Bodipy-Based Metal-Organic Frameworks Transformed in Solid States from 1D Chains to 2D Layer Structures as Efficient Visible Light Heterogeneous Photocatalysts for Forging C-B and C-C Bonds.

Boron dipyrromethene (also known as bodipy), as a class of versatile and robust fluorophores and a structural analogue of porphyrins, has received a great deal of interests in the field of light-harvesting and energy-transfer processes. However, the fabrication of bodipy monomers into metal-organic frameworks (MOFs) and the exploitation of their potential still lags behind the porphyrin MOFs. In this work, two bodipy-based MOFs, BMOF 1D with 1D chain structure and BMOF 2D with 2D layer structure, were assembled by using dicarboxyl-functionalized bodipy ligands. BMOF 1D can also be converted to BMOF 2D by inserting additional ligands into BMOF 1D to cross-link the adjacent chains into the rhombic grid layer. During this process, spontaneous exfoliation occurred simultaneously and resulted in the formation of several hundred nanometer thickness BMOF 2D (nBMOF 2D), which can be further exfoliated into one-layer MOF nanosheets (BMON 2D) by using the ultrasonic liquid exfoliation method in a high yield. Featuring the distinct bodipy scaffolds in the porous frameworks, both BMOF 2D and BMON 2D displayed high reactivity and recyclability in the photocatalytic inverse hydroboration and cross-dehydrogenative coupling reactions to afford α-amino organoborons and α-amino amides in moderate to high yields. This work not only highlights the cascade utilization of ligand installation and ultrasonic liquid exfoliation methods to provide the single-layer MOF sheets in high yields but also advances the bodipy-based MOFs as a new type of heterogeneous photocatalysts in the forging of C-B and C-C bonds driven by visible light.

A visible light/heat responsive covalent organic framework for highly efficient and switchable proton conductivity.

In recent years, covalent organic frameworks (COFs) have attracted enormous interest as a new generation of proton-exchange membranes, chemical sensors and electronic devices. However, to design high proton conductivity COFs, especially those with stimulus responsive performance remains a great challenge. Here, the first example of a light/heat switchable COF (COF-HNU9) has been synthesized by grafting a donor-acceptor Stenhouse adduct (DASA) within the channels of a ß-ketoenamine-based COF. DASA groups in the nanopores of COF-HNU9 undergo a reversible open-closed photoisomerization upon visible light irradiation and are recovered by heating. Thus, COF-HNU9 exhibits not only a remarkably high proton conductivity, but also a highly effective switching performance. Under visible light irradiation at 98% RH, the proton conductivity of COF-HNU9 increases by three orders of magnitude at 25 °C and is up to 0.02 S cm-1 at 80 °C. Furthermore, the proton conductivity does not display any significant decrease even after 20 switching cycles. These results have been rationalized by a Grotthuss-type mechanism and verified by DFT calculations. The stimuli-responsive COF is conceptually confirmed by an optical control device with the light/heat switching proton conductive COF-HNU9 film, which is able to remote-control the illumination and switching off of an LED lamp without any current amplifier.

Tailoring Multiple Sites of Metal-Organic Frameworks for Highly Efficient and Reversible Ammonia Adsorption.

The structural diversity and designability of metal-organic frameworks (MOFs) make these porous materials a strong candidate for NH3 uptake. However, to achieve a high NH3 capture capacity and good recyclability of MOFs at the same time remains a great challenge. Here, a multiple-site ligand screening strategy of MOFs is proposed for highly efficient and reversible NH3 uptake for the first time. Based on the optimized DFT results for various possible ligands, pyrazole-3,5-dicarboxylate with multiple sites was screened as the best ligand to construct robust MOF-303(Al) with Al3+. It is experimentally found that the NH3 adsorption capacity of MOF-303(Al) is as high as 19.7 mmol g-1 at 25.0 °C and 1.0 bar, and the NH3 capture is fully reversible and no clear loss of capture capacity is observed after 20 cycles of adsorption-desorption. Various spectral studies verify that the superior NH3 capacity and excellent recyclability of MOF-303(Al) are mainly attributed to the hydrogen bonding interactions of NH3 with multiple sites of MOF-303(Al).

