15 resultados para photochemical alteration
em Cambridge University Engineering Department Publications Database
Resumo:
The self-assembly of proteins and peptides into polymeric amyloid fibrils is a process that has important implications ranging from the understanding of protein misfolding disorders to the discovery of novel nanobiomaterials. In this study, we probe the stability of fibrils prepared at pH 2.0 and composed of the protein insulin by manipulating electrostatic interactions within the fibril architecture. We demonstrate that strong electrostatic repulsion is sufficient to disrupt the hydrogen-bonded, cross-β network that links insulin molecules and ultimately results in fibril dissociation. The extent of this dissociation correlates well with predictions for colloidal models considering the net global charge of the polypeptide chain, although the kinetics of the process is regulated by the charge state of a single amino acid. We found the fibrils to be maximally stable under their formation conditions. Partial disruption of the cross-β network under conditions where the fibrils remain intact leads to a reduction in their stability. Together, these results support the contention that a major determinant of amyloid stability stems from the interactions in the structured core, and show how the control of electrostatic interactions can be used to characterize the factors that modulate fibril stability.
Resumo:
In this paper, we report on the flexoelastic and viscoelastic ratios for a number of bimesogens compounds with the same generic structure. Values are obtained indirectly by measuring the flexoelectro-optic response in the chiral nematic phase. By varying the molecular structure we alter the bend angle, transverse dipole moment, and length of the molecule. First, to examine the influence of the bend angle we use a homologous series whereby the only alteration in the molecular structure is the number of methylene units in the aliphatic spacer, n. Results show that the flexoelastic ratio, e K, and the effective flexoelectric coefficient, e, both exhibit an odd-even effect with values for n=odd being greater than that for n=even. This is understood in terms of an increase in the bend angle of the molecule and an increase in the transverse dipole moment. Second, in order to investigate the impact of the dipole moment, we have altered the mesogenic units so as to vary the longitudinal dipole moment and used different linkages in the aliphatic spacer in an attempt to alter the transverse dipole moment. Qualitatively, the results demonstrate that the odd-spaced bimesogen with larger transverse dipole moments exhibit larger flexoelastic ratios. © 2007 The American Physical Society.
Resumo:
In this paper, we report on the flexoelastic and viscoelastic ratios for a number of bimesogens compounds with the same generic structure. Values are obtained indirectly by measuring the flexoelectro-optic response in the chiral nematic phase. By varying the molecular structure we alter the bend angle, transverse dipole moment, and length of the molecule. First, to examine the influence of the bend angle we use a homologous series whereby the only alteration in the molecular structure is the number of methylene units in the aliphatic spacer, n . Results show that the flexoelastic ratio, e/K , and the effective flexoelectric coefficient, e , both exhibit an odd-even effect with values for n=odd being greater than that for n=even . This is understood in terms of an increase in the bend angle of the molecule and an increase in the transverse dipole moment. Second, in order to investigate the impact of the dipole moment, we have altered the mesogenic units so as to vary the longitudinal dipole moment and used different linkages in the aliphatic spacer in an attempt to alter the transverse dipole moment. Qualitatively, the results demonstrate that the odd-spaced bimesogen with larger transverse dipole moments exhibit larger flexoelastic ratios.
Resumo:
Bone plays a key role in the paleontological and archeological records and can provide insight into the biology, ecology and the environment of ancient vertebrates. Examination of bone at the tissue level reveals a definitive relationship between nanomechanical properties and the local organic content, mineral content, and microstructural organization. However, it is unclear as to how these properties change following fossilization, or diagenesis, where the organic phase is rapidly removed and the remaining mineral phase is reinforced by the deposition of apatites, calcites, and other minerals. While the process of diagenesis is poorly understood, its outcome clearly results in the potential for dramatic alteration of the mechanical response of biological tissues. In this study, fossilized specimens of mammalian long bones, collected from Colorado and Wyoming, were studied for mechanical variations. Nanoindentation performed in both longitudinal and transverse directions revealed preservation of bone's natural anisotropy as transverse modulus values were consistently smaller than longitudinal values. Additionally, modulus values of fossilized bone from 35.0 to 89.1 GPa increased linearly with logarithm of the sample's age. Future studies will aim to clarify what mechanical and material elements of bone are retained during diagenesis as bone becomes part of the geologic milieu. © 2007 Materials Research Society.
