Synthesis, structural characterization, DFT and molecular dynamics simulations of dinuclear (μ-hydroxo)-bridged triethanolamine copper(II) complexes: efficient candidates towards visible light-mediated photo-Fenton degradation of organic dyes.

Multinuclear (di/tri) copper(II) complexes bridged through hydroxyl groups are very interesting coordination complexes owing to their potential applications in various fields. In this work, three novel dinuclear (μ-hydroxo)-bridged copper(II) complexes in the crystal form, namely, [Cu(3,5-DIFLB)(H)](HO) (1), [Cu(4-ClB)(H)](HO) (2), and [Cu(4-ETHB)(H)](HO) (3) (where DIFLB = difluorobenzoate, CLB = chlorobenzoate, ETHB = ethoxybenzoate, and H = triethanolamine), were isolated at room temperature using methanol and water in a 4 : 1 v/v ratio as a solvent. Furthermore, all three complexes (1-3) were characterised using spectroscopic (UV-vis, DRS, and FT-IR), electrochemical (CV) and single-crystal X-ray diffraction techniques.

Anilato-Based Coordination Polymers with Slow Relaxation of the Magnetization: Role of the Synthetic Method and Anilato Ligand.

We have prepared and characterized three coordination polymers formulated as [Dy(COCl)(fma)] ⋅ 4.5fma (1) and [Dy(COX)(fma)] ⋅ 4fma ⋅ 2HO with X=Br (2) and Cl (3), where fma=formamide and COX =3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone dianion with X=Cl (chloranilato) and Br (bromanilato). Compounds 1 and 3 are solvates obtained with slow and fast precipitation methods, respectively.

The Versatility of Ethylene Glycol to Tune the Dimensionality and Magnetic Properties in Dy-Anilato-Based Single-Ion Magnets.

We exploit the high versatility of the solvent ethylene glycol (eg = CHOH-CHOH) acting as a ligand with three different coordination modes: terminal (κ), chelate (κ), and bridge (1κ,2κ) to prepare a novel family of six different coordination polymers with Dy and three different anilato ligands (3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone dianion = COX, with X = H, Cl, and Br). With the X = H derivative (dhbq), we have prepared [Dy(dhbq)(eg)(μ-eg)]·4eg·2HO (), a 3D diamond-like network with a chelate and bridging eg molecules. With the X = Cl derivative (chloranilato), we have prepared [Dy(COCl)(eg)]·2eg·HO () and [Dy(COCl)(μ-eg)(HO)]·2eg·7HO ().

A rare example of a double metamagnetic transition leading to 2D and 3D long-range order in the two-dimensional pyrazine- and azido-bridged cobalt(II) compound [Co(pyz)(N)].

The synthesis, characterization, crystal structure and detailed magnetic properties of a pyrazine (pyz) and azido (N) bridged cobalt(II) compound of formula [Co(N)(pyz)] (1) are reported. Compound 1 shows a layered structure formed by Co(II) chains with double μ-N(κN,N) bridges that are further connected by μ-(pyrazine-κN,N) bridges. The layers present weak van der Waals interactions between azido terminal groups.

Clinical characteristics of adults suffering from high-functioning autism and comorbid obsessive-compulsive disorder.

Autism spectrum disorder (ASD) is a very heterogeneous disorder. Obsessive compulsive disorder (OCD) comorbidity, frequent in ASD, could be useful to define a specific ASD subtype. Our objective was to explore if adults with ASD and comorbid OCD could present a specific clinical profile of ASD in 89 high functioning-adult ASD patients.

L-Threoascorbic acid treatment promotes S. aureus-infected primary human endothelial cells survival and function, as well as intracellular bacterial killing, and immunomodulates the release of IL-1β and soluble ICAM-1.

Background: Vitamin C (ascorbic acid, AscH2) has been shown to enhance immunity. Here, we studied its immunomodulatory effect on human endothelial cells (ECs) during S. aureus infection.

Slow Relaxation of the Magnetization in Anilato-Based Dy(III) 2D Lattices.

