A pyrene-modified cobalt salophen complex immobilized on multiwalled carbon nanotubes acting as a precursor for efficient electrocatalytic water oxidation.

Immobilization of earth-abundant water oxidation catalysts (WOCs) on carbon supports to produce functional electrodes for electrochemical water splitting is a crucial approach for future clean energy production. Herein we report the non-covalent immobilization of a pyrene-bearing cobalt(ii) Schiff base complex (2) on the surface of multiwalled carbon nanotubes (MWCNTs) to form a hybrid anode for electrocatalytic water oxidation. The 2/MWCNT anode displayed excellent catalytic activity and durability in neutral aqueous solution, and a catalytic current density of 1.0 mA cm-2 was achieved at 1.15 V vs. the normal hydrogen electrode (NHE), corresponding to a low overpotential of 330 mV. A Tafel slope of 96 mV per decade was obtained. The Faradaic efficiency of oxygen evolution was more than 90% by bulk electrolysis measurement. After bulk electrolysis, the hybrid anode characterization using X-ray photoelectron spectroscopy (XPS) confirmed that complex 2 decomposed to form heterogeneous cobalt hydroxides and the cobalt hydroxides should be true catalytic active species, which are responsible for electrocatalytic oxygen evolution.

Characterization of a new subtype of allergen in dermatophagoides farinae-Der f 28.

BACKGROUND: House dust mites (HDMs) are the major sources of indoor allergens which induce asthma, dermatitis, rhinitis, and some other allergic diseases. Close to 30 sub-allergens have been identified. METHODS: Through analyzing the full genome sequence of dust mite, a new allergen whose primary structure belongs to the heat shock protein family was identified. The sequence of this allergen was determined by cDNA cloning. The allergenicity was assayed by skin prick test, Western-blot and enzyme-linked immunosorbent assay (ELISA). RESULTS: r-Der f 28 bound to serum IgE from mite allergic patients. Positive responses to r-Der f 28 were shown in 11.5% by skin prick testing from 26 DM-allergic patients. Airway hyperresponsiveness, serum specific IgE and IL-4 were significantly increased in allergic asthma mouse model sensitized to r-Der f 28. CONCLUSIONS: Der f 28 is a new subtype of allergen in dermatophagoides farinae.

Immunohistochemical identification of osteoclasts and multinucleated macrophages.

Osteoclasts are bone-resorbing multinuclear cells derived from hematopoietic stem cells which are specialised to carry out lacunar bone resorption. The immunophenotype of giant cell-containing bone lesions in a wide range of osteoclast-like giant cells was similarly assessed. Both multinucleated macrophages and osteoclasts were found to express CD68. Multinucleated macrophages, but not osteoclasts, expressed GrB and Ki67. CD13+/CD14+/CD68+/GrB-/Ki67-/CD56- all giant-cell lesions noted in giant cells of bone. Giant cells have an osteoclast phenotype in most giant cell-rich lesions of bone, which do not express the macrophage-associated antigens GrB and Ki67. Our results indicate that they are formed from osteoclast precursors of mononuclear phagocyte.

A two-dimensional hydrogen-bonded water layer in the structure of a cobalt(III) cubane complex.

A tetranuclear Co(III) oxide complex with cubane topology, tetrakis(2,2'-bipyridine-κ(2)N,N')di-µ2-carbonato-κ(4)O:O'-tetra-µ3-oxido-tetracobalt(III) pentadecahydrate, [Co4(CO3)2O4(C10H8N2)4]·15H2O, with an unbounded hydrogen-bonded water layer, has been synthesized by reaction of CoCO3 and 2,2'-bipyridine. The solvent water molecules form a hydrogen-bonded net with tetrameric and pentameric water clusters as subunits. The Co4O4 cubane-like cores are sandwiched between the water layers, which are further stacked into a three-dimensional metallo-supramolecular network.

Diaqua-bis-(1H-imidazole-κN(3))bis-(4-nitro-benzoato-κO(1))cadmium.

In the centrosymmetric title compound, [Cd(C(7)H(4)NO(4))(2)(C(3)H(4)N(2))(2)(H(2)O)(2)], the Cd(II) atom, located on an inversion center, is coordinated by two N atoms and four O atoms in an octa-hedral geometry. The inter-nal cohesion of the mol-ecule is enhanced by an intra-molecular O-H⋯O hydrogen bond. Inter-molecular O-H⋯O and C-H⋯O hydrogen bonds and π-π contacts [centroid-centroid distance = 3.6549 (2) Å] define two-dimensional networks parallel to (001), which are further connected by weaker C-H⋯O inter-actions into a weakly connected three-dimensional supra-molecular framework.

