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PubMed Journal Database | Dalton transactions (Cambridge, England : 2003) RSS

09:20 EDT 27th May 2019 | BioPortfolio

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Showing PubMed Articles 1–25 of 1,200+ from Dalton transactions (Cambridge, England : 2003)

Heterostructured NiFe oxide/phosphide nanoflakes for efficient water oxidation.

To realise the gradual replacement of noble metal-based materials for electrocatalytic energy conversion, numerous studies need to be focused on the compounds based on inexpensive 3d transition metals (such as Fe and Co). For achieving energetic electrocatalysis, elaborately designed nanostructures are urgently desired. Here, we reported a facile approach for the preparation of a NiFe oxide/phosphide (Ni2/3Fe1/3O/Ni4/3Fe2/3P) heterostructure with a 2-dimensional (2D) nanoflake-like morphology. Based on the ...

Modulating absorption and charge transfer in bodipy-carbazole donor-acceptor dyads through molecular design.

Three bodipy-based (BDP = 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) donor-acceptor dyads were designed and synthesized, and their ground-state and photophysical properties were systematically characterized. The electronic coupling between the BDP chromophore and an electron-donating carbazole (Carb) moiety was tuned by attachment via the meso and the beta positions on the BDP core, and through the use of various chemical linkers (phenyl and alkynyl) to afford mesoBDP-Carb, mesoBDP-phen-Carb, and betaBDP-a...

Molybdenum(ii) complexes with p-substituted BIAN ligands: synthesis, characterization, biological activity and computational study.

New complexes [Mo(η3-C3H5)X(CO)2(4-Y-BIAN)] (4-Y-BIAN = bis(4-Y-phenyl)-acenaphthenequinonediimine), with X = Br and Y = H, Me, OMe, COOH and X = Cl, Y = OMe, as well as the cation with X = NCMe and Y = OMe were synthesized, expanding the scope of this family. Two single crystal X-ray structures (X = Br, Y = Me, OMe) display a less symmetric arrangement (axial isomer), where one N donor atom is trans to the allyl group and the second to one CO. DFT studies showed similar energies for the two possible isome...

Electrocatalytic reduction of dioxygen by Mn(iii) meso-tetra(N-methylpyridinium-4-yl)porphyrin in universal buffer.

The electrochemical characterization of manganese(iii) meso-tetra(N-methylpyridinium-4-yl)porphyrin pentachloride ([Mn(TMPyP)Cl][Cl]4) via cyclic voltammetry (CV) and UV-vis spectroelectrochemistry (UV-vis SEC) was performed across the entire pH domain in aqueous buffered conditions. Assessment of the homogeneous electrocatalytic efficiency for the oxygen reduction reaction (ORR) from pH 3 to 6 using rotating-ring disk electrode experiments (RRDE) found it to be selective for water (82 to 93%). The observed...

Ligand effects on the structure, mixed-valence sites and magnetic properties of novel pentanickel string complexes.

We report the syntheses, characterization, electronic structures and magnetic properties of four redox pairs of novel nickel-extended metal-atom chain (EMAC) complexes containing pyridine-, naphthyridine- and sulfonyl-containing ligands (H2Tspnda and H2Mspnda) (1-2 and 5-6). We further study the corresponding phenyl-substituted ligands (H2Tsphpnda and H2Msphpnda) (3-4 and 7-8) to examine the details of ligand effects. The X-ray structure of one-electron-reduced [Ni5]9+ complexes shows shorter Ni-Ni bond dis...

Establishing the correlation between catalytic performance and N→Sb donor-acceptor interaction: systematic assessment of azastibocine halide derivatives as water tolerant Lewis acids.

A series of organoantimony(iii) halide complexes with a tetrahydrodibenzo[c,f][1,5]azastibocine framework were synthesized and employed as water tolerant Lewis acid catalysts. The results of a systematic structure-activity relationship study demonstrated that the strength of N→Sb donor-acceptor interaction could be synergistically modulated by tuning the properties of the nitrogen substituents and halogen atoms adjacent to the central antimony atom, and consequently resulted in distinct catalytic performa...

Red-emitting phosphors APF:Mn (A = Cs, Rb, K): synthesis, luminescence properties and application in solid-state lighting.

