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How many freeze-thaw cycles will liraglutide at 1 mg/mL tolerate?

Asked 15 Jul 2024Modified 21 months agoViewed 25k times
12

The specifics, since they change the answer: liraglutide · 1 mg/mL.

I have read the obvious sources and they disagree with each other, so I would rather ask people who have actually done this.

I have a working setup and a notebook, and I am prepared to be told that my setup is inadequate if that is the answer.

So: what is the actual procedure, and which steps matter as opposed to being ritual?

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TM
askedthermal_mass13k1715 Jul 2024
4Is the material lyophilised or already in solution? Completely different answer. – ruaidhri_o_shea 5 months ago
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4 Answers

Accepted answer first, then by votes
112

Accepted answer

Nobody has published a cycle count, and at 1 mg/mL the concentration tells you what a wrong guess costs: a 0.1 mL aliquot holds 0.1 mg and every microlitre is 1 µg. Damage from freezing is not gradual attrition — it is concentrated at the phase transitions, where ice excludes solute and the unfrozen fraction climbs well above 1 mg/mL for as long as the transition lasts. Two slow cycles can therefore do more than four fast ones, which is why a cycle count is the wrong unit in the first place. The way to make the number one is to make it one: split at reconstitution into single-draw aliquots, label each with 1 mg/mL and the date, and never thaw a container you will refreeze.

The short version: aliquot before freezing, thaw slowly, never refreeze a thawed aliquot, and count your cycles.

The mitigation is aliquoting. Divide the reconstituted solution into single-use volumes before the first freeze, and each aliquot then experiences exactly one cycle.

Degradation pathway by condition

PathwayDominant whenDetected by
DeamidationSolution, neutral to alkaline pHRP-HPLC, +1 Da on MS
OxidationLight, trace metals, peroxidesRP-HPLC, +16 Da on MS
HydrolysisSolution, extremes of pHRP-HPLC, fragment masses
AggregationAgitation, interfaces, high concentrationSEC, visual haze; often invisible on RP-HPLC
Freeze-concentration damageFreeze-thaw of buffered solutionSEC, loss of recovered content

Never refreeze a thawed aliquot. The whole point of aliquoting is that the aliquot is single-use, and refreezing it discards the benefit.

Cryoconcentration of solutes at the ice front is a well-documented mechanism in freeze-thaw damage to proteins and peptides.

Dry powder tolerates cycles far better than solution does.

edited 17 Aug 2024 by h_pergande — fixed an arithmetic slip in the third paragraph

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HP
answered · acceptedh_pergande71k15826 Jul 2024
The doubling-per-ten-degrees rule is the part I did not know and now use constantly. – sian_llewellyn 5 days ago
2Does the same reasoning apply to material already in solution, or is that a different curve? – pk_curve 2 months ago
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98

Buffer components crystallise at different rates during freezing, which shifts pH locally by a surprising amount.

During freezing, solutes are excluded from the ice lattice and concentrate into the residual liquid. Local concentrations can rise many-fold, which promotes aggregation independently of temperature.

The underlying point is that let a frozen vial reach room temperature before opening it. Opening a cold vial in humid air condenses water into the cake, which raises residual moisture and undoes what lyophilisation achieved.

Thaw slowly and never refreeze an aliquot.

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answeredDr_Yusuf_Adeyemi54k1476 Aug 2024
48

The honest answer is that people worry about the freezer temperature and should worry about the number of cycles.

A dry lyophilised powder is much less affected by a temperature cycle because there is no liquid phase for anything to concentrate into. Condensation on a cold vial opened warm is the real risk there.

Buffer salts crystallise at different points during freezing. Sodium phosphate is the classic example: the dibasic form crystallises first and the pH of the residual liquid falls by several units. That pH excursion is the real damage in many cases.

Aliquoting to eliminate repeated cycles is standard laboratory practice for exactly this reason.

The caveat is that aggregation is invisible in a clear solution below the threshold where it becomes visible.

Let a frozen vial reach room temperature before opening, or you condense water into it.

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answeredcoldpack_8850k3712 Nov 2024
6The desiccant point is under-appreciated and costs nothing to act on. – Dr_Colm_Fitzhenry 6 months ago
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39

The relevant physics is ice-front concentration: as water crystallises, everything dissolved is concentrated into the shrinking liquid phase, including buffer salts.

Count cycles rather than worrying about degrees. Minus twenty and minus eighty differ far less than one cycle and five do.

Count cycles, not degrees. The cycle is the damaging event.

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answeredpierce_count24k381 Nov 2024

Your answer

Ask PeptideStack is a static archive. Posting is closed, but the norms are worth stating: answer the question that was asked, show your working, cite the trial or the certificate, and say plainly where the evidence runs out.

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