Peptide-Polymer Conjugation

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Peptide-polymer conjugation is a new class of soft substances composed of natural and synthetic components. They have the potential to combine the advantages of proteins and synthetic polymers (i.e., the precise chemical structure and multiple functions of biomolecules, as well as the stability and processability of synthetic polymers) to produce mixed materials with properties that have not been realized by either component alone, and have a wide application prospect.

Strategies of Peptide-Polymer Conjugation

The reasonable design of peptide-polymer conjugation with desired properties requires customization of many parameters, including peptide sequence and length, chemical properties of the polymer, length of the polymer, solvent and coupling site for detailed structural characterization, in order to fully deduce the structure of the peptide and the conformation of the polymer chain.

The conjugation of polymer and peptide can be divided into two strategies, grafting to and grafting from, each of which can occur in solution or solid phase. End-functionalized polymers can be grafted onto peptides through complementary chemical active handles, or peptides can be used as large initiators, and the synthesized polymers can be polymerized by one of several different chemical substances. For example, nitrogen oxide-mediated polymerization, atom transfer radical polymerization or reversible addition-fragmentation chain transfer polymerization.

Advantage of Peptide-Polymer Conjugation

Peptide-polymer conjugation is a promising new type of soft materials, because the advantages of each component can complement each other. Peptides and proteins are self-assembled into natural structures encoded by their primary sequences to support a variety of complex functional arrays. They provide layered self-assembly on multiple length scales of molecular level, chemical function, selectivity and specificity, as well as dynamic response to external stimuli, which are of interest to the material community. However, the physical limitations of biomolecules, such as sensitivity to temperature, pH, organic solvents and degradation, inhibit their practical applications. The connection of properly selected synthetic polymers can alleviate these limitations by mediating the interaction between proteins and local media. By combining the hierarchical structure and chemical function of peptides and the stability and processability of polymers, peptide polymer conjugates may produce materials with high complexity and high modularization. Peptide polymer conjugates have great application prospects in a variety of biomedical applications.

Application of Peptide-Polymer Conjugation

  • Biomedical Application

Protein therapeutics

The most commonly used polymer in mixed biomaterials is PEG. PEG has been proved to be an effective strategy to enhance protein kinetic stability, obtain catalytic activity at very high temperatures, and improve the stability, pharmacokinetics and biodistribution of therapeutic proteins. The PEGylated proteins approved by FDA include Pegademase bovine, Pegaspargase, Pegloticase, Peginterferon alfa-2a and Peginterferon alfa-2b. The unique chemical properties of PEG, such as its high solubility, amphiphilic and inertia, are the key to its effectiveness. Variables such as the molecular weight of PEG, the number of PEG chains per protein, the structure of the polymer and its coupling sites can affect the half-life and protein activity in vivo.

Drug delivery

There are a lot of studies on the preparation of small molecular anticancer drugs and gene delivery micelles based on peptide-polyethylene glycol conjugates. The size of polypeptide-polyethylene glycol micelles is usually tens of nanometers, and there are various intermolecular interactions in the polypeptide blocks formed in the core to regulate the stability of micelles, prolong circulation and controlled drug release. Common anticancer drugs can enter the core of micelles by hydrophobic interaction or covalent binding to the side chain of the polypeptide chain. Compared with free drugs, micelles usually show higher efficacy and fewer side effects.

Gene delivery

As a non-viral vector of gene delivery technology, composite micelles are expected to open up a new strategy for the treatment of refractory vascular diseases. Cyclo (RGDfK) peptide (cRGD) was introduced into the polyethylene glycol terminal of polyethylene glycol-polyaspartic acid (DET) as a specific ligand on the surface of multi-chain micelles, CRGD peptides selectively recognize avb3 and avb5 integrins. Studies have shown that in HUVEC and VSMC, compared with ligand-free PEG-PAsp (Det) micelles expressing avb3 and avb5 integrins. The composite micelles containing cRGD-PEG-PAsp (Det) can significantly improve the efficiency of gene expression and cell uptake. CRGD-PEG-PAsp (Det) can be effectively used as a non-viral gene vector for angiopathy.

Tissue engineering

In tissue engineering, the development of bone-like biocompatible materials with higher mechanical properties requires innovative synthesis methods inspired by natural bone. Composite biomaterials based on polymer hydrogels and inorganic compounds are particularly attractive candidates for biomimetic bone design. Peptide-amphiphilic hydrogel modified by bioactive adhesion sequence Arg-Gly-Asp (RGD) has been proved to be the best scaffold for odontogenic cell proliferation and dentin and enamel regeneration. A biomimetic material for bone tissue regeneration was proposed, and a bone scaffold based on N-(2-hydroxypropyl) methacrylamide (HPMA) copolymer and complementary β-folding peptide was designed.

  • Nonbiomedical Application

In addition to typical biomedical applications usually associated with peptide-polymer binding gates, these materials can also affect non-biological applications, from gas separation to photoelectronics and catalysis. For example, peptide-polymer conjugates can be used to form porous films, which contain subnanochannels perpendicular to the surface, have unique transport and separation properties, and can be used as selective membranes for separation and protection of coatings. Oligopeptide-oligothiphene hybrids can form nanostructured capillary aggregates, which are promising for optoelectronic applications because of the self-assembly and stimulation reactivity provided by peptides and the semiconductor properties of thiophene blocks. They represent a class of novel biomimetic materials, which render orderly optoelectronic segments through the self-assembly of biological groups, and finally produce functions through the structure of the materials.

Our Services

  • Consultation and etablishing of the individual coupling strategies
  • Development of new peptide polymer conjugation
  • Peptide polymer conjugation related to protein therapeutics
  • Peptide polymer conjugation related to drug delivery
  • Customized peptide polymer conjugation


  1. Heredia, K. L., & Maynard, H. D. (2006). Synthesis of protein–polymer conjugates. Organic & biomolecular chemistry, 5(1), 45-53.
  2. Shu, J. Y., Panganiban, B., & Xu, T. (2013). Peptide-polymer conjugates: from fundamental science to application. Annual review of physical chemistry, 64, 631-657.
  3. Dehn, S., Chapman, R., Jolliffe, K. A., & Perrier, S. (2011). Synthetic strategies for the design of peptide/polymer conjugates. Polymer Reviews, 51(2), 214-234.
  4. Taylor, P. A., & Jayaraman, A. (2020). Molecular Modeling and Simulations of Peptide–Polymer Conjugates. Annual review of chemical and biomolecular engineering, 11, 257-276.
  5. Kagaya, H., Oba, M., Miura, Y., Koyama, H., Ishii, T., Shimada, T., ... & Miyata, T. (2012). Impact of polyplex micelles installed with cyclic RGD peptide as ligand on gene delivery to vascular lesions. Gene therapy, 19(1), 61-69.
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