Journal of Materials Science: Materials in Medicine, Feb 25, 2016
This work presents a combined experimentalnumerical framework for the biomechanical characterizat... more This work presents a combined experimentalnumerical framework for the biomechanical characterization of highly hydrated collagen hydrogels, namely with 0.20, 0.30 and 0.40 % (by weight) of collagen concentration. Collagen is the most abundant protein in the extracellular matrix of animals and humans. Its intrinsic biocompatibility makes collagen a promising substrate for embedding cells within a highly hydrated environment mimicking natural soft tissues. Cell behaviour is greatly influenced by the mechanical properties of the surrounding matrix, but the biomechanical characterization of collagen hydrogels has been challenging up to now, since they present non-linear poro-viscoelastic properties. Combining the stiffness outcomes from rheological experiments with relevant literature data on collagen permeability, poroelastic finite element (FE) models were developed. Comparison between experimental confined compression tests available in the literature and analogous FE stress relaxation curves showed a close agreement throughout the tests. This framework allowed establishing that the dynamic shear modulus of the collagen hydrogels is between 0.0097 ± 0.018 kPa for the 0.20 % concentration and 0.0601 ± 0.044 kPa for the 0.40 % concentration. The Poisson's ratio values for such conditions lie within the range of 0.495-0.485 for 0.20 % and 0.480-0.470 for 0.40 %, respectively, showing that rheology is sensitive enough to detect these small changes in collagen concentration and thus allowing to link rheology results with the confined compression tests. In conclusion, this integrated approach allows for accurate constitutive modelling of collagen hydrogels. This framework sets the grounds for the characterization of related hydrogels and to the use of this collagen parameterization in more complex multiscale models.
This is a repository copy of Changes in silk feedstock rheology during cocoon construction: the r... more This is a repository copy of Changes in silk feedstock rheology during cocoon construction: the role of calcium and potassium ions.
Journal of Biomedical Materials Research Part A, 2005
The development of a novel biocomposite of apatite (Ap) and collagen incorporating low-level addi... more The development of a novel biocomposite of apatite (Ap) and collagen incorporating low-level additions of silicon (Si) as an osseopromotive agent is detailed. Designed to mimic the structural and compositional characteristics of developing bone, this composite is produced via a coprecipitation method, through which the weight percentage of Ap (i.e., the Ap/collagen ratio) can be varied. Coprecipitates produced at Ap contents of 80 wt % (Ap/collagen ϭ 4:1), 60 wt % (Ap/collagen ϭ 3:2), and 40 wt % (Ap/collagen ϭ 2:3) Ap showed markedly different morphologies, ranging from ceramic-like particulates to rope-like macro-fibrils; at all three Ap contents, however, the nanostructural features of the composites remained qualitatively indistinguishable, with equiaxed Ap nanocrystals distributed randomly throughout a matrix of amorphous collagen. Si incorporation was observed to occur preferentially in the collagenous phase-a result with potential impact on local controlled release of Si.
Chemoresistance poses a great barrier to breast cancer treatment and is thought to correlate with... more Chemoresistance poses a great barrier to breast cancer treatment and is thought to correlate with increased matrix stiffness. We developed two-dimensional (2D) polyacrylamide (PAA) and three-dimensional (3D) alginate in vitro models of tissue stiffness that mimic the stiffness of normal breast and breast cancer. We then used these to compare cell viability in response to chemotherapeutic treatment. In both 2D and 3D we observed that breast cancer cell growth and size was increased at a higher stiffness corresponding to tumours compared to normal tissue. When chemotherapeutic response was measured, a specific differential response in cell viability was observed for gemcitabine in 2 of the 7 breast cancer cell lines investigated. MCF7 and T-47D cell lines showed gemcitabine resistance at 4 kPa compared to 500 Pa. These cell lines share a common phenotype of progesterone receptor (PGR) expression and, indeed, pre-treatment with the selective progesterone receptor modulator (SPRM) mifep...
Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2008
This paper describes research performed on a polymer-bonded sugar (PBS) consisting of 66% caster ... more This paper describes research performed on a polymer-bonded sugar (PBS) consisting of 66% caster sugar in a hydroxyl-terminated polybutadiene (HTPB) binder The mechanical response of the PBS and pure HTPB to applied loading at a strain rate of approximately 2000 s−1at temperatures from −80 to +22°C is presented. The materials were also characterized using dynamic mechanical analysis, X-ray tomography and quasi-static loading. These measurements are required for the development of intermediate strain rate constitutive models of polymer-bonded explosives, for which PBSs are a commonly used mechanical simulant.The current constitutive modelling suffers from a lack of experimental data on well-characterized composites and binders, especially at intermediate strain rates. This is particularly important for understanding the effects of mixing two materials. Applications of such modelling include explosive safety and fundamental understanding of the various deformation mechanisms. In this ...
This article is an open access article distributed under the terms and conditions of the Creative... more This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY
International Journal of Molecular Sciences, Oct 29, 2016
The mechanism by which native silk feedstocks are converted to solid fibres in nature has attract... more The mechanism by which native silk feedstocks are converted to solid fibres in nature has attracted much interest. To address this question, the present work used rheology to investigate the gelation of Bombyx mori native silk feedstock. Exceeding a critical shear stress appeared to be more important than shear rate, during flow-induced initiation. Compositional changes (salts, pH etc.,) were not required, although their possible role in vivo is not excluded. Moreover, after successful initiation, gel strength continued to increase over a considerable time under effectively quiescent conditions, without requiring further application of the initial stimulus. Gelation by elevated temperature or freezing was also observed. Prior to gelation, literature suggests that silk protein adopts a random coil configuration, which argued against the conventional explanation of gelation, based on hydrophilic and hydrophobic interactions. Instead, a new hypothesis is presented, based on entropically-driven loss of hydration, which appears to explain the apparently diverse methods by which silk feedstocks can be gelled.
Carbohydrate polymer technologies and applications, Dec 1, 2020
The clinical beliefs (expectations and demands) of veterinarians regarding herd-level strategies ... more The clinical beliefs (expectations and demands) of veterinarians regarding herd-level strategies to control mastitis, lameness, and Johne's disease were quantified in a numerical format; 94 veterinarians working in England (UK) were randomly selected and, during interviews, a statistical technique called probabilistic elicitation was used to capture their clinical expectations as probability distributions. The results revealed that markedly different clinical expectations existed for all 3 diseases, and many pairs of veterinarians had expectations with nonoverlapping 95% Bayesian credible intervals. For example, for a 3-yr lameness intervention, the most pessimistic veterinarian was centered at an 11% population mean reduction in lameness prevalence (95% credible interval: 0-21%); the most enthusiastic veterinarian was centered at a 58% reduction (95% credible interval: 38-78%). This suggests that a major change in beliefs would be required to achieve clinical agreement. Veterinarians' clinical expectations were used as priors in Bayesian models where they were combined with synthetic data (from randomized clinical trials of different sizes) to explore the effect of new evidence on current clinical opinion. The mathematical models make predictions based on the assumption that veterinarians will update their beliefs logically. For example, for the lameness intervention, a 200-farm clinical trial that estimated a 30% mean reduction in lameness prevalence was predicted to be reasonably convincing to the most pessimist veterinarian; that is, in light of this data, they were predicted to believe there would be a 0.92 probability of exceeding the median clinical demand of this sample of veterinarians, which was a 20% mean reduction in lameness. Currently, controversy exists over the extent to which veterinarians update their beliefs logically, and further research on this is needed. This study has demonstrated that probabilistic elicitation and a Bayesian framework are useful for evaluating the diversity and strength of veterinarians' clinical beliefs. The wide variations observed have implications for designing future projects. Although many factors influence disease control, nonetheless the heterogeneity in beliefs also raises concern over the extent to which a broadly consistent approach is currently being achieved; it supports the argument for more randomized clinical trials and for national programs to control nonstatutory endemic diseases.
The "wet-rail" phenomenon results in low adhesion between wheel and rail throughout the year, occ... more The "wet-rail" phenomenon results in low adhesion between wheel and rail throughout the year, occurring transiently on a slightly wet, or drying railhead. It has been previously proposed that it is caused by a mixture of iron oxides and small amounts of water (from dew or precipitation) on the railhead that form a friction reducing paste. This paper outlines a novel combination of rheology, modelling and experimental work using a twin disc test rig to determine how the rheology of this iron oxide paste affects adhesion. The yield strength of different types of iron oxides, along with solid oxide fraction of the friction reducing paste, was assessed and used as an input into an "adhesion model" for assessing water and oxide suspensions. The rheological and modelling results were compared against very low adhesion recorded in twin disc experimental validation when simulating the wet-rail phenomenon.