The search for two- and three-dimensional materials with slow relaxation of the magnetization (single-ion magnets, SIM and single-molecule magnets, SMM) has become a very active area in recent years. Here we show how it is possible to prepare two-dimensional SIMs by combining Dy(III) with two different anilato-type ligands (dianions of the 3,6-disubstituted-2,5-dihydroxy-1,4-benzoquinone: COX, with X = H and Cl) in dimethyl sulfoxide (dmso). The two compounds prepared, formulated as: [Dy(COH)(dmso)(HO)]·2dmso·18HO () and [Dy(COCl)(dmso)]·2dmso·2HO () show distorted hexagonal honeycomb layers with the solvent molecules (dmso and HO) located in the interlayer space and in the hexagonal channels that run perpendicular to the layers.

Slow Magnetic Relaxation in a Co Dy Trimer and a Co Dy Tetramer.

The combination of Co(III) and Dy(III) with a compartmental Schiff base ligand (H L=3-[(2-Hydroxy-3-methoxy-benzylidene)-amino]-propane-1,2-diol), presenting three different coordinating pockets, has allowed the synthesis of two novel Co(III)-Dy(III) complexes: [Co Dy(HL) ]NO  ⋅ 2CH CN (1), a rare example of trinuclear linear Co Dy complex (and the first with slow relaxation of magnetization in absence of a DC field) and [Co Dy (μ -OH) (HL) (OAc) ] ⋅ 4.6H O (2), the first tetranuclear Co Dy cluster with a rhomb-like structure where the Co(III) ions are connected along the short diagonal of the rhomb. 1 presents two different relaxation processes: a fast relaxation dominated by Quantum tunnelling (QT) and a slow relaxation with an energy barrier of 40 K.

Solvent-tuned ultrasonic synthesis of 2D coordination polymer nanostructures and flakes.

Herein, a new 2-dimensional coordination polymer based on copper (II), {Cu(L)(DMF)}, where L stands for 1,2,4,5-benzenetetracarboxylate (complex 1) is synthesized. Interestingly, we demonstrate that both solvent and sonication are relevant in the top-down fabrication of nanostructures. Water molecules are intercalated in suspended crystals of complex 1 modifying not only the coordination sphere of Cu(II) ions but also the final chemical formula and crystalline structure obtaining {[Cu(L)(HO)]·HO} (complex 2).

Stroke knowledge among emergency centre visitors: A cross-sectional multicenter survey.

Introduction: Stroke is a public health problem worldwide. Community stroke knowledge is crucial to guide the prevention approach. We aimed to evaluate the level of stroke knowledge among the visitors to Emergency Centres (ECs) in the southern region of Tunisia concerning factors of risk, symptoms, and treatment of stroke.

Field-induced single molecule magnet behavior of a dinuclear cobalt(II) complex: a combined experimental and theoretical study.

Two dinuclear cobalt(ii) complexes, [(dmso)CoIIL1(μ-(m-NO2)C6H4COO)CoII(NCS)] (1) and [(dmso)CoIIL2(μ-(m-NO2)C6H4COO)CoII(NCS)] (2) [dmso = dimethylsulfoxide, H2L1 = (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-methoxyphenol) and H2L2 = (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-ethoxyphenol)] have been synthesized and structurally characterized by single-crystal X-ray diffraction, magnetic-susceptibility measurements and various spectroscopic techniques. Each complex contains a cobalt(ii) center with a slightly distorted octahedral geometry and a second cobalt(ii) center with a distorted trigonal prismatic one. To obtain insight into the physical nature of weak non-covalent interactions, we have extensively used the Bader's quantum theory of atoms-in-molecules (QTAIM).

miRNA-23b as a biomarker of culture-positive neonatal sepsis.

Background: Neonatal sepsis remains an important cause of morbidity and mortality. The ability to quickly and accurately diagnose neonatal sepsis based on clinical assessments and laboratory blood tests remains difficult, where haemoculture is the gold standard for detecting bacterial sepsis in blood culture. It is also very difficult to study because neonatal samples are lacking.

Slow relaxation of the magnetization, reversible solvent exchange and luminescence in 2D anilato-based frameworks.

