Color-Tunable Binary Copolymers Manipulated by Intramolecular Aggregation and Hydrogen Bonding.

Construction of color-tunable luminescent polymeric materials with enhanced emission intensity and room-temperature phosphorescence (RTP) performance regulated by a single chromophore component is highly desirable in the scope of photoluminescent materials. Herein, a set of binary copolymers were facilely synthesized using free radical polymerization by selecting different types of polymer matrix and N-substituted naphthalimides (NPA) as chromophores. Surprisingly, the fluorescence emission of copolymers could be remarkably enhanced, because of the intramolecular aggregation of NPA manipulated by a single polymer chain in both solution and solid state. Moreover, RTP signals of binary copolymers were all clearly observed in the air without any processing procedure, because of the embedding of phosphors into hydrogen bonding networks after copolymerization with vinyl-based acrylamide monomers. Taking advantages of the synergistic effect of copolymerization-induced aggregation and copolymerization-induced rigidification to promote optical performance, UV stimulus-responsive luminescent polymer films with processability, flexibility, and adjustable emission wavelength were simply prepared using a drop-casting method in large scale, the setting of which is the basis for application in the fields of organic optoelectronics, information security, and bioimaging/sensing.

Tale of COF-on-MOF Composites with Structural Regulation and Stepwise Luminescence Enhancement.

Integrating metal-organic framework (MOF)-covalent organic framework (COF) allows versatile engineering of hybrid materials with properties superior to pristine components, especially COFs suffered from aggregation-caused quenching (ACQ), unlocking more possibilities to improve the luminescence of COFs. In this work, we prepared various MOF@COF composites with different COF layer thicknesses, in which stable UiO-66-NH2 served as the inner substrate and 1,3,5-benzenetricarboxaldehyde (BT), and 3,3'-dihydroxybenzidine (DH) were used to construct a COF layer. In addition to the conventional preparation method, we increased the ratio of BT and DH to be 1:2.5, and impressively, the morphologies of acquired UC (1:2.5) materials were quite different from the previous reticular structure and gradually extended from the spherical structure to the prickly structure with the increase of COF monomers. Remarkably, all of the UC materials possessed better luminescence properties than individual COF due to the limited COF layers. Meanwhile, UC-1 materials with an optimal COF layer displayed the strongest emission. In comparison with a single COF, the quantum yields of UC-1 and UC-1 (1:2.5) were increased nearly 7 times and 5 times, respectively. Moreover, the fluorescence of UC-1 materials was progressively enhanced via selective F- sensing. This work is expected to shed light on the potential hybridization of MOF-COF with structural adjustment, morphological design, and luminescence enhancement.

Tunable fluorescence emission based on multi-layered MOF-on-MOF.

Luminescent metal-organic frameworks (MOFs) have garnered considerable attention in various fields. Herein, we proposed a hierarchical confinement strategy based on MOF-on-MOF to tune luminescence emission ranging from blue to red including white light in a flexible way. The easily available ZIF-8 MOF was used as a host for the confinement of two kinds of size-matching dyes (perylene and rhodamine B) to obtain a layered ZIF-8@dye@ZIF-8@dye via in situ encapsulation and seed-mediated synthesis. ZIF-8@dye@ZIF-8@dye materials with different fluorescence emission in dispersed and solid states were both obtained by tuning the initial encapsulation concentration of dye and changing the structure of the inner and outer ZIF-8@dye layers. To our delight, ZIF-8@0.125perylene@ZIF-8@25RhB with white light emission in the dispersed state was obtained; meanwhile, ZIF-8@0.125perylene + 25RhB and mechanically mixed ZIF-8@0.125perylene + ZIF-8@25RhB could not realize white light emission under the same conditions, indicating that the proposed hierarchical confinement strategy facilitated white light regulation. Similarly, the emission of ZIF-8@dye@ZIF-8@dye in the solid state has also been investigated; ZIF-8@perylene@ZIF-8@3RhB with white light emission was obtained, while white light emission could not be achieved in ZIF-8@perylene + 3RhB and ZIF-8@perylene + ZIF-8@3RhB, which further indicated the importance of the hierarchical confinement strategy based on MOF-on-MOF. The proposed hierarchical confinement strategy may also inspire the development of other functional optical MOF materials.