... 1315, 32, 36 The results of Ryan et al.36 were particularly significant, since ... to this m... more ... 1315, 32, 36 The results of Ryan et al.36 were particularly significant, since ... to this model, the observed intensity was proportional to a particle scattering function (P), which depended ... The authors especially thank S. Freeburn, K. Noorsal, and A. Renouf, who helped to perform ...
Journal of Macromolecular Science, Part B, Mar 16, 2005
Uniaxial stress‐strain behavior of a wide range of polyurethane elastomers was compared with curr... more Uniaxial stress‐strain behavior of a wide range of polyurethane elastomers was compared with current models of rubber‐like elasticity. Although the data could be described well by a semi‐empirical model, a systematic discrepancy was observed with more theoretically based models. This took the form of an additional energy term during deformation, which depended on the polyurethane composition. Microdomain fragmentation may provide
Thermoplastic polyurethanes, such as Pellethane 2363 80A TM (Pel80A) and Pellethane 2363 55D TM (... more Thermoplastic polyurethanes, such as Pellethane 2363 80A TM (Pel80A) and Pellethane 2363 55D TM (Pel55D) are widely used in the medical device industry because of their biological and mechanical properties. However, premature failure in such devices has been observed and attributed to environmental stress cracking (ESC). The current work investigates the possibility of reducing ESC via bulk morphology manipulation. This can be achieved through various processing routes such as solvent-casting (SC) and hotpress quenching (HPQ). The effect of stress on the bulk morphology of Pel55D and Pel80A was evaluated using small-angle X-ray scattering (SAXS) in conjunction with tensile testing. SC samples exhibited greater phase separation compared with HPQ samples. Alignment of hard segment domains became apparent around the point of yield. Onset of ESC with respect to SC and HPQ routines was determined using the Zhao-Stokes glass-wool test with optical (OM) and environment scanning electron microscopy (ESEM). Improvement in biostability of Pel80A was found in HPQ samples compared to those that were SC. A secondary objective of this work was to investigate the effect of acetone pre-treatment on surface morphology. High resolution imaging of acetone treated and untreated SC Pel80A showed significant differences in surface morphology.
This article is an open access article distributed under the terms and conditions of the Creative... more This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY
Native silk proteins, extracted directly from the silk gland prior to spinning, offer access to a... more Native silk proteins, extracted directly from the silk gland prior to spinning, offer access to a naturally hydrated protein that has undergone little to no processing. Combined with differential scanning calorimetry (DSC), it is possible to probe the thermal stability and hydration status of silk and thus investigate its denaturation and solidification, echoing that of the natural spinning process. It is found that native silk is stable between −10 °C and 55 °C, and both the high-temperature enthalpy of denaturation (measured via modulated temperature DSC) and a newly reported low-temperature ice-melting transition may serve as useful quality indicators in the future for artificial silks. Finally, compared to albumin, silk's denaturation enthalpy is much lower than expected, which is interpreted within a recently proposed entropic desolvation framework which can serve to unveil the low-energy aquamelt processing pathway.
A combination of transmission electron microscopy~TEM! and in situ tensile testing in an environm... more A combination of transmission electron microscopy~TEM! and in situ tensile testing in an environmental scanning electron microscopy~ESEM! was used to evaluate the static bulk and dynamic surface morphologies of medical polyurethanes. TEM results showed phase-separated hard segment and soft segment structures. Surface morphology as a function of strain was studied using ESEM in conjunction with a tensometer.
