Reactivity of Cyclic (Alkyl)(amino)carbenes (CAACs) and Bis(amino)cyclopropenylidenes (BACs) with Heteroallenes: Comparisons with their N‐Heterocyclic Carbene (NHCs) Counterparts

Similarly to NHCs, CAAC_a and BAC_a react with CO₂ to give the corresponding betaines. Based on the carbonyl stretching frequencies of cis‐[RhCl(CO)₂(L)] complexes, the order of electron donor ability was predicted to be CAAC_a≈BAC_a>NHCs. When the betaines ν_asym(CO₂) values are used, the apparent ordering is BAC_a>NHCs≈CAAC_a that indicates a limitation for the use of IR spectroscopy in the ranking of ligand σ‐donating ability. Although all carbenes react with carbon disulfide to give the corresponding betaines, a second equivalent of CS₂ reacts with the BAC‐CS₂ leading to a bicyclic thieno[2,3‐diamino]‐1,3‐dithiole‐2‐thione, which results from a novel ring expansion process. Surprisingly, in contrast to NHCs, CAAC _a does not react with carbodiimide, whereas BAC_a exclusively gives a ring expanded product, analogous to that obtained with CS₂. The intermediate amidinate can be trapped, using the lithium tetrafluoroborate adduct of BAC_b as a carbene surrogate.     

On the physical origin of conical bubble structure under an ultrasonic horn

The cavitation field generated by an ultrasonic horn at low frequency and high power is known to self-organize into a conical bubble structure. The physical mechanism at the origin of this bubble structure is investigated using numerical simulations and acoustic pressure measurements. The thin bubbly layer lying at horn surface is shown to act as a nonlinear thickness resonator that amplifies acoustic pressure and distorts acoustic waveform. This mechanism explains the self-stabilization of the conical bubble structure as well as the generation of shock wave and the focusing at very short distance.     

Evaluation of antiangiogenic treatment effects on tumors' microcirculation by Bayesian physiological pharmacokinetic modeling and magnetic resonance imaging

A physiological pharmacokinetic (PBPK) model was used to estimate tumor microcirculation in nude mice with a grafted tumor. The kinetics of a rapid clearance blood pool agent, Vistarem, were investigated by dynamic MRI after bolus administration. Signal enhancements were recorded in arterial blood and in tumor tissue. To analyze these data, we developed a whole-body mathematical model of the agent's biodistribution using physiological parameters. The model included six compartments: arterial and venous plasma, tumor (split into capillaries and interstitium), and the rest of the body (also split into capillaries and interstitium). As an application, changes in tumor microcirculation parameters were evaluated in mice receiving either an antiangiogenic treatment (ZD4190) or a placebo. The analysis was performed in a Bayesian framework, and the model was fitted to experimental data using Markov Chain Monte Carlo techniques. Results showed a significant difference in tumor microcirculation between the two groups of mice when the microcirculation parameters are considered together. This whole-body physiological model enables to analyze jointly data in tumor tissue and in arterial blood. This leads to accurate estimates of microcirculation parameters and the evaluation of their uncertainty.     

Proposed experiments to probe the non-Abelian nu = 5/2 quantum hall state

We propose several experiments to test the non-Abelian nature of quasiparticles in the fractional quantum Hall state at nu = 5/2. In a simplified version of the experiment suggested by [S. Das Sarma, M. Freedman, and C. Nayak, Phys. Rev. Lett. 94, 166802 (2005).], interference is turned on and off when the number of localized quasiparticles between the interfering paths varies between even and odd. We find analogous effects in the thermodynamic properties of closed systems.     

Measuring the kinetics of biomolecular recognition with magnetic colloids

We introduce a general methodology based on magnetic colloids to study the recognition kinetics of tethered biomolecules. Access to the full kinetics of the reaction is provided by an explicit measure of the time evolution of the reactant densities. Binding between a single ligand and its complementary receptor is here limited by the colloidal rotational diffusion. It occurs within a binding distance that can be extracted by a reaction-diffusion theory that properly accounts for the rotational Brownian dynamics. Our reaction geometry allows us to probe a large diversity of bioadhesive molecules and tethers, thus providing a quantitative guidance for designing more efficient reactive biomimetic surfaces, as required for diagnostic, therapeutic, and tissue engineering techniques.     

