Steroidal alkaloid glycosides, esculeosides C and D, from the ripe fruit of cherry tomato

Two new steroidal alkaloid glycosides, esculeosides C and D, have been isolated from the ripe fruit of Cherry tomato [Lycopersicon esculentum var. cerasiforme (DUNAL) ALEF.], along with three known steroidal alkaloid glycosides, esculeoside A, esculeoiside B, and lycoperoside G. Their chemical structures were determined on the basis of spectroscopic data.     

DNA mismatch detection using a pyrene-excimer-forming probe

A pyrene-excimer-forming probe allowed the easy and sensitive detection of a single base mismatch in target DNA. This was due to the faster strand exchange rate compared to a fully-matched target.     

Distinction of absolute configuration at C-22 of C-23-hydroxyspirostane and C-23-hydroxyspirosolane glycosides

It has been revealed that the absolute configurations at C-22 of 23-hydroxyspirostane and 23-hydroxyspirosolane could be unambiguouly judged by the (1)H- and (13)C-NMR spectroscopies.     

Synthesis and properties of 2-(2-pyridyl)-1-azaazulene

The title azaazulene 3 was synthesized either by reaction of tropone with N-{(2-pyridyl)acetyl}pyridinium iodide in the presence of ammonium acetate or by palladium-catalyzed cross-coupling between 2-halo-1-azaazulene and 2-substituted pyridine. The compound shows relatively stronger basicity compared with 2,2′-bipyridyl. While 3 showed no emission from the S₁ state but from the S₂ state like azulene does, the protonated species of 3 exhibited emission from the S₁ state. Cationic metal-dependent absorption and emission relating to complexation were also studied.     

Screening a fragment cocktail library using ultrafiltration

Ultrafiltration provides a generic method to discover ligands for protein drug targets with millimolar to micromolar K(d), the typical range of fragment-based drug discovery. This method was tailored to a 96-well format, and cocktails of fragment-sized molecules, with molecular masses between 150 and 300 Da, were screened against medical structural genomics target proteins. The validity of the method was confirmed through competitive binding assays in the presence of ligands known to bind the target proteins.     

Spontaneous enrichment of one-handed helices by dissolution of quasiracemic crystals of a tetranuclear single helical complex

The left-handed isomer of the helical complex [LZn(3)La(OAc)(3)] was spontaneously enriched from 50 : 50 to 87 : 13 when the quasiracemate crystals were dissolved. The invertible helicity of [LZn(3)La(OAc)(3)] (global chirality) helps the quasiracemate formation and the fixed point chirality of the R,R-cyclohexanediamine moiety (local chirality) effectively controls the global chirality in solution.     

Luminescence Color‐Tuning through Polymorph Doping: Preparation of a White‐Emitting Solid from a Single Gold(I)–Isocyanide Complex by Simple Precipitation

We report the luminescent color tuning of a new complex, 2‐benzothiophenyl(4‐methoxyphenyl isocyanide)gold(I) ( 1 ), by using a new “polymorph doping” approach. The slow crystallization of the complex 1 afforded three different pure polymorphic crystals with blue, green, and orange emission under UV‐light irradiation. The crystal structures of pure polymorphs of 1 were investigated in detail by means of single‐crystal X‐ray analyses. Theoretical calculations based on the single‐crystal structures provided qualitative explanation of the difference in the excited energy‐levels of the three polymorphs of 1 . In sharp contrast, the rapid precipitation of 1 , with the optimized conditions reproducibly afforded homogeneous powder materials showing solid‐state white‐emission with Commission Internationale de l’Éclairage (CIE) 1931 chromaticity coordinates of (0.33, 0.35), which is similar to pure white. New “polymorphic doping” has been revealed to be critical to this white emission through spectroscopic and X‐ray diffraction analyses. The coexistence of the multiple polymorphs of 1 within the homogeneous powder materials and the ideal mixing of multiple luminescent colors gave its white emission accompanied with energy transfer from the predominant green‐emitting polymorph to the minor orange‐emitting polymorph.     

2,2′-Tethered Binaphthyl-Embedded One-Handed Helical Ladder Polymers: Impact of the Tether Length on Helical Geometry and Chiroptical Property

Synthetic breakthroughs diversify the molecules and polymers available to chemists. We now report the first successful synthesis of a series of optically-pure 2,2′-tethered binaphthyl-embedded helical ladder polymers based on quantitative and chemoselective ladderization by the modified alkyne benzannulations using the 4-alkoxy-2,6-dimethylphenylethynyl group as the alkyne source, inaccessible by the conventional approach lacking the 2,6-dimethyl substituents. Due to the defect-free helix formation, the circular dichroism signal increased by more than 6 times the previously reported value. The resulting helical secondary structure can be fine-tuned by controlling the binaphthyl dihedral angle in the repeating unit with variations in the 2,2′-alkylenedioxy tethering groups by one carbon atom at a time. The optimization of the helical ladder structures led to a strong circularly polarized luminescence with a high fluorescence quantum yield (28 %) and luminescence dissymmetry factor (2.6×10⁻³).