Metal–organic frameworks (MOFs) are an interesting and useful class of coordination polymers, constructed from metal ion/cluster nodes and functional organic ligands through coordination bonds, and ...have attracted extensive research interest during the past decades. Due to the unique features of diverse compositions, facile synthesis, easy surface functionalization, high surface areas, adjustable porosity, and tunable biocompatibility, MOFs have been widely used in hydrogen/methane storage, catalysis, biological imaging and sensing, drug delivery, desalination, gas separation, magnetic and electronic devices, nonlinear optics, water vapor capture, etc. Notably, with the rapid development of synthetic methods and surface functionalization strategies, smart MOF‐based nanocomposites with advanced bio‐related properties have been designed and fabricated to meet the growing demands of MOF materials for biomedical applications. This work outlines the synthesis and functionalization and the recent advances of MOFs in biomedical fields, including cargo (drugs, nucleic acids, proteins, and dyes) delivery for cancer therapy, bioimaging, antimicrobial, biosensing, and biocatalysis. The prospects and challenges in the field of MOF‐based biomedical materials are also discussed.
The synthesis and functionalization of metal–organic frameworks (MOFs) for biomedical applications in the delivery of cargos (drugs, nucleic acids, proteins, and dyes) for cancer therapy, bioimaging, antimicrobial, biosensing, and biocatalysis are overviewed, and the development prospects and challenges of MOF‐based theranostic systems are also discussed.
With the rapid development of materials science, porous organic polymers (POPs) have received remarkable attentions because of their unique properties such as the exceptionally high surface area and ...flexible molecular design. The ability to incorporate specific functions in a precise manner makes POPs promising platforms for a myriad of applications in molecular adsorption, separation, and catalysis. Therefore, many different types of POPs have been rationally designed and synthesized to expand the scope of advanced materials, endowing them with distinct structures and properties. Recently, supramolecular macrocycles with excellent host–guest complexation abilities are emerging as powerful crosslinkers for developing novel POPs with hierarchical structures and improved performance, which can be well‐organized at different spatial scales. Macrocycle‐based POPs could have unusual porous, adsorptive, and optical properties when compared to their nonmacrocycle‐incorporated counterparts. This cooperation provides valuable insights for the molecular‐level understanding of skeletal complexity and diversity. Here, the research advances of macrocycle‐based POPs are aptly summarized by showing their syntheses, properties, and applications in terms of separation, sensing, and catalysis. Finally, the current challenging issues in this exciting research field are delineated and a comprehensive outlook is offered for their future directions.
Macrocycles as an emerging class of building blocks are used for porous organic polymers owing to their easy functionalization, unique host–guest properties, modifiable conformations, and tunable chemistry. Facilitated by these features, macrocycle‐based porous organic polymers have attracted considerable attentions in the construction of advanced porous materials and excelled in adsorptive separation, optical sensing, and heterogeneous catalysis.
Severe disease and environmental pollution derived from heavy metal ions has become one of the major problems in global public health. In particular, mercury(II) as one type of highly poisonous ...pollutant can destroy human metabolism, central nervous system, and immune system, representing a critical threat to living systems. Therefore, exploitation of new strategies for designing and synthesizing eco‐friendly, efficient, and economical materials for selective detection and removal of Hg2+ is of great importance. Among the various measures for sensing, detection, and removal of mercury ions, advanced functional systems including nanomaterials, polymers, aggregation‐induced emission luminogens, and porous materials have attracted considerable attention over the past years due to their capabilities of real‐time detection, rapid removal, great anti‐interference, quick response, high selectivity, and low limit of detection. In this review, some efficient techniques and strategies for the detection and removal of mercury in aqueous solutions using the abovementioned functional materials are overviewed and the ways in which these advanced material systems are used to tackle the problem of mercury pollution are also discussed.
The recent advanced systems of mercury(II) ion detection and removal based on nanomaterials, polymers, AIEgens, and porous materials are summarized according to their quick response, high sensitivity, outstanding selectivity, and favorable removal efficiency as sensing platforms. Meanwhile, the development prospects, opportunities, and challenges in the field are also discussed.
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.