A series of multifunctional 2D frameworks prepared with Dy(iii) and the bromanilato ligand, formulated as: [Dy(COBr)(G)]·nG with G = HO, dimethylformamide (dmf) and dimethylsulfoxide (dmso), can exchange the coordinated and non-coordinated solvent molecules (G) in a reversible way. These multifunctional frameworks show field induced slow relaxation of the magnetization and luminescence that can be easily and reversibly modified by solvent exchange.

Multifunctional Ni(II)-Based Metamagnetic Coordination Polymers for Electronic Device Fabrication.

The combination of two 8-aminoquinoline-based Schiff base ligands (L1 and L2) with SCN and Ni(II) has led to the synthesis of two new one-dimensional thiocyanato-bridged coordination polymers: [Ni(L1)(NCS)] () and [Ni(L2)(NCS)] (). Both compounds are isostructural and consists of regular zigzag thiocyanato-bridged chains with very weak S···S interchain interactions. The measured room-temperature conductivities of compounds and (7.

Trinuclear Lanthanide Coordination Clusters: Single-Molecule-Magnet Behavior and Catalytic Activity in the Friedel-Crafts Alkylation Reaction.

A new multidentate ligand (H L) was synthesized by the condensation reaction of 4-tert-butyl-2,6-diformylphenol and 2-amino-4-nitrophenol. The reaction of the ligand with hydrated lanthanide nitrate produced two isostructural trinuclear coordination clusters: [DyLn L (DMF) (H O) ] ⋅ 3.8DMFLn=Dy (1) and Nd (2) (DMF=N, N-dimethylformamide).

Magnetic Properties of End-to-End Azide-Bridged Tetranuclear Mixed-Valence Cobalt(III)/Cobalt(II) Complexes with Reduced Schiff Base Blocking Ligands and DFT Study.

Two tetranuclear mixed-valence cobalt(III/II) complexes having the general formula [(μ-N){Co(L )(μ-OCCHNO)Co(N)}]PF (where HL and HL are two reduced Schiff base ligands) have been synthesized and characterized. The structures of both complexes show cobalt(II) and cobalt(III) centers with a distorted octahedral geometry with cobalt(III) and cobalt(II) centers located at the inner NO and outer O cavities of the reduced Schiff base ligands, respectively. The oxidation states of both cobalt centers have been confirmed by bond valence sum (BVS) calculations.

Pre- and post-synthetic modulation of the ordering temperatures in a family of anilato-based magnets.

We report the synthesis and characterization of six novel heterometallic molecule-based 2D magnets with the bromanilato ligand (COBr = 1,3-dibromo-2,5-dihydroxy-1,4-benzoquinone dianion) and six different benzene derivative molecules. The compounds, formulated as (NBu)[MnCr(COBr)]·1.75CHBr (1), (NBu)[MnCr(COBr)]·CHX with X = Cl (2), I (3) and CH (4) and (NBu)[MnCr(COBr)]·2CHX with X = CN (5) and NO (6), present the classical hexagonal honeycomb-(6,3) lattice with alternating Mn(ii) and Cr(iii) ions.

Delamination of 2D coordination polymers: The role of solvent and ultrasound.

Two novel cadmium-based 2D coordination polymers have been synthesized and characterized. Experimental results evidence that the best delamination processes occurs when weak interactions dominate the cohesion between layers and solvent molecules are occluded within the crystalline network. In this case, the delamination of the crystals occurs spontaneously in water.

A fluorescent layered oxalato-based canted antiferromagnet.

We report the synthesis and characterization of the first fluorescent oxalato-based canted antiferromagnet. Compound [DOC][MnFe(C2O4)3] (1) (DOC = 3,3'-diethyloxacarbocyanine) combines the well-known canted antiferromagnetic [MnFe(C2O4)3]- honeycomb layers with a fluorescent cationic cyanine-type fluorescent dye. Besides the expected spin canted antiferromagnetic order in the oxalato layer at ca.

Solvent-modulation of the structure and dimensionality in lanthanoid-anilato coordination polymers.

