Understanding gold-thiolate cluster emission from self-assembled monolayers upon kiloelectronvolt ion bombardment

This article focuses on the emission of organometallic clusters upon kiloelectronvolt ion bombardment of self-assembled monolayers. It is particularly relevant for the elucidation of the physical processes underlying secondary ion mass spectrometry (SIMS). The experimental system, an overlayer of octanethiols on gold, was modeled by classical molecular dynamics, using a hydrocarbon potential involving bonding and nonbonding interactions (AIREBO). To validate the model, the calculated mass and energy distributions of sputtered atoms and molecules were compared to experimental data. Our key finding concerns the emission mechanism of large clusters of the form MxAuy up to M6Au5 (where M is the thiolate molecule), which were not observed under sub-kiloelectronvolt projectile bombardment. Statistically, they are predominantly formed in high-yield events, where many atoms, fragments, and (supra)molecular species are desorbed from the surface. From the microscopic viewpoint, these high-yield events mostly stem from the confinement of the projectile and recoil atom energies in a finite microvolume of the sample surface. As a result of the high local energy density, molecular aggregates desorb from an overheated liquidlike region surrounding the impact point of the projectile.     

Stabilization effect of single-walled carbon nanotubes on the functioning of photosynthetic reaction centers

The interaction between single-walled carbon nanotubes and photosynthetic reaction centers purified from purple bacterium Rhodobacter sphaeroides R-26 has been investigated. Atomic force microscopy studies provide evidence that reaction center protein can be attached effectively to the nanotubes. The typical diameter of the nanotube is 1-4 nm and 15 +/- 2 nm without and with the reaction centers, respectively. Light-induced absorption change measurements indicate the stabilization of the P+(Q(A)Q(B))- charge pair, which is formed after single saturating light excitation after the attachment to nanotubes. The separation of light-induced charges is followed by slow reorganization of the protein structure. The stabilization effect of light-initiated charges by the carbon nanotubes opens a possible direction of several applications, the most promising being in energy conversion and storage devices.     

A Cationic Gold(I) Complex as a General Catalyst for the Intermolecular Hydroamination of Alkynes: Application to the One‐Pot Synthesis of Allenes from Two Alkynes and a Sacrificial Amine

Two very distinct chemical reactions, yet a single catalyst : A gold complex promotes the formation of tertiary enamines from a variety of terminal and internal alkynes. Subsequent addition of a terminal alkyne to the reaction mixture affords allenes (see scheme).

     

Synthesis of Allenylidene Lithium and Silver Complexes,and Subsequent Transmetalation Reactions

Alpha, beta, gamma! Amino substituents in alpha and beta positions allow the isolation of free carbenes, but even in the gamma position, their strong π‐electron‐donating properties permit the synthesis of allenylidene lithium adducts and silver complexes (see picture), which are ideal precursors for the preparation of various transition‐metal–allenylidene complexes.

     

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.