Charge-Assisted Hydrogen-Bonded Organic Frameworks with Inorganic Ammonium Regulated Switchable Open Polar Sites.

Surface open polar sites within the voids of porous molecular crystals define the localized physicochemical environment for critical functions such as gas separation and molecular recognition. This study presents a new charge-assisted hydrogen bonding (H-bonding) motif, by exploiting inorganic ammonium (NH4 + ) cations as H-bond donors, to regulate the assembly of C2 -symmetric carboxylic tectons for building robust H-bonded frameworks with permanent ultra-micropores and open oxygen sites. Diverse building blocks are bridged by tetrahedral NH4 + to expand distinctive H-bonded networks with varied pore architectures. Particularly, the open polar oxygen sites can be switched by altering NH4 + sources to tune the deprotonation of carboxyl-containing tectons. The activated porous PTBA·NH4 ·DMF preserves the pore architecture and open polar oxygen sites, exhibiting remarkably selective sorption of CO2 (107.8 cm3 g-1 ,195 K) over N2 (11.2 cm3 g-1 , 77 K) and H2 (1.4 cm3 g-1 , 77 K).

Multi-scale computer-aided design and photo-controlled macromolecular synthesis boosting uranium harvesting from seawater.

By integrating multi-scale computational simulation with photo-regulated macromolecular synthesis, this study presents a new paradigm for smart design while customizing polymeric adsorbents for uranium harvesting from seawater. A dissipative particle dynamics (DPD) approach, combined with a molecular dynamics (MD) study, is performed to simulate the conformational dynamics and adsorption process of a model uranium grabber, i.e., PAOm-b-PPEGMAn, suggesting that the maximum adsorption capacity with atomic economy can be achieved with a preferred block ratio of 0.18. The designed polymers are synthesized using the PET-RAFT polymerization in a microfluidic platform, exhibiting a record high adsorption capacity of uranium (11.4 ± 1.2 mg/g) in real seawater within 28 days. This study offers an integrated perspective to quantitatively assess adsorption phenomena of polymers, bridging metal-ligand interactions at the molecular level with their spatial conformations at the mesoscopic level. The established protocol is generally adaptable for target-oriented development of more advanced polymers for broadened applications.

Localized Surface Plasmon Resonance Meets Controlled/Living Radical Polymerization: An Adaptable Strategy for Broadband Light-Regulated Macromolecular Synthesis.

The photophysical process of localized surface plasmon resonance (LSPR) is, for the first time, exploited for broadband photon harvesting in photo-regulated controlled/living radical polymerization. Efficient macromolecular synthesis was achieved under illumination with light wavelengths extending from the visible to the near-infrared regions. Plasmonic Ag nanostructures were in situ generated on Ag3 PO4 photocatalysts in a reversible addition-fragmentation chain transfer (RAFT) system, thereby promoting polymerization of various monomers following a LSPR-mediated electron transfer mechanism. Owing to the LSPR-enhanced broadband photon harvesting, high monomer conversion (>99 %) was achieved under natural sunlight within 0.8 h. The deep penetration of NIR light enabled successful polymerization with reaction vessels screened by opaque barriers. Moreover, by trapping active oxygen species generated in the photocatalytic process, polymerization could be implemented without pre-deoxygenation.

An ultrathin photosensitizer for simultaneous fluorescence imaging and photodynamic therapy.

An ultrathin photosensitizer was prepared by immobilization of chlorin e6 (Ce6) and carbon dots (CDs) onto layered double hydroxide (LDH) nanosheets, which exhibited excellent fluorescence imaging and photodynamic therapy performance toward cancer theranostics.

Layered double hydroxide bio-composites toward excellent systematic anticancer therapy.

Multi-therapeutic methodologies have attracted considerable attention toward cancer therapy, which can overcome the limitation of a single therapy and achieve an optimized anticancer efficacy. Herein, we prepared a systematic anticancer drug by intercalating zinc phthalocyanines (ZnPc) into a layered double hydroxide (LDH) gallery, followed by loading doxorubicin (DOX) on the surface (denoted as ZnPc-DOX/LDH). ZnPc is accommodated in the interlayer region of the LDH, which results in a largely enhanced photodynamic therapeutic (PDT) efficiency; while the physisorbed DOX affords a chemotherapeutic effect. In vitro tests performed with KB cells indicate a synergistic anticancer performance as well as excellent biocompatibility compared with pristine ZnPc and DOX. This study demonstrates a promising bio-composite for PDT-chemotherapy systematic therapy, which shows potential application in the field of cancer therapy.