Spectral and HPLC Analyses of Synthesized Butin and Butein.

Butin and butein are significant bioactive flavanones derived from plants, existing as tautomers of each other. However, their physicochemical attributes, such as their spectral profiles under varying experimental conditions in aqueous solutions and established chromatographic methods for distinguishing between them, remain undetermined. In this study, we determined the basic properties of butin and butein using conventional spectroscopic, reversed-phase, and chiral HPLC analyses. The spectra of the synthesized butin and butein were analyzed using a UV-Vis spectrophotometer in several solvents with different polarities as well as in aqueous solutions at various pH values. Furthermore, the behavior of the measured spectra was reproduced by calculations to reveal the effects of the solvent and pH on the spectra of butin and butein in organic and aqueous solutions. Subsequently, we assessed the structural stability of butin and butein using reversed-phase HPLC, which revealed that butein is unstable compared with butin in a general culture medium. The synthesized butin was effectively separated into R- and S-isomers with positive and negative Cotton effects, respectively, via HPLC using a chiral column. These findings will aid in uncovering the individual properties of both butin and butein that may have been concealed by their tautomerism and enable the synthesis of S-butin, which is typically challenging and time-consuming to isolate.

Synthesis and Direct Observation of Chiral Supramolecular Polymer of Porphyrin Having Cholesteryl Groups.

We report the synthesis and microscopic investigations of two chiral helical porphyrin supramolecular polymers with different coordinating metals that are expected to be capable of serving as synthetic macromolecular motors driven by thermal fluctuations. Furthermore, based on their microscopic images, we propose a stepwise process for the formation of higher-order structures. These porphyrins formed completely different association states, and this was reflected in the marked differences in the shapes of the supramolecular polymers. The Cu-TChOAlaCPP supramolecular polymers formed H-aggregate rods in diisopropyl ether, then grew into superhelices and then into ribbons. On the other hand, Zn-TChOAlaCPP supramolecular polymers formed aggregates based on van der Waals interactions in diethyl ether, then grew into fibers and then grew into multiple-helices and ribbons. In addition, we imaged the interaction between long and short chains of the Cu-TChOAlaCPP supramolecular polymer by fast-scanning atomic force microscopy, and we indicated the availability as a macromolecular motor driven by thermal fluctuations.

Single-Molecule Unidirectional Processive Movement along a Helical Polymer Chain in Non-aqueous Medium.

In this work, a molecule "walking" along a single chain of a synthetic helical polymer, which is used as a rail on a substrate in an organic solvent at room temperature, is observed. The walking comprises the unidirectional processive movement of a short-chain molecule along a chiral helical chain in 3 nm steps, driven by Brownian motion and a tapping effect of the atomic force microscopy tip based on a flash ratchet mechanism. Furthermore, the rail consists of a long-chain substituted phenylacetylene polymer with pendant cholesteryl groups, along which the short-chain molecule can walk as a result of van der Waals interactions. The macromolecular motion is videoed using a fast-scanning atomic force microscope, and additionally, this phenomenon is also simulated by all-atom molecular dynamics calculations. On the basis of these results, we propose the principle of a polymer molecular motor. This is the first report of a synthetic walking machine of a chiral helical polymer driven by thermal fluctuation as an artificial life function.