A stable photoactive metal-organic framework UiO-66(Zr) sensitized by adsorbed or directly added rhodamine B dye exhibited photocatalytic activity for hydrogen evolution under visible-light illumination (λ≥ 420 nm). Using Pt as a co-catalyst, the adsorbed and directly added dye extremely enhanced the photocatalytic activity to 30 and 26 times the value afforded by bare Pt@UiO-66(Zr), respectively.

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We demonstrated that embedding of CdS on MOFs could significantly increase the photocatalytic efficiency of CdS for visible light-driven hydrogen production.

As the [2Fe] H subsite models of [FeFe]-hydrogenases, a series of PNP-chelated and -bridged diiron dithiolate complexes 1a−f and 2a−f together with the three related monophosphine complexes 3a−c were prepared by the selective substitutions of the all-carbonyl complex Fe 2 (μpdt)(CO) 6 (A, pdt = SCH 2 CH 2 CH 2 S) with aminodiphosphines (Ph 2 P) 2 NR (denoted as PNP) under different reaction conditions. The first UV irradiation of the toluene solutions of A with different PNP ligands (PNP = (Ph 2 P) 2 NR; R = (CH 2 ) 3 Me, (CH 2 ) 3 NMe 2 , (CH 2 ) 3 Si(OEt) 3 , C 6 H 5 , C 6 H 4 OMe-p, C 6 H 4 CO 2 Me-p) readily afforded the target PNP-chelated complexes Fe 2 (μ-pdt)(CO) 4 {(κ 2 -Ph 2 P) 2 NR} (1a−f), while the reflux of xylene solutions of A with the aforementioned PNP ligands produced the PNP-bridged complexes Fe 2 (μ-pdt)(CO) 4 {(μ-Ph 2 P) 2 NR} (2a−f). Comparatively, treatments of A and one type of PNP ligand with N-aryl substituents R (R = C 6 H 5 , C 6 H 4 OMe-p, C 6 H 4 CO 2 Me-p) in MeCN at room temperature in the presence of the decarbonylating agent Me 3 NO•2H 2 O formed the unexpected monophosphine complexes Fe 2 (μ-pdt)(CO) 5 {κ 1 -Ph 2 P(NHR)} (3a−c) and the minor chelated complexes 1d−f. All of the complexes 1a−f, 2a−f, and 3a−c have been characterized by elemental analysis, FT-IR, NMR spectroscopy, and particularly for 1a,b,d−f, 2b,d−f, and 3b by X-ray crystallography. Additionally, the electrochemical and electrocatalytic properties of complexes 1a and 2a as a pair of representative isomers have been evaluated and compared by cyclic voltammetry in MeCN as solvent in the absence and presence of HOAc as a proton source.

As a further exploration of the asymmetrically substituted diiron models for the active site of [FeFe]hydrogenases, two new types of small bite-angle aminodiphosphine [(Ph 2 P) 2 NR; denoted as PNP in this study]chelated diiron N-phenyl-aza-and ethanedithioate complexes Fe 2 (μ-xdt)(CO) 4 {κ 2 -(Ph 2 P) 2 NR} (1a−1e) and (2a−2e), respectively, were successfully synthesized by the carbonyl substitution reactions of all-carbonyl diiron complexes Fe 2 (μxdt)(CO) 6 (xdt = SCH 2 N(Ph)CH 2 S (adt NPh ) and SCH 2 CH 2 S (edt)) with PNP (PNP = (Ph 2 P) 2 NR, R = CMe 3 , CH 2 CHMe 2 , (CH 2 ) 3 Me, (CH 2 ) 3 Si(OEt) 3 , and (CH 2 ) 3 NMe 2 ) in the presence of Me 3 NO•2H 2 O or UV irradiation.All the new complexes obtained above have been well characterized by elemental analysis, FT-IR, NMR spectroscopy, and particularly for 1a, 1b, 2a, and 2d by single-crystal X-ray diffraction analysis. By comparison, 31 P{ 1 H} NMR and X-ray crystallographic studies have clearly revealed that the change of the dithiolate bridge from adt NPh to edt has a significant influence on the coordination geometry of the chelating PNP ligands in Fe 2 S 2 complexes, in which the basal−basal configuration in the adt NPh complexes 1a−1e is favorable whereas the apical−basal conformation in the edt complexes 2a−2e is main. In addition, the electrochemical properties of complexes 1b and 2b as a pair of representative counterparts are evaluated and compared by cyclic voltammetry in the absence and presence of HOAc as a proton source, indicating that they are found to be electrocatalytically active.

