199 research outputs found
Transferencia electrónica homogénea de clorofila y su derivado clorofilina en un electrodo de oro
Introduction: Chlorophyll is a light harvesting pigment, which absorbs light in the visible spectrum of sunlight and promotes electron transfer, Chlorophyllin (CHL) is One of the most important derivative molecules of chlorophyll. Nowadays, chlorophyll pigment and its derivatives are utilised in organic photosynthetic solar cells for their desirable photovoltaic properties. Cyclic voltammetry (CV) is an essential technique. It is extensively used to study electroactive species to interpret the intermediates of reactions, supply information about the thermodynamics of oxidation-reduction reactions and elucidate the kinetics of electron transfer reactions. Materials and Methods: Prior to the electrochemical study, the working gold (Au) electrode surface was prepared by immersing it in the various concentrations of chlorophyllin for a period time. The electrolyte was degassed by using N2 for approximately 30 minutes inside a Faraday cage before any electrochemical experiment was performed. A three electrode system was used with, Ag/AgCl as a reference electrode, graphiteas a counter and the working electrode (Au). Results and Discussion: As a route to develop new chemical systems for artificial photosynthesis, this work reports the effectiveness of different parameters in transferring electrons between chlorophyllin (CHL) pigment and the working electrode surface (gold). These parameters such as the adsorption time, the electrolyte nature and concentration and chlorophyllin concentration are investigated. The use of chlorophyllin as a redox mediator is examined, with a gold electrode being employed. The importance of gold electrode surface preparation in determining the mechanism of redox is described, and the environment of adsorption process of the different concentrations of chlorophyllin on the surface of the gold electrode has been elucidated in this study. Conclusiones: The electrochemical method showed that the cyclic voltammetry responses of studied adsorption chlorophyllin pigment on the gold electrode were more efficient. In addition, the redox reaction was successful electrochemically in aqueous solution thanthe organic solution. It was suggested that electrons reduce to the chlorophyllin pigment by adding active species in the bulk solution homogeneous transfer. Finally, detections of chl on spinach leaves using various methods are reported
Linking mineralisation process and sedimentary product in terrestrial carbonates using a solution thermodynamic approach
Determining the processes which generate terrestrial carbonate deposits
(tufas, travertines and to a lesser extent associated chemical sediments such
as calcretes and speleothems) is a long-standing problem. Precipitation of
mineral products from solution reflects a complex combination of biological,
equilibrium and kinetic processes, and the different morphologies of
carbonate sediment produced by different processes have yet to be clearly
demarked. Building on the groundbreaking work of previous authors, we propose
that the underlying control on the processes leading to the deposition of
these products can be most parsimoniously understood from the thermodynamic
properties of their source solutions. Here, we report initial observations of
the differences in product generated from spring and lake systems spanning a
range of temperature–supersaturation space. We find that at high
supersaturation, biological influences are masked by high rates of
physico-chemical precipitation, and sedimentary products from these settings
infrequently exhibit classic "biomediated" fabrics such as clotted micrite.
Likewise, at high temperature (>40 °C) exclusion of vascular
plants and complex/diverse biofilms can significantly inhibit the magnitude
of biomediated precipitation, again impeding the likelihood of encountering
the "bio-type" fabrics.
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Conversely, despite the clear division in product between extensive tufa
facies associations and less spatially extensive deposits such as oncoid
beds, no clear division can be identified between these systems in
temperature–supersaturation space. We reiterate the conclusion of previous
authors, which demonstrate that this division cannot be made on the basis of
physico-chemical characteristics of the solution alone. We further provide a
new case study of this division from two adjacent systems in the UK, where
tufa-like deposition continuous on a metre scale is happening at a site with
lower supersaturation than other sites exhibiting only discontinuous
(oncoidal) deposition. However, a strong microbiological division is
demonstrated between these sites on the basis of suspended bacterial cell
distribution, which reach a prominent maximum where tufa-like deposits are
forming.
