Aza-Triangulenium Fluorescent Dyes with Hydroxy Quenching

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Solution Overview

Problem

Current fluorescent dyes for sensing analytes, particularly pH, lack improved photophysical properties such as sensitivity and stability, limiting their effectiveness in monitoring and determining analyte concentrations.

Innovation Solution

Development of substituted aza-triangulenium fluorescent dyes with a hydroxy group attached to an aryl as a quenching group, which exhibit photoinduced electron transfer (PET) responsive properties, allowing for sensitive detection of analytes like H+, Na+, K+, Ca2+, O2, CO2, and metal ions across a wide pH range.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional fluorescent dyes are used for sensing analytes, then detection capability is provided, but sensitivity and photostability are insufficient

Engineering Contradiction:
ImprovephotostabilityVSAvoidsensitivity
Core Design Contradiction:
ReliabilityVSMeasurement precision

Solution Approach 1:

The patent employs composite fluorescent dye structures combining aza-triangulenium core with specific aryl-hydroxy quenching groups. This composite design integrates the photostable triangulenium scaffold with PET-active quenching moieties, achieving both high photostability and enhanced sensitivity through the synergistic combination of structural components.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent systematically modifies molecular parameters including substituent types (electron-donating/withdrawing groups), hydroxy group positions (ortho, meta, para), and counterions to optimize the balance between photostability and sensitivity. These parameter changes tune the PET efficiency and fluorescence quantum yield while maintaining structural stability.

Inventive Principle:
Principle #35Parameter changes

2Measurement precision

If fluorescent dyes with improved sensitivity are developed, then detection precision increases, but photostability may be compromised

Engineering Contradiction:
ImprovesensitivityVSAvoidphotostability
Core Design Contradiction:
Measurement precisionVSReliability

Solution Approach 1:

The fluorescent dye is segmented into functionally distinct modules: a photostable aza-triangulenium core responsible for fluorescence emission, and separate aryl-hydroxy quenching groups attached at specific positions. This segmentation allows independent optimization of each module's properties - the core provides photostability while the quenching groups provide sensitivity through PET mechanisms.

Inventive Principle:
Principle #1Segmentation

3Reliability

If new fluorescent dye structures are synthesized to improve performance, then sensitivity and stability are enhanced, but device complexity increases

Engineering Contradiction:
ImprovephotostabilityVSAvoidmolecular structure complexity
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The aza-triangulenium core structure serves multiple functions simultaneously: it provides the fluorescent chromophore, ensures photostability through its rigid aromatic system, and offers multiple attachment points for quenching groups. This multi-functionality reduces the need for additional auxiliary structures, managing complexity while achieving enhanced performance.

Inventive Principle:
Principle #6Universality (Multi-functionality)

4Adaptability or versatility

If conventional dyes are used for broad analyte detection, then versatility is limited, but maintaining simple structures is preferred

Engineering Contradiction:
Improveanalyte detection rangeVSAvoiddye structure complexity
Core Design Contradiction:
Adaptability or versatilityVSDevice complexity

Solution Approach 1:

The patent introduces local quality variations by placing identical hydroxy groups at different positions (ortho, meta, para) on the aryl rings, and by using different electron-donating/withdrawing substituents at specific locations. These localized modifications create dyes with tuned properties for detecting different analytes (H+, metal ions, pH) while maintaining the overall modular structure.

Inventive Principle:
Principle #3Local quality

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 new dyes demonstrate enhanced sensitivity and photostability, enabling reliable monitoring of analyte concentrations, even under harsh conditions, with modified quenching characteristics and long-term stability.

Implementation Method 1

When a PET responsive fluorescent molecule absorbs a photon, an excited electronic state is created and an electron transfer prevents the excited molecule from emitting a photon. Thus, the fluorescence of the dye is quenched.

Methodology Applied
Scientific EffectPhotoinduced electron transfer (PET): Photoelectric Effect

Implementation Method 2

When a PET responsive fluorescent molecule absorbs a photon, an excited electronic state is created

Methodology Applied
Scientific EffectPhoton absorption: Absorption (EM radiation)

Implementation Method 3

Fluorescence offers an ideal solution for detection and sensing applications, as readout signals of probes or sensors containing fluorescent molecules are done by light.

Methodology Applied
Scientific EffectFluorescence: Fluorescence

Data Source

PatentEP3060564B1Azatriangulenium salts as pet-quenched fluorescent probes
Publication Date: 2019.12.11 UNIVERSITY OF COPENHAGEN
  • EP3060564B1 patent drawingFigure 1a1~1a2
  • EP3060564B1 patent drawingFigure 1b1~1b2
  • EP3060564B1 patent drawingFigure 1c

AI summary

The present invention relates to a new class of substituted aza-triangulenium fluorescent dyes having a hydroxy group attached to an aryl as quenching group. The new substituted aza-triangulenium fluorescent dyes may be attached to a linker, conjugated to carrier molecule such as e.g. a protein, a nucleic acid, a lipid, or a saccharide, or deposited or immobilised on solid support materials. The substituted aza-triangulenium fluorescent dyes are useful for various purposes, including use in sensors for monitoring or determining the concentration of analytes, such as H+(pH), Na+, K+, Ca2+, O2, CO2, H2O2, ionic strength, redox potentials, metal ions,and metabolites.