Improved Catalytic Performance toward Selective Oxidation of Benzyl Alcohols Originated from New Open-Framework Copper Molybdovanadate with a Unique V/Mo Ratio.

A new organic-inorganic hybrid open-framework molybdovanadate with mixed-valences of vanadium (V4+ /V5+ =4/3) and molybdenum (Mo5+ /Mo6+ =8/2) cations has been synthesized. The complex possesses the unique V/Mo ratio (7/10), fascinating 8-C topological network and 1D 4-MR channels (7.793 Å×6.699 Å). Importantly, its catalytic activities for the selective oxidation of benzyl alcohol to benzaldehyde (oxidant: H2 O2 , 30 wt %) have been well evaluated. The results indicated that it exhibited improved catalytic activities (conv.: 96.8 %) compared with the catalyst (Cpyr)5 PV2 Mo5 W5 O40 [conv.: 88.51 %, Cpyr=(C16 H32 C5 H4 N)+ )], high recyclability and structural stability. Moreover, the conversions and selectivities (conv.: 82.4-92.5 %; sele.: 91.5-95.7 %) of the substrates containing electron donating groups (-OH, -CH3 , -OCH3 and -Cl) were significantly higher than those of the substrate containing electron withdrawing group (-NO2 ) (conv. 67.4 %; sele.: 80.8 %). This is due to the fact that the -NO2 with a large Hammett substituent constant is not conducive to the generation of transition state products. The studies revealed the complex could act as a highly efficient heterogeneous catalyst in selective oxidation of benzyl alcohols.

A highly efficient heterogeneous catalyst for selective oxidation of sulfides derived from an open-framework copper borovanadate containing a unique crown-shaped anion.

A novel 3D open-framework copper borovanadate with a unique crown-shaped anion [(VIVO)8(VVO)4B32O64(OH)8]12- and the largest ratio of Cu2+/borovanadate anions (6/1) has been successfully synthesized and systematically studied. The compound not only possesses high stability in a wide pH range of 3.2-10.8 (DMF solution), but also exhibits excellent catalytic activities for selective oxidation of sulfides.

Cost-Effective Machine Learning Based Clinical Pre-Test Probability Strategy for DVT Diagnosis in Neurological Intensive Care Unit.

In order to overcome the shortage of the current costly DVT diagnosis and reduce the waste of valuable healthcare resources, we proposed a new diagnostic approach based on machine learning pre-test prediction models using EHRs. We examined the sociodemographic and clinical factors in the prediction of DVT with 518 NICU admitted patients, including 189 patients who eventually developed DVT. We used cross-validation on the training data to determine the optimal parameters, and finally, the applied ROC analysis is adopted to evaluate the predictive strength of each model. Two models (GLM and SVM) with the strongest ROC were selected for DVT prediction, based on which, we optimized the current intervention and diagnostic process of DVT and examined the performance of the proposed approach through simulations. The use of machine learning based pre-test prediction models can simplify and improve the intervention and diagnostic process of patients in NICU with suspected DVT, and reduce the valuable healthcare resource occupation/usage and medical costs.

White light emission from a green cyclometalated platinum(ii) terpyridylphenylacetylide upon titration with Zn(ii) and Eu(iii ).

The cyclometalated Pt(ii) acetylide derivative with a 1,3-bis(N-octyl-benzimidazol-2-yl)benzene (N^C^N) ligand and a free terpyridine (TPY) receptor has been successfully synthesized and characterized. X-ray crystallography shows its inefficient conjugation degree between the [(N^C^N)Pt] and TPY planes. This bifunctional complex shows an enhanced 1MLCT/LLCT absorption band (ε = 3.30 × 104 dm3 mol-1 cm-1) centered at λmax = 365 nm, and the well-resolved vibronic-structured 3MLCT/LLCT emission bands (Φ = 0.08, τ = 3.43 µs) in the range of ca. 475-700 nm. Consecutive titrations show that added Zn2+ and Eu(HFA)3 bond to its free TPY receptor with 1 : 2 and 1 : 1 stoichiometry to form the heterotrinuclear Pt-Zn-Pt (Ka = 3.48 × 104 mol-1 dm3) and heterodinuclear Pt-Eu (Ka = 1.73 × 104 mol-1 dm3) complexes, respectively. A sensitizing effect of Zn2+ on the TPY unit, and the incomplete d → f energy transfer from the [(N^C^N)Pt(ii)] antenna donor to the Eu(iii) center with maximum efficiency of 51.8% are observed. Using an in situ mixed titration strategy, the R/G/B emission triads consisted of red [(TPY)Eu(HFA)3] and green [(N^C^N)Pt(ii)] dual phosphorescence and blue [(TPY)Zn(TPY)] fluorescence, which can be well balanced to realize the white-light-emission with CIE coordinates (x = 0.36, y = 0.36) by precisely controlling the molar ratio (9 : 1 : 2) of the parent complexes, Eu(HFA)3 and Zn(ClO4)2.

