632 research outputs found
Theoretical treatment of high-frequency, large-amplitude ac voltammetry applied to ideal surface-confined redox systems
A Logical Product Approach to Zonotope Intersection
We define and study a new abstract domain which is a fine-grained combination
of zonotopes with polyhedric domains such as the interval, octagon, linear
templates or polyhedron domain. While abstract transfer functions are still
rather inexpensive and accurate even for interpreting non-linear computations,
we are able to also interpret tests (i.e. intersections) efficiently. This
fixes a known drawback of zonotopic methods, as used for reachability analysis
for hybrid sys- tems as well as for invariant generation in abstract
interpretation: intersection of zonotopes are not always zonotopes, and there
is not even a best zonotopic over-approximation of the intersection. We
describe some examples and an im- plementation of our method in the APRON
library, and discuss some further in- teresting combinations of zonotopes with
non-linear or non-convex domains such as quadratic templates and maxplus
polyhedra
Automatic Abstraction for Congruences
One approach to verifying bit-twiddling algorithms is to derive invariants between the bits that constitute the variables of a program. Such invariants can often be described with systems of congruences where in each equation , (unknown variable m)\vec{c}\vec{x}$ is a vector of propositional variables (bits). Because of the low-level nature of these invariants and the large number of bits that are involved, it is important that the transfer functions can be derived automatically. We address this problem, showing how an analysis for bit-level congruence relationships can be decoupled into two parts: (1) a SAT-based abstraction (compilation) step which can be automated, and (2) an interpretation step that requires no SAT-solving. We exploit triangular matrix forms to derive transfer functions efficiently, even in the presence of large numbers of bits. Finally we propose program transformations that improve the analysis results
A certifying frontend for (sub)polyhedral abstract domains
Convex polyhedra provide a relational abstraction of numerical properties for static analysis of programs by abstract interpretation. We describe a lightweight certification of polyhedral abstract domains using the Coq proof assistant. Our approach consists in delegating most computations to an untrusted backend and in checking its outputs with a certified frontend. The backend is free to implement relaxations of domain operators in order to trade some precision for more efficiency, but must produce hints about the soundness of its results. Experiments with a full-precision backend show that the certification overhead is small and that the certified abstract domain has comparable performance to non-certifying state-of-the-art implementations
Interval Slopes as Numerical Abstract Domain for Floating-Point Variables
The design of embedded control systems is mainly done with model-based tools
such as Matlab/Simulink. Numerical simulation is the central technique of
development and verification of such tools. Floating-point arithmetic, that is
well-known to only provide approximated results, is omnipresent in this
activity. In order to validate the behaviors of numerical simulations using
abstract interpretation-based static analysis, we present, theoretically and
with experiments, a new partially relational abstract domain dedicated to
floating-point variables. It comes from interval expansion of non-linear
functions using slopes and it is able to mimic all the behaviors of the
floating-point arithmetic. Hence it is adapted to prove the absence of run-time
errors or to analyze the numerical precision of embedded control systems
Peptide immobilisation on porous silicon surface for metal ions detection
In this work, a Glycyl-Histidyl-Glycyl-Histidine (GlyHisGlyHis) peptide is covalently anchored to the porous silicon PSi surface using a multi-step reaction scheme compatible with the mild conditions required for preserving the probe activity. In a first step, alkene precursors are grafted onto the hydrogenated PSi surface using the hydrosilylation route, allowing for the formation of a carboxyl-terminated monolayer which is activated by reaction with N-hydroxysuccinimide in the presence of a peptide-coupling carbodiimide N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide and subsequently reacted with the amino linker of the peptide to form a covalent amide bond. Infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy are used to investigate the different steps of functionalization
A tomographic analysis of reflectometry data I: Component factorization
Many signals in Nature, technology and experiment have a multi-component
structure. By spectral decomposition and projection on the eigenvectors of a
family of unitary operators, a robust method is developed to decompose a
signals in its components. Different signal traits may be emphasized by
different choices of the unitary family. The method is illustrated in simulated
data and on data obtained from plasma reflectometry experiments in the tore
Supra.Comment: 27 pages Latex, 17 figure
The rapid formation of functional monolayers on silicon under mild conditions
We report on an exceedingly mild chemical functionalization of hydrogen-terminated Si(100) with unactivated and unprotected bifunctional α,ω-dialkynes. Monolayer formation occurs rapidly in the dark, and at room temperature, from dilute solutions of an aromatic-conjugated acetylene. The method addresses the poor reactivity of p-type substrates under mild conditions. We suggest the importance of several factors, including an optimal orientation for electron transfer between the adsorbate and the Si surface, conjugation of the acetylenic function with a π-system, as well as the choice of a solvent system that favors electron transfer and screens Coulombic interactions between surface holes and electrons. The passivated Si(100) electrode is amenable to further functionalization and shown to be a viable model system for redox studies at non-oxide semiconductor electrodes in aqueous solutions
Electron Transport Properties of Single-Molecule-Bearing Multiple Redox Levels Studied by EC-STM/STS
Multielectron systems as possible components of molecular electronics devices are attracting compelling experimental and theoretical interest. Here we studied by electrochemical scanning tunneling techniques (EC-STMicroscopy and EC-STSpectroscopy) the electron transport properties of a redox molecule endowed with two redox levels, namely, the hydroquinone/quinone (H2Q/Q) couple. By forming self-assembled monolayers on Au(111) of oligo-phenylene-vinylene (OPV) derivatized H2Q/Q moieties, we were able to explore the features of the tunneling current/overpotential relation in the EC-STS setup. The behavior of the tunneling current sheds light onto the mechanism of electron transport involving the redox levels of the H2Q/Q redox pair coupled to tip and substrate electrodes
Electrochemistry of nanozeolite-immobilized cytochrome c in aqueous and nonaqueous solutions
peer-reviewedThe electrochemical properties of cytochrome c (cyt c) immobilized on multilayer nanozeolite-modified electrodes have been examined in aqueous and nonaqueous solutions. Layers of Linde type-L zeolites were assembled on indium tin oxide (ITO) glass electrodes followed by the adsorption of cyt c, primarily via electrostatic interactions, onto modified ITO electrodes. The heme protein displayed a quasi-reversible response in aqueous solution with a redox potential of +324 mV (vs NHE), and the surface coverage (Gamma*) increased linearly for the first four layers and then gave a nearly constant value of 200 pmol cm(-2). On immersion of the modified electrodes in 95% (v/v) nonaqueous solutions, the redox potential decreased significantly, a decrease that originated from changes in both the enthalpy and entropy of reduction. On reimmersion of the modified electrode in buffer, the faradic response immediately returned to its original value. These results demonstrate that nanozeolites are potential stable supports for redox proteins and enzymes.ACCEPTEDpeer-reviewe
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