Collagen scaffolds are widely used in a range of tissue engineering applications, both in vitro and in vivo, where their permeability to fluid flow greatly affects their mechanical and biological functionality. This paper reports new insights into the interrelationships between permeability, scaffold structure, fluid pressure and deformation in collagen scaffolds, focussing in particular on the degree of closure and the alignment of the pores. Isotropic and aligned scaffolds of different occlusivity were produced by ice templating, and were characterised in terms of their structure and mechanical properties. Permeability studies were conducted using two experimental set-ups to cover a wide range of applied fluid pressures. The permeability was found to be constant at low pressures for a given scaffold with more open structures and aligned structures being more permeable. The deformation of scaffolds under high pressure led to a decrease in permeability. The aligned structures were more responsive to deformation than their isotropic equivalents with their permeability falling more quickly at low strain. For isotropic samples, a broad (1 - epsilon)(2) dependence for permeability was observed with the constant of proportionality varying with collagen fraction as the starting structures became more occluded. Aligned scaffolds did not follow the same behaviour, with the pores apparently closing more quickly in response to early deformation. These results highlight the importance of scaffold structure in determining permeability to interstitial fluid, and provide an understanding of scaffold behaviour within the complex mechanical environment of the body. Statement of significance Collagen scaffolds are widely used in tissue engineering applications, for instance to contribute with wound healing. Their permeability to fluid flow, such as water and blood, is important to ensure they perform efficiently when inside the body. The present study reports new insights into the relationships between permeability, scaffold structure, fluid pressure and deformation in collagen scaffolds. It presents in particular the experimental setups used to measure these properties and the result of comparisons between collagen scaffolds with different structures: aligned and isotropic (non-aligned). It indicates quantitative differences in terms of permeability, and the effects of compression on such permeability. The results contribute to the development and understanding of collagen scaffolds and their applications. (C) 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
The phase transition from water to ice is one which often occurs in the daily world around us. In fact, the transition from water to ice is unique in several ways and a process which continues to fascinate scientists in its complexity. At normal pressures, ice exists as a hexagonal crystal structure, which is held together via hydrogen bonding. 1 In comparison to the disordered liquid, molecules within the crystal structure of the solid are further apart, causing the density of ice to decrease during the transition from a liquid to a solid. 1 As the structure of ice forms, it has a tendency to exclude impurities or solutes rather than incorporating them into the crystal lattice. 1 Thus, ice is “self-cleaning” and solidification results in the spaces between ice grains being enriched in solutes. The self-cleaning nature of ice makes it useful for a number of applications, such as purifying solutes and creating porous structures, both of which are accomplished through a broad technique called ice-templating. a) Authors to whom correspondence should be addressed. Electronic addresses: kmp42@ cam. ac. uk, Tel.: þ44 01223 34560 and rec11@ cam. ac. uk, Tel.: þ44 01223 34324. Fax: þ44 01223 34567. b) E-mail: ah492@ cam. ac. uk c) E-mail: smb51@ cam. ac. uk
The potential applications of ice-templating porous materials are constantly expanding, especially as scaffolds for tissue engineering. Ice-templating, a process utilizing ice nucleation and growth within an aqueous solution, consists of a cooling stage (before ice nucleation) and a freezing stage (during ice formation). While heat release during cooling can change scaffold isotropy, the freezing stage, where ice crystals grow and anneal, determines the final size of scaffold features. To investigate the path of heat flow within collagen slurries during solidification, a series of ice-templating molds were designed with varying the contact area with the heat sink, in the form of the freeze drier shelf. Contact with the heat sink was found to be critical in determining the efficiency of the release of latent heat within the perspex molds. Isotropic collagen scaffolds were produced with pores which ranged from 90 μm up to 180 μm as the contact area decreased. In addition, low-temperature ice annealing was observed within the structures. After 20 h at −30 °C, conditions which mimic storage prior to lyophilization, scaffold architecture was observed to coarsen significantly. In future, ice-templating molds should consider not only heat conduction during the cooling phase of solidification, but the effects of heat flow during ice growth and annealing.
The structure of ice-templated collagen scaffolds is sensitive to many factors. By adding 0.5 wt% of sodium chloride or sucrose to collagen slurries, scaffold structure could be tuned through changes in ice growth kinetics and interactions of the solute and collagen. With ionic solutes (sodium chloride) the entanglements of the collagen molecule decreased, leading to fibrous scaffolds with increased pore size and decreased attachment of chondrocytes. With non-ionic solutes (sucrose) ice growth was slowed, leading to significantly reduced pore size and up-regulated cell attachment. This highlights the large changes in structure and biological function stimulated by solutes in ice-templating systems.