The construction of efficient enzyme mimetics for the hydrolysis of peptide bonds in proteins is challenging due to the high stability of peptide bonds and the importance of proteases in biology and industry. Metal-organic frameworks (MOFs) consisting of infinite crystalline lattices with metal clusters and organic linkers may provide opportunities for protease mimic which has remained unknown. Herein, we report that Cu2(C9H3O6)4/3 MOF (which is well known as HKUST-1 and denoted as Cu-MOF here), possesses an intrinsic enzyme mimicking activity similar to that found in natural trypsin to bovine serum albumin (BSA) and casein. The Michaelis constant (Km) of Cu-MOF is about 26,000-fold smaller than that of free trypsin indicating a much higher affinity of BSA for Cu-MOF surface. Cu-MOF also exhibited significantly higher catalytic efficiency than homogeneous artificial metalloprotease Cu(II) complexes and could be reused for ten times without losing in its activity. Moreover, Cu-MOF was successfully used to simulate trypsinization in cell culture since it dissociated cells in culture even without EDTA.

Soybean [Glycine max (L.) Merr.] stalk-based biochar was prepared using oxygen-limited pyrolysis. We evaluated phenanthrene (PHE) and Hg(II) sorption, from single and binary component solutions, onto prepared biochar. We found that the prepared biochar efficiently removed PHE and Hg(II) from aqueous solutions. The isotherms for PHE and Hg(II) sorption could be described using linear and Tóth models, respectively, both with high regression coefficients (R(2) > 0.995). When PHE and Hg(II) coexisted in an aqueous solution, we observed direct competitive sorption, each one suppressing another. Our results provide insight into the recycling of agricultural residues, and also a new application for removal of polycyclic aromatic hydrocarbons and heavy metals from contaminated water utilizing biochar from agricultural residue.

Though metal-organic frameworks (MOFs) have inspired potential applications in biomedicine, cytotoxicity studies of MOFs have been relatively rare. Here we demonstrate for the first time that an easily available MOF, Fe-MIL-101, possesses intrinsic activity against human SKOV3 ovarian cancer cells and suppress the proliferation of SKOV3 cells (IC50 = 23.6 μg mL−1) and normal mouse embryonic fibroblasts (BABL-3T3, IC50 = 78.3 μg mL−1) cells. It was more effective against SKOV3 cells than typical anticancer drugs such as artesunate (ART, IC50 = 96.9 μg mL−1) and oxaliplatin (OXA, IC50 = 64.4 μg mL−1), but had less effect on normal BABL-3T3 cells compared with ART (IC50 = 36.6 μg mL−1) and OXA (IC50 = 13.8 μg mL−1). Fe-MIL-101 induced apoptosis of human umbilical vein endothelial cells (HUVECs) via G0/G1 cell cycle arrest and decreased the mitochondrial membrane potential in HUVECs and induced apoptosis. Furthermore, Fe-MIL-101 exhibited stronger antiangiogenic effects in HUVEC cells than antiangiogenic inhibitor (SU5416) via downregulation the expression of MMP-2/9. Our results reveal a new role of Fe-MIL-101 as a novel, non-toxic anti-angiogenic agent that restricted ovarian tumour growth. These findings could open a new avenue of using MOFs as potential therapeutics in angiogenesis-dependent diseases, including ovarian cancer.