Mpemba Effect in Crystallization of Polybutene-1

The Mpemba effect and its inverse can be understood as a result of nonequilibrium thermodynamics. In polymers, changes of state are generally non-equilibrium processes. However, the Mpemba effect has been rarely reported in the crystallization of polymers. In the melt, polybutene-1 (PB-1) has the lowest critical cooling rate in polyolefins and tends to maintain its original structure and properties with thermal history. A nascent PB-1 sample was prepared by using metallocene catalysis at low temperature, and the crystallization behavior and crystalline structure of the PB-1 were characterized by DSC and WAXS. Experimentally, a clear Mpemba effect is observed not only in the crystallization of the nascent PB-1 melt in form II but also in form I obtained from the nascent PB-1 at low melting temperature. It is proposed that this is due to the differences in the chain conformational entropy in the lattice which influence conformational relaxation times. The entropy and the relaxation time can be predicted using the Adam-Gibbs equations, whereas non-equilibrium thermodynamics is required to describe the crystallization with the Mpemba effect

Self-assembly kinetics of amphiphilic dendritic copolymers

The self-assembly process of amphiphilic dendritic copolymers(ADPs) with a hydrophilic core and a hydrophobic shell was investigated via laser light scattering. The self-assembly occurs via a fast step and a slow step with different relaxation times. At the critical micelle concentration (CMC), the fusion of small micelles results in the rapid increase of the micelle size in the fast step. The slow step is associated with equilibrium through the fission and fusion of the micelles. The micelle size increases with the unimer concentration, which leads to a lower micelle concentration. The lower micelle concentration makes the relaxation time of the fast step increase with increasing unimer concentration. However, the fusion of larger micelles at higher concentration is more efficient to increase micelle size. The fusion of small micelles with large micelles at higher concentration accelerates the approaching equilibrium of the micelles except for the fission and fusion of micelles. With the increasing degree of amidation (DA), the relaxation time in the fast step increases and in the slow step it decreases

Crystalline structures and crystallization behaviors of poly(L-lactide) in poly(L-lactide)/graphene nanosheet composites

GNS existence in PLLA favors α′ crystal formation more than α crystal formation resulting in a shift of α′–α crystal formation transition toward high Tcs.</p

Human Hepatocytes with Drug Metabolic Function Induced from Fibroblasts by Lineage Reprogramming

SummaryObtaining fully functional cell types is a major challenge for drug discovery and regenerative medicine. Currently, a fundamental solution to this key problem is still lacking. Here, we show that functional human induced hepatocytes (hiHeps) can be generated from fibroblasts by overexpressing the hepatic fate conversion factors HNF1A, HNF4A, and HNF6 along with the maturation factors ATF5, PROX1, and CEBPA. hiHeps express a spectrum of phase I and II drug-metabolizing enzymes and phase III drug transporters. Importantly, the metabolic activities of CYP3A4, CYP1A2, CYP2B6, CYP2C9, and CYP2C19 are comparable between hiHeps and freshly isolated primary human hepatocytes. Transplanted hiHeps repopulate up to 30% of the livers of Tet-uPA/Rag2−/−/γc−/− mice and secrete more than 300 μg/ml human ALBUMIN in vivo. Our data demonstrate that human hepatocytes with drug metabolic function can be generated by lineage reprogramming, thus providing a cell resource for pharmaceutical applications

Investigations on the micellization of amphiphilic dendritic copolymers: from unimers to micelles

Since the micellization kinetics is influenced by polymer structure, the spherical three-dimensional topology of amphiphilic dendritic copolymers (ADPs) which hinders the phase separation during micellization is assumed to make the micellization kinetics different. In the literatures, most of the attention has been paid to the morphology transition or the morphology at equilibrium and the micellization kinetics of ADPs is rarely reported. In this study, the micellization processes of amphiphilic dendritic copolymers from unimers to the final equilibrium micelles were monitored by laser light scattering. Based on the closed association mechanism, the thermodynamics of micellization was analysed. The negative thermodynamic quantities indicate that the micellization of ADPs is driven by enthalpy. Based on the change of scattering intensity and hydrodynamic radius (Rh) with time, the detailed micellization kinetics was analysed, which contains two steps. By controlling the temperature and type of solvent, a system in which the concentration has little influence on Rh is obtained. The relaxation times of the two steps decrease with concentration, indicating that at higher concentration the rate of micellization is quicker. With the increasing mass fraction of the hydrophobic part, the relaxation times decrease and the driving force of micellization increases