Multifunctional Hf/Mn-TCPP Metal-Organic Framework Nanoparticles for Triple-Modality Imaging-Guided PTT/RT Synergistic Cancer Therapy.

BACKGROUND: Recent studies have validated and confirmed the great potential of nanoscale metal-organic framework (NMOF) in the biomedical field, especially in improving the efficiency of cancer diagnosis and therapy. However, most previous studies only utilized either the metal cluster or the organic ligand of the NMOF for cancer treatments and merely reported limited theranostic functions, which may not be optimized. As a highly designable and easily functionalized material, prospective rational design offers a powerful way to extract the maximum benefit from NMOF for cancer theranostic applications. MATERIALS AND METHODS: A NMOF based on hafnium (Hf) cluster and Mn(III)-porphyrin ligand was rational designed and synthesized as a high-performance multifunctional theranostic agent. The folic acid (FA) was modified on the NMOF surface to enhance the cancer targeting efficacy. The proposed "all-in-one" FA-Hf-Mn-NMOF (fHMNM) was characterized and identified using various analytical techniques. Then, in vitro and in vivo studies were performed to further explore the effects of fHMNM both as the magnetic resonance imaging (MRI)/computed tomography (CT)/photoacoustic imaging (PAI) contrast agent and as the photothermal therapy (PTT)/radiotherapy (RT) agent. RESULTS: A tumour targeting multifunctional fHMNM was successfully synthesized with high performance for MRI/CT/PAI enhancements and image-guided PTT/RT synergistic therapy properties. Compared with the current clinical CT and MR contrast agents, the X-ray attenuation and T1 relaxation rate of this integrated nanosystem increased 1.7-fold and 3-5-fold, respectively. More importantly, the catalase-like Mn(III)-porphyrin ligand can decompose H2O2 into O2 in tumour microenvironments to improve the synergistic treatment efficiency of PTT and RT. Significant tumour growth inhibition was achieved in mouse cancer models without obvious damage to the other organs. CONCLUSION: This work highlights the potential of fHMNM as an easily designable material for biomedical applications, could be an effective tool for in vivo detection and subsequent treatment of tumour.

Design and assembly of a chiral composite metal-organic framework for efficient asymmertric sequential transformation of alkenes to amino alcohols.

In this work, we report the successful construction of two chiral porous metal-metallosalan frameworks (1 and 2) by using dipyridylfunctionalized chiral Al(salen) and Mn(salen) separately, and then a composite crystal MOF 3 was constructed with 1 inside, which was encapsulated by 2 outside. The resulting composite crystal appeared to be highly enantioselective for the alkene epoxidation/epoxide aminolysis reactions with a maximum ee of 97%.

Chiral binary metal-organic frameworks for asymmetric sequential reactions.

Two chiral porous MOFs with precise and appropriate spatial arrangements of different metallosalen active sites are synthesized and used as efficient heterogeneous catalysts for asymmetric sequential alkene epoxidation/epoxide ring-opening reactions with enantioselectivity of up to 99%.

Chiral Covalent Organic Frameworks with High Chemical Stability for Heterogeneous Asymmetric Catalysis.

Covalent organic frameworks (COFs) featuring chirality, stability, and function are of both fundamental and practical interest, but are yet challenging to achieve. Here we reported the metal-directed synthesis of two chiral COFs (CCOFs) by imine-condensations of enantiopure 1,2-diaminocyclohexane with C3-symmetric trisalicylaldehydes having one or zero 3-tert-butyl group. Powder X-ray diffraction and modeling studies, together with pore size distribution analysis demonstrate that the Zn(salen)-based CCOFs possess a two-dimensional hexagonal grid network with AA stacking. Dramatic enhancement in the chemical stability toward acidic (1 M HCl) and basic (9 M NaOH) conditions was observed for the COF incorporated with tert-butyl groups on the pore walls compared to the nonalkylated analog. The Zn(salen) modules in the CCOFs allow for installing multivariate metals into the frameworks by postsynthetic metal exchange. The exchanged CCOFs maintain high crystallinity and porosity and can serve as efficient and recyclable heterogeneous catalysts for asymmetric cyanation of aldehydes, Diels-Alder reaction, alkene epoxidation, epoxide ring-opening, and related sequential reactions with up to 97% ee.

