UV-Vis Spectroscopy for Peptides

Learn how to accurately determine peptide concentration using ultraviolet-visible light absorption

Contents

Why Measure Peptide Concentration?

Imagine you've just synthesized a new peptide in the lab. Before you can run biological assays, test its activity, or publish your results, you need to answer one fundamental question: How much peptide do I actually have?

Accurate concentration determination is essential for:

🔬 Experimental Reproducibility
Ensuring consistent concentrations across experiments and between research groups
💊 Dose-Response Studies
Determining accurate IC₅₀, EC₅₀, or binding affinity values in biological assays
📊 Stock Solution Preparation
Making accurate dilutions for experiments and maintaining quality control
📝 Scientific Reporting
Publishing results with proper concentration units (μM, mg/mL, etc.)
🎯 Learning Objectives

By the end of this guide, you will be able to:

  • Apply the Beer-Lambert Law to convert absorbance measurements into concentrations with proper units
  • Determine when to use the 280nm method versus the 214nm method
  • Explain how to calculate extinction coefficients from peptide sequences

The Beer-Lambert Law

At the heart of UV-Vis spectroscopy is the Beer-Lambert Law, which describes the relationship between light absorption and concentration. When light passes through a solution, some wavelengths are absorbed by the molecules in solution. The amount of light absorbed is directly proportional to the concentration and the distance the light travels through the sample.

A = ε × c × l

Understanding Each Variable

A (Absorbance)
Dimensionless measure of light absorbed. Typical range: 0.1 - 1.0 for accurate measurements. Your spectrophotometer displays this value directly.
ε (Epsilon, Molar Extinction Coefficient)
Units: M⁻¹cm⁻¹. Describes how strongly your peptide absorbs light at a specific wavelength. This is sequence-specific and can be calculated.
c (Concentration)
Units: M (molarity) or mol/L. This is what we're trying to determine! Can be converted to other units like mg/mL or μM as needed.
l (Path Length)
Units: cm. The distance light travels through your sample. Standard cuvettes are 1 cm, so this often equals 1.

Rearranging for Concentration

Since we measure absorbance (A) and know the path length (l = 1 cm for standard cuvettes), we can rearrange the equation to solve for concentration:

c = A / (ε × l)

With l = 1 cm:
c (M) = A / ε
💡 Pro Tip

For best results, aim for absorbance values between 0.1 and 1.0. If your absorbance is too high (>1.0), dilute your sample. If too low (<0.1), use a longer path length cuvette or concentrate your sample. This ensures you're working in the linear range of the spectrophotometer.

⚠️ Common Unit Confusion

Remember that ε is in M⁻¹cm⁻¹, not L/(mol·cm). These are equivalent but M⁻¹cm⁻¹ is the standard notation. When you calculate c, you get molar concentration (M), which you can convert to mg/mL by multiplying by your peptide's molecular weight in g/mol and dividing by 1000.

280nm Method: Aromatic Amino Acids

The 280nm method is the most commonly used approach for peptides containing aromatic amino acids. At this wavelength, tryptophan (Trp) and tyrosine (Tyr) strongly absorb UV light due to their aromatic ring structures, while other amino acids contribute minimally.

Why 280nm?

The choice of 280nm isn't arbitrary - it's the wavelength where aromatic amino acids show peak absorption while minimizing interference from peptide bonds and other chromophores. This makes it ideal for specific quantification of peptides containing Trp and/or Tyr.

Calculating ε₂₈₀ from Sequence

The beauty of the 280nm method is that you can predict ε₂₈₀ directly from your peptide sequence using the following formula:

ε₂₈₀ = (nTrp × 5,500) + (nTyr × 1,490) + (nCystine × 125) M⁻¹cm⁻¹
Amino Acid Three-Letter One-Letter ε₂₈₀ (M⁻¹cm⁻¹) Notes
Tryptophan Trp W 5,500 Strongest absorber at 280nm
Tyrosine Tyr Y 1,490 Moderate absorption
Cystine Cys-Cys C-C 125 Only when forming disulfide bonds
Phenylalanine Phe F ~0 Absorbs at 257nm, not at 280nm
⚠️ Why is Phenylalanine (Phe) Excluded?

