Multi-channel transformations of 1,3-diarylpropynones under superelectrophilic activation conditions: concurrence of intra- and intermolecular reactions. Experimental and theoretical study

1,3-Diarypropynones undergo concurrent multi-channel transformations in Bronsted (FSO₃H, TfOH) and Bronsted–Lewis (HF–SbF₅, TfOH-SbF₅) superacids, leading intramolecularly to 3-arylindenones, or intermolecularly to 1,3,3-triarylpropenones, and dimeric structures. The outcome depends on the electronic donor-acceptor properties of the substituents in the aromatic rings of the 1,3-diarylpropynones, and on the added aromatic external π-nucleophiles. The orbital energies, atom charges, orbital contributions, and global electrophilicity indices of the cationic intermediates have been calculated by DFT methods to explain these transformations.     

Macroscopic pure state of light free of polarization noise

The preparation of completely nonpolarized light is seemingly easy; an everyday example is sunlight. The task is much more difficult if light has to be in a pure quantum state, as required by most quantum-technology applications. The pure quantum states of light obtained so far are either polarized or, in rare cases, manifest hidden polarization; even if their intensities are invariant to polarization transformations, higher-order moments are not. We experimentally demonstrate the preparation of the macroscopic singlet Bell state, which is pure, is completely nonpolarized, and has no polarization noise. Simultaneous fluctuation suppression in three Stokes observables below the shot-noise limit is demonstrated, opening perspectives for noiseless polarization measurements. The state is shown to be invariant to polarization transformations. This robust highly entangled isotropic state promises to fuel important applications in photonic quantum technologies.     

Photon propagation in a discrete fiber network: an interplay of coherence and losses

We study light propagation in a photonic system that shows stepwise evolution in a discretized environment. It resembles a discrete-time version of photonic waveguide arrays or quantum walks. By introducing controlled photon losses to our experimental setup, we observe unexpected effects like subexponential energy decay and formation of complex fractal patterns. This demonstrates that the interplay of linear losses, discreteness and energy gradients leads to genuinely new coherent phenomena in classical and quantum optical experiments. Moreover, the influence of decoherence is investigated.     

Specific heat capacity and thermodynamic properties of CuTeO3 and HgTeO3

Tellurites of CuTeO₃ and HgTeO₃ are synthesized and their specific molar heat capacities are experimentally determined for the first time. The tellurites discussed in the present paper are used for preparation of optical glasses with special properties for optoelectronics, nuclear and power industries. The tellurites synthesized are prepared for chemical analysis, differential thermal analysis and X-ray analysis. The use of the tellurites studied is related to knowing their thermodynamic properties like specific molar heat capacity (C _p,m), enthalpy \( \left( {\Delta_{{{\text {T}}^{\prime}}}^{\text{T}} H_{\text{m}}^{0} } \right), \) entropy \( \left( {\Delta_{{{\text {T}}^{\prime}}}^{\text{T}} S_{\text{m}}^{0} } \right) \) and Gibbs energy \( \left( { - \Delta_{{{\text {T}}^{\prime}}}^{\text{T}} G_{\text{m}}^{0} } \right) \) . The temperature dependences of their molar heat capacities are determined using the least squares method. The thermodynamic properties are calculated: entropy, enthalpy and Gibbs function.     

The Combinatorial Identity on the Jacobian Conjecture

The multidimensional sum with polynomial coefficients is computed with the help of the method of integral representation and computation of combinatorial sums. This sum was obtained in the attempt to prove the well known Jacobian conjecture (two-dimensional case). Supported in part by the Natural Sciences and Engineering Research Council of Canada on Grant NSERC-108343 and the Russian Fund of Fundamental Researches.Mathematics Subject Classifications (2000) combinatorics, algebra.     

Molecular dynamics simulation of aqueous solutions of 26-unit segments of p(NIPAAm) and of p(NIPAAm) "doped" with amino acid based comonomers

We have performed 75-ns molecular dynamics (MD) simulations of aqueous solutions of a 26-unit NIPAAm oligomer at two temperatures, 302 and 315 K, below and above the experimentally determined lower critical solution temperature (LCST) of p(NIPAAm). We have been able to show that at 315 K the oligomer assumes a compact form, while it keeps a more extended form at 302 K. A similar behavior has been demonstrated for a similar NIPAAm oligomer, where two units had been substituted by methacryloyl- l-valine (MAVA) comonomers, one of them being charged and one neutral. For another analogous oligomer, where the same units had been substituted by methacryloyl- l-leucine (MALEU) comonomers, no transition from the extended to the more compact conformation has been found within the same simulation time. Statistical analysis of the trajectories indicates that this transition is related to the dynamics of the oligomer backbone, and to the formation of intramolecular hydrogen bonds and water-bridges between distant units of the solute. In the MAVA case, we have also evidenced an important role of the neutral MAVA comonomer in stabilizing the compact coiled structure. In the MALEU case, the corresponding comonomer is not equally efficacious and, possibly, is even hindering the readjustment of the oligomer backbone. Finally the self-diffusion coefficient of water molecules surrounding the oligomers at the two temperatures for selected relevant times is observed to characteristically depend on the distance from the solute molecules.     