Previous work suggested that two-dimensional small-angle X-ray scattering (2D-SAXS) could offer a... more Previous work suggested that two-dimensional small-angle X-ray scattering (2D-SAXS) could offer a new method for evaluating the local variations of density, strain and principal strain direction within powder compacts, which arise due to the effects of friction and die shape. In order to test this method further, this work compared results from 2D-SAXS with finite element (FE) simulations using a modified density-dependent Drucker-Prager Cap (DPC) model, for compacts of complex shape, prepared using a cylindrical die, a flat-faced upper punch and shaped lower punches with three different central protrusions. Variations in compaction behaviour were observed, which were due to friction against the die walls and the punch shape. Good agreement was obtained between SAXS measurements and FE simulation, supporting previous indications. Hence, this combination of experimental and computational techniques appeared particularly powerful for investigating powder compaction behaviour, in considerable accuracy and detail. Moreover, observations of the compaction behaviour in the vicinity of the central protrusion may be relevant to tablets with embossed features or compacted artefacts of more complex shape.
Silk fibres are assembled via flow. While changes in the physiological environment of the gland a... more Silk fibres are assembled via flow. While changes in the physiological environment of the gland as well as the shear rheology of silk are largely understood, the effect of extensional flow fields on native silk proteins is almost completely unknown. Here we demonstrate that filament stretching on a conventional tensile tester is a suitable technique to assess silk's extensional flow properties and its ability to form fibres under extensional conditions characteristic of natural spinning. We report that native Bombyx mori silk responds differently to extensional flow fields when compared to synthetic linear polymers, as evidenced by a higher Trouton ratio which we attribute to silk's increased interchain interactions. Finally, we show that native silk proteins can only be spun into stable fibres at low extension rates as a result of dehydration, suggesting that extensional fields alone are unable to induce natural fibre formation.
Silk is one of the most intriguing examples of biomolecular selfassembly, yet little is understoo... more Silk is one of the most intriguing examples of biomolecular selfassembly, yet little is understood of molecular mechanisms behind the flow behavior generating these complex high-performance fibers. This work applies the polymer physics of entangled solution rheology to present a first microphysical understanding of silk in the linear viscoelastic regime. We show that silk solutions can be approximated as reptating polymers with "sticky" calcium bridges whose strength can be controlled through the potassium concentration. This approach provides a new window into critical microstructural parameters, in particular identifying the mechanism by which potassium and calcium ions are recruited as a powerful viscosity control in silk. Our model constitutes a viable starting point to understand not only the "flow-induced self-assembly" of silk fibers but also a broader range of phenomena in the emergent field of material-focused synthetic biology.
Journal of Materials Science: Materials in Medicine, Feb 25, 2016
This work presents a combined experimentalnumerical framework for the biomechanical characterizat... more This work presents a combined experimentalnumerical framework for the biomechanical characterization of highly hydrated collagen hydrogels, namely with 0.20, 0.30 and 0.40 % (by weight) of collagen concentration. Collagen is the most abundant protein in the extracellular matrix of animals and humans. Its intrinsic biocompatibility makes collagen a promising substrate for embedding cells within a highly hydrated environment mimicking natural soft tissues. Cell behaviour is greatly influenced by the mechanical properties of the surrounding matrix, but the biomechanical characterization of collagen hydrogels has been challenging up to now, since they present non-linear poro-viscoelastic properties. Combining the stiffness outcomes from rheological experiments with relevant literature data on collagen permeability, poroelastic finite element (FE) models were developed. Comparison between experimental confined compression tests available in the literature and analogous FE stress relaxation curves showed a close agreement throughout the tests. This framework allowed establishing that the dynamic shear modulus of the collagen hydrogels is between 0.0097 ± 0.018 kPa for the 0.20 % concentration and 0.0601 ± 0.044 kPa for the 0.40 % concentration. The Poisson's ratio values for such conditions lie within the range of 0.495-0.485 for 0.20 % and 0.480-0.470 for 0.40 %, respectively, showing that rheology is sensitive enough to detect these small changes in collagen concentration and thus allowing to link rheology results with the confined compression tests. In conclusion, this integrated approach allows for accurate constitutive modelling of collagen hydrogels. This framework sets the grounds for the characterization of related hydrogels and to the use of this collagen parameterization in more complex multiscale models.
This is a repository copy of Changes in silk feedstock rheology during cocoon construction: the r... more This is a repository copy of Changes in silk feedstock rheology during cocoon construction: the role of calcium and potassium ions.