CsBP2O6(OH)2: a second-order NLO material with a unique borophosphate anionic partial structure and strong SHG effect.

A noncentrosymmetric (NCS) alkali-metal borophosphate CsBP2O6(OH)2 (CBPO) containing a unique borophosphate anionic partial structure has been obtained through a mixed-solvent thermal method. Its structure could be regarded as a 1-D chain that is built by Cs+ cations and a unique anionic chain [BP2O6(OH)2]∞n- composed of BO4 and PO3(OH) groups. CBPO possesses a wide UV-vis transparent range and shows a strong SHG response. Moreover, we have well explored and established the origin of the SHG effect by dipole moment and PDOS calculations. This work will help inspire and stimulate scientists to discover more such excellent NLO materials.

A Novel Open-Framework Copper Borovanadate with Enhanced Catalytic Performance for Oxidation of Benzylic C-H Bond.

A novel open-framework copper borovanadate, with a 6-connected topological net and 1D 8-membered ring channels, has been obtained for the first time. The compound not only exhibits a unique -B3 O7 (OH)-Cu-B(OH)3 linkage and features the largest ratio between TM2+ (Cu2+ ) and the borovanadate anion, but also possesses enhanced catalytic performance, high recyclability, and stability during the oxidation of benzylic C-H bonds.

Series d-f Heteronuclear Metal-Organic Frameworks: Color Tunability and Luminescent Probe with Switchable Properties.

A series of five unique d-f heteronuclear luminescent metal-organic frameworks (MOFs) in an entangled polyrotaxane array and the light-harvesting block homonuclear zinc compound have been isolated successfully and characterized. The series of isostructural polymers feature 3,4-connected (4.82)(4.83.92)(6.8.9)2(6.92)(83) topology and high stability, exhibiting diverse void spaces. By taking advantage of the isostructural MOFs 2 and 3, the intensities of red and green emissions can be modulated by adjusting the ratios of EuIII and TbIII ions correspondingly, and white-light emission can be generated by a combination of different doped TbIII and EuIII concentrations. The Tb-Zn-based framework {[Tb3Zn6(bipy2)2(Hmimda)7 (H2O)3]·5H2O}n (3; H3mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid and bipy = 4,4'-bipyridine) can detect trace MgII ion with relatively high sensitivity and selectivity. Dehydrated MOF 3a shows a remarkable emission quenching effect through the introduction of I2 solids. Further investigation indicates that it exhibits turn on/off switchable properties for small solvent molecules or heavy-metal ions. Steady/transient-state near-IR luminescence properties for MOFs 1, 4, and 5 were investigated under visible-light excitation.

Cd3(MoO4)(TeO3)2: A Polar 3D Compound Containing d10-d0 SCALP-Effect Cations.

The new polar 3D cadmium molybdotellurite Cd3(MoO4)(TeO3)2 was obtained by means of a high-temperature solid-state method. Cd3(MoO4)(TeO3)2 is a monoclinic crystal system, and it exhibits the polar space group P21 (No. 4). The structure of Cd3(MoO4)(TeO3)2 can be viewed as a complicated 3D architecture that is composed of distorted CdOn (n = 6, 7) polyhedra, TeO3 trigonal pyramids, and MoO4 polyhedra. The compound features the first 3D NCS cadmium molybdotellurite with 1D 4- and 6-MR channels and a polar structure originating from the TeO3 groups, MoO4 groups, and displacements of d10 Cd2+ cations. The results were further confirmed by calculations of the net polarization. The UV-vis spectrum and thermal properties indicate that Cd3(MoO4)(TeO3)2 exhibits a broad transparent region and excellent thermal stability. SHG tests of Cd3(MoO4)(TeO3)2 revealed that its response is approximately the same as that of KH2PO4 at the same grain size between 105 and 150 µm and that it is phase-matchable.

Employing a new 12-connected topological open-framework copper borovanadate as an effective heterogeneous catalyst for oxidation of benzyl-alkanes.

