Synthesis of Cross-Chain Bridging Cryptands and Induction of Molecular Chirality.

In this study, we synthesized two cryptands featuring entangled tri- and tetra(ethylene glycol) linkers. The cryptand bearing short linkers was chiral without any asymmetric carbon atoms. After chiral high-performance liquid chromatography was used to separate the enantiomers, the absolute configuration of each cryptand was determined through single-crystal X-ray and circular dichroism analyses. The racemization of the cryptand possessing long linkers proceeded at room temperature.

Characterization of Cooked Nonglutinous Rice Cultivars Based on Flavor Volatiles and Their Change during Storage.

Characterizing fleshly cooked rice cultivars according to the volatile aroma compounds helps consumers select a favorite and is useful for the development of new cultivars that will have a pleasant aroma. In the present study, six Japanese nonglutinous cultivars, which were freshly harvested in 2021, were characterized based on their flavor volatiles after being freshly cooked. In order to extract the volatile compounds just after cooking, the vaporized compounds were extracted for 5 min using a solid-phase microextraction (SPME) fiber and were measured via gas chromatography/mass spectrometry (GC/MS). Multiple comparison tests statistically detected four volatile aroma compounds: 2-pentylfuran, nonanal, 4-vinylphenol, and indole. From among the six rice cultivars tested, the proportions of the latter two compounds showed significant differences, and in principal component analysis of cooked rice, these two best characterized freshly harvested and freshly cooked Japanese nonglutinous rice cultivars; indole was indicative of Nipponbare, and 4-vinylphenol was indicative of Koshihikari and Ichihomare. In the present study, changes in the volatile aroma compounds of the freshly cooked rice cultivars were found to slightly differentiate according to storage times: 2-pentylfuran tended to increase, nonanal first increased and then decreased, and 4-vinylphenol and indole either remained almost unchanged or were only slightly decreased during storage. Therefore, establishing the differences in rice cultivar types revealed that the characteristics of the flavor volatiles of freshly cooked rice after long-term storage significantly depend on how the rice cultivar is stored.

Development of Low Molecular Weight Ligands for Integrin αvß3.

We designed and synthesized non-peptide organic molecular ligands for integrin αvß3. Candidate ligands featured amidino analog and carboxy groups as binding sites on either side of a spacer, which consisted of benzophenone or an analog, such as diphenyl sulfide, diphenyl sulfoxide, diphenyl sulfone, or diphenyl ether. Competitive binding assays to integrin αvß3 with respect to [125I]echistatin were used to determine inhibitory activity of the synthetic ligands. Ligands bearing 2-aminobenzimidazoyl and glycyl groups separated by a benzophenone spacer demonstrated more potent binding than did a linear Arg-Gly-Asp (RGD) tripeptide that represents the native integrin αvß3 binding motif. Ligands possessing 2-aminobenzimidazoyl and carboxy groups and diphenyl sulfoxide or diphenyl ether spacers inhibited binding of [125I]echistatin with IC50 values similar to that of the linear RGD tripeptide.

Four- and two-armed hetero porphyrin dimers: their specific recognition and self-sorting behaviours.

In this study we self-assembled the four-armed porphyrin hetero dimer capsule Cap4, stabilized through amidinium-carboxylate salt bridges, in CH2Cl2 and CHCl3. The dimer capsule Cap4 was kinetically and thermodynamically more stable than the corresponding two-armed dimer Cap2. The number of arms strongly influenced their recognition behaviour; guests possessing small aromatic faces (e.g., 1,3,5-trinitrobenzene) preferred residing in the cavity of the two-armed capsule Cap2, rather than in Cap4, both thermodynamically and kinetically; in contrast, large aromatic guests (e.g., 9,10-dibromoanthracene) were encapsulated predominantly by Cap4 because of favourable entropic effects. The number of arms enabled self-sorting behaviour of the dimer formation; complexation studies using an equimolar mixture of the four porphyrin constituents of the two capsules revealed the quantitative formation of the corresponding dimers Cap2 and Cap4. Furthermore, we examined the specific molecular recognition of Cap2 and Cap4; NMR experiments of mixtures of Cap2 and Cap4 in the presence of favourable guests for Cap2 and Cap4 revealed that these guest molecules were encapsulated selectively by their preferred hosts.

Synthesis of a Mechanically Planar Chiral and Axially Chiral [2]Rotaxane.

In this study, we synthesized a [2]rotaxane that was both mechanically planar chiral and axially chiral, comprising a symmetrical bis-crown ether featuring a biphenyl moiety (as the macrocyclic component) and a symmetrical bis-ammonium salt (as the dumbbell-shaped component).

Base-induced multi-state fluorescence of a trefoil-shaped salicylaldehyde azine derivative.

A trefoil-shaped salicylaldehyde azine derivative bearing multiple acidic protons displays base-induced multi-state luminescence. The azine was prepared through the reaction of 1,3,5-triformylphloroglucinol with 4-methoxysalicylaldehyde hydrazone. 1H NMR spectroscopy revealed that the azine existed in solution at room temperature as an equilibrium mixture of two geometric isomers. The three-step deprotonation (four-state change) of the azine in solution was confirmed using 1H NMR, UV-vis absorption, and emission spectroscopy.

