Asymmetric Total Syntheses,Stereostructures, and Cytotoxicities of Marine Bromotriterpenoids Aplysiol B (Laurenmariannol) and Saiyacenol A

There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis.     

All Non-Carbon B3NO2 Exotic Heterocycles: Synthesis,Dynamics, and Catalysis

The B₃NO₂ six-membered heterocycle (1,3-dioxa-5-aza-2,4,6-triborinane=DATB), comprising three different non-carbon period 2 elements, has been recently demonstrated to be a powerful catalyst for dehydrative condensation of carboxylic acids and amines. The tedious synthesis of DATB, however, has significantly diminished its utility as a catalyst, and thus the inherent chemical properties of the ring system have remained virtually unexplored. Here, a general and facile synthetic strategy that harnesses a pyrimidine-containing scaffold for the reliable installation of boron atoms is disclosed, giving rise to a series of Pym-DATBs from inexpensive materials in a modular fashion. The identification of a soluble Pym-DATB derivative allowed for the investigation of the dynamic nature of the B₃NO₂ ring system, revealing differential ring-closing and -opening behaviors depending on the medium. Readily accessible Pym-DATBs proved their utility as efficient catalysts for dehydrative amidation with broad substrate scope and functional-group tolerance, offering a general and practical catalytic alternative to reagent-driven amidation.     

Organic–Inorganic Hybrid Gold Halide Perovskites: Structural Diversity through Cation Size

Crystal structures of a series of organic–inorganic hybrid gold iodide perovskites, formulated as A₂[Au^II₂][Au^IIII₄] [A=methylammonium (MA) ( 1 ) and formamidinium (FA) ( 2 )], A′₂[I₃]_1−x[Au^II₂]_x[Au^IIII₄] [A′=imidazolium (IMD) ( 3 ), guanidinium (GUA) ( 4 ), dimethylammonium (DMA) ( 5 ), pyridinium (PY) ( 6 ), and piperizinium (PIP) ( 7 )], systematically changed depending on the cation size. In addition, triiodide (I₃⁻) ions were partly incorporated into the AuI₂⁻ sites of 3 – 7 , whereas they were not incorporated into those of 1 and 2 . Such a difference comes from the size of the organic cation. Optical absorption spectra showed characteristic intervalence charge-transfer bands from Au^I to Au^III species, and the optical band gap increased as the size of the cation became larger.     

Linear and Nonlinear Optical Properties Of Racemic (±)2-(α-Methylbenzylamino)-5-Nitropyridine Single Crystals

Linear and nonlinear optical properties of racemic (±)2-(α-methylbenzylamino)-5-nitropyridine ((±)MBANP) single crystals have been comprehensively investigated and compared with those of the enantiomorph (–)2-(α-methylbenzylamino)-5-nitropyridine ((–)MBANP) crystals. (±)MBANP crystal exhibits very high chemical and physical stability, but relatively small nonlinear optical coefficients (d₃₁ = 6.8 pm/V, d₃₂ = 4.7 pm/V, d₃₃ = 0.84 pm/V). A comparison between the nonlinear optical coefficients of (±)MBANP and (–)MBANP demonstrates the validity of the oriented-gas model in molecular crystals that neglects all the contributions from intermolecular interaction.     

Measuring Light Field of Light Source with High Directional Resolution Using Mirrored Ball and Pinhole Camera

This paper presents a method of measuring a light field of a light source with high directional resolution using a mirrored ball and a pinhole camera. The light field describes a spatial and directional distribution of radiances from the light source. The directional distribution is expanded by a reflection on the mirrored ball, and the radiances are measured by a charge-coupled device (CCD) camera with a pinhole lens. The light source is laterally moved by a robot arm to measure the directionally expanded light field, and each pixel on a CCD can obtain the radiances from the light source through the pinhole lens with high directional resolution. The light field is estimated from the pixel value and the position of each pixel using a ray tracing technique. The light field of a krypton lamp was experimentally measured by the proposed method, and the accuracy of the measurement was evaluated against the irradiances measured by a spectro-radiometer at sample points.     

Association Behavior of 4-Acylpyrazolone Derivative and Tertiary Amine of High Molecular Weight in Antagonistic Synergistic Extraction of Palladium

To find an effective extraction and removal method for palladium(II), which is one of the main fission products from an acidic nuclear spent fuel solution, the extraction behavior of palladium(II) from a nitric acid medium by an acidic chelating extractant, 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5-one (HPMTP) and a tertiary amine of high molecular weight, tri-n-octylamine (TOA), has been studied by spectrophotometry. A noticeable antagonistic extraction effect was observed in the extraction system under the given conditions. To understand this phenomenon, a preliminary investigation was performed to explain the mechanism of this reaction. According to the theory of corresponding solutions (TCS), the association reaction between HPMTP and TOA is proposed in the organic phase. An associated species, HPMTP·TOA, formed through hydrogen bonding in a chloroform medium might be the main reason why an antagonistic extraction effect occurred. The association constant between HPMTP and TOA was calculated to be 2.86±0.05.     

Inhibitory effects of 3-O-acyl-(+)-catechins on Epstein-Barr virus activation

In the course of an exploratory investigation of antitumor-promoting catechins, 3-O-acyl-(+)-catechins of varying carbon lengths from C(4) to C(18) were assessed for inhibitory effects on the activation of the Epstein-Barr virus early antigen. Like 3-O-acyl-(-)-epigallocatechins, the (+)-catechin derivatives showed promising effects with the C-3 acyl chain of C(8)-C(11) carbon atoms.     

Synthesis, structure, and physical properties of 1,11-o-benzeno[2]orthocyclo[2](1,2)tropyliophane

The title compound (2) has been synthesized, the structure and the physical properties of which are investigated by X-ray, spectroscopic analyses, and MO calculations. There exists charge transfer (CT) interaction between the tropylium ion and the facing phenyl ring. From the pK_R⁺ value of 2, it can be clear that the cation 2 is stabilized by the CT interaction. In spite of the presence of bond weakening σ-π orbital mixing, the cation 2 withstands retro[4+4]type bond cleavage, which is quite interesting when compared to a facile cleavage for the congener with anthracene photodimer type structure.     

Selective chemical vapor deposition synthesis of double-wall carbon nanotubes on mesoporous silica

Double-wall carbon nanotubes (DWNTs) have been selectively synthesized over Fe/Co loaded mesoporous silica by catalytic chemical vapor deposition of alcohol. Several silica materials with desired pore diameter and morphology have been investigated for the DWNT growth. The diameter distribution and selectivity of the DWNT are found to depend on the reaction temperature, pore size, and thermal stability of the support material. A high-yield synthesis of DWNTs has been achieved at 900 degrees C over high-temperature stable mesoporous silica. The outer diameter of DWNTs is found to be in the range of 1.5-5.4 nm with a "d" spacing of 0.38 +/- 0.02 nm between inner and outer layers, which is much larger than those of multiwall carbon nanotubes.