Diazonium Salt Grafting for Robust pH Sensor Layers

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Solution Overview

Problem

Current pH optode technologies face challenges such as inhomogeneous dye layers, dye leaching, and limited durability due to physical trapping or electrostatic deposition methods, and covalent bonding techniques are complex and time-consuming, limiting their effectiveness for robust pH measurement across various media.

Innovation Solution

A radical chemical grafting process using aryl diazonium salt precursors to covalently attach colored indicators with aromatic primary amine functions to solid supports, optimizing grafting time and repeating steps with washing to ensure strong, durable indicator layers that maintain spectral properties for pH measurement.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If physical trapping or electrostatic deposition methods are used to attach pH indicators to solid supports, then the process is simple and quick, but the dye layers become inhomogeneous and dyes leach out, reducing durability

Engineering Contradiction:
Improvesimplicity of attachment processVSAvoiddurability of indicator layer
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent replaces physical trapping and electrostatic deposition methods with covalent bonding chemistry. The diazonium salt reacts chemically with the solid support surface to form strong covalent bonds, substituting weak physical interactions with robust chemical bonds that prevent dye leaching while maintaining manufacturing feasibility

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

Solution Approach 2:

The patent changes the bonding mechanism from physical to chemical by using diazonium salt precursors that undergo chemical reactions with the solid support. This parameter change in bonding strength and type enables durable attachment while preserving the spectral properties of the pH indicators

Inventive Principle:
Principle #35Parameter changes

2Reliability

If covalent bonding techniques are used to attach pH indicators to solid supports, then the attachment is robust and durable, but the process becomes complex and time-consuming

Engineering Contradiction:
Improvedurability of indicator layerVSAvoidcomplexity of grafting process
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent uses diazonium salt as an intermediary compound that facilitates covalent bonding between the pH indicator and the solid support. This intermediary approach simplifies the overall process by providing a reliable chemical pathway for attachment without requiring complex multi-step procedures

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent employs diazonium salt precursors that are prepared in advance and then applied to the solid support. This preliminary preparation of the bonding agent simplifies the grafting process by eliminating the need for complex in-situ generation of bonding groups during the attachment step

Inventive Principle:
Principle #10Preliminary action

3Reliability

If covalent bonding techniques are used to attach pH indicators to solid supports, then the attachment is robust and durable, but the process becomes time-consuming

Engineering Contradiction:
Improvedurability of indicator layerVSAvoidpreparation time
Core Design Contradiction:
ReliabilityVSLoss of time

Solution Approach 1:

The diazonium salt intermediary enables rapid covalent bonding reactions that proceed quickly under controlled conditions. This intermediary approach reduces preparation time compared to traditional covalent bonding methods that may require multiple steps or extended reaction times

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent optimizes reaction parameters such as concentration, temperature, and pH to accelerate the covalent bonding process. By changing these parameters, the grafting process achieves durable attachment in reduced timeframes while maintaining the integrity of the pH indicator molecules

Inventive Principle:
Principle #35Parameter changes

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

The process allows for the creation of robust, durable pH-sensitive layers on various solid supports, maintaining spectral properties and enabling reliable pH measurement across different media without affecting the indicators' properties, thus addressing the limitations of existing methods.

Implementation Method 1

a radical chemical grafting process using aryl diazonium salt precursors to covalently attach colored indicators with aromatic primary amine functions to solid supports

Methodology Applied
Scientific EffectRadical chemical grafting: Chemical Bonding

Data Source

PatentEP3283236B1Method for grafting a coloured indicator onto a solid substrate and implementation kit
Publication Date: 2020.09.16 COMMISSARIAT A LENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES
  • EP3283236B1 patent drawingFigure 1~2
  • EP3283236B1 patent drawingFigure 3A~3B
  • EP3283236B1 patent drawingFigure 4A~4B

AI summary

The present invention relates to a method for grafting, in a covalent manner, a coloured indicator having at least one aromatic primary amine function onto the surface of a solid substrate, including the steps that consist of: (a) preparing, from said coloured indicator having at least one aromatic primary amine function, the corresponding diazonium salt; (b) placing the solid substrate in contact with a solution containing the diazonium salt prepared in step (a) and subjecting said solution to non-electrochemical conditions for an optimal grafting time by means of which organic chains in which the units are derivatives of said diazonium salt are grafted, in a covalent manner, onto the surface of said solid substrate; (c) washing the solid substrate thus grafted; (d) repeating steps (b) and (c) or possibly steps (a) to (c) at least once. The present invention also relates to a kit for implementing such a method.