We show the key role that the size and shape of the solvent molecules may play in the dimensionality and structure of a series of lanthanoid-chloranilato coordination polymers. We report the synthesis, structure and magnetic properties of six different coordination polymers prepared with Er(iii) and chloranilato (C6O4Cl22- = 3,6-dichloro-2,5-dihydroxy-1,4-benzoquinone) and six different solvents: [Er2(C6O4Cl2)3(H2O)6]·10H2O (1), [Er2(C6O4Cl2)3(FMA)6]·4FMA·2H2O (2) (FMA = formamide = NH2CHO), [Er2(C6O4Cl2)3(DMSO)4]·2DMSO·2H2O (3) (DMSO = dimethy sulfoxide = Me2SO), [Er2(C6O4Cl2)3(DMF)6] (4) (DMF = dimethylformamide = Me2NCHO), [Er2(C6O4Cl2)3(DMA)4] (5) (DMA = dimethylacetamide = Me2NC(Me)O) and [Er2(C6O4Cl2)3(HMPA)(H2O)3]·H2O (6) (HMPA = hexamethylphosphormamide = (Me2N)3PO). We show how the different solvent molecules modulate and determine important structural parameters such as the coordination number and geometry, the shape and distortions of the cavities, the presence of solvent molecules in these cavities, the interlayer space and even the dimensionality of the structure.

Nanosheets of Two-Dimensional Magnetic and Conducting Fe(II)/Fe(III) Mixed-Valence Metal-Organic Frameworks.

We report the synthesis, magnetic properties, electrical conductivity, and delamination into thin nanosheets of two anilato-based Fe(II)/Fe(III) mixed-valence two-dimensional metal-organic frameworks (MOFs). Compounds [(HO)(HO)(phenazine)][FeFe(COX)]·12HO [X = Cl (1) and Br (2)] present a honeycomb layered structure with an eclipsed packing that generates hexagonal channels containing the water molecules. Both compounds show ferrimagnetic ordering at ca.

Comparison of the Antidepressant-Like Effects of Estradiol and That of Selective Serotonin Reuptake Inhibitors in Middle-Aged Ovariectomized Rats.

This study investigated the effect of age and that of the post-ovariectomy (OVX) time interval on the antidepressant (AD)-like effects of estradiol (E) and selective serotonin reuptake inhibitors (SSRIs) in middle-aged (10 month) OVX rats (10m-OVX). Acute or chronic effects of these treatments in 10m-OVX were compared with those (1) in young adult (4-month) OVX rats (4m-OVX) or with older (14-month) OVX rats (14m-OVX), at a short time: 2 weeks post-OVX (+2w) and (2) in 10m-OVX rats after a longer times: 4 or 8 months post-OVX (+4m or +8m). Using chronoamperometry in the CA3 region of the hippocampus, E at 20 pmol, a dose shown previously to inhibit the serotonin transporter (SERT) in 4m-OVX, had no effect in 10m-OVX+2w.

A Heterobimetallic Anionic 3,6-Connected 2D Coordination Polymer Based on Nitranilate as Ligand.

In order to synthesize new coordination polymers with original architectures and interesting magnetic properties, we used the nitranilate ligand (C₆O₄(NO₂)₂ = C₆N₂O₈), derived from the dianionic ligand dhbq (2,5-dihydroxy-1,4-benzoquinone = H₂C₆O₄). The use of this bis-bidentate bridging ligand led to [(DAMS)₂{FeNa(C₆N₂O₈)₃}·CH₃CN] (1) (DAMS⁺ = CHN₂⁺ = 4-[4-(dimethylamino)-α-styryl]-1-methylpyridinium), a 2D heterometallic coordination polymer presenting an unprecedented structure for any anilato-based compound. This structural type is a 3,6-connected 2D coordination polymer derived from the well-known honeycomb hexagonal structure, where Fe(III) ions alternate with Na⁺ dimers (as Na₂O units) in the vertices of the hexagons and with an additional [Fe(C₆N₂O₈)₃] anion located in the center of the hexagons connecting the three Na⁺ dimers.