A new 12-connected topological open-framework copper borovanadate with a unique B/V ratio (20/12) and a -B3O7(OH)-Na(µ-OH)[B(OH)2]-B3O7(OH)- connection mode has been hydrothermally obtained and characterized. It not only features the first 3-D copper(II) borovanadate which possesses the largest ratio of TM(2+) and borovanadate anion, but also displays highly catalytic activities for the oxidation of benzyl-alkanes.

Organotemplate-free synthesis of two open-framework metal borophosphates.

Two new isostructural metal borophosphates, |K2(H2O)|[CoB2P3O12(OH)] [M = Co (1), Ni (2)], have been hydrothermally synthesized with non-polluting K(+) ions instead of organic template-ethylenediamine. The two metal borophosphates are isostructural and constructed by the connection of tetrahedral layers and MO6 octahedra, giving rise to the 3-D intersecting 8-ring channels along the [010] direction. The negative charge of the framework is compensated by the K(+) ions located in the 8-ring channels. Like ethylenediamine, the K(+) ions also play an important structural directing role in the formation of the open framework. The framework shows a high thermal stability and is stable upon calcination at ca. 400 and 500 °C for 1 and 2, respectively. Considering the motion of K(+) ions, ionic conductivities of the two compounds were performed. The results indicated that they have similar activation energies of 0.94-1.09 eV and conductivities of 6.76 × 10(-8)-9.88 × 10(-8) S cm(-1) at 320 °C.

Near-IR Electrochromic Film Prepared by Oxidative Electropolymerization of the Cyclometalated Pt(II) Chloride with a Triphenylamine Group.

A cyclometalated platinum chloride [(L)PtCl] {L = 4-[p-(diphenylamino)phenyl]-6-phenyl-2,2'-bipyridine} was successfully synthesized and characterized by (1)H NMR, (13)C NMR, MALDI-TOF MS, elemental analysis, and X-ray crystallography. Its oxidative electropolymerization proceeds smoothly on the working Pt and ITO electrodes by cyclic voltammetry. The film thickness can be easily tuned by controlling the CV scan number. The orange hybrid polymer film shows the nondiffusion-controlled redox processes and a unusually inverse dependence of ac impedance on its thickness. As a result of switching of the MLCT/ICT and dication absorption transitions, the adherent metallopolymer film exhibits the low-voltage-controlled anodic coloration near-IR electrochromism with significant optical contrast ratio (ΔT% = 88.8% at 820 nm), fast response time (1.9 s for the coloration step and 2.3 s for the bleaching step), and high coloration efficiency (CE = 363.3 C(-1)·cm(2)).

A new linear bismuth coordination polymer based on 1,10-phenanthroline-2,9-dicarboxylic acid: ionothermal synthesis, crystal structure and fluorescence properties.

A new linear bismuth(III) coordination polymer, catena-poly[[chloridobismuth(III)]-µ3-1,10-phenanthroline-2,9-dicarboxylato-κ(6)O(2):O(2),N(1),N(10),O(9):O(9)], [Bi(C14H6N2O4)Cl]n, has been obtained by an ionothermal method and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR spectroscopy, thermal stability studies and single-crystal X-ray diffraction. The structure is constructed by Bi(C14H6N2O4)Cl fragments in which each Bi(III) centre is seven-coordinated by one Cl atom, four O atoms and two N atoms. The coordination geometry of the Bi(III) cation is distorted pentagonal-bipyramidal (BiO4N2Cl), with one bridging carboxylate O atom and one Cl atom located in the axial positions. The Bi(C14H6N2O4)Cl fragments are further extended into a one-dimensional linear polymeric structure via subsequent but different centres of symmetry (bridging carboxylate O atoms). Neighbouring linear chains are assembled via weak C-H···O and C-H···Cl hydrogen bonds, forming a three-dimensional supramolecular architecture. Intermolecular π-π stacking interactions are observed, with centroid-to-centroid distances of 3.678 (4) Å, which further stabilize the structure. In addition, the solid-state fluorescence properties of the title coordination polymer were investigated.

A new 3-D open-framework cadmium borovanadate with plane-shaped channels and high catalytic activity for the oxidation of cyclohexanol.

A new 3-D open-framework cadmium borovanadate with 6-connected topology was hydrothermally obtained and structurally characterized. It not only features new cadmium(II) borovanadate which possesses an open-framework structure with unique plane-shaped channels, but also exhibits interesting absorption properties and high catalytic activities for the oxidation of cyclohexanol.

