Total syntheses of the highly potent anti-cancer polyacetylenes, (S)-18-hydroxyminquartynoic acid, (S)-minquartynoic acid and (E)-15,16-dihydrominquartynoic acid

The total syntheses of three polyacetylenic natural products, (S)-18-hydroxyminquartynoic acid (1), (S)-minquartynoic acid (2) and (E)-15,16-dihydrominquartynoic acid (3), has been achieved. The Cadiot-Chodkiewicz cross-coupling reaction was used as the key step for the construction of tetrayne and triyne units.     

Diffraction aperture non-ideal behaviour of air coupled transducers array elements designed for NDT

Air coupled piezoelectric ultrasonic array transducers are a novel tool that could lead to interesting advances in the area of non-contact laminar material testing using Lamb wave's propagation techniques. A key issue on the development of such transducers is their efficient coupling to air media (impedance mismatch between the piezoelectric material and air is 90 dB or more). Adaptation layers are used in order to attain good matching and avoid possible serious signal degradation. However, the introduction of these matching layers modify the transducer surface behaviour and, consequently, radiation characteristics are altered, making the usual idealization criteria (of uniform surface movement) adopted for field simulation purposes inaccurate. In our system, we have a concave linear-array transducer of 64 elements (electrically coupled by pairs) working at 0.8 MHz made of PZ27 rectangular piezoceramics (15 mm x 0.3 mm) with two matching layers made of polyurethane and porous cellulose bonded on them. Experimental measurements of the acoustic aperture of single excited array elements have shown an increment on the geometrical dimensions of its active surface. A sub-millimeter vibrometer laser scan has revealed an extension of the aperture beyond the supposed physical single array element dimensions. Non-uniform symmetric apodized velocity surface vibration amplitude profile with a concave delay contour indicates the presumed existence of travelling wave phenomena over the surface of the outer array matching layer. Also, asymptotic propagation velocities around 2500 m/s and attenuation coefficient between 15 and 20 dB/mm has been determined for the travelling waves showing clear tendencies. Further comparisons between the experimental measurements of single array element field radiation diagram and simulated equivalent aperture counterpart reveal good agreement versus the ideal (uniform displaced) rectangular aperture. For this purpose an Impulse Response Method (IRM) has been used.     

c-director relaxation around a vortex of strength +1 in free-standing smectic-C films

The relaxation of director fields in freely suspended smectic films is studied experimentally by means of polarizing microscopy, and analyzed by solving the torque balance equation under appropriate initial and boundary conditions. We consider in particular the role of anchoring conditions of the c-director at particles and defects in the film. The structure of regular relaxation patterns allows to determine the elastic anisotropy of smectic materials. The splay elastic constant can exceed the bend constant by a factor of two and more. A remarkable consequence of this anisotropy is the stick-slip-like relaxation around a central defect of topological strength s = + 1.     

Preparation and characterization of (PVP + NaClO4) electrolytes for battery applications

A sodium ion-conducting polymer electrolyte based on polyvinyl pyrrolidone (PVP) complexed with NaClO₄ was prepared using the solution-cast technique. The cathode film of V₂O₅ xerogel modified with polyvinyl pyrrolidone was prepared using the sol-gel method. Investigations were conducted using X-ray diffractometry (XRD), Fourier transformation infrared (FT-IR) spectroscopy. The ionic conductivity and transference number measurements were performed to characterize the polymer electrolyte for battery applications. The transference number data indicated that the conducting species in these electrolytes are the anions. Using the electrolyte, electrochemical cells with a configuration Na/(PVP + NaClO₄)/V₂O₅ modified by (PVP) were fabricated and their discharge profiles studied.     

The Stability Criterion of a Semiconductor Superlattice in the Drift–Diffusion Approximation

A criterion for the electric stability of a semiconductor superlttice placed in a longitudinal electric field has been obtained using the drift–diffusion approximation. It is demonstrated that the account for the contact ohmicity yields a stability criterion that is different from that related to the negative differential conductivity.     

A semiempirical calculation of the fine and Zeeman structure of 4<Emphasis Type="Italic">p</Emphasis>4<Emphasis Type="Italic">f</Emphasis> and 4<Emphasis Type="Italic">p</Emphasis>5<Emphasis Type="Italic">f</Emphasis> configurations of Ge I. Gyromagnetic ratios

The gyromagnetic ratios (g-factors) belong to the most important characteristics of atoms. For the 4p4f configuration of a germanium atom experimental values of g-factors are available only for four levels, while similar experimental data on the 4p5f configuration of Ge I are absent. Therefore, a theoretical study of the fine and Zeeman structures is topical for determining the gyromagnetic ratios. All the calculations are performed in the one-configuration approximation with the energy-operator matrix containing a maximum possible number of interactions, including magnetic: spin-orbit (own and other), spin-spin, and also orbitorbit interaction. The fine structure has been examined in three (LS, LK, and jK) approximations in order to establish the nature of coupling in the systems studied and the reliability of g-factors. Apart from the g-factors, in studying the Zeeman splitting, its specific features—the crossing and anticrossing fields of magnetic components— have been determined. A comparative analysis of g-factors was performed that showed that our results are in agreement with the available, albeit few in number, experimental data. At all stages, the corresponding energy-operator matrices were numerically diagonalized, i.e., all the results presented in the paper were obtained in the intermediate coupling scheme.     

