302 7.7 Characterizing Physical Properties of Biological Samples in Bulk
7.7 CHARACTERIZING PHYSICAL PROPERTIES OF BIOLOGICAL
SAMPLES IN BULK
There are several methods that enable experimental measurements on relatively macro
scopic volumes of biological material that use, at least in part, biophysical techniques but
whose mainstream applications are in other areas of the biosciences, for example, test
tube length scale level experiments to measure the temperature changes due to biochem
ical reactions. Also though, bulk samples of biological tissue can be probed to generate
ensemble average data from hundreds or thousands of cells of the same type in that tissue,
but also encapsulating the effect from potentially several other cell types as well as from
extracellular material. This may therefore seem like a crude approach compared to the high
spatial precision methods utilizing optical techniques discussed earlier in this chapter; how
ever, what these methods lack in being able to dissect out some of the finer details of het
erogeneous tissue features they make up for in generating often very stable signals with low
levels of noise.
7.7.1 CALORIMETRY
One of the most basic biophysical techniques involves measuring heat transfer in bio
logical processes in vitro, which ultimately may involve the absorption and/or emission of
IR photons. The fact of calorimetry being a very established method takes nothing away
from its scientific utility; in fact, it demonstrates a measure of its robustness. Changes in
thermodynamic potentials, or state variables, such as enthalpy (H), may be measured dir
ectly experimentally. Other thermodynamic potentials that are more challenging to measure
directly such as entropy (S), or the Gibbs free energy (G) that depends on entropy, need to be
inferred indirectly from more easily measurable parameters, with subsequent analysis util
izing the first-order Maxwell’s relations of thermal physics to relate the different thermo
dynamic potentials.
The most quantifiable parameter is sample temperature, which can be measured using spe
cifically calibrated chambers of precise internal volumes, which typically include an integrated
stirring device with chamber walls maximally insulated against heat flow to generate an adia
batic measuring system. Time-resolved temperature changes inside the chamber can easily
be monitored with an electrical thermometer using a thermistor or thermocouple. Inside, a
biological sample might undergo chemical and/or physical transitions of interest that may be
exothermic or endothermic, depending on whether or not they generate or absorb heat, and
enthalpic change can be very simply calculated from the change in temperature and know
ledge of the specific heat capacity of the reactant mixture.
Isothermal titration calorimetry (ITC) is often used as an alternative. Here an adiabatic
jacket made from a thermally highly conductive alloy is used to surround the sample cell,
while an identical reference cell close enough to transfer heat very efficiently just to the
sample cell contains a reference heater whose output is adjusted dynamically so as to main
tain a constant measured temperature in the sample chamber. ITC has been used to study the
kinetics and stoichiometry of reactants and products through monitoring estimated changes
in thermodynamic potentials as a function of the titration of ligands injected into the sample
cell that contains a suitable reactant, for example, of ligand molecules binding to proteins or
DNA in the sample solution.
The heat transfer processes measured in biology are most usually due to a biochemical
reaction, but potentially also involve phase transitions. For example, different mixtures of
lipids may undergo temperature-dependent phase transition behavior that gives insight
into the architecture of cell membranes. The general technique used to detect such phase
transitions operates using similar isothermal conditions as for ITC and is referred to as dif
ferential scanning calorimetry.