Biopolymer scaffolds have great therapeutic potential within tissue engineering due to their large interconnected porosity and biocompatibility. Using an ice-templated technique, where collagen is concentrated into a porous network by ice nucleation and growth, scaffolds with anisotropic pore architecture can be created, mimicking natural tissues like cardiac muscle and bone. This paper describes a systematic set of experiments undertaken to understand the effect of local temperatures on architecture in ice-templated biopolymer scaffolds. The scaffolds within this study were at least 10mm in all dimensions, making them applicable to critical sized defects for biomedical applications. It was found that monitoring the local freezing behavior within the slurry was critical to predicting scaffold structure. Aligned porosity was produced only in parts of the slurry volume which were above the equilibrium freezing temperature (0°C) at the time when nucleation first occurs in the sample as a whole. Thus, to create anisotropic scaffolds, local slurry cooling rates must be sufficiently different to ensure that the equilibrium freezing temperature is not reached throughout the slurry at nucleation. This principal was valid over a range of collagen slurries, demonstrating that by monitoring the temperature within slurry during freezing, scaffold anisotropy with ice-templated scaffolds can be predicted.
In this paper, we show, for the first time, the key link between scaffold architecture and latent heat evolution during the production of porous biomedical collagen structures using freeze-drying. Collagen scaffolds are used widely in the biomedical industry for the repair and reconstruction of skeletal tissues and organs. Freeze-drying of collagen slurries is a standard industrial process, and, until now, the literature has sought to characterize the influence of set processing parameters including the freezing protocol and weight percentage of collagen. However, we are able to demonstrate, by monitoring the local thermal events within the slurry during solidification, that nucleation, growth and annealing processes can be controlled, and therefore we are able to control the resulting scaffold architecture. Based on our correlation of thermal profile measurements with scaffold architecture, we hypothesize that there is a link between the fundamental freezing of ice and the structure of scaffolds, which suggests that this concept is applicable not only for collagen but also for ceramics and pharmaceuticals. We present a design protocol of strategies for tailoring the ice-templated scaffold structure.
Ice-templating techniques, including freeze-drying and freeze casting, are extremely versatile and can be used with a variety of materials systems. The process relies on the freezing of a water based solution. During freezing, ice nucleates within the solution and concentrates the solute in the regions between the growing crystals. Once the ice is removed via sublimation, the solute remains in a porous structure, which is a negative of the ice. As the final structure of the ice relies on the freezing of the solution, the variables which influence ice nucleation and growth alter the structure of ice-templated scaffolds. Nucleation, the initial step of freezing, can be altered by the type and concentration of solutes within the solution, as well as the set cooling rate before freezing. After nucleation, crystal growth and annealing processes, such as Ostwald ripening, determine the features of the final scaffold. Both crystal growth and annealing are sensitive to many factors including the set freezing temperature and solutes. The porous structures created using ice-templating allow scaffolds to be used for many diverse applications, from microfluidics to biomedical tissue engineering. Within the field of tissue engineering, scaffold structure can influence cellular behavior, and is thus critical for determining the biological stimulus supplied by the scaffold. The research focusing on controlling the ice-templated structure serves as a model for how other ice-templating systems might be tailored, to expand the applications of ice-templated structures to their full potential. (C) 2014 AIP Publishing LLC.
In this paper we prove for the first time the key link between scaffold architecture and latent heat evolution during the production of porous biomedical collagen structures using freeze drying. Collagen scaffolds are used widely in the biomedical industry for the repair and reconstruction of skeletal tissues and organs. Freeze drying of collagen slurries is an industry standard, and until now, literature has sought to characterize the influence of set processing parameters including the freezing protocol and weight percentage of collagen. However, we are able to demonstrate, by monitoring the local thermal events within the slurry during solidification, that nucleation, growth and annealing processes can be controlled, and therefore we are able to control the resulting scaffold architecture. Based on our correlation of thermal profile measurements with scaffold architecture we hypothesize that there is a universal link between the fundamental freezing of ice and the structure of scaffolds which suggests that this concept is not only applicable for collagen, but also for ceramics and pharmaceuticals. We present a toolkit of strategies for tailoring the ice templated scaffold structure.
Cobalt antidot arrays defined within a Hall bar mesa have been fabricated using electron-beam lithography. The diameter of the circular antidots was fixed at 1μm with the antidot edge-to-edge spacing varying from 2to0.5μm in a square lattice and 0.4μm in a rotated square lattice. In-plane magnetoresistance measurements were carried out to investigate the magnetization reversal properties. Antidots greatly modify the domain configuration and work as domain wall pinning sites. As a result, the switching and saturation fields increase while the magnetoresistance ratio decreases with the inclusion of antidots and also with increasing antidot areal density. Micromagnetic simulations show that the magnetization reversal of antidot arrays proceeds with the formation and annihilation of domain walls, which is manifested as Barkhausen jumps in the transition regions of the magnetoresistance curves.
