Phosphorylated Fluorescent Dyes for STED Microscopy

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Solution Overview

Problem

Current fluorescent dyes used in microscopy, such as coumarin and rhodamine dyes, face challenges with photostability, solubility in aqueous solutions, and fluorescence quantum yield degradation upon bioconjugation, limiting their effectiveness in high-intensity imaging techniques like STED microscopy and FCS.

Innovation Solution

Development of novel fluorescent dyes with phosphorylated hydroxymethyl groups, specifically coumarins and rhodamines, that maintain high fluorescence quantum yields in aqueous solutions and after bioconjugation, offering improved photostability and solubility, suitable for applications like STED microscopy and FCS.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Illumination intensity

If conventional fluorescent dyes (coumarin and rhodamine) are used in high-intensity imaging techniques like STED microscopy, then the imaging resolution and intensity can be achieved, but photobleaching occurs and photostability deteriorates

Engineering Contradiction:
Improvelight intensity for STED microscopyVSAvoidphotostability
Core Design Contradiction:
Illumination intensityVSReliability

Solution Approach 1:

The patent modifies the molecular structure of fluorescent dyes by introducing phosphorylated hydroxymethyl groups, which changes the chemical parameters of the dye molecules. This structural modification enhances photostability and reduces triplet state formation, allowing the dyes to withstand high-intensity illumination in STED microscopy without rapid photobleaching

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates composite fluorescent dye structures by combining coumarin or rhodamine core structures with phosphorylated hydroxymethyl substituents. These composite molecular structures integrate the beneficial properties of both the parent dyes (brightness, quantum yield) and the phosphorylated groups (enhanced photostability, water solubility)

Inventive Principle:
Principle #40Composite materials

2Quantity of substance

If fluorescent dyes are used in aqueous solutions for biological applications, then solubility is improved, but aggregation and non-specific binding increase

Engineering Contradiction:
Improvesolubility in aqueous buffersVSAvoidaggregation and non-specific binding
Core Design Contradiction:
Quantity of substanceVSObject-generated harmful factors

Solution Approach 1:

The phosphorylation of hydroxymethyl groups introduces charged phosphate moieties to the fluorescent dye molecules, fundamentally changing their solubility parameters. This modification enables the dyes to dissolve in aqueous buffers without requiring organic co-solvents, while the charged phosphate groups provide electrostatic repulsion that prevents aggregation

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The phosphorylated hydroxymethyl groups act as intermediary structures that mediate between the hydrophobic aromatic core of the fluorescent dye and the aqueous biological environment. These groups provide hydrophilic, charged interfaces that enable water solubility while the spacer hydroxymethyl linkage maintains appropriate spacing to prevent non-specific binding

Inventive Principle:
Principle #24Intermediary (Mediator)

3Measurement precision

If fluorescent dyes are conjugated to biomolecules for labeling, then specific imaging of biological structures is achieved, but fluorescence quantum yield decreases

Engineering Contradiction:
Improveimaging specificity for biological structuresVSAvoidfluorescence quantum yield
Core Design Contradiction:
Measurement precisionVSUse of energy by moving object

Solution Approach 1:

The patent modifies the molecular parameters of fluorescent dyes by adding phosphorylated hydroxymethyl groups at specific positions on the coumarin or rhodamine core structures. This structural parameter change reduces steric hindrance and electronic perturbation during bioconjugation, thereby maintaining high fluorescence quantum yields even after attachment to biomolecules

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent segments the fluorescent dye molecule into distinct functional regions: a core chromophore (coumarin or rhodamine) responsible for fluorescence, phosphorylated hydroxymethyl groups providing solubility and reduced steric bulk, and reactive groups for bioconjugation. This segmentation allows each part to optimize its function independently, maintaining quantum yield during conjugation

Inventive Principle:
Principle #1Segmentation

4Quantity of substance

If organic solvents are used to dissolve fluorescent dyes for bioconjugation, then dye solubility is improved, but protein denaturation occurs

Engineering Contradiction:
Improvedye solubilityVSAvoidprotein denaturation
Core Design Contradiction:
Quantity of substanceVSObject-affected harmful factors

Solution Approach 1:

The phosphorylation of hydroxymethyl groups fundamentally changes the solubility parameters of the fluorescent dyes from hydrophobic to hydrophilic. This parameter change enables the dyes to dissolve in aqueous buffers without requiring organic co-solvents, thereby eliminating the harmful effect of protein denaturation while maintaining adequate dye solubility for bioconjugation reactions

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 phosphorylated dyes provide enhanced photostability and fluorescence quantum yields, enabling high-intensity imaging with reduced photobleaching and improved resolution, particularly in STED microscopy and FCS, while maintaining solubility in aqueous buffers.

Implementation Method 1

Water-soluble fluorescent markers are advantageous in this regard, because they do not require any organic solvents at all. Moreover, hydrophilic labels are less prone to aggregation and to non-specific binding with biological objects

Methodology Applied
Scientific EffectHydrophilic interaction: Hydrophile

Implementation Method 2

Coumarin and rhodamine dyes are known as bright fluorescent labels with large absorption coefficients, high fluorescent quantum yields

Methodology Applied
Scientific EffectFluorescence: Fluorescence

Implementation Method 3

Biological applications require fluorescent dyes absorbing and emitting in the red spectral region, because the excitation in this area reduces the background originating from autofluorescence of the cells

Methodology Applied
Scientific EffectAbsorption: Absorption (EM radiation)

Implementation Method 4

a red-shifted doughnut-shaped STED beam switches off the fluorescence of the excited molecules by stimulated emission (S1 → S0) everywhere, except in the very center of the doughnut, where the quenching intensity is zero

Methodology Applied
Scientific EffectStimulated emission:

Implementation Method 5

Other important qualities of the STED and common fluorescent dyes are high fluorescent quantum yields (Φfl) and oscillator strengths (high absorption coefficients, ε), low rate of triplet state formation

Methodology Applied
Scientific EffectTriplet state formation:

Data Source

PatentEP2768906B1Fluorescent dyes with phosphorylated hydroxymethyl groups and their use in light microscopy and imaging techniques
Publication Date: 2019.02.27 MAX PLANCK GESELLSCHAFT ZUR FOERDERUNG DER WISSENSCHAFTEN EV
  • EP2768906B1 patent drawingFigure 1A~1B
  • EP2768906B1 patent drawingFigure 2~3B
  • EP2768906B1 patent drawingFigure 4~5

AI summary

The invention relates to novel fluorescent dyes with phosphorylated hydroxymethyl groups, a method for preparing the same as well as to their use in imaging techniques. Said fluorescent dyes are coumarin, rhodamine or BODIPY dyes having of one of the following general formulae (I-III) wherein W = OP(0)Y1Y2 or P(0)Upsilon1Upsilon2, where Y1 and Y2 independently denote any of the following residues: OH, O(-), ORa and ORb, NHRa and NHRb, NRaRb and NRcRd, ORa and NHRb, ORa and NRbRc, NHRa and NRbRc; and any salt thereof.