Nitrate-Anion-Induced Formation of a 2D Metal-Organic Framework with an Unconventional Kagomé Lattice Exhibiting Methanol-Mediated Ketone Catalysis.

Metal-organic frameworks (MOFs) with kagomé lattice are attractive for their unique physical and chemical properties, but little attention has been paid to their catalytic properties. Herein, we report a 2D MOF based on a phosphonato-amino-carboxylate ligand (NaHL), i. e.

Layered lanthanide phosphonates Ln(2-qpH)(SO)(HO) (Ln = La, Ce, Pr, Nd, Sm): polymorphism and magnetic properties.

Polymorphic layered lanthanide coordination polymers provide opportunities to study the effect of intralayer and interlayer interactions on their magnetic dynamics. Herein we report a series of layered lanthanide phosphonates, namely, α-Ln(2-qpH)(SO)(HO) (Ln = Sm) (α-Ln), β-Ln(2-qpH)(SO)(HO) (Ln = Pr, Nd, Sm) (β-Ln) and γ-Ln(2-qpH)(SO)(HO) (Ln = La, Ce, Pr, Nd, Sm) (γ-Ln) (2-qpH = 2-quinolinephosphonic acid), which crystallize in monoclinic 2/ (α-Ln), triclinic 1̄ (β-Ln) and orthorhombic (γ-Ln) space groups, respectively. The structural differences between the β- and γ-phases lie not only in the intralayer but also in the interlayer.

Photo-responsive Single-Molecule Magnet Showing 0D to 1D Single-Crystal-to-Single-Crystal Structural Transition and Hysteresis Modulation.

Photo-responsive lanthanide-based single-molecule magnets (SMM) hold great promise for future switching and memory devices. Herein, we report a dysprosium phosphonate [Dy (SCN) (NO )(depma) (4-hpy) ] (1Dy), which features a supramolecular framework containing layers of hydrogen-bonding network and pillars of π-π interacted anthracene units. The photocycloaddition reaction of anthracene pairs led to a rapid and reversible single-crystal-to-single-crystal (SC-SC) structural transition to form the 1D coordination polymer [Dy (SCN) (NO )(depma )(4-hpy) ] (2Dy), accompanied by photoswitchable SMM properties with the reduction of effective energy barrier by half and the narrowing of the butterfly-like hysteresis loop.

Polymorphism modulates photoluminescence and magnetic dynamics of mononuclear dysprosium-anthracene complexes.

Complexes α-Dy(depma)Cl (α-DyCl), β-Dy(depma)Cl (β-DyCl) and β-Dy(depma)Br (β-DyBr) (depma = 9-diethylphosphono-methylanthracene) are reported. α-DyCl and β-DyCl are polymorphs showing distinct magnetic dynamics with energy barriers of 32.3 K and 66.

Surface potential-determined performance of TiCT (T = O, F, OH) and ZrCT (T = O, F, OH, S) MXenes as anode materials of sodium ion batteries.

Sodium ion batteries (SIBs) have attracted increasing attention due to their low cost and abundant reserves of sodium, but their ideal anode materials still need to be explored. MXenes could be candidate electrode materials due to their excellent electrical conductivity and large specific surface area. In this work, the theoretical performance of Ti- and Zr-containing MXenes TiCT (T = O, F, OH) and ZrCT (T = O, F, OH, S) as SIB anode materials is investigated.

Photocontrollable Magnetism and Photoluminescence in a Binuclear Dysprosium Anthracene Complex.

By incorporating photoreactive anthracene moieties into binuclear DyO motifs, we obtain two new compounds with the formulas [Dy(SCN)(L)(dmpma)] () and [Dy(SCN)(L)(dmpma)(CHCN)] (), where HL is 4-methyl-2,6-dimethoxyphenol and dmpma is dimethylphosphonomethylanthracene. Compound contains face-to-face π-π interacted anthracene groups that meet the Schmidt rule for a [4 + 4] photocycloaddition reaction, while stacking of the anthracene groups in compound does not meet the Schmidt rule. Compound undergoes a reversible single-crystal-to-single-crystal structural transformation upon UV-light irradiation and thermal annealing, forming a one-dimensional coordination polymer of [Dy(SCN)(L)(dmpma)(dmpma)] ().