A linear heterometallic bismuth-copper coordination polymer containing two types of organic ligands.

In the linear coordination polymer catena-poly[[[aqua(1,10-phenanthroline-κ(2)N,N')copper(II)]-µ-pyridine-2,6-dicarboxylato-κ(4)O(2):O(2'),N,O(6)-[(nitrato-κ(2)O,O')bismuth(III)]-µ-pyridine-2,6-dicarboxylato-κ(4)O(2),N,O(6):O(6')] dihydrate], {[Bi(III)Cu(II)(C7H3NO4)2(NO3)(C12H8N2)(H2O)]·2H2O}n, the Bi(III) cation is O,N,O'-chelated by the two pyridine-2,6-dicarboxylate ligands and O,O'-chelated by the nitrate anion, the nine coordinating atoms conferring a tricapped trigonal prismatic environment on the metal centre. Each pyridine-2,6-dicarboxylate ligand uses one of its carboxylate O atoms to bind to an aqua(1,10-phenanthroline)copper(II) unit, the Cu-O dative bonds giving rise to the formation of a ribbon motif. The Cu(II) cation exhibits a square-pyramidal geometry. The ribbon motif propagates along the shortest axis of the triclinic unit cell and the solvent water molecules are hydrogen bonded to the same ribbon.

Reticular three-dimensional 3d-4f frameworks constructed through substituted imidazole-dicarboxylate: syntheses, luminescence and magnetic properties study.

A family of heteronuclear metal organic frameworks (MOFs) using lanthanide and transition metal ion based on a rigid ligand of substituted imidazoledicarboxylic acid, namely, {[Ln2Zn2 (µ3-Hmimda)2 (µ3-mimda)2·4H2O]n·mn H2O}, Ln = Nd, m = 2 (1), Ln = Ho, m = 3 (2), Ln = Er, m = 2 (3), Ln = Yb, m = 3 (4), [Tb2Co2(µ3-Hmimda)2 (µ3-mimda)2·4H2O]n·2nH2O} (5) and [Dy2Co2 (µ3-Hmimda)2 (µ3-mimda)2·4H2O]n·nH2O} (6), (H3mimda = 1H-2-methyl-4,5-imidazole-dicarboxylic acid), have been developed and characterized. All the complexes (except for a little disparity for 1) are isostructural, and all crystallize in the monoclinic system. They possess an extended reticular-like porous structure constructed from corrugated 2D layers. Direct current (dc) magnetic susceptibility measurements for 1-5 indicated depopulation of the Stark components at low temperature and/or possible weak anti-ferromagnetic interactions within hetero-nuclear MOFs. Alternating current (ac) susceptibility studies reveal that the Dy(III)-Co(II) complex exhibits both possible ferromagnetic couplings and frequency-dependent out-of-phase signals, behaviour of single-ion magnet nature. Fluorescence properties of series complexes both in near-infrared (NIR) and visible regions have been comparatively studied.

A novel open-framework copper borophosphate containing 1-D borophosphate anion with 10-MR windows and 12-MR channels.

A novel open-framework copper borophosphate, Na5KCu3[B9P6O33(OH)3]·H2O (), has been synthesised by a boric acid flux method. Its structure can be viewed as a 3-D open framework constructed by the connection of Cu(II)O6 octahedra and 1-D (4,4)-connected borophosphate anionic structures composed of trigonal-planar BO2(OH) groups, tetrahedral BO4 and PO4 groups. The compound not only features a novel borophosphate anionic partial structure containing 1-D 12-MR channels, but also exhibits ferromagnetic interactions and high catalytic activity for the oxidative degradation of chitosan.

A novel dinuclear bismuth(III) coordination compound: bis(µ-pyridine-2,6-dicarboxylato)-κ4O2,N,O6:O6';κ4O2:O2',N,O6-bis[(azido-κN)(1,10-phenanthroline-κ2N,N')bismuth(III)] tetrahydrate.

A novel dinuclear bismuth(III) coordination compound, [Bi2(C7H3NO4)2(N3)2(C12H8N2)2]·4H2O, has been synthesized by an ionothermal method and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR, X-ray photoelectron spectroscopy and single-crystal X-ray diffraction. The molecular structure consists of one centrosymmetric dinuclear neutral fragment and four water molecules. Within the dinuclear fragment, each Bi(III) centre is seven-coordinated by three O atoms and four N atoms. The coordination geometry of each Bi(III) atom is distorted pentagonal-bipyramidal (BiO3N4), with one azide N atom and one bridging carboxylate O atom located in axial positions. The carboxylate O atoms and water molecules are assembled via O-H···O hydrogen bonds, resulting in the formation of a three-dimensional supramolecular structure. Two types of π-π stacking interactions are found, with centroid-to-centroid distances of 3.461 (4) and 3.641 (4) Å.

