Polyoxometalate-based metal organic frameworks (POMOFs): structural trends, energetics, and high electrocatalytic efficiency for hydrogen evolution reaction

The grafting of the triangular 1,3,5-benzene tricarboxylate linkers (denoted trim) on tetrahedral ε-Keggin polyoxometalates (POMs) capped by Zn(II) ions, formed in situ under hydrothermal conditions, has generated three novel POM-based metal organic frameworks (POMOFs). (TBA)(3)[PMo(V)(8)Mo(VI)(4)O(36)(OH)(4)Zn(4)][C(6)H(3)(COO)(3)](4/3)·6H(2)O (ε(trim)(4/3)) is a 3D open-framework built of molecular Keggin units connected by trim linkers, with channels occupied by tetrabutylammonium (TBA) counterions. ε(trim)(4/3) is a novel (3,4)-connected net, named ofp for open-framework polyoxometalate, and computer simulations have been used to evaluate its relative stability in comparison with ctn- and bor-like polymorphs, showing the stability of this novel phase directly related to its greatest density. A computational study was also undertaken with the aim of locating TBA molecules, the positions of which could not be deduced from single crystal X-ray diffraction, and further rationalizes their structure directing role. In (TBA)(3)[PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)][C(6)H(3)(COO)(3)] (ε(2)(trim)(2)), the building unit is not the molecular Keggin but a dimerized form of this POM. Their connection via trim linkers generates a 3D framework with channels filled by TBA cations. In (TBA)(3)[PMo(V)(8)Mo(VI)(4)O(37)(OH)(3)Zn(4)][C(6)H(3)(COO)(3)]·8H(2)O ([ε(trim)](∞)), zigzag chains are connected via the organic linkers, forming 2D grids. Modified electrodes were fabricated by direct adsorption of the POMOFs on glassy carbon or entrapment in carbon paste (CPE). A remarkable electrocatalytic hydrogen evolution reaction (HER) was detected with a yield greater than 95%, and a turnover number as high as 1.2 × 10(5) was obtained after 5 h. The reported POMOF-based electrodes are more active than platinum, with a roughly 260 mV anodic shift. Finally, the electrocatalytic activities of ε(trim)(4/3)/CPE electrodes in various XCl (X = Li, Na, K, Cs) media have been studied. This allowed us to detect a cation effect and propose an electrocatalytic mechanistic pathway for the HER.     

Interfacial water on hydrophobic surfaces recognized by ions and molecules

Recent spectrophotometric and molecular dynamics simulation studies have shown that the physicochemical properties and structures of water in the vicinity of hydrophobic surfaces differ from those of the bulk water. However, the interfacial water acting as a separation medium on hydrophobic surfaces has never been detected and quantified experimentally. In this study, we show that small inorganic ions and organic molecules differentiate the interfacial water formed on the surfaces of octadecyl-bonded (C(18)) silica particles from the bulk water and the chemical separation of these solutes in aqueous media with hydrophobic materials can be interpreted with a consistent mechanism, partition between the bulk water phase and the interfacial water formed on the hydrophobic surface. Thermal transition behaviour of the interfacial water incorporated in the nanopores of the C(18) silica materials and the solubility parameter of the water calculated from the distribution coefficients of organic compounds have indicated that the interfacial water may have a structure of disrupted hydrogen bonding. The thickness of the interfacial water or the limit of distance from the hydrophobic surface at which molecules and ions can sense the surface was estimated to be 1.25 ± 0.13 nm from the volume of the interfacial water obtained by a liquid chromatographic method and the surface area, suggesting that the hydrophobic effect may extend beyond the first solvation shell of water molecules directly surrounding the surfaces.     

Efficient catalytic decomposition of sulfuric acid with copper vanadates as an oxygen-generating reaction for solar thermochemical water splitting cycles

Copper pyrovanadate (Cu(2)V(2)O(7)) was found for the first time to achieve the high catalytic activity for the decomposition of sulfuric acid to evolve O(2) at moderate temperatures around 650 °C, which is essential for the development of solar thermochemical water splitting cycles.     

Synthesis of a phloroacetophenon[4]arene consisting of four isomers via the one-pot,acid-catalysed condensation of phloroacetophenone with benzaldehyde

A phloroacetophenon[4]arene (3) consisting of four isomers was synthesised for the first time via the condensation of phloroacetophenone and benzaldehyde in a one-pot reaction with refluxing toluene in the presence of catalytic amounts of TsOH·H₂O for a maximum yield of 64%. The conformational elucidation of four isomers (3a–d) by ¹H NMR spectroscopy and X-ray crystal structure analysis showed them to be cone, partial cone, 1,3-alternate and 1,2-alternate types of conformations, respectively.     

2,4-Dioxo(dimercapto)-1,5-benzodiazepino-13-couronne-2, Nouveau Macrocycle Complexant de L'ion Ag +

We describe herein the synthesis of new macrocycles 5 et 6 derived from 1,5-benzodiazepine-2,4-dione in a heterogenous media using phase transfer catalysis conditions. A crystallographic study by x-ray of 5 was carried out to confirm the structure suggested; moreover the macrocycle 6 presents chelating properties with respect to the ion Ag + easily observed by IR and UV spectroscopies.     

Diffusion-weighted echo-planar imaging of the head and neck using 3-T MRI: Investigation into the usefulness of liquid perfluorocarbon pads and choice of optimal fat suppression method

Purpose

To investigate whether image quality can be improved using liquid perfluorocarbon pads (Sat Pad) and clarify the optimal fat-suppression method among chemical shift selective (CHESS), water excitation (WEX), and short TI inversion recovery (STIR) methods in diffusion-weighted imaging (DWI) of the head and neck using 3-T magnetic resonance imaging. Correlations between results of visual inspection and quantitative analysis were also examined.

Material and Methods

This study was approved by our Institutional Review Board and informed consent was waived. DWI was performed on 25 subjects with/without Sat Pad and using three fat-suppression methods (6 patterns). Image quality was evaluated visually (4-point scales and lesion-depiction capability) and by quantitative analysis (signal-to-noise ratio (SNR) and contrast-to-noise ratio (CNR)). Two-way repeated-measures analysis of variance (ANOVA) was used to detect significant differences in scores of visual evaluation, SNR, and CNR.

Results

Mean visual evaluation scores were significantly higher with Sat Pad using STIR than without Sat Pad for all fat-suppression methods (P < 0.05). DWI with Sat Pad using STIR tended to be useful for depicting lesions. DWI using STIR showed reduced W-SNR (W: whole area of depicted structure) and CNR (between semispinalis capitis muscle and subcutaneous fat) due to fewer artifacts and uniform fat suppression.

Conclusion

Combining Sat Pad with STIR provides good image quality for visual inspections. When numerous artifacts are present and fat suppression is insufficient, higher SNR and CNR do not always provide good diagnostic image quality.