The selective composition control of the electron wavefunction in a GaAs/InGaAs double quantum well device is presented for two different gating schemes. In particular, electron-beam defined surface gates schemes allow the definition of non-ballistic quasi-one-dimensional conduction channels in each of the quantum wells and result in the ability to electrostatically move the electron wavefunction between the two materials. The use of such a device as the basis for a spin qubit, due to the differing g-factors, and the investigation of other spin-related phenomena in one-dimension are discussed.
The electronic structure of the Heusler alloy Co2TiSn is investigated here, with particular attention paid to its potential as a half-metallic ferromagnet. Ab initio calculations are performed using a plane wave pseudopotential code in the framework of density functional theory. These accurate calculations are done with convergence tolerances of 10(-5) and 10(-4) eV on the total energy and Fermi energy, respectively. The alloy is found not to be a half-metal. Minority spin electrons undergo distinctly hole-like dispersion at the Gamma point in k space while the majority spin bands are metallic with a multiply connected tube-like Fermi surface. Further, the computed minority band gap and spin polarization at the Fermi level are larger when the calculation is performed using the generalized gradient approximation.
The Heusler alloy, Co2CrAl, is an itinerant magnet that orders at T=333 K. We have measured its temperature-dependent anomalous Hall effect and magnetoresistance from room temperature down to low temperatures. The magnetoresistance is positive and very small. The anomalous Hall conductivity follows the magnetization with the ratio of the two quantities being constant over the whole temperature range, suggesting that the origin of the anomalous Hall effect is intrinsic.
Electrical spin injection in a narrow [100] In0.2Ga0.8As quantum well in a GaAs p-i-n optical device is reported. The quantum well is located 300nm from an AlGaAs Schottky barrier and this system is used to compare the efficiencies and temperature dependences of spin injection from Fe and the Heusler alloy Co2.4Mn1.6Ga grown by molecular-beam epitaxy. At 5K, the injected electron spin polarizations for Fe and Co2.4Mn1.6Ga injectors are 31% and 13%, respectively. Optical detection is carried out in the oblique Hanle geometry. A dynamic nuclear polarization effect below 10K enhances the magnetic field seen by the injected spins in both devices. The Co2.4Mn1.6Ga thin films are found to have a transport spin polarization of ∼50% by point contact Andreev reflection conductivity measurements.
Highly crystalline and almost monodisperse spinel cobalt-ferrite nanocrystals are synthesized in a one step process, which has very high coercivity at 10 K and exhibits superparamagnetic behaviour at 300 K.
High resolution pressure measurements in the zero-temperature limit provide a unique opportunity to study the behavior of strongly interacting, itinerant electrons with coupled spin and charge degrees of freedom. Approaching the precision that has become the hallmark of experiments on classical critical phenomena, we characterize the quantum critical behavior of the model, elemental antiferromagnet chromium, lightly doped with vanadium. We resolve the sharp doubling of the Hall coefficient at the quantum critical point and trace the dominating effects of quantum fluctuations up to surprisingly high temperatures.
μSR can be applied to the study of various dynamical processes in polymers. These processes may relate to carrier motion, as in studies of conducting polymers which make use of muon generated polarons to measure carrier diffusion rates. Alternatively the processes of interest may be related to the structural dynamics of the polymer, which can show dramatic changes around the glass transition temperature. We report here examples of the use of μSR to study the muon states and muon mobility in the polymers polyethylene and polytetrafluoroethylene, where coherent FμF precession signals have been observed. In the case of polystyrene, muon radical states formed on the phenyl ring have been used to make a detailed study of the dynamical freezing and onset of static disorder that accompanies the glass transition. Finally, we report a study of polaron diffusion in two polyphenylenevinylene conducting polymers.
Magnetic fields change the way that electrons move through solids. The nature of these changes reveals information about the electronic structure of a material and, in auspicious circumstances, can be harnessed for applications. The silver chalcogenides, Ag 2 Se and Ag 2 Te, are non-magnetic materials, but their electrical resistance can be made very sensitive to magnetic field by adding small amounts—just 1 part in 10,000—of excess silver 1 , 2 , 3 , 4 . Here we show that the resistance of Ag 2 Se displays a large, nearly linear increase with applied magnetic field without saturation to the highest fields available, 600,000 gauss, more than a million times the Earth's magnetic field. These characteristics of large (thousands of per cent) and near-linear response over a large field range make the silver chalcogenides attractive as magnetic-field sensors, especially in physically tiny megagauss (10 6 G) pulsed magnets where large fields have been produced but accurate calibration has proved elusive. High-field studies at low temperatures reveal both oscillations in the magnetoresistance and a universal scaling form that point to a quantum origin 5 , 6 for this material's unprecedented behaviour.