Dual-sensitized Eu(III)/Tb(III) complexes exhibiting tunable luminescence emission and their application in cellular-imaging.

Two novel dual-photosensitized stable complexes, namely [Eu(dpq)(BTFA)] (1) and [Tb(dpq)(BTFA)] (2), have been successfully assembled a mixed ligand approach using dipyrido[3,2-:2',3'-]quinoxaline (dpq) and 3-benzoyl-1,1,1-trifluoroacetone (BTFA). The crystallographic data reveal mononuclear lanthanide cores in both 1 and 2, in which each eight-coordinated Ln(III) ion is located in a slightly distorted dodecahedron (). The room-temperature photoluminescence spectra of complexes 1 and 2 indicate that both BTFA and dpq can effectively sensitize Eu(III) and Tb(III) characteristic luminescence.

Role of the A-Element in the Structural, Mechanical, and Electronic Properties of TiAC MAX Phases.

Combining metallic and ceramic properties, and as precursors for MXenes, MAX phases have attracted extensive attention. In recent years, A-element substitution has been demonstrated as an effective scheme to enrich the MAX family. To explore more possible MAX members, the structural, mechanical, and electronic properties and stabilities of 31 TiAC (A = Al, Si, P, S, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Os, Ir, Pt, Au, Hg, TI, Pb, Bi, and Po) configurations are investigated in this work.

Regulating the magnetic dynamics of mononuclear β-diketone Dy(iii) single-molecule magnets through the substitution effect on capping N-donor coligands.

A series of five mononuclear β-diketonate-Dy(iii) complexes, with formulas Dy(ntfa)(Br-bpy) (1), Dy(ntfa)(Br-bpy) (2), Dy(ntfa)(5,5-(CH)-bpy) (3), Dy(ntfa)(4,4-((CH))-bpy) (4) and Dy(ntfa)(4,4-(CH)-bpy) (5) (ntfa = 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, Br-bpy = 5-bromo-2,2'-bipyridine, Br-bpy = 4,4'-dibromo-2,2'-bipyridine, 5,5-(CH)-bpy = 5,5'-di-methyl-2,2'-bipyridine, 4,4-((CH))-bpy = 4,4'-di-tert-butyl-2,2'-bipyridine, and 4,4-(CH)-bpy = 4,4'-di-methyl-2,2'-bipyridine), have been prepared by altering the capping N-donor coligands. Dy(iii) ions in all complexes possess NO octa-coordinated environments, displaying a distorted square antiprismatic D symmetry in complexes 1-4, as well as a triangular dodecahedron D symmetry in 5. Magnetic investigations evidence the SIM behavior in the five complexes with the energy barriers (U) of 104.

A series of lanthanide(III) metal-organic frameworks derived from a pyridyl-dicarboxylate ligand: single-molecule magnet behaviour and luminescence properties.

The reactions of LnIII ions with a versatile pyridyl-decorated dicarboxylic acid ligand lead to the formation of a series of novel three-dimensional (3D) Ln-MOFs, [Ln3(pta)4(Hpta)(H2O)]·xH2O (Ln = Dy (1), Eu (2), Gd (3), Tb (4), H2pta = 2-(4-pyridyl)-terephthalic acid, x = 6 for 1, 2.5 for 2, 1.5 for 3 and 2 for 4).

Trends in C-O and N-O bond scission on rutile oxides described using oxygen vacancy formation energies.

Reactivity trends on transition metals can generally be understood through the d-band model, but no analogous theory exists for transition metal oxides. This limits the generality of analyses in oxide-based catalysis and surface chemistry and has motivated the appearance of numerous descriptors. Here we show that oxygen vacancy formation energy (Δ ) is an inexpensive yet accurate and general descriptor for trends in transition-state energies, which are usually difficult to assess.