Important research progress of metal–organic framework (MOF)‐based drug/cargo delivery systems and their applications in the field of materials science and biomedicine are introduced, especially in terms of cancer theranostics. This is illustrated by individual MOFs, stimuli‐responsive MOFs, and multifunctional MOFs. Additionally, the challenges and development directions of such nanoplatforms are discussed.
A luminescent conjugated macrocycle polymer (CMP) with strong two‐photon fluorescence property, namely, P5‐TPE‐CMP, is constructed from ditriflate‐functionalized pillar5arene and a ...1,1,2,2‐tetrakis(4‐ethynylphenyl)ethylene (TPE) linker through a Sonogashira–Hagihara cross‐coupling reaction. Significantly, in sharp contrast with the corresponding conjugated microporous polymer without synthetic macrocycles, P5‐TPE‐CMP shows an outstanding stability against photobleaching and exhibits highly selective cation sensing capability toward Fe3+ at different excitation wavelengths (both UV and red–near‐infrared regions). Meanwhile, its fluorescence could also be sufficiently quenched by 4‐amino azobenzene, a frequently used organic dye that is certified to be carcinogenic, as compared with a group of common organic compounds. This work paves a new way for enhancing the properties of porous organic polymers through the introduction of supramolecular macrocycles like macrocyclic arenes.
Conjugated macrocycle polymers are first constructed from ditriflate‐functionalized pillararene and a 1,1,2,2‐tetrakis(4‐ethynylphenyl)ethylene linker through a Sonogashira–Hagihara cross‐coupling reaction. They show excellent two‐photon fluorescence (TPF) and serve as a highly efficient TPF sensor for metal ions and organic molecules.
One of the major pursuits of biomedical science is to develop advanced strategies for theranostics, which is expected to be an effective approach for achieving the transition from conventional ...medicine to precision medicine. Supramolecular assembly can serve as a powerful tool in the development of nanotheranostics with accurate imaging of tumors and real‐time monitoring of the therapeutic process upon the incorporation of aggregation‐induced emission (AIE) ability. AIE luminogens (AIEgens) will not only enable fluorescence imaging but will also aid in improving the efficacy of therapies. Furthermore, the fluorescent signals and therapeutic performance of these nanomaterials can be manipulated precisely owing to the reversible and stimuli‐responsive characteristics of the supramolecular systems. Inspired by rapid advances in this field, recent research conducted on nanotheranostics with the AIE effect based on supramolecular assembly is summarized. Here, three representative strategies for supramolecular nanomaterials are presented as follows: a) supramolecular self‐assembly of AIEgens, b) the loading of AIEgens within nanocarriers with supramolecular assembly, and c) supramolecular macrocycle‐guided assembly via host–guest interactions. Meanwhile, the diverse applications of such nanomaterials in diagnostics and therapeutics have also been discussed in detail. Finally, the challenges of this field are listed in this review.
Nanotheranostics constructed from aggregation‐induced emission luminogens via supramolecular assembly have been extensively studied during the past decades and exhibit great potential in personalized and precision medicine. This advanced strategy also facilitates the development of integrated systems combining diagnosis and therapy.
The exploitation of new materials for adsorptive separation of industrially important hydrocarbons is of great importance in both scientific research and petrochemical industry. Nonporous adaptive ...crystals (NACs) as a robust class of synthetic materials have drawn much attention during the past five years for their superior performance in adsorption and separation. Pillararenes are the main family of macrocyclic arenes used for NACs construction, where the structure–function relationship has been intensively studied. In the past two years, some emerging types of synthetic macrocyclic arenes have been successfully brought into this research field, showing the gradual enrichment and diversification of NACs materials. This Minireview summarizes the recent advances of synthetic macrocycle‐based NACs, which are categorized by various practical applications in molecular separation. Besides, NACs‐based vapochromic supramolecular systems are also discussed. Finally, future perspectives and challenges of NACs are given. We envisage that this Minireview will be a useful and timely reference for those who are interested in new molecular and supramolecular crystals for storage and separation applications.
This Minireview describes the recent advances of synthetic macrocycle‐based nonporous adaptive crystals for molecular separation and vapochromic application.
