Backbone‑Modified Peptide Synthesis

N‑methylation, β/γ amino acids, peptoids, and peptide‑bond isosteres—engineered for stability, conformation, and permeability.

Backbone engineering for drug‑like behavior, robust assays, and protease‑resistant peptidomimetics.

Overview

What counts as a “backbone modification”?

In peptide chemistry, a backbone modification changes the peptide framework—such as the amide nitrogen (N‑methylation), α‑carbon stereochemistry (D‑amino acids), backbone length (β/γ amino acids), or the amide bond itself (e.g., ψ[CH2NH] reduced amide). These changes can reduce hydrogen‑bond donors, restrict conformational space, alter folding, and improve resistance to proteolysis—key levers for peptidomimetics, cyclic peptides, and permeability optimization.

Bio‑Synthesis provides custom synthesis of backbone‑modified peptides and peptidomimetics with project‑aligned purification and QC (HPLC/UPLC and LC‑MS when feasible). We support major backbone modification classes used in modern peptide and foldamer design—including N‑methylated peptides, β/γ amino acid peptides (foldamers), and peptoids (N‑substituted glycines).

N‑methyl peptides β/γ amino acids Peptoids (N‑substituted glycine) ψ[CH2NH] reduced amide Foldamers HPLC/LC‑MS QC
Backbone modification types including N-methylation, peptoids, alpha-methyl residues, D-amino acids, beta and gamma amino acids, and reduced amide bonds

Backbone modification types showing N-methylation, peptoids, α-methyl residues, D-amino acids, β/γ amino acids, and reduced amide bonds.

Which backbone modification should I choose?

Decision guide (fast)
Your goal Best first choice Notes
Protease resistance / stability D‑amino acids Often start at known cleavage sites
Permeability (esp. cyclic peptides) N‑methyl residues Reduces H‑bond donors; restricts conformations
Foldamer / non‑native secondary structure β/γ amino acids Backbone spacing changes; stable foldamers
Extreme protease resistance / peptidomimetic Peptoids (N‑substituted glycine) Side chains on amide N; protease‑resistant
Non‑cleavable bond / enzyme mechanism ψ[CH2NH] reduced amide Non‑hydrolyzable surrogate (position‑dependent)

For fastest scoping, send your sequence, intended use (assay vs drug discovery), and your failure mode (proteolysis, permeability, aggregation). We’ll propose a ranked modification plan and QC.

Practical rules
  • Start small: 1–3 backbone edits often outperform full redesign for SAR.
  • Keep motif integrity: avoid heavy backbone edits inside the minimal binding motif unless required.
  • Expect synthesis complexity: multiple N‑methyl and foldamer segments can require extra optimization.
  • Plan purification: backbone edits can shift hydrophobicity and retention.
backbone modified peptide N‑methyl peptide synthesis β‑amino acid peptides peptoid synthesis reduced amide isostere

Backbone‑modified amino acid list: major building‑block classes

There is no finite “complete” list of backbone‑modified amino acids across all chemistry—new building blocks and protected derivatives are continually developed. Below are the major, widely used categories that cover most backbone‑modified peptide and peptidomimetic designs.

Class Representative building blocks Backbone attribute & typical effect
D‑amino acids D‑Ala, D‑Val, D‑Leu, D‑Ile, D‑Phe, D‑Trp, D‑Tyr, D‑Lys, D‑Arg, D‑Ser, D‑Thr, D‑Asp, D‑Glu Inverts α‑carbon stereochemistry → shifts φ/ψ angles; often increases protease resistance
N‑methyl amino acids N‑Me‑Ala, N‑Me‑Val, N‑Me‑Leu, N‑Me‑Ile, N‑Me‑Phe, N‑Me‑Gly Removes backbone NH donor; restricts amide geometry; commonly used to improve permeability/stability
α,α‑disubstituted Aib (α‑aminoisobutyric acid), other α,α‑disubstituted residues Backbone steric constraint; helix induction and conformational bias
β‑amino acids β‑Ala, β2/β3 residues (e.g., β3‑hLeu, β3‑hPhe), cyclic β‑amino acids (e.g., ACPC) Adds extra backbone carbon (spacing) → foldamer behavior; often protease resistant
γ‑amino acids GABA and γ‑homo residues Longer spacing/flexibility; used for spacing control and foldamer design
Peptoids N‑substituted glycine (N‑alkyl / N‑aryl glycine units) Side chain on amide N; no backbone NH donor; strong protease resistance; peptidomimetic scaffold
Amide bond isosteres ψ[CH2NH] (reduced amide) and related non‑cleavable surrogates Replaces amide bond; can create non‑hydrolyzable linkages for stability or mechanism probes
Other backbone edits Thioamides (C=O→C=S), constrained proline analogs, cyclic/rigid foldamer monomers Changes carbonyl electronics or fixes torsion angles; used for conformational control and mechanistic studies

If you have a specific protected monomer (Fmoc/Boc derivative) in mind, send the catalog name or structure and we’ll confirm feasibility and route.