Modulating energetic performance through decorating nitrogen-rich ligands in high-energy MOFs.

In the presence of different nitrogen-rich ligands, two energetic MOFs with formulas [Ag(tza)] (1) and [Ag(atza)] (2) (Htza = tetrazole-1-acetic acid and Hatza = (5-amino-1H-tetrazole-1-yl) acetic acid) were successfully synthesized and characterized. X-ray single crystal structure analysis shows that both 1 and 2 have 2D layer-like topologies. The experimental and theoretical evaluations reveal the promising properties of both energetic compounds, such as prominent heats of detonation, high thermal stabilities, good sensitivities and excellent detonation performances.

Enhancing single-molecule magnet behaviour through decorating terminal ligands in Dy compounds.

The utilization of two isomorphic ligands with different substituents leads to two centrosymmetric Dy dimers, namely, [Dy(bfbpen)(HO)]·2I (1) and [Dy(bcbpen)(HO)]·2I·0.5HO (2) (Hbfbpen = N,N'-bis-(2-hydroxy-5-fluoro-benzyl)-N,N'-bis-(pyridin-2-ylmethyl)ethylenediamine and Hbcbpen = N,N'-bis-(2-hydroxy-5-chloro-benzyl)-N,N'-bis-(pyridin-2-ylmethyl)ethylenediamine). Although Dy ions in both compounds uniformly exhibit a square-antiprism geometry, the critical difference found in the terminal substituents of the two ligands fine-tunes the local crystal field around Dy centers and the dinuclear molecular structures of 1 and 2.

Solvent-induced single-crystal-to-single-crystal transformation and tunable magnetic properties of 1D azido-Cu(ii) chains with a carboxylate bridge.

By means of the solvent effect, three new azido-copper 1D coordination polymers, [Cu(4-aba)(N)] (1), [Cu(4-aba)(N)(CHOH)] (2), and [Cu(4-aba)(N)(CHOH)] (3) (4-aba = 4-azidobenzoic acid), were successfully prepared in the presence of Cu ion, NaN and 4-azidobenzoic acid. Interestingly, 1 can be employed as a precursor and transformed to 2 and 3via the coordination of methanol or ethanol, respectively. Meanwhile, the identical products of 1, namely 1a and 1b, could be obtained from both 2 and 3 by a dealcoholized process.

From fluorene molecules to ultrathin carbon nanonets with an enhanced charge transfer capability for supercapacitors.

It is a big challenge to synthesize ultrathin carbon nanonets with an enhanced charge transfer capability for high-performance energy storage devices. Herein, ultrathin carbon nanonets (UCNs) were successfully synthesized for the first time from fluorene, a typical aromatic molecule, by a template strategy for supercapacitors. The formation mechanism of UCNs was determined using Density Functional Theory and Materials Studio, in which the fluorene-derived radicals were assembled into UCNs in the template-confinement space with the assistance of KOH.

Concise Chemistry Modulation of the SMM Behavior within a Family of Mononuclear Dy(III) Complexes.

By means of the facile chemistry, structural assembly, and transformation of four mononuclear Dy(III) complexes, Dy(bpad)·CHOH·HO (1), Dy(bpad)(HO)·NO (2), [Dy(bpad)(tmhd)] (3), and [Dy(bpad)(btfa)] (4) (Hbpad = N-benzoylpyridine-2-carboxamidrazone, tmhd = 2,2,6,6-tetramethylheptane-3,5-dione, btfa = 3-benzoyl-1,1,1-trifluoroacetone), with distinct architectures and local symmetries were established. The disparity of the coordination geometries around the Dy(III) ion among these complexes impacts the strength of the crystal field and the local tensor of anisotropy ( D) of each Dy site and their relative orientations, therefore giving rise to diverse SIM behaviors with distinguishing relaxation energy barriers of 106.93 K for 1, 52.

