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Photochemical Electrocyclic Reactions: Stereochemistry01:26

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Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
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The reaction of weakly electrophilic aryldiazonium (also called arenediazonium) salts with highly activated aromatic compounds leads to the formation of products with an —N=N— link, called an azo linkage. This reaction, presented in Figure 1, is known as diazo coupling and occurs without the loss of the nitrogen atoms of the aryldiazonium salt. Highly activated aromatic compounds such as phenols or arylamines favor the diazo coupling reaction. The coupling generally occurs at the para...
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Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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Topoisomerases are enzymes that relax overwound DNA molecules during various cell processes, including DNA replication and transcription. These enzymes regulate positive and negative DNA supercoiling without changing the nucleotide sequence. DNA overwinding in a clockwise direction results in positively supercoiled DNA, whereas underwinding in a counterclockwise direction produces negatively supercoiled DNA.
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Thermally Switchable Photoactivity in Azobenzene-Functionalized DNA Condensates.

Ming-Di Gao1, Chao-Yang Guan1, Jia-Yao Wang1

  • 1State Key Laboratory of Synergistic Chem-Bio Synthesis, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China.

Advanced Materials (Deerfield Beach, Fla.)
|December 13, 2025
PubMed
Summary
This summary is machine-generated.

Researchers developed novel DNA condensates with tunable light responses for soft robotics. These materials change shape and dissolve with different light colors depending on temperature, enabling advanced adaptive functions.

Keywords:
DNA nanotechnologyazobenzeneliquid‐liquid phase separationphotofluidsphoto‐responsiveness

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Area of Science:

  • Materials Science
  • Soft Robotics
  • Biomedical Engineering
  • DNA Nanotechnology

Background:

  • Soft materials with environmental responsiveness are crucial for developing adaptive soft robotics and intelligent biomedical devices.
  • Liquid-liquid phase separation (LLPS) is a key self-assembly mechanism for creating functional soft materials.
  • Azobenzene derivatives are known photo-responsive molecules, but their integration into complex systems for tunable responses remains a challenge.

Purpose of the Study:

  • To engineer novel soft materials with multimodal photothermal adaptability using DNA condensates.
  • To investigate the temperature-dependent inversion of photo-response in azobenzene-conjugated DNA coacervates.
  • To explore the potential of these responsive materials in advanced applications requiring precise spatiotemporal control.

Main Methods:

  • Assembly of azobenzene-conjugated DNA condensates via liquid-liquid phase separation (LLPS).
  • Characterization of material response to visible and ultraviolet (UV) light at varying temperatures.
  • Analysis of the interplay between azobenzene photochemistry, DNA duplexes, and thermal properties (glass transition, melting temperatures).

Main Results:

  • Demonstrated a striking temperature-dependent inversion of photo-response in the DNA condensates.
  • At high temperatures, materials deformed with visible light and dissolved with UV light; at low temperatures, they reshaped with UV light and were inert to visible light.
  • Attributed the bidirectional control to confined azobenzene photochemistry and isomer-dependent shifts in thermal transition temperatures.

Conclusions:

  • Developed a novel platform of multi-responsive photofluids based on DNA condensates.
  • Achieved exquisite spatiotemporal control over material behavior through multimodal photothermal stimuli.
  • This work opens new avenues for designing sophisticated soft robots and biomedical devices with adaptive functionalities.