Heterogeneous Cu(I)-C Catalyst for Click Chemistry

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Solution Overview

Problem

The use of copper(I) catalysts in Click reactions is limited by toxicity to cells, degradation of biomolecules, and the need for manual handling due to the instability and short lifespan of Cu(I) ions, making automated processes and applications in living systems challenging.

Innovation Solution

The implementation of a heterogeneous Cu(I)-C catalyst system, where copper nanoparticles are embedded in activated charcoal, allowing for stable and efficient Click reactions in aqueous media without the need for external ligands or solvents, enabling automated and easy-to-use protocols for biomolecule labeling.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If Cu(I) catalyst is used in Click reactions, then reaction efficiency is improved, but toxicity to cells and degradation of biomolecules occurs

Engineering Contradiction:
Improvereaction efficiencyVSAvoidtoxicity to cells and biomolecule degradation
Core Design Contradiction:
ProductivityVSObject-affected harmful factors

Solution Approach 1:

The patent uses a heterogeneous catalyst system where copper nanoparticles are supported on a solid carrier (such as silica gel or magnetic particles). This intermediary structure allows the Cu(I) catalyst to function efficiently while preventing direct contact between free Cu(I) ions and biomolecules, thereby reducing toxicity and degradation. The solid support acts as a mediator that separates the catalytic function from the harmful effects.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent employs porous solid materials (e.g., silica gel with controlled pore sizes) as supports for the copper catalyst. The porous structure provides high surface area for catalytic activity while the pore size can be tuned to exclude large biomolecules, preventing them from accessing the copper centers and suffering degradation, thus resolving the contradiction between catalytic efficiency and biomolecule stability.

Inventive Principle:
Principle #31Porous materials

2Reliability

If free Cu(I) ions are used, then Click reaction activity is maintained, but stability and lifespan are reduced due to oxidation to Cu(II)

Engineering Contradiction:
Improvecatalyst activityVSAvoidcatalyst lifespan
Core Design Contradiction:
ReliabilityVSDuration of action of stationary object

Solution Approach 1:

The patent extracts the copper catalyst from the solution phase and immobilizes it on a solid support. This separation removes the copper species from the aqueous environment where oxidation occurs, thereby extending the catalyst's lifespan. The solid-supported catalyst can be stored and reused without the rapid oxidation that plagues free Cu(I) ions in solution.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The solid support creates a protected microenvironment around the copper nanoparticles, shielding them from oxygen and other oxidizing agents in the bulk solution. This localized inert environment maintains the copper in the active Cu(I) state for extended periods, resolving the stability issue while preserving catalytic activity.

Inventive Principle:
Principle #39Inert atmosphere (Inert environment)

3Stability of the object's composition

If organic solvents are added to dissolve ligands, then Cu(I) stability is improved, but biomolecules precipitate or form insoluble agglomerates

Engineering Contradiction:
ImproveCu(I) stabilityVSAvoidbiomolecule solubility
Core Design Contradiction:
Stability of the object's compositionVSReliability

Solution Approach 1:

The solid support acts as an intermediary that provides stabilization for Cu(I) without requiring organic solvents. The copper nanoparticles on the solid surface are stabilized by interaction with the support material, eliminating the need for organic ligands and solvents that would otherwise be required to stabilize Cu(I) in solution. This approach maintains biomolecule solubility while achieving Cu(I) stability.

Inventive Principle:
Principle #24Intermediary (Mediator)

4Reliability

If manual handling procedures are used, then careful control of Cu(I) reactions is achieved, but automation is prevented

Engineering Contradiction:
Improvereaction controlVSAvoidprocess automation capability
Core Design Contradiction:
ReliabilityVSExtent of automation

Solution Approach 1:

The heterogeneous catalyst system is designed to be self-contained and easy to handle. The solid-supported copper catalyst can be simply added to the reaction mixture, allowed to react, and then removed by filtration or decantation. This self-service approach eliminates the need for complex manual handling procedures while enabling automation, as the process requires minimal intervention and can be easily adapted to automated liquid handling systems.

Inventive Principle:
Principle #25Self-service

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This approach facilitates efficient, automated, and stable Click reactions in aqueous conditions, reducing toxicity and handling issues, enabling the labeling of biomolecules with high specificity and sensitivity, suitable for various applications including genetic analysis and diagnostics.

Implementation Method 1

the copper catalysed reaction of azides with alkynes to give 1,2,3-triazoles (the 1,3-dipolar Huisgen cycloaddition) has become the most widely used Click reaction

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

The Cu(I) is generated from Cu(II) not in an in situ reduction, but via a charcoal-mediated reduction, which allows pre-assembling and storage of the so-generated Cu(I) source for extended time

Methodology Applied
Scientific EffectReduction: Reduction

Implementation Method 3

Lipshutz et al. recently described the virtues of copper-in-charcoal (Cu-C) as a simple, inexpensive, and especially general and efficient heterogeneous catalyst

Methodology Applied
Scientific EffectAdsorption: Adsorption

Data Source

PatentEP2416878B1Click chemistry on heterogeneous catalysts
Publication Date: 2015.09.30 BASECLICK
  • EP2416878B1 patent drawingFigure 1(a)~1(b)
  • EP2416878B1 patent drawingFigure 2
  • EP2416878B1 patent drawingFigure 3

AI summary

The present invention relates to new methods and reagents for coupling molecules by a Click reaction using a heterogeneous catalyst system. Further, the present invention refers to novel devices for carrying out Click reactions.