Yttrium Sol-Gel Coating for Capillary Microextraction Stability

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Solution Overview

Problem

Current chromatographic techniques face limitations in sample preparation, particularly in capillary extraction methods, due to issues such as low sample capacity, mechanical damage, and instability under varying pH and thermal conditions, which hinder effective separation and analysis of chemical substances.

Innovation Solution

Development of sol-gels formed from tris(hydroxyalkoxy) yttrium and bis(hydroxyalkyl)amine-terminated poly(di)alkylsiloxane, which are used as coatings for capillary microextraction, providing enhanced stability and sensitivity for the extraction of analytes across a range of polarities.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Strength

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

Engineering Contradiction:
Improvemechanical stabilityVSAvoidsolvent stability
Core Design Contradiction:
StrengthVSReliability

Solution Approach 1:

The patent applies sol-gel chemistry to create a composite coating material that combines organic polymer components with inorganic silica network. This composite structure provides both mechanical integrity and chemical stability, resolving the contradiction between mechanical stability and solvent stability. The inorganic silica framework offers robustness against solvent and thermal degradation, while the organic components provide extraction functionality.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent modifies the physical and chemical parameters of the coating by controlling the sol-gel transition process. By adjusting parameters such as crosslinking density, network formation, and condensation degree during sol-gel processing, the coating transforms from a soft unbound layer to a rigid yet stable gel structure that maintains both mechanical and chemical stability.

Inventive Principle:
Principle #35Parameter changes

2Quantity of substance

If a polymer coating is applied on the outer surface of fused silica capillary, then sample pre-concentration is achieved, but thermal stability and solvent robustness are compromised

Engineering Contradiction:
Improvesample capacityVSAvoidthermal stability
Core Design Contradiction:
Quantity of substanceVSReliability

Solution Approach 1:

The sol-gel coating creates a composite material system where the inorganic silica-based gel network provides thermal stability and solvent robustness, while the incorporated organic functional groups maintain extraction capability. This composite structure allows the coating to withstand high temperatures and aggressive solvents that would degrade conventional organic polymer coatings.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent replaces conventional organic polymer coatings with a sol-gel derived inorganic-organic hybrid coating. This substitution transitions from a purely organic mechanical system to one that incorporates inorganic network structures, providing enhanced thermal and chemical resistance while maintaining the required sample pre-concentration functionality.

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

3Reliability

If sol-gel chemistry is used to chemically bond coating inside capillary, then solvent stability and thermal stability are improved, but coating complexity increases

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

Solution Approach 1:

The sol-gel process is a self-directed chemical transformation where the coating precursors automatically undergo hydrolysis and condensation reactions to form the gel network structure. This self-organizing process reduces the need for complex external control mechanisms and manual intervention, simplifying the overall coating application procedure despite the sophisticated chemistry involved.

Inventive Principle:
Principle #25Self-service

Solution Approach 2:

The patent employs preliminary action by pre-forming the sol-gel coating layers inside the capillary before the actual extraction process. The sol-gel precursors are introduced and allowed to undergo controlled hydrolysis and condensation, forming a stable network structure in advance. This preliminary coating formation eliminates the need for complex in-situ coating procedures during analysis.

Inventive Principle:
Principle #10Preliminary action

4Adaptability or versatility

If conventional CME with unbound coating is used for HPLC analysis, then hyphenation is achieved, but extraction sensitivity is limited

Engineering Contradiction:
Improvehyphenation capabilityVSAvoidextraction sensitivity
Core Design Contradiction:
Adaptability or versatilityVSMeasurement precision

Solution Approach 1:

The sol-gel coating creates a composite structure with high surface area and controlled porosity, providing numerous active sites for analyte interaction. The combination of inorganic silica framework and organic functional groups enhances extraction sensitivity through multiple interaction mechanisms, including adsorption, absorption, and complexation, while maintaining compatibility with HPLC hyphenation.

Inventive Principle:
Principle #40Composite materials

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 sol-gel coatings demonstrate improved thermal and solvent stability, increased extraction sensitivity, and durability, enabling efficient online hyphenation with HPLC, even under extreme conditions, and show superior performance compared to traditional coatings in extracting a variety of analytes.

Implementation Method 1

The sol-gel precursor may be hydrolyzed prior to self-condensation

Methodology Applied
Scientific EffectHydrolysis: Hydrolysis

Implementation Method 2

a sol-gel precursor having a structure (I) wherein R1 may be independently H, methyl, ethyl, propyl, s-propyl, butyl, s-butyl, isobutyl, t-butyl, pentyl, s-pentyl, isoamyl, neopentyl, or C6-alkyl, R2 may be independently H, methyl, ethyl, propyl, or F, and a, b, and c may be independently in a range of from 1 to 20

Methodology Applied
Scientific EffectCondensation: Condensation

Implementation Method 3

Sol-gel chemistry involves chemically bonding a (siloxane) polymer coating inside the capillary

Methodology Applied
Scientific EffectChemical Bonding: Chemical Bonding

Implementation Method 4

Analytes of interest can thereby be pre-concentrated on the small coated external surfaces of the fused silica capillary

Methodology Applied
Scientific EffectAdsorption: Adsorption

Data Source

PatentUS11630089B2Yttrium-containing sol-gel coating, its use, and manufacture
Publication Date: 2023.04.18 KING FAHD UNIVERSITY OF PETROLEUM AND MINERALS
  • US11630089B2 patent drawing
  • US11630089B2 patent drawing
  • US11630089B2 patent drawing

AI summary

Yttria containing hybrid organic-inorganic sol-gels may be used in coatings for capillary microextraction, optionally hyphenated to online HPLC analysis. The sol-gel reaction mixture can use an yttrium trialkoxyalkoxide, such as yttrium trimethoxyethoxide, and a [bis(hydroxyalkyl)-amino-alkyl]-terminated polydialkyl/arylsiloxane, such as [bis(hydroxyethyl)-amine] (BHEA)-terminated polydimethylsiloxane, that can undergo hydrolysis and polycondensation, to form coating materials. Capillaries coated with such sol-gels can have improved extraction efficiency compared, e.g., to pure yttria-based coatings. The CME-HPLC can analyze water samples containing analytes of varied polarity, with excellent extraction of amides, phenols, alcohols, ketones, aldehydes, and polyaromatic hydrocarbons and detection limits ranging from 0.18 to 7.35 ng/mL (S/N=3). Such capillaries can exhibit solvent stability at pH 0 to 14, RSD % between 0.6 to 6.8% (n=3), at a preparative reproducibility RSD between 4.1 and 9.9%.