Modular 18F Prosthetic Groups for Protein Labeling

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Solution Overview

Problem

Current methods for labeling proteins with 18F-based prosthetic groups are hindered by long synthesis times, poor radiochemical yields, and low specific activity, making it difficult to develop effective PET imaging agents for molecular imaging and therapeutic applications.

Innovation Solution

A modular platform for rapidly preparing water-soluble prosthetic groups, such as [18F]FPEGMA, which efficiently introduces 18F into proteins through site-specific conjugation, utilizing polyethylene glycol (PEG) based building blocks and the CuAAC reaction for high-yield and high-purity labeling.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If conventional 18F-based prosthetic groups are used for protein labeling, then radioactivity can be introduced into proteins, but the synthesis time is long and radiochemical yield is poor

Engineering Contradiction:
Improvelabeling efficiencyVSAvoidsynthesis time
Core Design Contradiction:
ProductivityVSLoss of time

Solution Approach 1:

The prosthetic group is divided into modular components (fluoride, PEG chain, maleimide) that can be assembled through sequential reactions. The CuAAC click chemistry enables modular assembly of the fluorinated PEG unit onto the maleimide-containing protein, allowing efficient one-pot conjugation that dramatically reduces synthesis time compared to conventional multi-step labeling protocols.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The invention changes the chemical parameters of the labeling reaction by using CuAAC click chemistry instead of conventional nucleophilic substitution. This parameter change enables the reaction to proceed under milder conditions with higher efficiency, achieving rapid conjugation at room temperature or physiological conditions, thereby reducing synthesis time and improving radiochemical yield.

Inventive Principle:
Principle #35Parameter changes

2Quantity of substance

If conventional labeling methods are used, then proteins can be labeled with 18F, but specific activity is low

Engineering Contradiction:
Improvespecific activityVSAvoidlabeling efficiency
Core Design Contradiction:
Quantity of substanceVSProductivity

Solution Approach 1:

The invention introduces site-specific labeling by incorporating a single cysteine residue at a predetermined position on the protein (away from the binding site). This local modification ensures that the 18F label is attached at a specific location, enabling high specific activity while preserving the protein's biological function and binding activity.

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The maleimide group serves as an intermediary that facilitates the attachment of the 18F-labeled PEG prosthetic group to the cysteine thiol on the protein. This intermediary approach enables efficient and specific conjugation, achieving high specific activity through controlled single-site labeling rather than random modification.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Reliability

If site-specific conjugation is performed, then biological activity is retained, but the process requires precise control of modification sites

Engineering Contradiction:
Improvebiological activity retentionVSAvoidconjugation control
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The protein is pre-engineered with a specific cysteine residue at a predetermined position (using PHESELECTOR methodology) before the labeling reaction. This preliminary genetic modification ensures that the subsequent chemical conjugation occurs at a single, controlled site that does not interfere with the protein's binding function, thereby simplifying the conjugation control while ensuring biological activity retention.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The invention uses genetically engineered proteins with incorporated cysteine residues as templates for site-specific labeling. By creating a copy or variant of the native protein with a strategically placed cysteine, the labeling process can be controlled at a specific site that mimics the native structure's functional requirements, ensuring both precision and biological activity.

Inventive Principle:
Principle #26Copying

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

This approach enables the rapid production of 18F-labeled proteins with improved conjugation efficiency and specific activity, retaining biological activity and facilitating effective molecular imaging and therapeutic applications.

Implementation Method 1

utilizing polyethylene glycol (PEG) based building blocks and the CuAAC reaction for high-yield and high-purity labeling

Methodology Applied
Scientific EffectCuAAC reaction: Catalysis

Data Source

PatentEP2400992B1Methods and compositions for protein labelling
Publication Date: 2015.07.22 GENENTECH INC
  • EP2400992B1 patent drawingFigure 1~2
  • EP2400992B1 patent drawingFigure 3~4
  • EP2400992B1 patent drawingFigure 5(a)~5(b)

AI summary

A modular platform is provided for rapid preparation of various water-soluble prosthetic groups capable to efficiently introduce 18F into proteins with 18F labelling reagents.