Conjugated porous polymers (CPPs) are a class of amorphous polymer networks that are, in their design, fully cross-linked and fully π-conjugated. The cross-linked nature of CPPs means that they have ...permanent intrinsic porosity (on the nanometer scale), which, in combination with the fully π-conjugated framework, makes these materials unique among the wider class of porous polymeric materials. In recent years, the need for new and efficient functional materials has driven the development of CPPs as versatile platforms for applications including (photo)catalysis, light harvesting, gas separation and storage, chemosensing, environmental remediation and energy storage. The efficiency of these materials towards these described applications is heavily influenced by the choice of molecular building blocks and synthetic conditions, allowing for facile tailoring and optimisation of the structure and properties. The aim of this review is to highlight select works on CPPs, including basic structural design principles, various synthetic protocols and topical applications of these versatile materials.
This review discusses conjugated porous polymers and focuses on relating design principles and synthetic methods to key properties and applications such as (photo)catalysis, gas storage, chemical sensing, energy storage and environmental remediation.
Hollow nanostructures have attracted significant research interest in drug delivery systems due to their high capacities for drug loading and unique physicochemical properties, showing great ...potential in specific biomedical applications. Herein, hollow porphyrinic metal–organic framework (H-PMOF) nanoparticles with a mesoporous spherical shell have been fabricated via a facile self-sacrificial ZIF-8 nanoparticle template strategy. The H-PMOF nanoplatform not only demonstrates a greatly enhanced photodynamic therapy efficacy compared with nonhollow porphyrinic MOF nanoparticles but also can be used as a superior drug carrier to co-load doxorubicin (DOX) and indocyanine green (ICG) with an ultrahigh drug-loading capacity of 635%. Furthermore, cancer cell membrane camouflage of the (DOX and ICG)@H-PMOF composite nanoparticles affords a biomimetic nanoplatform, that is, (DOX and ICG)@H-PMOF@mem (DIHPm for short), with an outstanding homologous tumor-targeting and immune-escaping ability. Interestingly, DIHPm shows both pH-controlled and near-infrared laser-triggered DOX release. Both in vitro and in vivo studies of DIHPm demonstrate an excellent imaging-guided synergistic photodynamic/photothermal/chemotherapy anticancer activity with negligible systemic toxicity. The development of the high-performance H-PMOF nanoplatform provides new insights into the design of MOF-based multifunctional nanomedicines for combination cancer therapy and precise theranostics.
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We successfully assembled the photocatalytic titanium-oxo cluster and photosensitizing porphyrinic linker into a metal-organic framework (MOF), namely PCN-22. A preformed titanium-oxo carboxylate ...cluster is adopted as the starting material to judiciously control the MOF growth process to afford single crystals. This synthetic method is useful to obtain highly crystalline titanium MOFs, which has been a daunting challenge in this field. Moreover, PCN-22 demonstrated permanent porosity and photocatalytic activities toward alcohol oxidation.
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Calix[4]arene 3d/4f Magnetic Cooler Karotsis, Georgios; Evangelisti, Marco; Dalgarno, Scott J ...
Angewandte Chemie (International ed.),
December 21, 2009, Volume:
48, Issue:
52
Journal Article
Peer reviewed
Chilling out: The first 3d/4f cluster based on calix4arenes (see picture; purple Mn, brown Gd, red O, blue N) has a high magnetic isotropy and a large number of molecular spin states that are ...populated even at low temperatures, whereas its ferromagnetic limit is approached only at high applied fields. These results enable the complex to be an excellent magnetic refrigerant for low‐temperature applications.
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Seemingly non-porous organic solids have the ability for guest transport and have also been shown to absorb gases, including hydrogen, methane and acetylene, to varied extents. These materials also ...show potential for gas separation technology, display remarkable water transport through hydrophobic crystals, and clearly show that molecules within crystals are capable of cooperating with guests as they move through non-porous environments. This work is presented within a broader topic which also encompasses crystal engineering and (microporous) metal-organic frameworks (MOF's).
With increasing concerns for the environmental impact of chemical manufacturing, reagents and processes that align with the principles of green chemistry are essential. The fundamental oxidation of ...organic substrates is no exception and in this report three distinct modes of green oxidation are demonstrated in a vortex fluidic device (VFD) under continuous flow: aerobic oxidation, oxidation using chlorine bleach, and oxidation using hydrogen peroxide. The VFD, which is a thin film microfluidic platform, revealed clear advantages in these oxidations in comparison to traditional batch reactor processing: Efficient mass transfer of gases in the dynamic thin film increased the rate of aerobic oxidations, and the intense micromixing allowed multi-phase oxidations to proceed efficiently, obviating the need for organic solvents and phase transfer catalysts. In addition, the rapid dissipation of heat in the VFD also improved the safety profile and stereoselectivity for exothermic oxidations.
A breathing 2-fold interpenetrated microporous metal−organic framework was synthesized with a flexible tetrahedral organic linker and Zn2 clusters that sorb CO2 preferably over N2 and H2
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Reaction of Gd(OAc)3·4H2O, salicylaldehyde and CH3ONa in MeCN/MeOH affords Gd12Na6(OAc)25(HCO2)5(CO3)6(H2O)12·9H2O.0.5MeCN (1·9H2O.0.5MeCN), whose structure describes a quadruple-wheel consisting of ...two {Na3} and two {Gd6} rings. The magnetic properties of 1 reveal very weak antiferromagnetic interactions between the GdIII ions, which give rise to a record magnetocaloric effect at low applied magnetic fields and low temperatures. The magnetic entropy change reaches −ΔS m= 29.3 J kg–1 K–1 for full demagnetization from B = 1 T at T = 0.5 K.
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Photodynamic therapy (PDT) is a promising strategy for cancer treatment. However, its efficiency is hindered by three key parameters, namely, limited penetration depth of external light, tumor ...hypoxia, and self-aggregation of photosensitizers. Herein, we fabricated a novel “all-in-one” chemiluminescence-PDT nanosystem through the integration of an oxygen-supplying protein (hemoglobin, Hb) and a luminescent donor (luminol, Lum) in hierarchically engineered mesoporous porphyrinic metal–organic framework (MOF) nanoparticles. Mechanistically, the in situ chemiluminescence of Lum is activated by the high concentration of H2O2 in 4T1 cancer cells and further catalyzed by Hb and then absorbed by the porphyrin ligands in MOF nanoparticles through chemiluminescence resonance energy transfer. The excited porphyrins then sensitize oxygen supplied by Hb to produce sufficient reactive oxygen species that kill cancer cells. The MOF-based nanocomposite demonstrates excellent anticancer activity both in vitro and in vivo, with eventually a 68.1% tumor inhibition rate after intravenous injections without external light irradiation. This self-illuminating, oxygen-self-supplying nanosystem integrates all essential components of PDT into one simple nanoplatform, demonstrating great potential for the selective phototherapy of deep-seated cancer.
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