Synthetic study of biphenylquinolizidine alkaloids I. Asymmetric total synthesis of lasubine I featuring organocatalyzed asymmetric intramolecular aza-Michael addition

A new procedure for the asymmetric total synthesis of lythraceous alkaloids with a 4-arylquinolizidine skeleton was developed, which involved an organocatalyzed asymmetric intramolecular aza-Michael addition.     

Artabotryols A – E,New Lanostane Triterpenes from the Seeds of Artabotrys odoratissimus

Six new lanostane triterpenes, artabotryols A, B, C1, C2, D, and E ( 1, 2, 3a, 3b, 4 , and 5 , resp.) have been isolated from the seeds of Artabotrys odoratissimus (Annonaceae). Their structures have been established as (3α,22S,25R)‐3‐hydroxy‐22,26‐epoxylanost‐8‐en‐26‐one ( 1 ), (3α,22S,25R)‐22,26‐epoxylanost‐8‐ene‐3,26‐diol ( 2 ), (3α,22S,25R,26R)‐26‐methoxy‐22,26‐epoxylanost‐8‐en‐3‐ol ( 3a ), (3α,22S,25R, 26S)‐26‐methoxy‐22,26‐epoxylanost‐8‐en‐3‐ol ( 3b ), (3α,22S,25R)‐3,22‐dihydroxylanost‐8‐en‐26‐oic acid ( 4 ) and (3α,7α,11α,22S,25R)‐3,7,11‐trihydroxy‐22,26‐epoxylanost‐8‐en‐26‐one ( 5 ) by spectroscopic studies and chemical correlations.     

Procyanidins are potent inhibitors of LOX-1: a new player in the French Paradox

Lectin-like oxidized LDL receptor-1 (LOX-1) is an endothelial receptor for oxidized LDL (oxLDL) and plays multiple roles in the development of cardiovascular diseases. We screened more than 400 foodstuff extracts for identifying materials that inhibit oxLDL binding to LOX-1. Results showed that 52 extracts inhibited LOX-1 by more than 70% in cell-free assays. Subsequent cell-based assays revealed that a variety of foodstuffs known to be rich in procyanidins such as grape seed extracts and apple polyphenols, potently inhibited oxLDL uptake in Chinese hamster ovary (CHO) cells expressing LOX-1. Indeed, purified procyanidins significantly inhibited oxLDL binding to LOX-1 while other ingredients of apple polyphenols did not. Moreover, chronic administration of oligomeric procyanidins suppressed lipid accumulation in vascular wall in hypertensive rats fed with high fat diet. These results suggest that procyanidins are LOX-1 inhibitors and LOX-1 inhibition might be a possible underlying mechanism of the well-known vascular protective effects of red wine, the French Paradox.     

Optimization of cation structure of imidazolium-based ionic liquids as ionic solvents for rechargeable magnesium batteries

A series of imidazolium cation-based ionic liquids (ILs) have been synthesized and examined as ionic solvents for rechargeable magnesium batteries. The electrolyte solutions consist of these ILs dissolving methylmagnesium bromide with tetrahydrofuran (MeMgBr/THF). The chemical structure of imidazolium cation much influenced the ionic conductivity and the electrochemical window of the system. A reversible process of cathodic deposition and anodic dissolution of magnesium has been successfully achieved at room temperature. The highest value of anodic peak current for magnesium dissolution was obtained in an optimized-structure IL with allyl and methoxyethyl groups as the substituents.     

Colorimetric Calibration of Video Cameras Using Two Color Constancy Models

Colorimetric calibration of color imaging devices is important to realize device independent color reproductions. However the calibration for digital or video cameras is difficult because a color image is acquired for unknown objects under various unknown illuminants. An experiment was carried out based on two computational color constancy models, the finite-dimensional linear model and the spectral sharpening model, to estimate colorimetric values using image data of a color chart captured by video camera. We estimated the colorimetric values by using a single reference reflectance with known spectral reflectance in a color chart under an unknown illuminant. The accuracy was evaluated by color differences in CIELAB color space and was compared on three different color charts under three different illuminants including a fluorescent lamp. It was confirmed that the two computational models do not require prior knowledge of illuminants and surfaces. The finite-dimensional linear model gave more accurate results than the spectral sharpening model in the simulations and experiments.     

Preparation of polymethylsilsesquioxanes by the base‐catalyzed hydrolytic polycondensation of triisopropoxy(methyl)silane

