300 research outputs found
Differential Cyclic Voltammetry - a Novel Technique for Selective and Simultaneous Detection using Redox Cycling Based Sensors
Redox cycling (RC) is an effect that is used to amplify electrochemical signals. However, traditional techniques such as cyclic voltammetry (CV) do not provide clear insight for a mixture of multiple redox couples while RC is applied. Thus, we have developed a new measurement technique which delivers electrochemical spectra of all reversible redox couples present based on concentrations and standard potentials. This technique has been named differential cyclic voltammetry (DCV). We have fabricated micrometer-sized interdigitated electrode (IDE) sensors to conduct DCV measurements in mixtures of 1mM catechol and 4mM [Ru(NH3)6]Cl3. To simulate the electrochemical behavior of these sensors we have also developed a finite element model (FEM) in Comsol®. The\ud
experimental data corresponds to the calculated spectra obtained from simulations. Additionally, the measured spectra can be used to easily derive standard potentials and concentrations simultaneously and selectively.\u
A closed form for the electrostatic interaction between two rod-like charged objects
We have calculated the electrostatic interaction between two rod-like charged
objects with arbitrary orientations in three dimensions. we obtained a closed
form formula expressing the interaction energy in terms of the separation
distance between the centers of the two rod-like objects, , their lengths
(denoted by and ), and their relative orientations (indicated by
and ). When the objects have the same length (),
for particular values of separations, i.e for , two types of
minimum are appeared in the interaction energy with respect to . By
employing the closed form formula and introducing a scaled temperature , we
have also studied the thermodynamic properties of a one dimensional system of
rod-like charged objects. For different separation distances, the dependence of
the specific heat of the system to the scaled temperature has been studied. It
is found that for , the specific heat has a maximum.Comment: 10 pages, 9 figures, 1 table, Accepted by J. Phys.: Condens. Matte
Electrochemistry-on-chip for on-line conversions in drug metabolism studies
We have designed an integrated 3-electrode electrochemical cell on-chip with high analyte conversion rates for use in drug metabolism studies. The electrochemical cell contains platinum working and counter electrodes and an iridium oxide pseudo-reference electrode. The pseudo-reference electrode has a pH sensitivity of −52 mV/s, and thus will provide a constant potential in solutions with known and constant pH. The average drift of the iridium oxide electrode is below 5 mV for a typical 15 min conversion experiment. We have been able to mimic the oxidative drug metabolism reactions catalysed by enzymes of the cytochrome P-450 family, normally occurring in the human body. With the chip, the different reaction products of both rat liver cell microsome and human liver cell microsome incubations have been observe
Spectroelectrochemical detection of p-benzoquinone and hydroquinone in an electrochemical microreator with an integrated ATR-IR IRE
Phase separation in mixtures of colloids and long ideal polymer coils
Colloidal suspensions with free polymer coils which are larger than the
colloidal particles are considered. The polymer-colloid interaction is modeled
by an extension of the Asakura-Oosawa model. Phase separation occurs into
dilute and dense fluid phases of colloidal particles when polymer is added. The
critical density of this transition tends to zero as the size of the polymer
coils diverges.Comment: 5 pages, 3 figure
Fabrication of Si-Au nanocone-nanoparticle array for homogeneous enhancement factor in Raman scattering
Flory-Huggins theory for athermal mixtures of hard spheres and larger flexible polymers
A simple analytic theory for mixtures of hard spheres and larger polymers
with excluded volume interactions is developed. The mixture is shown to exhibit
extensive immiscibility. For large polymers with strong excluded volume
interactions, the density of monomers at the critical point for demixing
decreases as one over the square root of the length of the polymer, while the
density of spheres tends to a constant. This is very different to the behaviour
of mixtures of hard spheres and ideal polymers, these mixtures although even
less miscible than those with polymers with excluded volume interactions, have
a much higher polymer density at the critical point of demixing. The theory
applies to the complete range of mixtures of spheres with flexible polymers,
from those with strong excluded volume interactions to ideal polymers.Comment: 9 pages, 4 figure
Equation of state for polymer liquid crystals: theory and experiment
The first part of this paper develops a theory for the free energy of
lyotropic polymer nematic liquid crystals. We use a continuum model with
macroscopic elastic moduli for a polymer nematic phase. By evaluating the
partition function, considering only harmonic fluctuations, we derive an
expression for the free energy of the system. We find that the configurational
entropic part of the free energy enhances the effective repulsive interactions
between the chains. This configurational contribution goes as the fourth root
of the direct interactions. Enhancement originates from the coupling between
bending fluctuations and the compressibility of the nematic array normal to the
average director. In the second part of the paper we use osmotic stress to
measure the equation of state for DNA liquid crystals in 0.1M to 1M NaCl
solutions. These measurements cover 5 orders of magnitude in DNA osmotic
pressure. At high osmotic pressures the equation of state, dominated by
exponentially decaying hydration repulsion, is independent of the ionic
strength. At lower pressures the equation of state is dominated by fluctuation
enhanced electrostatic double layer repulsion. The measured equation of state
for DNA fits well with our theory for all salt concentrations. We are able to
extract the strength of the direct electrostatic double layer repulsion. This
is a new and alternative way of measuring effective charge densities along
semiflexible polyelectrolytes.Comment: text + 5 figures. Submitted to PR
Interfacial tension and nucleation in mixtures of colloids and long ideal polymer coils
Mixtures of ideal polymers with hard spheres whose diameters are smaller than
the radius of gyration of the polymer, exhibit extensive immiscibility. The
interfacial tension between demixed phases of these mixtures is estimated, as
is the barrier to nucleation. The barrier is found to scale linearly with the
radius of the polymer, causing it to become large for large polymers. Thus for
large polymers nucleation is suppressed and phase separation proceeds via
spinodal decomposition, as it does in polymer blends.Comment: 4 pages (v2 includes discussion of the scaling of the interfacial
tension along the coexistence curve and its relation to the Ginzburg
criterion
Transition between Two Regimes Describing Internal Fluctuation of DNA in a Nanochannel
We measure the thermal fluctuation of the internal segments of a piece of DNA confined in a nanochannel about 50100 nm wide. This local thermodynamic property is key to accurate measurement of distances in genomic analysis. For DNA in 100 nm channels, we observe a critical length scale 10 m for the mean extension of internal segments, below which the de Gennes' theory describes the fluctuations with no fitting parameters, and above which the fluctuation data falls into Odijk's deflection theory regime. By analyzing the probability distributions of the extensions of the internal segments, we infer that folded structures of length 150250 nm, separated by 10 m exist in the confined DNA during the transition between the two regimes. For 50 nm channels we find that the fluctuation is significantly reduced since the Odijk regime appears earlier. This is critical for genomic analysis. We further propose a more detailed theory based on small fluctuations and incorporating the effects of confinement to explicitly calculate the statistical properties of the internal fluctuations. Our theory is applicable to polymers with heterogeneous mechanical properties confined in non-uniform channels. We show that existing theories for the end-to-end extension/fluctuation of polymers can be used to study the internal fluctuations only when the contour length of the polymer is many times larger than its persistence length. Finally, our results suggest that introducing nicks in the DNA will not change its fluctuation behavior when the nick density is below 1 nick per kbp DNA
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