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We conclude that at high supersaturation, the thermodynamic properties of
solutions provide a highly satisfactory means of linking process and product,
raising the opportunity of identifying water characteristics from
sedimentological/petrological characteristics of ancient deposits. At low
supersaturation, we recommend that future research focuses on
geomicrobiological processes rather than the more traditional, inorganic
solution chemistry approach dominant in the past
Interaction of temperature, salinity and extracellular polymeric substances controls trace element incorporation into tufa calcite
The influence of extracellular polymeric substances on carbonate mineral growth in natural settings remains one of the most poorly understood contributors to the growth of non-marine carbonate sediments. The influences of these materials are complicated by their association with living cells creating local microenvironments via metabolism and enzyme production, and by our uncertainty about the extracellular polymeric substances materials themselves. Different mixtures of extracellular polymeric substance molecules may behave in different ways, and differences in the local physical environment may alter how the mixtures influence mineral formation, and even result in different patterns of polymerization. Here, the influence of extracellular polymeric substances on calcite precipitation rate and Mg/Cacalcite in the absence of cells is investigated using extracts of extracellular polymeric substances from temperate fluvial tufa biofilm. The influence is complex, with the concentration of extracellular polymeric substances in solution altering deposition rate and trace element incorporation. Moreover, the results show interaction of the presence/absence of extracellular polymeric substances and both temperature and salinity. However, despite extracting extracellular polymeric substances from the same parent sample, a uniform influence was not found in these experiments, implying that the mixture is sufficiently variable within a sample for microenvironments within the biofilm to either promote or inhibit mineralization. As sedimentologists, we can no longer take the view that extracellular polymeric substances are a bystander material, or that they have a single set of coherent and predictable or intuitive influences. Rather, the emphasis must be on investigating the specific mixtures present in nature, and their complex and dynamic interaction with both mineral surfaces and hydrochemical conditions
Scaled free energies, power-law potentials, strain pseudospins and quasi-universality for first-order structural transitions
We consider ferroelastic first-order phase transitions with
order-parameter strains entering Landau free energies as invariant polynomials,
that have structural-variant Landau minima. The total free energy
includes (seemingly innocuous) harmonic terms, in the {\it
non}-order-parameter strains. Four 3D transitions are considered,
tetragonal/orthorhombic, cubic/tetragonal, cubic/trigonal and
cubic/orthorhombic unit-cell distortions, with respectively, and 2; and and 6. Five 2D transitions are also considered, as
simpler examples. Following Barsch and Krumhansl, we scale the free energy to
absorb most material-dependent elastic coefficients into an overall prefactor,
by scaling in an overall elastic energy density; a dimensionless temperature
variable; and the spontaneous-strain magnitude at transition .
To leading order in the scaled Landau minima become
material-independent, in a kind of 'quasi-universality'. The scaled minima in
-dimensional order-parameter space, fall at the centre and at the
corners, of a transition-specific polyhedron inscribed in a sphere, whose
radius is unity at transition. The `polyhedra' for the four 3D transitions are
respectively, a line, a triangle, a tetrahedron, and a hexagon. We minimize the
terms harmonic in the non-order-parameter strains, by substituting
solutions of the 'no dislocation' St Venant compatibility constraints, and
explicitly obtain powerlaw anisotropic, order-parameter interactions, for all
transitions. In a reduced discrete-variable description, the competing minima
of the Landau free energies induce unit-magnitude pseudospin vectors, with values, pointing to the polyhedra corners and the (zero-value) center.Comment: submitted to PR
Electrochemical measurement of antibody‐antigen recognition biophysics: thermodynamics and kinetics of human chorionic gonadotropin (hCG) binding to redox-tagged antibodies