Locking the Dynamic Axial Chirality of Biphenyl Crown Ethers through Threading.

This paper describes the syntheses of [2]rotaxanes comprising 23- and 26-membered biphenyl crown ethers as the macrocyclic components and secondary ammonium ions as the dumbbell-shaped components, and the locking of the dynamic axial chirality of the biphenyl moieties in these structures. Chiral high-performance liquid chromatography (HPLC) revealed that our [2]rotaxane featuring the 26-membered crown ether racemized at room temperature, but the racemization of the [2]rotaxane featuring the 23-membered crown ether did not proceed at room temperature over a period of three days. After separation of the enantiomers of the [2]rotaxane incorporating the 23-membered crown ether through chiral HPLC, we studied its racemization at elevated temperature. The rate of stereoinversion in dimethylsulfoxide (a polar solvent) was faster than that in o-dichlorobenzene (a nonpolar solvent), and herein we discuss these kinetic parameters.

Utilization of a Crown Ether/Amine-Type Rotaxane as a Probe for the Versatile Detection of Anions and Acids by Thin-Layer Chromatography.

A crown ether/amine-type [2]rotaxane was synthesized and utilized as a probe for the detection of acids and anions. The addition of acids to the amine-type [2]rotaxane solution generated corresponding crown ether/ammonium-type [2]rotaxanes, which were purified by silica gel column chromatography as ammonium salts. The isolated yields of the [2]rotaxanes, possessing a variety of anions, depended on the acidity and polarity of the counter anions. The behaviours of the ammonium-type [2]rotaxanes on thin-layer chromatography (TLC) silica gel reflected the properties of the counter anions. The treatment of the amine-type [2]rotaxane with acids afforded the corresponding ammonium-type [2]rotaxanes bearing several different anions. The ammonium-type [2]rotaxanes behaved similarly to the purified [2]rotaxanes on the TLC silica gel. Furthermore, we succeeded in the analysis of anions using mixtures of the amine-type [2]rotaxane and salts in an appropriate solvent. We demonstrated the detection of anions by the combination of TLC and the utilization of the [2]rotaxane probe.

Using SPME-GC/REMPI-TOFMS to Measure the Volatile Odor-Active Compounds in Freshly Cooked Rice.

The volatile odor-active compounds of cooked rice were evaluated using a method that combined solid-phase microextraction (SPME) with gas chromatography-resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (GC/REMPI-TOFMS). An SPME fiber was held at the upper levels of the cooked rice and given an extraction time of 5 min. By using a nanosecond ultraviolet (266 nm) pulsed laser for ionization, two compounds, 4-vinylphenol and indole, which are considered to be important for the characteristic flavor of cooked rice, could be detected from all types of cultivars measured in the present study-nonglutinous rice, glutinous rice, and aromatic rice. In the case of fresh nonglutinous rice, the amounts of introduction for 4-vinylphenol and indole to GC were ca. 70 and 20 pg, respectively. While both peak areas decreased with increases in the time needed to maintain warmth, the decreasing behaviors differed slightly with a noteworthy rapid decrease for indole. For nonglutinous rice, the peak areas for 4-vinylphenol were almost the same, whether it was fresh (measured within 1 month from harvest) or aged (measured 6-12 months after harvest), but those of indole significantly decreased following storage. We also found differences among cultivars: the peak area for 4-vinylphenol in nonglutinous rice was somewhat strong; the peak area for indole was intensely strong in glutinous rice; however, the peak areas for both 4-vinylphenol and indole were weak in aromatic rice. Volatile odor-active compounds were detected in a sensitive and time-resolved manner; therefore, the proposed method could be useful for differentiating varieties of cooked rice from the viewpoints of cooking conditions, freshness, and cultivar types.

A Five-layer π-Aromatic Structure Formed through Self-assembly of a Porphyrin Trimer and Two Aromatic Guests.

In this study we synthesized two- and four-armed porphyrins - bearing two carboxyl and four 2-aminoquinolino functionalities, respectively, at their meso positions - as a complementary hydrogen bonding pair for the self-assembly of a D2 -symmetric porphyrin trimer host. Two units of the two-armed porphyrin and one unit of the four-armed porphyrin self-assembled quantitatively into the D2 -symmetric porphyrin trimer, stabilized through ammidinium-carboxylate salt bridge formation, in CH2 Cl2 and CHCl3 . The porphyrin trimer host gradually bound two units of 1,3,5-trinitrobenzene between the pair of porphyrin units, forming a five-layer aromatic structure. At temperatures below -40 °C, the rates of association and dissociation of the complexes were slow on the NMR spectroscopic time scale, allowing the 1 : 1 and 1 : 2 complexes of the trimer host and trinitrobenzene guest(s) to be detected independently when using less than 2 eq of trinitrobenzene. Vis titration experiments revealed the values of K1 (2.1±0.4×105  M-1 ) and K2 (2.2±0.06×104  M-1 ) in CHCl3 at room temperature.