Resumo:
A recent study has found that toddlers do not compensate for an artificial alteration in a vowel they hear themselves producing. This raises questions about how young children learn speech sounds. © 2012 Elsevier Ltd.
Resumo:
Experiments are conducted to examine the mechanisms behind the coupling between corner separation and separation away from the corner when holding a high-Machnumber M∞ = 1.5 normal shock in a rectangular channel. The ensuing shock wave interaction with the boundary layer on the wind tunnel floor and in the corners was studied using laser Doppler anemometry, Pitot probe traverses, pressure sensitive paint and flow visualization. The primary mechanism explaining the link between the corner separation size and the other areas of separation appears to be the generation of compression waves at the corner, which act to smear the adverse pressure gradient imposed upon other parts of the flow. Experimental results indicate that the alteration of the -region, which occurs in the supersonic portion of the shock wave/boundary layer interaction (SBLI), is more important than the generation of any blockage in the subsonic region downstream of the shock wave. © Copyright 2012 Cambridge University Press.
Resumo:
Surface texturing has a great potential to improve tribological performance. First, possible texturing methods were identified and classified according to their physical principles. In sequence, some alternative texturing methods are presented. Some of them are already currently used either in industry or in laboratory, and innovations or simplifications are described for them. Others are innovative techniques. Some were explored only tentatively, where basic ideas and simple experimental investigations were developed to check their validity. Others were explored in more detail, so that their practical applicability could be identified. The first texturing method was photochemical texturing using a simple and cheap apparatus. Masking with inkjet printing before chemical etching was also successful to texture metallic samples. A new method involving electrochemical texturing, without the need to previously mask the samples to be textured have been studied in terms of voltage, current, mechanical configuration of the apparatus and electrolyte flushing. Another method aims to generate randomly distributed circular pockets on steel surfaces and involves dispersion of small acid droplets in oil. The final method involves the selective formation of hard areas on a steel surface by locallised diffusion, which should then develop into a texture during wear.
Resumo:
Experiments have been conducted to examine the mechanisms behind the coupling between corner separation and centreline separation when holding a normal shock in a rectangular channel. The study has focused on a M ∞ = 1.5 normal shock held in a wind tunnel with a parallel rectangular cross-section. The primary mechanism explaining the link between the corner separation size and the centreline separation appears to be the generation of compression waves which act to smear the adverse pressure gradient imposed upon other parts of the flow. In addition, the origin of the λ-foot leading leg appears to be depended upon the size of the corner separations. Experimental results indicate that the alteration of the λ-region, which occurs in the supersonic portion of the SBLI, is more important than the generation of any blockage in the subsonic region downstream of the shock wave. Copyright © 2012 by H. Babinsky, D.M.F. Burton.
Resumo:
Fifty years ago, FitzHugh introduced a phase portrait that became famous for a twofold reason: it captured in a physiological way the qualitative behavior of Hodgkin-Huxley model and it revealed the power of simple dynamical models to unfold complex firing patterns. To date, in spite of the enormous progresses in qualitative and quantitative neural modeling, this phase portrait has remained a core picture of neuronal excitability. Yet, a major difference between the neurophysiology of 1961 and of 2011 is the recognition of the prominent role of calcium channels in firing mechanisms. We show that including this extra current in Hodgkin-Huxley dynamics leads to a revision of FitzHugh-Nagumo phase portrait that affects in a fundamental way the reduced modeling of neural excitability. The revisited model considerably enlarges the modeling power of the original one. In particular, it captures essential electrophysiological signatures that otherwise require non-physiological alteration or considerable complexification of the classical model. As a basic illustration, the new model is shown to highlight a core dynamical mechanism by which calcium channels control the two distinct firing modes of thalamocortical neurons. © 2012 Drion et al.