Although phenylalanine has an aromatic ring with absorption maximum at 257nm (ε ≈ 197 M⁻¹cm⁻¹), it absorbs essentially zero at 280nm. This is why only Trp (5,500 M⁻¹cm⁻¹) and Tyr (1,490 M⁻¹cm⁻¹) are counted in the 280nm method. For peptides lacking Trp/Tyr, use the 214nm method instead where Phe contributes strongly (5,200 M⁻¹cm⁻¹).

📚 Understanding Cystine vs Cysteine

Cysteine (Cys, C): The free amino acid with a thiol (-SH) group. Does not contribute significantly to 280nm absorption.

Cystine: Formed when two cysteine residues create a disulfide bond (Cys-S-S-Cys). Each disulfide bond contributes 125 M⁻¹cm⁻¹. If your peptide has 4 cysteines forming 2 disulfide bonds, add 250 M⁻¹cm⁻¹ to ε₂₈₀.

Practical Example: Melittin

Let's calculate ε₂₈₀ for melittin, the principal active component of bee venom and a classic example in peptide chemistry:

Melittin: GIGAVLKVLTTGLPALISWIKRKRQQ

Step 1: Count aromatic residues
• Tryptophan (W): 1
• Tyrosine (Y): 0
• Cysteine (C): 0 (no disulfides)
Step 2: Calculate ε₂₈₀
ε₂₈₀ = (1 × 5,500) + (0 × 1,490) + (0 × 125)
ε₂₈₀ = 5,500 M⁻¹cm⁻¹
Step 3: Use in Beer-Lambert Law
If measured absorbance A₂₈₀ = 0.55:
c = 0.55 / 5,500 = 0.0001 M = 100 μM
✅ When to Use 280nm Method

Best for: Peptides with at least one Trp or Tyr
Advantages: Fast, non-destructive, highly specific
Limitations: Cannot be used for peptides lacking aromatic amino acids

214nm Method: Peptide Bonds

At 214nm, we're detecting the π→π* transition of the peptide bond itself. This makes the 214nm method universal - it works for ALL peptides, regardless of their amino acid composition. However, it's less specific than the 280nm method and requires more careful technique.

The Peptide Bond Chromophore

Every peptide bond absorbs light at 214nm due to the electronic transition in the C=O group. This means a 10-residue peptide (with 9 peptide bonds) will have a baseline absorption from these bonds alone, plus additional contributions from certain amino acid side chains.

Amino Acid Contributions at 214nm

While all peptides absorb at 214nm due to peptide bonds, different amino acids make additional contributions based on their side chain chromophores. The table below shows the complete breakdown:

Amino Acid Code ε₂₁₄ (M⁻¹cm⁻¹) Relative to Peptide Bond
Peptide Bond Baseline - 923
Tryptophan W 29,050 31.5× (strongest)
Tyrosine Y 5,375 5.8×
Phenylalanine F 5,200 5.6×
Histidine H 5,125 5.6×
Proline (non-N-terminal) P 2,675 2.9× (see warning)
Proline (N-terminal) P 30 0.03× (special case!)
Methionine M 980 1.1×
Cysteine C 225 0.24×
Glutamine Q 142 0.15×
Asparagine N 136 0.15×
Arginine R 102 0.11×
Glutamic Acid E 78 0.08×
Aspartic Acid D 58 0.06×
Isoleucine I 45 0.05×
Leucine L 45 0.05×
Valine V 43 0.05×
Lysine K 41 0.04×
Threonine T 41 0.04×
Serine S 34 0.04×
Alanine A 32 0.03×
Glycine G 21 0.02×
⚠️ CRITICAL: N-Terminal Proline Special Case

Proline at position 1 (N-terminus): ε = 30 M⁻¹cm⁻¹
Proline at any other position: ε = 2,675 M⁻¹cm⁻¹

This is an ~89-fold difference! When calculating ε₂₁₄ for Pro-rich peptides, you MUST account for whether proline is at the N-terminus. For example:

• PAPAPA: First P uses 30, others use 2,675 each
• APAPAP: All P's use 2,675 (none at N-terminus)

Ignoring this can cause 25%+ errors in concentration calculations for Pro-rich sequences!