A series of APF6:Mn4+ (A = Cs+, Rb+, K+) phosphors with single phases were obtained via a simple ion exchange method. These phosphors can exhibit red emission with a broad excitation band in the blue region. The optimized concentration of Mn4+ in APF6:Mn4+ was determined. The Racah parameters B and C of Mn4+ in APF6:Mn4+ were also calculated. The results indicate that Mn4+ in CsPF6:Mn4+ experiences the weakest crystal field among APF6:Mn4+. The phosphor CsPF6:Mn4+ prepared with the HPF6/K2MnF6 molar ratio o...

The first water-based synthesis of Ce(iv)-MOFs with saturated chiral and achiral C-dicarboxylate linkers.

Six different chiral and achiral alkane dicarboxylic C4-acids, i.e. succinic acid (H2SUC), dl-2-methylsuccinic acid (H2MS), 2,3-dimethylsuccinic acid (H2DMS) and aspartic acid (d-, l- and dl-H2ASP), were used to obtain Ce(iv)-MOFs via microwave assisted reactions. In water-based syntheses, MOFs with three different topologies, denoted as UiO-66 (fcu), CAU-41 (bcu) and CAU-44 (bct), were obtained within 30 min under mild reaction conditions. The MOFs were fully characterized and their structures were refined...

Ligand mixed-valence and electrical conductivity in coordination complexes containing a redox-active phenalenol-substituted ligand.

A new redox-active hydrazone ligand bearing a phenalenol group is described (phpl), which produces neutral six-coordinate Fe and Co complexes (1 & 2) with the ligands identified in different oxidation states; an open-shell anion radical and closed-shell dianion. An intense and very low-energy intervalence charge transfer (IVCT) band is identified in solid-state and in solution in the complexes. Single crystals of 1 are semiconducting (at 300 K, σ = 3.05 × 10-4 S cm-1 with Ea = 245 meV).

Three-dimensional nanocomposites with CoO nanosheets parallelly embedded in carbon network walls for enhanced lithium-ion storage.

Three-dimensional Co3O4/C nanocomposites are synthesized via a hydrogel assisted synthesis route. The carbon has a three-dimensional interconnected network structure, and ultrathin Co3O4 nanosheets (≈5.0 nm) are parallelly and uniformly embedded in the two-dimensional carbon network walls. This unique structure restricts the aggregation and pulverization of active materials, and ensures the continuity and efficiency of electron and ion transmission during the lithiation/delithiation process. As a result, ...

Iron-loaded amine/thiol functionalized polyester fibers with high catalytic activities: a comparative study.

Dispersion of iron nanoparticles (Fe-NPs) was achieved on polyester fabrics (PET) before and after the incorporation of dendrimers (PAMAM), 3-(aminopropyl) triethoxysilane (APTES) or thioglycerol (SH). The catalytic activity of the resulting materials (PET-Fe, PET-PAMAM-Fe, PET-APTES-Fe and PET-SH-FE) was comparatively investigated in the degradation of 4-nitrophenol (4-NP) and methylene-blue (MB). Full characterization through diverse instrumental methods allowed correlating the type of the organic moiety ...

Hydrothermal generation, structural versatility and properties of metal(ii)-organic architectures driven by a pyridine-tricarboxylic acid.

An aromatic tricarboxylic acid, 4-(6-carboxy-pyridin-3-yl)-isophthalic acid (H3cpia), was applied as a building block for the hydrothermal syntheses of a new series of twelve metal(ii) (M = Mn, Co, Ni, Zn, Cd, Pb) coordination compounds, namely [Mn(H2cpia)2(H2O)2] (1), [M(Hcpia)(phen)(H2O)2] (M = Co, 2; Ni, 3; Zn, 4), [Zn(Hcpia)(2,2'-bipy)(H2O)2]5·4H2O (5), [Zn2(μ-Hcpia)2(2,2'-bipy)2] (6), [M(μ-Hcpia)(phen)(H2O)]n (M = Co, 7; Cd, 8), {[Pb(μ4-Hcpia)]·2H2O}n (9), [Cd4(μ3-cpia)2Cl2(phen)6(H2O)2]·10H2O (...

Structure and reactivity of the first-row d-block metal-superoxo complexes.

