the data analysis depends in part on the material's constitutive behaviour, a series of increasingly complex constitutive models will be examined, including elastic, viscoelastic and theories that explicitly treat the multiphasic poroelastic nature of hydrogel materials. Results from the existing literature on agar and polyacrylamide mechanical properties are compiled and compared, highlighting the challenges and uncertainties inherent in the process of gel mechanical characterisation. © 2014 Institute of Materials, Minerals and Mining and ASM International.

Effect of size, composition, and morphology on magnetic performance: First-order reversal curves evaluation of iron oxide nanoparticles

© 2014 AIP Publishing LLC. Superparamagnetic nanoparticles are employed in a broad range of applications that demand detailed magnetic characterization for superior performance, e.g., in drug delivery or cancer treatment. Magnetic hysteresis measurements provide information on saturation magnetization and coercive force for bulk material but can be equivocal for particles having a broad size distribution. Here, first-order reversal curves (FORCs) are used to evaluate the effective magnetic particle size and interaction between equally sized magnetic iron oxide (Fe2O3) nanoparticles with three different morphologies: (i) pure Fe2O3, (ii) Janus-like, and (iii) core/shell Fe2O3/SiO2synthesized using flame technology. By characterizing the distribution in coercive force and interaction field from the FORC diagrams, we find that the presence of SiO2in the core/shell structures significantly reduces the average coercive force in comparison to the Janus-like Fe2O3/SiO2and pure Fe2O3particles. This is attributed to the reduction in the dipolar interaction between particles, which in turn reduces the effective magnetic particle size. Hence, FORC analysis allows for a finer distinction between equally sized Fe2O3particles with similar magnetic hysteresis curves that can significantly influence the final nanoparticle performance.