Construction and Sensing Amplification of Raspberry-Shaped MOF@MOF.

MOFs@MOFs (metal-organic frameworks, MOFs) possess precise customized functionalities and predesigned structures that enable the implementation of structure and property regulation for specific functions in comparison to traditional single MOFs. However, the synthesis and fluorescence properties of multilayer MOFs@MOFs are still worth improving. Herein, a fluorescent raspberry-shaped MOF@MOF was constructed via optimized seed-mediated synthesis by tuning the reaction time, reaction mode, and reaction concentration, involving the initial synthesis of the UiO-66-NH2 core and then the coating of the UiO-67-bpy shell. The raspberry-shaped UiO-66@67-bpy showed stable fluorescence and desirable sensing selectivity for the Hg2+ ion under the interference of other ions; meanwhile, the raspberry-shaped UiO-66@67-bpy indicated amplified sensing performance than pure UiO-66-NH2, mechanically mixed UiO-66-NH2 + UiO-67-bpy, and UiO-66@UiO-67 counterpart due to the accumulation effect of outer UiO-67-bpy toward Hg2+. Density functional theory (DFT) calculations including adsorption energy calculations and electronic density difference analysis further showed that the enhanced fluorescence quenching was possibly attributed to the outer UiO-67-bpy enrichment promoting the charge transfer between Hg2+ and the ligands of fluorescent UiO-66@67-bpy. The synergistic effect of MOFs@MOFs unlocks more possibilities for the construction of enhanced sensors and other applications.

Core-Shell MOFs@MOFs: Diverse Designability and Enhanced Selectivity.

Metal-Organic frameworks (MOFs), especially MOF-based composites, performed an irreplaceable role in the material fields. By virtue of the tailorability of MOFs, core-shell MOFs@MOFs composites with diverse designability and enhanced selectivity have inspired infinite scientific interest. This review will highlight an up-to-date overview of the designability and enhanced selectivity of core-shell MOFs@MOFs composites, covering the synthetic strategies of an epitaxial growth method, postsynthetic modification, and one-pot synthesis as well as the synergistic selective performance of the synthesized MOFs@MOFs in catalysis, adsorption and separation, and molecular recognition. Finally, the potential development trend and challenges toward core-shell MOFs@MOFs are addressed.

N-doped carbon dots covalently functionalized with pillar[5]arenes for Fe3+ sensing.

Fluorescent N-doped carbon dots (CN-dots) covalently functionalized with carboxylatopillar[5]arene (CP[5]), namely CCDs, have been prepared the first time. Compared with CN-dots without pillarene units, the newly constructed fluorescent CCDs could recognize Fe3+ with high selectivity. Therefore, such CCDs can potentially serve as a promising chemical sensor for Fe3+ ions.

Multifunctional Supramolecular Materials Constructed from Polypyrrole@UiO-66 Nanohybrids and Pillararene Nanovalves for Targeted Chemophotothermal Therapy.