Multivariate Metal-Organic Frameworks as Multifunctional Heterogeneous Asymmetric Catalysts for Sequential Reactions.

The search for versatile heterogeneous catalysts with multiple active sites for broad asymmetric transformations has long been of great interest, but it remains a formidable synthetic challenge. Here we demonstrate that multivariate metal-organic frameworks (MTV-MOFs) can be used as an excellent platform to engineer heterogeneous catalysts featuring multiple and cooperative active sites. An isostructural series of 2-fold interpenetrated MTV-MOFs that contain up to three different chiral metallosalen catalysts was constructed and used as efficient and recyclable heterogeneous catalysts for a variety of asymmetric sequential alkene epoxidation/epoxide ring-opening reactions. Interpenetration of the frameworks brings metallosalen units adjacent to each other, allowing cooperative activation, which results in improved efficiency and enantioselectivity over the sum of the individual parts. The fact that manipulation of molecular catalysts in MTV-MOFs can control the activities and selectivities would facilitate the design of novel multifunctional materials for enantioselective processes.

Chiral Cu(salen)-Based Metal-Organic Framework for Heterogeneously Catalyzed Aziridination and Amination of Olefins.

A homochiral 3D porous metal-organic framework was assembled from a chiral dicarboxylic acid-functionalized Cu(salen)-based catalyst and could serve as an efficient heterogeneous catalyst for aziridination and allylic amination of olefins. Besides easy separation and reuse of the catalyst, the chiral framework confinement could impart substrate size selectivity, enhance catalyst activity, and induce product enantioselectivity.

A Cr(salen)-based metal-organic framework as a versatile catalyst for efficient asymmetric transformations.

A porous Cr(salen)-MOF can serve as an efficient and effective heterogeneous catalyst for a series of important asymmetric transformations including the Nazarov cyclization, aminolysis reaction, and Diels-Alder and hetero Diels-Alder reactions, resulting in comparable or superior diastereo- or enantioselectivity with respect to the corresponding homogeneous systems.

Direct and post-synthesis incorporation of chiral metallosalen catalysts into metal-organic frameworks for asymmetric organic transformations.

Two chiral porous metal-organic frameworks (MOFs) were constructed from [VO(salen)]-derived dicarboxylate and dipyridine bridging ligands. After oxidation of V(IV) to V(V) , they were found to be highly effective, recyclable, and reusable heterogeneous catalysts for the asymmetric cyanosilylation of aldehydes with up to 95 % ee. Solvent-assisted linker exchange (SALE) treatment of the pillared-layer MOF with [Cr(salen)Cl]- or [Al(salen)Cl]-derived dipyridine ligands led to the formation of mixed-linker metallosalen-based frameworks and incorporation of [Cr(salen)] enabled its use as a heterogeneous catalyst in the asymmetric epoxide ring-opening reaction.

[Glycometabolism of patients with depression at first episode].

OBJECTIVE: To investigate glycometabolism of patients with depression at first episode. METHODS: Oral glucose tolerance test (OGTT) was performed in 100 patients with depression at first episode and 50 healthy subjects; the levels of fast blood plasma insulin were also measured. RESULT: There were no statistically significant differences in fast blood plasma insulin levels and postprandial blood glucose levels at 0 h, 1 h and 3 h (P>0.05); the fasting blood glucose (FBS), postprandial blood glucose levels in 2 h and area under OGTT curve of depression patients were significantly higher than those of healthy controls. The frequency of impaired glucose tolerance (IGT) in depression patients was higher than that in controls (P<0.05). CONCLUSION: Depression patients at the first episode are abnormal in glycometabolism, which may have clinical implication.

Multiple topological isomerism of three-connected networks in silver-based metal-organoboron frameworks.

Three 3D Ag-based metal-organoboron frameworks with unprecedented multiple topological isomerism of 3-connected networks were assembled and could control the release of silver ions in biocidal concentration in solution giving excellent antibacterial activities and durability against gram-negative bacteria and gram-positive human pathogens.