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Related Concept Videos

Cycloaddition Reactions: MO Requirements for Photochemical Activation01:12

Cycloaddition Reactions: MO Requirements for Photochemical Activation

2.2K
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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Cycloaddition Reactions: MO Requirements for Thermal Activation01:16

Cycloaddition Reactions: MO Requirements for Thermal Activation

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Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
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Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

2.7K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
2.7K

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Synthesis of Single-Crystalline Core-Shell Metal-Organic Frameworks
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Precision Nanocluster-Based Toroidal and Supertoroidal Frameworks Using Photocycloaddition-Assisted Dynamic Covalent

Kavalloor Murali Lakshmi1,2, Jose V Rival3, Pakath Sreeraj3

  • 1Electroplating and Metal Finishing Division (EMFD), Council of Scientific and Industrial Research (CSIR)-Central Electrochemical Research Institute (CECRI), Karaikudi, Tamil Nadu, 630003, India.

Small (Weinheim an Der Bergstrasse, Germany)
|January 23, 2023
PubMed
Summary
This summary is machine-generated.

Atomically precise nanoclusters self-assemble into hierarchical superstructures using light-induced dynamic covalent chemistry. This enables photocontrolled drug release and the creation of novel multifunctional materials.

Keywords:
5-fluorouracilcoumarindrug loadingdynamic covalent chemistryphotocycloadditionprecision nanoclustersself-assemblytoroidal superstructures

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Area of Science:

  • Nanotechnology
  • Materials Science
  • Supramolecular Chemistry

Background:

  • Atomically precise nanoclusters (NCs) are building blocks for self-assembled superstructures.
  • Current methods rely on non-covalent interactions, limiting reversible assembly.
  • Long-range reversible self-assembly via dynamic covalent chemistry on NCs remains unexplored.

Purpose of the Study:

  • Investigate long-range reversible self-assembly of NCs using dynamic covalent chemistry.
  • Demonstrate the formation of hierarchical superstructures via photocycloaddition reactions.
  • Explore applications in photocontrolled drug delivery.

Main Methods:

  • Synthesis of Au25 nanoclusters with thiolated umbelliferone ligands.
  • Utilizing [2+2] photocycloaddition for self-assembly.
  • Characterization using electron microscopy, AFM, and electron tomography.
  • Demonstration of a drug release model using 5-fluorouracil.

Main Results:

  • Au25 NCs self-assemble into colloidal toroids via photocycloaddition.
  • Toroids further assemble into macroscopic supertoroidal honeycomb frameworks.
  • Demonstrated reversible loading and unloading of an anticancer drug.
  • Hierarchical assembly from spherical aggregates to toroids to honeycomb structures observed.

Conclusions:

  • Dynamic covalent chemistry on NC surfaces provides a route for hierarchical multifunctional frameworks.
  • Photocontrolled assembly and disassembly enable applications in drug delivery.
  • This approach offers facile construction of advanced nanomaterials.