In the first-row of d-block metals, ten elements are included, such as scandium (Sc, 3d1), titanium (Ti, 3d2), vanadium (V, 3d3), chromium (Cr, 3d54s1), manganese (Mn, 3d5), iron (Fe, 3d6), cobalt (Co, 3d7), nickel (Ni, 3d8), copper (Cu, 3d104s1) and zinc (Zn, 3d10). The synthesis, characterization, and reactivity of first-row d-block metal-superoxo complexes are discussed together with the structures of the end-on (η1) and side-on (η2) metal-superoxo complexes in this review article. Electron transfer fr...

Studies of hysteresis and quantum tunnelling of the magnetisation in dysprosium(iii) single molecule magnets.

We report magnetic hysteresis studies of three Dy(iii) single-molecule magnets (SMMs). The three compounds are [Dy(tBuO)Cl(THF)5][BPh4] (1), [K(18-crown-6-ether)(THF)2][Dy(BIPM)2] (2, BIPM = C{PPh2NSiMe3}2), and [Dy(Cpttt)2][B(C6F5)4] (3), chosen as they have large energy barriers to magnetisation reversal of 665, 565, and 1223 cm-1, respectively. There are zero-field steps in the hysteresis loops of all three compounds, that remain in magnetically dilute samples and in samples that are isotopically enriche...

Chelate rings of different sizes with non-innocent ligands.

Redox-active unsaturated chelate ligands can be realised with different ring sizes of the resulting metallacycles. An overview is presented, starting from an exposition of non-innocent behaviour and chelate effects. A systematic approach is used to describe the most familiar situation, the metal complexes of 1,4-hetero-1,3-dienes in established forms (e.g. o-quinone, α-dithiolene, and α-diimine ligands) and with less common combinations of O, S, and N heteroatoms. The different steric and electronic condi...

Iridium porphyrin complexes with μ-nitrido, hydroxo, hydrosulfido and alkynyl ligands.

Iridium porphyrin complexes containing μ-nitrido, hydroxo, hydrosulfido, and alkynyl ligands have been synthesized and structurally characterized, and their oxidation has been studied. The alkyl-IrIII porphyrin complex [Ir(tpp)R] (tpp2- = 5,10,15,20-tetraphenylporphyrin dianion; R = C8H13; 1) was synthesized by reaction of [Ir(cod)Cl]2 (cod = 1,5-cyclooctadiene) with H2tpp in refluxing monoethylene glycol. Treatment of 1 with PPh3 and [(LOEt)Ru(N)Cl2] (LOEt- = [(η5-C5H5)Co{P(O)(OEt)2}3]-) gave [Ir(tpp)(R)...

Indium thiospinel In□InS - structural characterization and thermoelectric properties.

A detailed study of polycrystalline indium-based In1-x□xIn2S4 (x = 0.16, 0.22, 0.28, and 0.33) thiospinel is presented (□ - vacancy). Comprehensive investigation of synthesis conditions, phase composition and thermoelectric properties was performed by means of various diffraction, microscopic and spectroscopic methods. Single-phase α- and β-In1-x□xIn2S4 were found in samples with 0.16 ≤ x ≤ 0.22 and x = 0.33 (In2S3), respectively. In contrast, it is shown that In0.72□0.28In2S4 contains both α...

A novel sulfur quantum dot for the detection of cobalt ions and norfloxacin as a fluorescent "switch".

Sulfur nanomaterials exceed carbon nanomaterials in terms of the antimicrobial or antifungal properties. To date, there have been no reports on sulfur dots being used as fluorescence sensors. Herein, we report a simple assay based on aggregation-caused quenching (ACQ) of sulfur quantum dots (SQDs) to detect cobalt ions (Co2+). The S QDs allows the detection of Co2+ ions in the range of 0-9 × 10-5 mol L-1. This reliable, rapid, sensitive, and selective S QD probe has been utilized for the determination of t...

Highly selective CH and CO capture and magnetic properties of a robust Co-chain based metal-organic framework.

