A Chalcogen‐Bonding Cascade Switch for Planarizable Push–Pull Probes

Planarizable push–pull probes have been introduced to demonstrate physical forces in biology. However, the donors and acceptors needed to polarize mechanically planarized probes are incompatible with their twisted resting state. The objective of this study was to overcome this “flipper dilemma” with chalcogen‐bonding cascade switches that turn on donors and acceptors only in response to mechanical planarization of the probe. This concept is explored by molecular dynamics simulations as well as chemical double‐mutant cycle analysis. Cascade switched flipper probes turn out to excel with chemical stability, red shifts adding up to high significance, and focused mechanosensitivity. Most important, however, is the introduction of a new, general and fundamental concept that operates with non‐trivial supramolecular chemistry, solves an important practical problem and opens a wide chemical space.     

Radical-mediated hydroalkylation of 2-vinylpyrrolidine derivatives: a versatile entry into indolizidine alkaloids

A concise route for the preparation of two simple optically pure indolizidin-5-ones has been developed. The key chain elongation process was achieved using a triethylborane/catechol mediated hydroalkylation of Boc-protected 2-vinylpyrrolidines. By using complementary strategies, these two bicyclic lactams can be alkylated with complete control of the stereochemistry at C(5) and their conversion to a variety of indolizidine alkaloids such as coniceine, indolizidine 209 D and 167 B, 5-epi-indolizidine 249A and monomorine has been reported in the literature.     

Challenges in the understanding oxygen reduction electrocatalysis on transition metal oxides

Transition metal oxides are attractive noble metal-free catalysts of the oxygen reduction for application at the cathode of alkaline membrane fuel cells or metal-air batteries. However, despite of a rapidly increasing number of publications devoted to the oxygen electrocatalysis on transition metal oxides, a clear picture regarding the relations between their structure and composition on the one hand and electrocatalytic activity on the other hand is lacking. This short review discusses challenges facing researchers seeking to understand electrocatalysis of the oxygen reduction reaction on transition metal oxides.     

Dynamic instabilities during the continuous electro-oxidation of CO on poly- and single crystalline Pt electrodes

Dynamic instabilities during bulk CO electro-oxidation on poly- and single crystalline rotating Pt electrodes in different electrolytes were investigated experimentally. In sulphuric and perchloric electrolytic media, only bistability is observed. The dependence of the width of the bistable regime on some parameters is discussed. The addition of small amounts of chloride ions induces current oscillations under potentiostatic conditions on polycrystalline Pt, Pt(1 1 0) and Pt(1 0 0) electrodes. Existence range, shape and mean frequency of the mainly irregular kinetic oscillations vary significantly with the crystallographic structure of the electrode surface.     

Measurement of bone cyst fluid volume using k-means clustering

We designed a semiautomatic segmentation method to easily measure the volume of a bone cyst (simple or aneurysmal) from magnetic resonance imaging (MRI). This method only considers the fluid part of the cyst, even when there are several fluid intensities (fluid-fluid levels) or the cyst is multi-loculated. The nonhomogeneity phenomenon inherent in MRI was handled by a k-means clustering algorithm that classified all of the voxels corresponding to the cyst fluid as the same voxel intensity. Level-set segmentation was expanded into the whole cyst volume and the resulting segmented volume provided the measured cyst volume. The semiautomatic method was compared with the usual manual method (manual contour tracing) in terms of its ability to measure a known volume of water (gold standard) as well as the volume of 29 bone cysts. Both methods were equivalent with regards to the gold standard, but the semiautomatic method was more accurate. In terms of the experimental measurements, the semiautomatic method was more repeatable and reproducible, and less time-consuming and fastidious than the manual method. Our semiautomatic method uses only freeware and can be used routinely whenever measurement of a bone cyst volume is needed.     