Complete Formula for ε₂₁₄

ε₂₁₄ = (n-1) × 923 + Σ(amino acid contributions)

Where n = number of residues
(n-1) = number of peptide bonds

Example for GIGAVLKVLTTGLPALISWIKRKRQQ (26 residues):
= 25×923 + 1×29,050 + other amino acids
≈ 64,321 M⁻¹cm⁻¹

Academic Reference

📚 Citation

Kuipers, B.J.H. & Gruppen, H. (2007). "Prediction of molar extinction coefficients of proteins and peptides using UV absorption of the constituent amino acids at 214 nm to enable quantitative reverse phase high-performance liquid chromatography–mass spectrometry analysis." Journal of Agricultural and Food Chemistry, 55(14), 5445-5451.

✅ When to Use 214nm Method

Best for: Peptides lacking Trp/Tyr, HPLC monitoring, peptide libraries
Advantages: Universal (works for all peptides), good sensitivity
Limitations: Less specific, buffer interference, ±5-10% typical accuracy

Interactive Calculators

🧮 Calculator 1: Extinction Coefficient from Sequence

Enter your peptide sequence to automatically calculate ε₂₈₀:

🧮 Calculator 2: Concentration from Absorbance

Convert measured absorbance to concentration:

Worked Examples

Example 1: Melittin (Simple Case)

Given Information:
• Sequence: GIGAVLKVLTTGLPALISWIKRKRQQ (26 residues)
• Molecular Weight: 2,845.7 g/mol
• Measured A₂₈₀: 0.55
• Path length: 1 cm (standard cuvette)
Step 1: Calculate ε₂₈₀
Count aromatic residues: 1 Trp, 0 Tyr, 0 disulfides
ε₂₈₀ = (1 × 5,500) + (0 × 1,490) + (0 × 125) = 5,500 M⁻¹cm⁻¹
Step 2: Calculate molar concentration
c = A / ε = 0.55 / 5,500 = 0.0001 M = 100 μM
Step 3: Convert to mg/mL
c (mg/mL) = c (M) × MW (g/mol) × 1000 (mg/g) / 1000 (mL/L)
c (mg/mL) = 0.0001 × 2,845.7 = 0.285 mg/mL

Example 2: Aromatic-Rich Peptide

Given Information:
• Sequence: WYWYKY (6 residues)
• Measured A₂₈₀: 1.20
• Molecular Weight: 1007.5 g/mol
Step 1: Calculate ε₂₈₀
Count: 2 Trp, 2 Tyr, 0 disulfides
ε₂₈₀ = (2 × 5,500) + (2 × 1,490) = 11,000 + 2,980 = 13,980 M⁻¹cm⁻¹
Step 2: Calculate concentration
c = 1.20 / 13,980 = 0.0000858 M = 85.8 μM
c = 0.0000858 × 1007.5 = 0.0864 mg/mL

Example 3: Peptide with Disulfide Bonds

Given Information:
• Sequence: CYIQWCY (7 residues)
• Contains 1 disulfide bond (Cys1-Cys7)
• Measured A₂₈₀: 0.68
Step 1: Calculate ε₂₈₀
Count: 1 Trp, 1 Tyr, 1 disulfide bond
ε₂₈₀ = (1 × 5,500) + (1 × 1,490) + (1 × 125) = 7,115 M⁻¹cm⁻¹
Step 2: Calculate concentration
c = 0.68 / 7,115 = 0.0000956 M = 96 μM
Note: The disulfide bond adds only 125 M⁻¹cm⁻¹, which is less than 2% of the total ε₂₈₀. For peptides with multiple disulfides (like insulin), this contribution becomes more significant.

Example 4: When to Use 214nm Instead

Given Information:
• Sequence: AAAKAAAK (8 residues - no Trp or Tyr)
• Attempted measurement at A₂₈₀: 0.02 (very low signal)
Problem:
ε₂₈₀ = 0 M⁻¹cm⁻¹ (no Trp or Tyr)
Cannot use 280nm method!
Solution:
Switch to 214nm method where peptide bonds provide strong signal.
Approximate ε₂₁₄ for this sequence ≈ 8,600 M⁻¹cm⁻¹
(7 peptide bonds × 923 + amino acid side chain contributions)