Bis(2,2'-bipyridine-κ(2)N,N')(3-methyl-benzoato-κ(2)O,O')zinc 3-methyl-benzo-ate-3-methyl-benzoic acid-water (1/1/2).

The title compound, [Zn(C(8)H(7)O(2))(C(10)H(8)N(2))(2)](C(8)H(7)O(2))·C(8)H(8)O(2)·2H(2)O, is comprised of a Zn(2+) cation, two 2,2'-bipydine (bipy) ligands and one 3-methyl-benzoate anion (L(-)) together with one uncoordinating L(-) anion, one uncoordinating HL mol-ecule and two lattice water mol-ecules. The Zn(II) atom is coordinated by four N atoms of two bipy ligands and two O atoms from one L(-) ligand in a distorted octa-hedral geometry. Pairs of centrosymmetrically related complex mol-ecules form dimers via slipped π-stacking inter-actions between bipy ligands with an inter-planar distance of 3.470 (4) Å. The dimers are linked into supra-molecular chains along [111], via C-H⋯O hydrogen bonds. The uncoordinated L(-) anions, HL mol-ecules and water mol-ecules are connected with each other via O-H⋯O hydrogen bonds, forming chains between the metal complex chains and binding them together via C-H⋯O contacts. The resulting layers parallel to (010) are further assembled into a three-dimensional supra-molecular architecture through additional C-H⋯O inter-actions.

catena-Poly[[(diaqua-calcium)-bis-(µ-2-fluorobenzoato)-1':1κO:O,O';1:1''κO,O':O] 2,2'-bipyridine hemi-solvate].

In the title compound, {[Ca(C(7)H(4)FO(2))(2)(H(2)O)(2)]·0.5C(10)H(8)N(2)}(n), the Ca(II) atom is coordinated by eigth O atoms from four 2-fluoro-benzoate ligands and two water mol-ecules, resulting in a distorted CaO(8) square-anti-prismatic coordination environment. The 2-fluoro-benzoate ligand bridges two symmetry-related Ca(II) atoms, giving rise to a chain structure extending along [100]. The distances between the Ca atom and its two symmetry-related counterparts are 4.054 (2) and 4.106 (2) Å. The polymeric chains are connected by classical O-H⋯N hydrogen bonds into a layer structure parallel to (010). The layers are connected by non-classical C-H⋯F hydrogen bonds into a three-dimensional supra-molecular structure. O-H⋯O and C-H⋯O inter-actions also occur. The uncoordinated 2,2'-bipyridine mol-ecule is located on a centre of symmetry at the mid-point of the bond between the two heterocycles. One of the two benzene rings is disordered over two sites with occupancy factors of 0.60 and 0.40.

Aqua-(4-fluoro-benzoato-κO)bis-(1,10-phenanthroline-κN,N')manganese(II) 4-fluoro-benzoate trihydrate.

In the title compound, [Mn(C(7)H(4)FO(2))(C(12)H(8)N(2))(2)(H(2)O)](C(7)H(4)FO(2))·3H(2)O, the Mn(II) atom is coordinated by four N atoms from two chelating 1,10-phenanthroline ligands and two O atoms from one monodentate 4-fluoro-benzoate ion and one water mol-ecule, forming a distorted octa-hedral geometry. In the crystal, the three components are assembled into a tape structure along the a axis by O-H⋯O and C-H⋯O hydrogen bonds. Between the tapes, a π-π inter-action with a centroid-centroid distance of 3.569 (3) Šand a weak C-H⋯F hydrogen bond are observed.

Aqua-(4-carb-oxy-pyridine-2,6-dicarboxyl-ato-κO,N,O)(1,10-phenanthroline-κN,N')nickel(II).

The title compound, [Ni(C(8)H(3)NO(6))(C(12)H(8)N(2))(H(2)O)], contains an Ni(II) ion, a 1,10-phenanthroline (phen) ligand, a 4-carb-oxy-pyridine-2,6-dicarboxyl-ate (Hptc(2-)) anion and a coordinated water mol-ecule. The Ni(II) atom exhibits a distorted octa-hedral N(3)O(3) environment. O-H⋯O hydrogen bonding between coordinated water and carboxyl-ate O atoms, as well as π-π stacking inter-actions [inter-planar distances between phen rings = 3.293 (2) Å] lead to a supermolecular assembly.