Absolute asymmetric Strecker synthesis in a mixed aqueous medium: reliable access to enantioenriched α-aminonitrile.

Without using chiral sources, the Strecker reaction of achiral hydrogen cyanide, p-tolualdehyde and benzhydrylamine gave enantioenriched l- or d-N-benzhydryl-α-(p-tolyl)glycine nitriles with up to >99% ee in a mixed solvent of water and methanol. Therefore, total spontaneous resolution of α-aminonitriles could occur through a prebiotic mechanism of α-amino acid synthesis. Moreover, it was demonstrated that the repetition of partial dissolution and crystallization of a suspended conglomerate of aminonitrile under solution-phase racemization could generate the enantiomeric imbalance to afford, in combination with the amplification of chirality, an enantioenriched product in every case. Among the 73 experiments that were carried out, d- and l-enriched isomers occurred 36 and 37 times, respectively. This stochastic behavior, under achiral or racemic starting conditions, meets the requirements of the spontaneous absolute asymmetric Strecker synthesis. The implications of the present results for the origin of chirality of α-amino acids are discussed.

Synthesis of a Chiral [2]Rotaxane: Induction of a Helical Structure through Double Threading.

A helically chiral [2]rotaxane featuring two ammonium ion recognition sites in the dumbbell-like component and a calix-bis-crown ether as the macrocyclic component was synthesized, but with no chirality in either individual component. The enantiomeric nature of the isomers, separated through chiral HPLC, was apparent in their CD spectra, which were mirror images for all wavelengths.

Formation of [2]- and [3]Rotaxanes through Bridging under Kinetic and Thermodynamic Control.

An efficient synthesis of a doubly stranded [3]rotaxane has been developed through bridging of a pseudo[3]rotaxane featuring two axle components. Reversible azine formation was effective as the bridging reaction. Kinetic and thermodynamic conditions provided the [2]- and [3]rotaxanes, respectively.

Four-State Molecular Shuttling of [2]Rotaxanes in Response to Acid/Base and Alkali-Metal Cation Stimuli.

In this study, we synthesized [2]rotaxanes possessing three recognition sites-a dialkylammonium, an alkylarylamine, and a tetra(ethylene glycol) stations-in their dumbbell-like axle component and dibenzo[24]crown-8 (DB24C8) as their macrocyclic component. These [2]rotaxanes behaved as four-state molecular shuttles: i) under acidic conditions, the DB24C8 unit encircled both the dialkylammonium and alkylarylammonium stations; ii) under neutral conditions, the dialkylammonium unit was the predominant station for the DB24C8 component; iii) under basic conditions, when both ammonium centers were deprotonated, the alkylarylamine unit became a suitable station for the DB24C8 component; and iv) under basic conditions in the presence of an alkali-metal cation, the tetra(ethylene glycol) unit recognized the DB24C8 component through cooperative binding of the alkali-metal ion. In addition, we observed that the [2]rotaxanes exhibited selective recognition for metal cations. These shuttling motions of the macrocyclic component proceeded reversibly.

Asymmetric Strecker Reaction Arising from the Molecular Orientation of an Achiral Imine at the Single-Crystal Face: Enantioenriched l- and d-Amino Acids.

Strecker synthesis has long been considered one of the prebiotic reactions for the synthesis of α-amino acids. However, the correlation between the origin of chirality and highly enantioenriched α-amino acids through this method remains a puzzle. In the reaction, it may be conceivable that the handedness of amino acids has been determined at the formation stage of the chiral intermediate α-aminonitrile, that is, the enantioselective addition of hydrogen cyanide to an imine. Herein, an enantiotopic crystal surface of an achiral imine acted as an origin of chirality for the enantioselective formation of α-aminonitriles by the addition of HCN. In conjunction with the amplification of the enantiomeric excess and multiplication of enantioenriched aminonitrile, a large amount of near enantiopure α-amino acids, with the l- and d-handedness corresponding to the molecular orientation of the imine, is reported.

Five-State Molecular Shuttling of a Pair of [2]Rotaxanes: Distinct Outputs in Response to Acid and Base Stimuli.

In this study we synthesized two acid-/base-controllable [2]rotaxanes featuring aminodiazobenzene and aminocoumarin units, respectively, as chromophores and dibenzo[24]crown-8 and dibenzo[25]crown-8 units, respectively, as their macrocyclic components. Each [2]rotaxane contained N-alkylarylamine (ammonium) and N,N-dialkylamine (ammonium) centers as binding sites for their crown ether components. The absorption patterns of the chromophores were dependent on the position of the encircling macrocyclic component and the degree of protonation, with three distinct states (under acidic, neutral, and basic conditions) evident for each [2]rotaxane. The mixed [2]rotaxane system displayed stepwise and independent molecular shuttling behavior based on the degree of protonation of the amino groups in response to both the amount and strength of added acids or bases; as such, the system provided five different absorption signals as outputs that could be read using UV/Vis spectroscopy.