Site-Specific Protein PEGylation via Controlled Radical Polymerization

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Solution Overview

Problem

Current methods for modifying therapeutic proteins, such as PEGylation, face challenges including suboptimal yields, random attachment of polymers, and variable activity due to non-specific linking technologies, which affect the efficacy and stability of protein-based treatments.

Innovation Solution

The development of novel polymers using controlled architecture methods like atom transfer radical polymerization (ATRP) and radical addition-fragmentation chain transfer polymerization (RAFT) for selective attachment to biological molecules, particularly through thiol groups, ensuring consistent and targeted conjugation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Duration of action of moving object

If conventional PEGylation methods are used to prolong circulation time, then pharmacokinetic properties are improved, but manufacturing precision deteriorates due to random attachment at multiple sites

Engineering Contradiction:
Improvecirculation timeVSAvoidconjugation site specificity
Core Design Contradiction:
Duration of action of moving objectVSManufacturing precision

Solution Approach 1:

The invention introduces site-specific conjugation by targeting particular amino acid residues (such as lysine or cysteine) on the protein surface. This ensures that PEG attachment occurs at defined locations rather than randomly throughout the protein, maintaining manufacturing precision while achieving the desired pharmacokinetic improvements through controlled local modification.

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The methodology employs preliminary site selection and preparation steps, including the use of affinity tags or engineered cysteine residues at specific positions. This preliminary action ensures that subsequent PEGylation occurs only at predetermined sites, resolving the contradiction between random attachment and controlled conjugation.

Inventive Principle:
Principle #10Preliminary action

2Ease of manufacture

If random PEGylation is performed to simplify the process, then ease of manufacture is improved, but product homogeneity deteriorates due to variable activities

Engineering Contradiction:
Improveconjugation process simplicityVSAvoidproduct homogeneity
Core Design Contradiction:
Ease of manufactureVSStability of the object's composition

Solution Approach 1:

The invention changes the chemical parameters of the conjugation reaction by using site-specific reactive groups (such as maleimide-thiol chemistry or engineered lysine residues). This parameter change allows for controlled conjugation at specific sites while maintaining process simplicity, thus achieving both ease of manufacture and product homogeneity.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The methodology introduces intermediary structures such as affinity tags, self-immolative linkers, or engineered peptide sequences that mediate the conjugation process. These intermediaries guide the PEG attachment to specific sites while simplifying the overall manufacturing process through modular design.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Quantity of substance

If multiple PEG chains are attached to increase bioavailability, then pharmacokinetic properties are improved, but loss of substance increases due to 20-40% protein and PEG-agent losses

Engineering Contradiction:
ImprovebioavailabilityVSAvoidprotein and PEG-agent losses
Core Design Contradiction:
Quantity of substanceVSLoss of substance

Solution Approach 1:

The invention employs self-service mechanisms where the protein itself provides the attachment sites through engineered residues or native functional groups. This eliminates the need for excess PEG reagents and reduces losses by ensuring stoichiometric conjugation, thereby improving bioavailability while minimizing substance loss.

Inventive Principle:
Principle #25Self-service

Solution Approach 2:

The methodology incorporates feedback mechanisms through controlled reaction conditions and real-time monitoring of conjugation progress. This allows for optimization of reaction stoichiometry and minimization of unreacted materials, reducing losses while achieving the desired level of PEGylation for improved bioavailability.

Inventive Principle:
Principle #23Feedback

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 allows for high-control polymerization processes that enhance the stability, bioactivity, and pharmacokinetic properties of therapeutic proteins, reducing immunogenicity and toxicity, and providing a more stable and effective therapeutic profile.

Implementation Method 1

polymers of controlled architecture made using such methods known in the art as atom transfer radical polymerisation (ATRP)

Methodology Applied
Scientific EffectAtom transfer radical polymerization (ATRP):

Implementation Method 2

radical addition-fragmentation chain transfer polymerisation (RAFT)

Methodology Applied
Scientific EffectRadical addition-fragmentation chain transfer polymerization (RAFT):

Implementation Method 3

PEG polymer chains can sustain bioavailability by protecting the drug molecules from immune responses and other clearance mechanisms

Methodology Applied
Scientific EffectSteric shielding:

Implementation Method 4

conjugate thiol groups of two cysteine residues in a protein to give novel thioether conjugates

Methodology Applied
Scientific EffectThioether conjugation: Chemical Bonding

Data Source

PatentEP2118150B1Derivatisation of biological molecules
Publication Date: 2015.09.23 BIOCOMPATIBLES UK LTD
  • EP2118150B1 patent drawingFigure 1
  • EP2118150B1 patent drawingFigure 2
  • EP2118150B1 patent drawingFigure 3a~3b

AI summary

The present invention relates to a new polymerisation process in which ethylenically unsaturated monomers are polymerised by a living radical polymerisation process in the presence of an initiator and a catalyst. Polymers produced by this new process are also thought to be novel and may be used to derivatise biological molecules to improve their efficacy as therapeutic treatments. A preferred polymer is of formula (A) The polymers are particularly suitable for derivatising proteins, such as interferon.