A robust Co-based metal-organic framework, [Co3(L)(OH)2(H2O)4]·2DMF·2H2O (1), was synthesized under solvothermal conditions using pyridyl-decorated tetracarboxylic acid, 2,6-di(2',5'-dicarboxylphenyl)pyridine (H4L). Structural analysis demonstrates that 1 is a 3D framework based on 1D alternate Co4 chain units. The desolvated structure of 1a contains 1D open channels with a highly polar pore surface decorated with open metal sites, μ3-OH group and pyridyl group sites, exhibiting multipoint interactions b...

Metal-coordination driven intramolecular twisting: a turn-on fluorescent-redox probe for Hg ions through the interaction of ferrocene nonbonding orbitals and dibenzylidenehydrazine.

A unique C2 symmetric azine bridged bi-ferrocenyl receptor (4) has been modelled and synthesized. In this work, we are able to synthetically regulate conjugation of the dibenzylidenehydrazine fluorophore unit to unexpectedly reveal metal-coordination driven intramolecular twisting. The present probe shows a dramatic turn-on fluorescence response with 91 fold increment of quantum yield along with 17 nm blue shift upon binding with Hg2+ ions selectively with a limit of detection as low as 15 nM. Upon Hg2+ rec...

Toward a dodecanuclear molecular Re(i) box: structural and spectroscopic properties.

Two tetrapyridyl ligands of 1,2,4,5-tetraethynyl(4-pyridyl)benzene (tpeb) and tetra(4-pyridyl)-tetrathiafulvalene (TTF(py)4) were used to react with trinuclear (Re(CO)4)3(C3N3S3) (C3N3S3 = cyanurate trianion) moieties to afford hexanuclear [(Re(CO)3)6(tpeb)2(C3N3S3)2]·4CH3CN·toluene (1) and dodecanuclear [(Re(CO)3)12(TTF(py)4)3(C3N3S3)4]·8CH3CN·12DMF (2) boxes, respectively, under solvothermal conditions. Surprisingly, similar tetrapyridyl ligands with different core units (i.e., benzene and tetrathiafu...

Holmium, thulium and lutetium-octamolybdate MoO 1D chains: luminescence investigation of europium doped lutetium-octamolybdate.

In this work we report a novel lanthanide octamolybdate 1D chain type of structure formed with holmium, thulium and lutetium. This is a rare case of compounds built out of [Mo8O28]8- units. These compounds were prepared in a mild reaction synthesis starting from the commonly used heptamolybdate polyoxometalate (POM) [(NH4)6[Mo7O24]. Interestingly, in our previous study we have employed a very similar synthesis route for lanthanides with a larger ionic radius and obtained heptamolybdate clusters. For the lan...

A new, simple, and efficient strategy for the preparation of active antifungal biodegradable materials via ring-opening polymerization of l-lactide with zinc aryloxides.

In this work, zinc aryloxides supported by monodentate hydroxybiphenyls [ArOH: ortho-phenylphenol (o-XenOH), meta-phenylphenol (m-XenOH), or para-phenylphenol (p-XenOH] and N,N,N',N'-tetramethylethylenediamine (TMEDA) were used to develop active polymeric materials for antifungal agents for agricultural use. The direct reaction of ligand precursor ArOH with ZnEt2 (1 : 2) in a toluene/TMEDA mixture (1 : 10) afforded a series of three isostructural monomeric compounds, namely [Zn(o-XenO)2(TMEDA)] (1),...

Different functional group modified zirconium frameworks for the photocatalytic reduction of carbon dioxide.

Conversion of carbon dioxide (CO2) into useful chemicals is an important and urgent task from the energy and environment perspective. Herein, through a post-synthetic modification (PSM) approach, we synthesized three new metal-organic frameworks (MOFs) UiO-68-PSMs with different functional groups, namely, UiO-68-F, UiO-68-CH3 and UiO-68-OCH3, for the photocatalytic reduction of CO2. By introducing electron-withdrawing and electron-donating groups, UiO-68-PSMs showed different performance for the selective p...

Chemistry and applications of cyanoximes and their metal complexes.

During the past three decades, considerable research effort has been dedicated to a new class of organic ligands - cyanoximes - which have the general formula NC-C([double bond, length as m-dash]NOH)-R, where R is an electron-withdrawing group. The presence of the CN group makes cyanoximes ∼10 000 times more acidic and better ligands than other known conventional monoximes and dioximes. Also, in numerous cases, this group provides extra nitrogen donor atoms to support the formation of bridges between me...


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