Journal of Biomedical Materials Research Part A, 2005
The development of a novel biocomposite of apatite (Ap) and collagen incorporating low-level addi... more The development of a novel biocomposite of apatite (Ap) and collagen incorporating low-level additions of silicon (Si) as an osseopromotive agent is detailed. Designed to mimic the structural and compositional characteristics of developing bone, this composite is produced via a coprecipitation method, through which the weight percentage of Ap (i.e., the Ap/collagen ratio) can be varied. Coprecipitates produced at Ap contents of 80 wt % (Ap/collagen ϭ 4:1), 60 wt % (Ap/collagen ϭ 3:2), and 40 wt % (Ap/collagen ϭ 2:3) Ap showed markedly different morphologies, ranging from ceramic-like particulates to rope-like macro-fibrils; at all three Ap contents, however, the nanostructural features of the composites remained qualitatively indistinguishable, with equiaxed Ap nanocrystals distributed randomly throughout a matrix of amorphous collagen. Si incorporation was observed to occur preferentially in the collagenous phase-a result with potential impact on local controlled release of Si.
Chemoresistance poses a great barrier to breast cancer treatment and is thought to correlate with... more Chemoresistance poses a great barrier to breast cancer treatment and is thought to correlate with increased matrix stiffness. We developed two-dimensional (2D) polyacrylamide (PAA) and three-dimensional (3D) alginate in vitro models of tissue stiffness that mimic the stiffness of normal breast and breast cancer. We then used these to compare cell viability in response to chemotherapeutic treatment. In both 2D and 3D we observed that breast cancer cell growth and size was increased at a higher stiffness corresponding to tumours compared to normal tissue. When chemotherapeutic response was measured, a specific differential response in cell viability was observed for gemcitabine in 2 of the 7 breast cancer cell lines investigated. MCF7 and T-47D cell lines showed gemcitabine resistance at 4 kPa compared to 500 Pa. These cell lines share a common phenotype of progesterone receptor (PGR) expression and, indeed, pre-treatment with the selective progesterone receptor modulator (SPRM) mifep...
Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2008
This paper describes research performed on a polymer-bonded sugar (PBS) consisting of 66% caster ... more This paper describes research performed on a polymer-bonded sugar (PBS) consisting of 66% caster sugar in a hydroxyl-terminated polybutadiene (HTPB) binder The mechanical response of the PBS and pure HTPB to applied loading at a strain rate of approximately 2000 s−1at temperatures from −80 to +22°C is presented. The materials were also characterized using dynamic mechanical analysis, X-ray tomography and quasi-static loading. These measurements are required for the development of intermediate strain rate constitutive models of polymer-bonded explosives, for which PBSs are a commonly used mechanical simulant.The current constitutive modelling suffers from a lack of experimental data on well-characterized composites and binders, especially at intermediate strain rates. This is particularly important for understanding the effects of mixing two materials. Applications of such modelling include explosive safety and fundamental understanding of the various deformation mechanisms. In this ...
This article is an open access article distributed under the terms and conditions of the Creative... more This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY
International Journal of Molecular Sciences, Oct 29, 2016
The mechanism by which native silk feedstocks are converted to solid fibres in nature has attract... more The mechanism by which native silk feedstocks are converted to solid fibres in nature has attracted much interest. To address this question, the present work used rheology to investigate the gelation of Bombyx mori native silk feedstock. Exceeding a critical shear stress appeared to be more important than shear rate, during flow-induced initiation. Compositional changes (salts, pH etc.,) were not required, although their possible role in vivo is not excluded. Moreover, after successful initiation, gel strength continued to increase over a considerable time under effectively quiescent conditions, without requiring further application of the initial stimulus. Gelation by elevated temperature or freezing was also observed. Prior to gelation, literature suggests that silk protein adopts a random coil configuration, which argued against the conventional explanation of gelation, based on hydrophilic and hydrophobic interactions. Instead, a new hypothesis is presented, based on entropically-driven loss of hydration, which appears to explain the apparently diverse methods by which silk feedstocks can be gelled.