First trial of spatial and temporal fractionations of the delivered dose using synchrotron microbeam radiation therapy

The technical feasibility of temporal and spatial fractionations of the radiation dose has been evaluated using synchrotron microbeam radiation therapy for brain tumors in rats. A significant increase in lifespan (216%, p < 0.0001) resulted when three fractions of microbeam irradiation were applied to the tumor through three different ports, orthogonal to each other, at 24 h intervals. However, there were no long‐term survivors, and immunohistological studies revealed that 9 L tumors were not entirely ablated.     

N-doping of pentacene by decamethylcobaltocene

We demonstrate n-type doping of pentacene with the powerful reducing molecule decamethylcobaltocene (CoCp₂^*). Characterization of pentacene films deposited in a background pressure of CoCp₂^* by X-ray photoemission spectroscopy and Rutherford backscattering confirm that the concentration of incorporated donor molecules can be controlled to a level as high as 1%. Ultraviolet photoemission spectroscopy show Fermi level (E _F) shifts toward unoccupied pentacene states, indicative of an increase in the electron concentration. A 1% donor incorporation level brings E _F to 0.6 eV below the pentacene lowest unoccupied molecular orbital. The corresponding electron density of ∼10¹⁸ cm⁻³ is confirmed by capacitance–voltage measurements on a metal–pentacene–oxide–silicon structure. The demonstration of n-doping suggests applications of CoCp₂^* to pentacene contacts or channel regions of pentacene OTFTs.     

A three-dimensional articulatory model of the velum and nasopharyngeal wall based on MRI and CT data

An original three-dimensional (3D) linear articulatory model of the velum and nasopharyngeal wall has been developed from magnetic resonance imaging (MRI) and computed tomography images of a French subject sustaining a set of 46 articulations, covering his articulatory repertoire. The velum and nasopharyngeal wall are represented by generic surface triangular meshes fitted to the 3D contours extracted from MRI for each articulation. Two degrees of freedom were uncovered by principal component analysis: first, VL accounts for 83% of the velum variance, corresponding to an oblique vertical movement seemingly related to the levator veli palatini muscle; second, VS explains another 6% of the velum variance, controlling a mostly horizontal movement possibly related to the sphincter action of the superior pharyngeal constrictor. The nasopharyngeal wall is also controlled by VL for 47% of its variance. Electromagnetic articulographic data recorded on the velum fitted these parameters exactly, and may serve to recover dynamic velum 3D shapes. The main oral and nasopharyngeal area functions controlled by the articulatory model, complemented by the area functions derived from the complex geometry of each nasal passage extracted from coronal MRIs, were fed to an acoustic model and gave promising results about the influence of velum movements on the spectral characteristics of nasals.     

3000% high-field magnetoresistance in super-lattices of CoFe nanoparticles

We report on magnetotransport measurements on millimeter-large super-lattices of CoFe nanoparticles surrounded by an organic layer. Electrical properties are typical of Coulomb blockade in three-dimensional arrays of nanoparticles. A large high-field magnetoresistance, reaching up to 3000%, is measured between 1.8 and 10 K. This exceeds by two orders of magnitude magnetoresistance values generally measured in arrays of 3d transition metal ferromagnetic nanoparticles. The magnetoresistance amplitude scales with the magnetic field/temperature ratio and displays an unusual exponential dependency with the applied voltage. The magnetoresistance abruptly disappears below 1.8 K. We propose that the magnetoresistance is due to some individual paramagnetic moments localized between the metallic cores of the nanoparticles, the origin of which is discussed.     

Solitaire Lattices

 One of the classical problems concerning the peg solitaire game is the feasibility issue. Tools used to show the infeasibility of various peg games include valid inequalities, known as pagoda-functions, and the so-called rule-of-three. Here we introduce and study another necessary condition: the solitaire lattice criterion. While the lattice criterion is shown to be equivalent to the rule-of-three for the classical English 33-board and French 37-board as well as for any m×n board, the lattice criterion is stronger than the rule-of-three for games played on more complex boards. In fact, for a wide family of boards presented in this paper, the lattice criterion exponentially outperforms the rule-of-three. Received: February 22, 1999?Final version received: June 19, 2000