Novel nonperipheral octa-3-hydroxypropylthio substituted metallo-phthalocyanines: synthesis,characterization, and investigation of their electrochemical,photochemical and computational properties

The current study describes the synthesis, electrochemical, computational, and photochemical properties of octa (3-hydroxypropylthio) substituted cobalt (II) ( 4 ), copper (II) ( 5 ), nickel (II) ( 6 ) and zinc(II) ( 7 ) phthalocyanine derivatives. These novel compounds were characterized by elemental analysis,¹H,¹³C NMR, FT-IR, UV-Vis, and MS. The redox behaviors of these metallo-phthalocyanines were investigated by the cyclic voltammetric method. The optimized molecular structure and gauge-including atomic orbital (GIAO)¹H and¹³C NMR chemical shift values of these phthalocyanines in the ground state had been calculated by using B3LYP/6–31G(d,p) basis set. The outcomes of the optimized molecular structure were given and compared with the experimental NMR values. The photochemical properties including photodegradation and singlet oxygen generation of zinc(II) phthalocyanine were studied in DMSO solution for the determination of its photosensitizer behaviors.     

On the Formation of a Protic Ionic Liquid in Nature

The practical utility of ionic liquids (ILs) makes the absence (heretofore) of reported examples from nature quite puzzling, given the facility with which nature produces many other types of exotic but utilitarian substances. In that vein, we report here the identification and characterization of a naturally occurring protic IL. It can be formed during confrontations between the ants S. invicta and N. fulva. After being sprayed with alkaloid‐based S. invicta venom, N. fulva detoxifies by grooming with its own venom, formic acid. The mixture is a viscous liquid manifestly different from either of the constituents. Further, we find that the change results as a consequence of formic acid protonation of the N centers of the S. invicta venom alkaloids. The resulting mixed‐cation ammonium formate milieu has properties consistent with its classification as a protic IL.     

Reduction of RF-induced sample heating with a scroll coil resonator structure for solid-state NMR probes

Heating due to high power 1H decoupling limits the experimental lifetime of protein samples for solid-state NMR (SSNMR). Sample deterioration can be minimized by lowering the experimental salt concentration, temperature or decoupling fields; however, these approaches may compromise biological relevance and/or spectroscopic resolution and sensitivity. The desire to apply sophisticated multiple pulse experiments to proteins therefore motivates the development of probes that utilize the RF power more efficiently to generate a high ratio of magnetic to electric field in the sample. Here a novel scroll coil resonator structure is presented and compared to a traditional solenoid. The scroll coil is demonstrated to be more tolerant of high sample salt concentrations and cause less RF-induced sample heating. With it, the viable experimental lifetime of a microcrystalline ubiquitin sample has been extended by more than an order of magnitude. The higher B1 homogeneity and permissible decoupling fields enhance polarization transfer efficiency in 15N-13C correlation experiments employed for protein chemical shift assignments and structure determination.     

Synthesis and reactions of polymer-bound Ph3P=C=C=O: a quick route to tenuazonic acid and other optically pure 5-substituted tetramates

Polystyrene-bound cumulated ylide Ph3PCCO was prepared on a large scale in two steps. It reacts with Grignard compounds, amines and alcohols to give immobilized acyl, amide and ester ylides, respectively. Their Wittig reactions lead to alkenes free of phosphane oxide. Optically pure 5-substituted tetramates were obtained from reactions of resin-bound Ph3PCCO with alpha-ammonium esters in one step. The mycotoxin (-)-tenuazonic acid was accordingly prepared in just three steps.     

Thermodynamic phase diagram of the quantum hall skyrmion system

We numerically study the interacting quantum Hall Skyrmion system based on the Chern-Simons action. By noticing that the action is invariant under global spin rotations in the spin space with respect to the magnetic field direction, we obtain the low-energy effective action for a many-Skyrmion system. Performing extensive molecular dynamics simulations, we establish the thermodynamic phase diagram for a many-Skyrmion system.     

Anti-ferroelectric polarization transitions in quantum-dot-quantum-well arrays

With the improvement in fabrication techniques it is now possible to produce atom-like semiconductor structures with unique electronic properties. This makes possible periodic arrays of nanostructures in which the Coulomb interaction, polarizability and tunneling may all be varied. This theoretical study investigates the collective properties of 2D arrays and 3D face-centered cubic lattices of singly charged nanospherical shells, sometimes called 'quantum dot-quantum wells' or 'core-shell quantum dots'. We find that, for square arrays, the classical ground state is an Ising anti-ferroelectric (AFE), while the quantum ground state undergoes a transition from a uniform state to an AFE. The triangular lattice, in contrast, displays properties characteristic of frustration. Three-dimensional face-centered cubic lattices polarize in planes, with each layer alternating in direction. We discuss the possible experimental signals of these transitions.     

Algorithms for separable nonlinear least squares with application to modelling time-resolved spectra

The multiexponential analysis problem of fitting kinetic models to time-resolved spectra is often solved using gradient-based algorithms that treat the spectral parameters as conditionally linear. We make a comparison of the two most-applied such algorithms, alternating least squares and variable projection. A numerical study examines computational efficiency and linear approximation standard error estimates. A new derivation of the Fisher information matrix under the full Golub-Pereyra gradient allows a numerical comparison of parameter precision under variable projection variants. Under the criteria of efficiency, quality of standard error estimates and parameter precision, we conclude that the Kaufman variable projection technique performs well, while techniques based on alternating least squares have significant disadvantages for application in the problem domain.     

Remarkable properties of alkali halides and new techniques for determining Debye--Waller factors

We have used 70 Ci ¹⁸³Ta Mössbauer sources to measure the Debye--Waller factors of NaCl, KCl, and KBr single crystals for several of the (h00) and (nnn) Bragg reflections. We have found that the procedure used to analyze data by earlier workers leads to incorrect parameters in the Debye--Waller factor exponent, and we use a procedure that eliminates the need to introduce an empirical parameter to account for thermal expansion effects. We observe that both the cations and anions in NaCl and KBr have identical Debye--Waller factors in the [nnn] direction. We observe Q⁴ terms in NaCl and KCl, with some evidence for a Q⁴ term in KBr. The size of this contribution varies with the direction of momentum transfer and will be reported. We observe that the Debye temperature and the coefficient of the anharmonic Q² term also vary with direction of momentum transfer. We believe this to be the first definitive evidence for a non-spherical thermal cloud in a cubic crystal; the ions have a larger amplitude of oscillation in the [h00] direction than in the [nnn] direction. This effect is temperature dependent and greater at lower temperatures.     

Transverse interferometry of a hydrogen-filled capillary discharge waveguide

Transverse interferometric measurements are presented of the plasma channel formed in a hydrogen-filled capillary discharge waveguide recently used to generate 1 GeV electrons in a laser-driven plasma accelerator for the first time. The measurements were found to be in good agreement with nonlocal thermal equilibrium simulations, but showed significant differences with the results of a quasistatic model developed by Bobrova et al. [Phys. Rev. E. 65, 016407 (2001)]. The measurements are used to determine scaling laws for the axial electron density and matched spot size of the plasma channel, enabling optimization of the channel to specific applications.