Carbohydrate polymer technologies and applications, Dec 1, 2020
The clinical beliefs (expectations and demands) of veterinarians regarding herd-level strategies ... more The clinical beliefs (expectations and demands) of veterinarians regarding herd-level strategies to control mastitis, lameness, and Johne's disease were quantified in a numerical format; 94 veterinarians working in England (UK) were randomly selected and, during interviews, a statistical technique called probabilistic elicitation was used to capture their clinical expectations as probability distributions. The results revealed that markedly different clinical expectations existed for all 3 diseases, and many pairs of veterinarians had expectations with nonoverlapping 95% Bayesian credible intervals. For example, for a 3-yr lameness intervention, the most pessimistic veterinarian was centered at an 11% population mean reduction in lameness prevalence (95% credible interval: 0-21%); the most enthusiastic veterinarian was centered at a 58% reduction (95% credible interval: 38-78%). This suggests that a major change in beliefs would be required to achieve clinical agreement. Veterinarians' clinical expectations were used as priors in Bayesian models where they were combined with synthetic data (from randomized clinical trials of different sizes) to explore the effect of new evidence on current clinical opinion. The mathematical models make predictions based on the assumption that veterinarians will update their beliefs logically. For example, for the lameness intervention, a 200-farm clinical trial that estimated a 30% mean reduction in lameness prevalence was predicted to be reasonably convincing to the most pessimist veterinarian; that is, in light of this data, they were predicted to believe there would be a 0.92 probability of exceeding the median clinical demand of this sample of veterinarians, which was a 20% mean reduction in lameness. Currently, controversy exists over the extent to which veterinarians update their beliefs logically, and further research on this is needed. This study has demonstrated that probabilistic elicitation and a Bayesian framework are useful for evaluating the diversity and strength of veterinarians' clinical beliefs. The wide variations observed have implications for designing future projects. Although many factors influence disease control, nonetheless the heterogeneity in beliefs also raises concern over the extent to which a broadly consistent approach is currently being achieved; it supports the argument for more randomized clinical trials and for national programs to control nonstatutory endemic diseases.
The "wet-rail" phenomenon results in low adhesion between wheel and rail throughout the year, occ... more The "wet-rail" phenomenon results in low adhesion between wheel and rail throughout the year, occurring transiently on a slightly wet, or drying railhead. It has been previously proposed that it is caused by a mixture of iron oxides and small amounts of water (from dew or precipitation) on the railhead that form a friction reducing paste. This paper outlines a novel combination of rheology, modelling and experimental work using a twin disc test rig to determine how the rheology of this iron oxide paste affects adhesion. The yield strength of different types of iron oxides, along with solid oxide fraction of the friction reducing paste, was assessed and used as an input into an "adhesion model" for assessing water and oxide suspensions. The rheological and modelling results were compared against very low adhesion recorded in twin disc experimental validation when simulating the wet-rail phenomenon.
... 1315, 32, 36 The results of Ryan et al.36 were particularly significant, since ... to this m... more ... 1315, 32, 36 The results of Ryan et al.36 were particularly significant, since ... to this model, the observed intensity was proportional to a particle scattering function (P), which depended ... The authors especially thank S. Freeburn, K. Noorsal, and A. Renouf, who helped to perform ...
Journal of Macromolecular Science, Part B, Mar 16, 2005
Uniaxial stress‐strain behavior of a wide range of polyurethane elastomers was compared with curr... more Uniaxial stress‐strain behavior of a wide range of polyurethane elastomers was compared with current models of rubber‐like elasticity. Although the data could be described well by a semi‐empirical model, a systematic discrepancy was observed with more theoretically based models. This took the form of an additional energy term during deformation, which depended on the polyurethane composition. Microdomain fragmentation may provide
Thermoplastic polyurethanes, such as Pellethane 2363 80A TM (Pel80A) and Pellethane 2363 55D TM (... more Thermoplastic polyurethanes, such as Pellethane 2363 80A TM (Pel80A) and Pellethane 2363 55D TM (Pel55D) are widely used in the medical device industry because of their biological and mechanical properties. However, premature failure in such devices has been observed and attributed to environmental stress cracking (ESC). The current work investigates the possibility of reducing ESC via bulk morphology manipulation. This can be achieved through various processing routes such as solvent-casting (SC) and hotpress quenching (HPQ). The effect of stress on the bulk morphology of Pel55D and Pel80A was evaluated using small-angle X-ray scattering (SAXS) in conjunction with tensile testing. SC samples exhibited greater phase separation compared with HPQ samples. Alignment of hard segment domains became apparent around the point of yield. Onset of ESC with respect to SC and HPQ routines was determined using the Zhao-Stokes glass-wool test with optical (OM) and environment scanning electron microscopy (ESEM). Improvement in biostability of Pel80A was found in HPQ samples compared to those that were SC. A secondary objective of this work was to investigate the effect of acetone pre-treatment on surface morphology. High resolution imaging of acetone treated and untreated SC Pel80A showed significant differences in surface morphology.
