Combinatorial Chemistry & High Throughput Screening, 2005, 8, 499-512 499
1386-2073/05 $50.00+.00 © 2005 Bentham Science Publishers Ltd.
High Throughput Sonication: Evaluation for Compound Solubilization
Kevin Oldenburg
1
, Douglas Pooler
1
, Kurt Scudder
1
, Christopher Lipinski
2
and Michele Kelly
2, *
1
MatriCal, Inc., Spokane, WA,
2
Pfizer Global Research and Development, Groton, CT, USA
Abstract: Dissolution of organic compounds in DMSO in HTS plate or tube format is a difficult problem as
users move to higher compression plate formats. Precipitation of compounds from DMSO screening stocks is a
recognized problem in the HTS materials management process. The adverse effect of freeze thaw cycles on
DMSO stock solutions stored in plate format as a result of cherry picking operations has led to the gradual
replacement of plate-based storage with tube-based storage so as to minimize the number of freeze thaw cycles.
Compound solubility in DMSO is markedly decreased by uptake of small quantities of water. We attribute this
effect to the non ideal properties of DMSO water mixtures such that cavity formation in solvent, a necessary
step in dissolution, is more difficult in wet DMSO than in dry DMSO or in pure water. We report here that
efficient compound dissolution is possible even in 384 well format by the use of in-well plate-based
sonication. Surprisingly, compounds precipitated from DMSO stocks either by water uptake or repeated freeze
thaw cycles can be re-dissolved by low energy sonication. Finally, we demonstrate that precipitation of
compound from DMSO stock solutions is synergistically enhanced by water uptake into DMSO compound
stock solutions as well as by increasing the number of freeze thaw cycles.
Keywords: Sonication, compound solubility, freeze-thaw cycle, water in DMSO, precipitation, solubilization.
INTRODUCTION
Sonication has been used in basic science research for
over 40 years for such things as degassing of solutions [1],
lysing of mammalian [2], fungal [3], or bacterial cells [4],
shearing of DNA [5-6], and sonochemistry [7]. Sonication
has not been used in the high throughput arenas of
pharmaceutical chemistry and screening due primarily to the
fact that previously, sonicators could not accommodate the
number of samples that needed to be prepared at one time.
Anecdotally, a diverse compound collection may have up
to 20% of the compounds precipitated or degraded to at least
some extent. The proportion of insoluble compounds could
potentially be higher within a closely related chemical
library or structural class. As a consequence, when a high
throughput screening (HTS) campaign is performed against a
compound collection, a large number of samples are either
not in solution to the extent expected or are not in solution
at all, resulting in an inordinate number of “false negative”
results. In a worst-case scenario, the loss of this data can
lead to misinterpretation of the screening results and
consequently, directing chemistry down the wrong path or
missing potential lead compounds. More recently,
systematic investigations have been undertaken to better
understand the extent of this problem [8-10].
Compound solubility is governed by two basic laws:
kinetics and thermodynamics. Sonication can address one of
these, kinetics, but is not likely to affect the other,
thermodynamics. If a compound is soluble at a given
concentration, then sonication can be used to accelerate that
compounds solubility. That is, if the compound would
“normally” take hours or days to dissolve, sonication can be
used to drive that compound into solution in a matter of
*Address correspondence to this author at the Pfizer Global R&D; Groton,
CT 06340, USA; Tel: (860) 715-5125; Fax: (860) 715-9684; E-mail:
michele.a.kelly@pfizer.com
seconds. However, sonication, in most cases, can do nothing
about the thermodynamic portion of the equation. That is, if
a compound is only soluble to a concentration of 10 mM in
its lowest energy crystalline form, then sonication cannot be
used to drive it into solution at a higher concentration. It
will, however, insure that the compound is driven into
solution to the maximum extent allowed by
thermodynamics. The caveat to this statement is that because
sonication inputs energy into the sample, it may, in a local
environment convert a thermodynamically more stable less
soluble crystal form into a higher energy more soluble form,
perhaps even to an amorphous form. This is one possible
reason why sonication is effective in redissolving
precipitated materials. Conversely, high energy sonication
has been applied to induce crystallization of supersaturated
conditions [11-12].
In this paper, the degree of compound precipitation is
measured as a function of multiple freeze thaw cycles and of
water contamination present in a sample. 16 commercial
compounds chosen specifically to be representative of the
chemistry found in typical drugs were tested along with a
small Pfizer compound subset. Compound precipitation was
induced through a combination of water contamination to
the DMSO (dimethyl sulfoxide) dissolving the samples and
by multiple freeze thaw cycles. The ability of a multi-well
high throughput sonication system was then tested to
determine its ability to drive these precipitated compounds
back into solution. Optimal sonication conditions were
determined along with heating profiles during sonication,
possible contamination of samples with metal ions from the
sonication device, and effects of sonication on compound
stability were determined.
In general, sonication was capable of driving many of the
precipitated compounds back into solution and had no effect
on compound stability. In addition, compounds that
initially went into solution with difficulty (>5 hours