Migratory insertion of the R2P group into a nitrogen-nitrogen bond - a novel type of rearrangement in phosphorus-nitrogen ligand chemistry. 3. The rearrangement of triphosphinohydrazide ligand -N(PPh2)-N(PPh2)2 to triphosphazenide anion {[(Ph2P-N]2PPh2}- in the coordination sphere of divalent cobalt and nickel

Hydrazine dihydrochloride reacts with 3 equiv of Ph2PCl in tetrahydrofuran in the presence of triethylamine to give tris(diphenylphosphino)hydrazine (1) in 70% yield. Each nitrogen atom in 1 has a trigonal-planar environment according to X-ray analysis. Thermolysis of 1 at 130 degrees C results in the formation of two products: bis(diphenylphosphino)amine and octaphenylcyclotetraphosphazene. The interaction of free ligand 1 with NiBr2 affords a simple adduct [(Ph2P)2N-NH-PPh2]NiBr2, while its anionic (hydrazide) form undergoes rearrangement in a coordination sphere of divalent cobalt and nickel involving migratory insertion of the Ph2P group into a nitrogen-nitrogen bond. The reaction of 1 with cobalt bis(trimethylsilyl)amide, [(Me3Si)2N]2Co, yields the complex of phosphazenide-type (Me3Si)2N-Co[(Ph2PN)2PPh2] (2) in 86% yield. A similar reaction of 1 with nikelocene proceeds with substitution of one Cp ring to form durable 18-electron complex CpNi[(Ph2PN)2PPh2] (3).     

Increase in Autoantibodies-Abzymes with Peroxidase and Oxidoreductase Activities in Experimental Autoimmune Encephalomyelitis Mice during the Development of EAE Pathology

The exact mechanisms of multiple sclerosis (MS) development are still unknown, but the development of experimental autoimmune encephalomyelitis (EAE) in C57BL/6 mice is associated with the violation of bone marrow hematopoietic stem cells (HSCs) differentiation profiles associated with the production of harmful for human’s autoantibodies hydrolyzing myelin basic protein, myelin oligodendrocyte glycoprotein (MOG_35–55), and DNA. It was shown that IgGs from the sera of healthy humans and autoimmune patients oxidize many different compounds due to their H₂O₂-dependent peroxidase and oxidoreductase activity in the absence of H₂O₂. Here we first analyzed the change in the relative redox activities of IgGs antibodies from the blood of C57BL/6 mice over time at different stages of the EAE development. It was shown that the peroxidase activity of mice IgGs in the oxidation of ABTS (2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) is on average 6.9-fold higher than the oxidoreductase activity. The peroxidase activity of IgGs increased during the spontaneous development of EAE during 40 days, 1.4-fold. After EAE development acceleration due to mice immunization with MOG_35–55 (5.3-fold), complexes of bovine DNA with methylated bovine serum albumin (DNA-metBSA; 3.5-fold), or with histones (2.6-fold), the activity was increased much faster. The increase in peroxidase activity after mice immunization with MOG_35–55 and DNA-metBSA up to 40 days of experiments was relatively gradual, while for DNA-histones complex was observed its sharp increase at the acute phase of EAE (14–20 days). All data show that IgGs’ redox activities can play an important role in the protection of mice from toxic compounds and oxidative stress.     

Heteroleptic LaIII Anilate/Dicarboxylate Based Neutral 3D-Coordination Polymers

Three new 3D metal–organic frameworks of lanthanum based on mixed anionic ligands, [(La₂(pQ)₂(BDC)₄)·4DMF]_n, [(La₂(pQ)₂(DHBDC)₄)·4DMF]_n, [(La₂(CA)₂(BDC)₄)·4DMF]_n (pQ—dianion of 2,5-dihydroxy-3,6-di-tert-butyl-para-quinone, CA—dianion of chloranilic acid, BDC-1,4-benzenedicarboxylate, DHBDC-2,5-dihydroxy-1,4-benzenedicarboxylate and DMF-N,N′-dimethylformamide), were synthesized using solvothermal methodology. Coordination polymers demonstrate the rare xah or 4,6T187 topology of a 3D framework. The homoleptic 2D-coordination polymer [(La₂(pQ)₃)·4DMF]_n was obtained as a by-product in the course of synthetic procedure optimization. The thermal stability, spectral characteristics and porosity of coordination polymers were investigated.