Point‐to‐Point Ultra‐Remote Asymmetric Control with Flexible Linker

Kawasaki, Tsuneomi; Ishikawa, Yasuyuki; Yoshihiro, Minato; Otsuka, Toshihiko; Yonekubo, Shigeru; Sato, Iwao; Shibata, Takanori; Matsumoto, Arimasa; Soai, Kenso

doi:10.1002/chem.201605076

Cited by 5 publications

(6 citation statements)

References 57 publications

(19 reference statements)

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“…The only chiral factor is the initial enantiomeric imbalance of alkanol 1 itself as an asymmetric autocatalyst. In addition, asymmetric autocatalytic self-multiplication of multi-functionalized pyrimidyl alkanol 3 [49] and ultra-remote intramolecular asymmetric autocatalysis [50] were reported. Frank proposed a mechanism, i.e., a mathematical equation, of asymmetric autocatalysis without showing any chemical structure in 1953 [21].…”

Section: Discovery Of Asymmetric Autocatalysis With Amplification Of mentioning

confidence: 99%

Role of Asymmetric Autocatalysis in the Elucidation of Origins of Homochirality of Organic Compounds

2019

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Pyrimidyl alkanol and related compounds were found to be asymmetric autocatalysts in the enantioselective addition of diisopropylzinc to pyrimidine-5-carbaldehyde and related aldehydes. In the asymmetric autocatalysis with amplification of enantiomeric excess (ee), the very low ee (ca. 0.00005%) of 2-alkynyl-5-pyrimidyl alkanol was significantly amplified to >99.5% ee with an increase in the amount. By using asymmetric autocatalysis with amplification of ee, several origins of homochirality have been examined. Circularly polarized light, chiral quartz, and chiral crystals formed from achiral organic compounds such as glycine and carbon (13C/12C), nitrogen (15N/14N), oxygen (18O/16O), and hydrogen (D/H) chiral isotopomers were found to act as the origin of chirality in asymmetric autocatalysis. And the spontaneous absolute asymmetric synthesis was also realized without the intervention of any chiral factor.

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Section: Discovery Of Asymmetric Autocatalysis With Amplification Of mentioning

confidence: 99%

Role of Asymmetric Autocatalysis in the Elucidation of Origins of Homochirality of Organic Compounds

2019

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“…The results of this study show that controlling the orienta- positioning, work, force, information, control, and molecular agents. This unified mechanism covers a wide range of applications, including transduction of mechanical actions (biased positioning, work, force) in molecular motors or simpler nanoactuators [24], remote point-to-point control [25,26] (e.g., via the polymer-transduced force and positioning), information relay [27,28] or signal transduction, site-specific delivery of molecules [29] (e.g., in nanoassembly lines [53]), sensing (e.g., by site-specifically concentrating target molecules for higher detection sensitivity), and sorting of molecular cargos (e.g., on nanorobotic platforms [54]).…”

Section: B Unified Transduction and Relay Mechanism 474mentioning

confidence: 99%

“…These applications mostly have been demonstrated experimentally using other mechanisms, including steric hindrance [27,28] between closely packaged neighbors, chemical mechanisms [9,18,25,26,55] that inflict permanent changes to prevent repeatable operation, or by random intramolecular diffusion [29], etc. The orientation-based transduction is an alternative mechanism for actively controlled, repeatable, and long-range operation.…”

Section: B Unified Transduction and Relay Mechanism 474mentioning

confidence: 99%

“…Soft polymers are also used in nonmotor applications to transmit mechanical actions, control, information, and molecular agents from one location to another. Examples include mechanical transduction via polymer brushes, collectively [24], remote asymmetric control [25,26] through a single flexible molecular linker for the purpose of chemical synthesis, distant intramolecular relay of information [27,28] based on steric hindrance between nearest neighbors, and site-specific delivery of molecules [29] by a swinging polymer immobilized at one end.…”

Section: Introductionmentioning

confidence: 99%

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Mechanical transduction via a single soft polymer

et al. 2018

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Molecular machines from biology and nanotechnology often depend on soft structures to perform mechanical functions, but the underlying mechanisms and advantages or disadvantages over rigid structures are not fully understood. We report here a rigorous study of mechanical transduction along a single soft polymer based on exact solutions to the realistic three-dimensional wormlike-chain model and augmented with analytical relations derived from simpler polymer models. The results reveal surprisingly that a soft polymer with vanishingly small persistence length below a single chemical bond still transduces biased displacement and mechanical work up to practically significant amounts. This "soft" approach possesses unique advantages over the conventional wisdom of rigidity-based transduction, and potentially leads to a unified mechanism for effective allosterylike transduction and relay of mechanical actions, information, control, and molecules from one position to another in molecular devices and motors. This study also identifies an entropy limit unique to the soft transduction, and thereby suggests a possibility of detecting higher efficiency for kinesin motor and mutants in future experiments.

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“…First, the structures were designed for the study of far‐reaching inter and intramolecular chiral induction, providing an important contribution to the understanding of self‐replication and self‐perfection processes on the molecular level . These processes are important elements in the understanding of the initial events in the origin(s) of (terrestrial) life …”

Section: Introductionmentioning

confidence: 99%

Isotope chirality in long‐armed multifunctional organosilicon (“Cephalopod”) molecules

et al. 2018

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Long-armed multifunctional organosilicon molecules display self-replicating and self-perfecting behavior in asymmetric autocatalysis (Soai reaction). Two representatives of this class were studied by statistical methods aiming at determination of probabilities of natural abundance chiral isotopomers. The results, reported here, show an astonishing richness of possibilities of the formation of chiral isotopically substituted derivatives. This feature could serve as a model for the evolution of biological chirality in prebiotic and early biotic stereochemistry.

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Point‐to‐Point Ultra‐Remote Asymmetric Control with Flexible Linker

Cited by 5 publications

References 57 publications

Role of Asymmetric Autocatalysis in the Elucidation of Origins of Homochirality of Organic Compounds

Role of Asymmetric Autocatalysis in the Elucidation of Origins of Homochirality of Organic Compounds

Mechanical transduction via a single soft polymer

Isotope chirality in long‐armed multifunctional organosilicon (“Cephalopod”) molecules

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