On the motion control of microparticles by means of an electromagnetic field increasing with time for spectroscopic applications

The possibility of controlling the motion of microparticles by means of external electromagnetic fields (nonresonance laser radiation, in particular) that induce potential wells for such particles, which are characterized by fixed spatial distribution but deepen over time to a certain level, are analyzed. It is assumed that the particles are located in high vacuum and are affected by nondissipative external forces. Slowing down of relatively fast particles when they pass through the discussed potential wells is shown. Such slowing down of particles is demonstrated using a nonresonance laser beam with intensity increasing over time as an example. Specific features of particle dynamics in the electromagnetic fields under consideration in the case of a one-dimensional rectangular potential well are studied in detail based on simple analytical relations derived from the fundamental equations of classical mechanics. The methods of particle cooling and localization demonstrated in the present work can substantially increase spectroscopy resolution of various microparticles, including, under certain conditions, atoms and molecules.     

Porphyrin N-Pincer Pd(II)-Complexes in Water: A Base-Free and Nature-Inspired Protocol for the Oxidative Self-Coupling of Potassium Aryltrifluoroborates in Open-Air

Metalloporphyrins (and porphyrins) are well known as pigments of life in nature, since representatives of this group include chlorophylls (Mg-porphyrins) and heme (Fe-porphyrins). Hence, the construction of chemistry based on these substances can be based on the imitation of biological systems. Inspired by nature, in this article we present the preparation of five different porphyrin, meso-tetraphenylporphyrin (TPP), meso-tetra(p-anisyl)porphyrin (TpAP), tetrasodium meso-tetra(p-sulfonatophenyl)porphyrin (TSTpSPP), meso-tetra(m-hydroxyphenyl)porphyrin (TmHPP), and meso-tetra(m-carboxyphenyl)porphyrin (TmCPP) as well as their N-pincer Pd(II)-complexes such as Pd(II)-meso-tetraphenylporphyrin (PdTPP), Pd(II)-meso-tetra(p-anisyl)porphyrin (PdTpAP), Pd(II)-tetrasodium meso-tetra(p-sulfonatophenyl)porphyrin (PdTSTpSPP), Pd(II)-meso-tetra(m-hydroxyphenyl)porphyrin (PdTmHPP), and Pd(II)-meso-tetra(m-carboxyphenyl)porphyrin (PdTmCPP). These porphyrin N-pincer Pd(II)-complexes were studied and found to be effective in the base-free self-coupling reactions of potassium aryltrifluoroborates (PATFBs) in water at ambient conditions. The catalysts and the products (symmetrical biaryls) were characterized using their spectral data. The high yields of the biaryls, the bio-mimicking conditions, good substrate feasibility, evading the use of base, easy preparation and handling of catalysts, and the application of aqueous media, all make this protocol very attractive from a sustainability and cost-effective standpoint.     

Thermal conductivity and expansion of PbF2 single crystals

In order to check a phenomenon of the negative correlation between ionic and thermal conductivities of solid substances, we studied the thermal conductivity and expansion of cubic PbF₂ single crystals at 50–300 and 5.6–317 K, respectively. We found that lead difluoride had a thermal expansion coefficient α that was equal to (28.5 ± 0.3)10⁻⁶ K⁻¹ at 300 K, and a thermal conductivity coefficient k(T) was equal to 1.40 ± 0.07 W/(m K) at the same temperature. Thus, the thermal conductivity for PbF₂ is the lowest among fluorite-type MF₂ (M = Ca, Sr, Ba, Cd, Pb) thermal conductivities, whereas its fluoride-ion conductivity is the highest one among MF₂ (M = Ca, Sr, Ba, Cd, Pb) ionic conductors.

     

The influence of local phonon modes in a wide-band matrix on the tunnel current-voltage characteristics of quasi-zero-dimensional structures

Experimental results on the visualization of the density of states in InAs/GaSa(001) quantum dots that were obtained by tunnel atomic-force microscopy in an ultrahigh vacuum are presented. A one-dimensional (1D) model of dissipative quantum tunneling is proposed for describing experimental current-voltage characteristics of a tunnel contact between an atomic force microscope probe and the surface of InAs/GaAs (001) quantum dots. It was found that the influence of two local modes of the wide-band matrix on the probability of 1D dissipative tunneling leads to the appearance of several randomly spaced peaks in the field dependence. It was shown that the theoretical dependence agrees qualitatively with experimental the current-voltage characteristic of the atomic force microscope tip and the surface of InAs/GaAs(001) quantum dots.