Expeditive synthesis of homochiral fused tri- and tetrazoles-piperazines from β-amino alcohols

N-Cyanomethyl and N-propargyl β-amino alcohols are chlorinated with SOCl₂ and treated with NaN₃ in DMSO. A substitution/cycloaddition process affords in good yields, with high diastereoselectivity and a regioselectivity depending on the substitution pattern of the starting amino alcohol, fused tri- and tetrazoles-piperazines. These heterocycles were further lithiated with n-BuLi at the benzylic position and reacted diastereoselectively with a range of electrophiles.     

Three-dimensional GaN-Ga2O3 core shell structure revealed by x-ray diffraction microscopy

In combination of direct phase retrieval of coherent x-ray diffraction patterns with a novel tomographic reconstruction algorithm, we, for the first time, carried out quantitative 3D imaging of a heat-treated GaN particle with each voxel corresponding to 17 x 17 x 17 nm3. We observed the platelet structure of GaN and the formation of small islands on the surface of the platelets, and successfully captured the internal GaN-Ga2O3 core shell structure in three dimensions. This work opens the door for nondestructive and quantitative imaging of 3D morphology and 3D internal structure of a wide range of materials at the nanometer scale resolution that are amorphous or possess only short-range atomic organization.     

Compaction of single-chain DNA by histone-inspired nanoparticles

We elaborated a versatile experimental model of chromatin which consists of a single chain of long duplex DNA that interacts with well-defined cationic nanoparticles of various sizes. We found that the DNA compaction by nanoparticles is stepwise and progressive at the single-chain level. It is controlled by the ability of DNA to wrap nanoparticles, which is more efficient for larger particles and, similar to DNA-histone interaction, is optimal at a physiological salt concentration.     

Controlling speckle using lenses and free space

The correlation properties of speckle fields are studied for general paraxial systems. The previous studies on lateral and longitudinal speckle size for the case of free-space propagation (Fresnel transform) are generalized to the case of the linear canonical transform. These results have implications for the control of speckle size, through appropriate design of optical systems, with particular relevance for speckle interferometry.     

Use of apodization in quantitative spectroscopy

Apodization, which is a tool frequently used for cosmetic representation and efficient modeling of a spectrum, is now also adopted in techniques for the quantitative retrieval of parameters from observed spectra. Whether apodization can help in quantitative spectroscopy is the subject of debate in the literature. We find that, when the considered spectral range is wide enough to accurately model the instrument line shape, the same results can be obtained with and without apodization of the spectrum. However, when a truncation error is introduced by the limited extension of the modeled spectral interval, apodization can efficiently reduce this error. Therefore it is possible to save computing time by using apodization.     

Dynamics of the infinitely-thin kink

We consider the dynamics of the domain-wall kink soliton, in particular we study the zero mode of translation. In the infinitely-thin kink limit, we show that the zero mode is almost completely frozen out, the only remnant being a dynamically constrained four-dimensional mode of a single but arbitrary frequency. In relation to this result, we show that the usual mode expansion for dealing with zero modes - implicit collective coordinates - is not in fact a completely general expansion, and that one must use instead a traditional generalised Fourier analysis.     

A Pulsed EPR and DFT Investigation of the Stabilization of Coordinated Phenoxyl Radicals in a Series of Cobalt Schiff-Base Complexes

We recently demonstrated how the aerobic addition of acetic acid to N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexane-diamino Co^II, [Co(1)], leads to the formation of an unusual coordinated Co^III-phenoxyl radical. In this work, some of the structural aspects associated with the Schiff-base-derived ligand (1) that are crucial for the acid-mediated formation of the phenoxyl radical are investigated. For comparison with [Co(1)], we therefore studied the influence of acetic acid on two complexes: (1) the N,N′-bis(3,5-di-tert-butylsalicylidene)-1,2-ethane-diamino Co^II complex, [Co(2)], that lacks the cyclohexyl group of [Co(1)], and (2) the N′-disalicylidene-ethylenediamine Co^II salen complex, [Co(3)], that lacks both the tertiary butyl groups and the cyclohexyl groups. It is shown that the cyclohexyl group of [Co(1)] is not involved in the formation or stabilization of the phenoxyl radical, whereas the tertiary butyl groups of [Co(1)] play a crucial role. In addition, the characteristics of the phenoxyl radical, formed after aerobic addition of acetic acid to [Co(2)], are analyzed in detail by pulsed electron paramagnetic resonance, in combination with isotopic labeling. The experimental data are compared to density functional theory computations and to previous data on the acid-mediated phenoxyl radical of [Co(1)].     

Light scattering study of dispersion and attenuation of hypersound in adamantane

The Brillouin scattering techniques have been used to measure the velocity dispersion of hypersonic acoustic waves in the “high temperature” disordered cubic phase of adamantane. Shear waves, characteristic of the C₄₄ elastic constant, show no significant dispersion. Longitudinal waves propagating in the (001) plane show strong velocity dispersion. The measures have been performed at the same temperature T = 295.7 K. Using a classical single relaxation time model for the dispersion as a function of frequency at temperature T, the L-mode data have been correctly fitted.The importance of the dispersion $\text{(C}{}_{\mathrm{\infty }}\text{? C}{}_{\mathrm{o}}\text{)}\text{C}{}_0$ for the elastic constants is 20% for C₁₁, 51% for C₁₂ #1% for C₄₄ and ?2.8% for $\text{(C}{}_{11}\text{? C}{}_{12}\text{)}\text{2}$. The fitted relaxation time is τ ? 9 × 10^?11 sec.     

Polarization control in spun and telecommunication optical fibers

We consider the counterpropagating interaction of a signal and a pump beam in a spun fiber and in a randomly birefringent fiber, the latter being relevant to optical telecommunication systems. On the basis of a geometrical analysis of the Hamiltonian singularities of the system, we provide a complete understanding of the phenomenon of polarization attraction in these two systems, which allows to achieve a control of the polarization state of the signal beam by adjusting the polarization of the pump. In spun fibers, all polarization states of the signal beam are attracted toward a specific line of polarization states on the Poincaré sphere, whose characteristics are determined by the polarization state of the injected backward pump. In randomly birefringent telecommunication fibers, we show that an unpolarized signal beam can be repolarized into any particular polarization state, without loss of energy.     

Heralding two-photon and four-photon path entanglement on a chip

Generating quantum entanglement is not only an important scientific endeavor, but will be essential to realizing quantum-enhanced technologies, in particular, quantum-enhanced measurements with precision beyond classical limits. We investigate the heralded generation of multiphoton entanglement for quantum metrology using a reconfigurable integrated waveguide device in which projective measurement of auxiliary photons heralds the generation of path-entangled states. We use four and six-photon inputs, to analyze the heralding process of two- and four-photon NOON states-a superposition of N photons in two paths, capable of enabling phase supersensitive measurements at the Heisenberg limit. Realistic devices will include imperfections; as part of the heralded state preparation, we demonstrate phase superresolution within our chip with a state that is more robust to photon loss.