A novel alkaline earth strontium(II) coordination polymer: poly[hexaaquatetrakis(µ5-pyridine-2,6-dicarboxylato)bis(µ4-pyridine-2,6-dicarboxylato)(µ7-sulfato)heptastrontium(II)].

The title compound, [Sr7(C7H3NO4)6(SO4)(H2O)6]n, has been synthesized by an ionothermal method using the ionic liquid 1-ethyl-3-methylimidazolium ([Emim]Br) as solvent, and characterized by elemental analysis, energy-dispersive X-ray spectroscopy, IR and single-crystal X-ray diffraction. The structure of the compound can be viewed as a three-dimensional coordination polymer composed of Sr(2+) cations, pyridine-2,6-dicarboxylate anions, sulfate anions and water molecules. The compound not only exhibits a three-dimensional structure with a unique coordination mode of the sulfate anion, but also features the first example of a heptanuclear strontium(II) coordination polymer. The structure is further stabilized by O-H···O hydrogen bonds and π-π stacking interactions.

Enclosed passive infraversion lavage-drainage system (EPILDS): a novel safe technique for local management of early stage bile leakage and pancreatic fistula Post Pancreatoduodenectomy.

This study's objective was to test the new drainage apparatus called enclosed passive infraversion lavage-drainage system (EPILDS) in the treatment of bile leakage and pancreatic fistula Post Pancreatoduodenectomys. The EPILDS device has a design of a siphon. The inlet bag that contains the rinse liquid is put lower than the abdominal lacuna to be washed but higher than the outlet bag. The hydrostatic pressure difference between the inlet and outlet bags constitutes the driving force of the flow. The three-way cock valves are installed in the inlet and outlet tubes to facilitate the washing of occluded tubes. Two side by side Penrose drainage tubes were placed during the operation. One tube passed through the posterior side of pancreatico-jejunal and biliary-jejunal anastomoses, right paracolic gutter, and exited through an opening made in the right lower abdomen. Second tube came from the smaller sac, went through the anterior side of pancreatico-jejunal and biliary-jejunal anastomoses, and exited through an opening made in the left upper abdomen. Using this system, we successfully treated two patients. Both inlet and outlet volumes were observed to verify that the outlet exceeds the inlet volume. In conclusion, EPILDS has a simple and practical design. It changes the active washing process into a passive one, in which the input is controlled by the exiting fluid. This is the effective and safe system for treatment of severe bile leakage and pancreatic fistula at the early postoperative stage.

catena-Poly[bis(µ-2,2'-bipyridin-6-olato)-κ³N,N':O;O:N,N'-dicopper(I,II) [[tetrafluoridoniobium(V)]-µ-oxido]].

A novel copper-niobium oxyfluoride, {[Cu2(C10H7N2O)2][NbOF4]}n, has been synthesized by a hydrothermal method and characterized by elemental analysis, EDS, IR, XPS and single-crystal X-ray diffraction. The structural unit consists of one C2-symmetric [NbOF4]⁻ anion and one centrosymmetric coordinated [Cu2(obpy)2]⁺ cation (obpy is 2,2'-bipyridin-6-olate). In the [NbOF4]⁻ anion, each NbV metal centre is five-coordinated by four F atoms and one O atom in the first coordination shell, forming a square-pyramidal coordination geometry. These square pyramids are then further connected to each other via trans O atoms [Nb-O = 2.187 (3) Å], forming an infinite linear {[NbOF4]⁻}n polyanion. In the coordinated [Cu2(obpy)2]⁺ cation, the oxidation state of each Cu site is disordered, which is confirmed by the XPS results. The disordered Cu sites are coordinated by two N atoms and one O atom from two different obpy ligands. The [NbOF4]⁻ and [Cu2(obpy)2]⁺ units are assembled via weak C-H∙∙∙F hydrogen bonds, resulting in the formation of a three-dimensional supramolecular structure. π-π stacking interactions between the pyridine rings [centroid-centroid distance = 3.610 (2) Å] may further stabilize the crystal structure.