This article is an open access article distributed under the terms and conditions of the Creative... more This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY
Native silk proteins, extracted directly from the silk gland prior to spinning, offer access to a... more Native silk proteins, extracted directly from the silk gland prior to spinning, offer access to a naturally hydrated protein that has undergone little to no processing. Combined with differential scanning calorimetry (DSC), it is possible to probe the thermal stability and hydration status of silk and thus investigate its denaturation and solidification, echoing that of the natural spinning process. It is found that native silk is stable between −10 °C and 55 °C, and both the high-temperature enthalpy of denaturation (measured via modulated temperature DSC) and a newly reported low-temperature ice-melting transition may serve as useful quality indicators in the future for artificial silks. Finally, compared to albumin, silk's denaturation enthalpy is much lower than expected, which is interpreted within a recently proposed entropic desolvation framework which can serve to unveil the low-energy aquamelt processing pathway.
A combination of transmission electron microscopy~TEM! and in situ tensile testing in an environm... more A combination of transmission electron microscopy~TEM! and in situ tensile testing in an environmental scanning electron microscopy~ESEM! was used to evaluate the static bulk and dynamic surface morphologies of medical polyurethanes. TEM results showed phase-separated hard segment and soft segment structures. Surface morphology as a function of strain was studied using ESEM in conjunction with a tensometer.
Previous work suggested that two-dimensional small-angle X-ray scattering (2D-SAXS) could offer a... more Previous work suggested that two-dimensional small-angle X-ray scattering (2D-SAXS) could offer a new method for evaluating the local variations of density, strain and principal strain direction within powder compacts, which arise due to the effects of friction and die shape. In order to test this method further, this work compared results from 2D-SAXS with finite element (FE) simulations using a modified density-dependent Drucker-Prager Cap (DPC) model, for compacts of complex shape, prepared using a cylindrical die, a flat-faced upper punch and shaped lower punches with three different central protrusions. Variations in compaction behaviour were observed, which were due to friction against the die walls and the punch shape. Good agreement was obtained between SAXS measurements and FE simulation, supporting previous indications. Hence, this combination of experimental and computational techniques appeared particularly powerful for investigating powder compaction behaviour, in considerable accuracy and detail. Moreover, observations of the compaction behaviour in the vicinity of the central protrusion may be relevant to tablets with embossed features or compacted artefacts of more complex shape.
Silk fibres are assembled via flow. While changes in the physiological environment of the gland a... more Silk fibres are assembled via flow. While changes in the physiological environment of the gland as well as the shear rheology of silk are largely understood, the effect of extensional flow fields on native silk proteins is almost completely unknown. Here we demonstrate that filament stretching on a conventional tensile tester is a suitable technique to assess silk's extensional flow properties and its ability to form fibres under extensional conditions characteristic of natural spinning. We report that native Bombyx mori silk responds differently to extensional flow fields when compared to synthetic linear polymers, as evidenced by a higher Trouton ratio which we attribute to silk's increased interchain interactions. Finally, we show that native silk proteins can only be spun into stable fibres at low extension rates as a result of dehydration, suggesting that extensional fields alone are unable to induce natural fibre formation.
Silk is one of the most intriguing examples of biomolecular selfassembly, yet little is understoo... more Silk is one of the most intriguing examples of biomolecular selfassembly, yet little is understood of molecular mechanisms behind the flow behavior generating these complex high-performance fibers. This work applies the polymer physics of entangled solution rheology to present a first microphysical understanding of silk in the linear viscoelastic regime. We show that silk solutions can be approximated as reptating polymers with "sticky" calcium bridges whose strength can be controlled through the potassium concentration. This approach provides a new window into critical microstructural parameters, in particular identifying the mechanism by which potassium and calcium ions are recruited as a powerful viscosity control in silk. Our model constitutes a viable starting point to understand not only the "flow-induced self-assembly" of silk fibers but also a broader range of phenomena in the emergent field of material-focused synthetic biology.
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