Backbone modification categories we synthesize

N‑methylated peptides permeability • conformational restriction
N‑methyl peptide synthesis cyclic peptides peptidomimetics

N‑methylation adds a methyl group to the amide nitrogen, reducing backbone H‑bond donors and restricting conformational space—commonly used to improve stability and permeability in cyclic peptides and peptidomimetics (sequence‑dependent).

Practical note: multiple N‑methyl residues may require double coupling and route optimization.

β/γ amino acid peptides (foldamers) protease resistance • non‑native folding
β‑amino acids α/β peptides foldamers

β‑amino acids add an extra backbone carbon relative to α‑amino acids. β‑peptides and α/β‑peptides can form stable foldamer architectures and are widely used to increase protease resistance and control conformation.

Practical note: coupling and purification may require adjustment due to altered spacing/hydrophobicity.

Peptoids (N‑substituted glycines) protease resistance • peptidomimetic scaffold
peptoid synthesis N‑substituted glycine submonomer method

Peptoids place side chains on the amide nitrogen rather than the α‑carbon, typically improving resistance to enzymatic/protease degradation and enabling broad peptidomimetic design space.

Amide‑bond isosteres non‑cleavable bonds • mechanism probes
ψ[CH2NH] reduced amide non‑cleavable surrogate

Reduced amide (ψ[CH2NH]) and related isosteres can create non‑hydrolyzable bonds for stability enhancement or enzyme mechanism studies. Feasibility depends on the target position and sequence context.

D‑amino acid designs stability • stereochemical controls
D‑amino acids protease resistance matched controls

D‑substitutions invert backbone stereochemistry and can dramatically increase protease resistance. They’re also used as matched controls (L vs D) to validate binding specificity.

Related pages (internal links)

Connect backbone modification with constrained scaffolds, labeling, and challenging sequences.

Remove or adjust any link paths you’re not using yet—this block is designed to be modular.

Comparison matrix: attributes & trade‑offs

Backbone class Primary attribute Typical benefits Typical trade‑offs
N‑methyl Backbone NH blocked; conformational restriction Permeability/stability improvements in cyclic peptides (sequence‑dependent) Synthesis complexity increases with multiple N‑Me sites
β/γ AAs Backbone spacing changes; foldamer structures Protease resistance; stable non‑native folds Coupling/purification optimization may be needed
Peptoids Side chain on amide N; no backbone NH High protease resistance; broad peptidomimetic space Sequence‑function relationship differs from peptides
ψ[CH2NH] Non‑cleavable amide surrogate Stability enhancement; mechanism probes Position‑dependent feasibility; specialized building blocks
D‑AAs Stereochemistry inversion at α‑carbon Protease resistance; matched stereochemical controls Can alter binding if placed in core motif

Quality control & typical deliverables

Standard QC
  • Analytical HPLC/UPLC purity profile
  • Identity confirmation (LC‑MS when feasible)
  • COA + method summary
Backbone‑specific notes
  • Matched control sets (e.g., L vs D, N‑Me panel) available
  • Foldamer segments may shift retention/ionization
  • Non‑standard monomers may require custom analytical notes
When to add more

If your decision depends on stability, binding, permeability, or labeling efficiency, tell us and we’ll align QC to it.

FAQ

What is a backbone‑modified peptide?

A peptide containing building blocks that alter the backbone itself (amide N, stereochemistry, spacing, or the bond), which can change hydrogen bonding, folding, stability, and permeability versus standard α‑peptides.

Why are N‑methylated peptides popular?

N‑methylation reduces backbone H‑bond donors and can restrict conformational space—often used to increase stability and permeability in cyclic peptides and peptidomimetics (sequence‑dependent).

Are β‑amino acid peptides more protease resistant?

Often yes—β‑peptides and α/β‑peptides are used as foldamers and can resist proteolysis compared with native peptides, while adopting stable secondary structures.

Can you make peptoids (N‑substituted glycine) sequences?

Yes. Peptoids are commonly synthesized by solid‑phase methods and are valued for protease resistance and peptidomimetic design space.

Can you incorporate ψ[CH2NH] reduced amide bonds?

Yes—reduced amide bonds and related isosteres can be used as non‑cleavable surrogates for stability or enzyme mechanism studies. Feasibility depends on position and sequence context.

How should I specify a backbone‑modified project for quoting?

Send your sequence, the exact monomer(s) and position(s) (or “recommend”), your intended use (assay vs drug discovery), quantity/purity targets, and any constraints on preserving a motif.

Contact & quote request

For the fastest quote, send your sequence(s), backbone modification(s) + positions (or “recommend”), desired quantity/purity, and intended use. We’ll propose a practical synthesis route and QC plan aligned to your goals.

Fastest path
Fast quote checklist
  • Sequence(s) + terminal state (free vs capped)
  • Backbone modification(s) + positions (or “recommend”)
  • Intended use (stability, permeability, foldamer, mechanism)
  • Quantity (mg) + purity target
  • Any constraints (must keep motif unchanged)

Recommended reading

Peer-reviewed background on backbone modification strategies used in peptides and peptidomimetics.

Want a reading list tuned to your modification (N-Me vs β-AA vs peptoid vs ψ[CH2NH]) and target class? Tell us your application and we’ll tailor it.

Why Choose Bio-Synthesis

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