MACS Matchmaker

Off-chip amine DDI conjugation — protocol

The AminoLink DDI strategy conjugates a protein's primary amines (lysines or N-terminus) to a TCO-functionalised oligonucleotide off-chip, then hybridises the resulting protein–oligo conjugate to any Oligo|PEG chip via DNA-Directed Immobilization (DDI). The duplex is the weakest link, so the chip is regenerable between different ligands by an alkaline strip. Validated on antibodies, Fabs, nanobodies, Fc receptors, and other recombinant proteins.

From the catalogue

Order both kit components from the lino Biotech webshop:

ItemContentsWebshop
Oligonucleotide Conjugation Kit, AminoLinkMTz-PEG-NHS bifunctional linker + purification reagents; supports 100 µg of protein conjugation; protein size range 15–300 kDa; total turnaround < 4 hCHF 650
Oligo Adapter for Amine KitLyophilised, 10 nmol; 5′-TCO-modified ssDNA, one Seq ID (00–16) per vial; store at −20 °CCHF 195
Desalting Column, Zeba 7KBuffer-exchange between coupling stepsCHF 21
Spin Column, Amicon 10KFinal concentration / buffer exchange after IEXCHF 21

Strategy: two-step off-chip coupling

Conjugation proceeds in two sequential reactions in solution, followed by ÄKTA purification to isolate the mono-conjugated fraction:

  1. MTz-PEG4-NHS linker coupling. The NHS ester reacts with a primary amine on the protein, installing a methyltetrazine (MTz) handle. A 1:2 protein-to-linker molar ratio is used to favour mono-labelling.
  2. TCO-oligo click. The MTz handle reacts with a TCO-functionalised oligo via inverse-electron-demand Diels–Alder (IEDDA). A 1:3 protein-to-oligo ratio drives the reaction to completion.
  3. ÄKTA IEX purification. Ion-exchange chromatography on a Resource Q column separates free protein, mono-conjugate, bi-conjugate, and free oligos. Only the mono-conjugated fraction is collected for use.
MTz–PEG4–NHS linker structure
MTz–PEG4–NHS linker: methyltetrazine (right) connected via a four-unit PEG spacer to the NHS ester (left)
NHS ester structure
NHS ester (on linker)
Methyltetrazine (MeTz) structure
MeTz (installed on protein)
TCO (trans-cyclooctene) structure
TCO (on oligo)

Protocol

Step 1 — Protein preparation

Rehydrate lyophilised protein per the manufacturer specification. For liquid stocks, centrifuge at 14,000 rpm, 5 min, RT to pellet aggregates. Measure concentration by NanoDrop (A280, using the molar extinction coefficient ε₂₈₀ for the specific protein).

Step 2 — MTz-PEG4-NHS linker coupling

ParameterValue
LinkerMTz-PEG4-NHS (100 mM stock in DMSO)
Molar ratio1:2 protein : linker
Working linker concentration1 mM (dilute stock 100× in PBST pH 8.0)
BufferPBST pH 8.0
Incubation1–2.5 h, 25 °C, 500 rpm

Step 3 — TCO-oligo click

ParameterValue
OligoTCO-oligo (cs01, cs02, … — chip-sequence matched)
Oligo stock100–500 µM in PBST pH 7.4
Molar ratio1:3 protein : oligo
Incubation1.5 h, 25 °C, 500 rpm

Step 4 — ÄKTA IEX purification

Load the reaction mixture onto a Resource Q column (IEX). Use a salt gradient (Buffer A: low salt, Buffer B: high salt) with a 2 CV elution. Peaks elute in order:

  1. Non-conjugated protein (peaks A and B)
  2. Mono-conjugated protein–oligo (peak C) — collect this fraction
  3. Bi- and tri-conjugates (peaks D, E)
  4. Free oligos and poly-conjugates (peak F)

Typical yield: ~20% mono-conjugated from recovered protein, ~93% total protein recovery from the column.

Step 5 — Buffer exchange and concentration

Pool the mono-conjugate fractions. Buffer-exchange into PBST using an Amicon 10K 2 mL ultrafiltration unit (7,000×g, 7 min, 5 × PBST washes). Measure final concentration by NanoDrop; the 260/280 ratio should shift above 1.2 confirming oligo attachment.

Step 6 — Hybridisation to chip and measurement

ParameterValue
Ligand concentration200 nM in PBST
Flow rate10 µL/min
Contact time5 min
Chip typeOligo|PEG (any plex count)
SCK association flow rate30 µL/min (6-ch) / 60 µL/min (3–4-ch) / 100 µL/min (1-ch)
SCK dissociation flow rate200 µL/min
Regeneration (duplex strip)3 M guanidinium-HCl + 125 mM NaOH, 400 µL/min, 0.5 min

Optimal parameters at a glance

ParameterOptimal value
Linker : protein molar ratio2:1
Linker coupling bufferPBST pH 8.0, 25 °C, 500 rpm, 1–2.5 h
Oligo : protein molar ratio3:1
Oligo coupling conditionsPBST pH 7.4, 25 °C, 500 rpm, 1.5 h
Purification columnResource Q (IEX), 2 CV elution
Final bufferPBST, Amicon 10K buffer exchange
Hybridisation concentration200 nM
Hybridisation flow rate10 µL/min, 5 min
SCK association flow rate30 µL/min (6-ch) / 60 µL/min (3–4-ch) / 100 µL/min (1-ch)
SCK dissociation flow rate200 µL/min
Regeneration3 M GuHCl + 125 mM NaOH, 400 µL/min, 0.5 min

Practical notes

See also: immobilisation method comparison table.