Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Ion-transfer voltammetry at a polarized room-temperature molten salt/water interface.

Tetraoctylammonium cation forms a room-temperature molten salt (RTMS) with 2,4,6-trinitrophenolate anion. The RTMS is immiscible with water (W) and forms a stable RTMS/W interface. It has been shown that the RTMS/W interface can be electrochemically polarized. A well-defined voltammetric wave due to the transfer of thiocyanate ion across the RTMS/W interface was observed within the potential window. This is the first example of a polarized RTMS/W interface.     

How is chiral symmetry restored at finite density?

Taking into account pseudoscalar as well as scalar condensates, we reexamine the chiral restoration path on the chiral manifold. We shall see both condensates coherently produce a density wave at a certain density, which delays chiral restoration as density or temperature is increased.     

Temporal analysis of products (TAP) study on oxygen storage properties over Pt−Rh/CeO2 catalyst

The oxygen storage capacity of CeO₂, Ce_0.9Pr_0.1O₂, Pt?Rh/CeO₂ and Pt?Rh/Ce_0.9Pr_0.1O₂ was investigated by conventional GC pulse method and transient pulse techniques. It is shown that incorporation of PrO_y into CeO₂ matrix strongly promotes oxygen storage capacity (OSC) measured using the transient pulse technique. The improvement of OSC at low temperature is observed in Pt?Rh loaded onto CeO₂ and Ce?Pr catalysts.     

Exiguolide, a new macrolide from the marine sponge Geodia exigua

A new 20-membered macrolide designated exiguolide has been isolated from the marine sponge Geodia exigua, and its structure determined by interpretation of spectroscopic data. Exiguolide specifically inhibited fertilization of sea urchin (Hemicentrotus pulcherrimus) gametes but not embryogenesis of the fertilized egg.     

Performance evaluation of PVdF gel polymer electrolytes

A series of gel polymer electrolytes containing PVdF as homo polymer, a mixture of 1:1 Ethylene Carbonate (EC) : Propylene Carbonate (PC) as plasticizer and lithium-bistrifluoromethane sulphone imide [imide — LiN (CF₃SO₂)₂] has been developed. Amounts of polymer (PVdF), plasticizer and the imide lithium salt have been varied as a function of their weight ratio composition in this regard. Dimensionally stable films possessing appreciable room temperature conductivity values have been obtained with respect to certain weight ratio compositions. However, conductivity data have been recorded at different possible temperatures, i.e., from 20 °C to 65 °C. XRD and DSC studies were carried out to characterize the polymer films for better amorphicity and reduced glass transition temperature, respectively. The electrochemical interface stability of the PVdF based gel polymer electrolytes over a range of storage period (24 h – 10 days) have been investigated using A.C. impedance studies. Test cells containing Li/gel polymer electrolyte (GPE)/Li have been subjected to undergo 50 charge-discharge cycles in order to understand the electrochemical performance behaviour of the dimensionally stable films of superior conductivity. The observed capacity fade of less than 20% even after 50 cycles is in favour of the electrochemical stability of the gel polymer electrolyte containing 27.5% PVdF −67.5 % EC+PC −5% imide salt. Cyclic voltammetry studies establish the possibility of a reversible intercalation — deintercalation process involving Li⁺ ions through the gel polymer electrolyte.     

Infrared spectroscopic analyses of transformations of chemical species on the silica highly-reacted with gaseous BF3.

Transformations of chemical species formed by the reaction of gaseous BF3 with high pressure and silica preheated at 473 and 1093 K were studied with the use of infrared absorption spectrometry. The species containing -BF2 and the species containing >BF were transformed to each other on the highly-reacted silica depending on the pressure of BF3 in cell, and some of the species containing -BF2 were also desorbed without their transformations to the species containing >BF. H2O played important roles in these transformations.     

A Pseudo-Random Frequency Modulation Continuous Wave Coherent Lidar Using an Optical Field Correlation Detection Method

We propose a new detection method for a pseudo-random frequency modulation continuous wave (RM-CW) coherent lidar. The feature of this method is modulation of local beam with a time delayed pseudo-random sequence. Heterodyne detection and correlation detection between the received beam and the local beam are simultaneously carried out in an optical field. In the RM-CW coherent lidar using the optical field correlation detection method, the received equipment is greatly simplified. We carried out preliminary experiments and demonstrated that the new method is effective for detection of a CW coherent lidar.     

Chiral discrimination of a helically organized crown ether array parallel to the helix axis of polyisocyanate

The asymmetric polymerization of 4′‐isocyanatobenzo‐18‐crown‐6 with the lithium amide of (S)‐(2‐methoxymethyl)pyrrolidine successfully proceeded to afford end‐functionalized poly(4′‐isocyanatobenzo‐18‐crown‐6) with (S)‐(2‐methoxymethyl)pyrrolidine (polymer 2 ). In the circular dichroism (CD) spectrum of 2 , a clear positive Cotton effect was observed in the range of 240–350 nm corresponding to the absorption of the polymer backbone, indicating that 2 partially formed a one‐handed helical structure, which was preserved by the chirality of (S)‐(2‐methoxymethyl)pyrrolidine bonding to the terminal end in 2 . In the titration experiments for the CD intensity of 2 in the presence of D ‐ and L ‐Phe·HClO₄ (where Phe is phenylalanine), a small but remarkable difference was observed in the amount of the chiral guest needed for saturation of the CD intensity and in the saturated CD intensity, indicating that the extremely stable, one‐handed helical part should exist in the main chain of 2 , which was not inverted even when the unfavorable chiral guest for the predominant helical sense, L ‐Phe·HClO₄, was added. In addition, helical polymer 2 exhibited a chiral discrimination ability toward racemic guests; that is, the guests were extracted from the aqueous phase into the organic phase with enantiomeric excess. The driving force of the chiral discrimination ability of 2 should certainly be attributed to the one‐handed helical structure in 2 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 325–334, 2006