Multifunctional supramolecular nanomaterials capable of targeted and multimodal therapy hold great potential to improve the efficiency of cancer therapeutics. Herein, we report a proof-of-concept nanoplatform for effective chemophotothermal therapy via the integration of folic acid-based active targeting and supramolecular nanovalves-based passive targeting. Inspired by facile surface engineering and designable layer-by-layer assembly concept, we design and synthesize PPy@UiO-66@WP6@PEI-Fa nanoparticles (PUWPFa NPs) to achieve efficient synergistic chemophotothermal therapy, taking advantage of the desirable photothermal conversion capability of polypyrrole nanoparticles (PPy NPs) and high drug-loading capacity of hybrid scaffolds. Significantly, pillararene-based pseudorotaxanes as pH/temperature dual-responsive nanovalves allow targeted drug delivery in pathological environment with sustained release over 4 days, which is complementary to photothermal therapy, and folic acid-conjugated polyethyleneimine (PEI-Fa) at the outmost layer through electrostatic interactions is able to enhance tumor-targeting and therapeutic efficiency. Such PUWPFa NPs showed efficient synergistic chemophotothermal therapy of cervical cancer both in vitro and in vivo. The present strategy offers not only the distinctly targeted drug delivery and release, but also excellent tumor inhibition efficacy of simultaneous chemophotothermal therapy, opening a new avenue for effective cancer treatment.

Multistimuli Responsive Core-Shell Nanoplatform Constructed from Fe3 O4 @MOF Equipped with Pillar[6]arene Nanovalves.

An intelligent theranostic nanoplatform based on nanovalve operated metal-organic framework (MOF) core-shell hybrids, incorporating tumorous microenvironment-triggered drug release, magnetic resonance imaging (MRI) guidance, sustained release, and effective chemotherapy in one pot is reported. The core-shell hybrids are constructed by an in situ growth method, in which Fe3 O4 particles with superior abilities of MRI and magnetic separation form the core and UiO-66 MOF with high loading capacity compose the shell, and then are surface-installed with pillararene-based pseudorotaxanes as tightness-adjustable nanovalves. This strategy endows the system with the ability of targeted, multistimuli responsive drug release in response to pH changes, temperature variations, and competitive agents. Water-soluble carboxylatopillar[6]arene system achieved sustained drug release over 7 days due to stronger host-guest binding, suggesting that the nanovalve tightness further reinforces the desirable release of anticancer agent over a prolonged time at the lesion site.

Polymer Nanoassembly as Delivery Systems and Anti-Bacterial Toolbox: From PGMAs to MSN@PGMAs.

Researches on cargo delivery systems have received burgeoning attention and advanced rapidly. For synthetic nanodevices, polymer nanoassemblies and their inorganic-organic hybrid materials, especially smart mesoporous silica nanoparticle (MSN)-polymer hybrids (e. g., MSN@PGMAs), have attracted increasing attention in recent years. Their superior characteristics and unique features such as dynamic transition of morphology endow them the ability to efficiently entrap cargo molecules and undergo smart cargo delivery and release in response to various external stimuli. In this Personal Account, we present our recent research progress in the construction of cargo delivery systems based on polymers, poly(glycidyl methacrylate) (PGMA) and its derivatives in particular, ranging from polymer nanoparticles, reverse micelles, to vesicles and reverse vesicles, and their performance in the delivery and controlled release of model molecules and therapeutic agents. Significantly, MSN-PGMA hybrid nanoassemblies (MSN@PGMAs), constructed with the aid of atom transfer radical polymerization, host-guest interactions, or layer-by-layer self-assembly techniques, and their potential bio-related applications and anti-bacterial applications as new nanocarriers are reviewed. Finally, the prospects and challenges of such nanoplatforms are also discussed.

Metal-Organic Framework (MOF)-Based Drug/Cargo Delivery and Cancer Therapy.

Metal-organic frameworks (MOFs)-an emerging class of hybrid porous materials built from metal ions or clusters bridged by organic linkers-have attracted increasing attention in recent years. The superior properties of MOFs, such as well-defined pore aperture, tailorable composition and structure, tunable size, versatile functionality, high agent loading, and improved biocompatibility, make them promising candidates as drug delivery hosts. Furthermore, scientists have made remarkable achievements in the field of nanomedical applications of MOFs, owing to their facile synthesis on the nanoscale and alternative functionalization via inclusion and surface chemistry. A brief introduction to the applications of MOFs in controlled drug/cargo delivery and cancer therapy that have been reported in recent years is provided here.