Ionicity-dependent proton-coupled electron transfer of supramolecular self-assembled electroactive heterocycles

Herein, we investigate the electrochemical properties of a class of Supramolecular Self-associated Amphiphilic salts (SSAs). We show that varying ionic strength of an SSA solution can cause a switching of the thermodynamics and kinetics of electron transfer. The effect of self-assembly on proton-coupled electron transfer has implications for the understanding of electron transfer kinetics in aqueous organic redox flow batteries, especially at high concentration where organic–organic intermolecular interactions become dominant even for highly soluble organic species

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 $\vec{c} \cdot \vec{x} = d \mod m$, (unknown variable m)$is a power of two,$\vec{c}$is a vector of integer coefficients, and$\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

An Electrochemical Sensor Based on Nanostructured Hollandite-type Manganese Oxide for Detection of Potassium Ions

The participation of cations in redox reactions of manganese oxides provides an opportunity for development of chemical sensors for non-electroactive ions. A sensor based on a nanostructured hollandite-type manganese oxide was investigated for voltammetric detection of potassium ions. The detection is based on the measurement of anodic current generated by oxidation of Mn(III) to Mn(IV) at the surface of the electrode and the subsequent extraction of the potassium ions into the hollandite structure. In this work, an amperometric procedure at an operating potential of 0.80 V (versus SCE) is exploited for amperometric monitoring. The current signals are linearly proportional to potassium ion concentration in the range 4.97 × 10−5 to 9.05 × 10−4 mol L−1, with a correlation coefficient of 0.9997

Palladized silver as new cathode material: Evidence of a one-electron scission for primary alkyl iodides

Silver electrodes modified by ‘‘palladization” thanks to an immersion in acidic solutions of Pd2+ salts, exhibit exceptional catalytic capabilities especially in the cleavage of primary alkyl halides used as standard systems in order to evaluate the catalytic activity. Such chemically modified surfaces characterized by the formation of an Ag/Pd-based alloy showed large potential shifts compared to the use of glassy carbon or even smooth silver cathodes. Specifically, these palladium-doped silver surfaces were successfully used for cleaving carbon–iodine bonds. Thus, preliminary results have revealed that palladized silver electrodes behave quite differently from smooth silver and showed exceptional catalytic capabilities. Cathodic reductions were achieved in dimethylformamide, acetonitrile, and propylene carbonate. While smooth silver cathodes generally entailed two-electron cleavage reactions (evidence of two clearly separated steps in propylene carbonate), palladized silver interfaces always yield catalytic cleavages of carbon–iodine bonds according to single one-electron processes with the transient formation of a free alkyl radical leading to homo-coupling processes

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

Tracking Monocytes and Macrophages in Tumors With Live Imaging

In most cancers, myeloid cells represent the major component of the immune microenvironment. Deciphering the impact of these cells on tumor growth and in response to various anti-tumor therapies is a key issue. Many studies have elucidated the role of tumor-associated monocytes and tumor-associated macrophages (TAM) in tumor development, angiogenesis, and therapeutic failure. In contrast, tumor dendritic cells (DC) are associated with tumor antigen uptake and T-cell priming. Myeloid subpopulations display differences in ontogeny, state of differentiation and distribution within the neoplastic tissue, making them difficult to study. The development of high-dimensional genomic and cytometric analyses has unveiled the large functional diversity of myeloid cells. Important fundamental insights on the biology of myeloid cells have also been provided by a boom in functional fluorescent imaging techniques, in particular for TAM. These approaches allow the tracking of cell behavior in native physiological environments, incorporating spatio-temporal dimensions in the study of their functional activity. Nevertheless, tracking myeloid cells within the TME remains a challenging process as many markers overlap between monocytes, macrophages, DC, and neutrophils. Therefore, perfect discrimination between myeloid subsets remains impossible to date. Herein we review the specific functions of myeloid cells in tumor development unveiled by image-based tracking, the limits of fluorescent reporters commonly used to accurately track specific myeloid cells, and novel combinations of myeloid-associated fluorescent reporters that better discriminate the relative contributions of these cells to tumor biology according to their origin and tissue localization

Direct Electrochemistry and Electrocatalysis of Hemoglobin at Mesoporous Carbon Modified Electrode

The novel highly ordered mesoporous carbon (known as FDU-15), prepared by the organic-organic self-assembly method was been used for first time for the immobilization of hemoglobin (Hb) and its bioelectrochemical properties were studied. The resulting Hb/FDU-15 film provided a favorable microenvironment for Hb to perform direct electron transfers at the electrode. The immobilized Hb also displayed its good electrocatalytic activity for the reduction of hydrogen peroxide. The results demonstrate that mesoporous carbon FDU-15 can improve the Hb loading with retention of its bioactivity and greatly promote the direct electron transfer, which can be attributed to its high specific surface area, uniform ordered porous structure, suitable pore size and biocompatibility. Our present study may provide an alternative way for the construction of nanostructure biofunctional surfaces and pave the way for its application to biosensors