CRYSTALLIZATION AND MELTING OF POLY(ETHYLENE OXIDE)CONFINED IN NANOSTRUCTURED PARTICLES WITH CROSS-LINKED SHELLS OF POLYBUTADIENE

Small fixed aggregates of a poly(ethylene oxide)-block-polybutadiene diblock copolymer(PEO-b-PB)in THFsolution were obtained by adding a selective solvent for PB blocks,followed by cross-linking the PB shells.Themorphologies of the nanostructured particles with a cross-linked shell were investigated by atomic force microscopy andtransmission electron microscopy.The average behaviors of the PEO crystallization and melting confined within thenanostructured particles were studied by using differential scanning calorimetry experiments.For the deeply cross-linkedsample(SCL-1),the crystallization of the PEO blocks was fully confined.The individual nanoparticles only crystallized atvery low crystallization temperatures(T_cs),wherein the homogenous primary nucleation determined the overallcrystallization rate.For the lightly cross-linked sample(SCL-2),the confinement effect was T_c dependent.At T_c(?)42℃,thecrystallization and melting behaviors of SCL-2 were similar to those of the pure PEO-b-PB diblock copolymer.At T_c>42℃,SCL-2 could form PEO lamellae thicker than those of the pure PEO-b-PB crystallized at the same T_c.

Confined Crystallization Behaviors of Cross-linked Comb-like Copolymers

Cross-linked PEG-based copolymers were obtained via synthesis of polyethylene glycol （PEG） and methoxy polyethylene glycol （MPEG） by the bridging and/or cross-linking agent of 2,4-tolylene diisocyanate （TDI） and/or hexamethylene-l,6-diisocyanate homopolymer （HDI trimer）. The effects on the crystallization behaviors of the samples could be found with the changes in molecular weight of MC-PEG and molecular weight of SC-PEG in certain cross-linked density. It is revealed that the samples appear not to crystallize when the molecular weight of MC-PEG and SC-PEG are 1000 g/mol or less than that. The samples begin to crystallize when the molecular weight of either MC-PEG or SC-PEG reaches 2000 g/mol. The crystallinity of crystallized MC-PEG decreases with the increasing molecular weight of uncrystallized SC-PEG and the crystallinity of crystallized SC-PEG declines with the rise of molecular weight of uncrystallizable MC-PEG. The chains of SC-PEG （M_n = 2000 g/mol） can fold and align easilier than those of MC-PEG （M_n = 2000 g/mol）, when the content of PEG is the same.

Microporous Organic Nanotube Networks from Hyper Cross-linking Core-shell Bottlebrush Copolymers for Selective Adsorption Study

We report a synthesis of microporous organic nanotube networks（MONNs） by a combination of hyper cross-linking and molecular templating of core-shell bottlebrush copolymers. The intrabrush and interbrush cross-linking of polystyrene（PS） shell layer in the core-shell bottlebrush copolymers led to the formation of micropores and large-sized nanopores（meso/macrospores） in MONNs, respectively, while selective removal of polylactide（PLA） core layer generated mesoporous tubular structure. The size of PLA-templated mesoporous cores and porous structure both at micro-and meso-scale could be controlled by simple tuning of the ratio of core/shell or the PLA core fraction in the bottlebrush precursors. Moreover, the resultant MONNs showed a highly selective adsorption capacity for the positively charged dyes on the basis of multi-porosity and carboxylate group-rich structure. In addition, MONNs also exhibited effective performance in size-selective adsorption of biomacromolecules. This work represents a new avenue for the preparation of MONNs and also provides a new application for molecular bottlebrushes in nanotechnology.

Studies on Immobilization of Aminoacylase From Aspergillus Oryzae on Macroporous Carriers

<正> Synthesized macroporous cross-linked copolymers of methyl acrylate-divinyl benzene (MA-DVB), acrylamide-N,N’-methylenebisacrylamide (AAM-BIS) and their functionalized products were used for immobilization of aminoacylase from Aspergillus oryzae. Effects of the carrier properties on the activity of immobilized aminoacylase were investigated and effects of substrate concentration, pH, phosphate buffer concentration and temperature on the immobilized aminoacylase were compared with those of the soluble aminoacylase. A column of immobilized aminoaoylase was prepared and used for continuous resolution of N-acyl-DL-methionine; the operational stability of immobilized enzyme was also investigated.