The size-dependent behavior of different crystalline, colloidal monoacid an
d complex triglycerides in aqueous dispersion is investigated, mainly by di
fferential scanning calorimetry and X-ray diffraction. With decreasing part
icle size the melting range of the triglycerides broadens and shifts to low
er temperatures. The melting of particles in small-size dispersions (e.g.,
with mean particle sizes around 100 nm) of even, saturated monoacid triglyc
erides such as tripalmitin and trimyristin is characterized by a sequence o
f discrete sharp transitions which are not due to polymorphism. This comple
x melting process is observed with different types of stabilizers. The sequ
ence of melting events originates from the shape and layered structure of t
he triglyceride nanocrystals leading to successive discrete transitions cor
responding to the melting of particle fractions with different thickness. I
n dispersions of complex triglycerides, the individual transitions are less
sharp or even undetectable. The heat of fusion and the crystallization tem
perature of the nanoparticles decrease slightly with decreasing particle si
ze whereas the rate of polymorphic transitions increases. Moreover, dispers
ions containing extremely small nanoparticles display an X-ray diffraction
pattern indicating the presence of a crystal form that seems not to have be
en described previously for these triglycerides.