Urea-Functionalized Sol-Gel Coatings for Capillary Stability

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Solution Overview

Problem

Current capillary microextraction techniques face limitations such as low sample capacity, mechanical damage, and instability in thermal and solvent conditions, particularly when combined with high-performance liquid chromatography (HPLC), due to the use of unbound thin-layer coatings which lack robustness and stability.

Innovation Solution

The development of urea-functionalized surface-bonded sol-gel coatings formed by condensing bis(trialkoxysilylalkyl)urea with bis(hydroxyalkyl)amine-terminated poly(di)alkylsiloxane, which are chemically bonded to the capillary surfaces, enhancing stability and extraction efficiency.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Strength

If unbound thin-layer coating is used in capillary microextraction, then mechanical damage is avoided, but solvent stability and thermal stability deteriorate

Engineering Contradiction:
Improvemechanical stabilityVSAvoidsolvent stability
Core Design Contradiction:
StrengthVSReliability

Solution Approach 1:

The patent replaces mechanical bonding (physical adsorption) with chemical bonding (covalent attachment) by using sol-gel chemistry to form a chemically bonded coating layer on the capillary surface. This substitution provides both mechanical stability and solvent stability simultaneously, resolving the contradiction between avoiding mechanical damage and achieving solvent stability.

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

Solution Approach 2:

The patent employs composite sol-gel materials comprising organic and inorganic components that form a hybrid coating structure. This composite material combines the mechanical flexibility needed to avoid damage with the chemical stability required for solvent resistance, thereby resolving the contradiction between mechanical stability and solvent stability.

Inventive Principle:
Principle #40Composite materials

2Strength

If unbound thin-layer coating is used in capillary microextraction, then mechanical damage is avoided, but thermal stability deteriorates

Engineering Contradiction:
Improvemechanical stabilityVSAvoidthermal stability
Core Design Contradiction:
StrengthVSTemperature

Solution Approach 1:

The patent replaces mechanical bonding with chemical bonding through sol-gel chemistry, creating a covalently attached coating that maintains structural integrity at elevated temperatures. This chemical bonding mechanism provides thermal stability while preserving mechanical stability, resolving the contradiction between avoiding mechanical damage and achieving thermal stability.

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

Solution Approach 2:

The sol-gel composite coating combines organic polymer matrices with inorganic crosslinked networks, creating a hybrid structure that exhibits enhanced thermal stability while maintaining mechanical flexibility. This composite approach resolves the contradiction between mechanical stability and thermal stability.

Inventive Principle:
Principle #40Composite materials

3Reliability

If sol-gel chemistry is used to chemically bond coating, then solvent stability improves, but device complexity increases

Engineering Contradiction:
Improvesolvent stabilityVSAvoidcoating preparation complexity
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent merges multiple functions into a single sol-gel coating process: surface bonding, coating formation, and functional group immobilization are all achieved in one step. This consolidation simplifies the overall procedure despite the chemical complexity of sol-gel chemistry, resolving the contradiction between achieving solvent stability and maintaining procedural simplicity.

Inventive Principle:
Principle #5Merging (Combining)

Solution Approach 2:

The sol-gel system exhibits self-assembly and self-crosslinking properties, where the coating forms and bonds to the surface automatically through hydrolysis and condensation reactions. This self-service characteristic reduces the need for complex external control mechanisms, thereby resolving the contradiction between solvent stability and procedural complexity.

Inventive Principle:
Principle #25Self-service

4Ease of manufacture

If conventional PDMS coating is used, then ease of manufacture is maintained, but extraction sensitivity deteriorates

Engineering Contradiction:
Improvecoating application simplicityVSAvoidextraction sensitivity
Core Design Contradiction:
Ease of manufactureVSMeasurement precision

Solution Approach 1:

The patent introduces specific functional groups (urea, amino, carboxylic acid) at localized positions within the coating structure to enhance extraction sensitivity for specific analyte classes, while maintaining the overall simplicity of the PDMS coating system. This local functionalization resolves the contradiction between ease of manufacture and extraction sensitivity.

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The patent modifies the chemical parameters of the coating by incorporating sol-gel derived functional groups into the PDMS matrix, changing the coating's chemical properties to improve extraction sensitivity while preserving the ease of application through sol-gel chemistry. This parameter modification resolves the contradiction between manufacturing simplicity and extraction sensitivity.

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

These coatings improve the thermal and solvent stability, increase extraction sensitivity, and enable effective online hyphenation with HPLC, achieving lower detection limits and higher reproducibility for a wide range of analytes from non-polar to highly polar compounds.

Implementation Method 1

condensing bis(trialkoxysilylalkyl)urea with bis(hydroxyalkyl)amine-terminated poly(di)alkylsiloxane

Methodology Applied
Scientific EffectCondensation: Condensation

Implementation Method 2

chemically bonded to the capillary surfaces

Methodology Applied
Scientific EffectChemical bonding: Chemical Bonding

Data Source

PatentUS11629235B2Urea-functionalized sol-gel
Publication Date: 2023.04.18 KING FAHD UNIVERSITY OF PETROLEUM AND MINERALS
  • US11629235B2 patent drawing
  • US11629235B2 patent drawing
  • US11629235B2 patent drawing

AI summary

Urea and amine comprising sol-gel hybrid coatings have been developed for numerous applications, including capillary microextraction-high performance liquid chromatographic analysis from aqueous samples. A fused silica capillary may be coated from the inside with surface bonded coating material and may be created by in-situ sol-gel reaction(s). Urea-functionalized coatings can be immobilized on the inner surface of a capillary by condensing silanol groups of capillary and sol-solution. Urea functionalized, sol-gel coated capillaries may be installed, e.g., in HPLC manual injection ports, and optionally pre-concentrated analytes including phenols, ketones, aldehydes, and/or polyaromatic hydrocarbons, from highly polar to non-polar, maybe analyzed by online extraction and high-performance liquid chromatographic. Such coatings may achieve sensitivities with lower detection limits (S/N=3) of 0.10 ng/mL to 14.29 ng/mL, with reproducibilities of <12.0% RSD (n=3), or <10.0% RSD (n=3) by exchanging the capillary of the same size.