Fluorogenic Glycosidase Substrates with Self-Collapsing Spacers

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Solution Overview

Problem

Current methods for detecting glycosidase activity are not sufficiently reliable due to probe instability, slow enzymatic response, and diffusion of the fluorophore, leading to background fluorescence and reduced sensitivity.

Innovation Solution

Development of novel glycosidase substrates with a self-collapsing spacer tandem that incorporates an ESIPT fluorophore, ensuring stability in the absence of the target enzyme, rapid enzymatic response, and minimal background fluorescence, allowing for precise and sensitive detection of glycosidase activity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional fluorogenic substrates are used for detecting glycosidase activity, then fluorescence detection can be implemented, but the probe is unstable and releases fluorescence in the absence of the target enzyme, leading to high background noise and reduced sensitivity

Engineering Contradiction:
Improvedetection reliabilityVSAvoidbackground fluorescence
Core Design Contradiction:
ReliabilityVSObject-generated harmful factors

Solution Approach 1:

The substrate is divided into three functional modules: a fluorophore (HPQ derivative), a self-immolating spacer, and a glycosyl group. This segmentation allows the fluorophore to be masked during storage and only activated when the complete substrate is cleaved by the target enzyme, preventing premature fluorescence and reducing background noise

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The substrate is pre-designed with a self-immolating spacer that is primed to trigger fluorophore release upon enzymatic cleavage. The spacer contains a triggering group that, when released by glycosidase action, automatically initiates a cascade reaction leading to fluorophore liberation, ensuring rapid and reliable signal generation before diffusion can occur

Inventive Principle:
Principle #10Preliminary action

2Productivity

If existing fluorogenic substrates are used, then glycosidase activity can be detected, but the enzymatic response is slow and the fluorophore diffuses into the medium, reducing detection sensitivity

Engineering Contradiction:
Improveenzymatic response speedVSAvoiddetection sensitivity
Core Design Contradiction:
ProductivityVSMeasurement precision

Solution Approach 1:

The self-immolating spacer is pre-configured with a triggering group that immediately activates the fluorophore release mechanism upon enzymatic cleavage. This preliminary arrangement ensures that the fluorophore is liberated and precipitates at the activation site before diffusion can significantly reduce signal intensity, achieving both rapid response and high sensitivity

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The substrate utilizes HPQ (6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid) or its derivatives as the fluorophore, which exhibits a large Stokes shift and strong fluorescence emission. The transformation from non-fluorescent substrate to highly fluorescent product provides a strong signal for sensitive detection

Inventive Principle:
Principle #32Color changes

3Measurement precision

If more substrate is used to improve detection sensitivity, then signal strength increases, but the quantity of substance increases, potentially increasing toxicity and reducing ease of operation

Engineering Contradiction:
Improvedetection sensitivityVSAvoidsubstrate quantity
Core Design Contradiction:
Measurement precisionVSQuantity of substance

Solution Approach 1:

The HPQ-based fluorophore exhibits extremely strong fluorescence emission with high quantum yield. This intense signal allows detection sensitivity to be achieved with minimal substrate concentration, reducing the quantity of substance required and potentially lowering toxicity while maintaining high measurement precision

Inventive Principle:
Principle #32Color 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 new substrates provide high specificity and rapid transformation kinetics, reducing the quantity needed and minimizing toxicity, enabling sensitive and reliable detection of glycosidase activity, suitable for in vivo imaging and applications in life sciences.

Implementation Method 1

The class of fluorophores leading to an intramolecular proton transfer in an excited state, called ESIPT

Methodology Applied
Scientific EffectESIPT (Excited State Intramolecular Proton Transfer):

Implementation Method 2

The R0-O bond present in the compounds of formula (I) is capable of being cleaved, by hydrolysis, in the presence of a glycosidase enzyme acting as a catalyst for the cleavage reaction

Methodology Applied
Scientific EffectHydrolysis: Hydrolysis

Implementation Method 3

the possibility of designing fluorophores that emit bright fluorescence in the solid state, a rare property among all known fluorophores. This latter performance allows the production of a high intensity signal at the activation site, with minimal dilution caused by diffusion

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Data Source

PatentEP3555112B1Fluorogenic glycosidase substrate and associated detection method
Publication Date: 2023.12.06 ECOLE NORMALE SUPERIEURE DE LYON
  • EP3555112B1 patent drawingFigure 1~2
  • EP3555112B1 patent drawingFigure 3~4B
  • EP3555112B1 patent drawingFigure 5

AI summary

The invention relates to novel glycosidase substrates of formula (I), wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R'9, V, X, Y and Z are as defined in claim 1, and a method for detecting the presence of a catalytically active glycosidase by means of one of said substrates.