Otoprotective effects of ethosuximide in NOD/LtJ mice with age-related hearing loss.

Despite long-term efforts to elucidate the mechanisms responsible for age-related hearing loss (AHL), there is currently no available treatment strategy able to provide a cure. Apoptotic cell death, including that of hair cells and spiral ganglion neurons (SGNs) in the cochlea has been proposed to be the classic theory behind the development of AHL. As calcium signaling plays key roles in signal transduction in apoptosis, in this study, we selected ethosuximide, which is able to block T-type calcium (Ca2+ion) channels, suppressing Ca2+.

Harnessing the hidden genetic diversity for improving multiple abiotic stress tolerance in rice (Oryza sativa L.).

To develop superior rice varieties with improved yield in most rainfed areas of Asia/Africa, we started an introgression-breeding program for simultaneously improving yield and tolerances of multiple abiotic stresses. Using eight BC1 populations derived from a widely adaptable recipient and eight donors plus three rounds of phenotypic selection, we developed 496 introgression lines (ILs) with significantly higher yield under drought, salt and/or non-stress conditions in 5 years. Six new varieties were released in the Philippines and Pakistan and many more are being evaluated in multi-location yield trials for releasing in several countries.

Hearing Improvement in A/J Mice via the Mouse Nerve Growth Factor.

Objectives: To investigate the otoprotective effects of mouse nerve growth factor (mNGF) in A/J mice.

Methods: The mice at postnatal day 7 (P7) were randomly separated into a mNGF treated group (mNGF group) and a distilled water (for injection) treated group (control group). The mNGF dissolved in distilled water or distilled water alone was given to the mice once every other day from P7 by intramuscular injection in the hips.

A new copper species based on an azo-compound utilized as a homogeneous catalyst for water oxidation.

A new azo-complex [(L)Cu(II)(NO3)] [L = (E)-3-(pyridin-2-yldiazenyl)naphthalen-2-ol (HL)], was prepared via a one-pot synthetic method at 60 °C and was structurally characterized by IR, EA, PXRD and single crystal X-ray diffraction. In addition, TGA studies indicated that the complex was stable in air. The redox properties were determined by cyclic voltammetry, which revealed that the complex could be utilized as a catalyst for water oxidation under mild conditions.

Genome-wide response to selection and genetic basis of cold tolerance in rice (Oryza sativa L.).

Background: Cold stress is an important factor limiting rice yield in many areas of high latitude and altitude. Considerable efforts have been taken to genetically dissect cold tolerance (CT) in rice using DNA markers. Because of possible epistasis and gene × environment interactions associated with identified quantitative trait loci, the results of these genetic studies have unfortunately not been directly applicable to marker-assisted selection for improved rice CT.

Size-selective carbon nanoclusters as precursors to the growth of epitaxial graphene.

The nucleation and growth mechanisms of graphene on Rh(111) via temperature-programmed growth of C(2)H(4) are studied by scanning tunneling microscopy and spectroscopy, and by density functional theory calculations. By combining our experimental and first-principles approaches, we show that carbon nanoislands form in the initial stages of graphene growth, possessing an exclusive size of seven honeycomb carbon units (hereafter labeled as 7C(6)). These clusters adopt a domelike hexagonal shape indicating that bonding to the substrate is localized on the peripheral C atoms.

Atomic and molecular adsorption on RhMn alloy surface: a first principles study.

Density functional theory calculations have been employed to study the effects of alloy on energetics and preferential adsorption sites of atomic (H, C, N, O, S), molecular (N(2), NO, CO), and radical (CH(3), OH) adsorption on RhMn(111) alloy surface, and underlying electronic and structural reasons have been mapped out. We find that though Mn is energetically favorable to stay in the subsurface region, the RhMn surface alloy may be developed via the segregation induced by strong interaction between oxygen-containing species and Mn. Independent of adsorbates (not including O and OH), the interactions between these species and Rh atoms are preferential, and enhanced in general due to the ligand effects induced by Mn nearby.