Resumo:
The construction of protein-based photoelectrochemical cells that produce a variety of alternating currents in response to discontinuous illumination is reported. The photovoltaic component is a protein complex from the purple photosynthetic bacterium Rhodobacter sphaeroides which catalyses photochemical charge separation with a high quantum yield. Photoelectrochemical cells formed from this protein, a mobile redox mediator and a counter electrode formed from cobalt disilicide, titanium nitride, platinum, or multi-walled carbon nanotubes (MWCNT) generate a direct current during continuous illumination and an alternating current with different characteristics during discontinuous illumination. In particular, the use of superhydrophobic MWCNT as the back electrode results in a near symmetrical forward and reverse current upon light on and light off, respectively. The symmetry of the AC output of these cells is correlated with the wettability of the counter electrode. Potential applications of a hybrid biological/synthetic solar cell capable of generating an approximately symmetrical alternating current are discussed. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Computational modelling and characterisation of nanoparticle-based tuneable photonic crystal sensors
Resumo:
Photonic crystals are materials that are used to control or manipulate the propagation of light through a medium for a desired application. Common fabrication methods to prepare photonic crystals are both costly and intricate. However, through a cost-effective laser-induced photochemical patterning, one-dimensional responsive and tuneable photonic crystals can easily be fabricated. These structures act as optical transducers and respond to external stimuli. These photonic crystals are generally made of a responsive hydrogel that can host metallic nanoparticles in the form of arrays. The hydrogel-based photonic crystal has the capability to alter its periodicity in situ but also recover its initial geometrical dimensions, thereby rendering it fully reversible and reusable. Such responsive photonic crystals have applications in various responsive and tuneable optical devices. In this study, we fabricated a pH-sensitive photonic crystal sensor through photochemical patterning and demonstrated computational simulations of the sensor through a finite element modelling technique in order to analyse its optical properties on varying the pattern and characteristics of the nanoparticle arrays within the responsive hydrogel matrix. Both simulations and experimental results show the wavelength tuneability of the sensor with good agreement. Various factors, including nanoparticle size and distribution within the hydrogel-based responsive matrices that directly affect the performance of the sensors, are also studied computationally. © 2014 The Royal Society of Chemistry.
Resumo:
Tuneable optical sensors have been developed to sense chemical stimuli for a range of applications from bioprocess and environmental monitoring to medical diagnostics. Here, we present a porphyrin-functionalised optical sensor based on a holographic grating. The holographic sensor fulfils two key sensing functions simultaneously: it responds to external stimuli and serves as an optical transducer in the visible region of the spectrum. The sensor was fabricated via a 6 nanosecond-pulsed laser (350 mJ, λ = 532 nm) photochemical patterning process that enabled a facile fabrication. A novel porphyrin derivative was synthesised to function as the crosslinker of a polymer matrix, the light-absorbing material, the component of a diffraction grating, as well as the cation chelating agent in the sensor. The use of this multifunctional porphyrin permitted two-step fabrication of a narrow-band light diffracting photonic sensing structure. The resulting structure can be tuned finely to diffract narrow-band light based on the changes in the fringe spacing within the polymer and the system's overall index of refraction. We show the utility of the sensor by demonstrating its reversible colorimetric tuneability in response to variation in concentrations of organic solvents and metal cations (Cu 2+ and Fe2+) in the visible region of the spectrum (λmax ≈ 520-680 nm) with a response time within 50 s. Porphyrin-functionalised optical sensors offer great promise in fields varying from environmental monitoring to biochemical sensing to printable optical devices. This journal is © the Partner Organisations 2014.