Investigating Acrylic Acid Polymerization by Using a Droplet-Based Millifluidics Approach

We present herein the basic concept of droplet-based millifluidics as an original tool to monitor polymerization kinetics. As a proof of concept, we use aqueous droplets of acrylic acid mixed with sodium persulfate at various pH as polymerization microreactor models. According to the pH and the temperature, completion could be obtained within a minute. Despite the fact that this reaction is quite fast and exothermic, we were able to acquire data in order to obtain valuable information about the polymerization kinetics. We were also able to estimate the overall activation energy for polymerization rate. Furthermore, offline analyses by Size Exclusion Chromatography show high molecular weights and high polydispersities. These results set the stage for further studies of polymerization reactions where detailed basic kinetic data must be acquired in conditions which cannot be investigated by using conventional batch glassware (i.e. high temperatures or concentrations). This new approach can also be used as an efficient High Throughput Screening tool.     

Longevity risk in pension annuities with exchange options: The effect of product design

We consider defined benefit pension plans that, at retirement age, allow the participant to choose between a single life annuity and a joint and survivor annuity. We compare two plans that differ in terms of how pension rights are accrued. In one plan, the participant accrues the right to receive a single life annuity, and can exchange that annuity for an actuarially equivalent joint and survivor annuity at retirement date. The opposite holds in the other plan. We show that both plans are affected by longevity risk in two ways. First, the participants’ choices at retirement age affect the ratio of survivor benefits over single life benefits, and, therefore, affect the natural hedge potential that arises from combining single life and survivor annuities. Second, uncertainty in the rate at which the participant will be allowed to exchange one type of annuity for the other at retirement date induces uncertainty in the level of the nominal rights for single life and survivor annuities, respectively. We compare the two plans, and show that longevity risk is substantially lower in case rights are accrued in the form of a joint and survivor annuity.     

Exploring the electronic band structure of individual carbon nanotubes under 60 T

Nano-sciences, and in particular nano-physics, constitute a fascinating world of investigations where the experimental challenges are to synthesize, to address (for instance optically or electrically) to explore and promote the remarkable physical properties of new nano-materials. Somehow, one of the most promising realization of nano-sciences lies in carbon-based nano-materials with sp² covalent bonds. In particular, carbon nanotubes, graphene and more recently ultra-narrow graphene nano-ribbons are envisioned as elementary bricks of the future of nano-electronics. However, prior to such an achievement, the first steps consist in understanding their fundamental electronic properties when they constitute the drain–source channel of a gated device or inter-connexion elements. In this article, we present the richness of challenging experiments combining single-object measurements with an extreme magnetic environment. We demonstrate that an applied magnetic field (B), along with a control of the electrostatic doping, drastically modifies the electronic band structure of a carbon nanotube based transistor. Several examples will be addressed in this presentation. When B is applied parallel to the tube axis, a quantum flux threading the tube induces a giant Aharonov–Bohm conductance modulation mediated by Schottky barriers whose profile is magnetic field dependent. In the perpendicular configuration, the applied magnetic field breaks the revolution symmetry along the circumference and non-conventional Landau states develop in the high field regime. By playing with a carbon nanotube based electronic Fabry–Perot resonator, the field dependence of the resonant states of the cavity reveals the onset of the first Landau state at zero energy. These experiments enlighten the outstanding efficiency of magneto-conductance experiments to probe the electronic properties of carbon based nano-materials. To cite this article: S. Nanot et al., C. R. Physique 10 (2009).     

Readily Available Primary Aminoboranes as Powerful Reagents for Aldimine Synthesis

Primary aminoboranes (RNHBR₂), which are readily available by spontaneous dehydrocoupling of amines and boranes cleanly react at room temperature with aldehydes to give aldimines. The overall transformation from amines to aldimines can be conveniently performed by a sequential one‐pot reaction. This synthetic strategy is especially useful for electron poor and bulky amines which are reluctant to react with aldehydes under dehydration conditions. Using a Glorius robustness screen, we show that this methodology is chemoselective, and functional group tolerant. Computational and experimental data support the irreversible formation of the aldimine product in marked contrast with traditional methods.