Conjugated macrocycle polymers (CMPs) integrated using the macrocyclic confinement effect make imposing restrictions feasible on the growth of metal nanoparticles with confined size and high ...dispersion. For a proof‐of‐concept exploration, a novel nanoscale CMP is reported, denoted as DMP5‐TPP‐CMP, comprising two representative types of macrocyclic compounds, i.e., pillararene and porphyrin, as alternating strut/node components in the skeleton. With abundant anchoring sites, CMP implanted with Pd nanoparticles (Pd@DMP5‐TPP‐CMP, Pd@CMP for short) is successfully obtained through a simple post‐treatment, exhibiting remarkable catalytic activity in Suzuki–Miyaura coupling (SMC) and nitrophenol reduction. The as‐prepared Pd@CMP material shows favorable performance in expediting the process of SMC with an appreciable yield even under mild conditions, as well as in facilitating the electron transfer process from borohydride to nitrophenol through metal–hydride complex to produce aminophenol with a very short transformation time of 3 min and superior apparent kinetic rate constant k
app of 1.9 × 10−2 s−1, higher than most palladium supports. Significantly, this multifunctional Pd@CMP composite material not only enriches the family of CMPs, but also sheds light on the development of green catalysts with excellent stability and easy recyclability without deactivation.
Conjugated macrocycle polymer nanoparticles consisting of dual macrocyclic compounds (pillarene and porphyrin) as alternating strut/node components in the skeleton are first prepared, followed by the immobilization of Pd nanoparticles via a simple post‐treatment method. The resulting composite nanomaterials exhibit excellent stability, remarkable catalytic activity, and easy recyclability in Suzuki–Miyaura coupling and nitrophenol reduction.
Nanotechnology has attracted much attention because it possesses many advantages to engineer new organized nanomaterials and endow them with improved performance. In recent decades, mesoporous silica ...nanoparticles (MSNs) have been proven to be excellent solid supports owing to their superior properties. Molecular and supramolecular switches have also received a lot of interest in the past decade on account of their unique features. Materials derived from the combination of MSNs as solid supports and molecular/supramolecular switches as movable entities have emerged in the literature and are playing prominent roles in materials science nowadays. Thus, in this review, we chose to gather significant and typical examples of intelligent materials, which comprise MSNs surface-immobilized with molecular and supramolecular switches, and overview their wide applications in many fields such as controlled release of cargo molecules for disease therapy and cell imaging. Utilizing the switching ability of molecular and supramolecular switches, smart hybrid nanomaterials are endowed with intelligently controllable properties in response to a variety of external stimuli such as pH variation, enzyme, light irradiation, temperature, redox, magnetic field, competition, and ultrasound. In order to rationalize the presentation concisely, we will introduce molecular switches and supramolecular switches cooperated with MSNs based on their different features and the actuations they are responsive for.
This review summarizes the recent advances of molecular and supramolecular switches installed on mesoporous silica nanoparticles.
The design and synthesis of new synthetic macrocycles has driven the rapid development of supramolecular chemistry and materials. Pillarnarenes, as a new type of macrocyclic compounds, are used as a ...promising type of building blocks for switchable supramolecular systems due to their versatile functionalization and the ability of binding toward various guest molecules. A number of guests can form inclusion complexes with pillarnarenes and their derivatives in solution, which are sensitive to different external triggers. Interestingly, the pursuit of complex stimuli‐responsive functional materials and devices has largely motivated the shift of pillarnarene‐based switches from solution media to surfaces for controllable macroscopic motions on solid platforms. Facilitated by the facile modification of pillarnarenes on various solid supports and the dynamic binding of host–guest complexes, numerous functional hybrid materials with adjustable physical or chemical properties and integrated functionalities have been reported in the last decade. Here, the advance of supramolecular switches in solution and on surfaces based on pillarnarenes and derivatives with an emphasis on the efforts and the latest contributions from the field is discussed.
The supramolecular switches based on pillarnarene derivatives that have been investigated in solution and further shifted to the solid surfaces of materials for collective amplified motions controlled by actuations are reviewed. The afforded materials present combined features of stimuli‐responsiveness of pillarnarene‐based switches and intrinsic properties of solid supports and show applications in various aspects.