Base‐catalyzed hydrolytic polycondensation of trialkoxymethylsilane was investigated to synthesize polymethylsilsesquioxanes (PMSs). The reaction of trimethoxy(methyl)silane and triethoxy(methyl)silane with tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and also coline gave insoluble gels. Polymethylsilsesquioxane (PMS‐IP) was obtained by the reaction of triisopropoxy(methyl)silane (MTIPS) with tetrabutylammonium hydroxide as a catalyst. PMS‐IP was composed primarily of T² and T³ units. The percentage of T³ units and the molecular weight of PMS‐IP increased with increases in the molar ratios of catalyst and water to MTIPS and with the reaction time. PMS‐IP was soluble in organic solvents, except for methanol, and was separated by extraction with hexane and methanol into low‐ and high‐molecular‐weight fractions of M_w 2800–4000 and 7300–88,300, respectively. PMS‐IP coating films were prepared by dip coating on the organic, inorganic, and metal substrates, using the acetone–isopropyl alcohol solution of PMS‐IP. Since PMS‐IP solutions prepared with tetrabutylammonium hydroxide were hardly used because of the low content of hydroxy groups in the polymer, they showed low adhesion when compared with those solutions prepared with hydrochloric acid. The dielectric constant of the coating film prepared from the high‐molecular‐weight PMS‐IP was 2.6. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3623–3630, 2005     

Control of peroxyoxalate chemiluminescence by nitrogen-containing ligand quenching: turning off and on by ligand-metal ion host-guest interactions

The control of peroxyoxalate chemiluminescence (PO-CL) by the coordination of nitrogen-containing ligands and metal cations was investigated. Turning the CL off and on was done by PO-CL using 15-monoazacrown-5-tethered anthracene and alkali metal ions. CL quenching and regeneration was also observed in the separated molecular system of 15-monoazacrown-5 and the fluorophores. CL quenching by a number of ligands bearing dipicolylamino groups was evaluated by these PO-CL reactions and found to be closely related to their oxidation potentials, which is dependent on the Weller rate law for electron exchange and this provides strong support for the existence of the CIEEL PO-CL process. When Zn²⁺ or Cu²⁺ are added to the PO-CL system quenched by the ligand, N-[2-(2,2′-dipicolylamino)ethyl]aniline, CL was turned on because the electron donating ability of the ligands was modulated. This was controlled by the coordination of the studied metal ions and, therefore, this system results in CL because of host-guest interactions.     

Study on the pressure induced charge transfer phase transition in (C5H11)4N(FeFe(C2O2S2)3) by means of μSR spectroscopy

We have investigated the magnetic properties of iron mixed-valence complexes, (n-C_nH_2n+1)₄N[Fe^IIFe^III(dto)₃] (dto = C₂O₂S₂, n = 3, 5), in which not only a ferromagnetic transition but also a novel charge transfer phase transition (CTPT) take place [1]. This CTPT can be observed under ambient pressure for n = 3, while it appears abruptly above 0.5 GPa for n = 5 [2]. Recently, we have measured the muon spin relaxation (μSR) for the CTPT of n = 3, which revealed the dynamical process of electron-transfer between Fe^II and Fe^III and its frequency was estimated at about 0.1 MHz [3]. To investigate the pressure induced CTPT for n = 5, we carried out the μSR measurement for n = 5 at 150 K between 0.30 and 0.64 GPa with the ⁴He gas-operated pressure system. The asymmetry of the muon spin relaxation for n = 5 with Cu-Be pressure cell was almost constant up to 0.55 GPa, while it rapidly decreased with increasing pressure above 0.60 GPa. This result shows that the applied pressure causes the spin fluctuation due to the CTPT, which induces the decrease of the asymmetry of muon spin relaxation. This experiment can correctly decide the phase transition pressure from the absence to the appearance of the CTPT for n = 5.     

Ultrasensitive CE for heavy metal ions using the variations in the chemical structures formed from new octadentate fluorescent probes and cationic polymers

Novel fluorescent probes have been developed for the ultratrace detection of heavy metal ions by capillary electrophoresis using laser-induced fluorescence detection. Based on a molecular design, the probes are composed of an octadentate chelating moiety, a macrocyclic DOTA (tetraazacyclododecanetetraacetic acid) and an acyclic DTPA (diethylenetriaminepentaacetic acid) frame, a spacer and a fluorophore (fluorescein). These were chosen on the basis of their ability to form kinetically inert and highly emissive complexes, and to prevent a quenching effect even with heavy and paramagnetic metal ions. Addition of a cationic polymer, polybrene, in the separation buffer provided high resolution and simultaneous detection of Ca(2+), Mg(2+), Cu(2+), Zn(2+), Ni(2+), Co(2+), Mn(2+), Cd(2+) and Pb(2+). The direct fluorescence detection of these metal ions with high sensitivity at lower ppt levels, typically 2-7 × 10(-11) M (potentially sub-ppt), was successfully achieved. While separation of anionic compounds using a counter cation ("Ion Association (IA)" mode) is typically controlled by the ion association equilibrium constants, K(ass), it was found that differences in the mobilities, μ(ep(IAC)), of the ion association complexes formed between the probe complexes and counter cations are the driving forces for separation in this new method. This suggests that each of the polybrene-probe complexes has different chemical structures among metal ions, which were able to be determined by CD spectra in this investigation. This novel separation mode was termed the "Ion Association Complex (IAC)" mode, distinct from the IA mode.     

Certain values of Hecke L-functions and generalized hypergeometric functions

We compare two calculations due to Bloch and the author of the regulator of an elliptic curve with complex multiplication which is a quotient of a Fermat curve, and express the special value of its L-function at s=0 in terms of special values of generalized hypergeometric functions.