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Chirality is the most intriguing yet essential facet of nature, governing life’s biochemical processes and precision. It can be observed from a snail shell pattern in a macroscopic world to an amino acid, the minutest building block of life. Most of the snails around the world have right-coiled shells because of the intrinsic chirality in their genes. All the amino acids present in the human body exist in an enantiomerically pure state, except for glycine - the sole achiral amino acid.
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The concept of prochirality leads to the nomenclature of the individual faces of a molecule and plays a crucial role in the enantioselective reaction. It is a concept where two or more achiral molecules react to produce chiral products. A typical process is the reaction of an achiral ketone to generate a chiral alcohol. Here, the achiral reactant reacts with an achiral reducing agent, sodium borohydride, to generate an equimolar mixture of the chiral enantiomers of the product. For example, an...
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Chirality is most prevalent in carbon-based tetrahedral compounds, but this important facet of molecular symmetry extends to sp3-hybridized nitrogen, phosphorus and sulfur centers, including trivalent molecules with lone pairs. Here, the lone pair behaves as a functional group in addition to the other three substituents to form an analogous tetrahedral center that can be chiral.
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It is essential to understand the difference between chiral and achiral interactions and the implications thereof in optical activity and their applications. Just as our feet, which are chiral, interact uniquely with chiral objects, such as a pair of shoes, but identically with achiral socks, enantiomers of a molecule exhibit different properties only when they interact with other chiral media. An example of a significant implication from this facet is the phenomenon known as optical activity,...
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Efficient and reversible chirality induction between protein and achiral plasmonic assemblies.

Ziwei Zhou1, Ningwei Sun2, Nina Tverdokhleb2,3,4

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Summary
This summary is machine-generated.

Mechanical stretching of proteins in gold nanoparticle assemblies creates strong, reversible chiral optical activity. This breakthrough allows dynamic control over chiroptical responses in achiral plasmonic systems without complex fabrication.

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Area of Science:

  • Plasmonics
  • Chirality
  • Biophysics

Background:

  • Biomolecular chirality typically exhibits optical activity in the deep ultraviolet.
  • Artificial chiral plasmonic nanostructures offer stronger responses at visible and near-infrared wavelengths.
  • A key challenge is transferring natural biomolecular chirality to achiral plasmonic systems without complex 3D nanofabrication.

Purpose of the Study:

  • To investigate if mechanical stretching of proteins can induce and control chiroptical activity in achiral plasmonic systems.
  • To explore the potential for dynamic modulation of plasmon-coupled circular dichroism.

Main Methods:

  • Mechanical stretching of protein molecules anchored within achiral gold nanoparticle assemblies.
  • Measurement of chiroptical response (ellipticity and dissymmetry factor).
  • Cyclic stretching and relaxation experiments.
  • Computational simulations and in situ spectroscopy.

Main Results:

  • Mechanical stretching significantly enhances and reversibly modulates plasmon-coupled circular dichroism.
  • Achieved an ellipticity of 1.18° and a dissymmetry factor of 0.2, surpassing conventional methods.
  • Demonstrated over 100 cycles of reversible switching through stretching and relaxation.
  • Deformation of proteins alters their conformation and dipole alignment, strengthening the plasmonic chiral response.

Conclusions:

  • Mechanical stretching provides a novel route to achieve dynamically controllable chiroptical activity in achiral plasmonic assemblies.
  • Small biomolecular deformations can profoundly influence the plasmonic responses of larger nanostructures.
  • This method offers a pathway to harness biomolecular chirality for advanced optical applications.