Cavitand-functionalized SWCNTs for N-methylammonium detection

Single-walled carbon nanotubes (SWCNTs) have been functionalized with highly selective tetraphosphonate cavitand receptors. The binding of charged N-methylammonium species to the functionalized SWCNTs was analyzed by X-ray photoelectron spectroscopy and confirmed by (31)P MAS NMR spectroscopy. The cavitand-functionalized SWCNTs were shown to function as chemiresistive sensory materials for the detection of sarcosine and its ethyl ester hydrochloride in water with high selectivity at concentrations as low as 0.02 mM. Exposure to sarcosine and its derivative resulted in an increased conductance, in contrast to a decreased conductance response observed for potential interferents such as the structurally related glycine ethyl ester hydrochloride.     

Lewis Acid trapping of an elusive copper-tosylnitrene intermediate using scandium triflate

High-valent copper-nitrene intermediates have long been proposed to play a role in copper-catalyzed aziridination and amination reactions. However, such intermediates have eluded detection for decades, preventing the unambiguous assignments of mechanisms. Moreover, the electronic structure of the proposed copper-nitrene intermediates has also been controversially discussed in the literature. These mechanistic questions and controversy have provided tremendous motivation to probe the accessibility and reactivity of Cu(III)-NR/Cu(II)N(?)R species. In this paper, we report a breakthrough in this field that was achieved by trapping a transient copper-tosylnitrene species, 3-Sc, in the presence of scandium triflate. The sufficient stability of 3-Sc at -90 °C enabled its characterization with optical, resonance Raman, NMR, and X-ray absorption near-edge spectroscopies, which helped to establish its electronic structure as Cu(II)N(?)Ts (Ts = tosyl group) and not Cu(III)NTs. 3-Sc can initiate tosylamination of cyclohexane, thereby suggesting Cu(II)N(?)Ts cores as viable reactants in oxidation catalysis.     

Tuning and predicting biological affinity: aryl nitriles as cysteine protease inhibitors

A series of aryl nitrile-based ligands were prepared to investigate the effect of their electrophilicity on the affinity against the cysteine proteases rhodesain and human cathepsin L. Density functional theory calculations provided relative reactivities of the nitriles, enabling prediction of their biological affinity and cytotoxicity and a clear structure-activity relationship.     

Anion Sensing in Aqueous Media by Photo-active Transition-Metal Bipyridyl Rotaxanes

A chloride anion templation methodology is utilized in the construction of novel transition-metal rhenium(I) and ruthenium(II) bipyridyl appended [2]rotaxanes. (1) H?NMR spectroscopic titrations reveal the ability of the rotaxanes to selectively bind chloride over the more basic oxoanions, with the ruthenium(II) bipyridyl appended rotaxane strongly binding chloride in 30?% water. Photophysical investigations demonstrate the ability of the rotaxanes to sense anions in aqueous media, with chloride being selectively complexed, in general agreement with NMR spectroscopy determined anion binding data.     

Intracellular pH measurements made simple by fluorescent protein probes and the phasor approach to fluorescence lifetime imaging

A versatile pH-dependent fluorescent protein was applied to intracellular pH measurements by means of the phasor approach to fluorescence lifetime imaging. By this fit-less method we obtain intracellular pH maps under resting or altered physiological conditions by single-photon confocal or two-photon microscopy.     

Ab Initio structure determination of vaterite by automated electron diffraction

"This is a mineral about which there has been much discussion" is a typical statement about vaterite in older standard textbooks of inorganic chemistry. This polymorph of CaCO(3) was first mentioned by H. Vater in 1897, plays key roles in weathering and biomineralization processes, but occurs only in the form of nanosized crystals, unsuitable for structure determination. Its structure could now be solved by automated electron diffraction tomography from 50 nm sized nanocrystals.     

Gravitational self-force correction to the binding energy of compact binary systems

Using the first law of binary black-hole mechanics, we compute the binding energy E and total angular momentum J of two nonspinning compact objects moving on circular orbits with frequency Ω, at leading order beyond the test-particle approximation. By minimizing E(Ω) we recover the exact frequency shift of the Schwarzschild innermost stable circular orbit induced by the conservative piece of the gravitational self-force. Comparing our results for the coordinate-invariant relation E(J) to those recently obtained from numerical simulations of comparable-mass nonspinning black-hole binaries, we find a remarkably good agreement, even in the strong-field regime. Our findings confirm that the domain of validity of perturbative calculations may extend well beyond the extreme mass-ratio limit.     

Impact of trailing wake drag on the statistical properties and dynamics of finite-sized particle in turbulence

We study by means of an Eulerian-Lagrangian model the statistical properties of velocity and acceleration of a neutrally-buoyant finite-sized particle in a turbulent flow statistically homogeneous and isotropic. The particle equation of motion, besides added mass and steady Stokes drag, keeps into account the unsteady Stokes drag force-known as Basset-Boussinesq history force-and the non-Stokesian drag based on Schiller-Naumann parametrization, together with the finite-size Faxén corrections. We focus on the case of flow at low Taylor-Reynolds number, Re_λ?31, for which fully resolved numerical data which can be taken as a reference are available [Homann H., Bec J. Finite-size effects in the dynamics of neutrally buoyant particles in turbulent flow. J Fluid Mech 651 (2010) 81-91]. Remarkably, we show that while drag forces have always minor effects on the acceleration statistics, their role is important on the velocity behavior. We propose also that the scaling relations for the particle velocity variance as a function of its size, which have been first detected in fully resolved simulations, does not originate from inertial-scale properties of the background turbulent flow but it is likely to arise from the non-Stokesian component of the drag produced by the wake behind the particle. Furthermore, by means of comparison with fully resolved simulations, we show that the Faxén correction to the added mass has a dominant role in the particle acceleration statistics even for particles whose size attains the integral scale.     

Rotational dynamics of bottom-heavy rods in turbulence from experiments and numerical simulations

We successfully perform the three-dimensional tracking in a turbulent fluid flow of small axisymmetrical particles that are neutrally-buoyant and bottom-heavy, i.e., they have a non-homogeneous mass distribution along their symmetry axis. We experimentally show how a tiny mass inhomogeneity can affect the particle orientation along the preferred vertical direction and modify its tumbling rate. The experiment is complemented by a series of simulations based on realistic Navier–Stokes turbulence and on a point-like particle model that is capable to explore the full range of parameter space characterized by the gravitational torque stability number and by the particle aspect ratio. We propose a theoretical perturbative prediction valid in the high bottom-heaviness regime that agrees well with the observed preferential orientation and tumbling rate of the particles. We also show that the heavy-tail shape of the probability distribution function of the tumbling rate is weakly affected by the bottom-heaviness of the particles.