Example 5: Using 214nm Method

Given Information:
• Sequence: AAPAAKAPA (9 residues with proline)
• Measured A₂₁₄: 0.750
• Molecular Weight: 766.4 g/mol
Step 1: Calculate ε₂₁₄
• Peptide bonds: 8 × 923 = 7,384
• Proline at position 3 (not N-terminal): 1 × 2,675 = 2,675
• Proline at position 8 (not N-terminal): 1 × 2,675 = 2,675
• Alanine: 5 × 32 = 160
• Lysine: 2 × 41 = 82
Total ε₂₁₄ ≈ 12,976 M⁻¹cm⁻¹
Step 2: Calculate concentration
c = 0.750 / 12,976 = 0.0000578 M = 57.8 μM
c = 0.0000578 × 766.4 = 0.0443 mg/mL
Note: If the first proline were at the N-terminus (PAAPAKAPA), ε₂₁₄ would be 2,645 less (10,331 M⁻¹cm⁻¹), causing a 25% error if ignored!

Troubleshooting & Tips

Common Problems and Solutions

❌ Problem: Absorbance Too High (>1.0)

Cause: Concentration is too high for accurate measurement
Solution: Dilute your sample 2-10 fold and remeasure. Multiply your final concentration by the dilution factor. Example: If you dilute 1:10 and measure 0.50, your original sample was 10× more concentrated.

❌ Problem: Absorbance Too Low (<0.1)

Cause: Concentration is too low, or peptide lacks chromophores at this wavelength
Solution: • Concentrate your sample if possible
• Use a longer path length cuvette (5 cm or 10 cm)
• For 280nm: Switch to 214nm method if no aromatic amino acids
• For 214nm: Check for buffer interference

❌ Problem: Negative or Strange Absorbance Values

Cause: Improper blanking, dirty cuvettes, or air bubbles
Solution: • Blank with your exact buffer (same pH, salt concentration)
• Clean cuvettes thoroughly with ethanol and lint-free wipes
• Check for air bubbles - tap cuvette gently to release them
• Ensure sample and blank temperatures match

❌ Problem: Inconsistent Measurements

Cause: Temperature fluctuations, peptide aggregation, or instrument drift
Solution: • Allow samples to equilibrate to room temperature
• Add 0.1% Tween-20 or similar detergent to prevent aggregation
• Run a standard protein (BSA) to verify instrument performance
• Ensure cuvette positioning is consistent

Best Practices

✅ Buffer Considerations

• At 280nm: Most common buffers (PBS, Tris, HEPES) are fine
• At 214nm: Avoid buffers with strong UV absorption (acetate, imidazole)
• Always blank with the same buffer used to dissolve your peptide
• pH can affect Tyr absorption at 280nm (pKa ≈ 10.1)

✅ Sample Preparation

• Centrifuge samples to remove particulates (13,000 rpm, 5 min)
• Use fresh buffer - old buffers can develop contaminants
• Store peptide solutions at -20°C if not using immediately
• Avoid multiple freeze-thaw cycles when possible

✅ Quality Control

• Measure in triplicate and report average ± standard deviation
• Run a wavelength scan (250-300nm) to check for impurities
• Verify peptide identity with mass spectrometry when possible
• Document all conditions (pH, buffer, temperature)

Decision Tree: Which Method to Use?

🌳 Quick Decision Guide

START HERE: Does your peptide have Trp or Tyr?
↓ YES → Use 280nm method (specific, accurate, easy)
↓ NO → Use 214nm method (universal, works for all peptides)

Special applications:
• HPLC monitoring → Always use 214nm (universal detection)
• Peptide libraries → Use 214nm (works for all sequences)
• Aromatic-rich peptides → 280nm is best (minimal interference)

🚀 Coming Soon: PepDraw Pro Features

Upgrade to PepDraw Pro for advanced UV-Vis spectroscopy tools

📊 Automated ε₂₁₄ Calculator
Sequence-specific extinction coefficient prediction with all 22 amino acids
🎯 N-Terminal Proline Detection
Automatic handling of special cases like N-terminal Pro
🔬 Amino Acid Breakdown
Detailed contribution analysis showing which residues dominate absorption
⚗️ Buffer Compatibility
Database of buffer interference at 214nm with recommendations
📈 Batch Calculations
Upload CSV of sequences and get concentration data for entire libraries

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