2,2'-Bipyridine-cyclo-pentane-1,2,3,4-tetra-carb-oxy-lic acid (1/1).

The asymmetric unit of the title compound, C(10)H(8)N(2)·C(9)H(10)O(8), contains a half-molecule of 2,2'-bipyridine and a half-molecule of 1,2,3,4-cyclopentanetetracarboxylic acid, both components being completed by crystallographic inversion symmetry. In the crystal, the mol-ecules are assembled into chains extending along [010] by O-H⋯N hydrogen bonds; adjacent chains are linked by O-H⋯O hydrogen bonds into a three-dimensional network.

Aqua-(2,9-dimethyl-1,10-phenanthroline-κN,N')diformato-κO,O';κO-nickel(II) monohydrate.

The asymmetric unit of the title compound, [Ni(HCO(2))(2)(C(14)H(12)N(2))(H(2)O)]·H(2)O, contains a mononuclear complex mol-ecule hydrogen bonded to a lattice water mol-ecule. The Ni(II) atom exhibits a distorted octa-hedral coordination geometry formed by the N atoms from a 2,9-dimethyl-1,10-phenanthroline ligand, two O atoms of a chelating formate anion, one aqua O atom and one O atom of a coordinating formate anion. The mol-ecules are assembled into chains extending along [100] through by O-H⋯O hydrogen bonds. The supra-molecular chains are further linked into layers parallel to (011) by weak π-π packing inter-actions [centroid-centroid separation = 3.768 (2) Å]. The resulting layers are stacked to meet the requirement of close-packing patterns.

Poly[hexa-aqua-bis-(µ(3)-hepta-nedioato-κO:O':O'')dimagnesium].

In the title compound, [Mg(2)(C(7)H(10)O(4))(2)(H(2)O)(6)](n), the Mg(II) ion is coordinated by three aqua ligands and three O atoms from three heptanedioato ligands in a distorted octa-hedral geometry. Each heptanedioato ligand bridges three Mg atoms, generating polymeric layers parallel to the bc plane. The polymeric layers related by translation along the a axis inter-act further via O-H⋯O hydrogen bonds, which consolidate the crystal packing.

Urea-adipic acid (2/1).

The asymmetric unit of the title co-crystal, 2CH(4)N(2)O·C(6)H(10)O(4), contains two urea mol-ecules and two half-mol-ecules of adipic acid; the latter are completed by crystallographic inversion symmetry. The crystal packing is stabilized by O-H⋯O and N-H⋯O hydrogen bonds, generating a chain along [110]. Additional weak inter-chain O-H⋯O and N-H⋯O inter-molecular inter-actions lead to the formation of a three-dimensional network.

(2,2'-Bipyridine-κN,N')bis-(3-meth-oxy-benzoato-κO,O)copper(II) mono-hydrate.

The title compound, [Cu(C(8)H(7)O(3))(2)(C(10)H(8)N(2))]·H(2)O, is comprised of a Cu(II) ion, two 3-meth-oxy-benzoate ligands, a 2,2'-bipyridine (bipy) ligand and one uncoordinated water mol-ecule. The Cu(II) ion and the water O atom lie on a twofold axis. The Cu(II) ion exhibits a six-coordinate distorted octa-hedral geometry, with two N atoms from the bipy ligand [Cu-N = 1.9996 (16) Å] and four O atoms from two 3-meth-oxy-benzoate ligands [Cu-O = 1.9551 (15) and 2.6016 (16) Å]. The mol-ecules are linked by O-H⋯O and C-H⋯O hydrogen bonds, forming a three-dimensional network.

Tetra-µ-2-methyl-benzoato-κO:O'-bis-[(ethanol-κO)copper(II)].

In the title dinuclear complex, [Cu(2)(C(8)H(7)O(2))(4)(C(2)H(5)OH)(2)], four 2-methyl-benzoato anions form a cage around two Cu(II) ions in a syn-anti configuration. Two ethanol mol-ecules coordinate the Cu atoms in apical positions, giving an overall square-pyramidal coordination geometry. The Cu⋯Cu separation is 2.600 (1) Å. In the crystal, mol-ecules are assembled into chains extending in [001] through O-H⋯O hydrogen bonds.

(Benzoato-κO)bis-(1,10-phenanthroline-κN,N')copper(II) chloride benzoic acid disolvate.

