Amorphous solid dispersions stabilized by one or more polymer(s) have been widely used for delivering amorphous drugs with poor water solubilities, and they have gained great market success. Polymer selection is important for preparing robust amorphous solid dispersions, and considerations should be given as to how the critical attributes of a polymer can enhance the physical stability, and the in vitro and in vivo performances of a drug. This article provides a comprehensive overview for recent developments in the understanding the role of polymers in amorphous solid dispersions from the aspects of nucleation, crystal growth, overall crystallization, miscibility, phase separation, dissolution, and supersaturation. The critical properties of polymers affecting the physical stability and the in vitro performance of amorphous solid dispersions are also highlighted. Moreover, a perspective regarding the current research gaps and novel research directions for better understanding the role of the polymer is provided. This review will provide guidance for the rational design of polymer-based amorphous pharmaceutical solids with desired physicochemical properties from the perspective of physical stability and in vitro performance.

The amorphous form of a drug usually exhibits higher solubility, faster dissolution rate, and improved oral bioavailability in comparison to its crystalline forms. However, the amorphous forms are thermodynamically unstable and tend to transform into a more stable crystalline form, thus losing their advantages. In order to investigate and suppress the crystallization, it is vital to closely monitor the drug solids during the preparation, storage, and application processes. A list of advanced techniques—including optical microscopy, surface grating decay, solid-state nuclear magnetic resonance, broadband dielectric spectroscopy—have been applied to characterize the physicochemical properties of amorphous pharmaceutical solids, to provide in-depth understanding on the crystallization mechanism. This review briefly summarizes these characterization techniques and highlights their recent advances, so as to provide an up-to-date reference to the available tools in the development of amorphous drugs.

This paper provides a viewpoint of the technology of the fast-scanning calorimetry with the relaxation behavior of disordered side chains of poly[2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-C12) around the glass transition temperature of the side chains (T_g,γ). PBTTT is an ideal model of the high-performance copolymer of poly(alkylthiophenes) with side chains. The γ₁ relaxation process of the disordered side chains of PBTTT was detected as a small endothermic peak that emerges before the γ₂ relaxation process. It shows an increase with increasing temperature as it approaches the glass transition temperature of the disordered side chains of PBTTT. The ductile–brittle transition of PBTTT in low temperatures originating from the thermal relaxation process is probed and illustrated by physical aging experiments. The signature is shown that the relaxation process of the disordered side chain of PBTTT at low temperatures varies from Arrhenius temperature dependence to super Arrhenius temperature dependence at high temperatures. These observations could have significant consequences for the stability of devices based on conjugated polymers, especially those utilized for stretchable or flexible applications, or those demanding mechanical robustness during tensile fabrication or use in a low-temperature environment.