Photoinduced electron/energy transfer–reversible addition–fragmentation chain transfer (PET–RAFT) polymerization represents a versatile and highly efficient method for polymerizations of wide-ranging monomer variances upon solar energy harvesting. Although significant progress has been achieved, several drawbacks are still associated with existing photocatalysts, such as toxicity of transition metals, high cost, poor stability, and unavoidable purification procedures because of the photobleaching effect, to name a few. Herein, 1,4-diethynylbenzene-linked xanthene dye-conjugated porous polymers (CPPs) have been established as potential heterogenous photocatalysts of PET–RAFT polymerization. With this two-dimensional planar architecture, we demonstrate dual-stimuli toggling of RAFT polymerization using two different external physical manipulations: light “ON”/“OFF” and solution pH “LOW”/“HIGH”. In addition, these CPPs endowed radical polymerizations with various impressive features such as compatibility of diverse monomer formulations, unique oxygen tolerance, and ppm-level catalyst dosage. Demonstrations of chain extension and catalyst recycling further highlight the robustness and performance of this CPP catalyst. Through the study of structure–property relationship using the experimental analyses, we envisage that a series of xanthene dye-functionalized CPPs can be developed as visible light-absorbing organocatalysts rivaling transition-metal photocatalysts.

This study examined the unique and interactive effects of various career-specific parenting practices (i.e., parental career support, interference, and lack of engagement) on Chinese high school students’ career decision-making self-efficacy (CDSE) as well as the mediating role of autonomy in such associations. Based on data from 641 Chinese high school students (47.6% male; mean age = 15.28 years old, SD = 0.49) in 2016, two moderated mediating effects were identified. Higher level of parental career engagement strengthened the positive association between parental career support and adolescents’ autonomy, which in turn, was associated positively with adolescents’ CDSE. Parental career interference related negatively with adolescents’ CDSE via autonomy when lack of parental career engagement was low, but related positively with adolescents’ CDSE via autonomy when lack of parental career engagement was high. These findings advance our understanding of the underlying processes between career-specific parenting practices and adolescents’ CDSE. Implications for practices were discussed.

Light-driven polymerization, such as photoinduced electron/energy transfer−reversible addition−fragmentation chain transfer (PET-RAFT) polymerization, enables biological benign conditions and versatile functional polymer structure design, which is readily used in protein−polymer bioconjugates. However, conventional metalloporphyrinic homogeneous catalysts for PET-RAFT polymerization suffer from limited aqueous solubility and tedious purification. Here we demonstrate the design of PET-RAFT photocatalyst from the reticular assembled Zr−porphyrinic metal−organic frameworks (MOFs), along with a biomacromolecule-based chain transfer agent, as efficient bioconjugation tools in water. Our methodology offers manufacturing advantages on bioconjugates under mild conditions such that MTT (3-[4,5dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) and cytotoxicity assays have shown the preservation of the protein integrity, bioactivity, and high cell viability after PET-RAFT polymerization. We find that the fast kinetics are benefiting from the ultrahigh loading of metalloporphyrins in MOF-525-Zn. This heterogeneous catalyst also allows us to maintain living characteristics to incorporate myriads of monomers into block copolymers. Other advantages like easy postreaction purification, reusability, and high oxygen tolerance even in an open system are demonstrated. This study provides a tool of highly efficient heterogeneous photocatalysts for polymer−protein bioconjugation in aqueous media and paves the road for biological applications.

Given the scalability and vast applicability of the heterogeneous catalysts and the burgeoning interests in biorelated applications, the interpenetrating polymer network catalysts will facilitate the realization of green, precise and efficient polymerization.

Magnetic Janus nanocomposites enabled robust toggling of RAFT photopolymerization of myriad monomer formulations using a single nanocatalyst with three orthogonal external physical manipulations.