In the title complex, [Cu(C(7)H(5)O(2))(C(12)H(8)N(2))(2)]Cl·2C(6)H(5)CO-OH, the Cu(II) ion is coordinated by one carboxyl-ate O atom from a benzoate anion and four N atoms from two phenantroline ligands in a distorted five-coordinate trigonal-bipyramidal CuON(4) chromophore. The Cu(2+) and the Cl(-) ion are imposed by a twofold rotation axiss which also bisects the equally disordered benzoate anion. In the crystal, the mol-ecules are assembled into chains along [010] by C-H⋯Cl, O-H⋯Cl and C-H⋯O hydrogen-bonding inter-actions. The resulting chains are further connected into two-dimensional supra-molecular layers parallel to [100] by inter-chain π⋯π stacking inter-actions [centroid-centroid distance = 3.823 (5) Å] between the phenanthroline ligands and the benzoic acid mol-ecules, and by C-H⋯O hydrogen-bonding inter-actions. Strong π⋯π stacking inter-actions between adjacent phenantroline ligands [3.548 (4) Å] assemble the layers into a three-dimensional supra-molecular architecture.

Disodium dihydrogen pyridine-2,3,5,6-tetra-carboxyl-ate trihydrate.

In the title compound, 2Na(+)·C(9)H(3)NO(8) (2-)·3H(2)O, the asymmetric unit consists of two Na(+) cations, one dihydrogen pyridine-2,3,5,6-tetra-carboxyl-ate dianion (H(2)pdtc(2-)) and three water mol-ecules coordinated to the Na(+) cations. The configuration of the anion is stabilized by intramolecular O-H⋯O hydrogen bonding between vicinal carboxylate/carboxy groups. The Na(+) cations are bridged by the H(2)pdtc(2-) dianions, generating layers extending infinitely in sheets parallel to (001), and further pillared by the water mol-ecule linkers to build up a three-dimensional framework.

catena-Poly[[[diaqua-copper(II)]-bis-(µ(2)-di-4-pyridyl disulfide-κN:N')] bis-(hydrogen phthalate) monohydrate].

The asymmetric unit of the title compound, {[Cu(C(10)H(8)N(2)S(2))(2)(H(2)O)(2)](C(8)H(5)O(4))(2)·H(2)O}(n), contains one Cu(II) ion, two bridging di-4-pyridyl disulfide (4-DPDS) ligands of the same chirality, two coordinating water mol-ecules, two hydrogen phthalate anions and one uncoordinated water mol-ecule. The polymeric structure consists of two types of polymeric chains, each composed from repeated chiral rhomboids. The Cu(II) ions adopt a distorted octa-hedral coordination geometry and are coordinated by four pyridine N atoms and two water O atoms. The coordinated water mol-ecules and hydrogen phthalate anions are located between the repeated rhomboidal chains, and form hydrogen bonds with the coordinated water mol-ecules.

Potassium (2,2'-bipyridine-κN,N')bis-(carbonato-κO,O')cobaltate(III) dihydrate.

In the title compound, K[Co(CO(3))(2)(C(10)H(8)N(2))]·2H(2)O, the Co(III) atom is coordinated by two bipyridine N atoms and four O atoms from two bidentate chelating carbonate anions, and thus adopts a distorted octa-hedral N(2)O(4) environment. The [Co(bipy)(CO(3))(2)](-) (bipy is 2,2'-bipyridine) -units are stacked along [100] via π-π stacking inter-actions, with inter-planar distances between the bipyridine rings of 3.36 (4) and 3.44 (6) Å, forming chains. Classical O-H⋯O hydrogen-bonding inter-actions link the chains, forming channels along (100) in which the K(+) ions reside and leading to a three-dimensional supra-molecular architecture.

µ-Succinato-κO:O-bis[(2,2'-bipyridine-κN,N')copper(II)] succinate dodeca-hydrate.

In the title compound, [Cu(2)(C(4)H(4)O(4))(C(10)H(8)N(2))(4)]C(4)H(4)O(4)·12H(2)O, C(10)H(8)N(2)), the centrosymmetic dinuclear cations, succinate anions and water mol-ecules are hydrogen bonded into layers parallel to (010). The Cu atom is square-pyramidally coordinated by one atom of the succinato ligand and four N atoms of two 2,2'-bipyridine ligands. The 12 water mol-ecules form a new type of water cluster.