The thermodynamics and kinetics of antigen binding under diffusive conditions to an electrode surface modified with ferrocene-tagged antibodies is studied within this work, and realised experimentally for the case of human chorionic gonadotropin (hGC) as the antigen with monoclonal anti-hCG antibodies immobilised on an electrode surface via a molecular wire platform. The formation of the antigen-antibody complex is monitored through the blocking of the ferrocene voltammetry, thereby enabling the fractional coverage of the electrode binding sites to be unravelled as a function of time. It is found that, at low antigen concentrations, a Frumkin adsorption isotherm fits the data, with repulsive interactions between bound antigens playing a significant rôle, with an affinity constant that is an order of magnitude larger than in the case of an untagged antibody, suggesting that the chemical hydrophobicity of the redox tag may encourage stronger binding. Comparison of the experimental temporal data with relevant diffusion-adsorption models under activation control allows for the extraction of the kinetic parameters; at zero coverage, the rate constants for adsorption and desorption are, respectively, larger and smaller than the untagged antibody. The kinetic study enables the confirmation that this type of platform may be utilised for rapid (15 min) and quantitative electroimmunoassay. This is validated through proof-of-concept analytical measurements, yielding a limit of detection around 25 mIU mL−1 (corresponding to 2.7 ng mL−1) – a value used clinically for urine hCG measurements corresponding to around four weeks of gestational age
Electrochemical Quantification of D-Glucose during the Production of Bioethanol from Thermo-Mechanically Pre-treated Wheat Straw
Mechanical pre-treatment (disc refining) of wheat straw, at both atmospheric and elevated pressure, is shown to be an efficient process to access fermentable monosaccharides, with the potential to integrate within the infrastructure of existing first-generation bioethanol plants. The mild, enzymatic degradation of this sustainable lignocellulosic biomass affords ca. 0.10-0.13 g/g (dry weight) of D-glucose quantifiable voltammetrically in real time, over a two hundred-fold range in experimental laboratory scales (25 mL to 5.0 L), with pressure disc refining of the wheat straw enabling almost twice the amount of D-glucose to be generated during the hydrolysis stage than experiments using atmospheric refining (0.06 – 0.09 g/g dry weight). Fermentation of the resulting hydrolysate affords 0.08 – 0.10 g/g (dry weight) of ethanol over similar scales, with ethanol productivity at ca. 37 mg/(L h). These results demonstrate that minimal cellulose decomposition occurs during pressure refining of wheat straw, in contrast to hemicellulose, and suggest that the development of green, mechanochemical processes for the scalable and cost-effective manufacture of second-generation bioethanol requires improved cellulose decomposition
New Symmetries in Crystals and Handed Structures
For over a century, the structure of materials has been described by a
combination of rotations, rotation-inversions and translational symmetries. By
recognizing the reversal of static structural rotations between clockwise and
counterclockwise directions as a distinct symmetry operation, here we show that
there are many more structural symmetries than are currently recognized in
right- or left-handed handed helices, spirals, and in antidistorted structures
composed equally of rotations of both handedness. For example, though a helix
or spiral cannot possess conventional mirror or inversion symmetries, they can
possess them in combination with the rotation reversal symmetry. Similarly, we
show that many antidistorted perovskites possess twice the number of symmetry
elements as conventionally identified. These new symmetries predict new forms
for "roto" properties that relate to static rotations, such as rotoelectricity,
piezorotation, and rotomagnetism. They also enable symmetry-based search for
new phenomena, such as multiferroicity involving a coupling of spins, electric
polarization and static rotations. This work is relevant to structure-property
relationships in all material structures with static rotations such as
minerals, polymers, proteins, and engineered structures.Comment: 15 Pages, 4 figures, 3 Tables; Fig. 2b has error
Electrochemically Induced Mesomorphism Switching in a Chlorpromazine Hydrochloride Lyotropic Liquid Crystal
The discovery of electrochemical switching of the Lα phase of chlorpromazine hydrochloride in water is reported. The phase is characterized using polarizing microscopy, X-ray scattering, rheological measurements, and microelectrode voltammetry. Fast, heterogeneous oxidation of the lyotropic liquid crystal is shown to cause a phase change resulting from the disordering of the structural order in a stepwise process. The underlying molecular dynamics is considered to be a cooperative effect of both increasing electrostatic interactions and an unfolding of the monomers from "butterfly"-shaped in the reduced form to planar in the oxidized form
Rotation Symmetry Spontaneous Breaking of Edge States in Zigzag Carbon Nanotubes
Analytical solutions of the edge states were obtained for the (N, 0) type
carbon nanotubes with distorted ending bonds. It was found that the edge states
are mixed via the distortion. The total energies for N=5 and N>=7 are lower in
the asymmetric configurations of ending bonds than those having axial rotation
symmetry. Thereby the symmetry is breaking spontaneously. The results imply
that the symmetry of electronic states at the apex depends on the occupation;
the electron density pattern at the apex could change dramatically and could be
controlled by applying an external field.Comment: 19 pages, 3 figure
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